Rhenium Alloys

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NGR
1813
University ofVirginia Library

TN799.R45 S3813
SEL Rhenium alloys, by E.M. Sav
inju
UX 001 138 770
UNIVERSITY / CE
VIRGINIA
CHARLOTTESVILLE
LIBRARIES
TT
69 - 5508
E.M. Savitskii, M.A.Tylkina, and K. B. Povarova
RHENIUM ALLOYS
PUBLIC DOCUMENT
BINDING
COPY
ALDERMAN LIBRARY
UNIVERSITY OF VIRGINIA
GIFT
Translated from Russian
Published for the U.S. Department of the Interior

and the National Science Foundation , Washington , D.C.
by the Israel Program for Scientific Translations
E. M. Savitskii, M. A. Tylkina, and K. B. Povarova
RHENIUM ALLOYS
( Splavy reniya)
Izdatel'stvo "Nauka"
Moskva 1965
Translated from Russian
Israel Program for Scientific Translations

Jerusalem 1970
TT 69- 55081
Leitner.
TN
799
R4553813
Copyright © 1970
Israel Program for Scientific Translations Ltd.
IPST Cat . No. 5511
Translated by Ch . Nisenbaum, Chem . Eng .

Edited by D. Slutzkin
Printed in Jerusalem by IPST Press

Binding: Wiener Bindery Ltd. , Jerusalem
Table of Contents
Page
Foreword . . . 1
Preface 3
Bibliography 6
PART 1
RHENIUM SOURCES AND TECHNOLOGY
Chapter 1. Sources of Rhenium 8

1. The history of the discovery of rhenium 8
2. The geochemistry of rhenium . 8
Chapter II. Industrial Sources of Rhenium 10
1. Molybdenum concentrates and the products of their treatment 10
2. Copper concentrates and products of their processing 11

3. Effluents from the treatment of copper shales . 11
4. Industrial effluent waters 11
Chapter III. Extraction of Rhenium 12
1. Extraction of rhenium from molybdenite concentrates and

from products of their processing . 12
2. Extraction of rhenium from copper concentrates and from

products of their treatment 13
3. Extraction of rhenium from effluents of the treatment of
copper shales ... 13
4. Extraction of rhenium from solutions by cementation 14
5. Ion exchange and sorption 14
6. Chlorination of dust with sublimation of rhenium chlorides . . 15

7. Extraction of rhenium from metal wastes 16
Bibliography for Chapters I – III 16
PART 2
PRODUCTION AND PROPERTIES OF METALLIC RHENIUM
Chapter IV . Production of Metallic Rhenium 20
1. Reduction of potassium perrhenate by hydrogen 20

2. Reduction of ammonium perrhenate by hydrogen . 20
Page
3. Reduction of ammonium and potassium perrhenates by

pressurized hydrogen . 22
4. Electrolytic production of rhenium 23
5. Thermal decomposition of rhenium compounds 24
6. Methods for the production of very pure rhenium 24
Chapter V. Production of Metallic Rhenium . 27

1. Powder metallurgy of rhenium 27
2. Melting menium 29
Chapter VI. Plastic Deformation of Rhenium 33

1. Cold working of rhenium . 33
2. Hot deformation of rhenium 42
3. Recrystallization of rhenium . 42
Bibliography for Chapters IV – VI 49
Chapter VII . Chemical Properties of Rhenium . 52

1. The valence states of rhenium 52
2. Compounds of rhenium with oxygen . . . 54
3. Compounds of rhenium with carbon O . 59

4. Compounds of rhenium with halogens . 60
5. Rhenium phosphides 63
6. Compounds of rhenium with sulfur . 63
7. Compounds of rhenium and nitrogen . 64

8. Thermodynamic characteristics of compounds of rhenium with
oxygen 64
9. Thermodynamic characteristics of rhenium halides . 68

germanium and silicon 70
sulfur 71
12. Melting and boiling points 71
13. Crystal structure of rhenium compounds 71

14. Electrical properties of rhenium compounds 74
15. Magnetic properties of rhenium compounds . 74
Bibliography for Chapter VII . . 75
Chapter VIII . Physical Properties of Rhenium 80

1. Crystal structure 81
2. Melting point 82
3. Boiling point and vapor pressure 83

4. Density 84
5. Specific heat 85
6. Thermodynamic characteristics 86
7. Thermal conductivity 87
8. Thermal expansion 87
iv
Page
9. Electrical resistivity 88
10. Magnetic properties 93
11. Superconductivity . . . 94
12. Optical properties . 96

13. Arc spectrum 97
Chapter IX . Mechanical Properties of Rhenium 99

1. Modulus of elasticity 99
2. Strength , ductility, hardness . 100
3. Long -time strength . 106
Bibliography for Chapters VIII – IX . 107
PART 3
PHASE DIAGRAMS OF RHENIUM
Chapter X. Binary Phase Diagrams 110

1. Factors determining reactions between elements O . 110
2. Method of preparation and study of rhenium alloys for the
construction of phase diagrams 114
3. Reaction of rhenium with elements of group I . . 116
4. Reaction of rhenium with elements of group II . 117
5. Reaction of rhenium with elements of group III . 118
6. Reaction of rhenium with elements of group IV 121
7. Reaction of rhenium with elements of group V 128
8. Reaction of rhenium with elements of group VI 135
9. Reaction of rhenium with elements of group VII . . 142
10. Reaction of rhenium with elements of group VIII . 143
Chapter XI. Ternary Phase Diagrams . 154
1. Ternary phase diagrams of rhenium - tungsten and a third

metal 154
2. Ternary phase diagrams of rhenium - tantalum and a third
metal 160
3. Ternary phase diagrams of thenium and nonmetals 162
Chapter XII . The Reaction of Rhenium with Some Elements . . 165
1. Formation of compounds in rhenium - containing alloys 165

2. Formation of solid solutions in rhenium systems 169
Bibliography for Chapters X – XII 172
PART 4
PROPERTIES AND USES OF RHENIUM ALLOYS
177
Chapter XIII. Preparation and Treatment of Rhenium Alloys
1. Classification of rhenium alloys . . 177
2. Mechanism of the influence of rhenium on other metals 178
3. Heat treatment of alloys . 185
Page
4. Preparation and deformation of alloys of rhenium with

tungsten and molybdenum . 185
5. Production and deformation of rhenium - chromium alloys 189
6. Production and deformation of alloys of rhenium with niobium ,

tanta lum , and vanadium 190
7. Recrystallization of rhenium alloys 190
Chapter XIV . Mechanical Properties of Rhenium Alloys • 198

1. Rhenium - tungsten alloys .. 198
2. Molybdenum - rhenium alloys . 206
3. Ternary tungsten -molybdenum - rhenium alloys 214
4. The ductile – brittle transition temperature of tungsten
rhenium and molybdenum - rhenium alloys 216
5. Chromium - rhenium alloys 219
6. Niobium -rhenium and tantalum -rhenium alloys 220
7. Rhenium - titanium alloys 221
8. Nickel - rhenium alloys 222
9. Ternary nickel - chromium - rhenium alloys . . 222
10. Manganese -rhenium alloys 224

11. Palladium - rhenium alloys 225
12. Iron - cobalt - rhenium alloys 226
13. Iron - chromium -nickel -rhenium alloys 227
14. Cobalt - chromium -nickel - rhenium alloys . 228
15. Wear resistance of rhenium and its alloys 230
Chapter XV . Weldability of Rhenium and Its Alloys 232

1. Welding rhenium ... 232
2. Welding molybdenum - rhenium alloys 233
3. Welding tungsten - rhenium alloys 235
4. Welding ternary tungsten -molybdenum -rhenium alloys 235
5. Rhenium alloying of molybdenum weld metal . 235
6. Welding titanium alloys . 238
Chapter XVI . Elastic Properties and Thermal Expansion of Rhenium

Alloys 240
1. Elasticity of molybdenum -rhenium alloys . 241
2. Elasticity of tungsten - rhenium alloys 242
3. Elasticity of niobium -rhenium alloys 242
4. Characteristic temperature of molybdenum - rhenium and

niobium rhenium alloys . . 243
5. Elasticity of rhenium disilicide . 244
6. Internal friction of molybdenum - rhenium alloys . 244
7. Thermal expansion of molybdenum - rhenium alloys 246

8. Thermal expansion of rhenium alloys containing niobium ,
tantalum , cobalt , chromium , nickel , and silicon 247
Bibliography for Chapters XIII – XVI . 248
vi
Page
Chapter XVII. Physical Properties of Rhenium Alloys . 251
1. Electrical resistivity of alloys of rhenium with molybdenum

and tungsten 251
2. Electrical resistivity of alloys of rhenium with noble metals . . 255
3. Electrical resistivity of alloys of rhenium with copper ,
manganese , chromium , iron, cobalt , nickel, or tantalum 257
4. Electrical resistivity of rhenium - rich alloys . . 258
5. Semiconductor properties of rhenium compounds O . 259
6. Magnetic properties of rhenium alloys 261
7. Superconductive rhenium alloys 262

8. Thermal conductivity and optical properties of rhenium alloys 270
Bibliography for Chapter XVII 270
Chapter XVIII. Use of Rhenium and Its Alloys in Electronics and

Electrical Engineering . . 272
1. Rhenium as an electron emitter 272
2. Rhenium as cathode material for a thermionic transducer
(TIT ) .. 278
3. Rhenium as the base of high - temperature cathodes 281

4. Rhenium and its alloys in structural elements in vacuum tubes
and other devices 289
Conclusion 292
Bibliography for Chapter XVIII 293
Chapter XIX . The Use of Rhenium and Its Alloys in Thermocouples 296
1. Thermocouples made of rhenium coupled with noble metals 296

2. Thermocouples made of rhenium coupled with tungsten ,
molybdenum , or their alloys 0 299
3. Thermocouples made of tungsten coupled with a tungsten

rhenium alloy , or of two tungsten-rhenium alloys 300
4. Thermocouples made of molybdenum - rhenium alloys 305

5. Rhenium - carbon thermocouples 305
6. Manganese - nickel base alloys with rhenium 305
7. Thermoelectromotive force of molybdenum - rhenium alloys
coupled with copper and aluminum 306
Conclusion 307
Chapter XX. Rhenium and Its Alloys for Use as Electric Contacts . 308
1. Contact resistance 309
2. Volt - ampere characteristics . 312

3. Erosion resistance • 314
4. Corrosion of contacts 317
5. Reliability of operation 320

Conclusion 321
Bibliography for Chapters XIX - XX 322
vii
Page
Chapter XXI . Diffusion Treatment of Rhenium . Rhenium and Rhenium

Alloy Deposits . . 325
1. Diffusion in rhenium -molybdenum alloys . . 325
2. Diffusion in rhenium -tungsten alloys O . 327
3. Diffusion treatment of rhenium 329
4. Electroplating with rhenium and its alloys . 332
5. Rhenium coatings from the gaseous phase . 338
Bibliography for Chapter XXI . .... 341
Chapter XXII. Corrosion Resistance of Rhenium and Its Alloys . 343

1. Oxidation of rhenium .. 343
2. Corrosion resistance of rhenium alloys 345
3. Corrosion of rhenium in acid and alkaline solutions . . . 348
4. Effect of molten metals on rhenium 349
Bibliography for Chapter XXII .. 350
Chapter XXIII . Catalytic Properties of Rhenium 352

Conclusion 354
Bibliography for Chapter XXIII 354
Literature on the Analytical Chemistry of Rhenium . 0 356
List of Abbreviations . 357
viii
FOREWORD
This monograph was written by scientists of the Laboratory of Heat

Resistant Alloys and Rare Metals of the Baikov Institute of Metallurgy .
The authors started their studies on rhenium and rhenium alloys at the
Kurnakov Institute of General and Inorganic Chemistry, AN SSSR , in 1953 .
The studies were continued on a wider scale at the Institute of Metallurgy
in 1955, when sufficient rhenium became available and the techniques of
vacuum arc melting and heat treatment were more developed , so that
investigations on a modern scientific basis were possible . During the last
ten years more than twenty phase diagrams of rhenium alloys have been
constructed , and many alloys of rhenium with refractory metals have been
developed . We have also studied different techniques of machining and
forming these alloys , and together with other institutions have tested parts thus
made for electric vacuum devices, in electronic equipment construction , and
other branches of industry .
At present scientific investigations in the field of rhenium are of great
importance .
When we started our studies rhenium was a " laboratory novelty ." Today
it is a rare , expensive , but fairly well- known metal, which shows how
rapidly rhenium and its alloys have been developed .
Rhenium is of great interest not only because of its physicochemical
properties and applications in modern industry as a material for thermo
couples , springs, and corrosion- resistant vibration electric contacts ,
cathodes of thermoelectronic transducers , and other parts of electric
vacuum devices, but chiefly because of its unique influence in decreasing
the ductile- brittle transition temperature , in retarding recrystallization ,
and in increasing the weldability of tungsten and molybdenum . Brittleness
at room and low temperatures , particularly after welding and
recrystallization, are the chief drawbacks of these heat- resistant and
relatively inexpensive metals for use in the rocket and electronic industries .
Rhenium, germanium , uranium , and some other elements show that
today the industrial importance of a metal depends on whether the metal
can help produce materials needed in modern industry, and not on its
yearly output . Hence, the great interest shown today in rhenium and
its alloys .
The purpose of this monograph is to summarize our data and that of
others on the structure and physicochemical properties of rhenium , its
alloys and compounds , and to find the proper use for them . At the same
time this book is to a certain extent an encyclopedia on rhenium , its alloys ,
and its compounds .
Limited space prevented us from including a chapter on the analytical
chemistry of rhenium, but a bibliography is given at the end of the book .
1
We wish to express our profound gratitude to corresponding member of
AN SSSR N. E. Alekseevskii, to Doctor V. I. Bibikova, to candidates I. E.
Dekabrun , S. U. Danishevskii , G. N. Kleban , A.S. Kotel'nikova , M. S.
Mirgalovskaya , 2. M. Sominskaya , and to engineers 0. A. Babareko ,
V. A. Grodko , and B. P. Kiselev, for their work in reviewing the individual
chapters .
We should also like to thank Mrs. L. L. Zhdanova for her graphical work .
TRANSLATION EDITOR'S NOTE
For technical reasons Z in this book denotes free energy or Gibbs free energy,
which in Western literature is usually designated as G.
2
PREFACE
Rhenium was discovered in 1925, and during the following 10- 15 years
only its chemistry was studied . The scarcity of rhenium in the earth's
crust , and the lack of methods for its production , hindered research , and
in particular the application of this new metal .
Rhenium was almost forgotten soon after its discovery, but attracted the
attention of the U. S. Air Force during World War II . Investigations were
greatly accelerated in 1950 .
Studies on the physicochemical properties of rhenium and its alloys are
being successfully carried out in many countries ( USSR , East Germany,
Poland, USA, England, France, West Germany, etc. ) and rhenium is
produced by several firms .
In West Germany the problem of the production of rhenium from zinc
powder is studied chiefly at the Institute of Nonferrous Metals in Freiberg .
In the USA studies on rhenium are concentrated mainly at the Battelle
Institute and the University of Tennessee . These studies are supported by
the Civil Aeronautics Board , the Atomic Energy Commission , and the BBC
Scientific Center in Cambridge .
In England rhenium is studied and produced at the electronics
laboratories in Baldock, and in the laboratories of Johnson , Mathew and Co.
In France rhenium is being studied at the Physical Laboratories of the
School of Standards in Paris .
In West Germany rhenium is being investigated at the Laboratory of
Inorganic Chemistry of the Technische Hochschule in Munich , and by the
firm " Gereis " (Hanau ) / 1 , 4 /.
New rhenium alloys with valuable properties for the electronic and
precision industries, heat- resistant alloys for thermocouples, alloys with
high ductility, wear resistance and corrosion resistance , and alloys with .
other valuable physical properties have been developed /2-5 /.
The demands of industry for such alloys are great, and exceed the supply.
The production of rhenium is low not only because of its scarcity but also
because existing deposits are little used . Figure 1 shows the content of
various elements in the earth's crust 16 / , and rhenium is at the apex of the
pyramid . However , in its vicinity we find elements which are widely used in
industry, for example , tungsten , molybdenum , gold , silver , antimony ,
cadmium , beryllium , etc.
Today one of the most urgent problems is to find more raw material
for the production of rhenium, and to develop efficient methods for the
production of rhenium from these materials . According to K. B. Lebedev / 1 /
the world production (excluding the USSR ) of rhenium was as follows :
Year 1930 1940 1942 1944 1948 1950 1952 1954 1958 1960 1962
Production in kg. 80 400 10 10 50 700 800 900 1500 2000 2500
3
Яе
Bi Te Au
SE Pd
Jntg cd TmAg
Lu S6
WHE TL MO
Се EU HO
or As
Te T6
Y8 Sn
Cs Er Th
Dy Cd 8
Pr
Sm SC Со P8
Ga
Cu
Се Lo NB Y
Ni
No li
0,015
0,017 Cr 2n
0,023 0.034 V
sr
0,037 S
0,065 Ba
0,068
0,093 P
0,10 Нn
0,45 li
Mg
1.87
2.50 к
2.50 Να
2,60
Ca
4,65 Fe
8.05
AL
29,50
Si
420
FIGURE 1. Content of different elements in the earth's crust (wt % ).
4
According to certain sources /7 / the USA alone can produce 9 – 13 tons
of rhenium annually. More than one hundred plants in the USA use rhenium
/8 /. Rhenium is expensive , but recently, as production increased and
methods for the extraction of rhenium became more efficient , the cost
dropped . The cost of 1 kg of rhenium powder produced from ammonium
perrhenate was 1500 dollars in 1958 and 1200– 1330 dollars in 1963. The
price of 1 kg of rhenium as sintered rods has decreased during the same
period from 1720 dollars to 1600 dollars /8— 10 /.
Rhenium salts , rhenium powder, and various semifinished products of
rhenium and rhenium alloys are produced by about 20 firms in the USA
and by more than 10 firms in England, West Germany, France , and
Austria /7 , 11 /.
The growing interest in rhenium is shown by the fact that no less than
four conferences on the subject have been held during the last six years ,
namely , the First All- Union Conference on Rare Metal Alloys in Moscow in
1957 , the First All- Union Conference on Rhenium in Moscow in 1958 , the
International Symposium in Chicago (USA ) in 1960 , and the Second All- Union
Conference on Rhenium in Moscow in 1962. The proceedings of these
conferences have been published in /2—5 / .
Great progress has been made in the production , study, and application
of rhenium and rhenium alloys since the First All- Union Conference on
Rhenium in 1958, in particular in the technology of the extraction of rhenium
from molybdenum raw materials and in the production of the pure metal
(electrolysis , thermal dissociation in gases , vacuum melting of rhenium,
etc. ) . Various methods of coating metals with rhenium have also been
developed /2—5 /.
Very pure simple crystals of rhenium have been produced in the USSR
and in England by the electron arc zone refining process , and the fine
structure and mechanism of deformation of rhenium crystals could thus be
studied .
The analytical chemistry of rhenium has been considerably expanded ,
new methods for determining rhenium and its gas content have been
developed , and new analytical apparatus built .
It is very encouraging that Soviet science is leading in research on
rhenium alloys . Of the twenty-seven rhenium binary phase diagrams known,
eighteen have been constructed in the Soviet Union . The crystallochemistry
of rhenium alloys is also more developed inside the USSR than outside .
Soviet institutions and plants have carried out extensive research on the
physical, chemical and technological properties of rhenium and its alloys ,
and have determined fields of their application in modern industry .
Success has been achieved by close cooperation between research
institutes and industrial plants .
The application of rhenium and of rhenium alloys has been extended in
some branches of industry ( electrovacuum technique , precision industry,
and production of high- temperature thermocouples and heat- resistant
materials ) .
The demand for rhenium, in contrast to that for other rare metals ,
considerably exceeds the supply due to the opportune and widespread
search for fields of application . Therefore, rhenium should be used only
where it can be of greatest use .
The present monograph deals mainly with the structure, physicochemical
properties , and application of rhenium and its alloys . The book has
5
four main parts . The first part describes the resources of raw material
and the metallurgy of rhenium . These problems are discussed rather
briefly and in a general way . More details can be found in the monograph
of K. B. Lebedev / 1 / and in some other reviews ( 3—5 / . The second part
gives methods for the production of metallic rhenium and describes its
physicochemical properties . Chapter IV deals briefly with fundamental
methods of the production of metallic rhenium from its salts by reduction,
electrolysis , and thermal decomposition of halides . The production of
compact rhenium by powder metallurgy and vacuum arc and electron- beam
melting is described in Chapter V. The chemical, physical, and mechanical
properties of wrought rhenium are discussed in Chapters VI - IX . To
clarify these problems we used literature data and our own experimental
results . We have also discussed controversial data .
The third part gives phase diagrams , and the fourth describes the
properties and application of rhenium alloys . The two last and most
important parts contain the experimental data of the authors , and the
conclusions drawn from these data and existing literature data .
Binary phase diagrams have been systematized according to the periodic
system . The few existing ternary phase diagrams of rhenium are also given .
The third part ends with a theoretical summation of the data on the
physicochemical interactions of rhenium with other elements , and a review
on the specific properties of this metal .
The part " Properties and Applications of Rhenium " has 11 chapters . We
thought it necessary to discuss the properties of the alloys and their
applications , particularly when the properties were very specific and
defined the application of the materials . This applies particularly to
chapters on the application of rhenium and its alloys for electric contacts
and other purposes . Chapters XIII- XVI at the beginning of this part
describe the properties of rhenium alloys as constructional materials
( heat resistance , wear resistance , high ductility ), and particularly the
problems of workability, of the production of semifinished products , and
of welding. The plating with costly rhenium is discussed in Chapter X.
Bibliography
1. Lebedev , K. B. Renii (Rhenium) . – Metallurgizdat . 1963 .

2. Sbornik " Redkie metally i splavy " ( Collection of Papers " Rare Metals
and Alloys " ). – Metallurgizdat . 1960 .
3. Sbornik " Renii" ( Collection of Papers " Rhenium " ). Izdatel'stvo AN
SSSR . 1961 .
4. " Rhenium ." Amsterdam , New York, Elsevier Publishing Company .
1962 .
5. Sbornik " Renii" (Collection of Papers " Rhenium " ). Moskva ,
Izdatel'stvo " Nauka ." 1964 .
6. Vlasov , K. A. Periodicheskii zakon i izomorfizm elementov (Periodic
Law and Isomorphism of Elements ) . – Moskva, Izd . Instituta
Mineralogii i Geologii Redkikh Elementov . 1963 .
7. Blon , R.H. et al . Rhenium Catalysts . Ind . Engng Chem . , 53 ( 2 ) : 108 .
1961 .
6
8. Rhenium , Tungsten . Am . Metal Market , 14. 1961 .
9. Rhenium . Minerals Yearbook , 1 : 1368. 1962 , 1963 .
10. Notes on Gallium and Rhenium . Am . Metal Market , p . 16. 17 August
1963 .
11. Increasing Production and Uses of Rhenium . Am . Metal Market ,
p . 68. 16 February 1964 .
7
Part 1
RHENIUM SOURCES AND TECHNOLOGY
In this part we shall give a short review of the present knowledge on the
geochemistry of rhenium and the available sources of the material , and of
the chemical technology of its extraction from rhenium - containing products
/1-4 /
Chapter 1
SOURCES OF RHENIUM
1. The history of the discovery of rhenium

The existence of a chemical element with an atomic number of 75 was
predicted by Mendeleev , who called this element dvimanganese ( 5–7 ).
He thought that its chemical properties should be similar to those of
manganese . It is believed that rhenium was discovered in 1925 by
Noddack and Tacke 8 /, and given its name in honor of the Rhine province
in Germany . However, the first discovery of rhenium is challenged by
Druce and Loring ( England ) / 9 /, who produced potassium perrhenate, but
their report was published several months after the report of Noddack and
Tacke . At the same time the work of Czech scientists was published /10 / .
Long before this Russian chemists had discovered a new element, which
they called devium / 11 , 12 / or il'men ' . This had chemical properties and
an atomic weight similar to those of rhenium .
Since rhenium is very scattered in the earth's crust it was very difficult
to obtain it in any large amount , and the first gram of metal was produced
only in 1929 / 14 /. The first production of rhenium on an industrial scale
by the Feit method / 15 / was started in the thirties . In 1942 a method for
extracting rhenium from the dust collected during the roasting of molybdenum
ores was developed at the University of Tennessee .
2. The geochemistry of rhenium
Rhenium is a rare and very scattered element , which has no ores of its
own . It has been found in many minerals (of molybdenum , copper , lead, zinc ,
platinum , tungsten , niobium , etc. ) and in rocks , meteorites , and even in the
spectrum of the sun .
In 1930 Noddack and Noddack / 16 / found that the content of rhenium
in the earth's crust is 1 · 10-7 % . According to data obtained in 1961 ( 17 ),
8
this content is ( 5–7 ) · 10- ? wt % ( 3.2 • 10-6 wt % in mixtures of basic rock
and 6.2 · 10-7 wt % in acid rock ) . Lebedev and Ageev / 18 ), and Rodzaevskii
/ 19 /, believe that the content of rhenium is one order of magnitude higher
(up to 1 10-8 wt % ) .
The content of rhenium in the earth's crust should not , however, be
considered as definitely determined .
The highest concentration of rhenium is found in molybdenites . Consider
able amounts of rhenium are also found in high- temperature sulfide ores ,
particularly those of copper , molybdenum , titanium, platinum , and others .
Rhenium is also found in granite pegmatites (alvite , gadolinite ,
thortveitite , zircon, orangite , columbite , tantalite , euxenite , fergusonite )
in concentrations of from 0.1 to 2.57 g / ton / 16 , 20 ). Minerals of the
platinum group of tungsten and manganese (osmiridium , platinum ore ,
manganese minerals , hübnerite , scheelite) contain less than 0.1 g / t of
rhenium / 16 , 21 /; sulfide minerals ( altaite , sperrylite , arsenopyrite ,
heredorfite , galenite , bornite , enargite , germanium, chalcopyrite ,
chalcosine, pyrite , pyrrhotine, pentlandite , berzelianite , argentite ,
bismuthinite , clausthalite ) contain 0.1 to 0.8 g /t of rhenium / 1 , 16 /;
uranium ores contain from 50 to 1000 g /t of rhenium /22— 24 / and
bituminous deposits (copper shale ) 0.01 g /t of rhenium /25 /.
Rhenium is found in meteorites also . The maximum content of rhenium
in iron meteorites is 0.33— 1.8 g /t , and the average content is only
0.01 g /t /26 /.
Rhenium is found together with molybdenum because of the similarity in
chemical properties (affinity for sulfur , volatility of halides and of
oxyhalides , etc. ) and also because of the similar dimensions of their atomic
radiuses and of the radiuses of their tetravalent ions . The concentration
of rhenium in molybdenites from different countries varies considerably
/4, 16 , 25, 27 , 30 /. Molybdenite from Stavanger in Norway contains
3100 g /t of rhenium, and molybdenite from Shirakawa in Japan only 10 g /t.
Despite the low and varying content of rhenium in molybdenites, these ores
are considered to be rich in comparison with other minerals , and they are
the chief source of rhenium .
A new source of rhenium has lately been found in the Dzheskazgan
copper sandstone . The concentration of rhenium in this sandstone is
several thousand times its clarke . It has been found that large amounts of
rhenium are present in the impregnated sulfide deposits of the first phase
of the mineralization of the Dzheskazgan deposits / 31– 35 /. No rhenium
has been found in the second phase of mineralization .
It is believed that rhenium, like molybdenum , forms a finely dispersed
sulfide / 32 , 36 /. According to other data /37 / rhenium forms a mineral of
its own that is embedded in other minerals as individual deposits . A study
of the Dzheskazgan deposits / 38-40 /, which although poor in basic
components ( copper , lead, zinc ) have a concentration of rhenium several
times higher than that usually encountered , has led to the discovery of a
rhenium mineral called Dzheskazganite . This mineral is present as thin
loop- shaped streaks and fringes around bornite , which contains large
amounts of blue chalcosine . Since the streaks are very thin (rarely 0.1 mm )
and intimately interwoven with other minerals they cannot be separated .
It is thought /39 ' that the composition of the mineral is CuReS4 .
We believe that new sources of rhenium should be sought .
9
Chapter 11
INDUSTRIAL SOURCES OF RHENIUM
Today the main sources of rhenium are as follows : 1 ) molybdenite

concentrates and products of their treatment; 2 ) copper concentrates and
products of their treatment ; 3 ) effluents of the treatment of copper shale ;
and 4 ) industrial waters .
1. Molybdenum concentrates and the products of their

treatment /1 /
Rhenium is extracted from the powder produced when molybdenum
sublimates are roasted during shaft smelting of copper shales ( East
Germany ) / 1 , 51 /, and from effluents formed during the hydrometallurgical
treatment of roasted molybdenite concentrates ( USSR ) .
The first stage of treatment of rich or lean molybdenum concentrates
is oxidation roasting. An investigation of the roasting of molybdenum
concentrates in a boiling layer /41— 44 /, during which both molybdenum
and rhenium oxides are formed, showed that rhenium exists in the products
of this roasting as Re207, Re03, and Re0g . The lower oxides of rhenium
are not stable at the roasting temperatures . The oxidation roasting of
molybdenum concentrates can lead to the formation of perrhenates of
calcium , copper , iron , and other metals that dissociate little at the
temperature of roasting, and all these probably remain in the ash .
The oxidation of rhenium sulfide starts at 200- 300°C . During roasting,
about 30— 85% of rhenium oxides sublime , depending on the type of furnace
(tubular, multihearth muffle type) /43— 45 /. The sublimation of rhenium
sulfide in these furnaces is incomplete due to insufficient oxidation, and
partial sintering and nodulizing of the concentrate during roasting .
While boiling layers are being roasted in furnaces , 85–96% of rhenium
sublimes /43, 44 /, since the material is friable and fine grained with no
nodulated products of roasting .
Rhenium can be caught from the gaseous phase by dust collectors in
amounts of from 30—70% of the metal that passed into the gas / 1 , 46 /. The
conditions for this collection have not yet been sufficiently investigated .
Under favorable conditions , rhenium oxide can condense into particles of
10-4 – 10-5 cm size (fog, smoke ) . The best results are obtained by wet electric
purification , by which almost the whole content of rhenium ( 89–96% ) can be
collected . Most of the rhenium passes into solution as an acid , and the rest
remains in the slime /43 , 44 , 47 , 48 /. According to /47 /, the most effective
10
system consists of a dry dust extractor , a scrubber , a bubbler , and a wet
electric filter , which collects the rhenium ( about 83% ) in solution . The
total content of rhenium collected by this system ( solution plus slime ) is 96% .
The dust produced when the concentrates are roasted also settles in
the gas ducts , and can serve as another source of rhenium as it contains
1000- 2000 g of rhenium per ton of dust / 1 /.
2. Copper concentrates and products of their processing

Rhenium- containing copper ores and products of their processing are a
very promising source of rhenium / 18, 19 , 49, 50 / . During flotation about
80% of the rhenium passes into the concentrate . The differences in the nature
of rhenium in ores , in concentrates, and in tailings have not yet been
sufficiently investigated .
The existing methods of smelting copper concentrates lead to different
distributions of rhenium between the products of smelting.
During treatment of pure copper concentrates 50— 75% of rhenium is
removed with the gases , and the rest passes into the matte . The extraction
of rhenium from these gases has not yet been studied , since the gases are
very voluminous and hot .
During the conversion of matte rhenium passes almost completely into
the gaseous phase , and much is lost . Part , however , is caught on wet
electric filters during the production of H2SO4.
3. Effluents from the treatment of copper shales
Copper shales from the Mansfeld deposit ( East Germany ) contain

1.8-2% of Cu and very little sulfur . Therefore they need no roasting and
can be directly reduced by smelting in a shaft furnace . A crust is left on
the furnace walls in amounts of 5-6% of the total content of matte . The
content of rhenium in these crusts is about 50 g /t / 1 , 51 /, and this was a
source of rhenium extraction by the Feit method from 1930 until World
War II . Since then rhenium has been extracted from the rhenium - richer
( 0.043% Re ) lead- zinc dust produced by shaft smelting copper shales / 52 /.
4. Industrial effluent waters
During the flotation of rhenium - containing ores ( copper and copper

molybdenum ores ) , rhenium can pass partially into solution , and is lost
together with the flotation water if active agents which dissolve sulfides
are used . The dry residue from the filtrate of the molybdenum concentrate
contains up to 1 g Re / t /1 /.
Effluents of the hydrometallurgical treatment of lean molybdenum
concentrates are another source of rhenium 153 , 54 /. When molybdenum
concentrates are roasted some of the rhenium remains in the ash and passes
into solution when the ash is leached by a soda solution . Calcium molybdate
is precipitated and the solution contains 15 – 40 mg Re / liter / 54 /, which
can be extracted .
11
Chapter III
EXTRACTION OF RHENIUM
There are many methods for the extraction of rhenium . These consist
of two main stages : 1 ) dissolution of rhenium compounds , and 2 ) precipitation
of rhenium from these solutions . A review of the methods of rhenium
extraction is given by Lebedev / 1 /.
Rhenium from rhenium - containing products is dissolved by the following
methods : 1 ) direct leaching by aqueous solutions ; 2 ) direct leaching by
aqueous or alkali solutions containing oxidants ; 3 ) sintering with lime and
leaching by water; 4 ) repeated roasting of dust , sublimation , and leaching
by water; 5 ) leaching by acids or salts .
The methods by which rhenium is precipitated from the solution can be
divided into four groups : 1 ) precipitation of rhenium as sparingly soluble
compounds (potassium perrhenate , sulfides , organometallic compounds , etc. ) ;
2 ) cementation methods ; 3 ) absorption methods ; 4 ) electrolytic deposition .
1. Extraction of rhenium from molybdenite concentrates

and from products of their processing
Direct leaching by water / 1 /. This method can be used for dust
produced by intense oxidation roasting . Rhenium is present as a soluble
heptoxide . The method has been employed since 1942 at the University of
Tennessee at Knoxville ( USA ) . The dust is leached by water , the sediment
is allowed to settle and is separated , and potassium perrhenate is
precipitated from the solution of perrhenic acid by potassium chloride .
The filtered perrhenate is repeatedly recrystallized until 99.9% pure
crystals of KRe04 are obtained . The mother liquors from each recrystalli
zation are evaporated and reused .
If the dust contains rhenium in the form of sparingly soluble compounds
(trioxide , dioxide , or sulfide ) , it can be leached by water containing an
oxidant (chlorine, hypochlorite, chlorine or bromine water , nitric acid ,
or finely powdered pyrolusite ) /55-57 /.
The physicochemical principles of the hydrometallurgical method for the
production of rhenium are given in / 58 /.
Sintering dust with lime / 1 /. A moist mixture of dust and
slaked lime is heated in an electric muffle furnace at 600°C , and the product
is leached . The crude potassium perrhenate is repeatedly recrystallized ,
and the yield of rhenium from this salt is 80— 87% . The losses during
deposition are 7 – 10 % and during recrystallization 5 – 8% / 1 /. This method
is simple and is widely used .
12
Sintering with mirabilite . This method prevents the rhenium
which remains in the ash from subliming, and the rhenium is leached . The
yield of rhenium is 93.5 % /45 /.
Leaching in autoclaves . The sublimation of rhenium is also
prevented by leaching molybdenum concentrates directly in autoclaves by
solutions of sodium carbonate /59 /, by sodium hydroxide or ammonia under
oxygen pressure /60 /, or by a solution of sodium hydroxide containing
cupric oxide as an oxidant /61 /.
2. Extraction of rhenium from copper concentrates and

from products of their treatment
Extraction of rhenium from the dust of copper

smelting plants . Rhenium can be extracted from this type of dust
by the same methods used to extract rhenium from the dust produced
by roasting molybdenum concentrates / 1 /.
Extraction of rhenium from copper concentrates before
smelting . Lebedev / 1 / believes that the method of selective extraction
of rhenium directly from rhenium- containing copper concentrates before
pyro- or hydrometallurgical treatment is most promising, since losses of
rhenium during smelting are prevented and special dust - catching
equipment is unnecessary . The following three methods for extracting
rhenium from concentrates are now being developed .
1 ) The concentrate is leached in three stages by agitation and aeration
in alkaline solutions of 90°C . No copper passes into solution during this
process . Rhenium dissolves as a result of leaching three times by an
oxidizing solution . The metal is extracted on adsorption columns /37 /.
2 ) The concentrates are leached by water or by weakly alkaline
solutions in an autoclave under air or oxygen pressure . Autoclaves of the
horizontal type are used for leaching by water containing lime . In this way
up to 70% of rhenium passes into solution . It is extracted by activated
carbon or ion exchange resins .
3 ) Rhenium can be leached from concentrates by sodium hydroxide
solution without an autoclave . The rhenium is then deposited on zinc . The
yield of rhenium ( in % of total content of Re in concentrate ) obtained by this
method is as follows : rhenium sponge 70 % ; final product 50 — 55% / 1 , 63 /.
3. Extraction of rhenium from effluents of the treatment

of copper shales
Extraction of rhenium from the lead - zinc dust

produced during shaft smelting of copper shales /64 - 66 /.
These dusts contain up to 15 % of bitumens . When they are dried in a
cylindrical furnace the bitumens burn and leave a fine coke . This contains
small amounts of copper , silver , cadmium , iron , and rhenium . At the
Mansfeld plant this fine coke is heated at 1000°C in an inert or slightly reducing
atmosphere . Rhenium sulfide sublimes and is oxidized to rhenium heptoxide
13
at the gas outlet of the furnace . The cooled gases pass through bag filters .
In the lead distillate rhenium is present as a pentoxide , which can easily
be separated by leaching in water .
Copper and cadmium are removed from rhenium - containing solutions by
treatment with zinc dust in the cold , and then with sodium sulfide and
sulfuric acid . Re207 is precipitated . The precipitate is filtered , calcined
with sodium carbonate , and treated with hot alkali solutions . Rhenium
passes into solution as sodium perrhenate , and is precipitated by potassium
chloride as potassium perrhenate . It is so pure that no recrystallization is
necessary .
4. Extraction of rhenium from solutions by cementation
Cementation of rhenium from acid molybdenum mother

liquor solutions . This process consists in cathodic reduction of
perrhenate by hydrogen . If the amount of active hydrogen atoms is sufficient,
the reduction proceeds to metallic rhenium , otherwise low- valence oxygen
compounds of rhenium are produced . The rhenium is deposited on iron , and
consists of 60 – 75% of metallic rhenium and 25– 40% of ReO2.2H20 /67 , 68 /.
According to other sources , spongy iron can extract 90% of the Re and
90% of the Mo from the solution / 69, 70 ). The extracted deposit containing
0.51 % Re is roasted with lime , and calcium salts of rhenium and molybdenum
are produced . The roasted product is leached by water , and calcium
perrhenate passes into solution . Rhenium can be deposited in the usual way .
Cementation of rhenium from alkaline molybdenum
mother liquor solutions / 1 ). Cementation of rhenium is accompanied
by dissolution of zinc in the alkaline solution , and the approximate
composition of the precipitate is ReO2 · 2H20 . The total concentration of
Re in the deposit is up to 0.2% .
5. Ion exchange and sorption
Ion exchange . Rhenium and molybdenum can give Moo and MoO3* ,
and Re04 and Re0 ions , that differ in composition and valency .
Complete separation of these ions on the Soviet TM resin is possible .
The resin has a capacity of 4.45 mg- equiv /g at pH = 1 /71–73 /. If the
solution is acidified to 0.5 N in hydrochloric acid, rhenium is completely
absorbed by the active groups of the resin and can be extracted by a 10%
solution of sodium hydroxide . The methods for extracting Re from lean
solutions ( 10- 12 mg /l of Re ) by ion exchange and sorption have been
investigated in /74 /. Twenty- three types of weakly , moderately, and
strongly basic anion exchange resins have been studied and the factors
influencing their exchange capacity determined . Of the resins studied , the
following had the highest exchange capacities : VDP ( 10.59 % ), ASD- 5
(6.93-6.76 % ), AM (6.01 - 5.96% ), and AV- 18 (5.07–5.39 % ).
To separate rhenium from molybdenum we took advantage of the different
forces binding the rhenium and molybdenum ions to the IRA- 400 anion
exchange resin /75 /.
14
The separation of rhenium from molybdenum can also be based on the
different signs of the ions of these elements in solution . At a certain pH
the total amount of molybdenum is present as cations , but rhenium
remains as an anion . With SBS cation exchange resins and sulfonated coal
it is possible to separate molybdenum from rhenium in solutions containing
these elements in the ratio of 1 : 3 to 300 : 1 . Sulfonated coal absorbs 50 times
more molybdenum than the SBS resin /76 /.
The sorption of rhenium , molybdenum , selenium , and tellurium on
AV- 18, EDE- 10 , and Al- 1 anion exchange resins in various media has been
investigated . The maximum separation of rhenium from these elements
was obtained on the AV- 18 resin in 1–1,5 N HCl and in 2.5-5N NaOH /77 /.
The anion exchange resin IRA- 400 (IRA- 410 ) can also be used to separate
rhenium from molybdenum , arsenic , and selenium /78 /.
Adsorption . An apparatus for extracting molybdenum and rhenium
by adsorption from the mother liquor produced during treatment of poor
molybdenum concentrates is used in industry / 53, 70, 79 – 80 ). The
molybdenum is extracted by passing solution (pH = 3 ) through columns packed
with the sulfonated anion exchange resin " Espatit AN - 1 . " The solution
contains up to 20 mg /l of Re and about the same amount of Mo ; it is passed
into adsorption filters packed with " KAD " activated carbon , on which both
metals are completely adsorbed . The molybdenum is extracted by a solution
of ammonia . Rhenium is extracted from these filters by a solution of
sodium carbonate . A method for regenerating the activated carbon has also
been developed, and it is possible to extract molybdenum and rhenium
separately by alkali solutions . Carbon can be regenerated by ammonia to
produce ammonium perrhenate / 1 /.
The influence of various impurities ( sulfates and chlorides of copper ,
zinc sulfate , and chloride and sulfate ions ) on the adsorptive capacity of
" KAD " activated carbon /81 / has been studied .
Several types of activated carbon have been investigated , and AG- N ,
AG- 3 and AG- 5 have proved to be the best /82 /. Carbon can be regenerated
3 – 4 times , and then its activity drops to 60% of its initial value /83 /.
To extract rhenium from very poor industrial and natural waters a
method has been developed for selective concentration of rhenium from
neutral or weakly alkaline media, using activated carbon saturated with
methylene blue as a complex- forming agent . With this method 96 - 98% of
rhenium can be absorbed , also from solutions containing molybdenum and
tungsten /37 , 62 , 84 / .
6. Chlorination of dust with sublimation of rhenium chlorides
The separation of rhenium and molybdenum is based on the different

boiling points of molybdenum dichloride and of rhenium trioxychloride . The
chlorination is carried out at 450° C by a mixture of chlorine and oxygen
( 1 : 3 by volume). The sublimate consists of oxychlorides of molybdenum
and rhenium , from which up to 95 % of the Re and 0.5 % of the Mo present in
the molybdenum concentrate can be removed by fractional distillation . The
rhenium to molybdenum ratio in the initial concentrate is 1 : 1250 , and in the
absorber it is 1 : 5.
15
The method of chlorination has not yet been accepted industrially, but
it can be used to extract rhenium from the dust produced during roasting
of molybdenum concentrates /85 /.
7. Extraction of rhenium from metal wastes
As we have already mentioned , rhenium is an expensive metal and its

reserves and supply are limited . Therefore , great attention should be paid
to the extraction of rhenium from wastes , particularly as the concentration
of rhenium in these wastes is rather high . In molybdenum alloys the content of
Re can be up to 50% , while even in the richest concentrates its content is
not more than a few hundredths of one percent . The process of rhenium
extraction from metal wastes is relatively simple and inexpensive .
As the demand of industry for rhenium- containing materials increases .
the amount of reprocessed rejects of cast and wrought materials (wire , foil),
used parts , etc. , also increases .
The old method of dissolving alloys in mixtures of nitric acid and
hydrogen peroxide /86 / is not very effective since the dissolution is slow,
and the apparatus must be made of chemically resistant materials . The
present method for extracting rhenium from tungsten alloys containing
3 – 20% of Re is more efficient / 87 ). The alloy is heated to 500 – 600°C
with sodium nitrate . Nitrogen oxides are evolved and water- soluble salts
formed . When cool , these can easily be leached by hot water to form
solutions of sodium perrhenate and sodium tungstate . From these solutions
potassium perrhenate can be precipitated by potassium chloride , and
tungsten remains in solution . From 90 to 94 % of rhenium in the alloy can be
converted into potassium perrhenate .
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45. Lebedev , K. B. and Yu . N. Men zhulin . Izv. AN KazSSR , seriya
" Metallurgiya," No.1 : 43 . 1958.
46. Savraev , V.P. - Sbornik " Renii," p . 79. Moskva, Izdatel'stvo
" Nauka ." 1964 .
47. Savraev , V. P. and B. A.Sankov . Tsvetnye Metally, No. 12:53 .
1960 .
48. Petrov , V.M. Izuchenie obzhiga v kipyashchem sloe reniisoder
zhashchikh molibdenitovykh kontsentratov (Investigation of Roasting
in a Boiling Layer of Rhenium - Containing Molybdenum Concentrates ) .
Author's Summary of Thesis . Krasnoyarskii Institut Tsvetnykh
Metallov , Moskva . 1961 .
49. Fleischer , M. Chron . mines d'outre mer , 28 ( 290 ) : 3 . 1960 .
50. Lebedev , K. B. Sbornik " Renii," p . 3. Izdatel ' stvo AN SSSR . 1961 .
51. Florov , V.A. , editor . Tsvetnaya metallurgiya Tsentral'noi i
Vostochnoi Germanii (Metallurgy of Nonferrous Metals of Central
and Eastern Germany ). Metallurgizdat . 1947 .
52. Getskin , L. S. – Tsvetnye Metally, No.3 : 22 . 1957 .
53. Lebedev , K.B. Proizvodstvo molibdata kal'tsiya ( Production of
Calcium Molybdate ). Izdatel'stvo AN KazSSR . 1962 .
54. Kovyrshin , V.G. and V. K.Appolonov . - Tsvetnye Metally,
No. 8:67 . 1957 .
55. Hampel , A. Rare Metals Handbook, p . 347. 1954 .
56. Trone v , V.G. Khimicheskaya Nauka i Promyshlennost ' , 1 , No. 5 .
1956 .
57. Abashin , G.I. Sbornik " Renii," p . 51. Izdatel'stvo AN SSSR . 1961 .
58. Postnikova , S. V., V.1 . Bibikova , and P.I. Fedorov . Sbornik
" Renii," p . 36. Moskva , Izdatel'stvo " Nauka," p . 36. 1964 .
59. Sobol ' , S.I. , V.I. Spiridonova , and E.I.Gulya e va . Sbornik
"Renii," p . 56. Izdatel'stvo AN SSSR . 1961 .
60. Darbinyan , M. V. Sbornik " Renii," p . 67. Izdatel'stvo AN SSSR .
1961 .
61. Ponomareva , E.I. and K. B. Lebedev . Trudy Instituta
Metallurgii i Obogashcheniya AN KazSSR , 4:28 . 1962 .
62. Rodzaevskii , V.V. and A.E. Belousova . Byulleten ' TSIINTsvet
met , No. 12 ( 161 ) : 33 . 1960 .
63. Lebedev , K. B. , S. A. Ageev , N. A. Okhotnikova , V. V.
Ermilov , E. S. Raimbekov , and M.I. Filimonov . Sbornik
" Renii," p . 40. Moskva, Izdatel ' stvo " Nauka . " 1964 .
64. Feit , W. · Z. angew . Chem . , 46 : 216 . 1933 .
65. Lindemann , G. Neue Hütte , 2 ( 2 – 3 ) : 200 . 1957 .
66. Lebedev , K. B. and M. M. Magin . Metallurgicheskaya i Khimi
cheskaya Promyshlennost ' Kazakhstana , No. 2. 1959.
67. Zuev , B.N. and O. A.Suvorova . – Trudy Instituta Metallurgii i
Obogashcheniya AN KazSSR, 1 : 102 . 1959 .
18
68. Zuev , B.N. Tsementatsiya reniya iz sernokislykh rastvorov
perrenatov tsinkom i zhelezom ( Deposition of Rhenium from
Sulfuric Acid Solution of Perrhenates by Zinc and Iron ) . – Author's
Summary of Thesis . Institut Metallurgii i Obogashcheniya AN
KazSSR , Alma - Ata . 1953 .
69. Kovyrshin , V. G. and V. K. Appolonov . - Tsvetnye Metally,
No. 8. 1957 .
70. Lebedev , K.B. and V. V. Rodzaevskii . Sbornik " Renii," p . 62 .
Izdatel'stvo AN SSSR . 1961 .
71. Ryabchikov , D.I. and A. I. Lazarev . Dokl . AN SSSR , No. 4:62 .
1953 .
72. Ryabchikov , D.I. , M. M. Senyavin , and K. V.Filippova .
Zhurnal Analiticheskoi Khimii , 7 : 3 . 1952 .
73. Ryabchikov , D.I. , M. M. Senyavin , and K. V.Filippova . -
Zhurnal Analiticheskoi Khimii , 8 : 4 . 1953 .
74. Bibikova , V.I. , V.V.Il'chenko , and Z. A.Semenova .
Sbornik " Renii," p . 44. Moskva , Izdatel'stvo " Nauka." 1964 .
75. Fischer , S. and V. Meloche . – Analyt. Chem ., 24 (7 ) : 1100 . 1952 .
76. Ginzburg , L. B. and E. P. Shkrobot . - Trudy Gosudarstvennogo
Instituta Tsvetnykh Metallov, No. 12:89 . 1956 .
77. Darbinyan , M. V. and D. S. Gaiba kyan . Sbornik " Renii ," p . 50 .
Moskva , Izdatel'stvo " Nauka ." 1964 .
78. Zimmerley , S. R. and J. D. Prater . U.S. Pat.No.2876065 , 1959,
79. Rodzaevskii , V.V. Byulleten' TSIINTsvetmet, No. 23 ( 172 ) : 37 .
1960 ,
80. Ryabchikov , D.I. , A.I. Lazarev , and B.N. Ranskii . - Dokl .
AN SSSR , 92 ( 4 ) : 777 . 1953 .
81. Okhotnikova , N. A. , V.V.Ermilov , E.S.Raimbekov , and
M.I.Filimonov . Sbornik " Renii," p . 61. Izdatel'stvo " Nauka."
1964 .
82. Lebedev , K. B. and T. Sh . Tyurekhod z haeva . Trudy Instituta
Metallurgii i Obogashcheniya AN KazSSR , 6. 1963 .
83. Lebedev , K. B. and T. Sh . T yurekhodzha eva . Sbornik " Renii, "
p . 55. Moskva, Izdatel'stvo " Nauka . " 1964 .
84. Rodzaevskii , V. V. and A.I. Lazarev . Zavodskaya Laboratoriya ,
27 ( 10 ) : 1203 . 1961 .
85. Basitova , S.M. and S. B. Davidyants . Sbornik " Renii," p . 20 .
86. Lazarev , A.I. - ZhPKh, 33 ( 2 ) : 69. 1961 .
87. Abashin , G.I. Tsvetnye Metally, No. 5:69 . 1960 .
19
Part 2
PRODUCTION AND PROPERTIES OF
METALLIC RHENIUM
Chapter IV
PRODUCTION OF METALLIC RHENIUM
There are three chief methods of rhenium production : 1 ) reduction of

potassium ( ammonium ) perrhenates by hydrogen; 2 ) thermal dissociation of
halides or of other rhenium compounds ; 3 ) electrolytic deposition from
aqueous solutions .
The simplest of these methods is the reduction of potassium perrhenate,
but the product is highly contaminated by potassium and other impurities .
Very pure rhenium powder can be obtained from ammonium perrhenate or
by the halide or electrolytic methods . The electrolytic method and thermal
dissociation of halides are used for producing rhenium deposits .
1. Reduction of potassium perrhenate by hydrogen
As we have already seen the extraction of rhenium from concentrated

products leads to the production of potassium perrhenate . At about 600°C
the reduction of potassium perrhenate proceeds as follows:
KREO 3 /2H2 -- Re + KOH + 3H20 .
Today several variants of this method are used /1 – 12 / in which the

reduction is carried out in two stages : the first at 450 – 500° C (below the
melting point of KRe04) and the second at 900 – 1000°C .
The rhenium powder produced by this method /10 / is dark gray and its
bulk density is 1.5 g /cm ' . This powder contains (% ) : Fe - 0.005 – 0.01 ;
Ca + Mg – 0.003 – 0.005; Cu - 0.0006; O2 – 0.15 – 0.20 .
2. Reduction of ammonium perrhenate by hydrogen

This method of reduction gives a purer metal than the above method .
The process is based on the reaction :
2NHAREO . +- 7H, - 2NH3 + 2Re + 8H,0,
during which the ammonia formed is evolved .

The industrial process for the reduction of ammonium perrhenate is
similar to that for potassium perrhenate .
20
Today most of the rhenium produced by reduction is obtained from
ammonium perrhenate , which is prepared by the methods explained below :
Sublimation of Re207 / 12 – 16 /. Potassium perrhenate is reduced
by hydrogen to obtain commercial rhenium powder , which is oxidized by
oxygen at 800°C . The heptoxide formed is dissolved in water, and the
solution is neutralized by ammonia to forin ammonium perrhenate / 12 , 13 /.
Most of the potassium is removed in this way , but some of it enters the
sublimate . If the initial powder contains 0.2 – 0.4% of potassium , some
fractions of NH4Re04 crystals contain a few hundredths of one percent .
The method of purifying rhenium by the sublimation of rhenium heptoxide
is effective for powder with a low content of potassium ( 0.02 – 0.04 % ) . To
reduce the content of potassium it has been recommended /14 / that the
oxidation be carried out at about 460 °C with dry oxygen .
In / 15 / the method of sublimation of Re2O7 was used to extract rhenium
from tungsten- rhenium alloy scrap containing 20 % of Re .
The rhenium powder produced by the reduction of ammonium perrhenate
contained the following impurities (% ) : Fe ~ 0.0004; Al ~ 0.0005; Ni < 0.0003;
Cu < 0.0005, Si ~ 0.01 ; Ca < 0.002; Mg – 0.003; K - 0.02 ; Na < 0.005 .
Sintered rods were obtained from the powder with a density of 19.0 –
19.3 g / cm"; these could be easily press worked / 16 /.
Sulfide method /6, 17 /. The potassium perrhenate is dissolved in
a hot 10% solution of hydrochloric acid , and rhenium sulfide ReqS7 is
precipitated by passing hydrogen sulfide through the solution . The ReqS7
is treated by ammonia to form a suspension, and oxidized by hydrogen
peroxide . The solution is evaporated , the residue is treated by nitric acid
and an ammonia solution , and then again evaporated . The mixture of
ammonium perrhenate and ammonium nitrate obtained is dried , and
reduced by hydrogen at 1000°C . The yield of metal from potassium
perrhenate is 90 % . The metal produced in this way is very pure but the
method is very complex .
Another method can also be used / 9 , 10 / . Rhenium obtained from
potassium perrhenate is dissolved in nitric acid . The solution is added to
an ammonia solution and the product is evaporated until ammonium
perrhenate is precipitated .
Ion exchange method . If a solution of potassium perrhenate is
passed through a cation exchanger / 18 / the following reaction takes place:
( cat . ) H + KRe04 - (cat . ) K+ + HRe04 .
The solution of rhenic acid that emerges from the column is neutralized
by ammonia , and the ammonium perrhenate is evaporated and crystallized .
The cation exchange resin KU- 1 or sulfonated coal has been used . The
maximum exchange capacity of this resin is 40% , and the operating exchange
capacity 32% .
In / 19 /, ammonium perrhenate was obtained from potassium perrhenate
in cation exchange columns packed with cation exchange resins in the H* and
NH+ forms . The solution of ammonium perrhenate was evaporated , and the
dry product reduced in two stages by a current of hydrogen . The above
method for obtaining rhenium from potassium perrhenate by means of ion
exchange and reduction in a current of hydrogen / 19 / has been used in
England to extract the metal from its alloys and from analytical precipitates .
Extraction . In this method rhenic acid is extracted from an acidified
solution of potassium perrhenate by organic solvents . The rhenic acid is
21
reextracted by a solution of ammonia . The organic solvents that can be
used include alcohols , for example , isoamyl alcohol / 14 , 20 / , amines ,
tributyl phosphate /21 , 22 / , and other extractants .
The extraction of rhenic acid from an acidified solution of potassium
perrhenate by tributyl phosphate and then by an ammonia solution gives
ammonium perrhenate containing : K -1.3 . 10-3% ; Na s 3 · 10-4 %; Ca -
1 : 10-3 %; Cu , Mn , C < 3 · 10-5 % ; Mg, Al, Fe, Nis 1 · 10-4 % . The extraction
of rhenium into the organic phase is 99.6% complete /22 /.
It is believed that of the above methods of converting potassium
perrhenate into ammonium perrhenate extraction is the simplest and most
effective .
3. Reduction of ammonium and potassium perrhenates

by pressurized hydrogen
Potassium and ammonium perrhenates can be reduced in solution and
in the solid state at " low " ( 200 – 300°C ) temperatures and high pressures
( 20 – 100 atm ) / 7 , 23 - 25 / .
Reduction of potassium and ammonium perrhenate solutions containing
HCl by pressurized hydrogen can produce intermediate compounds , for
example , (NH4 )2 ReCle and (NH4)2 ReCl4, which can be used to prepare
oxygen- free highly pure rhenium /7 , 25 /. The reduction takes place as
follows :
2NH ,ReOn+ 12HCI + 3H, ( NH4)2 ReCle + - HoReCle + 8H20;

H ,ReCle + 2NHACI ( NH4)2 ReClo + 2HCl ;
(NH4 )2 ReCle+ H, → ( NH4 )2 Recla + 2HCl ( at 300-325°C in a solution of HCl);
( NH4 )2 Recle + 2H2 → Re + 2NH3 + 6HCI (at 400-500 ° C in the solid state ) .
The thermodynamical calculations for the reduction of potassium

perrhenate in solution are given in /23 /:
2K Res + 3H2 → 2Re 2-+ 2KOH + 2H20,
KROA + 3 /2H2-→ Re + KOH + 3H20 .
The redox potentials of the Re04 /ReO2 and ReO2 /Re systems , and also
of the hydrogen electrode at different pH values and temperatures of the
solution and at different pressures of hydrogen , have also been calculated .
The conditions for the precipitation of rhenium from potassium
perrhenate solutions at elevated temperatures and under high pressures of
hydrogen have also been studied in /23 /. From potassium perrhenate at
concentrations of 25 — 150 g / 1, 98 — 99% Re can be precipitated at
200° C under a hydrogen pressure of 60 atm . Rhenium powders produced by
reduction in autoclaves under optimum conditions contain not more than
0.002 – 0.003% K , Na , and Ca , which corresponds to the purity of rhenium
obtained from ammonium perrhenate . The method of production in
autoclaves is appreciably shorter than that from ammonium perrhenate .
22
4. Electrolytic production of rhenium
This method of production has been studied by several authors /26 – 42 /.

Today the electrolytic method is used to produce gray rhenium powder or
thin bright rhenium deposits . The same method can be used to prepare a
number of binary and ternary rhenium alloys .
Rhenium is deposited from the Re04 anion . The hydrogen overvoltage
of rhenium is very low due to the considerable sorption of atomic hydrogen
by rhenium and penetration of the gas into the metal /29 , 31 /.
Rhenium electrodeposits are not resistant to corrosion because of the
considerable stresses , the presence of microcracks , possible oxidation of
rhenium hydride , and the presence of rhenium oxides . Electrolytic rhenium
annealed at 800° C and sintered at 2500° C is resistant to corrosion due to
the relief of stresses and removal of hydrogen and all traces of electrolytes
and oxides / 35 / .
Much research has been carried out and patents issued for electroplating
bright rhenium from solutions containing potassium perrhenate , the chief
industrial raw material for producing rhenium .
Rhenium is ususally plated from solutions containing potassium
perrhenate and free sulfuric acid .
Rhenium deposits have also been obtained from phosphoric acid ,
oxalic acid , citrates , and ammonium citrate solutions /27 , 30 /.
The anodes for rhenium plating are usually made of platinum , and
rhenium is plated on W, Mo , Cu and Cu alloys , graphite , Ti and Ti alloys ,
steels , Al , and Ni and Ni alloys .
It has been found / 31 / that the best deposits at a maximum cathodic
current efficiency and with the lowest consumption of current can be
obtained from solutions containing 15 g / 1 of potassium perrhenate and
12 – 15 g / l of sulfuric acid (pH 0.9 – 1.0 ) . The current density should be
10 – 15 A /dm and the temperature of the solution 85 – 90°C . The cathodic
current efficiency is 19 -- 24% . If the solution contains more than 10 g / 1
of sulfuric acid , sooty deposits are obtained that consist chiefly of oxides .
The electrodeposition of rhenium from sulfate solutions containing
ammonium sulfate has been studied in / 35 , 37 , 42 ) . The influence of the
concentration of ammonium sulfate , the current density, and the tempera
ture and pH of the solution, on the external appearance of the deposit and on
the cathodic current efficiency has been determined , and polarization curves
have been recorded for the deposition of rhenium. The cathodic current effi
ciency can be increased by adding sulfuric acid, ammonium sulfate , etc.
The authors of /41 , 42 / used an alternating current , which produced a
finer powder more suitable for powder metallurgy than that obtained by
direct current electrolysis /42 /.
For the electrolytic production of rhenium powder by direct current ,
the following operating conditions are recommended / 34 /:
Variant I : NH4Re04, 100 g / 1; H2SO4, 100 g / 1 ; (NH4 )2SO4, 60 g / l ; current
density, 100 – 200 A / dm ?.
Variant II : potassium perrhenate, 50 g / l; ammonium sulfate , 40 g/ l;
H2SO4, 75 g/ 1 ; anode, platinum ; cathode, tantalum ; current density,
100 A / dm2 .
To produce rhenium powder by a reversing current the same electrolyte
is used as for direct current . The density of the plating current is
100 - 200 A/dm², and that ofthe reverse current 50 - 100 A/ dm². The ratio
to / 1, = 25 sec /5 sec = 5 , and tot, = 30 sec / 4 sec = 7.5 /41 , 42 / .
23
The electrolytic rhenium powders contain the following amounts of
impurities /34 , 42 /: 02 , 0.15 % ; K, 2.5 . 10-3%; Na, 1 . 10-3% ; Ca, 2 . 10-3 % ; Fe ,
< 1 : 10-3 % ; Cu , Ni, Al , Mo and Sb , < 1 : 10-3 % of each; Pb , Cd , As , Bi , Sn ,
< 1 : 10-3 % of each , and traces of manganese and silicon.
The electrochemical method gives metallic rhenium of a high degree of
purity, but no satisfactory powders for sintering have yet been obtained by
this method .
5. Thermal decomposition of rhenium compounds
The method of thermal decomposition can be used to produce metallic

rhenium and rhenium deposits from gaseous phases /7 , 43 — 46 / by
decomposing rhenium halides , rhenium carbonyl , and higher rhenium
oxides . The production of rhenium coatings by this method is described on
p . 338. Here we shall discuss thermal decomposition only as regards the
production of metallic rhenium .
If vapors of rhenium chloride are passed over a tungsten wire at
temperatures above 1000°C and at a low pressure or in a mixture of
hydrogen and nitrogen , the chlorides dissociate and metallic rhenium is
deposited on the wire . If the temperature is increased to 1500 – 1800°C
the density of the rhenium deposit increases . Rhenium layers up to
0.2 -0.3 mm thick can be deposited on 0.03 – 0.01 mm tungsten wire .
In /43 / a dark- green rhenium chloride (probably rhenium tetrachloride )
was produced synthetically at 50 – 100° C . The temperature of the heating
element was 1000 – 1200°C . The metallic rhenium was deposited on a wire
heated to 800°C , and the deposition was so rapid that the thickening of the
wire could be observed visually . The same method was employed in /44 /.
It was found that rhenium tribromide can be decomposed in the same way
as volatile Re207 by passing a mixture of hydrogen and of nitrogen through it .
The thermal decomposition of other halides and of higher oxides of rhenium
on wire gives a metal of somewhat inferior quality /7 , 45, 46 /.
6. Methods for the production of very pure rhenium
The " chloride method" ( reduction of rhenium dioxide by hydrogen ) .

In this method / 11 , 12 / commercial rhenium is heated in hydrogen at 1000°C for
1 hour to reduce all oxides . The product is chlorinated at 750° C to rhenium
pentachloride (boiling point 330°C ) . This pentachloride is hydrolyzed at
10°C to ReO2 · H2O, which contains up to 75 % of metal . The product is
filtered, washed , and dried , and then converted to perrhenic acid by adding
a 30% solution of H2O2 . The perrhenic acid is neutralized by a concentrated
solution of NH4OH, and the crystals of ammonium perrhenate are filtered,
and used for further treatment .
Rhenium dioxide is the chief product of the reaction , and is reduced by
hydrogen at 400 or 600°C . The powder obtained by this method can be
compressed to almost the same density as the product of sintering the
rhenium powder formed by reducing potassium perrhenate /47 / . The yield
of the chloride method is 95% of Re .
The chloride method /11 , 12 ) is more rapid and gives purer rhenium
than reduction of potassium perrhenate, as the chief impurity, potassium ,
24
is not removed in the latter process . Therefore , at the Battelle Institute
(USA ) the chloride method is used to produce rhenium for research. The
purity of rhenium obtained from potassium and ammonium perrhenates
and by the chloride method is shown in Table 1 / 11 , 12 /.
The chloride method for producing rhenium has been studied in / 14 /.
Rhenium chloride was obtained by chlorinating rhenium powder prepared
by reducing potassium perrhenate by hydrogen . The conditions under which
rhenium pentachloride is decomposed by water have also been studied . It
has been found that although in the chloride method alkali and alkaline- earth
metals are almost completely removed from rhenium, silicon and iron are
not removed (Table 2 ) . This agrees with the data of / 11 , 12 ).
TABLE 1. Content of impurities in rhenium obtained by different methods /11 , 12
Content of impurity , %
Impurity
reduction of potassium reduction of ammonium reduction of rhenium
perrhenate perrhenate dioxide
Aluminum 0.009 0.094 0.008

Calcium 0.008 0.017 0.002
Chromium 0.004 -
Copper o 0.0012 0.0021 0.0002

Iron 0.05 0.024 0.012
Lead .
Magnesium 0.002 0.038 0.005
Manganese 0.007 0.002 0.007
Molybdenum 0.15
Nickel . 0.003
Potassium 0.41
Silicon . 0.005 0.028 0.015
Sodium 0.15
Tungsten
Total 0.793 0.205 0.049
This impurity was not found in the first batches of rhenium produced by this method, but in later batches
it was present in amounts of up to 0.40 % .
TABLE 2. Content of impurities in rhenium powders obtained by reducing KRe04,

and purifying by the chloride method
Impurity
Starting powder made Powder obtained by
of KRe04 reducing ReO2
Iron 0.001 0.001
Copper 0.0015 0.003
Nickel 0.002 0.002
Silicon 0.01 0.01
Alurn inum 0.0007 0.0003
Calcium . 0.008 0.002
Magnesium 0.003 0.002
Potassium 0.05 0.002
Sodium 0.002
The powders obtained by reducing ReO2 could easily be pressed into

rods. Rods sintered by the ordinary process in vacuo at a maximum
25
temperature of 2300°C had a density of 16 - 17 g / cm3, which is 80% of the
theoretical ( i.e. , lower than the density of powders produced from ammonium
perrhenate ) .
The same data were found in / 11 , 12 ) . Preliminary experiments showed
that these rods are difficult to work by ordinary methods .
Vacuum heating . Another method for purifying rhenium prepared
from potassium perrhenate is to sublime the volatile impurities in vacuo / 9 /.
The compressed rods of rhenium are heated under a pressure of 1.10-4 mm
Hg at up to 2500°C . The influence of temperature and of the duration of
heating on the completeness of purification was studied and it was found
that heating at 2300 – 2500°C effectively removes most impurities present
in metallic rhenium . The purity of the metal after removal of impurities is
99.988% . The intense removal of iron starts at 2200° C , of potassium and
calcium above 2300°C , and of lead and tin at 2500°C . The content of gases
has not been determined . The content of impurities decreases greatly after
prolonged heating . in this way a metal with the following content of
impurities can be obtained (% ) : Pb , Sn , Cd and Sb < 0.0001 (each) ; Al , Cu
and Bi < 0.001 ; Fe , 0.0004; Mo , 0.001 ; Ni , 0.0005; K , 0.003 -0.0035; Na ,
0.0003 ; Ca < 0.0025 .
Literature sources from outside the USSR indicate that some American
and English firms produce very pure rhenium , but they do not state by what
method . Thus , the Chase , Brass and Copper Co.(USA ) / 77–79 / and
Engelhard Industries Limited ( England ) /80 - 82 / produce 99.99 % pure
rhenium . It has been reported that Engard's Johnson Matthey Co.
( England ) produces rhenium powder 99.9999% pure and even 99.99999 %
pure /83 /
26
Chapter V
PRODUCTION OF METALLIC RHENIUM
Metallic rhenium can be produced by powder metallurgy methods ,

vacuum melting , or precipitation from the gaseous phase .
1. Powder metallurgy of rhenium
Today one of the principal methods of obtaining metallic rhenium is

powder metallurgy , using a technique similar to that for the production of
refractory metals such as tungsten, molybdenum , etc. The initial material
is rhenium powder produced from potassium or ammonium perrhenate by
electrolysis or another method described above .
A method is reported in / 10 , 48 / for producing rhenium from the powder
obtained by reducing potassium or ammonium perrhenate . The pure
rhenium powder is used to prepare malleable , ductile rhenium . Rhenium
powder obtained from ammonium perrhenate is pressed into bars under a
pressure of 4 – 5 tons /cm² , and presintered at 1000°C in an atmosphere of
hydrogen . The bars are sintered in hydrogen at 1100° C for five minutes ,
and then the temperature is raised to 2400°C at the rate of 10 ° C /minute.
The pars are held at this temperature for 20 minutes . The density of the
sintered bars prepared from rhenium powder that has been obtained from
ammonium perrhenate is 19 – 19.5 g /cm". The bars can be readily pressed .
In the USA (Chase Brass and Copper Co. ) /49 / bars were prepared from
rhenium powder with a particle size of approximately 1.8 m , obtained by
reducing potassium perrhenate . The apparent density of the powder is
2.95 g / cm (11% of the theoretical ) . Pressing is carried out at 39 -
46.5 kg / mm², without binders or lubricants. The density of the pressed
bars is 9.5 g / cm ( 45 % of the theoretical ) . Shrinkage as a result of
pressing fluctuates from 3 : 1 to 6 : 1 . The density after sintering depends
on the potassium content in the sample . At potassium contents of less than
0.006 % , 0.02 – 0.05% , 0.06 – 0.1 % , and above 0.1% , the density is more
than 90% , 80 - 88% , 70 – 80% , and 65 – 75 % , respectively , of the theoretical .
At the Battelle Memorial Institute (USA ) / 50 / rhenium bars are made
from rhenium powder produced by reducing ammonium perrhenate . Rhenium
powder with a particle size of 1 to 20 h was pressed into bars . During this
process the pressure of 47 kg / mm² was optimum , and assured a green
density of the bar of 30 40% -5
of the theoretical . The bars were presintered
in vacuo at a pressure of 10 mm Hg and at 1200°C for 2 hours to a density
of up to 40 – 45 % of the theoretical. This was sufficient to impart a high strength
27
3.1012
2.10-2
to the bars and permit working . The final
.210-3
1.5 2
1.5 2
1.5 3
.10-
.10-
.10-
sintering was carried out in a current of
hydrogen in a sintering apparatus . An
K
electric current of approximately 1200 A
1.10-9
1< .10-9
1<.10-3
< .100
was passed through the bars at a potential
1: 0-3
1< :10
of 6 to 8 V. The temperature of the bars
1
Na
was increased to 2700 ° C , which is
approximately 90% of the melting point ,
2.10-2
2.10-3
8.10-3
.10º
5.<1 10-3 and the bars were held at this temperature
8. 3
10-
for 1 hour . The density of 60 – 65 g bars

Μο
?1.5
•11• 0- produced by this method is 85 – 93% of
10-3 the theoretical , and the bars can be readily
.10-2
1.5 -2
.5<10-3 pressed .
7.5
.10
1.1
The method of preparation of rhenium

Si
powder has an appreciable effect on its

Impurities
y , and consequently on the properties

5.10-4
5.103
.5<10-4
.5<10-4
.5<10-4
.5<10-4
of the compact rhenium article prepared

from it , and on its subsequent treatment .
Cu
In / 51 – 52 / research is reported on the

,%
influence of the method of preparation of

5.10-4
5.10-4
3.10-3
.<510-4
.5<10-4
rhenium powder on the properties of the

1:5<0-4
compact rhenium articles .

Ni
In / 51 / the author studied rhenium

1.10-3
prepared from ammonium perrhenate ,

1.10-9
1<.10-3
1<.10-3
.1<10-3
.1<10-9
which was additionally purified by three

methods : by solution in water , by
Mg
sublimation , and by the chloride method .

7.10-4
3.10-3
The chemical composition of ammonium

510-4
.5 10-4
5.10
°5.10
perrhenate purified by different methods

.<
and of the rhenium powder , as well as the

Al
characteristics of the sintered bars made

< .10-3
2.103
<.10-3
2<.10-3
2.10-3
composition
from the powder , are given in Tables 3

ammonium
2.10-3
perrhenate
Chemical
and 4 / 51 /. The bars made of rhenium

TABLE
2
2
Ca
powder produced by the sublimation

/51
of
3.
method were a little less strain- hardened

3.10-4
3.1004
<1.10-4
3.10-4
6.10-9
by rolling. However , even in this case

1:30-4
Characteristic
the hardness of plates after a 7 – 15%

ammonium
Fe
perrhenate
reduction was over 300 Hy, and

acturing
intermediate annealing was required . In

recrystallizing
rolytic
chlorination
forging , all the bars made of powder

plant ved
Produced
of
(metallic
Purified
purified by chlorides began to disintegrate

manuf
Recei
electr
powde
from
.Purified
from
after a few blows . Rhenium bars made

twice
by
sublimation
of powder that had been obtained from

by
ammonium perrhenate had small cracks

Purified
when forged to 3.25 mm diameter .

by
Rhenium bars of the remaining batches

.)powderm
rheniu
were forged without breakage to rods with

1.5 mm diameter, and then drawn through
dies to 0.5 mm wire . During drawing , hard
:. tial
calciferous soap was applied as lubricant .

Ini
It is clear that the purest rhenium powder

was obtained by the sublimation method .
28
TABLE 4. Properties of rhenium bars, sintered in hydrogen , and of rhenium powder prepared from ammonium
perrhenate purified by different methods /51 /
Characteristic of
ammonium perrhenate
Initial ... 23.8 0.30 0.4 0.05 13 85-92 25 177
Purified by recrystallizing
twice ... 24.7 0.18 0.35 0.05 13 85-92 19.2 182
Purified by sublimation . 27 0.17 0.25 0.05 12 80-90 19.2 277-340

12 42-75
Purified by chlorination . 25 0.6 2,4 0.06 17 163
Received from manufac
turing plant ... 26 0.09 0.35 0.05 13 78-80 17.2 142
Produced from ele -
lytic powder . . 24 0.2 0.35 0.06 12.5 80-85 18.5 170
Admixtures of calcium , copper , iron , nickel and aluminum decrease

the ductility of rhenium /50 /. The presence of moisture in the hydrogen
used for the reduction of NH Re04 causes a large decrease in the density
of the bars and impairs their workability. Dry hydrogen with a dew point of
-25°C to -30°C should be used for reduction /48 /.
Calcium in an amount of 0.001 – 0.1 % in the powder has almost no effect
on the density of bars and does not impair their workability . However ,
potassium has the most unfavorable effect on the workability of rhenium ,
and a content above 0.015 % in the rhenium powder causes a sharp decrease
in the density of bars and impairs their ductility /48 /.
The authors of /48 / believe that it is not possible to obtain rhenium
powder with a potassium content below 0.12 – 0.14 % by reducing KRe04
even after most thorough washing . Powders produced by this method
cannot be used for the preparation of a ductile metal. To produce ductile
metal by the powder metallurgy method , the most suitable raw material
is NH4Re04 made by dissolving rhenium sublimates or by the extraction
method . This conforms with the data of /51 /. During sintering the bars
are freed from potassium . If the bars are held for 2 – 3 hours at a
temperature of 1700 – 2000° C , more than 90% of the K is removed /48 /.
The authors of /52 / studied the behavior of potassium , calcium , and
phosphorus during the production of metallic rhenium by the reduction of
ammonium perrhenate by hydrogen , by the radioactive isotope method . It was
found that phosphorus escapes during reduction and sintering . The phosphorus
content in the bars decreases to 0.5 % ofthe initial content . The potassium
content decreases to 33 – 50% of the initial extent , primarily during sintering .
Calcium escapes only during sintering . Appreciable purification from
impurities , especially from gases , can be achieved by vacuum sintering.
2. Melting rhenium
The production of cast rhenium with a melting point of 3170°C , as well
as of its alloys with refractory metals , is possible only by the method of arc
29
29 melting with either a consumable or nonconsumable electrode and electron
bombardment / 53 – 56 / . Because of their high chemical activity , rhenium
and its alloys are melted either in vacuo or in an atmosphere of purified
inert gases, argon or helium . Figure 2 shows the exterior of the laboratory
equipment for melting rhenium and its alloys .
FIGURE 2. Installations for melting rhenium and its alloys :

a for arc melting; b – for electron - beam zone melting.
The initial material for arc melting with nonconsumable electrodes can
be metallic rhenium in any form ( metal- ceramic rhenium after
presintering, sintering , or compacting , etc. ) .
To decrease the gas content it is preferable to use material after vacuum
sintering . According to our data , rhenium ingots weighing up to 500 grams
can be produced by melting with a nonconsumable electrode .
For arc melting with a consumable electrode , sintered bars of metal
ceramic rhenium can be used , or rhenium bars produced by the haloid
method . To produce alloys it is preferable to prepare alloyed bars first.
It is also possible to produce alloys by using bundles of rods of the individual
metals as a consumable electrode .
Arc melting is carried out on a copper water - cooled hearth with a tungsten
or rhenium nonconsumable electrode in an atmosphere of either argon or
helium under a pressure of 200 mm Hg . The temperature of the cathode tip
is approximately 4000 °C , and melting takes place rapidly . To obtain a
homogeneous composition , the ingots are remelted several times . Cast
rhenium has a bright mirror- like surface / 53 /. During melting there may
be insignificant contamination by tungsten from the electrode . The amount
of impurities present in the original powder ( sodium , aluminum , iron ,
copper , manganese , nickel, etc. ) is greatly decreased in the cast rhenium ,
since at the melting point of rhenium a number of impurities may sublime
and the material become partially refined / 53 /.
30
FIGURE 3 a . Semifinished products made of cast rhenium :
1 and 2 arc -melted ingots; 3 – rod; 4 – single crystal; 5 – plate ;
6 – foil; 7 – wire ,
FIGURE 3 b. Ingot of Mo - Re alloy produced by arc melting;

diameter 50 mm .
As in the case of arc - melted refractory metals , the rhenium ingot has a
coarse - grained structure , which is not uniform in depth . Sintered rhenium
has a fine- grained porous structure . The hardness of cast rhenium is
150 – 250 Hy. Figure 3 a shows photographs of rhenium ingots produced by
arc and electron- beam melting, and of semifinished products .
31
Today, by means of the vacuum- melting method with a consumable
electrode it is possible to produce ingots of alloys of rhenium with tungsten
and molybdenum weighing up to 20 kg ( Figure 3b ) . For uniform distribution
of components the ingots are usually remelted . To reduce the grain size of
arc - melted tungsten and molybdenum the molten metal is collected in a
settling reservoir and then poured into a water- cooled chill mold or into a
rotating casting mold (centrifugal casting ) . To decrease their oxygen
content , ingots of refractory metals are deoxidized by adding carbon ,
hafnium , titanium , zirconium , vanadium , or rare earth metals / 55 /.
Sometimes these additives are used admixed with structure modifiers (boron ,
carbides , etc. ) . All the above methods of increasing the purity and
improving the structure are fully applicable to rhenium and its alloys , and
should be tested in the near future in the laboratory and in pilot plants .
According to the data of Savitskii and Chuprikov , the deoxidation
of rhenium by the addition of lanthanum ( 0.01 wt % ) during vacuum arc
melting reduces the oxygen content from 0.015 to 0.008% . The principal
drawback of rare earth metals for deoxidizing rhenium is the difficulty of
introducing them into the melt during arc melting . At present few data are
available on the electron- beam melting of polycrystalline rhenium . We may
assume that by adding rare earth metals to rhenium melts under conditions
of electron- beam vacuum melting , when the holding time of a melt in vacuo
can be considerably increased , the deoxidation of rhenium can be much
more effective . Double melting ( electron beam + arc ) can also be used for
controlling the grain size .
To produce highly pure metals , especially as single crystals , zone
melting is used .
The author of / 56 / describes the production of single crystals of rhenium
by zone melting a cast rhenium rod . A molten zone was created in the rod . The
zone moved at the rate of 2 mm / min in a vacuum of 10-4 — 10-5 mm Hg. By
this method single crystals of rhenium were produced , 5 mm in diameter
and up to 100 mm long. According to the data of / 57 ), single crystals of
rhenium contain less than 0.001 wt % of O2.
32
Chapter VI
PLASTIC DEFORMATION OF RHENIUM
The workability of a metal or alloy is determined by the following

factors : a ) nature of metal (alloy) , its composition and structure; b ) method
of deformation , i.e. , nature of the siressed state ; c ) conditions of
deformation (temperature , rate , degree of deformation and influence of the
external medium ) / 58 /.
According to modern theories , metals and alloys are physicochemical
systems consisting of crystals of the base metal with impurities ,
alloying elements , and crystallographic defects , distributed within the
grains and along the grain boundaries . The mechanical and physical
properties of such a system depend on the nature of the metal , the
properties and distribution of the structural components of metal and
nonmetal impurities , and the crystallographic defects . This distribution
can be either favorable or unfavorable for plastic deformation . The
pressworking of metals and of alloys is governed by specific laws : of shear
stresses , of constant volume , of the lowest resistance , of similarity , of
additional stresses , and of the nonuniformity of plastic deformation / 59 /.
The process of plastic deformation of a polycrystalline material with
complete strengthening leads to a change in shape , an orientation of the
grains , the formation of a texture and the accumulation of potential energy
( residual stresses ) , and of intragranular and intergranular defects / 59 , 61 / .
The development of a scientifically founded theory on the plastic
deformation of rhenium is only beginning, and the existing experimental
data are incomplete and often very approximate .
1. Cold working of rhenium
Cast and sintered rhenium can be successfully cold worked . An

interesting feature of rhenium which distinguishes it from other metals is
its very high work hardenability. Even small degrees of deformation
greatly increase its hardness and resistance to deformation and reduce its
ductility. The maximum permissible degree of deformation of
commercially pure rhenium is 40 – 60% .
The work hardening can be determined from the increase in hardness .
The hardness of rhenium parts obtained by different deformation processes
( forging, drawing , rolling ) is given in Figure 4 a .
33
The intensity of work hardening is characterized by the slope of stress
strain curves plotted in log- log coordinates /60 /. The coefficient of the
intensity of work hardening can be written as :
algo
alge
where u is the yield stress ; e is the deformation ; T is the temperature . For

rhenium m = 0.372 at room temperature , compared to m = 0.2 for
molybdenum and tungsten .
Another method for evaluating work hardenability of metals of various
strengths is the determination of the slope of the stress - strain curve
plotted for the real stress . According to this method rhenium is work
hardened 3.5 times more than tungsten and molybdenum /62 /.
a b
210 30
GB
m²
6, 0.22
602
GB
kg
/m
800
gm²
%8
/,Hv
140 20
km
600
400
200
0
20
70
x
Degree of deformation, %
10 20 30
FIGURE 4. Dependence of the hardness (a ) and of the mechanical properties

under tensile stress ( b) of commercially pure rhenium on the degree
of deformation :
1 -3.8 mm sintered rod ; 2 – 2,12 mm wire; 3 – 0.25 mm thick sheet;

4 - 3.8 mm thick sheet.
The mechanical properties of rhenium are changed greatly by plastic

deformation . The dependences of the ultimate strength , the yield strength ,
the hardness , and the elongation , on the degree of cold working are shown
in Figure 4 /62 /. For annealed rhenium 0s = 115 kg /mm² , Hy = 250 kg /mm²,
elongation 8 = 25% . After a 30 – 50% reduction OB = 225 kg /mm² , Hy
= 800 – 900 kg / mm² , and 8 = 2% .
The increase in hardness is most rapid at lower degrees of deformation.
Thus, a 5 % deformation increases the hardness from 290 to 550 kg /mm² (i.e.,
almost double ) . Further deformation has less effect on the hardness /63 /.
The mechanism of deformation and the reason for the high work
hardenability of rhenium have been studied by many authors , who used
polycrystalline rhenium and rhenium single crystals /65, 66 /. Churchman
/64 / investigated the deformation of coarse- grained , polycrystalline
rhenium obtained by deforming cast rhenium and then annealing at 2200 -
2600° C . He found that the mechanism of deformation of polycrystalline
34
rhenium is the same as that of other metals with a close - packed hexagonal
lattice , and a cla ratio similar to that of rhenium but less than the ideal
ratio ( titanium , zirconium , beryllium ) . For rhenium cla = 1.616 compared
to cla = 1.633 for ideal, hexagonal , close- packed lattices . With decrease in
the size of the grains of rhenium the ultimate strength increases and the
rate of work hardening increases also .
TABLE 5. Critical shear stresses for some metals with a hexagonal lattice /65 /
Component of the critical

shear stress
Metal 8 , % (at 20 ° C )
slip (0001 ) slip (1010 )

Beryllium 1.41 6.68 5 (with no preferential
orientation)
Rhenium 0,91 1,69 25
Titanium 6.33 1.41 50 (for iodide titanium )
Zirconium 3.37 0.91 40 ( for iodide zirconium )
Polycrystalline rhenium and single crystals become deformed by slip

along the (0001 ) and (1010} planes , and sometimes along the ( 1011 ) .
Twinning takes place along the ( 1121 ) , (1122) , and ( 1012 ) systems;
twinning along the (1121) plane is predominant.
a 6/1010) ( 1010)
.5.5
.6.62 • P+ P
8-80 D + B
B+ B
P
B •P+ P
9. 15 :154
B
( 0001) (1120 70001) ( 1120 )
с
35
Stress
/,kgm²
28
m
21
( 1010 )
( 0001) ( 1120 )
30 sr
Elongation , %
FIGURE 5. Deformation of rhenium single crystals:
a - initial orientation of rhenium single crystals; b - dependence of the initial
mechanism of deformation on the orientation of the crystals; c – load -elongation
diagram for specimen No.4. B – slip along the planes of the basis (0001 ), P- slip
along the planes of the prism (1010 ); D - twinning; the numbers beside the points
are those of the specimen ( see Table 6) .
The deformation of rhenium single crystals has been studied /65 / by

cutting each crystal in half and grinding two planes on each half at an
35
The intensity of work hardening is characterized by the slope of stress -
strain curves plotted in log- log coordinates /60 /. The coefficient of the
intensity of work hardening can be written as :
alg
o
mogalgela
& r'
.
where u is the yield stress ; E is the deformation ; T is the temperature . For

rhenium m = 0.372 at room temperature , compared to m = 0.2 for
molybdenum and tungsten .
Another method for evaluating work hardenability of metals of various
strengths is the determination of the slope of the stress - strain curve
plotted for the real stress . According to this method rhenium is work
hardened 3.5 times more than tungsten and molybdenum /62 / .
a b
210 30
бв
?m/0.22
602
m
2
6,GB
kg
800
k, gm²
Hv
20
/m
600
400
70
200 of
0
20 10 20 30
Degree of deformation , %
FIGURE 4. Dependence of the hardness (a) and of the mechanical properties
under tensile stress (b ) of commercially pure rhenium on the degree
of deformation :
1-3.8 mm sintered rod ; 2 – 2.12 mm wire; 3 – 0.25 mm thick sheet ;

4 – 3.8 mm thick sheet.
The mechanical properties of rhenium are changed greatly by plastic

deformation . The dependences of the ultimate strength , the yield strength ,
the hardness , and the elongation , on the degree of cold working are shown
in Figure 4 /62 /. For annealed rhenium 08 = 115 kg /mm² , Hy = 250 kg /mm² ,
elongation o -25 % . After a 30 – 50% reduction OB = 225 kg /mm² , Hy
= 800 – 900 kg / mm² , and o 2% .
The increase in hardness is most rapid at lower degrees of deformation .
Thus , a 5 % deformation increases the hardness from 290 to 550 kg /mm² (i.e.
almost double ) . Further deformation has less effect on the hardness 163 /.
The mechanism of deformation and the reason for the high work
hardenability of rhenium have been studied by many authors , who used
polycrystalline rhenium and rhenium single crystals /65, 66 /. Churchman
/64 / investigated the deformation of coarse- grained , polycrystalline
rhenium obtained by deforming cast rhenium and then annealing at 2200 –
2600° C . He found that the mechanism of deformation of polycrystalline
34
rhenium is the same as that of other metals with a close- packed hexagonal
lattice , and a cia ratio similar to that of rhenium but less than the ideal
ratio (titanium , zirconium , beryllium ) . For rhenium cla = 1.616 compared
to cla = 1.633 for ideal, hexagonal , close- packed lattices . With decrease in
the size of the grains of rhenium the ultimate strength increases and the
rate of work hardening increases also .
TABLE 5. Critical shear stresses for some metals with a hexagonal lattice /65 /
Component of the critical

shear stress
Metal 8 , % (at 20 ° C )
slip (0001) slip ( 1010 )
1.41 6.68 5 (with no preferential
Berylliuin
orientation )
Rhenium 0.91 1..69 25
Titanium 6.33 1.41 50 (for iodide titanium )
Zirconium 3.37 0.91 40 ( for iodide zirconium )
Polycrystalline rhenium and single crystals become deformed by slip

along the (0001 ) and (1010) planes , and sometimes along the ( 1011 ) .
Twinning takes place along the {1121 } , ( 1122) , and (1012 ) systems;
twinning along the ( 1121) plane is predominant.
a G / 1070) b ( 1010 )
P
os os •P
.6-64 • P+ P
8.80 D + B B+B
P
B P+ P
9. 15.152
0 D D
8 ( 1120 )
70001) ( 1120) 70001)
с
35
Stress
/k, gm²
28
m
21
( 1010 )
( 0001 ) ( 1120)
10 30 SC
Elongation, %
FIGURE 5. Deforination of rhenium single crystals:
a - initial orientation of rhenium single crystals; b – dependence of the initial
mechanism of deformation on the orientation of the crystals; c – load -elongation
diagram for specimen No.4 . B - slip along the planes of the basis (0001 ), P – slip
along the planes of the prism (1010 ); D – twinning; the numbers beside the points
are those of the specimen ( see Table 6) .
The deformation of rhenium single crystals has been studied /65 / by

cutting each crystal in half and grinding two planes on each half at an
35
emoved from these planes
angle of 90° to one another . The upper layer was rem
by electropolishing . The orientation of each crystal was determined by the
Laue method. The crystals were elongated at the rate of 10-4 m /sec .
It was found that the chief mechanism of deformation of the rhenium
single crystals with an orientation shown in Figure 5 a is slip along the
(0001 ) and ( 1010 ) planes , while the main process of deformation in crystals
with an orientation close to the ( 0001 ) apex is complex twinning ( Figure 5b ) .
The twins ( 1121) are predominant . It has also been found /64 / that slip can
occur along the planes of the pyramid ( 1011 ) , but since the specimens
studied in this work were polycrystalline this additional mechanism of
deformation could be the result of a reaction between crystals .
The AB boundary on Figure 5b separates the crystals deformed at the
start by slip along planes ( 0001 ) and those deformed along the (1010) planes ,
and its position indicates that the critical shear stress during slip along
the (0001 ) plane is only about half the critical shear stress for slip along
the ( 1010) plane . This assumption has been confirmed experimentally.
TABLE 6. Mechanical properties of rhenium single crystals determined by tensile tests

Number of
specimen in
00.21 OB , OB actual, 8, %
kg/mm2 kg/mm²
Figure 5 kg /mm2
4 5.6 35.9 93.6 42
6a 3.0 42.1 65.3 43
3 4.9 44.2 40
8 4,2 40.8 70.3 36
9 5.3 35.1 63.2 40
15 8.4 43.5 69.0 61
The average experimental values of the critical shear stress are :

1.48 kg /mm² for slip along the ( 0001 ) plane and 2.19 kg / mm² for slip along
the ( 1010} plane, i.e. , a ratio of 0.67 .
The critical shear stresses for several metals with a hexagonal crystal
lattice and slip along the same planes are given in Table 5 /65 / . The
authors of /65 / believe that these values are rather too low , since the
modulus of elasticity of rhenium is rather high ( 47,300 kg / mmº ) . The high
critical stresses for titanium have been explained by the susceptibility of
this metal to impurities with which it forms interstitial solid solutions .
Churchman /64 / explained the existence of three slip systems for rhenium
single crystals ( 1010 } , (1011 ) , and (0001 ) by the high concentration of
the interstitial solid solution . Geach et al . /65 / believe that slip along the
{ 1011 } plane is due to the polycrystalline state of the material .
According to the same authors /65 /, the strengthening of the crystals
dP / A .
is characterized by a coefficient de kg / mm², where P is the applied load;
A , is the initial cross - sectional area , and ε is the elongation , and also by a
coefficient of strengthening by shear dS da '
where s is the critical shear
stress , and a is the plastic deformation by shear slip for different specimens
at the initial stage of deformation .
36
The data on yield strength , nominal and actual strength, and elongation
are given in Table 7 .
TABLE 7. Rate of strengthening of rhenium single crystals /65/

No.of speci dP / A , DS No.of speci dP/A, ds
men in de da ' dc da
men in
Figure 5 kg /mm² kg/mm? Figure 5 kg /mm ? kg/mm ?
4 163.0 21.8 9 208.7 42.2

6а 167.2 30.2 15 172.2 35.1
6 163.7 29.5 15 a 227.0 42.2
5 394.2 70.3 7 130.0
8 201.7 51.3 2 105.4
8a 251.6 63.2
The data in Tables 6 and 7 were obtained with specimens whose initial
orientation and chief mechanism of deformation are shown in Figures 5 a
and 5 b /65 /.
The stress- strain curve in Figure 5c shows that a linear relationship
exists for at least the first 5 % of elongation . The orientation of single
crystals determines the rate of their work hardening. Slip along plane
( 1010 ) leads to a higher rate of work hardening than slip along plane ( 0001 ) .
Duplex slip along the ( 1010 ) plane leads to an even greater strengthening
of the metal (Figure 5 a and b , and Table 7 ) .
It is believed that during deformation the rate of work hardening of
polycrystalline rhenium is somewhat higher than that of single crystals /64 /.
Geach /65 / believes that polycrystalline rhenium is strengthened more
than other metals because of the higher rate of strengthening of rhenium
single crystals . This is due to their higher elastic constants , and the
interaction of individual crystals , which stimulates the mechanism of
repeated deformation .
According to other sources /64 / rhenium is strengthened more than
other metals with a hexagonal lattice because of its lower stacking fault
energy . If we consider the elastic constants of rhenium , by relating
DS
da (coefficient of strengthening by shear ) to the shear modulus we find that
this ratio is equal to 3 · 10-3, which is commensurable with the value
4 . 10-3 for highly work- hardened f.c.c.crystals /66 /. Thus, the influence
of the elastic properties is predominant.
As we have already mentioned , the rate of work hardening of rhenium
single crystals depends on their orientation . In polycrystalline specimens
the crystals are oriented in different directions , and therefore the rate of
work hardening also differs . Such an inadequate strengthening of grains
raises stresses at the grain boundaries and leads to intergranular cracking
of the polycrystalline specimens during deformation . It has been found /64 /
that this process is suppressed by slip along planes parallel to the grain
boundaries .
By alloying rhenium with up to 0.1 wt % of tungsten the susceptibility of
Re to work hardening increases /67 /, but alloying with more tungsten or
molybdenum (up to 10 wt % ) decreases the rate of work hardening, and
greater deformations are possible without cracking than in the case of pure
37
rhenium /65 /. It has been found that rhenium impurities can be placed in
the following order, according to their increasing influence on hardenability:
tungsten , molybdenum , iron /67 /. It is obvious that the high work
hardenability of rhenium is due to its twinning ability .
The influence of solution heat treatment on the ductility of rhenium has
been studied /65, 68 / . It was found that the ductility of arc melted Re
ingots can be increased by quenching from 200°C below the melting point
/65 /. This increase in ductility is due to the formation of vacancies in the
crystal lattice and to the transition of some of the impurities from the grain
boundaries into the solid solution . By rolling such cast materials it was
possible to produce considerable deformations ( 40% reduction ) without
cracking .
FIGURE 6. Traces of slip on the surface of rhenium single

crystals after stretching:
a
single crystal A , slip plane (1010) X 250); b – single
crystal B , slip plane (0001 ) 670) .
It has lately been found that even small amounts of interstitial impurities
(oxygen , nitrogen , hydrogen and carbon ) form hydrides , oxides , nitrides
and carbides , which are very harmful to the strength and the ductility of
refractory metals . The distribution of these brittle and often low- melting
nonmetallic compounds in the form of films or sheaths along the grain
boundaries of the metal is especially detrimental / 54 / .
The increase in the ductility of rhenium after solution heat treatment is
due to the increased solubility of interstitial impurities (oxygen , nitrogen ,
hydrogen ) in the metal, and to the decrease in their concentration at the
grain boundaries where they form a brittle phase which weakens the grain
boundaries .
38
The influence of oxygen on the mechanism of deformation of rhenium
single crystals at room temperature was studied by stretching the samples
to 2% elongation ( Figure 6 ) 1697. It was found that , other conditions being
equal, an increase in the content of oxygen from 0.002% ( single crystal A )
to 0.006% (single crystal B ) leads to an increase in the clo ratio and to a
change in the mechanism of plastic deformation . In crystal slip occurs
along the ( 1010 ) ( 1120 ) system only, and in crystal B along the (0001 ) ( 1120)
system also . A comparison of these data with those given in Table 5 /65 /
shows that the magnitudes of the critical shear stresses along these planes
are influenced by the purity of the crystal . Apparently, in all highly pure
metal crystals with a ca ratio less than the ideal, slip occurs preferably
along the ( 1010 ) ( 1120 ) systems . Additional slip systems are probably
formed because the usual slip planes are blocked if the content of oxygen is
increased .
Changes in the fine structure of rhenium of different degrees of purity
during deformation has been studied /57 , 70 / . The processes of work
hardening and recovery of highly pure rhenium deformed by uniaxial
compression on a press and by all- sided compression in steel rings
were also investigated /70 / . The microdefects in the crystal lattice were
determined by harmonic analysis . It has been found that all- sided
compression in steel rings produces certain average stresses . The relative
microdeformation in the crystal lattice of deformed rhenium is smallest in
the ( 100) direction . For line ( 102 ) ε, = 1.8.10-3, and for the secondary
reflection from the same plane & , = 1.7.10-3. The microdistortions of the
lattice are only slightly relieved by annealing at up to 600° C .
The physical influence of oxygen and other gases on the ductility of
rhenium was studied in / 57 /. The content of gases in the metal was as
follows :
Commercially pure cast rhenium 0.020 – O2 ; 0.0004 Hz; 0.0003 N2
Rhenium single crystals < 0.001 – O2 ; 0.0003 H2; 0.0002 N2
Microdeformations of rhenium were induced by rubbing with emery paper .

The distortion of the fine crystal structure of deformed rhenium of different
degrees of purity was determined from the broadening of the X- ray
interference maxima after deformation (Table 8 ) .
TABLE 8. Results of the deformation of rhenium of different degrees of purity by

rubbing with emery paper
D.109, cm E.10 ? Oresidy

Rhenium da. 103 kg /mm ? kg /mm²
Commercially pure cast

rhenium 6.4 500 320
Single crystal rhenium 3.3 4.5 500 225
Note . D- Dimensions of the field of coherent scattering of X - rays ( FCS) ;

Δα
a is the relative deformation of the fields of coherent scattering; Oresid is the
residual stress .
It can be seen that the purity of rhenium greatly influences the

distortions of the crystals after deformation .
39
Commercially pure materials have a larger FCS after deformation by
rubbing . The FCS of pure rhenium is small ( 3.3 • 10-6 cm ) and comparable
to that of ductile molybdenum ( 2.5 • 10-6 cm ) .
The microdeformation Aala of the lattice of commercially pure rhenium
is about 1.5 times that of pure rhenium single crystals , and it is believed
/ 57 / that the differences in D and Aala are due to the different ductilities
of these materials . in commercially pure rhenium deformation before
failure is small, and the fragmentation of the initial crystal structure is
less than in rhenium single crystals . Slip in this type of rhenium is
hindered by impurities , and so the accumulation of residual stresses is
much greater than in rhenium single crystals . The magnitudes of internal
Δα
stresses o -E , which lead to the failure of rhenium during deformation
resid
have been determined (Table 8 ) . The average magnitude of internal stresses
Oresid that lead to failure of the metal, and the degree of their localization in
the crystal lattice , depend on the purity of the rhenium . The presence of
oxygen in rhenium leads to local accumulation of stresses during plastic
flow and so the ductility decreases . It is believed / 57 / that the change in
the plastic flow of rhenium caused by oxygen may be due to directional
reactions between interstitial impurities in the lattice of the metal and the
fields of internal stresses of dislocations .
The influence of rare earth metals lanthanum , cerium, yttrium , and
others , and the deformability of rhenium /68 / were studied with commercially
pure arc - melted rhenium ( 99.9% ) containing 0.015 % O2. It was found
analytically that the addition of 0.02% Ce decreases the content of oxygen
in rhenium to 0.011% , and the addition of 0.01 % La decreases the content of
oxygen to 0.003% . Rhenium containing 0.01% La can be upset on a Gagarin
press to 70% deformation, but unalloyed rhenium can be upset to only
45 – 50% deformation . However, an increase in the content of rare earth
metals above 0.02% decreases the ductility of rhenium alloys, as a new
phase rich in rare earth metals is precipitated along the grain boundaries
/68 /. Attempts to deoxidize rhenium by adding 1% of thorium, aluminum,
zirconium, titanium , or uranium were not successful / 50 /.
The ductility of rhenium at room and elevated temperatures is greatly
reduced by oxygen that forms low- melting rhenium oxides which are
precipitated along the grain boundaries (Figure 7 c ) 171 /. Oxides along the
grain boundaries of rhenium weaken the intergranular forces and cause
brittle intergranular failure , even after a small deformation . Figure 7 b
illustrates well the appreciable weakening of the boundaries of rhenium by
oxides , as it shows the microstructure of polycrystalline rhenium containing
0.022 % O2 after cold rolling to 25 % reduction. This metal starts to fail
along the grain boundaries , but under identical conditions polycrystalline
rhenium containing 0.002% O can be cold rolled to 70% reduction without
failure ( Figure 7 a ) /71 / . Obviously , rhenium freed from oxygen impurities
has a much higher ductility .
There are only a few theoretical papers on the mechanism of deformation
of rhenium single crystals . There are also few papers on the technique of
deformation of rhenium and the production of semifinished products . The
production of 0.025 mm rhenium foil and 0.076 mm diameter rhenium wire
is briefly described in /72, 77 — 79, 84, 85 /. The production of 0.28 mm
diameter wire from sintered rhenium prepared from purified ammonium
perrhenate is given in /73 /. The rods were cold forged to 1.25 mm
40
diameter by 5 – 10% reduction per pass , and annealed in hydrogen
between the passes at 2200 – 1700°C for 30 min - 2 hours , depending on
the diameter of the product . Before the wire was drawn , its surface was
slightly oxidized in hot nitric acid and covered by Aquadag. The surface
of the drawn wire was smooth without burrs or cracks .
FIGURE 7. Microstructure of cold - rolled rhenium specimens with different contents

of oxygen :
a – zonal electron - beam melting, 0.002% O2, deformation 70 % , no cracks ( 200);
b
arc melting, 0.022 % O2, deformation 25%, intergranular cracks (x 200); c -
oxide on the boundary of rhenium crystals, 0.0220% O2 (x10,000 ).
The method of shaping sintered rhenium /74 / prepared in the same way
as in /73 / is as follows : forging and cold drawing with intermediate
anneals in hydrogen at 1300 — 1400°C ( 2.5 – 3 mm diameter wire should be
heated for 5 min , and thinner wire for only 1 – 3 min ) . The wire to be
annealed was passed through the furnace at the rate of 10 m /min . The
authors point out that rhenium wire deformed in this way had good
ductility, and that the total deformation produced by several passes between
anneals was 50% ( 7 — 10% per pass ) .
It is clear that at the annealing temperatures recommended in /74 / the
internal stresses in the metal are relieved , and recrystallization starts .
But grains do not grow to such dimensions as at 1700 – 2200 °C , and
therefore the metal has a fine - grained structure free of internal stresses ,
and strong enough to prevent rupture during drawing . It is also highly
ductile , and the wire can be bent to 180 °, but before annealing the wire
could be bent to 12 — 26° only /74 /.
41
The production of foil from sintered and cast rhenium is described in
175 /. The deformation was carried out at room temperature to small
reductions , with frequent intermediate anneals . In 1963 , the authors
together with Ipatova, Amosov , and Karavaitsev developed a method for
producing wire (up to 20u diam ) , and together with Starkov, Korchagin,
Fokin , and Nesterova , a method for preparing foil (up to 30u thick ) . The
external appearance of rhenium semifinished products is shown in Figure 3 a
(p . 31 ) .
2. Hot deformation of rhenium
It has been shown that cold working of rhenium is a rather time- and
labor- consuming process , and that high- temperature anneals in vacuo
between passes take up the most time and not the deformation proper. Thus,
time and power are wasted, and the equipment is inefficiently used . The
cost of the semifinished rhenium is thus increased .
The high oxidizability of rhenium causes hot shortness when rhenium is
hot worked in air . The grain boundaries of hot - worked rhenium ingots
contain precipitates formed when gases , in particular oxygen, are absorbed .
The main component of the grain boundary precipitate is Re207, melting at
297°C . Therefore , hot working of rhenium is possible in vacuo only, or in
a protective atmosphere /49, 50, 53 , 76 /. All attempts to hot work rhenium
before 1963 failed .
Together with Freze we studied the behavior of rhenium during hot
rolling in vacuo . We used cast rhenium which had been melted in purified
helium . The 350 g ingots were upset by a hammer at room temperature to
70% reduction, and annealed between passes in vacuo . The 3.6 mm thick
plates were rolled at 1350 50°C in a 3 · 10-6 mm Hg vacuum on a two- high
rolling mill . The specimens , but not the rolls , were heated to 1350°C
after each pass . The hardness of rhenium before deformation was 37 H RC
and after hot working to a 1.1 mm thickness ( reduction ~ 70% ) the hardness
increased to Il Rc = 50 – 53. This shows that rhenium is greatly work
hardened even at 1350 °C . Under these conditions of deformation there is no
recrystallization .
As far as we know , this work is the first successful attempt to hot work
cast rhenium, and it confirms that hot working of this metal is possible .
Our experiments on hot working rhenium in a protective steel shell were
quite successful, so that we may believe that rhenium , like other refractory
metals , can be hot worked not only in vacuum mills but also in protective
shells of steel, nickel , or molybdenum .
3. Recrystallization of rhenium
It is important to know the recrystallization temperature of rhenium not

only to choose the correct methods of press working and annealing but also
the correct operating temperatures for rhenium parts and semifinished
products . Recrystallization of rhenium has been extensively studied,
mainly by Soviet scientists /50 , 63, 64, 68, 70 /.
42
A study on the recrystallization of cold- worked sintered rhenium is
described in / 50 , 63 /.
I
o1
8 * 2
Grain
1000
size
mm
,10
7
.4 800
0.5 % Th
600
400
gmº
200
/k,Hy
800
m 1.0 % Th
800 600
700
400
/mm²
Hus
kg
600 200
800
500 2.0 % Th
600
400
400
300
200
700 900 1100 1300 1500 1700 K.T. 700 900 1100 1300 1500 1700
Annealing temperature, °C Annealing temperature, ° C
a b
FIGURE 8. Dependence of the hardness and grain size of cold -worked sintered rhenium (a),
and of rhenium alloyed with thorium (added as thorium oxide) (b), on the temperature of
annealing:
– 40 % .
1- degree of deformation 10 % ; 2 -20 % ; 3 – 30 % ; 4 -
In /50 / rods of sintered rhenium prepared from potassium perrhenate

were cold forged to a reduction of 10, 20, 30, and 40% and then annealed . The
specimens were then heated at the rate of 100°C per hour from 700 to
1700°C . The dependence of the hardness and grain size of rhenium on the
annealing temperature and on the degree of deformation is shown in
Figure 8 a . Heating to below 800°C has little effect on the hardness of the
metal. Heating to 900 – 1300°C leads to recrystallization of specimens
with 10, 30, and 30 % reduction, accompanied by a decrease in hardness
to 300 – 350 kg / mm² , but there is no change in grain size . Specimens
deformed to 10% reduction have a less distorted lattice and recrystallize
more slowly. Further increase in the temperature causes grain growth .
Specimens after 40% reduction were most fragmented and showed the
smallest grain growth as a result of heating.
Intense grain growth starts at 1200 — 1400°C . Secondary grain growth
begins at more elevated temperatures . The average grain size under all
conditions is small, and varies from 4 to 104. The authors of /50 / believe
that sintered rhenium is completely recrystallized at 1500°C, but to reduce
hardness to 300 kg / mm² they suggest that the annealing temperature be
increased to 1700 – 1750°C and the holding time to 2 hours . No X- ray study
of the process of recrystallization was carried out in / 50 /.
43
We investigated the recrystallization of cast and sintered commercial
rhenium after rolling /63 /. A diagram of primary recrystallization is shown
in Figure 9. This diagram was constructed from the data of microstructural
and X- ray analyses and hardness measurements . The starting material
was forged rods of sintered rhenium ( grain size 4 - 5u ) prepared from
potassium perrhenate . The specimens were cold rolled to 5, 10, 20, 30 ,
and 48 % reduction (48 % was the maximum permissible reduction ) . The
specimens were then vacuum annealed at 1400, 1550, 1600 , 2000 and 2400°C
for 1 hour .
Diameter
2400
e
grain
ur
36
g
in
at
u,of
al
er
32 2200
ne
mp
An
te
28
,°C
24 2000
20
16 1800
1600
Tv
1400
10 20 30 40 SO
FIGURE 9. Recrystallization diagrams of sintered rhenium .
" ь is the temperature of the beginning of recrystallization .
It was found that the temperature at which recrystallization of sintered

rhenium starts decreases with increase in the degree of deformation , from
1850° C for 5% reduction to 1600 – 1750° C for 20% reduction , and to
1500° C for 30 -- 48% reduction . The maximum grain size was 37 u after a
critical reduction of 10% and annealing at 2400° C . After other reductions
and annealing at up to 2000° C the grains grow more evenly. Annealing at
2400°C leads to a marked grain growth (after 30% reduction there is a
four- fold increase in size ) . The microstructure of sintered rhenium is
shown in Figure 10 , h and i . At all deformations the hardness of the metal
decreases at annealing temperatures corresponding to the temperature of
the beginning of recrystallization . After annealing at above 2000°C the
difference in the hardness is small and the hardness of the annealed
material is HB = 150 — 170 kg / mm² .
The differences between the data given in /50 / and /63 / are due to
differences in purity , density, and preliminary treatment of the original
rods of sintered rhenium .
44
FIGURE 10. Microstructure of cast (a -9 , 200 , and of sintered ( h – i) rhenium , x 450
( polarized lighư :
a – initial structure of cast rhenium ; b after 30 % reduction and annealing at 1750 ° C ; C –
after 60 % reduction; d after annealing at 2400C ; e- after 5% reduction and annealing
at 2400 ° C ; f - after 30 % reduction and annealing at 2400° C ; g - deformation twins in cast
rhenium ; h – after 48 % reduction and annealing at 1600 ° C ; i – after 48 % deformation ard
annealing at 2400 ° C .
The recrystallization diagram of cast rhenium published in /63 / is shown

in Figure 11 a. As starting material ingots of commercially pure rhenium
were used, which had been arc melted in an argon atmosphere . To refine
the coarse- grained structure usual under these conditions of melting
(Figure 10 a ), the ingots were cold worked by upsetting and rolling to a total
45
reduction of 30 – 35 % , with intermediate vacuum anneals at 1750°C . The
coarse - grained structure disappeared , and the material that was later used
had a recrystallized polyhedral structure with grains of 40 u diameter
( Figure 10b ).
Diame
grain ter
1
of
,h
400
a
300
200
100
ng reu
2400
i at
o An
ne
al
te
Hillli
opoer 2200
m
, °C
o oo180
JimillisiTolle t 0
will Willisille 01112
பயப்படாயார்
irilline pa
1200
0 20 40 60
11000
Degree of deformation, %
Rc
80
n
io 60
e m at
60 re o r 5 0
g f
De of de ,%
40 y
o
20
0
1000 1400 1600 2200
Annealing temperature , °C
FIGURE 11. Recrystallization diagram of cast commercially
pure rhenium ( a), and dependence of the hardness of cast
rhenium on the degree of deformation and the annealing
temperature (b) .
ip is the temperature of the beginning of recrystallization .
The specimens were cold rolled to 5, 7.5, 10 , 20 , 27.5, 30 , 40, 50 and

60% reduction . The maximum permissible reduction was 60% . Cold
working of rhenium leads to grain fragmentation . Small deformations cause
deformation twins , characteristic of metals with a hexagonal lattice
(Figure 10g) . The deformed specimens were annealed at 1000 – 2400°C
for 1 hour .
46
The temperature at which recrystallization of rhenium starts decreases
with increase in deformation , from 1750°C for 5% deformation to 1550° C
for 10% deformation , to 1350° C for 20% deformation , and to 1200°C for
40 – 60% deformation . There is no appreciable grain growth after
annealing at 1600°C .
Diameter
of
grain
400
,u
300
200
100
e 2400
ng ur
i at 2 200
al e r
ne mp
An te 2000 , ° C
1800
1600
1400
1200
1000
900
0 20 40 60
b
FIGURE 12. Recrystallization diagram of highly pure cast rhenium
(purified by zone electron - arc melting) .
tb is the temperature of the beginning of recrystallization .
Intense grain growth ( secondary recrystallization ) starts during

annealing at 2000°C . The size of the initial grains ( 50u ) is retained up to
1600°C , and increases to 130u on heating to 2400°C ( Figure 10d ) . In
specimens after 30 — 40% deformation the diameter of the grain changes
from 20u after annealing at 1100 °C to 334 after annealing at 1600° C and to
604 after annealing at 2400° C (Figure 10f ) . The critical degree of
deformation of cast rhenium annealed at 1600 °C is 10% , and it decreases
with increase in the annealing temperature to 5% at 1750 – 2400°C . The
photomicrograph of rhenium annealed at 2400°C ( Figure 10 e ) clearly shows
the large grains produced by the critical deformation . The dependence of
the hardness of cast rhenium on the deformation and the annealing
temperature is shown in Figure 11 b .
The rapid decrease in the hardness of cold- worked cast rhenium starts
at the temperature of the beginning of recrystallization, and depends on the
degree of deformation of the metal . The decrease is retarded at 2000° C
as a result of secondary recrystallization . The hardness of all specimens
was 130 – 150 kg / mm² after annealing at 2400° C .
The data of /64 / confirm those obtained in /63 / . Churchman found that
at 1650 and 1800°C deformed cast rhenium is only partially recrystallized .
At 1600°C the recrystallization takes place at the intersections of the twin
crystals, and at 1800°C new grains grow on the bases of the twins . Heating
to 2500°C leads to complete recrystallization and the formation of equiaxial
grains /64 /.
47
Recrystallization of highly pure rhenium after zone refining by electron
arc melting was studied in /68 / ( Figure 12 ) . The coarse - grained structure
was destroyed by cold rolling to 35 – 40% reduction , and by 1 hour
intermediate anneals at 1500°C . The grains of the starting specimens were
474 in diameter , and the hardness Hy was 100 kg / mm² . The specimens
were cold rolled to 70% deformation . It was found that the temperature
at which recrystallization starts in highly pure rhenium decreases with
increase in deformation from 1500° C for 5% reduction to 1300°C for
10% reduction , 1150°C for 20% reduction, and to 1000°C for specimens with
40 – 70% reduction . The critical degree of deformation decreases from
10% for annealing at 1200°C to 3 – 5 % for annealing at 1750 — 2400°C . The
grains of specimens after 30 – 40% reduction annealed at 2400°C are not
larger than 1144. Highly pure rhenium can be work hardened as much as
sintered rhenium or rhenium obtained by arc melting .
The recrystallization of rhenium that had been deformed by all- sided
compression in steel rings was studied in /70 /. It was found that rhenium
deformed to 50% reduction started to recrystallize at 600° C , i . e . , at half
the temperature at which recrystallization started in rhenium that had been
deformed by uniaxial compression to the same reduction /63 /. The authors
of /70 / explain the low recrystallization temperature of rhenium deformed
by all- sided compression by energy considerations . If the metal is
compressed from all sides the latent energy of deformation is considerably
increased , since the total external energy applied is consumed to distort
the crystal lattice only, and no elastic displacement of grains takes place .
It is also believed that recrystallization is a diffusionless mechanism / 70 / .
These theories are very interesting, but they need verification .
There are no literature data on the influence of impurities and alloying
elements on the recrystallization of rhenium except /62 /, in which the
influence of thorium was investigated . Thorium , which greatly inhibits the
recrystallization of tungsten , is one of the most frequent additions to
tungsten in the electrovacuum industry .
Sims and Jaffee /62 / studied sintered specimens prepared from a
mixture of rhenium and thorium oxide powders by the usual method , and
found that thorium decreases the temperature at which rhenium starts to
recrystallize ( Figure 8b ) . It was found that if such rods are welded in a
current of hydrogen at 2700°C the thorium oxide is not reduced . Rhenium
alloys containing 0.5, 1.0 , and 2.0% of thorium ( as thorium oxide ) deformed
to 10, 20 , 30, and 40% reduction were used to study recrystallization .
The alloys were annealed at 700 – 1700°C . It was found that thorium oxide
has little influence on the properties of rhenium rods during deformation .
The minimum temperature at which the hardness dropped to 325 kg / mm²
or below after 1 hour of annealing was taken as the recrystallization
temperature . The curves in Figure 8 b show that thorium oxide decreases
the recrystallization temperature of rhenium , although there are some
exceptions (e.g. , alloys containing 1 % of thorium oxide ) . The recrystalli
zation temperature of rhenium containing 2% of thorium oxide is 200°C
lower than that of pure rhenium , irrespective of the degree of preliminary
deformation .
48
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47. Druce , 1.G. " Rhenium " . Cambridge Univ . Press , 51. 1948 .
48. Abashin , G.I. Sbornik " Renii," p . 130. Moskva , Izdatel ' stvo
" Nauka ."' 1964 .
49. Port , J.H. " Rhenium ." New York – Amsterdam . 1962 .
50. Sims , C. T. , C. M.Graighead , and R.I. Jaffee . J. Metals ,
7 : 168 . 1955 .
51. Pavlova , E.I. Sbornik " Renii," p . 117. Moskva , Izdatel'stvo
" Nauka ." 1964 .
52. Koneva , K. T. and G.I. Abashin . – Sbornik " Renii, " p . 128. Moskva ,
Izdatel'stvo " Nauka . " 1964 .
53. Savitskii , E.M. and M.A. Tylkina . Trudy Instituta Metallurgii
AN SSSR . Izdatel'stvo AN SSSR , No. 1 : 158 . 1957 .
54. Savitskii , E. M. , G. S. Burkhanov , and Ch . V. Kopetskii .
Izv . AN SSSR , OTN , Metallurgiya i Gornoe Delo , No. 6:12 . 1963 .
55. Savitskii , E.M. , V.F.Terekhova , 1. V. Burov , and O. P.
Naumkin . Splavy redkozemel'nykh metallov ( Alloys of Rare
Earth Metals ) . Izdatel'stvo AN SSSR . 1962 .
56. Savitskii , E. M. , Ch. V.Kopetskii , A.I. Pekarev , and M.I.
Novosadov . Izv . AN SSSR , OTN , Metallurgiya i Toplivo ,
No. 6:74 . 1961 .
57. Savitskii , E.M. , G. E.Chuprikov , and A. A.Babareko . - Izv .
AN SSSR , OTN, Metallurgiya i Gornoe Delo, No. 3 : 166 . 1963 .
58. Savitskii , E. M. Vliyanie temperatury na mekhanicheskie svoistva
metallov i splavov (Influence of Temperature on the Mechanical
Properties of Metals and Alloys ) . – Izdatel'stvo AN SSSR . 1957 .
59. Gubkin , S.l. Plasticheskaya deformatsiya metallov ( Plastic
Deformation of Metals ) . – Metallurgizdat . 1960 .
50
60. Pugh , J.M. J. Metals , 10 : 335 – 340. 1958 .
61. Fridman , Ya . B. Mekhanicheskie svoistva metallov ( Mechanical
Properties of Metals ) , p . 137 , edition 2 . Metallurgizdat . 1952 .
62. Sims , S. T. and R.I.Jaffee . – J. Metals , 8 : 913 - 917. 1956 .
63. Savitskii , E. M. , M.A. Tylkina . and K. B. Povarova . Dokl .
AN SSSR , 129, No.2 . 1959 .
64. Churchman , A. T. Transactions of the Metallurgical Society of
AIME, 218 : 262 — 267. 1960 .
65. Geach , G. A. , R. A.Jeffrey , and E. Smith . " Rhenium ." New York –
Amsterdam . 1962 .
66. Mises , R.von . Z. angew . Math . und Mech . , 8 : 161 . 1928 .
67. Savitskii , E. M. , M. A. Tylkina , and G. E.Chuprikov . - ZhNkh,
7 ( 9 ) : 2272. 1962 .
68. Savitskii , E. M. and G. E.Chuprikov . – Izv. Vysshikh Uchebnykh
Zavedenii, seriya Tsvetnaya Metallurgiya, No. 3:16 . 1965 .
69. Savitskii , E.M. and G. E. Chuprikov . Izv . AN SSSR , OTN ,
Metallurgiya i Toplivo , No.6 : 68 . 1962 .
70. Frantsevich , I. N. and N. E. Shiyanovskaya . Dokl . AN SSSR ,
142 ( 6 ) : 1291 1293. 1962 .
71. Savitskii , E. M. and G.E.Chuprikov . Sbornik " Renii," p . 110 .
Moskva , Izdatel'stvo " Nauka .' 1964 .
72. Materials and Design Engng., 21 ( 6 ) : 140 . 1960 .
73. Pavlova , E.I. – Sbornik " Renii," p . 117. Moskva , Izdatel'stvo
" Nauka." 1964 .
74. Karavaitsev , V.I. Sbornik " Renii," p . 122. Moskva, Izdatel'stvo
" Nauka." 1964 .
75. Savitskii , E. M. , M. A. Tylkina , L. L. Zhdanova , L. A. Z ubkova
et al. Issledovaniya po zharoprochnym materialam (Investigation of
Heat - Resistant Materials ) . Izdatel'stvo AN SSSR , 9 : 194 – 203 .
1962 .
76. Lebert , G. " Rhenium . " New York - Amsterdam , p . 126. 1962 .
77. Chase Issues . New Data on Rhenium Alloys , Tubing . Amer . Metal
Market , p . 15. March 9 , 1964 .
78. Commercial Production of Rhenium Metal . Chem . Ind . , No. 38 : 1189 .
1959 .
79. Manufacture of Rhenium . Metal Treatment and Drop Forging,
No. 224 : 207 . 1964 .
80. Rhenium and Rhenium Alloys . Engineer , 116 (5628 ) : 949. 1963 .
81. Rhenium and Rhenium Alloys . Engineer, 100 (22) :439. 1962 .
32. Sidelights on Newer Metals . Amer . Metal Market , p.7. Oct. 16 , 1963 .
83. Rhenium Finds Market as Alloying Element . Chem . Engng . News ,
41 ( 40 ) : 31 - 32 ; Battelle Techn . Rev. , No.1 : 374 . 1964 .
84. Kohl , W. H. Materials and Techniques for Electron Tubes . New York
London , pp . 519 — 573. 1960 .
85. Northwest Industries Manufacturing Titanium and Refractory Metals .
Amer . Metal Market , p . 13. Sept. 25, 1963 .
51
Chapter VII
CHEMICAL PROPERTIES OF RHENIUM
In this chapter we shall give some data on the reactions of rhenium with
oxygen , carbon , halides , and other elements , that are important for the
production of rhenium and its alloys . The chemistry of rhenium is described
also in / 1 – 4 /.
1. The valence states of rhenium
Rhenium belongs to group VII of the periodic table . In its reactions with
various other elements and with complexants it has a valence of from +7 to -1 .
The chemical analogues of rhenium are manganese and technetium .
Re * /1 , 4 ). Rhenium is in the heptavalent state in a number of the most
important and stable rhenium compounds such as Re207, and HRe04 and its
salts .
Re6 / 1 , 4 ). The most important compounds of hexavalent rhenium are
Re03, ReF6, ReOC 14, ReO2F2, etc.
Re" /1 , 4 ). Unlike manganese and technetium , rhenium can form
pentavalent halides , e.g. , ReCl, and ReF5 . The compounds of pentavalent
rhenium are less stable in aqueous solutions than those in which rhenium
is in a different valence state . Complex compounds of pentavalent rhenium
are more stable than halides , but they also decompose at high pH values .
Re4+ / 1 , 4 /. Tetravalent compounds of rhenium and technetium are the
most well known (dioxides , disulfides , halides , oxyhalides , and some
complexes ) .
Re ** /1 , 4 /. Almost all known compounds of trivalent rhenium and
technetium are complexes . Exceptions are Rel3, ReBr3, and ReCl3 .
Re2* /4—6 /. Tronev / 5,6 / was the first to obtain solid K ReCl4 in which
rhenium is divalent .
Re * /4 /. The only simple monovalent rhenium compounds known are
Rel and Re20 . Complexes of monovalent rhenium include Re (CN )6" , Re ( CO )51 ,
etc.
Re" /4 /. The existence of rhenium compounds in which rhenium acts
with a valence of -1 , such as rhenides , similar to halides , was doubtful
until recently . However , by physical methods 17 / it has been found that
rhenium also forms bonds of the metal — hydrogen type .
Dilute solutions of potassium rhenide were first obtained /8 / by passing
a cold solution of potassium perrhenate in sulfuric acid through a column
filled with zinc amalgam . The colorless solution could be reoxidized to
perrhenate :
Re- +-8F3+ = 892+ + Reit.
52
A dilute solution of rhenide was produced by reducing perrhenate on a
mercury electrode /9 /.
A solid rhenide ( KRe • 4H2O ) was prepared by reducing potassium
perrhenate by potassium in moist diethylenediamine / 10 /.
The problem of the composition and structure of rhenides has frequently
been discussed in the literature . Potassium rhenide prepared by reducing
potassium perrhenate by potassium in an aqueous solution of diethylene
diamine is given the formula K2ReH3 / 11 /, but this requires further
scientific confirmation .
Compounds of rhenium with different valencies have different stabilities .
According to the data of /2 /, pentavalent rhenium compounds are less
stable in aqueous solutions than other Re compounds . During the reaction
3Re5 + Re + 2Re4*, the redox potential of Re* /Res* is certainly lower
than that of Res* /Re** 12 . This decomposition is also favored by the low
solubility of rhenium dioxide .
Pentavalent Re is stable in complex compounds only, but these
compounds decompose if the pH is increased / 12 /.
Compounds of pentavalent rhenium are easily oxidized even in acid
solutions . In the air this process is slow , but with permanganate , iodates ,
or mercuric chloride , the reaction is rapid /2 /. The electrochemical
anodic oxidation potential in 8N HCl is more than 0.8 V / 13 /.
The Re " /Res* redox potential varies from 0.3 to 0.5 V /27.
Tetravalent rhenium can exist in solution only in the form of complex
compounds , which decompose to the dioxide if the pH of the solution is
increased . The normal redox potential Re * /Re4* at pH = 0 calculated
from the reactions
Reon + 4H + + 3e ReO2 + 2H , 0
and
Reo , + 8H+ + 6C1 + 9e Recia + 4H20
is equal to 0.5 V /4 /.
Trivalent rhenium is unstable in solution . It can exist in hydrochloric
acid solutions in the form of chlororhenic acid H ( Re3*c14) or its salts .
Stannous chloride or chromium chloride can reduce heptavalent rhenium
to trivalent in 8 – 9 N HC1 / 12 /.
Potentials of rhenium / 14 – 17 /. Below we give a diagrammatic
representation of the potentials of rhenium in acid and alkaline solutions
/ 14 – 17 /.
Acid solutions
( +0.363)
( +0.252) ( +0.51)
1
Re 40.4 ) Re (+0.3) Re **(+ 0.2) Reo (+0.61) Reo , (+0.4) Reo ;
|( +0,15 ) Recl,( +0.3 ) ReCa (+-0.5)
53
Alkaline solutions
(-0.576 ) (-0.595 )
Re(-0.4 ) Re( -0.6 ) Re(OH ) (-0.53) Reo (-0.5) RcO2 (-0.7 ) Reb ;
-0.591
The electrode potential of rhenium with reference to a normal calomel

electrode with 2N H2SO4 is equal to 0.6 V , so that in the electromotive series
rhenium lies between copper and thallium / 1 /.
2. Compounds of rhenium with oxygen

Rhenium oxides
The following rhenium oxides are known : ReO4( Re208) , tetroxide (octoxide ) ;
Re207 heptoxide; Re03, trioxide ; Re205, pentoxide ; ReO2 , dioxide ; Re203,
sesquioxide ; Reo ( R202 ); oxide ; and Rezo , rhenous oxide .
The higher oxides are acidic , and the lower ones are probably alkaline .
The existence of tetroxide and pentoxide is doubtful .
Many authors believe that the tetroxide (octoxide ) of rhenium is either
a modification of rhenium heptoxide , a deliquescent heptoxide, or finely
powdered perrhenic acid with traces of moisture /27.
This compound is a volatile colorless solid produced by oxidizing
rhenium or rhenium dioxide at temperatures not above 150°C in a rapid
current of oxygen /19 /. Octoxide reacts with water to form perrhenic acid
+ +
and hydrogen peroxide : Rez08 + 2H20 - 2HRO4 + H2O2. It can also react
with potassium hydroxide to give potassium perrhenate , and with hydrogen
sulfide to form rhenium heptasulfide : Re2O8 + 8H2S RezS7 + 8H2O + S .
Rhenium heptoxide is the most stable rhenium oxide . It is formed
by heating rhenium or one of its oxides in the air or in oxygen above 160°C ,
preferably just below red heat / 1 /. Rhenium heptoxide is a light - yellow
volatile solid which readily deliquesces in the air and reacts with water to
give perrhenic acid / 1 /. Rhenium heptoxide sublimes without decomposition
at 297 °C . In the gaseous state Re207 is a monomer . It dissolves in ethyl
and methyl alcohols and in acetone , but not in ether or carbon tetrachloride .
Gaseous Re20 , is stable in nitrogen , oxygen , chlorine , and in a vacuum
up to 400°C . It decomposes at 800° C in a vacuum .
Rhenium heptoxide is reduced by carbon monoxide and sulfur dioxide to
lower oxides , and at 480°C – 500°C it is reduced completely by hydrogen to
metallic rhenium . With dry hydrogen sulfide Re2O7 forms ReqS7.
Rhenium trioxide is an intermediate product formed by the
reaction between rhenium or its dioxide and nitric acid , or by incomplete
oxidation of rhenium or its compounds in the air . It can also be formed as
an unstable product by reducing perrhenic acid or its salts / 1 /, and also
by the reaction between rhenium and Re2O7 in the absence of air at
200 – 250°C /20 /: 3Re207 + Re = 7Re03, or at 300 °C Re207 + ReO2 = 3Re0g /21 /.
Rhenium trioxide can also be produced at 145° C by decomposing
compounds obtained by the reaction between the heptoxide and dioxane, or by
heating the heptoxide in CO / 3 /.
54
Rhenium trioxide is a red substance with a metallic luster / 1 /. It is
believed that in the gaseous state this compound is a monomer .
If heated to 400°C in vacuo , rhenium trioxide decomposes to the dioxide
and heptoxide . Rhenium trioxide combines easily with oxygen to form the
heptoxide , and in a solution containing an excess of potassium hydroxide
it gives rhenium perrhenate and an unstable rhenate . When fused with
sodium oxide rhenium trioxide gives sodium perrhenate and sodium rhenite :
2NagO + 3Rez = 2NaReos + Na Rego
Rhenium trioxide is stable in dilute solutions of acids and alkalis . When

heated in a current of hydrogen it is reduced to the dioxide and then to
metallic rhenium .
The existenceofrhenium pentoxide is doubtful. According to / 18 / , this
compound is a purplish- red powder formed by heating a mixture of rhenium
and its heptoxide in a sealed pyrex tube :
4Re + 5R20 = 7Re,Os.
Rhenium pentoxide gives a " green band " made up of thin lamellas , and
is bottle- green in color . It is stable in dry air and can be heated in oxygen
to 300°C, or with sulfur to 190°C , without changing / 1 /. Rhenium pentoxide
does not react with dry HCl or with hydrochloric acid solutions , but with
dry chlorine it forms an oxytetrachloride / 1 /.
This oxide does not dissolve in dilute or concentrated solutions of HCI
or H2SO4, or in solutions of KOH , but it reacts with warm nitric acid
( concentrated or dilute ) , and with fused alkali hydroxides / 1 /.
It has recently been found that the hydrate of rhenium pentoxide can
exist in sulfuric acid solutions . If 0.024 M perrhenic acid is electrolyzed
at a cathodic potential of 0.80 V , a black deposit is formed , in which
rhenium is pentavalent . This deposit dissolves to form a dark- blue
colloidal solution /22 /.
Rhenium dioxide can be obtainedby one of severalexistingmethods. The
most widely used is the partial reduction of ammonium perrhenate or of
rhenium heptoxide in hydrogen at 300°C , or by contact with rhenium at
600 °C :
3Re 2 Re207 = 7Re02.
Hydrated rhenium dioxide can also be obtained by hydrolyzing hexahalogen

rhenates /3 /, by reducing solutions of perrhenic acid or its salts by
hydrogen /23 /, by electrolyzing an acid solution / 1 /, by evaporating
perrhenic acid with hydrazine, by decomposing complex compounds of
pentavalent rhenium by water , by prolonged heating of rhenium with rhenium
heptoxide at 600 — 650°C , by thermal decomposition of Re0g /24 /:
4Re03-→ 2RCO , + Re ,O , + 7,02 ,
or by reducing perrhenic acid or its salts in solutions of hydrochloric acid

with mercury, zinc , potassium iodide , or chlorides of tin, chromium , or
vanadium . The hydrated oxide formed during the production of ReO2 from
solutions is dehydrated by heating in vacuo at 650 — 680° C /23 /. The
55
dehydrated dioxide can be reduced to pyrophoric rhenium by heating in a
current of hydrogen . Rhenium dioxide heated at 750° C in the absence of
oxygen or in vacuo decomposes into rhenium and the volatile rhenium
heptoxide / 1 /.
Rhenium dioxide is a reducing agent , and in contact with gaseous HCl it
forms an oxychloride . Rhenium dioxide reacts with sulfur dioxide , and in thi
presence of oxidizing agents (nitric acid, hydrogen peroxide , chlorine or
bromine water ) it is easily oxidized to perrhenic acid / 1 /.
When fused with alkalis in the presence of air rhenium dioxide forms
perrhenates (KRe04) , in the absence of air it forms rhenites ( NazReO3) ,
and in excess air it forms hyporhenites (NazRe04 ) which are unstable in
moist air .
Rhenium dioxide is slightly soluble in water .
Rego , is apparently a mixture of a solid solution of two oxides
ReO2 · 2Re03 /4 /.
Rhenium sesquioxide is a black solid which is rapidly oxidized in air to
perrhenic acid . The hydrate of this oxide can be obtained by electrolyzing
rhenium trichloride or by the reaction between rhenium trichloride and
alkalis in the absence of air /25 / . Even if the product is dried in vacuo ,
pure Re2O3 is not obtained / 1 /.
Rhenium sesquioxide is easily oxidized in solutions of ferric sulfate and
potassium permanganate . Under the influence of alkalis this oxide is
decomposed to derivatives of di- , tetra- , and hexavalent rhenium .
Chemically rhenium sesquioxide resembles hydrated ferrous oxide .
Rhenium oxide is a dark amorphous substance , apparently ReO.H20 / 26 /
and is obtained by reducing perrhenic acid by cadmium in dilute air- free
hydrochloric acid containing 83.2 – 85.85% Re and water . This compound
is difficult to dehydrate . In the air it reacts with HCl and with alkalis . It
is slowly oxidized by the oxygen in the air , and it is very soluble in nitric
acid and bromine water /2 /.
Rhenous oxide (Re20 ) is prepared by reducing a dilute solution of
perrhenic acid by zinc and hydrochloric acid (i.e. , by hydrogen ) in an air
free medium /26 /. The yield is 25 % . The black deposit of RezO can be
dissolved in bromine water and nitric acid , but it is almost insoluble in
alkaline solutions of chromate or ferric sulfate . The oxide has the formula
Re20 · 2H2O .
The solubility of rhenium oxides in different solvents has not yet been
sufficiently studied , but qualitative indications on the subject are given in
/ 17 /.
Perrhenic acid
Perrhenic acid (HRe04 ) can be obtained : 1 ) by direct interaction of

+
rhenium heptoxide and water: Re207 + H2O 2HRe04; 2 ) by oxidizing rhenium
with nitric acid : 3Re + 7HNO3 = 3HRO4 + 2H2O + 7NO; 3 ) by oxidizing lower
rhenium oxides with nitric acid , hydrogen peroxide , chlorine water , or
other oxidizing agents : 2Re02 + 4H2O + 3Cl2 = 2HR04 + 6HC1 (the hydrochloric
acid is removed by heating ); 4 ) by oxidizing rhenium sulfide by nitric acid
or another strong oxidizing agent /1 /; 5 ) from perrhenate solutions by ion
exchange; and 6 ) by electrolysis of perrhenates .
5511 56
The dilute solutions obtained by these methods can be concentrated by
evaporation on a water bath . The colorless liquid is twice as heavy as water ,
and contains more than 60% of pure perrhenic acid .
Perrhenic acid is a strong monobasic acid . It dissolves magnesium ,
iron , and zinc , with evolution of hydrogen . A reaction between this acid
and oxides , hydroxides , and carbonates , of different metals gives normal
perrhenates , Mg ( ReO4)2 , Al ( ReO4) 3, Cu ( Re04)2 , etc. / 1/.
Perrhenic acid neutralizes alkalis , and it can be titrated in the presence
of ordinary indicators (methyl red , methyl violet , phenolphthalein ).
Solutions containing more than 60% of perrhenic acid are yellowish- green
and are difficult to titrate .
The dissociation constant of perrhenic acid can be determined by
measuring the light absorption /27 /. The constant of the first stage of
dissociation of perrhenic acid is equal to 40 ( compared to 10 for perchloric
acid , 400 for permanganate, and 0.02 for periodic acid ) . Pauling /28 /
found an empirical relationship between the strength of an acid and its
structure . Acids of the XO m ( OH ) n type have dissociation constants equal
to ~ 10-2 , 10-5, and 10-8 for m = 1 , 2, and 3 , respectively . Perrhenic acid
with m = 2 cannot be precipitated from an aqueous solution , although its
salts exist / 29 , 30 /:
Reo + 20H1-7 (ReOH (OH);}) ReO33- + H2O3.

Neither the hydrate nor the anhydride of this acid can be obtained from
solutions of perrhenic acid . After evaporation the colorless dilute solution
turns yellow- green , and the spectra have additional lines of the undissociated
acid . Further heating leads to the evaporation of heptoxide /3 /.
Perrhenic acid is stable and difficult to reduce . It is not changed even
by passing of a current of hydrogen through it . Neither the acid nor its
salts have any noticeable oxidizing properties except that they liberate
bromine from hydrobromic acid .
Perrhenic acid can be reduced to a mixture of rhenium and rhenium
dioxide by sodium amalgam , stannous chloride , or hydrozine , and to
rhenium dioxide by zinc in hydrochloric acid / 1 /.
In its reactions with reducing agents the perrhenate ion resembles the
perchlorate ion more than the permanganate /3 / .
Solutions of ferrous , stannous , and titanous sulfates in concentrated
sulfuric acid reduce potassium perrhenate to pentavalent rhenium compounds .
A solution of chromium chloride in sulfuric acid reduces perrhenate to
derivatives of tetravalent rhenium / 31 /.
The reduction of perrhenates proceeds slowly and in several stages . The
valence of Re in the product depends on the reducing agent and the medium .
The valence is higher in more acid media (Table 9 ) .
The behavior of perrhenates during polarographic titration is described
in /3 , 7 , 34 /
Rhenium salts
Rhenites are salts of the acid H2Re03, whose existence has not yet
been confirmed .
The Na ReO3 and K ReO3 rhenites are stable . They do not change during
heating in nitrogen up to 600°C , and are similar to manganites . These
57
compounds react slowly with dilute acids to give rhenium dioxide and a
sodium or potassium salt of the acid . Concentrated hydrochloric acid
converts rhenites into chlororhenates or free chlororhenic acid .
K2Re03 + 8HCI H ,ReClo - + - 2KC1 + 3H20 ( 1 ) .
The production of CareO5 by heating rhenium dioxide with calcium oxide

in vacuo at 450 – 600°C has been reported . This salt is stable up to
1200° C , but in water it hydrolyzes to rhenium , rhenium dioxide , and
calcium perrhenate / 35 /.
Perrhenates . Perrhenates are salts of perrhenic acid and are the
most important compounds of rhenium . Their solubility in water is given
in Table 10 / 36 / . We shall discuss only perrhenates which are important
industrially for the production of metallic rhenium .
Potassium perrhenate (KRe0g) is produced by the reaction
between hot perrhenic acid and potassium hydroxide : HRed + KOH = KRO4 +
H2O , and also by adding potassium chloride to perrhenic acid HRO4 + KC1
KRO4 + HCl 1. This salt is precipitated as anhydrous tetragonal
bipyramidal crystals . The deposit can be either polycrystalline if
precipitated from a dilute hot solution , or it consists of single crystals if
it is precipitated from a supersaturated hot solution .
TABLE 9. Chemical reduction of perrhenate ions
Valence of
Medium , N Reducing agent
reduced ion
HCI 0.6-3.2 Zn -- Hg 2+3

1.0-4.0 Sn2+ , Tis + , V2+ ,Cr? + 4
4.8-6.4 Zn --Hg 3+4
8-10 Sn2+ 5 + 4 + 7
8-10 Cr2 + 3
HCI N2H4 44
H3PO , 4
H2SO4 1 Sn3+ , Tis+ , V2 + , Cr2 + 4
<3.6 Zn – Hg 0+ 1
Cd -- Hg 4
10--18 Zn – Hg 4
10-18 Bi — Hg 5
18 Cr2 + 5+4
The solubility of potassium perrhenate in water is very low and is greatly

influenced by temperature /1 , 36 – 38 /.
One hundred milliliters of water dissolve 1.158 g of KRO4 at 23.8°C ,
9.484 g of KRe04 at 100.3 °C , and 39.7 g of KRe04 at 194°C .
The addition of potassium chloride or hydroxide to the solution decreases
the solubility of potassium perrhenate , and this forms the basis of a method
for purifying the perrhenate from chromates , molybdates , tantalates,
osmiates , and tungstates / 1 /.
Potassium perrhenate is insoluble in acid solutions , even in perrhenic
acid .
When neutral or slightly acid solutions of potassium perrhenate are
electrolyzed , rhenium and rhenium dioxide are deposited on mercury and
58
platinum electrodes . It has been found / 39 / that the deposited rhenium
forms an amalgam with mercury .
Sodium perrhenate (NaRe0g ) can be obtained by the same method
as potassium perrhenate , but heating is not necessary . Sodium perrhenate
is the most soluble of all perrhenates in water ( 100 ml of water at 20° C
dissolve 100 g of sodium perrhenate ) . Sodium perrhenate is hygroscopic
and colorless / 1 /.
Ammonium perrhenate (NH4ReOn ) is produced by the reaction
between perrhenic acid and ammonium hydroxide . At 20°C a saturated aqueous
solution contains 6% of this salt , which at elevated temperatures can be
reduced by hydrogen to metallic rhenium . The salt is decomposed by heat
to ammonia (gas ) , rhenium heptoxide (gas ), and rhenium dioxide (black
deposit ) / 1 ).
TABLE 10. Solubility of perrhenates in water
Temperature, °C
Perrhenate
0 30 50
Solubility , mole/ 100 mg /36/

Li ReOd 2H20 1 1.40 1.40
Na Reos 0.378 0.532 0.636
K Reos 1.24 . 10-9 5.08-10-3 11.1.10-3
NH ,Red 1.03.10-2 3.25.10-2 5.99.10-2
RORO 1.16-10-3 4.68.10-3 10.5-10-3
CsReos 0.86.10-3 2.87.10-3 6,40.10-3
Solubility , g /100 g /40 – 42 /

Ag Re04 0.43 1.39 2.71
TIRO 0.115 0.298 0.555
Be (ReOl)2 Decomposes to a basic salt
Mg (ReOs)2 283.6
Ca (ReOs )2 187.0
Sr (Red) 110.1
Ba (ReOs) 1.52 8.13 21.51
Zn (ReOs)2 313,6
Cd (ReOs)2 497,5
Hg (ReOs)2 Decomposes to a basic salt
Cu (ReOl)2 210.4
Pb (ReOu)2 4.4,14 14.81 1 29.63
Perrhenic acid (HRe04 ) can form complex salts with NH2 / 1 , 43 ) . The
ammines are usually readily soluble in water .
The solubility of some perrhenates is given in Table 10 .
Anhydrous perrhenates of manganese , cobalt , and iron are readily
soluble in water . At 25°C more than 200 g of each of these substances can
be dissolved in 100 g of water .
3. Compounds of rhenium with carbon

Rhenium forms no carbides but only complex compounds containing carbon .
Rhenium carbonyl ( Re (CO ); 12 is formed by the reaction between
carbon dioxide and rhenium compounds (rhenium heptoxide and potassium or
59
ammonium perrhenates ) at 250 — 270°C and a pressure of 350 – 500 atm /48 /
The colorless crystals of carbonyl are soluble in organic solvents and can
be sublimed .
The existence of rhenium carbonyl halides Re (CO );X and ( Re (CO ),X )
(where X is a halogen ) has been reported / 44 - 47 ). These compounds are
colorless and insoluble in water . They sublime without decomposition in
an atmosphere of CO .
At 240° C rhenium carbonyl reacts with some amines to give compounds
that can be considered as derivatives of carbonyl halides in which the
halogen is substituted by an amine , for example , by pyridine:
( Re (CO )s)a + CsH $ N 2Re (CO), CsHsN + 4CO .
The carbonyl decomposes at 400°C .

Amines also react with rhenium carbonyl halides to form compounds
such as ReCl (CO )2 · 2C5H5N . Carbonyls and carbonyl halides react with hot
potassium methanol to give K ( Re (CO ), 0 , H ) / 49 /.
4. Compounds of rhenium with halogens

Rhenium fluorides
The following fluorides are known : ReF7 , ReF . , ReF , and ReF4 .
Rhenium heptafluoride (ReF ,)was obtained only recently /50 / by
passing fluorine at a pressure of 250 mm Hg through rhenium heated to
300 – 400° C . This compound is volatile and it can be purified by heating
at 400° C in an atmosphere of fluorine .
Rhenium hexafluorine (ReFo ) / 51 - 54 / can be obtained by the
action of fluorine on rhenium at 125°C / 52 ). At - 180°C the crystals of
rhenium hexafluoride are bright yellow and above 0°C lemon - yellow . At
18.8 °C ReFo melts to a yellow - brown liquid but its vapor is almost colorless .
Rhenium hexafluoride can be reduced to pentafluoride by tungsten
carbonyl and by an excess of tungsten hexafluoride . ReFo can be reduced
to ReF4 by hydrogen at 200° C , by carbon dioxide at 300° C , by sulfur dioxide
at 400° C , by rhenium at 400 – 500°C , and also by copper , gold , or aluminum .
ReFg reacts with oxygen , potassium peroxide , or potassium permanganate ,
to give rhenium oxytetrafluoride or rhenium trioxyfluoride . It reacts with
water to form hydrated rhenium dioxide , perrhenic acid , and hydrofluoric
acid :
3ReFe + 10H2O = ReO2 + 2HROA + 18HF.
Rhenium hexafluoride reacts with glass and some organic substances ,

such as lubrication oils , petroleum ether , etc.
The action of ReFo on silicon dioxide at room temperature proceeds as
follows : SiO2 + 2Re F6 = 2ReOF4 + SiF4 . The compound obtained is stable up
to ~ 300° C .
Rhenium pentafluoride (ReFg ) is formed by the reaction between
ReFo and tungsten carbonyl. The pentafluoride decomposes in vacuo at
180°C into ReFg and ReF4 / 55 /.
60
Rhenium tetrafluoride ( ReF4) / 52 , 56 / is produced by reducing
rhenium hexafluoride in hydrogen at 200° C or in sulfur trioxide at 400°C ,
although it is believed that in the latter case a mixture of ReFs and ReF4
is formed / 52 /.
Rhenium chlorides
Rhenium heptachloride ( ReC17) has been prepared by the action

of concentrated hydrochloric acid on nonpurified rhenium preparations /56 /.
However this has not been confirmed by later studies / 57 , 58 /, and therefore
the existence of this compound is still doubtful .
Rhenium hexachloride ( ReC16 ) was obtained /57 / by heating
rhenium in an excess of chlorine at 650°C . The product was always
contaminated by rhenium tetrachloride . The existence of ReCl6 has also
not been clearly proved .
Rhenium pentachloride ( ReCl5) is a brown- black solid with red
brown vapor formed by treating rhenium with excess chlorine at 400 -- 500° C .
The product is purified by sublimation in vacuo . ReCls can also be produced
by heating of AgreClo / 59, 60 / . Rhenium pentachloride is the most volatile
ofthe rhenium chlorides /61 /. If vapors of ReCl, are heated they dissociate
into chlorine and rhenium trichloride .
It has been found /60 / that ReCl, can also be produced by treating
rhenium heptoxide with carbon tetrachloride at 400°C . When rhenium
pentachloride is heated with oxygen , chlorine and rhenium oxychlorides are
formed :
16ReCl, + 140 , = 10ROCI, + 6ReO ,Cl + 1701,.
The reaction between rhenium pentachloride and alkalis or water leads

to gradual decomposition , which can be depicted as follows : 3ReCl3 +
16NaOH = 2Re (OH )4 + NaReO4 + 15NaCl + 4H2O . Rhenium pentachloride reacts
with ammonia , too .
The synthesis of rhenium tetrachloride ( ReCle) has been reported
in / 58 , 61 , 62 ). This is a dark -brown, almost black substance which is stable
in dry air and sublimes when heated . Rhenium tetrachloride hydrolyzes to
rhenium dioxide , hydrochloric acid , and other products . Its reaction with
hydrochloric acid gives a solution probably containing chlororhenic acid .
Other authors / 59 / have not confirmed the existence of rhenium
tetrachloride , since a ratio of Re : C1 = 1 : 4 in the product may also indicate
the presence of ReoCl4 or of a mixture of ReCl3 and ReCl5 / 1 !.
Rhenium trichloride (ReCl3) is formed as a primary product
during the reaction of rhenium with chlorine , or the thermal decomposition
of ReCl, in nitrogen / 1 ), when silver rhenate is heated in vacuo to 350 –
400°C , or when ReCl, is heated in an inert gas 13 /.
Rhenium trichloride forms reddish-black or violet hexagonal crystals
and a dark- green vapor . It gives intense red solutions with water , acetone ,
ether, glacial acetic acid , and hydrochloric acid . With KCl it forms KReCl4
and with ammonia ReCl3 · 14NH3, ReCl3 • 7NH3, and ReCl3 · 6NH3 /63 / .
In hydrogen ReCl3 is reduced at 250 – 300°C to rhenium and HCl without
the formation of lower chlorides / 1 /.
61
When heated with oxygen it reacts as follows / 1 /:
6ReCl2 +- 70, = 4 ReOzC1 + 2RCOCI + 3CI .
Rhenium bromides
Rhenium forms tribromides and tetrabromides , ReBrg and ReBr4 / 1 ).

Green- black rhenium tribromide (ReBr3) is formed by heating
metallic rhenium in bromine vapor at 300°C /64 /, or by dissolving rhenium
sesquioxide in hydrobromic acid .
Ii ReBrz is heated in oxygen at 400°C a blue oxybromide is formed . The
vapor of ReBr3 is dark green .
Rhenium iodides
Only three iodides are known at present : Relq, Rel; and Rel /65 /.
According to /65 – 66 / rhenium iodides cannot be obtained directly from
the metal and iodine (pure or in solution ), but only indirectly from complex
iodides . Thus , perrhenic acid can be reduced by hydriodic acid to
hexaiodorhenic acid , which decomposes to rhenium and rhenium tetraiodide .
In the presence of excess iodine the latter can be further decomposed at
350°C to Rel3, and at 110°C it can be decomposed to Rel in a current of
nitrogen by removing the iodine vapor .
Rhenium tetraiodide Relqis a black substance obtained by the reaction
between cold HI and HReO4 and evaporating the solution . Reld is very
hygroscopic and readily soluble in water , acetone , and ether /65 /. Rely
is hydrolyzed to a hydrated dioxide ReO2 .nH20. Rely rapidly decomposes
in vacuo to Relz and RI at room and elevated temperatures .
Rhenium triodide Relz forms black crystals and can be obtained
by heating Rely to 350°C in a soldered tube /65 /. Relz is sparingly soluble
in water and dilute acids , and almost insoluble in alcohol , acetone , and ether .
Relz loses iodine in a vacuum , particularly when heated /65 /.
Rhenium iodide Rel is formed by heating Rely to a constant weight
at 110°C in a current of nitrogen containing small amounts of iodine /65 /.
Rhenium forms different oxyhalides / 1 , 51 , 52 , 55, 67 — 74 ), most of
which are unstable as they decompose in the air and are hydrolyzed . The
following rhenium oxyfluorides are known : ReOF4/51, 52, 55 /, ReO2F2
/52 , 55 /, ReO2F3, ReOFs /67 , 68 / and ReO3F /69–71 /.
The preparation and properties of oxychlorides have been described in
several works: Re03C1 /72 – 74 %, ReO2Clz / 1 , 75 /, ReoCl4 /72 /, ReoCl2
176 /. ReO3Br and ReO2Br2 are described in /77 /, and the production of
ReoBr2 in /78 /. No data are available on the preparation of oxyiodides .
Double rhenium halides are obtained by the reaction between rhenium
halides and halides of other metals .
K2ReF8, NazReFs, and other fluororhenates have been produced /3 ,
78 — 84 /. Most of these compounds are unstable in air .
62
Chlororhenates are salts of chlororhenic acid H2ReCl6 K2ReCl6 is
described in /85 - 87 /, RbReCle and CsReCle in / 1 /, and Ag2ReCle in /86 /.
Complex salts of the type K3ReC16 , K4RezCli , (NH4)2ReCl4, Ag3ReCle
/ 1 , 5, 88 / , and also acid complex compounds of the type (NH4)2ReClo and
(NH4)3ReClo /89 / are also known.
5. Rhenium phosphides
It was found that rhenium reacts with phosphorus above 750 – 800°C to
form the following phosphides: triphosphide ReP3, diphosphide Re P2,
monophosphide ReP, and Re2P /90 /.
6. Compounds of rhenium with sulfur
Rhenium heptasulfide (ReqS7) can be obtained by passing hydrogen

sulfide for a long time through a solution of perrhenate :
2H ReOn + 7H2S = RezS, + 8H ,O .
This compound is also formed in the reaction between acidified solutions

of potassium perrhenate and sodium thiosulfate /91 /.
Rhenium heptasulfide is a dark- brown, almost black substance , sparingly
soluble in water , but readily soluble in nitric acid , in which it decomposes
to rhenic acid , and sulfur or sulfur dioxide , or even sulfuric acid .
When heated in air rhenium heptasulfide burns to give a white smoke
of rhenium heptoxide :
2RezS , + 3502 = 2Rezor + 14502.
When heated in a current of nitrogen or carbon monoxide ReqS7 forms

rhenium disulfide (ReqS7 = 2ReS2 + 3S) / 1 /.
Rhenium disulfide (ReS2 ) is formed by the reaction between
rhenium and sulfur at room temperature , and also when rhenium hepta
sulfide is decomposed in an inert gas .
Rhenium disulfide is a black substance , stable in the air , but when
heated it decomposes to rhenium oxide and sulfur. Rhenium disulfide is
difficult to oxidize , but it reacts readily with hot nitric acid , even dilute .
At elevated temperatures it is reduced by hydrogen to metal .
Rhenium trisulfide (ReS3) has been described in / 92 / only, and
according to the data given it decomposes at 800°C into sulfur and rhenium
disulfide.
Qualitative data on the solubility of rhenium sulfide in different solutions
are given in /17 /.
Rhenium forms not only sulfides but also thioperrhenates . Those of
potassium , lead , mercury, thallium , ammonium , rubidium , and cesium
have been prepared / 1 , 91 /. The compounds are salts of the stable
thioperrhenic acid HRO3S /91 ), which rapidly decomposes into rhenium
sulfide and rhenic acid .
63
7. Compounds of rhenium and nitrogen
A rhenium nitride ( ReNo.43) is formed by passing ammonia over rhenium

salts NH_Re04 and ReCl3 at 300 – 350°C /93 /. The K2Re03N compound has
also been obtained , and it is believed that this will give absorption lines in
the infrared region / 94 / .
8. Thermodynamic characteristics of compounds of

rhenium with oxygen
The physical properties of chemical compounds formed by rhenium with

nonmetals have been little studied . Most existing data include the boiling
point and melting point of the compounds , and also their thermodynamic
characteristics . Recently, data have appeared in the literature on the
crystal structure of chemical compounds and the magnetic properties of
some complexes . Data on the intermetallic compounds of rhenium are
given in Part 3, " Phase Diagrams of Rhenium ."
The heat , entropy , and free energy of formation of some rhenium oxides
are given in Tables 11 – 13. These data were taken from different papers .
According to the data of /95 /, the heat of formation of ReOz ( solid ) is
equal to 83.0 kcal / mole . By burning rhenium the authors apparently obtained
rhenium heptoxide and rhenium hexoxide . The direct determination given
in / 14 / is probably more accurate .
The heat of formation of Re207 has been determined by various methods ,
and is as follows :
Re03 ( solid ) + 1 /2O2 (gas ) + Re207 ( solid ) AH = -6 6 kcal / mole / 15 / ;
2Re ( solid ) + 7/202 (gas ) = Re207 ( solid ) DH = - 295.9 +2.0 kcal / mole / 14 /.
The value AH= -6 6 kcal / mole is not exact , since the correction for
the incomplete burning of the oxide is not known . The value AH = - 295.9+
2.0 kcal / mole / 14 ) is commensurable with earlier data on the values
AH = -297.5+ 2.0 kcal /mole / 95 /. The authors of / 14 / suggest an average
value of AH - 296.71 0.8 kcal / mole .
The entropy of Re2O7 found by various methods is:
1 ) method of additivity /15 / :48.6 cal / mole • ° C;
2 ) comparison with TC207 ( solid ) /14/:44.9 cal / mole • °C;
3 ) from the entropy of KRe04 ( solid ) and the entropy of dehydration of
HRe04 (solid ) : 38.6 cal / mole • °C . Hence , the average value of the
entropy is 44.03 3.6 cal / mole • °C / 14 /.
Thermodynamic characteristics of thermal transfor
mations of rhenium oxides . Re207. Heat of fusion Lfus = 15.8+ 0.1
kcal / mole; free energy of fusion AF fus 15.810 — 27.6 T kcal / mole / 14 /;
heat of sublimation Lsubı= 35.5 kcal / mole / 98 /, 33.41 3.5 kcal / mole / 101 ,
102 /; entropy of sublimation ASsubı = 58.4 cal / mole · °C /98 /; free energy of
sublimation AF.subi 33.500 — 55.6 T cal / mole / 10 /, 16.885 kcal / mole /103 /,
37 kcal/ g - atom / 14 /; heat of vaporization Lvap- 17.7+ 0.1 kcal / mole /14 /,
18.11 3.5 kcal / mole / 14 , 101 /, 18.06 kcal / mole / 104 /; free energy of
vaporization Afvap = 17.700 — 28.0 T cal / mole /14 /. The thermodynamic
characteristics of the sublimation of rhenium oxide are given in Table 14.
64
TABLE 11. Heat of formation of some rhenium oxides at 25 ° C
Heat of formation , References

Compound AH 298 kcal /mole
Reo , ( solid ) -70 /2 /

-101.3 / 14 /
Reoz ( solid) -83.0 195/
-146.0 + 3.0 / 14 /
Re2O , (solid) -6 + 6 /15/
-295.9 +2.0 /14/
-297.5+ 2.0 /95 /
-296.71 0.8 (average ) / 14,951
HROA ( liquid ) -189.2 + 0.08 / 14/
-161.7 /96 /
-182.2 + 1 / 97 /
KREO , (solid ) -263.0 /14 , 36 , 95/
-298.4 /14 /
NHAROA ( liquid) -218.4 / 96 /
Reod (ion ) -190.3 /14/
TABLE 12. Entropy of formation of some rhenium oxides at 25 ° C
Entropy 5298 Entropy of formation

Compound cal/ mole . ° C as298 , cal /mole · °C
ReO2 (solid ) 17.4 /15/ -40.5 (14 )

Reog (solid ) 19.31 2.5 /16 / 1.6 / 98 /
19.8 / 98 / -61.5 /14 /
-64.2 /98 /
Rezo , (solid ) 49.5 /15 / -63.1 2.5 /99 /
-44.0 + 3.6 /14 /
-38.6 /14/
-48.6 /15 /
-142 / 98 /
HREO , ( liquid) 50 /15 / -44.9 /14/
HREO , ( solid ) -74.2 /100/
KREO , ( solid ) -30.9 / 14 /
Reoj ( ion) 48.3 /100/ -82.0 /14 /
Vapor pressure of rhenium oxide . For rhenium trioxide the

dependence of log p on temperature over the temperature range 325 – 420°C
can be written as / 105 /:
10,882
log p = T
+15,16 ,
where p is mm Hg. The isothermal- isobaric potential of sublimation

AZ ; = 49,785 – 56.17 .
The determination of the vapor pressure of ReO3 above 440° C is difficult
since the equilibrium of the reaction 3ReO 2 ReO2 + Re207 is appreciably
shifted to the right. The vapor pressure of ReO3 calculated from the
formula / 105 / attains 760 mm Hg at 614° C . The vapor pressure of
rhenium heptoxide is given in Table 15 .
65
TABLE 13. Free energy of formation of some rhenium
oxides at 25 ° C / 14 , 16 /
Free energy of form ation

Compound AF 8 kcal / mole
29 )
ReO2 ( solid ) -89.2

Re0g (solid) -127.3
-128.1
Rezo , (solid ) -167.11 0.8
HRO4 ( liquid ) -258.7
TABLE 14. Thermodynamic characteristics of the sublimation of rhenium oxides

Heat of sublimation , Entropy of sublimation,
Compound L , kcal /mole as sub , kcal /mole • ° C
40.1
ReO2
Re03
49.48 }/1051
65.64
56.1
TABLE 15. Vapor pressure of rhenium heptoxide Re2O7 /16 /

T, ° C 230 250 265 280 295 300 310 325 340 360
P , mm Hg 3.0 10.9 26.5 61.2 135 160 210 312 449 711
The saturated vapor pressure of rhenium dioxide was measured

over the temperature range 650 — 785°C /105 /. Above 785°C the
disproportionation of rhenium dioxide is appreciable . The temperature
dependence can be written:
14347
logp = T + 11.65,
Hence az;= 65,637 – 40.11 T. The vapor pressure of ReO2 reaches

760 mm Hg at 1363°C .
The dissociation pressure of some perrhenates as a function of
temperature was determined in / 106 /.
For molten potassium perrhenate KRe04:
14,188
log p = T + 13.28 ;
For solid Ca (ReO4)2:

8080
logo т +7.33 ;
For solid Cu (Re04 )2:
4781
logp т
+5.67 .
The temperature dependence of the vapor pressure of HRO4 ( solid ) has

been studied /97 /.
66
The low - temperature heat capacity and some thermodynamic
characteristics of potassium perrhenate (KRO ) (solid ) and of the perrhenate
ion ReO4 at temperatures of 10 – 3000K were determined in /100 ). The heat
capacity Cp was found with an accuracy of 12% , except at very low
temperatures .
TABLE 16. Heats of solution of some oxygen -containing rhenium com pounds
Heat of solution in water ,
Compound References
kcal /mole
Rezo , 13.2 / 15 /
KROA 7.68 / 36 /
NaRe04 13.8 115,107/
NHẠReO, 1.83 /36/
Over the range of temperatures studied the temperature dependence of

the heat capacity is almost linear . At 10 , 100 200 , and 298.16° K Cp is
equal to 0.400 , 16.921 , 24.840 , and 29.303 cal / g- atom · degree , respectively .
No transformations of KRe04 have been found over this temperature range .
The thermodynamic characteristics of solution ,
dehydration , and neutralization of some oxygen
containing rhenium compounds .
The heats of solution of four oxygen- containing rhenium compounds are
given in Table 16 .
The following thermodynamic data on the dehydration of HRe04 at
298.1° K are given in / 147:
AH ° -= 4460+0.18
2HROA ( solid) = Rezo, ( solid) + H20 (gas) AF° 11.02 +0.10 cal/mole
cal /mole; ;
AH ° = 500+ 0.1 cal /inole ;

2HRO (solid ) = Rezo, ( solid) + H2O (liq)
AF° = 2418 + 0.8 cal /mole .
The entropy of dehydration of HROA ( solid ) , according to 2HR04 ( solid ) =

Re207 (solid ) + H20 is AS = -3.2 cal / mole • degree / 97 /.
The free energy of solution of KRO4 is 4047 cal / mole , and the entropy
is 32.71 cal / mole • degree / 100 /.
Rhenium carbonyl /108 /. The rhenium carbonyl Rez (CO ) 10 is a
volatile rhenium compound used as the starting material for the production
of rhenium from gases . Rhenium carbonyl undergoes a low- temperature
phase transformation at 90.2 - 91.8° C , but this phase has not yet been
identified .
The results of the measurements of the saturated vapor pressure of
rhenium paracarbonyl are given in Table 17 / 108/. The measurements were
carried out by the dynamic method .
In the log p = f ( 1/1 ) coordinates the data lie on a straight line represented
by the equation :
4152
logp = 10.68 т
67
TABLE 17. Saturated vapor pressure of rhenium carbonyl
T, ° C P , mm Hg T , ° C P , mm Hg
78.0 0.072 113.0 0.914

78.4 0.070 113.1 0.875
78.7 0.077 113.7 0.867
95.9 0.288 133.8 2.673
97.2 0.320 135.5 3.452
The latent heat of sublimation is equal to 19.0 kcal / mole or 29.1 cal / g .
The kinetics of the thermal decomposition of rhenium carbonyl have been
studied / 108 /. Rhenium carbonyl starts to decompose fairly rapidly at 420 ° C .
The rate constant of the decomposition of rhenium carbonyl at different
temperatures is represented by the equation: log k = 6.326 – 4073 / T.
Below 315°C the decomposition of the carbonyl is a first order reaction .
The order of the reaction at 315 – 420° C is not known .
9. Thermodynamic characteristics of rhenium halides
Rhenium chlorides and oxychlorides / 98 / . Rhenium

chlorides ( ReCl3 and ReC15 ) and also rhenium oxychloride (ReCl4) are used
to produce rhenium by the method of thermal dissociation .
The vapor pressure and the dissociation pressure of rhenium pentachloride
and the dissociation constants of ReCls (gas ) at 250 – 400°C were measured
by the flow method . The equilibrium values of these magnitudes at a given
temperature were obtained by extrapolating to zero rate the particular
magnitudes corresponding to the various rates of passing argon . In these
calculations it was assumed that the molecules of rhenium pentachloride
do not polymerize in the gaseous state .
The vapor pressure of rhenium monoxytetrachloride was measured by
two methods: by determining the boiling point using an ebuliometer , and
by the flow method . From the agreement between the data of these two
methods it can be concluded that the molecules of ReoCl4 are not polymerized
in the gaseous state .
Some thermodynamic data on these compounds are given in Table 18 ,
and the chief thermodynamic characteristics of chlorides and oxychlorides
of rhenium in Table 19 .
According to the data given in / 109 / , the free energy of ReCl3, is of , 298
- 44 cal / mole .
The variation in Af = f ( T ) has been calculated for the following reactions :
ReCls (gas) ReCig (gas) + Cl2 47,800—47.51

2ReCls (gas) = 2Re+ 5Cl2 149,600–123,07
ReCl3 (sol) ReCl3 (gas) 36,000--32.07
- 89,400--114.57
5ReCl3 ( gas) 23ReCls (gas)+ 2Re ΔFI,
2ReCl (gas) 22Re + 3Cl2 54,000–28.01
3ReOCIe (gas) = ReO ;Cl (gas) + 2Re + 5,5Cl2 171,200—134,6T
3Recla (gas) ReO3 (gas) + 2Re + 6C12 211 600--150,9T
7ReOČla (gas) = Rez07 (gas) + 5Re + 14C12 442,603 --- 287.47T
The behavior of the chlorides and oxychlorides of rhenium at different

temperatures / 98 / has been predicted by analyzing their thermodynamic
characteristics .
68
TABLE 18. Experimental thermodynamic data on rhenium chlorides and oxychlorides /98/
Dependence of log p on AS Tempera
AH
Reaction the temperature cal /mole • ture
kcal/mole
( P in mm Hg) °C range , ° C
2670
Recls (sob) = Recls (gas) log Preci, = 7.06 12.2+ 1,2 19.5 +2 100-250
5600
ReCls (sol) log P CI , = 12.5 - т
25.6+ 3 4316 100--250
ReCl3 (sol) + Cl2 Pal
P 2480
Recls (gas) = 108 recis 3.4 -
T
11.8+ 1 15.641.5 250--410
ReCl3 ( sol) + Cl2
7.63 2380
ReОCla (liq) = log PREOCI. T 10.9+0,2 22.1 +0.5 30--228
z ReoCls (gas)
( according to boiling point) 2180
ReoCl. ( liq) = logP Reoclo = 7,22 -
9.8+ 1 20.1 + 2 30-228
т
ReoCl. (gas)
( flow method)
ion
TABLE 19. Thermodynamic characteristics of some chlorine -containing compounds of rhenium /98, 109 /
ization
forma
vapor
sublimat
n
ole
Heat
egree-
Heat
formatio
Entropy
Entropy
limation
cal
'I, ap
of
of
Heat
/ ole
kcal
/ ole
sub
/°C•m
/ ole
/ ole
Heat
kcal
,L v
opy
5621
sion
/k', cal
mkcal
mkcal
d•cal
,Lfuse
of
fu
AS
of
m
of
of
,
m
tion
Entr
Compound
,an
Lsubl
,
mole
,
298
AS2983
,
o
,
)
Recl, (solid ) -63 44 46 36.0 32.0

ReCls (solid ) -87 62 -81 12.2 19.5
ReOCL ( solid) -116 60 -81 127 1.8 10.9 28.0
REOCL ( gas) 85.7
Re0gCl (solid) -147 58.7 -51.4 10.3 1.4 8.9 27.0
Thermodynamic properties of bromides , fluorides ,

and oxyfluorides of rhenium / 109— 114 / . According to the data
of / 109 / the heat of formation of ReBrz is oH 298= - 39 kcal / mole , the free
energy is AF29 = -33.6 kcal / mole , the entropy is sº = 44.0 cal / mole • °C /109 / .
The data of / 101 – 102 / give the heat of formation of ReF6 (liq ) as
AH998 = -278+ 20 kcal / mole . The heat of formation of ReFo is AH 298
,
- 275 kcal / mole / 110 , 113 /, and the free energy of° = - 252 kcal /mole
/ 110, 112 ). The heat of vaporization of ReF6 is -6.91 0.4 kcal /mole /110 ,
112 .
The vapor pressure of ReF5, Re0F4 , ReOF6, ReO2F3 over the temperature
range 0 – 172° C has been determined / 111 /.
Equations for determining vapor pressure
ReFg ( liq ) (48.0–1400) 9.024-3037 / T
ReOF4 ( liq ) (108-1720 ) 10.09-3206 / T
ReOFA (solid ) (50-1070) -11.88-3888 / T
ReOF5 (liq) (41 – 730 ) log p = 7.727-1678.6 / T
ReOF, ( solid ) ( 30-410) 8.620–1958.9/ 1
ReOFs (solid) (0-300) 9.581-2250.1 /T
ReO2Fz (liq ) ( 90-1700) 10.36-3437 / 1
The saturated vapor pressure of ReF , has been measured / 114 /.

Some physical constants of rhenium fluorides and rhenium oxyfluorides
are given in Table 20 / 114 / .
69
TABLE 20. Thermodynamic constants of some fluorides and oxyfluorides of rhenium
ReFs 13.880 28.1

ReF6 6.857 22.3 7.796
ReOF 4 3230 8.478 14.590 32.7 17.820
ReOFs 1220 3.886 1339 3.868 7.720 22.3 8.940 10.280
ReO2F4 15.700 34.3
10. Thermodynamic characteristics of compounds of

rhenium with germanium and silicon
The interaction of rhenium with germanium has been studied / 115 /.
When heated , rhenium interacts with germanium to form ReGez . The vapor
pressure of mixtures of the elements produced by the decomposition of the
compound was measured by the diffusion method . It was found that at the
dissociation temperature of ReGe, the vapor pressure of a mixture of
rhenium with germanium is close to the vapor pressure of pure germanium .
An increase in the concentration of rhenium in the pure phase decreases
the partial pressure of germanium .
The heats of formation of ReGe, and of ReSiz have been found:
' / Re (solid) + Si ( gas) → 1/2 ReSiz (solid) AH°= -118 + 15 kcal/mole,

1/2 Re (solid) + Ge (gas) → /2 ReGe, ( solid ) AH°= -94 + 10 kcal /mole .
This comparison shows that the structural energy of the compounds of

rhenium with elements of group IV decreases with decrease in the negative
valence of these elements and with transition from the first to the third
period . The formation of ReCx compounds in the Re - C system has been
shown / 115 /, and the heat of formation was found to be – 1720 15 kcal / mole .
However , other authors /116 / found that no carbides are formed when
rhenium reacts with carbon .
Rhenium forms three compounds with silicon / 117 /. From the available
data on the systems formed by Re with these three elements , we believe that
at least two compounds should be formed in the rhenium – germanium
system . The existing phase diagram of the rhenium germanium system
/ 115 / must be verified.
The free energies of the compounds formed in the rhenium - silicon
system have been determined / 118 /:
Re Si 21.250_5,49T
Resi AF - 26,580_0.94T
Resiz - 55.030 + 0.74T
70
According to the authors of / 118 / , RezSi and ReSi are unstable at room
temperature and are converted into ReSiz . This , however, has not been
confirmed by later research on the rhenium - silicon system /1171.
11 , Thermodynamic characteristics of compounds of

rhenium with sulfur
Rhenium heptasulfide (ReqS7) . The temperature dependence of the

dissociation pressure of rhenium heptasulfide can be written as /119 /:
4800
logp = T
+8.86 .
Over the temperature range 260— 410°C the pressure changes from 0.62 to
64.74 mm Hg .
From these data the temperature dependence of the free energy of
formation of ReqS7 from ReS2 can be expressed by the equation found by the
method of averages :
AZ° = 21,394 - 39.77 .
The free energy at 25°C is equal to about 9584 cal / mole .

Rhenium disulfide (ReS2 ). The temperature dependence of the
saturated vapor pressure of ReS2 can be written as /105 /:
4976
logp T + 3.214 .
The heat of formation of ReS2 is – 42 kcal / mole / 119 /; according to

other data AH 288 = – 46 kcal / mole ( 113 ), or AH298 42,51 4.0 kcal / mole
(102 ). The free energy of formation AF298 44 kcal / mole ( 113 ). The
entropy of formation AS288 - 20.0 cal • °C / mole /15 /. The temperature
dependence of the isothermal- isobaric potential of ReS2 can be represented
by the equation: AZ°= 22,665—1523 T /105 / . The heat of sublimation of
ReS2 L subl is 22.66 kcal / mole /105 /.
12. Melting and boiling points
The melting and boiling points of a number of rhenium compounds

determined by several authors are given in Table 21 .
13. Crystal structure of rhenium compounds
Heptavalent rhenium compounds have regular stereochemical

characteristics due to the complete absence of external 6s and 5d electrons .
In these compounds rhenium has a tetrahedral configuration .
The unit cell of rhenium trioxide consists of an octahedron of oxygen
with an atom of rhenium in the center connected to each of the corners / 126 /.
This structure is similar to that of perovskite (MIT ;IVO3) , which has an
71
additional metal ion in the center of the unit cell . Similar phases which
have specific magnetic properties have recently been studied / 127 /: [ Ba2M ]
ReVlO6 and Ba (M.Re ! j03, where MI and M II are monovalent and divalent
metals .
TABLE 21. Melting and boiling points of rhenium com pounds
Compound Mp, °C Bp. °C
Re2O , ~ 220 /19 / Sublimes at 300 /19 /

304 / 1 / 297 /1 /
300.3+ 0.03 /97 /
KROA 552 + 3 / 120 / 1378 (at 763 mm Hg) /36 /
518 /121 / 1359 (at 752 mm Hg) /36 /
555 /36 /
NaRe04 ~ 300 /1 / ; 414 /36 / Decom poses at > 500 /120 /
ReCig Sublimes without melting Sublimes at 500-550 /19 /
ReCl4 180 / 63 / 250 /63 /
ReClg 260 /63 / 330 /63 /
ReOzci 3-4 /59 / 128 /122 / , 131 /59 /
ReO2Cl2 23.9 / 75 / 300 (in vacuo) / 75 /
ReOC14 29-30.5 / 72 / 223 /72 /
The crystal structure of ReO2 is of the type of the isomorphic MoO2 . It

consists of a distorted rutile lattice in which the atoms of the metal are
twinned .
ReO2 has an orthorhombic lattice with the following parameters : a =
1.810 , b 5.643 , and c = 4.601 Å , with a space group p 21/c / 128 /.
Rhenium heptoxide also has an orthorhombic lattice ( a = 15.25; b = 5.48 ;
с
12.5 Ă ) with 8 molecules in the unit cell / 129 /. The thermodynamic data
indicate that the bonds in this compound are not of the same type as in the
dioxide or trioxide . The existence of a molecular lattice with a tetrahedral
coordination of rhenium within the molecules is possible . The tetrahedral
coordination is also found in solid perrhenates / 130 /. The hydrates of
lanthanum perrhenate have been studied / 131 /. It has been found that these
compounds belong to the prismatic class of the monoclinic system and
have the following parameters : La (ReO4)3 • 2H20 a : b : c = 0.9379 : 1 : 0.5502 ,
B = 102 ° 46 ' ; La (ReO4)3 : 3H20 a : 0 : c = 1.0715 : 1 : 1.5633; B = 93° 57 ' .
Rhenium trioxychloride and rhenium trioxybromide also have a
tetrahedral structure /132 – 133 / .
The ReOF3 compound has a tetragonal lattice with the following
parameters : a = 8.54 , c = 8.21 Å .
Hexahalogenorhenates of type M [ Re (halogen ).) , and rhenium hexafluoride,
hexachloride and carbonyl also have an octahedral coordination / 134-137 /. The
carbonyl has a direct rhenium — rhenium bond which is longer than that of
metallic rhenium , and the angle of the octahedron is equal to 45° / 138 /.
The length of the bonds and the coordination numbers of rhenium compounds
It has been found that cations of pyridinium ( Py H )* and the dimeric
complex anion, consisting of two atoms of rhenium , 8 atoms of halogen ,
and apparently two atoms of hydrogen , are the structural units of
tetrahalogenorhenates (11 ) of pyridinium . The atoms of the halogen form a
square prism within which two atoms of rhenium are located on the axis
of the fourth order . The unusually short distance in Re-Re ( 2.22 Å in
( PyH ) HReCl4 and 2.21 A in a- ( PyHJHReBr4) indicates the ternary nature
72
of the metal –metal bond . All rhenium - halogen bonds ( length of
bond Re - C1 = 2.43 Å and of Re - Br = 2.48 Å) are covalent. Each atom of
rhenium forms o - bonds with the neighboring atoms of rhenium , four atoms
of halogen , and apparently one atom of hydrogen . Two 17 - bonds between
two atoms of rhenium make the metal - metal bond a ternary one .
TABLE 22. Length of bonds and coordination numbers of rhenium compounds

Coordination
Bond number of
Length of Ionic radius
Compound Reference
rhenium
bond , Å of Re, Å
Re - o ReO2 6 / 127,128 /
|Re0₃ 6 1.87 Reivo.55 /126 /
III
|Reo , 4 /130 /
ReOCI 4 1.76 /1221
ReOjF 4 1.66 132 /
Re -F Refo 6 1.98 /136/
ReF 6 2.02 RelV0.66 /84,140/
ReOgF 4 1.86 / 132 /
I
Re -C1 ReOgCI 4 2.23 (122 )
Recia 6 2.37 RelV0.56 134 /
Re - Br ReBra 6 2.50 ReTV0.55 / 135/
y Re- Re Re 12 1.37 / 28 /
Rz( CO) 16 6 1.51 (1387
Re - CI II RegOC110 ) 6 2.38 1139, 159/
Re - CI ( ResCl12 )9 7 2,36 1139, 1597
Re - Br (PyH ) H ReBra 2.48 139, 159/
Re - P ReOC13 [ PE12Ph ] 2 6 2.46 / 139 , 159/
Re - CI (PyH ) ReCla 6 2.43 1139, 159/
Re - Cl ReOCIIPEI,Ph12 6 2.43 1139, 1591
It has been found that the single crystals of the KtRe2OClio · H20 compound
have a space group of 14 / mmm , with a = 7.070+ 0.004 Å, 5 = 17.719 + 0.005 Å
/ 141 /.
A number of complex pentavalent rhenium compounds with ethylene
diamine and pyridine with a coordination number of 6 are also known / 158 /.
The complex hexavalent rhenium ions ( Re (CN )8) have a coordination
number of 8 / 142 /.
Tetravalent rhenium readily forms complex compounds with an
octahedral syngony and a coordination number of 6 for all three elements
participating in the formation of electronegative complexes /143 /.
The structure of the compounds of trivalent rhenium has been studied
/ 144 – 147 , 159 /.
The basic structural unit of some trivalent rhenium compounds
( ReCl3, CsReCl4) is the trimeric complex ion of the [ Re:C112) 3- type with
double Me – Me bonds and a coordination polyhedron in the shape of a
pentagonal bipyramid /139 /. The Rel compound has a cubic structure with
a = 9.33 X /148 / .
A number of complex compounds of monovalent rhenium with a
coordination number of 6 are known . In these compounds rhenium has an
octahedral configuration and a de- configuration of paired spins : Re (CN ) ,
Re (CO )51, etc. /143 /.
73
14. Electrical properties of rhenium compounds
The electrical properties of rhenium compounds have not yet been
sufficiently investigated. The conductivity of ReSe, at 24°C is 6.75 · 10-5
ohm-.cm and at 64° C it is 10.7 · 10-5 ohm - 1.cm-?.
According to / 21 , 126 / the resistivity of rhenium oxide is as follows
(ohm · cm ):
12.10-3 at 20° C
Reos (1 : 10-4 at the temperature of liquid air
18.10-6 at 20 ° C
ReO2
12.10- at the temperature of liquid air .
15. Magnetic properties of rhenium compounds
The 5dºs electrons of rhenium determine its valence . The d- electrons

have parallel spins and take up separate orbits with identical energy . If
groups of atoms are located round an ionized atom of rhenium , the energy
of the d orbits changes . For an octahedral coordination three d orbits ( de )
have a lower energy than the other two ( d , ) orbits , and for the tetrahedral
coordination the opposite is true . The difference in energy is greater for
the octahedral coordination than for the tetrahedral . An ideal moment is
never reached in any of these cases because of the mutual influence of
factors such as pairing of orbital spins , antiferromagnetism , and the
paramagnetism which is temperature independent /63, 150 /.
All compounds of heptavalent rhenium are diamagnetic , as expected from
the total absence of 50+ 6s electrons in heptavalent rhenium / 144 /.
Compounds of hexavalent rhenium are paramagnetic , due to the presence
of single unpaired electrons . It has been found that rhenium trioxide Re03
is slightly paramagnetic /21 /.
Most compounds of penta valent rhenium are diamagnetic , since their
outer electrons are paired . But the complex ions ( ReF81", ( ReO2 ( CN )4]:-,
and ReCls and ReFs are paramagnetic / 151 / .
The diamagnetism of the compounds and complexes of pentavalent
rhenium is explained by the rule of nine orbits , eight of which are used for
bonds and the ninth creates a space for two unpaired electrons /142 /.
It has been found that for ReF3 the Curie point 0 is 508°K, and for
ReF 0-100°K /143 /.
A number of compounds of tetravalent rhenium (oxides and sulfides ) are
diamagnetic . The compounds of rhenium with a valence of less than 4 have
very unusual magnetic properties. Most of these compounds are
diamagnetic , although appreciable paramagnetism might be expected .
It has been found that the diamagnetism of a number of compounds of
divalent and trivalent rhenium is due to the existence of multiple Me – Me
bonds /139 — 159 /. The ions ofthe complex compounds of the[ Re (IV ) halogen ]?
type are paramagnetic and have three spins / 152 /. The magnetic moment
of these complexes is somewhat lower than the theoretical value of 3.88 mV .
This is due to an antiferromagnetic influence . Rhenium dioxide ReO2 is
also slightly paramagnetic /21 /, in contrast to manganese dioxide which is
74
highly paramagnetic . It has been found that the oxyhalides of the
( C13ReoReC1514- type are either diamagnetic or very slightly paramagnetic
1157 /. The diamagnetism indicates an interaction of the metal - metal type
through the atoms of oxygen / 144 /.
The magnetic properties of complex organic rhenium compounds have
been investigated in / 144 , 145, 147 , 153 - 155 /. In these compounds
rhenium has a valence of +5 , +4 , +3 , +2 , and +1 . In the compounds studied
both paramagnetic and diamagnetic substances have been found. The
magnetic moments of some complex fluorides of hexavalent rhenium are
given in / 156 /
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1940 .
78
132. Lotspiel . Diss . Abs . , 19 : 340 . 1958 .
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dvukh valentnogo i shestivalentnogo reniya (Crystal Structure of
Divalent and Hexavalent Rhenium Compounds ) . – Author's
Summary of Thesis . IONKh im . N. S. Kurnakova . 1964 .
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79
Chapter VIII
PHYSICAL PROPERTIES OF RHENIUM
The atomic number of rhenium is 75; rhenium belongs to the VIIth group
(subgroup A ) , 6th period (third long period ) of the periodic table, and is an
analogue of manganese and of technetium . Rhenium is a transition element .
The electron configuration of the free atom of rhenium can be written as :
1s 2s 2p 3s 3p 320 452 4p 400 4f 5sa 5p 50s 6pm. The atomic weight of rhenium
182
is
186.31+ 0.02 . The following isotopes of rhenium are known / 1 – 57: Re ?
Re183, Re 184, Re185, Re186 Re187, Re188 Re189, Re190 and Re191. The most
common isotopes have atomic numbers of 185 and 187 , and they occur
naturally in the ratio 1 : 1.62 (Table 23 ) .
TABLE 23
Radiation energy , MeV

Percent
Isotope Half life Decay modes
abundance particles Y - rays
0
75Rel18 2.4 days B+ 1.1 0.106 ; 0.88
Re 182 12.7 hr EC 0.11 ; 0.127 ; 0.222 ;

0.250; 0.346
Re 182 64 hr EC 0.110 ; 0.127 ; 0.222 ;
0.250; 0.346
Re183 156 days EC 0.081 ; 0.252
Rel & 50 days EC 0.159; 0.206 ; 0,244 ;
0.784 ; 0.89
Re14 2.2 days EC 0.043; 0.159
IT
Re 185 37.07
Re 186 3.8 days (95 % ) 1.07 ( 76 % )
EC ( 5 % ) 0.93 ( 24 % )
0.3 (0.05 % )
187m 0.072; 0.134
Re 5.3x10-7 sec IT
Re187 62.93 5 • 1010 уг B 0.4

Re 188 m 22 min IT 0.0635 ; 0.092 ;
0.106
Re 188 16.9 hr < 1.9 ( 1 % ) from 0.15 to 1.95
1.961 ( 20 % )
2.116 ( 79 % )
Re 189 150 days 0.2 1.0
Re > 5 yr 0.75
Note . B + is emission of positive B -particles; B – is emission of negative B -particles; EC is capture of

orbital electrons; IT is isothermal transition .
80
The thermal neutrons of rhenium have the following characteristics
/ 5, 6 /:
Interaction of thermal
Energy of the lowest
Isotope neutrons, o, barns,
resonance , eV
at 2200 m / sec
185
Red 100 + 8 2.18+ 0.04
Re187 63 + 5 4.40 + 0.09
Re 84 + 4
The ionization potentials of rhenium are lower than those of its analogues,
manganese and technetium . It has been found /7 / that the ionization potential
during the Re to Rel transition is equal to 7.87 V, and during the Re to Re*
transition it is 79 V. The minimum interatomic distance of rhenium is
2.740 Å 18 /
The atomic volume of rhenium is equal to 8.9 cm / g - atom / 97, and to
8.82 cm 3 / g -atom ( at absolute zero ) according to /21. The atomic radius
of rhenium iş equal to 1.375 , /10 /. The calculated diameter of rhenium
ions is 0.68 Å /11 /, and the diameter of Re** is 0.56 Å 17 /.
The interplanar distances of the chief lines of the X - ray spectrum found
in / 12 / are as follows (Ă ):
Lai 1.4298 LA
La 1.4407 Ly 1,0589
Lao 1.4240 L. 1.0299
LBI 1.2339 Lyo 1.0236
Le . 1.2038
By means of the line La, it is possible to detect 5 · 10-8 g of pure rhenium ,

and by means of Lø, it is possible to determine 5 · 10-7 g of rhenium in 50 g
of molybdenum .
1. Crystal structure
Rhenium has a hexagonal close- packed lattice . The parameters of the

crystal lattice of rhenium found by various authors are given in Table 24 .
From an analysis of the lattice parameters of rhenium obtained by
various methods , and consequently for rhenium of various degrees of purity
/ 17 /, it is seen that the interstitial impurities tend to expand the lattice
and the substitutional impurities can either expand or compress the lattice .
The data on the parameters of the crystal lattice of rhenium in a coarse
grained upset rod indicate that it contains a large number of substitutional
impurities , and as a result the parameters are considerably smaller than
usual .
The data obtained for fine- grained upset rhenium / 17 / agree well with
those of the same research work on a purified rhenium powder and with the
results of / 15 /. Therefore, the lattice parameters a = 2.760 , c = 4.460 A,
and cla = 1.616 can be considered as the most reliable . These parameters
are smaller than those found by other authors and this indicates that the
rhenium studied in / 17 / was denser and purer .
81
TABLE 24. Crystal lattice parameters of rhenium
O
Parameter ,
cla Year References
Characteristic of rhenium
Re from KRe04 2.755 + 0.001 4.450 + 0.002 1.615 + 0.001

2.765 4.470 1.616 } 1931 /13 , 14 ;
2.760 4.458 1.615 1933 115 /
Sintered in vacuo 2.7548 4.4484 1.6147
Sintered in hydrogen 2.7546 4.4480 1.6151 1937 /13 /
2.7553 + 0.0004 4.4493 + 0.0003 1.615 / 14 /
2,765 4.470 1.616 1942 ( 10, 16 /
Purified powder 2.760 + 0.001 4.458 1 0.001 1.615
Haloid coarse -grained
rhenium 2.753 + 0.001 4.445 + 0.001 1.615 1956 /17 /
Haloid fine - grained
rhenium 2.760 + 0.005 4.460 0.005 1.616
Cast rhenium with
0.001% O2 2.757 + 0.001 4.456 + 0.001 1.616 1963 18 /
The influence of oxygen on the parameters of the crystal lattice of

rhenium obtained by arc melting ( Table 25 ) has been studied / 18 /.
TABLE 25. Influence of the oxygen content on the crystal lattice parameters of
arc -melted rhenium
o
Lattice parameters , A
cla
Content of Oz , %
c
0.004 2.757 4.463 1.619

0.007 2.759 4.468 1.620
0.009 2.758 4.467 1.620
It can be seen from the table that an increase in the content of oxygen
in rhenium leads to an increase in the parameter c. Parameter a remains
unchanged , as in other metals with a hexagonal close- packed lattice
(a- titanium , a- zirconium , beryllium , zinc ) / 15 , 19, 20 /.
2. Melting point
Data on the melting point of rhenium according to different authors / 13 ,

16 , 17 , 21 – 25 / up to 1956 are given in Table 26 .
The melting points of rhenium given differ because of differences in the
purity and density of the rhenium used , and the different methods for
determining the melting point . The melting point of rhenium was found in
/22 / by the method the " drilled hole " in a specimen of compressed and
sintered rhenium containing 0.01% of impurities . In / 17 / the melting point
was also measured by the method of the " drilled hole " in a rod of
sintered rhenium obtained from highly pure ammonium perrhenate with a
total content of impurities not exceeding 0.005 % . The optical pyrometer
82
was calibrated by means of pure metals under the same conditions . The
following melting points of rhenium were found: 3175°C , 3184°C , and 3180°C .
The true melting point was taken as 3180+ 20°C . A comparison of the data
shows that the most probable melting point of rhenium is 3180 20°C . Thus ,
the melting point of rhenium is 240°C below that of tungsten ( 3410°C ) .
TABLE 26. Melting point of rhenium
Melting point, Year References Melting point, Year References

°C °C
3170 - 50 1937 /13 / 3170 1946 / 24 /

3167 + 50 1930 / 21 / 3162 1955 /25/
31 70 60 1931 /22 / 3180 + 20 1956 /17/
3170 1943 / 23 /
3. Boiling point and vapor pressure
The boiling point of rhenium is 5630°C /25, 26 / which is lower than that
of tungsten only ( 5900°C ) . According to other data /8 /, the boiling point of
rhenium is also 5900 ° C .
The vapor pressure of rhenium and of other high- melting metals has
been studied at different temperatures and pressures /25 / by Langmuir's
method of weight loss . A wire was heated in vacuo at a constant temperature
for a definite time (Table 27 ) .
TABLE 27. Experimental data on the vapor pressure of rhenium /25 /

Temperature Rate of Vapor pressure
Time , sec vaporization ,
°C "K 8 •cm .• sec abs. atm mm Hg
2221 2494 259.2 1.54.10-8 1.24.10-9 9.39.10-7

2250 2523 151.2 3.23.10-8 2.61.10-9 1.98-10-6
2332 2605 30.6 7.35.10-8 6.04.10-9 4.59.10
2475 2748 54.00 6.96-10-7 5.56-10-8 4.23.10-5
2480 2753 23.40 4.67-10- ? 3.93.10-8 2.99.10-5
2606 2879 7.20 2.77-10-6 2.38.10-7 1.81-10
2726 2999 1.560 8,41-10-5 7.37.10-7 5.60.10
The vapor pressure of rhenium determined by this method is about the

same as that of tantalum (Figure 13 ) .
The vapor pressure over liquid rhenium was also studied /25 /. From
the melting point of rhenium ( 3453°K ) to the boiling point of rhenium
( 5900° K) the vapor pressure increases as follows (abs . atm ):
3453 ° K . . 3.64.10-5 5000 ° K . .7.44.10-2

3500 .5.09.10-5 5500 .0.349
4000 . 1.08-10-3 5900 1.000
4500 1.14.10
83
The rate of vaporization of rhenium increases with increase in tempera
ture as follows /8 /:
2380 2564 2774 3022 3368 3767
Temperature , ° C
Rate of vaporization ,
g /cm². sec 1.55 . 10-? 1.50 · 10-6 1.44 : 10-5 1.39 · 10-4 1.34 10-3 1.27 . 10 "?
The rate of vaporization of the metal is one of the factors which

determine its maximum service temperature . The maximum service
temperature at which the weight loss of the specimen as a result of
vaporization does not exceed 1 % after 10 hours of service has been found
/27 , 28 /. For rhenium this temperature is equal to 2380° C , for tungsten
it is 2560°C , and for molybdenum 1910°C .
4. Density
According to its density rhenium occupies the fourth place after osmium
( 22.6 g / cm° ) , iridium ( 22.5 g / cm °) , and platinum ( 21.5 g / cm °) . The density
of rhenium was measured by different research
workers , and the rather differing data they
obtained are given in Table 28. The chief
104
reason for the discrepancies in the values
Re is the difference in the purity and compact
Τα Но
w ness of the rhenium specimens studied , and
104 also the different methods of investigation .
The density of rhenium formerly
accepted ( 20.53 g /cm3 ) was calculated from
,P m
the atomic weight of rhenium and data on

Hg
m
103 the lattice parameters /22 /. The experi

mental density (given in the same paper )
was 20.9 g / cm3. It was thus assumed that
the lattice parameters had been inaccurately
calculated .
In / 17 / the density of rhenium was
determined using a rod 3.8 mm in diameter
10-7 and 163 mm long, which had been forged
3.00 3.80 4.20 from a rod 5.8 mm in diameter.
1.100 The density thus found was 21.03 + 0.01 g /
cm3. The theoretical density based on
FIGURE 13. Dependence of the va por X- ray analysis / 17 / is equal to 21.04 g /cm " .
pressure of rhenium and of some other The authors of this monograph together
high -melting metals on temperature.
with O. Kh . Khamidov found the density of
highly pure rhenium , prepared by arc
melting in vacuo, using the method of
direct immersion .
The experimentaldensity (21.014 0.01g /cmº)corresponds quite accurately
to the value we calculated ( 21.02 g /cmº ) from the lattice parameters .
The most probable density of highly pure rhenium is 21.014 0.01 g / cm3.
84
TABLE 28. Density of rhenium
Characteristics of rhenium Method of determination Density, g / cm Year References
Pure sintered rhenium X - ray method 20.53 1931 / 22 /

Direct determination 20.9
21 1942-1946 /16 , 24 /
Sintered and forged
rhenium Direct determination 21.03 + 0.01 * 1956
/17 /
Precipitated from halides X - ray method 21.04 + 0.01
Cast Direct determination 21.01 + 0.01 1965 E.M.Savitskii
M. A. Tylkina
Kh . Khamidov
For a temperature of 20°C.
5. Specific heat
The specific heat of rhenium at room temperature is of the same order

of magnitude as that of other high- melting metals , for example , molybdenum
( 0.061 cal / g ° C ) or tungsten (0.0324 cal / g °C ) /29 /. If the temperature is
increased the specific heat of rhenium increases also .
Specific heat of rhenium /13 , 26 , 30 /

T.C c. T, ° C
cal/ g . ° C cal/g . ° C
0-20 0.03262 0–600 0.03455
0 0.03356 0-700 0.03488
0-100 0.03289 0-800 0.03521
0-200 0.03322 0-900 0.03554
0-300 0.03355 0-1000 0.03587
0-400 0.03388 0-1100 0.03620
0-500 0.03422 0-1200 0.03653
0-20 0.032222
According to the data of /8 /, the specific heat of rhenium at 25 — 2000°C is :
T , °C c ,cal / g -atom : degree

25 6.143
50 6,7
1000 7.2
1500 8.0
2000 8.8
The specific heat Cp of rhenium at low temperatures has been studied

over the range 1.2 – 24.6°K, that is above and below Tx, the transition point
into the superconductive state /31 /. From the jump in cp in the absence of a
magnetic field it has been found that Tx= 1.699 1.10-3 ° K . Under normal
conditions at 1.7 — 4.2 ° K Cp can be calculated from the Sommerfeld- Debye
formula: c = 7 + 1944 ( T70 ) , where p = 2.257 • 10-3 joule /mole · °C is the
coefficient for the electron part of Cp, and 0 407.4° K is the Debye
temperature .
An exception here is the range 1.7 — 2.15° K, apparently due to the
superconductivity of inclusions . Above 10°K Cp ( T) lies below the Sommerfeld
Debye curve , which indicates a decrease in 0. In contrast to that under
85
normal conditions , the temperature dependence of the electron field of the
specific heat Ces of superconductive rhenium is governed by an exponential
law : Ces/y7x = aexp (- 67 , /T ), where a = 11.68; b = 1.64 . From the measured
magnitudes of cp the differences between cp for the normaland superconductive
states have been calculated .
The specific heat of sintered rhenium at low temperatures (from 20° to
300° K ) was measured by the method of adiabatic calorimetry / 32 / ( Table 29 ) .
A number of other thermodynamic functions of rhenium are also given in
this table .
TABLE 29. Some thermodynamic functions of rhenium at 20-3000K
pi Hº - H - H.) pi H- Hi ( F - HH ).
cal / T S. T
so T cal /
Tº, 8- cal / kcal / kcal / TºK 8- cal / kcal/ kcal /
atom . mole : mole . mole atom . mole • mole . mole •
degree degree degree degree degree degree degree degree
20 0.146 0.049 0.037 0.012 120 4.843 3.735 2.343 1.392
25 0.316 0.096 0.072 0.024 140 5.197 4.511 2.728 1.783
30 0.541 0.173 0.131 0.042 160 5.459 5.223 3.054 2.169
35 0.820 0.277 0,209 0.068 180 5.648 5,878 3.332 2.546
40 1,147 0.407 0.305 0,102 200 5.804 6.480 3.570 2.910
45 1.508 0.563 0.419 0.144 220 5.936 7.038 3.778 3.260
50 1.885 0.741 0.547 0.194 240 6.041 7.559 3.963 3.596
60 2.520 1.143 0.824 0.319 260 6.110 8.046 4.125 3.921
70 3.084 1.575 1.107 0.468 280 6.143 8.500 4.269 4.231
80 3.569 2.020 1.386 0.634 298,16 6.143 8.887 4.383 4.504
90 3.963 2.463 1.644 0,819 300 6,144 8.924 4.394 4.530
100 4.305 2.899 1.893 1,006
Note.cp – specific heat; S- molar entropy; H- enthalpy; F – free energy .
The specific heat of rhenium at high temperatures (up to 1473°K ) was

determined in / 33 /. The specific heat at 0 – 20°K was found by extra
polation , and the magnitudes are 0.5 % lower than those obtained in /36 /
for the same temperature range .
Cp = a + 6T - T * + 2 % ,
where a = 5.73; b = 1.234; c = 0 /37 /.

According to / 33 /, 3R = -66°C , while according to /32 / 3R = -51 °C .
This difference is not great if we take into account the possible errors
through extrapolation .
6. Thermodynamic characteristics
The heat of sublimation of rhenium at absolute zero (0°K ) is 186.855+

# 1.015 kcal / mole /25 /.
The heat of sublimation of rhenium at 25°C ( 298°K ), AH, = 187 kcal / mole ,
is given in /97, and agrees well with the data of /25 /. The molar entropy
of rhenium at 298.16° K is 8.89+ 0.03 cal / mole • degree . Above 200° the
accuracy of measuring the entropy is = 0.3% , while below 20° it is
$ 0.049 cal / mole • degree /33 /.
86
The thermodynamic properties of rhenium were studied in greater detail
at 298.16 – 2000°K (Table 30 ) / 34 /.
TABLE 30. Temperature dependence of some thermodynamic properties of rhenium
Temperature, K
Property
298.16 500 1000 1500 2000
Specific heat
1.25 4,58 8.21 12.2
( solid ) H, - H203, kcal/mole .
( gas) Hi - Hog kcal/mole . 1.003 3,49 5.97 8.45
Molar entropy
9 12.2 16.8 19.7 22.0
( solid ) Sp, cal/mole • degree
(gas) Sp, cal/mole • degree . 45.14 47.71 51.15 53.17 54.60
Free energy
( solid ) F - F39 , cal/mole degree . . 9 9.7 12.2 14,2 15.9
The following thermodynamic properties of rhenium are given in / 34 /:
7.9
Heat of fusion Lfus, kcal /mole . .
152
Heat of vaporization Lyap, kcal/mole .
Entropy of fusion AS fus , cal/mole .. 2.3

Entropy of vaporization AS vapº cal /mole 26.2
7. Thermal conductivity
The thermal conductivity of rhenium according to /2 / is 0.17 cal / cm • °C •

sec , and according to /35 / it is 0.14 cal / cm • °C • sec , which is half that of
molybdenum (0.31 cal / cm C : sec ), about 1/3 of that of tungsten (0.48 cal /
cm • °C • sec ) /29 /, and 0.18 times that of copper ( 0.923 cal / cm • °C • sec ) .
8. Thermal expansion
The thermal expansion of rhenium has been studied by a number of

authors . In /22 / the linear expansion of rhenium was determined at room
temperature and at 1917°C by the X- ray method . The coefficient of thermal
expansion is an anisotropic property, and it has been found that in the direction
[ 001 ] (parallel to the axis chap= 12.45 · 10-6 1 8 % , and in the direction ( 100)
(perpendicular to the axis c ) ag = 4.67 • 10-6+ 8 % . This means that th
expansion along the c axis is 2.6 times greater than along the a axis and
that it varies with temperature . However, these data were obtained on
polycrystalline specimens , and they should be verified on single crystals .
In / 17 / the coefficient of linear expansion was determined by a self
recording dilatometer over the range 20 – 1000°C using annealed rods of
sintered rhenium 3.81 mm in diameter and 76.2 mm long .
The coefficient of linear expansion over different temperature ranges is
as follows (10 / ° C ):
87
20—100 ° C 6.6 20- 600 ° C 6.7
20—200 ° 6.6 20— 700 . 6.7
20—300 ° 6.6 20- 800 6.8
20–400 ° 6.6 20- 900 6.8
20—500 ° 6.7 20_1000 6.8
It can be seen from these data that the coefficient increases slightly with
increase in temperature .
The average coefficient over the range 20 – 500 ° C is 6.7 · 10-6 / °C ,
which is somewhat larger than that of molybdenum ( 5.4 • 10-6 / °C ) / 36 / and
of tungsten ( 4.45 • 10-6 / °C ) / 36 / over the same temperature range . Thus ,
rhenium like other high- melting transition metals has a relatively low
coefficient of linear expansion which varies little over a wide range of
temperatures .
9. Electrical resistivity
The electrical properties of rhenium have been studied by several

authors on sintered rhenium specimens of various purities and densities .
In / 37 / the electrical resistivity was
determined at 0.16 ° C and recalculated for
20° C using the temperature coefficient taken
21.2 from /22/ ( 3.11 . 10-3per 1 °C over the range
0– 100°C) . The value obtained is 19.Quohm.cm .
The electrical resistivity of rhenium at
20.8
room temperature , and the influence of
cold working on it , have been found / 17 ).
20.4 The measurements were carried out on
, ohm
specimens of sintered wire 1.27 – 1.5 mm

cs
.u m
in diameter and 203 mm long, annealed to

20.0 a hardness below Hy 300 , and on wire cold
drawn to a reduction of 6.5 to 24.2 % . The
results are shown in Figure 14. The
19.6 increase in the electrical resistivity of
rhenium after cold working is due to
increase in the interatomic distances .
19.2
The data on the electrical resistivity of
annealed wire are very scattered , but the
18.8
average value of 19.41 0.25 uohm'cm
8 16 24 agrees well with the data of /37 /, and is
Degree of deformation , % somewhat lower than that of /22 /
( p = 21.11 15% ) .
FIGURE 14. Dependence of the electrical
resistivity of menium at room temperature The electrical resistivity of cold - worked
on the degree of deformation : wire also shows a certain scattering . It has
been found that 25 % reduction increases
1 – average resistivity at room temperature. the electrical resistivity by 2 uohm.cm.
It is quite possible that this is the reason
why our data differ from those of /22 /. Apparently , the rhenium used in
this work was insufficiently annealed .
5511 88
The above data show that the electrical resistivity of rhenium is 3 – 4
times higher than that of molybdenum ( 5.2 • 10-6 ohm .cm ) and of tungsten
( 5.5 . 10-8 ohm .cm ) /29 /. The high electrical resistivity of rhenium is a
very valuable quality for the production of heating elements and vacuum
apparatus .
Influence of temperature on the electrical

resistivity of rhenium
The temperature coefficient of the electrical resistivity of rhenium is
given in Table 31 .
TABLE 31. Electrical resistivity of rhenium /35 , 38 /

Temperature coefficient
Electrical resistivity , of the eiectrical
Temperature, C uohm : cm
resistivity , 1 / ° C · 103
-253 0.015
-200 2.3
-100 10.0
0 17.5
20 19.3
100 25.4 3.95
300 40.0 3.83
500 52.0 3.58
700 63.0 3.33
900 72.5 3.13
1100 80.5 2.94
1300 87.0 2.78
1500 93.0 2.58
1700 98.5 2.44
1900 103,0 2.31
2100 106.5 2.17
2300 109.0 2.04
It has been found / 38 / that the temperature coefficient of the electrical

resistivity of rhenium at 20 °C is 3.9 . 10-3 / °C , and that it is positive at
least up to 2600°K (Figure 15a, Table 31 ). The temperature dependence of
the resistivity of rhenium at elevated temperatures can be written as :
p = 7.25 + 9.88.10-27 – 3,10-10-57 + 4.0.10-97 %,
where p is the electrical resistivity of rhenium , uohm · cm , and T is the

temperature , °K .
The variation in the electrical resistivity of rhenium at low temperatures
has been studied in /35, 39 /.
Like a number of other metals, rhenium is a superconductor at low
temperatures .
According to /397, the temperature of the transition of rhenium to the
superconductive state is 1.699+ 0.001 ° K .
89
The variation in the electrical resistivity of rhenium at 0 - 20° K is shown
in Figure 15 b / 39 /. The resistivity was measured on highly pure rhenium
specimens melted in an arc furnace (PdP273 = 0.00068 ) .
The resistivity of rhenium at low temperatures was measured in /39 /,
and it was found that it decreases rapidly with decrease in temperature .
Temperature, K .... 288 273 78 64 20 15 10 4 1.8
Electricalresistivity ,uohm.cm
. cm 19.50 18.58 2.62 1.64 0.0270 0.0161 0.0130 0.0126 0.0126
Puohm
:cm
a
110
90
d
. mm
80 160
uoh
200 600 1000 1400 1800 2200 2500

c
203 1. X
с ( 0001)
‫وهمماه‬
‫ومامه‬
09 120
202 07
1
100 200
40 아가
P100kg / cm ?
201 b
20F 40
0
5 15 30 60 90 120 150
TX
9 , degrees
FIGURE 15. Dependence of the electrical resistivity on temperature :

a - at elevated temperatures; b - at low temperature; c- dependence of the electrical resistivity on
pressure; d – on the magnetic field at 4.2° K ; 1-2 – specimen with an axis parallel to the binary axis of
the crystal in an electric field of strength 55 and 25 koersted, respectively; 3 – specimen with an axis
parallel to the hexagonal axis of the crystal, H= 25 koersted .
These data and Figure 15b show that for rhenium po = 0.0126 uohm.cm.
The resistivity increases with increase in temperature ( Ts) as a result of
the change in the average length of the free path of electrons , which is
proportional to Tø. The experimental data on the temperature dependence
of the electrical resistivity of rhenium at from 1.6 to 20°K can be
represented by:
p = Po + p .,
where po= 0.0126 mohm .cm and pi = 4.5 · 10-3 to uohm • cm, which means
that the experimental data agree well with the theoretical /39/.
90
Influence of pressure and the magnetic
field on the electrical resistivity of rhenium
The influence of high pressures (up to 250,000 kg / cm?) on the electrical

resistivity of pure rhenium has been studied /40 /.
The measurements were carried out at room temperature in a chamber
calibrated against the known jumps in the electrical resistivity of Bi, Ba,
and Ti . The specimens were made of rhenium wire 0.6 – 0.8 mm in
diameter . The medium that transferred the pressure was silver chloride .
The dependence of the R /R 30 ratio on pressure was studied , where Rso
corresponds to the resistivity at a pressure of 30,000 kg / cm² and R is the
resistivity at a given pressure ( Figure 15 c ) . In rhenium , as in other
metals, the electrical resistivity decreases smoothly with increase in
pressure . This decrease is greater at 30,000 – 100,000 kg / cm² (for
rhenium 22.5 % ) and smaller at 100,000 - 250,000 kg / cm² ( for rhenium 7.8% ) .
The variation in the electrical resistivity of single crystals of rhenium
in a magnetic field was studied in /41 , 42 / using crystals with different
orientations . The dependence of the resistivity of rhenium on the angle o
of a single crystal with reference to a constant magnetic field is shown in
Figure 15 d .
It has been found that rhenium has an open Fermi surface . The maximum
change in the resistivity of rhenium specimens if the temperature is
decreased from room temperature to the temperature of liquid helium is :
P (300° K)
- 2100 .
P (4.2 ° K )
Influence of the purity of rhenium on its

electrical resistivity
The influence of metallic and gaseous impurities on rhenium and its

electrical resistivity was investigated in /43 , 44 /.
In /43 / the influence of oxygen on the electrical properties of rhenium
was studied (Table 32 ) .
TABLE 32. Influence of oxygen on the electrical resistivity of rhenium

Temperature
Method of production Content of gases determined by gas analysis, wt % Electrical coefficient of
resistivity , electrical
of alloy
uohm · cm resistivity ,
O2 H2 N2
025-100 ° C
Zone electron - beam

melting . . 0.0021 0.0005 0.0006 17.20 4.36
Arc melting with a non 0.0081 0.0004 0.0005 18.51 4.35
consumable rhenium 0.012 0.0003 0.0005 20.11
electrode (briquettes 0.018 0.0006 0.0008 20.52 4.36
made of Re + Re201) 0.020 0.0006 0.0025 22.60 4.29
0.022 0.0005 0.0008 22.85 4,31
91
The starting material was sintered rhenium ( 99.99% pure ) prepared from
ammonium perrhenate . Rhenium alloys containing oxygen were prepared by
arc melting with nonconsumable rhenium electrodes . The oxygen was
introduced as rhenium oxide . Rhenium with a minimum content of oxygen
was prepared by the method of zone refining by electron- beam melting . The
content of gases was determined by the methods developed by the same
authors /43 /. The electrical resistivity at 25 and 100°C and its temperature
coefficient were measured potentiometrically with specimens upset-5
at room
temperature to 40% reduction and annealed in vacuo (about 10 mm Hg ) at
1750° C for 1.5 hours .
TABLE 33. Influence of impurities of tungsten , molybdenum , and iron, on the

electrical properties of rhenium
Electrical
Temperature
Content of impurities in rhenium , coefficient of
found by chemical analysis , wt % resistivity at 25 °C ,
electrical resis
uohm . cm
W Μο Fe
tivity, 425–100° C
19.85 4.47
TUTTI
0.05 19.92 4.07

0.10 21.4 3.55
0.01 20.1 4.23
0.048 20.8 3.63
0.10 22.1 3.38
0.02 20.06 4.31
0.06 20.24 4.07
0.10 21.2 3.98
The influence of metallic impurities (tungsten, molybdenum , and iron )

on the resistivity of rhenium was investigated in /44 /. Rhenium from dust
of the molybdenum - producing industry contained a few hundredths of one
percent of these impurities , retained in sintered compact rhenium and
after melting. The experiments were carried out on cast specimens
prepared by arc melting with a nonconsumable rhenium electrode . The
content of gases in the ingot was : O2, 0.013 – 0.015 % ; H2, 0.0006% ; and N2,
0.0004% . The electrical resistivity was measured potentiometrically
with specimens 20 X 1.5x1.5 mm deformed to 40% reduction and annealed
at 1800°C (Table 33 ) .
The data given in Tables 32 and 33 shows that oxygen has more influence
on the electrical resistivity of rhenium than metallic impurities .
The resistivity of rhenium containing 0.0021 % of Oz is 17.2 uohm .cm ,
and that of rhenium containing 0.022% of oxygen is 22.85 uohm.cm. Oxygen
has almost no influence on the temperature coefficient of the resistivity ,
which varies within the limits of experimental error.
Although metallic impurities have little influence on the electrical
resistivity of rhenium , they have more influence on its temperature
coefficient, and decrease it appreciably.
Oxygen has an appreciable influence on the electrical resistivity of
rhenium, probably because the dissolution of an interstitial impurity
(oxygen ) distorts the lattice of the solid solution more than the dissolution of
metals with an electron structure of the valence shells close to that of
rhenium ( tungsten, molybdenum , iron ) .
92
The most reliable value of the electrical resistivity is 17.20 uohm .cm
obtained by testing rhenium purified by zone refining . Obviously, all
previous data on the electrical resistivity of rhenium obtained on sintered
wire are too high . Unfortunately , in none of these works are data given on
the content of gases or other impurities in rhenium , and therefore a
comparison of the results does not help assess the purity of the tested metal.
10. Magnetic properties
Rhenium , like tungsten and molybdenum , is paramagnetic . The average

data on the magnetic susceptibility of rhenium found by various authors are
given in Table 34 .
TABLE 34. Magnetic susceptibility of rhenium
Magnetic susceptibility Year References

Degree of purity x 10-6
99.5 % Re + 0.5 % K20 +0.367 1941

+0.366 + 0.006 1935 / 13 /
Pure rhenium + 0.046 1931
+0.369 1933 /14 /
The magnetic susceptibility of rhenium changes little when the

temperature is increased from – 180 to +21.5°C / 13 /.
Magnetic suscepti
Temperature , °C
bility x 106
-180 0.368
- 79 0.366
24 0.372
0 0.373
15 0.373
20.2 0.368
21.5 0.357
The above data were obtained on sintered rhenium containing 99.5%

metal and 0.5 % K2O .
In /39 / the magnetic properties of rhenium were studied at about 1 ° K .
The dependence of the total induction B on the applied field H at
temperatures above and below 1 ° K, on the intensity of magnetization I at
temperatures above 1 °K , and on the saturation magnetization of the
specimens below 1 ° K , has been studied .
Figure 16 a shows the temperature dependence of the magnetic
permeability of rhenium powder (after different stages of treatment ) at
1-2,5° K .
93
11. Superconductivity
The superconductivity of rhenium lias been studied by many authors
/37 , 39 , 45 – 50 /.
The anisotropy of the transition field in rhenium single crystals /45 /
R... K
was studied on single crystal specimens with R300 °K 1500, and a
diameter of about 2.3 mm . The specimens were deformed by stretching
to 44% reduction . During the deformation the shear took place along a
single system of planes ( 1010 ) . The specimens were located in a magnetic
field parallel or perpendicular to the slip planes . It was found that the
critical field H. of transition from the superconductive state to a normal
state is at a minimum if it is perpendicular to the slip planes . This
anisotropy of H. disappears after the specimens are annealed at 2700°C
for 1.5 hours . These results are explained by the formation of superconduc
tive fibers along the dislocations /45 /.
According to the data given in /46 / the temperature of the transition of
sintered rhenium to a superconductive state (determined by measuring the
electrical resistivity) is equal to 0.85°K.
permeability
Mgauss
Magnetic
1.0 b
,k
0.8 60
0.6
-
40
0,4
20
0.2
10 1.5 2.0 25 2.1 2.2 2.3 2.4

T, X TX
FIGURE 16. Dependence of the magnetic permeability u (a) and of the critical
magnetic field H (b) on temperature :
1 rhenium powder; 2 – after compression at a pressure of 15,5 kg/cm²; 3 –
after sintering in vacuo at 1460°C for 12 hr; 4 – cast rhenium .
The transition temperature Tc of 99.8 % pure rhenium powder annealed

at 800°C in vacuo for 2.5 hr was measured by the magnetic method /47 /.
Figure 16 b shows the temperature dependence of the critical field of
rhenium . The transition temperature Tc in a zero magnetic field is equal
to 2.42°K. The slope of the curve (dH /dT )r in Figure 16 b is equal to
235 gauss / degree . The electron part of the specific heat Ces = TT could be
found from the formula p = ( V /89 ) (dH /dT)?T = Tc and is equal to 4.6 . 10 ^* cal /
mole • degree? /47 /. The y/V ratio , where ő is the atomic volume of
rhenium , is equal to 5.2 • 105 cal/ cm /degree?.
According to /39 /, y = 1.97 millijoules /mole • degree? ( 4.608 · 10-4 cal /
mole • degree? ) and this agrees well with the data of /47 /, but the
colorimetric measurement of rhenium /48 / gave a higher result , p =
2.45 millijoules / mole • degree? ( 5.906 · 10-4 cal /mole •degree? ) .
94
Figure 17 /47 / shows the dependence of y/V on Tc for a number of
superconductors . It is thus possible to compare the values of y for rhenium
and other metals . According to N , all metals can be divided into two
subgroups , for each of which FNV is an approximately linear function of Tc.
The authors of /47 / believe that such division can supersede the earlier
one into " soft " and " hard" superconductors , according to which /39 /
rhenium is a " soft " superconductor because of its ideal superconductivity,
but at the same time it is a " hard" superconductor because of its mechanical
properties .
The influence of the purity, method of production, and preliminary
treatment of rhenium on Tc was studied in /39 / by magnetic methods . The
data for cast specimens indicate an ideal
18 V
superconductivity . The boundaries of the
-Nb
intermediate state are sharp, and the
16 residual moment is low /39 /.
The addition of 1.5 % of tungsten
?•d'/•megree
cYlv
increases the Tc and the critical magnetic

al
Ta
field of rhenium .
Cold working also increases the Tc of
rhenium . Thus , when a cast specimen
was ground , the Tc increased from 1.699
to 2.75° K .
RE For haloid rhenium Tc = 2.4°K , and the
*Zr6Th o Pb residual resistance is about twice as high
TAL In HD as that of cast rhenium . The critical field
2 Zn
De necessary to suppress the superconductivity
11 is also considerably higher than that in
2 6
8 10 cast rhenium /39 /.
T, K
The boundary of the transition into the
FIGURE 17. Dependence of y/V on Tc superconductive state of specimens obtained
for some superconductors. by sintering (cold working and intermediate
anneals at 1700°C ) is also sharp, but there
is a considerable residual moment . If the
specimens are turned on lathes there is a considerable increase in Tc and
in the critical field . Annealing in vacuo improves the superconductive
properties , and annealing in hydrogen leads to an increase in Tc apparently
due to contamination of the specimens during annealing /39 /.
For nonsintered rhenium powders Tc = 2.2 - 2.4° K /39 /. The rhenium
powder had few impurities , and therefore the high Tc cannot be due to their
influence .
The influence of the initial treatment on the superconductive properties
of rhenium prepared from ammonium perrhenate is shown in Figure 16 a
/ 39 /. In each case the induction B for a constant field 13 was measured
as a function of temperature . Curve 1 for noncompressed powders shows
Tc = 1.8 - 2.5 K. For most powder particles the transition to the super
conductive state terminates at 1.8°K . For compressed powder (curve 2 )
Tc is also equal to 1.8 – 2.5°K, but most of the metal passes into the
superconductive state at 2.5ºK . The authors of /39 / explain this by
assuming that in compressed specimens the grains with a higher Tc screen
shield the grains with a lower Tic and hinder the passage of the magnetic current
through the latter . It is also possible that internal stresses are present as
in turned specimens . Curve 3 of the annealed specimens is shifted to
95
1.76°K , and it is less diffuse . The cast specimens (curve 4 ) have a super
conductive behavior closest to the ideal. Apparently, melting helps to
homogenize the composition of the specimen and removes impurities that
increase the Tc.
The influence of pressure (up to 2500 atm ) on the temperature of
transition to the superconductive state of rhenium was studied /49 / on
specimens with residual resistivity p /P273 = 0.006 . The specimens were 2 cm long
and 0.25 cm in diameter . The transition to a superconductive state was
recorded by the change in the effective magnetic permeability in a magnetic
field with an amplitude of 0.3 gauss and a frequency of 80 Hz . It was found
that dTc/dP = 1.71 0.9 · 10-12 °c / dyne cm². The temperature dependence
of dHcIdP (He is the critical field ) was calculated from this result and the
temperature coefficient of expansion at between 0 and 10°K; dH IdP = 2.7 +
1.3 (TIT ) . 10-10 gauss .cm / dyne /49 /.
Critical field of pure rhenium / 39 /. The critical magnetic
field of pure rhenium (for these specimens Tc = 1.699 + 0.001 ° K ) was found
on specimens of arc- melted rhenium which have the most ideal superconduc
tivity .
For rhenium the Hc (T) function deviates from the parabolic law : Hc
= H, 11 — (TIT )'). The same deviations were found for indium, thallium , tin,
and vanadium .
For the rhenium specimens studied , He was equal to 2016 2 oersted . The
authors of /39 / believe that the deviation of the critical field of rhenium
from the parabolic law governing the temperature dependence may be
similar to those found for indium , thallium , tin , and vanadium over the
whole range of temperatures down to 0°K .
During the study of the superconductivity of rhenium / 39 / it was found
that the Debye temperature for this metal is 0 = 294° K . We believe that
this temperature agrees well with those found by others ( 0 = 283°K
according to /46 / and 0 = 310°K according to /37 /), particularly if we take
into account that the rhenium used in / 46 / and / 37 / was contaminated and
had a residual resistivity 28 times that of the rhenium investigated in / 39 /.
12. Optical properties
The optical properties of rhenium after different processing are given

in Table 35 / 13 /.
TABLE 35. Optical properties of rhenium
Process
Wave Reflectivity , Diffraction Absorption
length , Å % coefficient coefficient
Filing 5890 45.1 2.34 1.03

Polishing 5890 56.9 3.00 1,15
Grinding 5890 57.6 3.18 1,12
The spectral emissivity of rhenium En , as first determined in / 21 /,

is equal to 0.42 . No indication is given in this work on the temperature at
96
which the measurement was carried out . In /50 / it was found that En =
0.366 at 2800 ° C .
The spectral emissivity of rhenium / 17 / was determined over a wide
temperature range ( 1300 – 3000°C ) for 2= 0.655. The dependence of E, on
the temperature of an absolutely black body is given in Figure 18 / 17 /.
Ea
0.6
0.4
0.2
1200 1600 2000 2400 2 800
1, ° C
FIGURE 18. Curve of spectral emissivity of rhenium according to
different authors /17 , 21 , 50 /:
1- /21 / ; 2 - /50 / .
This graph shows that an increase in temperature leads to an almost

linear decrease in En .
Marple /51 / thoroughly studied the dependence of the emissivity E of
rhenium on the wavelength and the temperature at 1537 – 2777°C . He found
that over this temperature range the emissivity is 0.41 – 0.44 for ^ -
= 0.4-0.5 m ; 0.36 for à = 14 ; and 0.23–0.27 for a = 2.5 – 3.04 . As in the
case of tungsten , the " Drude boundary" for rhenium lies above 54 .
13. Arc spectrum
About 2000 lines were found in the arc spectrum of rhenium over the
range of 2300 — 8800 A during a study of potassium perrhenate. The chief
lines and their relative intensities are given in Table 36 / 12 ).
TABLE 36. Arc spectrum of rhenium

Wavelength , Intensity Wavelength , Intensity Wavelength , IntensityllWavelength, Intensity
A A Å
2887.66 60 3725.76 50 4522.71 100 6350,73 50

2992,35 50 4136.45 100 4791.42 6605,17 60
2999.39 80 4144.36 60 4889.15 2000 6813,37 100
3067.38 50 4222.46 200 4923.93 80 6829.91 120
3399.31 60 4257.61 50 5270.98 6971.48 60
3424.61 120 4358.69 50 5275,57 1000 7024.10 50
3451.88 200 4394.37 80 5834.31 300 7640,92 80
3460.46 600 4513.31 300 6307.70 7912.90 50
3464.72 400 4516.62 50 6321.88 100
97
The most sensitive lines for the identification of rhenium are the blue
line ( 4889.15 Å ) and 2 green lines ( 5270.98 and 5275.57 Å ) , which are some
of the most intense lines of the visible spectrum .
The identification of rhenium by lines 3451.88, 3460.46 and 3464.72 Å
is difficult in the presence of manganese , but the presence of up to 30%
Mo has no influence on their intensity . By means of those lines it is possible
to determine down to 0.002% of Re .
The long- wave regions of the arc spectrum from 7200 Å to 11,000 Å
were investigated with infrared plates , and a number of new lines were
found / 12 /. Up to 200 lines over the range of 2320 – 2500 Å / 12 / have been
investigated .
Rhenium has been found in meteorites in the Soviet Union , United States ,
and South Africa / 12 /.
98
Chapter IX
MECHANICAL PROPERTIES OF RHENIUM
Rhenium is the only refractory metal in groups V – VII with a close

packed hexagonal lattice , as the other refractory metals have a cubic face
centered lattice .
Therefore it is interesting to compare some mechanical properties of
rhenium at room temperature with those of tungsten and molybdenum , which
are very widely used in industry and have a face - centered cubic lattice .
Tungsten has a higher melting point than rhenium ( 3410°C ) and molybdenum
a lower ( 2620° C ) ( Table 37 ) .
TABLE 37. Mechanical properties of molybdenum , tungsten , and rhenium at room temperature
/8 , 29, 52-55 /
Property Molybdenum Tungsten Rhenium
Modulus of elasticity, kg/mm² . 33,600 41,500 47,000

Hardness ( recrystallized metal),
kg /mm2 150 290 250 - 280
Hardness (deformed metal), kg /mm² 200-250 350-400 500 - 800
CB , kg/mm² (recrystallized metal ) . 50-90 60-110 115 - 120
OB , kg/mm ? (deformed metal) 160 200 240
Soho ( recrystallized metal) 5-15 0 10-25

8 % (deformed metal) 4 3 5
A considerable part of the data given in Table 37 was obtained on

sintered material of commercial grade /8 , 29 , 53 , 55 /.
It can be seen from Table 37 that rhenium is stronger and more ductile
than tungsten and molybdenum . In addition , rhenium is ductile at 20° C ,
while molybdenum and tungsten of commercial purity are brittle at this
temperature .
It is particularly important that recrystallized rhenium , unlike
recrystallized tungsten and molybdenum , is also highly ductile .
1. Modulus of elasticity
During a study on the Poisson ratio of a number of elements it was found

2
that the modulus of elasticity of rhenium is equal to about 51,330 kg /mm
/56 /. According to / 17 ), the modulus of elasticity of rhenium is 47,000 kg /
mm². In this work the modulus was determined by the tensometric method
99
using annealed , sintered , and forged rhenium rods 3.81 mm in diameter ,
with the middle part ground to a diameter of 3.17 mm . The modulus was
calculated from the experimental stress- strain curve during unloading . Any
possible error can only decrease the modulus . The modulus of elasticity
of rhenium is lower than that of osmium and iridium only , which are equal
to 57,000 and 53,830 kg / mm² , respectively /29 /. It should be pointed out
that osmium , like rhenium , has a hexagonal close- packed lattice .
49
Re Ir
42
-10gm²
/,k%E
m
Rh
635
ALN
28 MO
.cr
21
14 Ceo
Mgo
Nb Tho
7 ZrSLOy
200 400 600 800 7400

1000 1200 1400
FIGURE 19. Dependence of the modulus of elasti

city of refractory materials on temperature .
The temperature dependence of the modulus of elasticity of rhenium over

the range of 20 – 880° C was studied on annealed rods 3.2 mm in diameter
and 150 mm long by the resonance method in helium . If the temperature is
increased the modulus increases almost linearly:
T , ° C .. 20 140 260 370 480 600 650 700 810 880
E .102 , kg /mm² 473 458 443 430 419 410 402 399 386 378
A comparison of the temperature dependence of the modulus of elasticity

of a number of refractory materials ( Figure 19 ) / 57 / shows that at all
temperatures rhenium remains more ductile than other materials , except
iridium , and possibly osmium on which no data are given in this diagram .
2. Strength , ductility, hardness

Mechanical properties at room temperature
The strength and the ductility during tensile tests on rhenium wire
obtained by deposition of the metal from halides on tungsten wire has been
studied / 56 , 17 /. According to the data given in / 56 / , the ultimate strength
and the elongation of 0.25 mm diam wire (diameter of tungsten wire,
100
0.03 mm ) were 49.2 kg / mm² and 24% , respectively . The ultimate strength
of 3 – 5 mm diam wire given in / 17 / (52.7 kg /mmº) agrees well with that
found in / 56 / , but the elongation is considerably lower (only 3% ) . This may
be because the wire investigated in / 17 / consisted of coarse rhenium
grains , loosely bound to one another, suspended on the tungsten wire .
TABLE 38. Mechanical properties of wrought and recrystallized sintered rhenium at room temperature /53 , 17 /
After rolling sheet to different
After annealing
degrees of deformation , %
Property
wrought sheet 12.9 24.7 30.7
0.02 kg /mm ? 18.8 22.2 17.6 29,5 111.3

ei kg/mm 29.5 91.7 162.2 195.3 197.4
00.2 , kg /mm² 32.7 94.5 171.5 208.6 217.7
OB , kg /mm² 115.5 117.6 175.0 214.9 225.4
Ó , ** % 24.0 28 8 2 2
9 21.7 30 24 1 1
• The strain coefficient is 261 kg/mm², and the strain -hardening exponent is 0.353 .
The gauge length of the rod is 12.7 mm , and of the sheet 25.4 mm .
Sims and Jaffee /17, 53 / thoroughly studied the mechanical properties of
sintered rhenium at room and elevated temperatures . The forged and
annealed rhenium rods tensile tested in / 17 / were 3.81 mm in diameter
with some sections ground to 3.17 mm diameter . A specially designed
extensometer was attached to the specimens and stress - strain curves
were recorded for each experiment.
The strength and ductility of wrought and annealed rolled rhenium sheet
were tested in / 53 /. After the first pass the 0.25 mm thick sheets were
cold rolled to 10, 25, and 30% reduction . The results given in Table 38
show that when the rate of work hardening is increased, the strength of the
metal increases considerably .
It was found /58 / that foil 100 4 thick produced from cold- rolled rods of
sintered rhenium and annealed at 1700°C for 30 minutes had an ultimate
strength of 145 – 160 kg / mm² . Wrought foil had a microhardness of
900 kg /mm², and recrystallized foil a microhardness of 500 kg / mm² .
Rhenium is highly work hardened by strain . The strain- hardening
coefficient, which characterizes the influence of work hardening by strain
on the mechanical properties , was determined in /17 /.
Curves representing the average true stresses in stretching
rhenium , molybdenum / 17 ), nickel and copper /59 / are given in Figure 20 .
The relationship between the true stress o and the true strain 8 can be found
from the formula o = Bon, where B is the strain coefficient (true stress at
unit strain ) and n is the strain- hardening coefficient ( determined from the
slope of the curve of true stress ) (Table 38 ) .
Figure 20 shows that the strain- hardening coefficient of rhenium is about
the same as that of nickel and copper, but much higher than that of molybdenum .
The high work- hardening of rhenium is accompanied by high tensile
strength and high ductility, and rhenium is the only metal which has such
a good combination of properties . Figure 21 a shows the influence of strain
on the strength , ductility, and hardness of rhenium / 17 , 53 /.
101
700
/k6, gm²
m
Re
70
MO
Ni
Cu
0.001 0.01 0.10

True strain , 8 , mm /mm
FIGURE 20. True stress -strain curves of rhenium , molyb
denum , nickel and copper .
Hv, kg/mm²
900
69, kg /mm²
200 Gazte 30 +800 2241
gm²
700 196
,kGoaz
C/m
168
150 20 + 600
140
500 112
84
100 10 + 400
56
300
28
50 0
0 20 40 60 800 1600 24.00
Reduction , % T, C
a
FIGURE 21. Dependence of mechanical properties of rhenium on strain

(a) and on temperature ( b ) :
1-2 – hardness according to Sims ( rods nd sheet, respectively ); 3 –
hardness according to authors; 4 – annealed wire 1.27 – 1.65 mm
diameter; 5 the same after 9% reduction; 6 the same after 15 %
reduction .
The mechanical properties of cast rhenium were investigated by

Savitskii, Tylkina, and Chuprikova /44 , 60 , 61 /. The rhenium for their
experiments was obtained by arc melting on a copper water- cooled hearth
using nonconsumable tungsten /60 / or rhenium /44 , 61 / electrodes , or by
electron- beam zone refining /44 , 61 /.
The rhenium ingots were upset at room temperature to 40% reduction
and annealed at 1750° C for 1.5 hours /44, 61 /. The tensile tests were
carried out on a Gagarin press with a load of 1.ton and a rate of elongation
of 1,16 mm per minute , using flat microspecimens (15 X 1.5x 1.5 mm ) or
specimens of the Gagarin type 2.5 mm in diameter . The latter were cut
from arc - melted ingots or from zone - refined rods , and their working part
was 2.5 mm in diameter and 15 mm long . The specimens were ground ,
102
electrolytically polished , and once again annealed at 1750 – 1800°C for one
hour to relieve the work hardening of the surface . The results of the tests are
given in Tables 39 and 40 .
TABLE 39. Influence of the content of gaseous impurities on the mechanical properties of cast rhenium /61 /
Upset to 40 %
HB , kg/mm² reduction and
anne a led
Oxygen , Hydrogen , Nitrogen , Method of melting
wt % wt % wt %
upset to
OB »
cast 40 % reduction 8, %
and annealed kg /mm²
0.0021 0.0005 0.0006 148 131 53.2 21.1 Zone electron -beam
melting
0.0081 0.0004 0.0005 187 182 Melting with a non
0.012 0.0003 0.0005 191 187 65.8 16.1 consum able rhenium
0.018 0.0006 0.0008 249 235 73.5 11.0 electrode in a helium
0.020 0.0006 0.0025 260 255 83.0 9.2 atmosphere , Melting
0.022 0.0005 0.0008 272 272 86.2 5.0 of Re with Rez07
TABLE 40. Influence of tungsten , molybdenum , and iron on the mechanical properties of rhenium * / 44 /
Impurity , % Cast 40% reduction Deformed and annealed
HB : HB , HB : OB »
W Μο Fe 2 8, %
kg /mm kg /mm² kg /mm² kg /mm2
200 590 200 67.0 11

0.02 202 628 198 67.3 10
0.05 211 681 207 68.4 10
0.10 220 707 219 72.3 8
0.01 215 621 219 66.8 11
0.048 224 675 215 67.4 9
0.10 229 691 229 71.1 8.5

-
0.02 195 585 195 67.0

0.06 202 601 202 69.2 9.5
0.10 209 663 207 72.1 9.0
• The content of gases in all specimens was: O2 , 0.013 -0.015 % ; H2, 0.006%; and N2, 0.0004%.
The purity of a metal greatly influences its properties . Gaseous

impurities which form interstitial solid solutions with transition metals
have a particularly great influence on the properties of metals . Tables 39
and 40 show the influence of gaseous impurities (nitrogen , oxygen, hydrogen )
and of metal impurities (tungsten , molybdenum, iron ) on the mechanical
properties of cast rhenium .
It can be seen that an increase in the content of oxygen from 0.002 to
0.022 % almost doubles the hardness and increases the strength more than
1.5 times , but the elongation decreases to one quarter . It is clear that
oxygen is the most detrimental impurity in rhenium .
Iron, tungsten, and molybdenum have little influence on the mechanical
properties of cast rhenium , as they form substitutional solid solutions with
rhenium , but oxygen forms an interstitial solid solution .
103
Tungsten , molybdenum , and iron somewhat decrease the ductility
and increase the work hardening of rhenium .
TABLE 41. Strength and ductility of annealed rhenium - thorium alloys

Content of thorium oxide , %
Propercy
0.0 0.5 1.0 2.0
00.01 , kg/mm? 18.4 16.2 19.0 16.0

00.1, kg/mm ? 29,5 27.7 29.7 29.7
00.2 , kg/mm ? 32.6 31.3 33.3 33.9
OB, kg/mm² 114.8 100.8 94.5 95.9
1 e = 12.7 mm)
8 , % ('cal 24 14 11 14
$, % 21.7 16 16 16
The influence of thorium on the mechanical properties of sintered

rhenium (thorium was added as oxide during sintering and was not reduced )
has been studied / 53 /. The addition of thorium to rhenium decreases its
strength and ductility but has almost no influence on its work hardening
characteristics (Table 41 ) .
In /60 / the ductility of rhenium was determined by compression on a
press at room temperature and at 1000° C . During static compression of
coarse - grained cast rhenium at 20°C the reduction was 25 — 30% and the
ultimate strength in compression was more than 200 kg / mmº .
Mechanical properties at elevated temperatures

The properties of rhenium at elevated temperatures are also more
favorable than those of other refractory metals . The hardness of annealed
tungsten, molybdenum , and rhenium at different temperatures is given in
Table 42/54 , 62 /.
TABLE 42. Hardness of tungsten , molybdenum , and

rhenium at different temperatures
Testing Hardness, kg /mm²

temperature ,
°C Mo W Re
-194 370 400

20 146 286 274
400 78 137 210
600 80 125 208
800 82 111 204
1000 75 85 144
1050 73 134
The hardness of rhenium , like that of other refractory metals (tungsten ,

molybdenum ), decreases with temperature , but its softening is not so rapid
and at 1000°C rhenium is almost a twice as hard as tungsten .
104
TABLE 43. Mechanical properties of rhenium at elevated temperatures /53 /
Annealed After 99% reduction After 15 % reduction
Testing
temperature , OB , OB , OB ,
°C 8, % , % 8 8, % 4. %
kg /mm ? kg /mı ? kg /mm ?
20 119,5 10 16 152 8 6 237 2
500 80,2 19 107 7 122 1
2-3 2-3 87.2
|
‫ܝܝܕ‬
‫ܝܕܝ‬
1000 60 1--2 69 3
1500 26,7 1-2 2 26 2 28.1 10
2000 15,5 2-3 10.5
-
2300 5.4 1-2 2
I
Note , Rhenium wire 1.27 -1.65 mm in diameter was tested .
Increased deformation of rhenium increases its ultimate strength at

room and elevated temperatures ( Figure 21 b , and Table 43 ) up to its
recrystallization temperature . Above the temperature of the
end of recrystallization the strength of deformed rhenium does not differ
from that of annealed rhenium /53 /.
a
1. ° C b
-18 550 1100 1850 2200
112 Re
k, gm²
Ta Re
Gs
105
,kgm²
/m
m/Gs
Ah
Ir
70
W
Pt
56
Pd
35
28
Mb
Ptyy MO
x Mo
RU
Cro
02 04 ав
800 1600 24.00 Homologous (corresponding
T,X temperature, Tim
FIGURE 22. Dependence of the ultimate strength of rhenium and soine other
refractory metals on temperature :
a - strength at the testing temperature; b – strength of rhodium , iridium , and
ruthenium (high purity) and of platinum , palladium , and rhenium (commercially
pure) at homologous corresponding temperatures.
At elevated temperatures the strength of rhenium is higher than that of

other refractory metals of groups VI – VIII at all temperatures ( Figure 22 a ,
and b ) /63 , 64 , 65 / . The ductility of cast coarse- grained rhenium has been
studied /60 / by upsetting on a drop hammer at 1000°C in an argon
atmosphere, and it was found that the maximum reduction by upsetting is
60 % , and that the metal fails along the grain boundaries .
105
3. Long - time strength
Rhenium has a high long- time strength . Long- time strength tests were
carried out /53 / on wire specimens 1.25 mm in diameter and 78.7 –
116.8 mm long in an inert atmosphere of a mixture of helium and hydrogen .
The specimens were heated by an electric current . The results are given
in Table 44 .
TABLE 44. Long - time strength tests on rhenium at elevated temperatures

Testing tempe Time to rupture
rature , °C Stress, kg/mm² Elongation , %
-
25 100 hr 9.8 ( specimen 38 mm long);
specimen did not rupture
500 70.3 Specimen ruptured during loading
63.3 2 sec
52.7 3 min
45.7 3.2 hr 5.6 (specimen 25.4 mm long
1000 56.2 30 sec 2
49.2 40 sec 2
42.2 5.0 min 2
35.2 3.7 min 2

28.1 16.5 hr 2 (specimen 116.8 mm long)
1500 6.6 4.6 hr 1.0 ( specimen 63.5 mm long)
2000 0.77 12.3 hr 4.4 ( specimen 63.5 mm long)
700
42
100 hr 600 1000 1400 1800 *
/6,kgm
m
m/k, gm²
1000 hr 600 1000 1400 "

610
RT
5000
70 1000
500 28
o1
1000
•2
15000
7 1500
2300
Mo
Nb Re
2000
07
20 30 500 1000 1500 2000
T /K * Lgt)•1004 1,° C
FIGURE 23. Long - time strength and FIGURE 24. Dependence of the long -time strengti
ultimate strength of pure rhenium , of rhenium (10 -hour tests) and of some other
K = 5: refractory metals on temperature .
1 - ultimate strength ; 2 – long
time strength . The numbers beside
the curve denote the temperature
in ° C ; RT – room temperature .
106
The relationship between the data on tests of long- time and short- time
strength at elevated temperatures was found from the Larson- Miller curve
( Figure 23 ) . It was found that K = 5 is the best value . Figure 23 also
gives a scale which relates stress to temperature for rupture times of
100 - 1000 hours .
The sharp increase in the ductility of rhenium in contrast to that of
other metals does not start at the beginning of recrystallization, but at
more elevated temperatures , when the recrystallization is already complete
(above 2000°C ) .
Comparative data on the temperature dependence of long- time strength
(testing time 10 hours ) for molybdenum , tungsten, niobium , and rhenium ,
are given in Figure 24 / 53 , 64 , 65 /. At elevated temperatures the long- time
strength of rhenium is somewhat higher than that of tungsten , and
appreciably higher than that of molybdenum and niobium .
At present it is difficult to explain why rhenium retains its high
temperature strength more than other refractory metals . It can be assumed
that the specific structure ( site of atoms in the hexagonal close- packed
lattice ) /66 /, the high melting point , and the exceptionally high specific
gravity , which indicate the existence of strong interatomic binding forces
in rhenium , determine the high strength of rhenium at elevated tempera
tures during long- time and short-time tests .
Bibliography for Chapters VIII - IX

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109
Part 3
PHASE DIAGRAMS OF RHENIUM
In this part we shall discuss the binary and ternary phase diagrams of
rhenium , and also the interaction of rhenium with elements for which no
phase diagram has yet been constructed . The phase diagrams are divided
according to the groups of the periodic table .
Data are at present available on the interaction of rhenium with 54 of
the 104 existing elements only . This is quite understandable , as the
element was discovered only in 1925. The reaction of rhenium with
transition metals , which include elements of the greatest industrial
importance , have been most widely studied . There are almost no data on
the interaction of rhenium with elements of groups 1 - III , although the
nature of the interaction of rhenium with lithium , sodium , and other elements
would be of great interest . Today , we have data on 27 complete binary
phase diagrams of rhenium , 18 of which were constructed in the Laboratory
of Rare Metals and Alloys of the Baikov Institute of Metallurgy between
1955 and 1964 .
Chapter X
BINARY PHASE DIAGRAMS
1. Factors determining reactions between elements

Phase diagrams show the physicochemical reactions between components ,
and the phase composition and structure of alloys at different temperatures
under conditions of a thermodynamic equilibrium , in a most general and
reliable way / 1 – 4 /.
One of the chief tasks of modern metallurgy is to produce new alloys
with the properties required . Obviously, the development of such alloys
must be based on phase diagrams , from which it is possible to predict the
physical, mechanical, and technological properties of the alloys , and
their application under different conditions . The nature of the reaction
between elements is determined by a number of physicochemical factors .
According to the theory of metal alloys , these factors are : the electron
structure of elements , their valence state , atomic radius , potential , heat
of vaporization, melting point , boiling point , density, and type and
parameters of the crystal lattice, etc.
The physicochemical properties of elements are determined by the
electronic configurations of their atoms , and consequently by their position
in the periodic table . Rhenium belongs to subgroup VIIA and the third
long period of the periodic table, and it has all the characteristic features
of this group of transition metals .
110
TABLE 45. Structure of the valence shells of transition elements of groups IV – VIII of the
periodic table /5 /
Group of periodic table

Long
period IVA VA VIA VII A VIII A VIII B VIIIC
Ti V Mn Fe Ni Co
I 30 452 3d 4.52
302 4s 3d5 451 306 451 30 % 45 % 309 48
Zr Nb Мо Tc Ru Rb Pd
II
442 55 4d45s1 40 % 551 4d6 551 407 551 40 * 551 40110
Hf Ta W Re Os Jr Pt
III 5d 6s
5d2 6s 50 % 6s 5d " 6s 5d6s 5d® 6s 507 6s
The structure of the valence shells of transition metals (Table 45 ) is

very complex, because of the very close energy levels , for example, 5d
and 6s in elements of the third long period / 5 /.
Electrons can readily pass from one level to another as a result of
change in temperature or pressure or of a reaction with other atoms. This
transition changes the valence of the element . This explains why transition
metals exist in several valence states . Research during the last years has
shown that the distribution of electrons in a free atom differs appreciably
from the distribution of electrons in a crystal .
Table 46 gives data on the atomic radius , potential, melting point, and
compressibility under hydrostatic compression , of rhenium and a number
of other elements whose reactions with rhenium have been studied . This
table also shows the crystal structure of monomorphic metals and of all
modifications of polymorphic metals (the structure of the low - temperature
modification is given first).
The atomic radiuses /6 /, in Angström units , are given for a
coordination number of 12 , and were calculated from lattice parameters
of elements with one of the following three crystal lattices : body- centered
cubic , face- centered cubic , and hexagonal close -packed. The atomic
radiuses of the other elements were determined by Pauling, Laves , and
others .
The dimensional factor with reference to rhenium was calculated from
the formula :
Ar
Re . 100 %
' Re
where rx and rRe are the atomic radiuses of a certain element and of
rhenium , respectively . According to the Hume- Rothery and Goldschmidt rules ,
the formation of a continuous series of solid solutions is possible if the
dimensional factor does not exceed 8 – 15% . A necessary condition for the
formation of a continuous series of solid solutions is that the crystal
structures of the elements must be isomorphic ( see Table 46 ) /7 /.
Electronegativity /9 /. All elements can be ordered in such a way
that the square of the difference between the atomic numbers of two
elements is approximately proportional to the heat evolved during the
formation of a bond between these two elements . This scale is known as
the " Electronegativity scale," and was suggested by Pauling. Gordy found
that the electronegativity of elements can be determined from the number
111
TABLE 46. Some physicochemical constants of elements 14,6 – 15 /
Element Crystal
structure
Copper FCC 1.278 -7.65 0.98 1.1 1033 7.49

Silver . 1.445 +5.09 0.92 1.16 960 9.740
Gold 1.442 +4.87 0.93 1.15 1063 5.664
Lithium BCC 1.562 +13.60 0.95 1.13 181 84.83
Zinc HCP 1.394 +1.38 1.50 0.58 419.5 16.39
Mercury · Rhombohedral 1.573 +14.4 1.80 0.28 -38.87 34.7
Beryllium .
HCP 1.128 -17.96 1.42 0.66 1284 9.772
Scandium HCP/ BCC 1.641 +19.35 1.27 0.81 1539 17.1
Yttrium HCP 1.801 +30.98 1.20 0.88 1502 26.79
Gadolinium 1.802 +31.05 1.20 0.88 1312 25.59
Terbium 1.782 +29.6 1.21 0.87 1356 24.6
Erbium 1.757 +27.78 1.22 0.86 1497 23.88
Boron Tetragonal 0.98 -28.73 1.91 0.17 2225 5.48
Aluminum FCC 1.432 +4.15 1.48 0.60 660 13.59
Gallium , Rhombic 1.411 +2.62 1.48 0.60 29.6 17.2
Titanium HCP/ BCC 1.462 +6.33 1.62 0.46 1668 9.328
Zirconium HCP/ BCC 1.602 +16.51 1.48 0.60 1850 11.77
Hafnium 1.580 +14.91 1.48 0.60 2222 8.98
Thorium FCC 1.798 +30.76 1.36 0.72 1751 18.07
Carbon (graphite) Hexagonal 0.916 -33.38 2.54 -0.46 3827 29.01
Silicon Cubic ; diamond 1.319 -4.07 1.82 0.26 1412 9.924
type
Germanium . 1.369 -0.44 1,77 0.31 936 12.7
Vanadium . BCC 1.346 -2.11 1.85 0.23 1905 6.057
Niobium 1.468 +6.76 1.77 0.31 2468 5.761
Tantalum 1.467 +6.69 1.77 0.31 2998 4.89
Chromium 1.282 -6.76 2.15 -0.07 1875 5.154
Molybdenum 1.40 +1.82 2.05 0.03 2615 3.598
Tungsten .
1.408 +2.40 2.05 0.03 3380 3.034
Uranium Orthorombic / 1.56 +13.45 1.89 0.19 1131 9.926
tetragonal
Manganese 1.264 -8.07 2.22 -0.14 1244 16.44
Cubic /cubic/
tetragonal/
cubic
Technetium HCP 1.360 -1.09 2.10 -0.02 2170 3.30
Rhenium 1.375 0 2.08 0 3180 2.64
Iron BCC /FCC / 1.274 -7.35 2.21 -0.13 1535 5.826
BCC
Cobalt HCP / FCC 1.252 -8.95 2.26 -0.18 1492 5.1 22
Nickel FCC 1.246 -9.38 2.24 -0.16 1453 5.26
Ruthenium HCP 1.339 -2.62 2.12 -0.04 2280 3.057
Rhodium FCC 1.345 -2.18 2.12 -0.04 1960 3.626
Palladium FCC 1.376 +0.07 2.08 0 1552 5.423
Osmium . HCP 1.353 -1.60 2.10 -0.02 3027 2.35
Iridium FCC 1.357 -1.31 2.10 -0.02 2443 2.76
Platinum 1.387 +0.87 2.07 0.01 1769 3.523
Note , BCC is body -centered cubic ; FCC is face - centered cubic ; HCP is hexagonal close -packed .
112
of valence electrons n and the covalent radius r, and can be calculated
from Ex= 0.31 (0+ 1) + 0.50 /6 ). The constants in this formula were found
from a graph representing the dependence of * 1 on En.
There are certain discrepancies between the data of Pauling and Gordy
on the covalent radiuses and the number of valence electrons , particularly
for transition metals .
If the difference between the atomic radiuses of two metals does not
exceed 8 – 15% , and the electronegativity difference is not greater than
0.2 -0.4 , the metals have a high mutual solubility .
The larger the electronegativity difference between two metals , the
greater is the tendency of the metals to form intermetallic compounds ,
and the lower is their mutual solubility .
If the electronegativity difference between the elements is large, the
heat of formation of compounds is also high, and the compound itself is
very stable .
Table 46 gives the electronegativities of all elements taken from /6 /,
except those of iron, cobalt, nickel, copper, silver, and gold, which were
taken from / 10 /.
The electronegativity difference can be calculated from the formula:
An = Erre — Enx
The melting points were taken from /7 /.
The last constant characterizes the forces of the interatomic bonds in
the substance . Metals with similar interatomic binding forces can be
expected to interact to form wide regions of solid solutions . At a certain
difference between the interatomic binding forces the regions of solid
solutions are usually wider at the side of the metal in which the interatomic
binding forces are smaller / 14 /.
The compressibility under hydrostatic compression /8 /,
together with the modulus of elasticity, is an indication of the ductility of an
1 dV
element and can be calculated from the formula B v dp cm /kg (x 106) .
The compressibility characterizes the ability of a metal to withstand
considerable deformation of its crystal lattice without changing its type .
Obviously , other conditions being equal, a greater compressibility means
a greater dissolving power of a metal for another element .
From the Hildebrand and Mott criteria /6 / it is possible to
evaluate the miscibility of liquid elements with a probability of about 70% .
According to Hildebrand , liquid phases separate if the heat of solution
exceeds 2RT. Mott extended the theory of Hildebrand , and assumed that if
the components tend to form a compound, the probability of immiscibility
decreases . It should be pointed out that no immiscibility of rhenium with
transition metals has been found . At present only three metals are known
that do not mix with rhenium , namely, gold , copper, and silver .
It can be seen that from the existing theories the nature of the interaction
between elements can be predicted .
Several methods also exist for determining the position of individual phase
regions on the diagram , in particular the position of the eutectics , the curve
of solubility in the solid state, and also the liquidus and solidus . We believe
113
that in this book there is no need to give the equations for calculating these
data , since they can be found in a number of special books . The calculation
methods are insufficient for completely determining all factors which
influence the interaction of elements , and they cannot be the only or the
chief methods for constructing phase diagrams . At present phase diagrams
are constructed from the most reliable experimental data . The experimental
method is very labor- consuming, and this is why all possible binary phase
diagrams have not yet been constructed .
2. Method of preparation and study of rhenium alloys

for the construction of phase diagrams
A study of systems of refractory and chemically active elements
involves considerable experimental difficulties . Therefore , we used special
methods for constructing phase diagrams of rhenium with refractory
transition metals , and used high- temperature vacuum equipment developed
in the Laboratory of Refractory and Rare Metals of the Baikov Institute of
Metallurgy. When we started to construct phase diagrams in 1955 , the
chief method of preparation of refractory alloys was sintering . Alloys
prepared in this way can give no reliable data on the position of the individual
phases on the diagram because of the incomplete homogeneity of the alloys .
The phase diagrams of rhenium alloys were constructed from the data
of studies on cast alloys by methods of physicochemical analysis (micro
structural , X- ray, thermal analysis , determination of the melting point,
measurements of hardness , electrical resistivity, and of the microhardness
of the structural components and of the individual phases ) . In some cases
we also measured the mechanical properties of the alloys (hardness ,
strength, and ductility) at different temperatures .
Later we shall very briefly describe some general data on the methods
used to construct phase diagrams . Certain features of the individual
systems can be found in the original papers by the present authors .
Preparation of alloys . The alloys of all systems were prepared
by vacuum arc melting with a nonconsumable electrode on a water
cooled copper hearth. The melting was carried out in vacuo or in a medium of
purified inert gases (pressure 200 – 400 mm Hg) . From some alloys we
prepared specimens to determine their mechanical and other properties .
From alloys with good workability we prepared rods of the required
diameter by forging the ingots. Specimens of alloys that were brittle and
had a poor workability were cast directly in the molds of the arc furnace,
for which a special hearth was constructed in the laboratory . Cylindrical
and standard specimens of refractory and brittle metals and alloys for
mechanical tests could be prepared .
The alloys were produced by direct melting of the components or by
melting one component with preliminarily prepared alloys . Thus, rhenium
alloys with low -melting metals ( for example , aluminum ) with melting points
differing by more than 2000°C from that of Re were prepared in the
following way: the alloys represented by the middle part of the phase
diagram ( 30 — 70% ) were prepared by direct melting of the components .
Alloys with a high content of one of the components were formed by melting
with an alloys . The very low- melting alloys were produced in an induction
114
furnace at temperatures close to the melting points of the low- temperature
components . The composition of the alloys was controlled by chemical
analysis and by weighing .
Determination of the melting point . Melting point determinations
of alloys that melt at 2000 – 3400°C are quite difficult. The ordinary method of
thermal analysis for studying low- melting alloys is unsuitable . We used
the so-called " drop" method , with which the melting point of any refractory
metal can be found with an accuracy of 25°C . The melting point was
measured in a special device designed in our laboratory , with 3 X 5 X 8 mm
specimens . A hole four times as deep as its diameter was drilled
in the side wall of the specimen . The internal walls were rather
rough , and thus conditions were created for an absolute black body,
which increased the accuracy of the measurements . The tests can be
carried out in vacuo ( 10-4 mm Hg ) or in an inert gas atmosphere . The
specimens were heated by an electric current .
The melting point was determined at the moment the first drop of liquid
metal appeared in the opening by means of an optical pyrometer calibrated
against pure metals under the same conditions . With this method it is
possible to determine only the temperature at which melting starts and thus
the solidus line can be drawn on the phase diagram . It is believed that this
method of measuring the melting point of binary alloys containing phases
with greatly different melting points gives the temperature at which the low
melting phase starts to melt . The temperature at which the high- melting
phase starts to melt is determined at the moment the opening is completely
filled with liquid metal. If the concentration of the low- melting phase in the
alloy is low , this method gives only the temperature at which the high
melting phase starts to melt .
Microstructural analysis . Metallographic studies show the
dependence of the microstructure of alloys of a given system on
their composition and temperature . Thus , by microstructural
analysis it is possible to determine with a high degree of accuracy the
boundaries of the phase regions (homogeneous and heterogeneous ) and the
nature of the reactions in this system (eutectic , peritectic , etc. ) . We
studied the microstructure of cast alloys and of alloys after various heat
treatments (hardening, annealing, etc. ) .
It should be pointed out that the determination of the phase equilibrium
in refractory alloys is quite a long procedure , and that the diffusion
processes are slow even at elevated temperatures . The necessity of heating
the specimens at elevated temperatures for a long time creates some
experimental difficulties . Quenching from elevated temperatures (up to
2 500°C ) was carried out in the same device in which the melting point was
determined . The alloys were cooled in vacuum oil . However , this method
of quenching , as well as other methods (quenching the ingot and heating in
an arc furnace ), makes prolonged heating of the specimens at elevated
temperatures difficult . To attain conditions close to the phase equilibrium
of the alloys , we heated the specimens for 2 – 100 hours at 2400 – 1500°C
in vacuum furnaces ( about 10-3 – 10-5 mm Hg ) , and cooled them to 800 –
1000°C at the rate of about 800°C per minute . At such a cooling rate no
diffusion processes took place , and the cooled alloys had the same phase
composition as they had at the temperature from which they were quenched .
The specimens were annealed at about 1000°C in ordinary silite furnaces
for 500 – 1000 hours . The specimens were sealed in double vacuum quartz
ampules .
115
The microsections of all alloys were prepared by ordinary methods of
grinding with emery paper and polishing with felt moistened with an
aqueous suspension of chromium oxide . Rhenium alloys with metals of
group IV (titanium , zirconium , hafnium ) and of group V (vanadium , niobium ,
tantalum ) were etched in different mixtures of concentrated hydrofluoric
and nitric acids , depending on the composition of the alloy. The micro
sections of pure rhenium and of alloys of rhenium with tungsten and
molybdenum were prepared by electropolishing and etching in a 10% solution
of sodium hydroxide ( potential 22 V; current 500 – 600 mA; time
2 – 3 min ) . Chromium- rich and aluminum- rich rhenium alloys were
electrolytically etched in solution used to etch chromium and aluminum .
The operating conditions were varied according to the content of rhenium
in the alloy . The microsections were examined and photographed in
polarized light , as is usual with specimens of pure rhenium and rhenium
rich alloys .
X- ray analysis . We used this method to determine the types and
the parameters of the crystal lattices of the components of the alloys , and
thus their phase composition and in some cases also the solubility limit in
the solid state .
For our X - ray studies we used powder specimens and a copper,
molybdenum , or chromium target . The parameters of a number of new
intermetallic compounds of rhenium were determined .
Thermal analysis . The temperatures of the phase transformations
in a number of alloys of rhenium with low -melting metals , for example
aluminum , were determined by thermal analysis, that is by recording
the cooling and heating curves . In the method of microthermal analysis
developed in our laboratory tungsten – rhenium thermocouples are used ,
and a transformation at up to 1600 or 1700°C in 0.2-0.3 g specimens can
be found to within + 7 ° C .
Measurement of hardness and electrical resistivity .
N. S. Kurnakov described a relationship between these properties and the
phase composition of an alloy . Hardness and electrical resistivity data on
alloys help to determine the formation of a new phase with different
properties . We also measured the microhardness of the structural
components of the alloys . Together with data of microscopic and X- ray
analysis this helps to determine the composition of the alloy accurately.
In a number of cases we constructed a composition- property diagram .
3. Reaction of rhenium with elements of group I
Subgroup A
Copper , silver , gold / 16 , 17 ). The reaction of rhenium with

silver and copper was studied in / 16 /. Fifteen different methods were tried
to obtain alloys of rhenium with these two metals . The components were
added as pure metal or as different compounds . It was found that it is
impossible to prepare binary or ternary alloys of rhenium with these metals
because of the complete immiscibility of the components in the liquid or
solid state . This could be expected from theoretical considerations .
116
By X - ray analysis it was found that rhenium does not dissolve in liquid
or solid gold /17 /.
Subgroup B
Hydrogen / 18 /. It was found that HRe is formed at about 5°C by the

action of 95 % sulfuric acid and granulated zinc coated with an amalgam
containing 5% Hg on sodium perrhenate .
Lithium . The authors of /19 / indicate the formation of hydrated LiRe .
4. Reaction of rhenium with elements of group II
Subgroup A
Zinc /20 /. Rhenium scarcely reacted with molten zinc kept at 520°C
for one hour .
Mercury . A rhenium amalgam was obtained by the electrolysis of an
aqueous solution of potassium perrhenate with a mercury cathode /21 /. It
was found that rhenium powder does not react at 300° C with mercury in a
reducing atmosphere /22 /.
Subgroup B
Beryllium /23 - 27 /. The existence of a BezRe compound ( 91.18 wt % O
Re ) with a hexagonal lattice of the MgZn2 type ( Laves phase ) ( a = 4.345 A ,

( = 7.101 A, cla - 1.631 /23 /) was proved by the X - ray method . A BezoRe
compound with a cubic lattice of the Ok type ( a = 11.52 A ) was found in /24 / .
According to /25 /, the system also contains a ReBe22 compound with a face
centered cubic lattice ( a = 11.5611 0.003 A ), which belongs to the Fd3m space
group .
Bulanov and Frantsevich /26 / studied sintered beryllium - rhenium
specimens with different contents of rhenium , and found that a BezRe
compound is formed by a peritectic reaction . A microstructural X- ray
analysis combined with microhardness tests showed that the solubility of
BezRe in beryllium is equivalent to 0.5 – 1 at . % Re , the maximum
solubility of beryllium in BezRe is 30 at . % Be , the maximum solubility of
BezRe in rhenium is equivalent to 10 at . % Be , and the maximum solubility
of rhenium in BezRe is 32.3 – 40 at . % Re . The addition of rhenium to
beryllium raises the melting point from 1280 ° C for pure beryllium to
1740°C for a beryllium alloy with 1% Re , 1780°C for an alloy with 2% Re , and
1840°C for an alloy with 5% Re .
The beryllium- rich part of the system with up to 45 wt % ( 3.79 at. % )
Re was studied by microstructural and X- ray analysis , and by hardness
measurements on cast alloys /27 /. It was found that alloys with 8.8 wt %
( 0.45 at . % ) Re have a eutectic between beryllium and the BezoRe compound .
117
Beryllium dissolves not more than 1 wt % Re at the eutectic point and less
than 0.7 wt % Re at 600°C . The Bezo Re compound in an alloy with 44.7 wt %
( 3.77 at . % ) Re has a Re content closest to the theoretical, and a lattice
parameter of 11.533 +0.002 , /27 /.
5. Reaction of rhenium with elements of group III
Subgroup A
Scandium /28 /. X- ray analysis of cast alloys has shown the existence
of two compounds: ScRe , with a MgZn, type structure (a = 5.271 A , C =
8.592 Å , cla 1.680 ) and Sc5Re24 with a TisRe24 type structure ( structure of
Q- Mn type) with a = 9.65 Å.
The scandium - rhenium phase diagram constructed by Savitskii , Tylkina
and Khamidov is of the peritectic type, and includes two intermetallic
compounds ( Figure 25 a ) .
Re , wt %
rzaylısan.|
20 40 60 80
1,°C
3000
-Scher
ASC 1360 Re, wt %

V25709 Τ, °C 20 40 60 80
a tici at . % 3400
2 500
L
Y, RE
1000 3000
SC 2 4 L
Re, at . % 2030
2600
2000 252 / "
1
> 99 %)
2 200
1535
1500 1800 | 1552
1360 °
A SCK 14.50
1400 F21 %
Fa -Y
1000 1000
SC 20 60 80 Re Y 20 40 60 80 RC
Re , at . % Re , at . %
a
Re , at . %
T, C 20 40 60 80
3200
Alfa
Re
L
2400
2000 :25
1600 1590225
1485125
800 69017
-600 "
AL 20 40 60 80 Re
Re , wt %
с
FIGURE 25. Rhenium -scandium phase diagram ( a), rhenium - yttrium phase diagram
( b ), and rhenium - aluminum phase diagram (c) .
118
The X- phase (ScsRe24) of the a- Mn type (a = 9.6448 Å ) is formed by a
peritectic reaction ( L + B = X ) at 2570°C . The microhardness of the x- phase
is 1225 kg / mm2 .
The 1 - phase (ScRez ) is of the Laves type. It has a hexagonal close - packed
crystal lattice ( a = 5.270 A , C = 8.590 Å , cla 1.630 ) and is formed by a
peritectic reaction ( L + x a) at 2030 °C . The microhardness of the 1 - phase
is 930 kg / mm2.
The ScRez and Sc5Re24 intermetallic compounds have very narrow regions
of homogeneity and are stable . Scandium and ScRez form a eutectic with
about 1 at . % of rhenium at 1360° C .
At the temperature of the peritectic transformation rhenium dissolves
about 5-6 at . % Sc , and scandium dissolves less than 1 at . % Re .
Yttrium /29 , 30 /. By microstructural and X- ray analysis Lundin and
Klodt /29 / constructed an yttrium - rhenium phase diagram of the peritectic
type (see Figure 25b ) . At 2520°C a Re Y intermetallic compound is formed
by the peritectic reaction L + B 3 Re2Y (B - rhenium -base solid solution ). The
Re2Y compound has the following parameters : a = 5.397 0.002 Å , C = 8.824 +
0.002 X , and cla = 1.635. It has been found /30 / that the Re2Y compound is
a Laves phase with a MgZn, type structure (C14 ) ( a = 5.397 0.002 Å, c =
8.819 +0.002 Å , and cla = 1.634) . It can be seen from the phase diagram
that rhenium dissolves not more than 1 at . % Y. The polymorphic
transformation Q - Y - Y- Y is a peritectoid reaction , at a temperature which
has not yet been determined . The y - Y- phase dissolves not more than 1% Re .
A eutectic with 5 — 10 at . % Re exists at 1450° C between y - Y and Re2Y .
Gadolinium , terbium and erbium . Savitskii, Tylkina , and
Khamidov carried out X- ray studies on cast alloys of rhenium with
gadolinium , terbium , and erbium , and found compounds of the MgZn, type
with a Laves phase structure . A GdRe, compound has the following
parameters: a = 5.412 Å , C = 8.827 Å , cla = 1.631 . TbRez has the following
parameters : a = 5.397 Å, C = 8.797 Å, cla = 1.63, and for ErRez , a = 5.363 Å ,
C = 8.758 Å and cla = 1.633 .
Lutetium . The existence of a LuRe, compound of the MgZn2 type with
a Laves phase structure ( a = 5.336 Å , c = 8.721 Å , cla = 1.634) has been
found /30 a .
Subgroup B
Boron / 31 — 34 /. Neshpor, Padderno , and Samsonov /31 / studied boron

rhenium powder specimens of the following compositions by X- ray analysis :
Re4B, RezB , RezB2 , ReB , Re3B4, Re2B3, ReB2 , and Re2B5. The specimens
were compressed and siniered in vacuo at 1900°C for 0.5 – 2 hours .
The structure of the materials formed differed from that of the well
known boride phases . The authors of / 31 / carried out an X - ray analysis ,
and believe that the system contains a r - phase in the region of 20 – 35 at . % B
with a tetragonal lattice (a = 5.47 Å, and c = 4.73 Ă ), and a y ' - phase in
alloys containing more than 40 at . % B. Directly after sintering , an alloy
with 33.3 at. % B (Re2B ) had a tetragonal structure of the e - phase Me2B5
( a = 2.97 Å and c = 13.8 Å ), which was transformed into a y- phase after
prolonged standing in the air . In the whole system the phase transformations
take place by a gradual reconstruction of the crystal lattice .
119
32
FIGURE 26. Microstructure of rhenium - aluminum alloys:

a – 1.5 wt % Re , cast, a.x200 ; b – 4.5 wt % Re , cast , a + AlzRe . X500 ; c – the same
after annealing at 570 ° C for 500 hr , a + AliRe . X500 ; d – 60.5 wt % Re, cast, a +
AlRe . X 500 ; e – the same after annealing at 570° C for 500 hr , AlzRe + Ali2Re. X 500 ;
f - 85 wt % Re after annealing at 570 ° C for 500 hr , AlzRe + Alx Rey + X. X 500. Non
equilibrium state : g -95 wt To Re annealed at 1600°C for 1.5 hr , X + B . X 500 ; h
99.6 wt o Re after annealing at 1600 ° C for 1.5 hr , 2. X500 .
5511 120
According to /32 /, the boron- rhenium system has three stable phases:
orthorhombic ResB, hexagonal Re7B3, and hexagonal ReB3. The tetragonal
Re B2 phase , found in /31 /, was not described in /32 /. The ReB2 compound
found in / 33 / has the formula ReB1.94. All lines are indexed on the basis of
a hexagonal structure with a = 2.900 Å , c = 7.478 Å .
The boron- rhenium system contains a ReB compound with a structure
of the TiB type (a = 6.12 Å, b = 3.06 Å, 4.56 A ) / 34 /.
Aluminum /35 – 38 /. Savitskii, Tylkina, and Povarova /35 /
constructed an aluminum - rhenium phase diagram (see Figure 25c ) from
the data of studies on cast alloys by thermal, microstructural , and X- ray
analyses , and by measuring the melting point , hardness , and microhardness
of the specimens . An X- ray study of these alloys was carried out in /36 /.
The system has 4 intermetallic compounds : X - phase ( AlyRez ) , AlRe (Al Rey),
Al2Re , and Ali2Re . The X- phase is formed by a peritectic reaction,
L + B 2 % (where ß is a rhenium - base solid solution ), at 2000 °C and contains
about 90 wt % Re, which corresponds approximately to the stoichiometric
formula AlzRez. The X - phase has a lattice of the a - Mn type ( a = 9.58 Å )
and belongs to the 143 m - 1'd space group . The microhardness of the
compound is 800 kg / mm². The AlRe (Al Rey) compound is formed by the
peritectic reaction L + X Al Rey at 1590°C , and contains about 45 50 at . %
Re . Its crystal structure differs from that of the AlRe compound found in
137 ), with a probable structure of the CsCl type ( a = 2.88 Å) . The AlRe
compound is formed by the peritectic reaction, L + Al Rey = Al2Re at
1485 ° C , and contains 77.5 wt % Re . Its microhardness is about 1000 kg /mm².
The structure of this compound has not yet been determined , but it is
probably isostructural with WAl2 or MoAlz, which have also not yet been
studied . The Ali2Re compound is formed by the peritectic reaction a +
Al2Re 2 Al12Re (where a is an aluminum- base solid solution ) at 600°C , and
contains 36.7 wt % ( 7.7 at . % ) Re .
This compound is very brittle ( microhardness 360 kg / mm² ) , and it is
isostructural with cubic Al12W and A112Mo ( a = 7.528 + 0.001 Å), space group
Ym – TĂ. At the temperature of the peritectic reaction L + A12Re za
( 690°C ) aluminum dissolves up to 1.75 wt % ( 0.26 at . % ) Re , and at 500° C it
dissolves up to 1.25 wt % ( 0.2 at . % ) Re . The region of rhenium - base solid
solutions does not extend beyond 0.4 wt % ( 2.8 at . % ) Al at 1900 °C , and it
narrows with decrease in temperature . Characteristic microstructures of
aluminum- rhenium alloys are shown in Figure 26. According to / 38 / ,
ReAlĄ, ReAle, and ReAl12 intermetallic compounds are formed in the
aluminum - rhenium system . The ReAl4 compound ( 36.7 wt % Al ) has a
triclinic crystal lattice ( a=9.13 Å, q = 99.5 °; b = 13.8 Å; B = 94°; c = 5.16 Å ;
7 = 103.5 ° ).
Gallium /39 /. It has been found that at 800°C liquid gallium does not
interact with rhenium .
6. Reaction of rhenium with elements of group IV

Subgroup A
Titanium /40 – 43 /. Savitskii , Tylkina , and Zot'ev /40, 41 / were

the first to construct a titanium - rhenium phase diagram ( Figure 27 a ) from
121
data of microstructural analysis , and measurements of the microhardness ,
hardness , and melting points of cast alloys . This phase diagram is a
peritectic one . Specimens containing about 95 wt % ( 82.5 at . % ) Re form a
TigRe24 (x- phase ) compound at 2750°C by the peritectic reaction L + B = X
(B is a rhenium - base solid solution ) . The microhardness of this compound
is 2000 kg / mm² . It has a cubic body- centered lattice of the a- Mn type
( a = 9.59 kX ) , an electron concentration of 6.48 electrons / atom , and a
density of 17.73 g / cm '. The atoms in this compound are ordered /42 /. It
can be seen from the phase diagram /41 / that rhenium decreases the
temperature of the polymorphic a - Ti = ß - Ti transformation from 885° for
pure titanium to 650°C for an alloy containing 20 wt % Re , Q- Ti has a
hexagonal close - packed lattice, and dissolves less than 0.5 wt % Re . The
addition of more than 20 wt % Re to titanium leads to stabilization of the
B - phase . Alloys containing less than 20% Re and quenched from the
B - region undergo a martensitic transformation . A cubic titanium phase in
an alloy containing 15 % Re can be retained after quenching from 800°C , and
in an alloy containing 24 wt % Re it can be retained after quenching from
6 50° C . Alloys containing 10 – 15 % Re quenched from the B- field contain a
B - phase and a metastable w - phase .
Ageev , Karpinskii, and Petrova /43 / studied the mechanism of the
decomposition of the B - solid solution with specimens of titanium alloys
containing 19.91 wt % Re . According to the authors this content of rhenium
is the minimum for stabilizing the B - phase by quenching . During the initial
stage the decomposition of the B - phase at 400°C is accompanied by the
precipitation of a metastable w - phase . If the heating is prolonged to 100 hours
the w - phase is transformed to an a - phase . The authors /43 / found that the
B - titanium solid solution decomposes as follows : B - B + w Bta .
The phase diagram ( Figure 29 a ) shows that the solubility of titanium in
rhenium is low , but it has not yet been accurately determined .
Zirconium /40 , 44 – 47 ). Savitskii , Tylkina, and Tsyganova /44 /
studied zirconium- rhenium cast alloys by microstructural analysis and by
measuring the melting point and the hardness of the material . They were
the first to construct a phase diagram of this system ( see Figure 27 b ) .
Kripyakevich , Savitskii, and Tylkina /45 / found the intermetallic compounds
formed in this system , and calculated their parameters . Three intermetallic
compounds were formed by peritectic reactions . The Re24Zr6 compound
( x - phase ) has a lattice of the a-Mn type and is formed at 2500° C by the
peritectic reaction L + B = x (B is a rhenium-base solid solution ) . The lattice
parameters of the X - phase vary from a = 9.693 kX for an alloy with 80.6 at . %
Re to a = 9.626 kX for an alloy with 82 at . % Re . This indicates that the
intermetallic compound has a variable composition . The hardness of this
compound is 1000 kg / mm² . The ReaZr compound (1 -phase) has a hexagonal
close- packed structure of the MgZn, type ( a = 5.21 – 5.25 A , C 8.5 - 8.56 Å ,
cla = 1.63 ) . These parameters agree well with the data of / 46 , 47 / ( a =
5.251 Å , C = 8.576 Å, cla = 1.613). The phase diagram indicates that the
RezZr compound is formed at 2450°C by the peritectic reaction L + Rez4Zr5z
RezZr . The hardness of this compound is 1200 kg / mm² . The ZrRe
compound has a structure similar to that of the o - phases (tetragonal lattice
with a = 10.12 Å , c = 5.42 Å , cla = 0.535). The hardness of the ZręRe
compound is 700 – 800 kg / mm2 . This compound is formed at 1900 °C by the
peritectic reaction L + RezZr = Zr Re.
122
Re, at . %
T, ° C 20 40 60 80 d
3000
L
2.300
2.500
Re , at. %
10 20 40 60 2450°
1,6 A
Tigre
3000 2000
2750 HT 1900
L
2.500
1500 1600 °
2000
2025 B
1000
1500
550 °
500 Ia
1000
r
500
46
Ti 20 60 80 Re Zr 20 40 60 80 Re
Re,wt % Re, wt %
a b
Re , at . %
Tool 20 40 60 80
,R=Heal
f
,Rey
Hif
,-HRef
3000
L
ri
2.500
12280925”
(2100925
2000
1500
1309? 15 °
1000
Нf 20 40 60 80 Re
Re ,wt %
с
FIGURE 27. Phase diagrams of rhenium -titanium ( a ), rhenium -zirconium (b) , and
rhenium - hafnium (c) .
The same authors /40 / also found a ReZr2 compound melting at about
1900°C . The region of solid solutions of rhenium in ß- Zr extend up to
15 wt % ( 8 at . % ) Re at 1600°C and narrows to 8 wt % ( 4 at . % ) at the
temperature of the eutectic transformation ( 550 – 600° C ) . The temperature
of the polymorphic a - Zr ß - Zr transformation decreases from 862 to
550 - 600 °C if the content of rhenium is increased . At 550 – 600° C a
eutectic decomposition of the B - solid solution takes place B = a + ReZr2 .
Q-Zirconium dissolves 0.5 wt % Re at 700 – 800° C and 3 wt % Re at 400° C .
The B - Zr solid solution is separated from ReZr2 by a LEB + ReZr2
123
eutectic at 1600° C and 25 wt % ( 12.5 at . % ) Re . In zirconium - rich alloys with
about 5.6 at . % Re and quenched from 1000°C a metastable w - phase was found .
Similar phases were present in systems of titanium with other elements .
The solubility of zirconium in rhenium at temperatures close to their
melting points is not greater than 2 wt % . Characteristic microstructures
of zirconium- rhenium alloys are shown in Figure 28.
FIGURE 28. Microstructure of cast zirconium -rhenium alloys . x 200:

a - 1% Re , a ; b – 40 % Re, a to; C - 60 % Re , o + 1; d – 85% Re, \ + X ; e – 92 % Re, X ;
f - 95% Re , x + B .
Hafnium /30 , 48 — 50 /. A hafnium- rhenium phase diagram (Figure 27 c )

was constructed by Savitskii, Tylkina, Gladyshevskii, Tsyganova, and
Mulyaeva /48 /, who investigated cast alloys by microstructural and X- ray
of the specimens . This system has three intermetallic compounds formed
124
by peritectic reactions . The maximum solubility of hafnium in rhenium at
the melting point is less than 0.5 wt % . The solubility limit on the diagram
is represented by a broken line . The HfRe24 compound with 82.7 at . % Re is
formed at 2975°C by the peritectic reaction Lty HigRe24 (y is a solid
solution of hafnium in rhenium ) .
An accurate determination of the lattice parameters showed that this
compound has a variable composition, and that the lattice parameter varies
from a = 9.682 Å for an alloy with 85% Re to a = 9.708 Å for an alloy with
82.1% Re . The microhardness of this compound is 1130 – 1200 kg / mm² .
According to earlier data of the same authors /49 /, the Hf5Re24 compound
has a parameter a = 9.713 + 0.005 A. The lattice parameter of Hf5Re24 is
close to those of x - phases which have an a - Mn type lattice , and had
previously been found in rhenium- titanium and rhenium- zirconium systems .
When an alloy containing 93% Re was annealed at 1000°C for 150 hours, an
intermetallic compound designated as A was observed, but the structure
has not yet been determined /49 /. However , in a further study on this
system by the same authors /48 / the existence of compound A was not
confirmed . The phase diagram shows that HfRez is formed by the peritectic
reaction L + HfgRe24 HfRez at 2850°C , and that the compound forms a
Laves phase with a crystal structure of the MgZn, type . At 800°C the
lattice parameters of homogeneous alloys vary from a = 5.248 A and cu
8.592 X for alloys containing 66% Re to a = 5.235 Å and c = 8.569 Å for alloys
with 69 % Re . The microhardness of the HfRe, compound is 1500 kg / mmº .
According to / 49 /, the HfRez compound has the following parameters :
a = 5.248 1 0.001 Ă , C = 8.592 0.002 Å, and cla = 1.637 . A HfRez compound
with a MgZn type structure was also observed in / 30 /.
According to /48 /, HfzRez is formed at 2280°C by the peritectic reaction
L + HfRez 3Hf3Rez. The crystal structure of this compound has not yet
been determined , but by comparing X- ray photographs the authors concluded
that the structure of HfzRez is similar to that of Zr2Re (o - phase ) . The
microhardness of the HfzRez compound is 1000 kg / mm² .
It should be pointed out that in an earlier work /40 / the same authors
found a compound, probably with composition HfRe, in a system containing
33 — 40% Re . The composition of HfzRez has been accurately determined
/48 /. At 1250°C hafnium dissolves less than 3 % Re /48 /.
The addition of rhenium to hafnium stabilizes the B - phase and decreases
the temperature of the polymorphic transformation to 1250°C . Since the
temperature of the polymorphic transformation of hafnium has not been
accurately determined /48 /, this part of the phase diagram in Figure 27c
is drawn by broken lines . The region of homogeneity of the B - Hf- solid
solution is 13% Re at 1250°C , and 15% Re at 1500° C . At 1250°C the cubic
modification of alloys with 13% Re undergoes a eutectic decomposition
B = a + HfzRez . At 2100°C alloys with 17 – 18 wt % Re undergo a eutectic
transformationLB+ HfzRez .
A comparison of the hafnium - rhenium phase diagram / 48 / ( see Figure 27c )
with phase diagrams of alloys of rhenium with other metals of group IVA
( titanium , zirconium ) shows that the hafnium - rhenium phase diagram is
similar to the zirconium- rhenium diagram in structure , number of inter
metallic compounds , their structure and mode of formation /44 /.
Taylor /50 / studied cast hafnium - rhenium alloys , and constructed an
approximate phase diagram of this system . According to his data the
system contained the following phases : a rhenium- base B - solid solution
125
containing up to 2.5 % Hf at 2600°C (this agreed approximately with the data
of /48 / ) , an intermediate bertholidea , near the HfRe7 compound with a
lattice of the a- Mn type, apparently formed by a peritectic reaction
L + ReqHf HfRe7 at about 3000°C , and a eutecticLy+ HfRe7with about
2.5% Hf, which lies between the y - phase region and HfRe7. The melting
point of this eutectic has not yet been accurately determined , but is
probably about 2920 + 50°C .
It is also believed /50 / that HfRez is formed by the peritectic reaction
L + y = HfRez (at 2.5 % Hf) , and that a eutectic exists between HfRe, and
HfRez . The bertholide e is formed over a narrow range of homogeneity ,
and corresponds , approximately, to a composition of HfRea . It has the
structure of a hexagonal Laves phase of the MgZn type (C14 ) with a =
5.293 Å, and c = 8.584 Å . This agrees with the data of /30 /. The melting
point of HfRez has not yet been accurately determined , but it is above
3100°C . The bertholide phase o exists over the range of 45.5 – 41.5 % Re,
not far from the Hf11Reg composition , and it is formed at about 2780°C by
the peritectic reaction L + HfRez Hf11Reg. The structure of this phase has
not yet been clarified . The B- Hf solid solution extends over the region up
to 15.5 % Re at the temperature of the eutectic LÈB + Hf11Reg ( 1880°C ) . The
Q - Hf solid solution exists over a very narrow region . The eutectoid ß za +
Hf11Reg exists at 14.5 % Re at 1260° C . The temperature of the polymorphic
transformation in pure hafnium is 1950°C .
It is interesting to compare the two phase diagrams (hafnium- rhenium )
which have been constructed {48, 50 /. This comparison shows that the data
on the formation of solid solutions on the basis of a -Hf, B - Hf, and rhenium
agree well . The above phase diagrams show the existence of three
intermetallic compounds , and in general their concentration limits agree
also .
The chief differences are on the structure of the intermetallic compounds
in the hafnium - rhenium system . A compound with an x- phase (a- Mn )
structure has been described in both papers , but in /48 / it is given the
stoichiometric formula of Hf5Re24 , and in / 50 / it is given the formula
HfRez. A compound with a Laves phase structure (HfRez ) was also
mentioned in both papers . A HfzRez compound with about 40% Re was found
in / 48 /, and is related to the o - phases . According to /50 / the compound
which exists over this range of concentrations is a Laves phase , and it was
given the structural formula Hf11Reg . There are considerable differences
in these papers on the melting point and the method of formation of the
intermetallic compounds . According to /48 /, all three compounds are
formed by peritectic reactions , but according to /50 / one of them (HfRez)
is formed congruently , and this explains why rhenium - rich alloys have a
eutectic . This eutectic was not found in /48 /.
Thorium / 51 /. Niemiec / 51 / carried out X- ray studies on cast and
sintered thorium- uranium alloys , and found a ThRe, compound with a
narrow range of homogeneity, about 66.6 at . % Re , which has a Laves phase
structure with a hexagonal crystal lattice of the MgZn type (C14) . The
lattice parameters of the compound are as follows : a = 5.498 + 0.003 A ,
c = 9.116 1 0.003 A , and cla = 1.658 . The theoretical density of this compound
is 16.83 g /cm , but the density determined by the picnometric method is
16.48 g / cm ' . In alloys containing 10 – 60 at . % Re the ThRe, compound is
in a state of equilibrium with a thorium- base solid solution , and in alloys
containing 75 – 90 at . % Re this compound is in a state of equilibrium with a
126
uranium - base solid solution . The boundaries of both solid solutions have
not yet been determined , but apparently the solubility is low at both sides
and does not exceed 2.5 – 3 at . % , since the lattice parameters of the solid
solutions scarcely change with variation in the concentration of the dissolved
metal . Compounds with the structure of o - phases or X- phases (a - Mn ) ,
like those formed in systems containing metal analogues of thorium
(titanium , zirconium , hafnium ), have not been found in the thorium - rhenium
system .
T.C
3000
Ressly
Resiz
Rest
C ,wt %
0,5 10 15 20 25 1200
7.C
3180
2000 Res acela
L 1132
3000
1100
C
1.
2500 a
16.9 % 1000
1000
Q+ C
2000 950
1500
20 30 Re 20 40 60
Be Cat . % Si,at. %
b с
a
FIGURE 29. Phase diagrams of rhenium -carbon ( a ), mhenium - silicon (b) , and rhenium -germanium (c) .
Subgroup B
Carbon /52 , 53 /. It has been found /52 / that the reaction between
rhenium powder and methane at 2200°C does not lead to the formation of
carbides , but up to 1 % of carbon dissolves in rhenium . If rhenium powder
reacts with carbon monoxide at 470 – 600° C , a compound is formed which
according to /52 ) is a rhenium carbide that decomposes above 1600°C into
its elements . Rhenium dissolves up to 1% of carbon .
Hughes / 53 / constructed the rhenium side of the carbon- rhenium phase
diagram ( Figure 29 a ) by microstructural and X - ray analysis , and by
measuring the hardness and the melting point of cast alloys . This phase
diagram is a eutectic one . It has been found that liquid rhenium can dissolve
large amounts of carbon , but in solid rhenium the solubility of carbon is
only 11.7 at . % at 2480°C , and 4.2 at . % at 1800° C . No rhenium carbides
have been found in this system . This system has a eutectic lying between
the solid solution of carbon in rhenium and pure graphite . It contains
16.9 at . % Re and melts at 2480 + 50°C La
( - Re + graphite) . The phase
diagram of the rhenium- carbon system is similar to that of the carbon
nickel and carbon - copper systems .
127
Silicon /54 – 56 /. Rhenium- silicon alloys prepared by sintering at
1600° C contain a Resi, compound with a tetragonal lattice of the MoSi2 type,
and an ReSi compound with a cubic lattice similar to that of FeSi, Cosi,
NiSi , and MnSi / 54 /.
It has been found that this system contains three silicides /55 /. The
RezSi and ReSi compounds are unstable at room temperature and are
transformed into ReSiz + Re . The structure of RezSi has not yet been
determined .
Knapton / 56 / studied cast specimens by X- ray and microstructural
analysis and by measuring the liquidus temperature . He was the first to
construct an approximate rhenium- silicon phase diagram ( see Figure 29b ) .
The existence of the following three silicides in this system has been
confirmed :
1 ) ReSiz which forms congruently at 1980 ° C and has a tetragonal cii
structure ( a = 3.131 Å , C = 7.676 Å ). These data differ little from the
parameters given in / 54 /: Q = 3.129 Å, c = 7.674 Å. Silicon and ReSiz form
a eutectic at about 1100 – 1200 ° C .
2 ) ReSi is formed by a peritectic reaction between the melt and ReSiz at
about 1800°C , and it has a cubic lattice of the B20 type ( a = 4.774 Å ) . These
data agree with those given in /54 /: a = 4.775 A.
3 ) ResSiz is formed congruently at 1960° C , and it has a tetragonal lattice
of the Cr5Siz (TI ) type and a structure with a = 9.53 and c = 4.81 Ă .
Re5Siz and ReSi form a eutectic at 1820°C . The solubility of silicon in
rhenium is low . Rhenium and ResSiz form a eutectic containing 33 at . % Si
(melting point 1900°C ) . RegSi described in /55 / was not found in /56 /.
The authors of / 56 / believe that the compound given the formula RezSi
in / 55 / has in fact a stoichiometric formula of ResSiz.
Germanium /57 /. A germanium- rhenium phase diagram constructed
from the data of two studies on cast specimens is shown in Figure 29 c .
This system contains a rhenium germanide ReGe , formed at 1132° C by
the peritectic reaction Gel + Res 3 ReGez . On the germanium side a
eutectic is formed at 950°C , which is 8°C lower than the melting point of
germanium . The maximum solubility of rhenium in germanium at this
temperature is believed to be 3 at . % Re .
Tin /20 / . Rhenium is almost insoluble in molten tin .
7. Reaction of rhenium with elements of group V
Subgroup A
Vanadium /58 – 62 ). Greenfield and Beck / 58 / carried out X- ray

and microstructural studies on four cast alloys annealed at 1200° C for
72 hours and found that vanadium dissolves 40 at . % Re , and rhenium
dissolves 38 at . % V. No intermediate phases have been found in this
system .
Tylkina, Povarova, and Savitskii /59, 60 / carried out microstructural
and X- ray studies on cast alloys and measured their hardness and melting
points . They were the first to construct a vanadium- rhenium phase
diagram ( Figure 30 a ) . This phase diagram is of the peritectic type. It has
been found that over a narrow range at 75 at . % Re a o - phase (VRez) is
128
formed with the following parameters: a = 9.36 Å , 4.86 Å, cla = 0.52.
The o - phase is formed at 2490°C by the peritectic reaction L + Bao , where
B is a rhenium - base solid solution . The o - phase has a microhardness of
1800 kg / mm², and it is stable from above 1500°C up to its melting point
( 2490°C ) only . A eutectoid decomposition of the o - phase into a vanadium
base solid solution (a ) and a rhenium- base solid solution (B) (o Za + B) takes
place at 1500°C . Rhenium dissolves not more than 1.5 wt % ( 5 at . % ) of
vanadium . The region of vanadium- base a - solid solutions extends up to
87 wt % ( 65 at . % ) Re , and is almost uninfluenced by temperature. The
temperature at which the alloys consisting of vanadium- base solid solution
starts to melt increases from 1830°C carbon- reduced vanadium to 2290°C
for alloys containing 43 — 45.5 at . % Re . The starting crystals of the a- solid
solution are formed either directly from the melt or by the peritectic
reaction L + oza at 2290°C . The characteristic microstructures of alloys
are given in Figure 31 .
Re , at . %
Re , wt % 20
20 40 60 80 T.C
T/ C 3000
3000
520
L
2600
2600 -2490: 25
12290125 2200
2340
2200
a
1800
1800
-1500
1400
1400
a
1000
1000
V 20 40 60 80 Ae Nb 20 60 80 Re
Re ,at. % Re , wt %
a b
Re, at . %
20 60 80
7,6
3000 2010 + 25
L
2680115
x
of
2500
2 404
2000
x
1500
1000
Τα 20 40 60 80 Re
Re ,wt %
с
FIGURE 30. Phase diagrams of rhenium -vanadium ( a), rhenium -niobium (b )

and rhenium - tantalum ( c ).
129
Approximate vanadium- rhenium phase diagrams , which are very similar
to that constructed in /60 /, have lately been constructed /61 , 62 /. However,
the temperature of the peritectic and eutectic transformations are not given .
Apparently the lack of stability of the o - phase below ~ 1500°C and its
decomposition into two solid solutions explain why the o - phase was not found
in the vanadium - rhenium system studied in / 58 /.
SIGURE 31. Microstructure of vanadium - rhenium alloys:

a -
- 65 at . % Re , after annealing at 1450° C for 6 hr , twins a . x 200 ; b – 71.4 at . % Re ,
cast, a + o. X450; c – 71.4 at.o Re , after annealing at 1450ºC for 6 hr, a + (a + b ) .X450;
d – 75 at. % Re , after annealing at 1450° C for 6 hr , o + ( a + b ) . X450; e-- 90 at . % Re ,
cast, ( +0).X450; f – 90 at. % Re, after annealing at 1450° C for 6 hr, B + (a + B) . x450.
Niobium / 58, 63 – 68 /. Savitskii , Tylkina , and Povarova /63 / studied

niobium- rhenium alloys by microstructural and X- ray analyses , and by
measuring the melting point, hardness and microhardness (see Figure 30 b ) .
They were the first to construct a phase diagram of this system . This system
has a large region of niobium- base a - solid solutions , which extends to about
130
64 wt % ( 46.5 at. % ) Re at the melting point , and narrows with decrease in
temperature to 56 wt % ( 38.5 at . % ) Re at 1000°C . The homogeneous region
of B - solid solutions of niobium in rhenium has been approximately
determined . Apparently rhenium dissolves not more than 2 – 5 wt %
Nb at temperatures close to the melting point. The x - phase
(a - Mn type) is formed by a peritectic reaction between the melt and the
rhenium solid solution at 2520° C ( L + B = x) . The lattice parameter of the
X- phase is a = 9.67 A for alloys containing 83,4 wt % Re , and decreases
with increase in the content of Re to a = 9.61 A for alloys containing 90.9wt %
of rhenium which indicates a wide region of homogeneity of the phase with
82 – 93 wt % (69.5 - 86.5 at . % Re ) . The hardness of the X- phase varies
from ? 050 to 1150 kg / mm² . An X- phase in the niobium- rhenium system has
been described in / 58 , 64 , 65 /.
According to Greenfield and Beck / 58 / the x- phase in alloys containing
60 – 82 at . % Re annealed at 1200°C for 72 hr has a lattice parameter a =
9.67 Å , which agrees well with the data of /63 /.
In /64 / thelattice parameter of the x -phase is given as a= 9.676 Å for
an alloy containing 75 at . % Re . The x- phase was given a structural
formula of NbRe22, and it was concluded that the atoms in the lattice are
ordered . In /65 / it was found that the x- phase of an alloy with 75 at . % Re
has a lattice parameter of 9.638 Å.
Figure 30 b /63 / shows that the niobium - uranium system has a o - phase
with about 56 57 at . % Re formed by the peritectic reaction L + XEO
between the molten alloy and the X- phase at about 2400°C . The o - phase
exists over a very narrow range of concentrations and temperatures , and
is decomposed by a eutectoid reaction o Do + X into a niobium- base a - solid
solution and an x phase. The lattice parameters of the o - phase are as
follows : a = 8.75 Å , c =- 4.06 A , cla = 0.52 . The region of the o - phase is
separated from that of the niobium - base a- solid solution by a eutectic ,
Lato , melting at 2340°C and containing 67 — 68 wt % ( 50 – 51 at . % ) Re .
There are different views on the temperature at which the o - phase can
exist in niobium- rhenium alloys /58 , 65 /. According to /58 / the o - phase
exists in alloys containing about 50 at . % Re and annealed at 1000°C for
120 hr ( a = 9.72 Å, c = 5.07 Å, cla = 0.52 ). The same authors found no o - phase
in alloys annealed at 1200° C , and concluded that this phase is stable below
1200°C only.
According to /65/ the o - phase ( a= 9.78 Å, < = 5.11 Å, cia = 0.523) in an
alloy containing about 50 at . % Re is stable from above 1200°C up to its
melting point . At 1200°C the o - phase decomposes to give an X- phase .
Three new variants of the niobium- rhenium phase diagram were
constructed between 1959 and 1961 /66 -- 68 /. Knapton /66 / based his phase
diagram on X- ray and microscopic studies , and on measurements of the
melting point . His phase diagram agrees fundamentally with that given in
163 ). The system has a region of a niobium- base solid solution extending
to 46 at . % Re at the melting point , and narrowing to 43 at . % Re at 1000°C .
Rhenium dissolves not more than 1.5 at . % Nb . The X - phase in this
system melts congruently at 2800 °C and forms a eutectic with the rhenium
base solid solution containing 88 at . % Re and melting at 2700° C . The region
of homogeneity of the x- phase extends from 63 at . % Re to 87 at . % Re . The
lattice parameter varies from 9.78 Å for an alloy containing 62 at . % Re to
9.619 Ă for an alloy containing 90 at . % Re . The o- phase was found in
cast alloys of this system only . In alloys containing 55 or 60 at . % Re, the
131
o - phase was found together with the X- phase in a niobium- base solid solution ,
and it is believed /66 / that it exists over a narrow range of temperatures
and composition . It is formed peritectically at 2450°C ( 57 at . % Re ) by a
reaction between the melt and the x- phase , and with the niobium- base
solid solution forms a eutectic containing 53 at . % Re and melting at 2400°C .
The temperature at which the o - phase decomposes into a- and x - phases has
not yet been determined .
The niobium - rhenium phase diagram was constructed by Levesque and
Bekebrede /67 ), and differs from that constructed in /63, 66 /. The region
of the niobium- base a- solid solution extends from 40 % Re at 1200 ° C to
42.5 at . % Re at 1290°C . A eutectic between the q- and the X- phases is
formed , containing 47.5 at . % Re and melting at 2380° C . At 1075° C a
peritectic transformation a + x = takes place at 50 at . % Re . The region
of homogeneity of the x- phase extends from 64 – 87 at . % Re .
TABLE 47. Characteristics of the niobium -rhenium system according to different authors
Phase Characteristics /63/ /66 / /67/ / 68 /
Niobium -base a Maximum solubility of rhenium ,

solid solution at. % Re ... 46.5 46 45.5
Minimum solubility of rhenium ,
at. % Re ( 1000 ° C ) . 38.5 43 40 – 42.5 45.5
-
o - phase Homogeneity range , at . % Re ~ 57 ~ 57 54
Temperature of peritectic L + x =
Bo , ° C ~ 2400 2450 2465
Temperature and composition of
the peritectoid a + x BO 1075°
50 %
the eutectic Leato ..... 2340 ° 24000 2435 °
51% 53% 48 %
Temperature of the eutectoid
o e a + x , °C 2340-2200 2162
X - phase Homogeneity range, at . % Re 69.5 63-87 64-87 61.5
86.5 87
Temperature of the peritectic
L + Bex , ° C 2520
the eutectic L Ba + x 2380 °
47.5%
Temperature of the peritectic
L + B #X, ° C ... 27830 27150
88% 88 %
Temperature of formation of the
x - phase (open maximum ), ° C 2800
Uranium -base B Maximum solubility of niobium ,
-
solid solution at .% 5
Minimum solubility of niobium ,

at . " 2 1.5
Note . According to /67/ the a +XP o transformation is peritectoid , but according to /63/ it is eutectoid .
The niobium-rhenium phase diagram constructed by Giessen, Nordheim , and

Grant /68 / is based on microstructural and X- ray analyses and on
measurements of the melting point . It agrees completely with the phase
132
diagram given in /66 /. The system has a wide region of niobium- base a
solid solutions extending to 45.5 at . % Re at 2162°C which is little influenced
by temperature . The region of rhenium- base B - solid solution extends to
4 at . % Nb at 2715°C , and narrows greatly with decrease in temperature.
The X- phase exists over a wide range of concentrations ( 61.5 – 87 at . %
Re ) , and it melts congruently at a temperature very close to the temperature
of the eutectic L 3X + B ( 2715°C , 88 at . % Re ) . The o - phase is formed at
54 at . % Re by a peritectic reaction L + Xao at 2565° C . The o - phase is
separated from the a - phase by a eutectic Laato containing 48 at . % Re
and melting at 2435°C . The o - phase undergoes a eutectic transformation
oza + X at 2162°C .
Some authors consider that the transformations between the o , a, and
x - phases in solid alloys are eutectoid reactions , and others believe that
they are peritectoid .
The four chief variants of niobium- rhenium phase diagrams /63, 66 — 68 /
are described in Table 47. It can be seen that there is good agreement
between the data on the ranges of concentrations over which niobium and
rhenium solid solutions exist , and also o- and X - phases . The main
difference between these variants is in the temperature range of the
existence of the a - phase and the nature of the formation of the X- phase .
We believe that the existence of an open maximum during the formation of
the X- phase and also of the eutectic between the x- phase and the rhenium
base B - solid solution has not been convincingly confirmed by microstructural
analysis , and that the difference between the temperature of the open
maximum and the temperature of the eutectic is so small that this part of
the phase diagram given in /66 , 68 / is not accurate .
Tantalum /40 , 58, 64 , 65, 69–71 /. The tantalum- rhenium phase
diagram ( see Figure 30 c ) was first constructed by Tylkina, Tsyganova, and
Savitskii, from the data of microstructural and X- ray analyses, and of
measurements of the melting point, hardness , and microhardness of the
corresponding alloys . A very wide region of tantalum- base a - solid
solutions was found up to 49 wt % ( 48 at . % ) Re at a temperature close to
the melting point . This region is little influenced by temperature . Rhenium
dissolves less than 5 at . % Ta . The solubility curve of tantalum in rhenium
is tentatively drawn on this diagram . The system has two intermetallic
compounds , o and X. The x - phase has a structure of the a- Mn type, and is
formed by the peritectic reaction L + B = X at 2830°C from the molten phase
and the rhenium- base B - solid solution . The homogeneity range of this phase
extends from 64 — 84.8 wt % (63.5 – 84.5 at . % ) Re . The lattice parameter
of the x- phase varies from a= 9.621 Å for an alloy containing 82.5% Re to
9.65 Å for an alloy with 64.4 % Re . The hardness of these alloys is
1700 - 1800 kg / mm² respectively .
The existence of an X- phase in the tantalum- rhenium system was proved
in / 58, 64, 65 /. According to /58 /, the x- phase exists over the wide range
of concentrations 63 — 75 at. % Re ( a = 9.711 Å). According to /64 /, the
lattice parameter of the x- phase of an alloy with 75% Re is a=' 9.676 Å.
According to /65 ), an x - phase was found in an alloy containing 75 at . % Re ,
with a parameter a= 9.683 Å.
The o - phase of the system ( Figure 30 c ) ( Ta Rez) has a ß - U type structure
(69 ), and a hardness of 1500 kg / mm² ( a= 9.630 Å, c = 4.928 Å , cla = 0.514).
The homogeneity range of the o - phase extends from 54 to 60 at . % Re . The
133
o - phase is formed by the peritectic reaction L + X Zoat 2680°C from the
melt and the x- phase . The tantalum- base a - solid solution is separated from
the o - phase by a eutectic melting at 2400° C and containing ~ 50% Re . The
o - phase of the tantalum- rhenium system was also studied in / 58 , 65 / .
According to / 58 /, the o - phase is formed over a narrow range of concen
trations at about 60 at . % Re ( a = 9.72 Å , 5.07 Å , cla = 0.52 ) . It is
believed /65 / that the o - phase (Ta Rez) is stable above 1200°C up to its
melting point , and that its parameters are : a = 9.809 Å, c = 5.123 A,
cla = 0.523 for an alloy containing about 50 at . % Re . In the same paper / 65 /
an unknown phase with a structure different from that of the tantalum - base
solid solution was found in an alloy containing 25 at . % Re annealed at
1000° C for 7 days .
In a later work Brophy , Schwarzkopf, and Wulff /71 / constructed a
tantalum- rhenium phase diagram by measuring the melting point of cast
alloys , and analyzing them by X - ray and microstructural methods . The
solubility of rhenium in tantalum is 48 wt % at 2460°C and 45 wt % at
1200° C . The solubility of tantalum in rhenium is 5% at 2755° C and 3% at
2010°C . This system has two intermetallic compounds : an x - phase , and
also a o - phase ( a = 9.69 A, cla = 0.52 ) formed at 2740°C by a peritectic
reaction over a narrow range of concentrations ( 59.5 % Re ) which is
decomposed at 2460°C by a eutectoid reaction into a tantalum- base solid
solution . The X- phase (TaRe22) is formed congruently at 2790°C and contains
79% Re . It has a homogeneity range from 65 to 80% Re at 1200°C . The
Q - Ta is separated from the o - phase by a eutectic containing 51 % Re and
melting at 26 90 ° C , and the B- Re is separated from the X- phase by a eutectic
containing 16% Ta and melting at 2755°C . It has been found that the lattice
parameter of the % -phase increases with increase in the content of rhenium .
TABLE 48. Characteristics of the tantalum -rhenium system according to different authors
Phase Characteristics /69 / /71 /
Tantalum - base a -solid Maximum solubility of rhenium , at . % Re 48 47

solution 48 44
Minimum solubility of rhenium , at . % Re
o - phase 54-60 60
Homogeneity range , at.9% Re
Temperature of peritectic L + x = 0 , °C 2680 2740
Temperature and composition of eutectic Leato . 24000 26900
500 % 51 % Re
Temperature of eutectoid o Batx , °C 2460
X - phase Homogeneity range , at . % Re 63.5-84.5 65-80
Temperature of peritectic L + B 2X 2830
Temperature and composition of the open maximum 27900
790% Re
Temperature and composition of eutectic L 2B + x . 2755 °
16 % Ta
Rhenium -base solid 5 5
Maximum solubility of tantalum , ar . % Ta
solution Minimum solubility of tantalum , at . % Ta 3
A comparison of two variants of tantalum - rhenium phase diagrams

( Table 48 ) shows that the concentration regions of the tantalum- and
rhenium - base solid solutions agree well. Both systems contain two
intermetallic compounds , ao- and an x- phase , and the concentration
regions of these agree also . The differences lie in the temperature range
134
of the stability of the o - phase and in the characteristics of formation of the
X - phase . It is clear that the reason for the differences between these two
variants may be that the two alloys studied were not in the same state of
equilibrium . The existence of a eutectic between the X- phase and the
rhenium- base B - solid solution found in /71 / is doubtful. The data of
microstructural analysis are not sufficient to solve the problem , and the
difference between the temperature of the open maximum of the -phase
and the eutectic temperature is very small .
Subgroup B
Nitrogen /47 , 72 , 73 /. Attempts to obtain rhenium - nitrogen compounds

by passing nitrogen over metallic rhenium at 200 – 1000 °C have not been
successful. Rhenium nitride ReN 0.43-4 ( RezN ) was obtained by passing
ammonia over the rhenium salts NH4Re04 and ReCl at 300 – 350° C . The
ReN 0.43-x compound has a face - centered cubic lattice (a = 3.92 Å ) . The
nitride is unstable and decomposes in vacuo at 280°C . An X- ray study of
rhenium alloys containing less than 1 - 2 % of nitrogen showed that the nitride
has a hexagonal lattice . Rhenium nitride ReN 0.34 ( Re3N ) was obtained in /73 /.
Phosphorus /47 , 74 /. Re2P and RePut , have been produced /47 /.
The type of lattice of these compounds is not yet known . It has been found
174 / that rhenium reacts with phosphorus above 750 — 800° C to form Re P3,
ReP2, ReP . (RePitx) and Re2P compounds . The lattices of these compounds
have not yet been determined .
Arsenic /47 , 75 ). The existence of ReAS2.1-2.3 (or Re :As7) with an
unknown lattice has been proved .
Bismuth /76 /. It has been found that sintered rhenium is not wetted
or corroded when held in bismuth at 1000°C for 250 hr . After the test the
bismuth contained 0.006% Re .
8. Reaction of rhenium with elements of group VI
Subgroup A
Chromium /40 , 58 , 64, 77 – 81 /. The literature data on the chromium

rhenium system are very contradictory . In /77 / it was found that the
melting points ( solidus ) of several alloys of the system prepared by
sintering lie between the melting points of chromium and rhenium . The
phase diagram constructed in /78 / shows that these two metals form solid
solutions : the region in the vicinity of chromium is not clearly defined , and
the existence of a peritectic or eutectic is possible . The melting points of
the alloys lie between those of pure metals . No intermetallic compounds
have been found in this system .
Savitskii and Tylkina /40 , 79 / found an intermetallic compound ( RezCra )
in alloys containing 70 – 80 wt % Re . The intermetallic compound formed in
this system has been thoroughly studied / 58 , 64 , 80 /.
135
Re , at. %
7, ° C 20 40 60 80
3000
Re , at . %
20 40 60 80
2600
1. ° C
42350 3000
2261
2200
2600 2570 °
2500
1800 2200
po
a 1850 "
1400 1800
1400
1000
1000
Cr 20 40 60 80RC MO 20 40 60 80 Re
Re , wt % Re , wt %
a b
Re ,at. %
20
40 60 80
7,5
L
3000 2899
2815
2500
2000
1500
1000
20 60 80 Rc
Re, wt %
с
TABLE 32. Phase diagrams of rhenium -chromium ( a), rhenium -molybdenum ( b),
and rhenium - tungsten (c) .
Cast alloys annealed at 1200°C were investigated by the X- ray method

/58 /, and it was found that an alloy containing 63.2 at . % Re consists of a
o - phase with the following parameters : a = 9.23 Å, c = 4.80 Å, and cla = 0.52 .
The o - phase is formed over a very narrow range of concentrations .
According to /64 / the o - phase ( CrRez) has the following parameters :
= 4.83 Å , cla = 0.519, and an electron concentration of 6.6
a = 9.31 A , C =
electrons / atom . An X- ray study of an alloy containing 62.5 at . % Re /80 /
showed that there is no direct indication of the existence of highly ordered
atomic combinations in the o - phase . By microstructural and X- ray analyses
and by measuring the hardness and the melting point of the specimen ,
Savitskii , Tylkina , and Povarova constructed a chromium- rhenium phase
diagram ( Figure 32 a ) , which differs radically from the phase diagram
given in /78 /. According to /81 / the system has a large region ofchromium
base solid solutions with a maximum solubility up to 78 - 80 wt % ( 48.5 —
52 at . % ) Re , which narrows to 68 wt % ( 36 at . % ) Re at 1000°C . At a
temperature equal to its melting point rhenium dissolves not more than 5 wt % Cr.
136
The initial crystals of the chromium - base solid solutions are formed either
directly from the melt or by the peritectic reaction L + 0 B a at 2280°C
between the melt and the o - phase . The o - phase (Cr2Rez ) is formed by the
peritectic reaction L + ß zo at 2350°C between the melt and the uranium
base B - solid solution . The homogeneity range of the o - phase is 83 - 87 wtº
( 57 – 64.6 at . % ) Re , and the lattice parameters are : a = 9.23 Å , c = 4.80 Å ,
cla = 0.52 , which agrees with the data given in / 58 , 64 /. The hardness of this
phase is 1050 — 1170 kg / mm² .
Molybdenum /40 , 58 , 64 , 70 , 79, 82 - 87 /. Savitskii , Tylkina, and
Povarova /82 / were the first to construct a molybdenum - rhenium phase
diagram ( Figure 32 b ) from the data of microstructural and X- ray analyses
and of hardness and melting point measurements . Earlier the same authors
/ 40, 79 / had constructed an approximate molybdenum -rhenium phase
diagram , which was then made more accurate /82 / in the region of the
% -phase .
The molybdenum - rhenium phase diagram ( Figure 32b ) is of the peritecti
type and shows the existence of two intermetallic compounds (o- and X
phases ) . The system has a large region of molybdenum - base a - solid
solutions extending to 58 wt % ( 42 at . % ) Re at the melting point , which
narrows to 46 wt % ( 30.5 at . % ) Re at 1100° C . The molybdenum -base solid
solution is formed either directly from the melt or by a peritectic reaction
at 2500°C between the melt and the B - phase ( L to Ra ) . The liquidus and
solidus of the molybdenum -base solid solution have minima at about 43 -
46% Re and at 2450+ 30° C .
According to Ageev and Shekhtman /83 /, the lattice parameter of the
molybdenum - base solid solution decreases with increase in the content of
rhenium from 3.14 Å for pure molybdenum to 3.12 Å for an alloy containing
53 wt % Re .
The region of rhenium- base ß- solid solutions extends to about 10 wt% Mo
at the melting point , and narrows to 2 – 3 wt % Mo at 1100° C . The o - phase
(MozRez) is formed over the region 68 – 80 wt % ( 52.5 – 67.5 at . % ) Re at
2570°C by a peritectic reaction between the molten metal and the rhenium
base solid solution : L + B BO . The lattice parameters of the o - phase are :
a = 9.54 Å , c = 4.95 Å , cla = 0.52 /83 /; its hardness is 1850 kg / mm², and its
electrical resistivity 3.1 · 10-4 ohm · cm .
The existence of a o - phase in molybdenum - rhenium alloys has been
indicated in several papers / 58 , 64, 70 , 79 , 84 /. According to /70 / the
c - phase has the composition Remo , and the authors of /84 / indicate that the
o - phase of an alloy containing 60 at . % Re has a tetragonal lattice ( a = 9.988 ?
c = 4.983 A ) . According to this work the homogeneity range of the o - phase
extends from 49 — 70 at . % Re . Cast alloys annealed at 1200° C were studied b
microstructural and X -ray analyses / 58 /, and it was found that they contain two
intermetallic compounds : a o - phase with a region of 48 — 67 at . % Re
( a= 9.58 – 9.54 Å , c = 4.96 – 4.95 Å, cla = 0.52) and a phase of the a-Mn type
containing above 79 at . % of rhenium ( a = 9.55 A ) . The authors of /64 / state
that the o -phase has the composition Mo Rez, a tetragonal lattice ( a = 9.57 Å
c = 4.98 Å , cla = 0.52 ) , and an electron concentration of 6.6 electrons / atom .
The phase diagram in Figure 32 b shows that at 1850°C an X- phase with ai
Q - Mn type lattice is formed by the peritectic reaction o + B = x from the
o - phase and the rhenium- base B - solid solution . The homogeneity range is
87 – 90 wt % ( 77.6 – 83.6 at. % ) Re, a = 9.55 Å .
137
Approximate data on the phase diagram were given by Knapton /85 ), and
a corrected version of the same phase diagram by the author of /86 /. The
region of the a - solid solution of rhenium in molybdenum extends from
43 at . % at 2440°C to 29 at . % of Re at 900°C . The solubility of molybdenum
in rhenium varies from 15 at . % Mo at 2500 ° C to 8 at . % Mo at 900 °C . The
o - phase exists over a wide range of concentrations from 52 to 71 at . % Re ,
and it is formed by a peritectic reaction between the rhenium- base solid
solution and the melt at 2520°C . The o- phase has the following parameters :
a = 9.610 – 9.563 Å, 4.994 – 4.980 Å , cla = 0.52. The o - phase and the
mulybdenum- base solid solution form a eutectic containing 50 at . % , which
melts at 2440°C . It is believed that at 1100 — 1150 ° C the - phase decompose :
eutectically into a- and x- phases . The x- phase (a- Mn type) is formed by a
peritectoid reaction between the o - phase and the rhenium- base solid solution
at 1800 – 1850°C . The homogeneity range of the x- phase extends between
76 and 77.5 at . % Re at 1800 ° C , and between 76 and 78 at . % Re at 1200° C .
After annealing at 1200°C the lattice parameter of the x - phase is a = 9.593
9.598 Å .
Dickinson and Richardson /87 / also constructed a molybdenum - rhenium
phase diagram . The region of solid solutions of rhenium in molybdenum
varies from 59 wt % (42.5 at. % ) at 2505° C to 46 wt % ( 29.5 at . % ) at 1200 °C .
The solubility of molybdenum in rhenium varies from 12 wt % (21 at. % ) Mo
at 2645°C to 3 wt % ( 6 at . % ) at 1600° C . The o - phase is formed by a peritectii
reaction between the melt and the rhenium - base solid solution at 2645° C .
The homogeneity range extends from 55 to 67 at . % Re . Between the o- and
the a - phases there is a eutectic containing 65 wt % (about 49 at . % ) Re , which
melts at 2505° C .
The X- phase is forrned by a peritectoid reaction at 2080°C , and contains
86 wt % ( 76 at . % ) Re . The three variants of the molybdenum- rhenium phase
diagrams are compared in Table 49 .
TABLE 49. Characteristics of the molybdenum -rhenium system according to different authors
Phase Characteristics /81 / /87/ / 86 /
Molybdenum - base a Maximum solubility, at . % Re 42 42.5 43
solid solution Minimum solubility , at . % Re 30 29.5 29

Temperature of peritectic L + 0 2Q , °C . 2500
o - phase Homogeneity range, at . % Re 52.7-67.5 55-67 52-71
Temperature of peritectic L + 2O , °C . 2570 2645 2520
Temperature of eutectic L = ato, ° C 2505 2440
X - phase Homogeneity range, at . % Re 77.7-83 76 76 - 79
Temperature of peritectoid o + b x , °C . 1850 2080 1850
Rhenium -base B - solid Maximum solubility, at . % Mo 17 21 15
solution Minimum solubility, at . % Mo 5 6 9
It can be seen from this table that the concentration ranges of the
individual phases given in the three variants of the molybdenum - uranium
phase diagrams agree well . The main difference is that the authors of
/86 , 87 / maintain that the o- and a - phases form a eutectic , but according
to /82 / the a - phase is formed peritectically from the o - phase . We believe
that microstructural analysis does not confirm the existence of a eutectic in
this region .
138
Tungsten /40, 58 , 65, 70 , 84 , 88 - 90 /. Becker and Moers /88 /
constructed the liquidus curve of the rhenium- tungsten system , and found an
intermetallic compound Re3W2 with a narrow homogeneity range ,
corresponding to the maximum on the liquidus curve at 3007 50°C . This
compound forms two eutectics : with the tungsten- base solid solution
containing 50.6% Re (melting point 2892°C ) , and with the rhenium- base
solid solution containing 67.5 % Re (melting point 2822°C ) . X- ray studies
failed to indicate any solubility of Re3W2 in rhenium , but it was found that
Re3W, has a limited solubility in tungsten .
Tentative data on the tungsten- rhenium phase diagram were published by
Savitskii and Tylkina /40 /, and a corrected variant by Savitskii , Tylkina ,
and Shishkina /89 /. The tungsten- rhenium phase diagram first constructed
is peritectic . It has been found that this system has two intermetallic
compounds (a o- and an X- phase ) . The system (Figure 32 c ) also has a wide
region of tungsten- base a- solid solutions , which extends up to 45 % Re at a
temperature close to the melting point , and narrows to 32% Re at 1100°C .
It can be assumed that further studies on alloys consisting of solid solutions
of rhenium in tungsten which have been wrought and subjected to prolonged
high temperature anneals will make it possible to correct the position of the
solubility boundary and to determine whether the solid solution can
decompose . This is also true of the solid solution of rhenium in molybdenum ,
chromium , vanadium , niobium , and tantalum . The o - phase ( Re3W2 ) is
formed at 2890°C by a peritectic reaction between the melt and the tungsten
base solid solution: La Bo . The o - phase has the following lattice
parameters: a = 9.53 Å, c = 4.95 Å, cla= 0.52 . Its hardness is 2000 kg / mm²,
and its homogeneity range extends from 40 to 66% Re . It can be seen from
the phase diagram in Figure 32c that the region of the rhenium - base
B - solid solution is wide and extends to 15 % W at the melting point , and
narrows to 12% W at 1100°C . The rhenium- base solid solution is separated
from the o - phase by a eutectic containing 75% Re , which melts at 2815° C
( Leo + ß ) .
It has been found that this system also has an x - phase with a structure of
the Q - Mn type ( a = 9.57 Å) , a hardness of 1500 kg/ mm², and a narrow
homogeneity range at about 75% Re . The X - phase is formed at 1050°C by a
peritectoid reaction between the o - phase and the rhenium- base solid solution
( o + B #X ) . The characteristic microstructures of the tungsten- rhenium
alloys are shown in Figure 33 .
The o - phase of the tungsten- rhenium system was also studied in /58, 64,
70, 84 /. According to /70 /, W2Rez has a o - phase structure . The homogeneity
range of the o - phase (RezWz ) which contains 55 – 65 % Re was studied /84 /,
and it was found that an alloy containing 59.5 at . % Re has the following
lattice parameters : a = 9.645 Å , c = 5.038 Å.
It has been found that specimens annealed at 1200°C contain two inter
metallic compounds: a o - phase (W2Rez) with 37 58 at . % Re ( a = 9.55 A,
c = 4.96 A ) and an x -phase (type a - Mn ) from 73 at . % Re to almost pure
rhenium ( a= 9.588 A) / 58 /.
According to /64 /, the o - phase has a tetragonal lattice with the following
parameters: a = 9.59 A, C = 5.00 A, cla = 0.52, and an electron concentration
of 6.6 electrons / atom .
139
b
FIGURE 33. Microstructures of tungsten -rhenium alloys:

a - cast tungsten , 200; b -40% Re, cast, a + 0.X 200 ; c – 50 % Re , cast, o. X200 ;
d – 72 % Re , cast, 8 + B . X340 ; e – 72 % Re , annealed at 1000 ° C for 200 hr , o + X.X200;
f - Re , cast . X 200 .
Dickinson and Richardson / 90 / also constructed a tungsten- rhenium phase

diagram . The solubility of rhenium in tungsten decreases from 37% Re at
3000°C to 28% Re at 1600°C . The solubility of tungsten in rhenium decreases
from 20% W at 2800°C to 11% W at 1600°C . The o - phase is formed at 3000°C
by a peritectic reaction, and has a homogeneity range from 43.5 to 71 wt % Re
above the temperature of the peritectoid and from 43.5 to 66% Re below the
temperature of the peritectoid . The x- phase is formed at 2125°C by a
peritectoid reaction between the o- and B - phases at about 73% Re . The
o - phase is separated from the B- phase by a eutectic containing 74 % Re and
melting at 2825°C .
A comparison between that data of /89 / and /90 / (Table 50 ) shows that
the two variants of the phase diagram agree well. There is a difference
only in temperature of the peritectoid reaction o + B = X .
140
TABLE 50. Characteristics of the tungsten - rhenium system according to different authors
Phase Characteristics / 89/ /90/
Tungsten -base a - solid Maximum solubility, at . % Re 37 at 37 at

solution 2280 ° 30000
Minimum solubility , at. % Re 32 at 28 at
11000 16000
o - phase Homogeneity range , at. % Re 45-66 43.5-71
° C 2890 3000
Temperature of peritectic L + a po,
X - phase 75 73
Homogeneity range , at . % Re
Temperature of peritectoid transformation o + B X ,°C 1050 2125
Rhenium - base s - solid Maximum solubility at 2800° C , at. % W 15 20
solution Minimum solubility , at . % W 12 at 11 at
11000 16000
Temperature and composition of eutectic L 20 + B . 2815 ° 2825 °
75 % 74 %
Uranium / 91 – 94 /. It has been found /91 / that the reaction between

rhenium and uranium at 1250°C leads to the formation of a eutectic . A
uranium - rhenium phase diagram for the whole range of concentrations was
constructed / 93 / from the results of X- ray, microstructural, and thermal
analyses , and by measuring the melting points of cast alloys (Figure 34 a ) .
The system has two intermetallic compounds . A URez intermetallic
compound ( 61% Re ) with a Laves phase structure (C14 ) /92 / is formed from
the melt at 2200°C , and undergoes an allotropic transformation (orthorhombic
structure ) at 180°C . The U2Re compound has been found / 94 /, and is
formed at 750°C from y - U and URe, as the result of the peritectoid reaction
Y - U + URE, BU Re. The URez compound forms a eutectic with the solid
solution of uranium in rhenium containing 65.5 % Re (melting point 2105 ° C ),
and with the solid solution of rhenium in y- U containing 10.5% Re (melting
point 1105°C ) . The UzRe compound forms eutectoids with solid solutions of
rhenium in ß - U at 681 °C (containing 6% Re ) and with a - U- base solid
solutions containing 1.4% Re at 643°C . The maximum solubility of rhenium
in a - U is 0.4% at 643° C , in ß - U it is 1.9 % Re at 681 ° C , and in y - U it is
6 wt % Re at 681° C , and 7% Re at 975°C . At room temperature rhenium
dissolves 0.6% U, and somewhat more at 2000°C . Alloys of B - uranium
containing more than 1,2% of rhenium and alloys of y- uranium containing
more than 7% of rhenium can be readily supercooled to room temperature .
If y - U alloys containing more than 7% Re are rapidly cooled , a direct
poa ' transformation takes place (a ' is a uranium- base supersaturated solid
solution ) .
Plutonium / 95 /. There are reports on the existence of Purez in the
Pu - Re system , with a Laves phase structure of the MgZn, type, and
parameters a = 5.396 X, C = 8.729 Å, cla = 1.618 .
Subgroup B
Oxygen /96 /. Rhenium forms a number of oxides with oxygen:

Re04 (Re208), Re207, ReO3, Rez05, ReO2, Re2O3, Reo (Re2O2 ) , and Rezo .
141
Re, at . %
20 40 60 80 Re, wt %
1, C 20 40 60 80
1, ° C 3000
3000
-Uhey
L
2600
2500 1, °C Re, at . %
—
əy'n
12 16
2105 1000
2200
2000
900
1800
1500
800
1105 ° 750 ° 1410 °
ery 1400
73750
1000 681
681 750 ° 700 A 12100
‫م‬. - Mn
Pir - Mn
500 6430 600
64 ° 1000FA -Mn 925°
180 ° fa - Mr
500 600
U 20 40 60 80 Re U 4 12 Mn 20 40 60
Re , wt % Re , wt % Re at. %
a b с
FIGURE 34. Phase diagrams of rhenium -uranium (a , b ), rhenium -manganese (c) .
Sulfur /47 , 96 , 97 /. Sulfur forms ReS2 and ReqS7 sulfides with rhenium .
The type of crystal lattice of these is unknown . The ReS2 compound has a
monoclinic - deformed defective structure .
Selenium / 96 , 97 /. Rhenium forms the following rhenium selenides
with selenium : ReSe2 which has highly oxidizing properties , and the unstable
RezSe 7 selenide which decomposes at 300°C in vacuo into ReSex and
selenium .
9. Reaction of rhenium with elements of group VII

Subgroup A
Manganese /40 , 98 , 99 /. Savitskii, Tylkina, Kirilenko and Kopetskii

/98 / constructed a peritectic manganese- rhenium phase diagram (Figure 34c
from studies on cast alloys by microstructural and X- ray analyses and by
measurements of their melting points . The phase diagram extends from
0 – 80 at . % Re . The o - phase in this system contains 52.24 at . % ( 78.77 wt % )
Re , and is formed by a peritectic reaction between the melt and solid
rhenium , apparently at a temperature above 1700° C . The lattice parameters
of the o - phase of an alloy containing 22.9% Re are as follows : a = 9.11 xX ,
c = 4.92 KX, cla = 0.54 .
Earlier, Ageev , Savitskii, and co- workers / 99 / found that the o - phase
of the manganese- uranium alloy containing 52.24 at . % Re ( a = 9.14 « X ,
с
4.75 KX, cla = 0.52 ) had a hardness of 1000 kg /mm12 .
The phase diagram in Figure 36 c / 98 / shows that the q- Mn- base solid
solution contains up to 5.5 at . % ( 16 wt % ) Re . The lattice parameter of the
Q- Mn- base solid solution varies from 8.894 KX for pure manganese to
8.924 “X for an alloy containing 5.56 at . % Re , which agrees with the data
142
by the same authors in /40 /. It has been found that the s- Mn- base solid
solution is formed at 1410° C by the peritectic reaction L + B - Mn . The
peritectoid transformations in this system are as follows : 6 +0 By at
1315° C , y + JRB at 1210°C , and ß + JBQ at 925° C . It should be pointed
out that the temperature of the last peritectoid reaction agrees well with
that given in /40 /, according to which the temperature of the polymorphic
Q 3 transformation in alloys containing 24.6 wt % Re is 910°C .
Technetium /100 /. An X- ray analysis of cast and annealed alloys
showed that technetium forms a continuous series of solid solutions with
rhenium , with a hexagonal close - packed lattice .
Subgroup B
Fluorine , chromium , bromine and iodine 196 /. With these

elements rhenium forms the following compounds: ReF4, ReF6; ReCl3,
( ReC14 ) , ReCls, ( ReC16) , ( ReC17); ReBrz, ReBr4, and Rel4.
10. Reaction of rhenium with elements of group VIII
Iron /64 , 99, 101 , 102 /. Eggers / 101 / constructed an iron - rhenium
phase diagram (up to 50 wt % Re , Figure 35 a ) from data of structural and
thermal analyses and measurements of the hardness of the specimens . This
system has highly homogeneous phases: an e - phase (FezRez ) stable up to
room temperature and containing about 70 wt % Re , an n - phase ( Fe3Re ) which '
forms a melt and decomposes by a eutectoid reaction at 51.5 wt % Re and
1205 ° C into y- and e - phases . The s - phase is formed at 1540°C by a peritectic
reaction at 7 wt % Re between the melt and the n - phase . The 6 - phase
decomposes eutectically into y- and n- phases at 21 wt % Re and 1375° C . The
solubility of rhenium in the r - phase varies from 14% Re at 1375° C to 40% Re
at 1205°C , but later it decreases to 37% Re at 895°C . The a - phase can be
formed from ar - phase or by a peritectic reaction between the y- and e - phases
at 45 wt % Re and 895° C. The temperature of the y - pa -phase transfor
mation is a minimum of 800°C at about 27% Re , and the binary (a + y ) region
is narrow . At room temperature the a - phase dissolves 29 % Re . The
temperature of the magnetic transition decreases from 768° C for pure iron
to 680°C for an alloy containing 30% Re .
It has been found /64 / that the FezRez compound is a o - phase ( a= 9.08 Å,
c = 4.72 Å, cia = 0.52) with an electron concentration of 7.6 electrons / atom .
It has been found / 99 / that an alloy with 73.55 wt % Re contains a o - phas
with the following parameters: a = 9.02 Å, c = 4.69 Å, cla = 0.52. The micro
hardness of the o - phase is 1230 kg / mm² . According to / 102 /, the system
has another intermetallic compound FezRe3, with a structure (or super
lattice ) of the B- Mn type ( a = 6.43 Å) . This system should be further
investigated .
143
2.500
Re, wt % 7,66
Fragegy
20 40 60
1 ,° C 2000
1600
( 1527 ) 1540 ° 1500

b
Lol
1400
1000
E
12050
1200 500
24
Y
1000 Co 20 40 60 80 he
Re,wt %
3000
895 °
L
800
2000
680 °
Magnetic
600 transition a
1000L
fe o 20 Ni 20 40 60 80 Re
Re , at . % Re ,wt %
a с
FIGURE 35. Phase diagrams of rhenium -iron ( a ), rhenium -cobalt (b ),

and rhenium -nickel ( c ) .
Cobalt /40 , 103 /. Koster constructed a rhenium- cobalt phase diagram

/103 / from data of thermal , microstructural, X- ray, and magnetic analyses
( Figure 35b ) . It has been found that the system contains a continuous series
of solid solutions with a hexagonal lattice . The temperature of the poly
morphic yze transformation increases from ~ 500°C for pure cobalt to the
temperature of the peritectic . The equilibrium line above 1200°C has been
drawn on the phase diagram tentatively . Rhenium causes a linear decrease
in the Curie points Oy and 0. The boundary of the ferromagnetic region lies
at 25 wt % Re . It has been found that the lattice parameters of all alloys lie
on a straight line which connects the lattice parameters of both components .
Savitskii and Tylkina /40 / measured the melting points of alloys over
the whole concentration range . They also confirmed the existence of a
continuous series of solid solutions between rhenium and the hexagonal
modification of cobalt . They measured the hardness of the alloy and found
that it has a maximum at about 70% Re .
Nickel / 40, 104 / . Pogodin and Skryabina / 104 / constructed a rhenium
nickel phase diagram of the peritectic type ( Figure 35 c ) from data of thermal,
microstructural , and X- ray analyses . Both metals form limited solid
solutions . No intermetallic compounds have been found in this system . The
region of nickel- base solid solutions extends up to 40 wt % Re at 1200°C ,
and narrows to 31 wt % Re at 1000°C . At 1200°C rhenium dissolves up to
26 wt % Ni. The nickel- base solid solution is formed by a peritectic reaction
144
between the melt and a rhenium- base solid solution containing 63 wt % Re
at 1600°C .
Measurements of the melting point and hardness , and a microstructural
analysis of this system /40 / confirm the data given in /104 /. The rhenium
side of this system should be further investigated .
at . % Re, at . %
20 40 60 40 60 80
Ru
a
80 d Os
2500 3100
20006 3000
o
a a
o
1500 29006 o O
o
1000 22 2800
Ru Re Os Re
30 60 50 60
b e
Rh 2620 : 25 80
2800
2500 2500
OOO o lo O o
2000 2000 o 0000 o
O
0 0 00000
1500 a B
a 1500
B
1000 orde 101 10000 100 000 OLO
Rh codedRe Re
40 60 80 40 60 80
с f
Pd PC
2500 2500
2450 °
2000 2000
1650 °:25
1500 1500
a B
a
10000 costo 1000
1 1
Pd 20 40 60 80 Re Pt 20 40 60 80 Re
RB,wt % Re, wt %
FIGURE 36. Phase diagrams of rhenium -ruthenium ( a),
rhenium - rhod ium ( b), mhenium - palladium ( c), rhenium
osmium ( d), rhenium -iridium (e), and rhenium -platinum ( f).
Ruthenium /105 /. Savitskii, Tylkina, and Polyakova /105 / constructed

a ruthenium- rhenium phase diagram from the data of microstructural and
X- ray analyses and measurements of the hardness and melting point of cast
alloys . With rhenium ruthenium forms a continuous series of solid solutions
over the whole range of concentrations . The melting points of these alloys
increase smoothly from the melting point of ruthenium ( 2250°C ) to the
melting point of rhenium ( 3170°C ) . The hardness of cast and annealed
rhenium- ruthenium alloys has a gently sloping maximum at about 30 — 40 wt %
Re . The lattice parameter of the solid solution (hexagonal close -packed
lattice ) increases smoothly with increase in the content of rhenium
(Figure 36 a ) .
145
FIGURE 37. Microstructure of rhenium -palladium alloys. X200:
a - palladium ; b – 5 % Re; c -25% Re ; d – 40 % Re; e – 999 Re .
Rhodium 106 /. Tylkina, Tsyganova , and Savitskii constructed a

rhodium- rhenium phase diagram from studies by microstructural and
Y- ray analyses , and by measuring the melting points , hardness , and
microhardness of cast alloys ( Figure 36 b ) . This diagram is of the peritectic
type and has limited solid solutions . At 2620 + 25°C a peritectic L + B Ba
transformation occurs , where a and B are rhodium- and rhenium-base
solid solutions , respectively. At 1000°C rhodium dissolves 19 wt %
( 12 at . % ) Re . With increase in the Re content , the lattice parameters of
the rhodium- base solid solutions decrease from 3.80 Å for pure rhodium to
3.64 Å for an alloy containing 12 at . % Re . The region of rhenium- base
solid solutions extends up to 15 wt % ( 24 at . % ) Rh .
Palladium / 106 , 107 /. Tylkina, Tsyganova, and Savitskii /106 /
constructed a palladium- rhenium phase diagram from data ofmicrostructural
and X- ray analyses and measurements of the melting point and hardness of
alloys and the microhardness of the structural components of cast alloys .
146
The palladium - rhenium phase diagram (Figure 36 c ) is of the peritectic
type and has two limited solid solutions . No intermetallic compound has
been found in this system . Characteristic microstructures of these alloys
are shown in Figure 37. At 16 50° C a peritectic transformation L + B BQ
takes place , where a and ß are palladium- and rhenium- base solid solutions ,
respectively . The solubility of rhenium in palladium is up to 19 wt %
( 11 at . % ) Re . With increase in the content of rhenium the lattice parameter
of the palladium - base solid solution decreases from a = 3.882 Å for pure
palladium to 3,65 A for an alloy containing 11 at . % Re . This agrees with
the data of /107 /, in which palladium alloys containing up to 45 wt % Re
were studied by microstructural and X- ray analyses and by measurements
of hardness , thermoelectromotive force (TEMF ) and electrical resistivity .
The region of the rhenium- base solid solution on the phase diagram has
been drawn tentatively, since alloys with more than 1 % Pd could not be
obtained .
Osmium /108, 109 /. Tylkina, Polyakova, and Savitskii / 108 /
constructed an osmium - rhenium phase diagram ( Figure 36 d ) from data of
microstructural and X- ray analyses and by measuring the melting point and
hardness of the alloys . With rhenium , osmium forms a continuous series
of solid solutions . The temperature of the solidus increases smoothly from
the melting point of osmium ( 3050°C ) to the melting point of rhenium
( 3170°C ) . The hardness of cast and annealed alloys varies , and a flat
maximum is formed at 30 — 40 % Re . An X- ray analysis has shown the
presence of a solid solution with a hexagonal close- packed lattice . The
parameters of this phase increase smoothly with increase in the content of
rhenium . Three osmium- rhenium alloys were investigated by X- ray
method . The lattice parameters and the cla ratios are given in /109 /. The
data of both papers agree approximately .
Iridium / 106, 110 /. Iridium- rhenium alloys were studied in /110 /
to determine whether they can be used for thermocouples . By testing
sintered alloys it was found that at low temperatures iridium dissolves
about 5 wt % Re . The solubility of iridium in rhenium is up to 60 wt % at
2000°C and 50 wt % at low temperatures .
Tylkina, Tsyganova, and Savitskii / 106 / constructed an iridium
rhenium phase diagram of the peritectic type (Figure 36 e ) . They indicated
the existence of two limited solid solutions by microstructural and X - ray
of cast specimens . No intermetallic compounds have been found in this
system . At 2800°C a peritectic reaction L + B za takes place , where a
and B are iridium- base and rhenium- base solid solutions , respectively .
The solubility of rhenium in iridium is 35% Re at the temperature of the
peritectic and decreases to 28% Re at 1000°C . The solubility found in / 110 /
is higher than that given in / 106 /. This difference is apparently due to the
different methods of preparation of the alloys . The lattice parameter of
the solid solution changes from 3.8312 Å for pure iridium to 3.65 Å for an
alloy containing 28% Re . The region of single- phase rhenium- base solid
solutions extends to 45 % Ir at 2800° C , and narrows to 40% Ir with decrease
in temperature .
Platinum / 111 - 113 /. The thermoelectric properties of alloys
containing up to 20 wt % Re , their microstructure and ductility, were
studied in / 111 /. All the alloys investigated are in the region of platinum
base solid solutions . It has been found that rhenium appreciably increases
the electrical resistivity and the thermoelectromotive force of the alloys .
147
pounds
table
periodic
the
elements
with
rhenium
of
com
intermetallic
formation
temperature
nd
aparameters
sattice
Composition
51.
,lTABLE
tructure
Temperature lattice
crystal
of
Parameters
Xe
R
- Compounds Homogeneity of
formation
, lattice
crystal
of
Type References
system formed Re
,%
range a,Å
°C A4, cla
Hydrogen HRe /18

Lithium Lire /19
Beryllium Bezze cubic
-centered
Face 11.561 /25
Be
Re 91.18
wt
% Hexagonal
Mg2n
the
of
,type 4.345 7.101 1.631 /23
30
—0
4at
.% 1>840 The
same /26
Bezore Cubic 11.52 /24
11.533 2/ 7
Scandium Sc
Rez MgZn2
the
of
Hexagonal
type 5.270 8.590 1.630 /28
2030 The
same 5.271 8.592 1.630 tt
Scgre
za 2570
* Cubic
the
a
ofn
-M
type 9.6448 tt
9.65 /28
Yttrium Re2Y 66.6
.%
at ,type
MgZn
the
of
Hexagonal 5.39 8.819 1.634 /30
2520 The
same 5.397 8.824 1.635 /29
148
Gadolinium GdReq 5.412 8.827 1.631 tt
Terbium TbRez 5.397 8.797 1.63 ft
Erbium Errez 5.363 8.758 1.633 tt
Lutetium Lurez 5.336 8.721 1.634 a/30
Boron -
865
-yat
.%phas
0 e Tetragonal 5.47 4.73 /31
at
.%
€-66.7
phase 2.97 13.8 /31
Y'-pat6<
.%0
hase /31
ReB typ
TiBe 6.12 3.06 4.56 /34
ReB2 .%
at
33 Hexagonal 2.900 7.478 /33
RezB Orthorhombic /32
ReqB3 Hexagonal /32
ReB3 Hexagonal /32
Aluminum Al2Rez wt
90
% 2000 Cubic
the
a
-M
ofn
type 9.58 3/, 56
)(x-phase
5Rey
–
%
)4(AIwtRe05l 1590 /,356
AlzRe 77.5
%
wt 1485 MType
, 02A1
W2A1 ,3/ 65
Alize %
wt
37 600 cubic
M012A1
, 12A1
WType 7.528 ,3/ 658
IARe CѕСІ
Type 2.88 /37
AlRe Triclinic 9.13 1b=3.8
&= 5.16 /38
"@14 Y. 103.51
Titanium 24TisRe wt
95
% 2750 Cubic
the
a
-M
ofn
type /41
)(x-phase 9.59 /42
Zirconium Rez4Z15 %880
-2
.at *
2500 The
same 9.626-9.693 /,445
)(x-phase
Req2r 2450 MgZn
the
of
Hexagonal
,type -5.25
5.21 8.5-8.561.63 /,454
)-p(hase 5.251 8.576 1.613 / 67
/,4
ReZ12 *
1900 Tetragonal
the
B-Utofype 10.12 5.42 0.535 /,445
)(o-phase
Hafnium HfgRe
24 80
-2
8at
.% 2975
* Cubic
the
of
-M
an
type 9.682-9.708 ,49
/748
)(x-phase
HfRey *
3000 Hexagonal
MgZn
the
,tof
ype 150
/
p(a-) hase
HfRez *
2850 The
same 8.592-8.569
5.248-5.235
1.637 /,4/489
HfRez 3
> 1001 5.293
8.584 /50
HfzRez at33
—
4.%0 *
2280 o-hase
the
of
ZręRe
ptype /,498
Hfu
Res 41.5
-5.5
4at
.% *
-2780 unknown
Structure /50
Thorium ThRez 66.6
at
.% Hexagon
the
tMgZn
,of
ype al 5,498 9.116 1.658 /51
p(a-) hase
Silicon Siz
Re at
33
.% 1
1980 C11
Tetragonal 3.131 7.676 /56
Re
Si %50
.at 1880 B20
Cubic 4.774 /54,56
149
RegSiz at
.~2
6% †
1960 Tetragon
the
of
Crg
type
Sig al 9.53 4.81 /156
Rezsi /55
Germanium ReGez at33
.% *
1132 /57
Vanadium )(o-pVRe
hase
z .%
at
75 2490 9.36 4.83 0.52 /159
,60
Niobium Nb
Reza 69.5
-
86.5
at
.% *
2520 the
Cubic
-M
a
ofn 9.61-9.67 163
/
I
p)(x-hase 9-(823
%)wt
The
same 9.67 /58
75
at
.% (6)
9.67 /64
"75
.at 11 9.638 /65
63
at
87
.% 2800 9.619-9.78 /66
8
-
at
.%
-7
61.5 27151 /68
NbRe -
.56
%at
57 *~2400 the
of
tTetragonal
B-Uype 8.75 4.06 0.52 /63
p(o-) hase .50
at
% The
same 9.72 5.07 0.52 /58
at
50
.% 9.78 5.11 0.523 /
165
57
at
.% 2450 /66
)(51ontinued
CTABLE
lattice
crystal
of
Parameters
R
-
Xe Compounds Homogeneity of
Temperature lattice
crystal
of
Type References
system formed ,%e
Rrange ,°C
formation 0
Å
,a cla
lum
Tanta TaRezz 862
at
.%–6.5 2830 Cubic
the
of
M n
-atype 9.621-9.65 /69
-
)(x-phase –8(673
%)wt
%63
–75 The
same 9.711 /58
at
75
.% (6)
9.67 /64
75
.%
at 9.683 /
165
65 80
wt
% 1
2790 11 9.80–9.62 /71
Ta
Reg 6
-
54
.%
at0 *
2680 Tetragonal
B-U
tthe
ofype 9.630 4,928 0.514 /69
p-(o) hase 6~
.0
at
% The
same 9.72 5.07 0.52 /
158
(9)
9.80 (3)
5.12 0.523 /
165
59.5
at
.% 2740 The
same 9.69 0.52 /
171
Nitrogen X-ReN043 Cubi
cface
- entecred 3.92 /72
ReNo.34 /73
Phosphorus Re2R, e P
)x+P1 known
not
lattice
of
Type /
147,74
150
,RReP
eP32
Arsenic -2.
ReA352.1 known
not
lattice
of
Type /147,75
Chromium CrąRez 657
–4
.at
% *
2280 Tetragonal
the
of
type
B-U 9.23 4.80 0.52 158,81
/
p(o-) hase –
8( 73
%)wt
9.31 4.83 0.519 /
164
Molybdenum Mo
Reg 652.5
-7.5
.%
at *
2570 type
B-U
the
of
Tetragonal 9.54 4.95 0.52 /,823
p(o-) hase %)(68-80
wt
at
749
.%–0 The
same 9.988 4.983 //84
648
at
."-7 9.58-9.54 -4,95
4.96 0.52 /58
60
at
.% 9.57 4.98 0.52 /64
at
.71
% 52 2520 9.610-9.563 -4.980
4.994 0.52 8/ 6
6at55
-7
.% 2645 10 /87
pX- hase 77.6
-3.6
8at
.% 1850 Cubic
the
of
M n
a-type 9.55 /82,83
9wt
%)-(807 The
same
79
.
at
% 9.55 /58
76
-7,5
7at
.% 1800 9.593-9,598 /86
1850
** 11
76
.%
at *
2080 17 /87
;)(86
wt
Tungsten RegWz %6
6
-
40 2890 B-Utype
the
of
Tetragonal 9.53 4.95 0.52 /89
p(o-) hase -65
55
% The
same 9.645 5.038 0.52 /84
58
-
37
% 9.55 4.96 0.52 /58
9.59 5.00 0.52 /64
43.5
71
% 3000 10
/90
)(x-phase .%
at
75 **
1050 Cubic
the
a
-M
ofn
type 9.57 /89
at
7.%>3 The
same 9.588 /58
.73
at
% 2125
** /90
Uranium URez 61
wt
% 22001 above
the
Zn
Mg
Hexagonal
,tofype 9/, 23
)(a-phase orthorhombic
below
°C,and
180
°C
180
UzRe ** 0
75 /,934
-
Plutonium Purez MgZn
the
of
Hexagonal
,type 5.396 8.729 1.018 /9a 4
Oxygen )( ezog
RReO4 known
not
lattice
Type
of 195
/
Rez07
Reo
,
Rez08
Regos
ReO2
151
Rezo
,
Reo
RO(,) 2e
Rezo
Sulfur Re
Sy -deformed
Monoclinic
defective /47,95-971
-
-
structure
ReqS7 not
known
lattice
of
Type
Selenium Res
Rey
Se ez The
same /95-97
Manganese o-phase 52,24
.
at
% >700
1 Tetragonal
the
B-Utofype 9.14 4.75 0.52 /99
,7(7wt
%87 The
same 9.11 4.92 0.54 198
/
Fluorine ReF4
,R eF /95
Chlorine ReCl
, 195
/
ReC14
1
ReCls
1
ReCle
1
,ReCl
1
Bromine ReBr3
,ReBra 195
/
lodine Rela /95
1
5511
)(51ontinued
CTABLE
lattice
crystal
of
Parameters
R
X
-e Compounds of
Temperature
Homogeneity
lattice
crystal
of
Type References
system formed ,%e
Rrange ,°C
formation
Iron FezRez ~
70
wt
% /101
-
-
p)•(o- hase
FezRez 73.55
wt
% tTetragonal
the
of
B-Uype 9.08 4,72 0.52 /64
-
p(e-) hase 9.02 4.69 0.52 /99
152
Fegre ~51.5
wt
% not
known
lattice
of
Type /101
-
)-p(nhase
RezFez Structure
of
type
-M
Rn 6.43 /102
1
-
-
reaction
.by
aeritectic
pformed
Compound
.
preaction
.Compound
aeritectoid
by
formed
ompound
Ccongruently
†.melts
Khamidov
. nd
ylkina
aTSavitskii
,ff
by
Data
Tzhebyatovskii and Berak / 112 / constructed a platinum- rhenium phase
diagram from data on X- ray and microstructural analyses and measurements
of the hardness and melting point of cast specimens . This phase diagram
is of a peritectic type (Figure 36 f), and shows the existence of limited
solid solutions . At 2450°C a L + B Ba peritectic transformation takes place
(a and B are platinum- base and rhenium- base solid solutions, respectively ) .
Rhenium dissolves 40% Pt and platinum dissolves 40% Re . The solubility is
almost unaffected by temperature .
All compounds formed in binary rhenium systems are given in Table 51 .
153
Chapter XI
TERNARY PHASE DIAGRAMS
There are very few papers on ternary phase diagrams of rhenium . Those
existing give only tentative data on the phase equilibrium in the system at
a certain temperature , and in other papers the positions of the phase regions
are determined from the phase composition of the starting binary systems
and studies of two or three ternary alloys . Therefore , these data must be
considered as preliminary only , and this system must be more thoroughly
studied .
At present, ternary phase diagrams of alloys of rhenium with transition
refractory metals , such as tungsten , tantalum , molybdenum , niobium ,
chromium , vanadium , titanium , and zirconium , are of greatest interest .
Of systems with nonmetals , those with oxygen and carbon are the most
important .
We have divided the ternary phase diagrams into three groups : 1 ) phase
diagrams of rhenium - tungsten with a third metal; 2 ) phase diagrams of
rhenium- tantalum with another metal; and 3 ) all other phase diagrams of
rhenium with metals or nonmetals . Rostoker /114/ constructed diagrammatic
isothermal sections of concentration triangles from literature data , but he
also carried out microstructural and X - ray studies on only 2 - 4 alloys
represented by the composition triangle . From these data the author drew
diagrammatically the lines which limit the phase regions in the ternary
systems of rhenium with refractory materials . Rostoker did not carry out
the usual studies on ternary alloys by methods of instrumental analysis . As
the experiments were insufficient , experimentally based corrections were
necessary . Nevertheless , the above variants of the phase diagrams are of
great interest , and can be used for the development of ternary alloys .
1. Ternary phase diagrams of rhenium - tungsten and

a third metal
Rhenium - tungsten- vanadium . From literature data on binary

systems , and from studies on two ternary alloys ( 30 — 40% W, 5 – 10% V
and 65 – 50% Re ), Rostoker / 114 / assumes that the limits of solubility of
ternary solid solutions of rhenium in tungsten and vanadium are straight
lines which join the solubility limits of binary solid solutions of rhenium in
tungsten and vanadium ( Figure 38 a ) .
154
Rhenium- tungsten - niobium . From studies on two ternary alloys
containing 40 – 43.5 % W, 14 – 25% Nb, and 46 – 31.5 % Re , and from
literature data on binary systems , Rostoker / 114 / plotted the boundary of
ternary solid solutions of rhenium in tungsten and niobium ( Figure 38b ) .
Rhenium - tungsten - tantalum . A complete ternary phase
diagram of the tantalum- tungsten- rhenium system was constructed by
Wulff and Brophy / 115 / from the data of microstructural and X - ray analyses ,
and measurements of the melting points of cast alloys . The ternary
tungsten- tantalum - rhenium three - dimensional phase diagram with two
isothermal sections corresponding to the phase composition of alloys at
1200 -- 2020°C and 2530 — 2680°C is shown diagrammatically in Figure 39.
To construct the ternary diagram the authors used literature data of the
corresponding binary phase diagram of tantalum - tungsten , tungsten
rhenium , and tantalum - rhenium systems .
Re
a
b
1000-1500 ° 1000-1500 °
W V NO RE
FIGURE 38. Schematic phase diagram of ternary systems of rhenium (range 1000 – 1500 ° C ):
a – rhenium - tungsten - vanadium ; b – rhenium - tungsten -niobium .
The ternary tungsten- tantalum - rhenium system has a wide region of

a - ternary solid solutions of rhenium in tantalum and niobium ; the solubility
limit of ternary solid solutions extends from the Ta 45% Re to the W - 28%
Re alloy at 1200°C . The surface of maximum solubility shows that the
solubility is almost unaffected by temperature . No transformation has
been found in the solid solution . The ternary system has the same two
intermetallic phases as the binary ( a o- and an X- phase ) . No new ternary
phases have been found . At temperatures above the decomposition point of
the o- phase of the tantalum - rhenium system , the homogeneity range of the
o- phase extends through the whole ternary system . At lower temperatures
the region of the o - phase narrows . The region of the X- phase extends
through the whole ternary system at temperatures below that of the
peritectoid formation of the X- phase in the tungsten - rhenium system , and
it narrows at higher temperatures . The addition of tungsten to tantalum
rhenium alloys increases the stability of the o- phase and decreases the
stability of the x - phase . The region of the rhenium- base B- solid solution
is narrow , and it is bounded by the solubility limit which extends from the
155
Re - 3% Ta alloy to the Re – 11% W alloy. This position of phases in the
ternary systems indicates that a quaternary phase equilibrium exists . The
temperature of the quaternary phase equilibrium lies below the temperature
of the eutectic L BO + B ( 2825°C ) in the tungsten- rhenium system , and
below the eutectic L BX + B ( 2755°C ) in the tantalum - rhenium system , but
above the temperature of the peritectic L + X BO ( 2740°C ) in the tantalum
rhenium system , and above the temperature of the peritectoid o + Bax
(2125°C ) in the tungsten- rhenium system . The phase diagram in Figure 39
shows an isothermal region bounded by four nonparallel lines , which form
the sides of a quadrangle . Each corner of this represents one of the four
phases L , B , O , or X , each saturated with reference to the other . Figure 39
also shows that the ternary phase spaces which begin at the peritectic
L + XBo tantalum- rhenium and the peritectoid o + B = x (tungsten- rhenium )
extend to the plane of the quaternary equilibrium . The compositions of the
four mutually saturated phases have not yet been determined . The ternary
regions in the tantalum- tungsten- rhenium system are very narrow .
3410
3180 °
2965
2680
2530 °
Re
2020 "
1200
Ta
FIGURE 39. Diagram of reactions in the rhenium -tungsten

tantalum system .
A diagrammatic isothermal section was constructed /114 / from

literature data on the binary systems and from studies on three cast alloys .
This section, which corresponds to the phase composition of alloys of the
tungsten- tantalum- rhenium system at both 1000 and 1500°C , differs somewhat
from that constructed /115 / . We believe that the variant of the phase diagram
given in / 115 / is more reliable (Figure 39 ) .
156
Rhenium - tungsten - chromium . Rostoker /114 / studied four
ternary alloys of the tungsten- chromium- rhenium system , and found that
the phase relationships in the ternary systems are very complex (Figure 40 ) .
A wide range of a - ternary solid solutions of rhenium in tungsten and in
chromium exists at 1500°C (Figure 40 a ) . At 1000° C the ternary a-
a - solid
solution decomposes into two solid solutions Q1 +02, like in the tungsten
chromium binary system . Two possible variants of the position of phases at
1000°C in the ternary tungsten- chromium- rhenium system are shown in
Figure 40 .
Re RB
7
a
b
a , *062
w
Re Cr W Cr
az
Olymaz
o
Cr
FIGURE 40. Rhenium -tungsten -chromium system (isothermal sections):

a – 1500°C ; b – 1000°C ; C – 1000° C (possible variant).
Rhenium - tungsten - molybdenum . Tylkina, Povarova, and

Savitskii /116 / constructed part of a ternary phase diagram of the tungsten
molybdenum - rhenium system from the results of microstructural analysis
and measurements of the hardness and melting point of the specimens . They
studied the part of the phase diagram from the side of the tungsten- base
and molybdenum - base a - solid solution containing up to 50 wt % ( 40 — 45 at . % )
Re . In the tungsten- molybdenum system tungsten forms a continuous series
of solid solutions with molybdenum .
A diagrammatic three - dimensional phase diagram of the tungsten
molybdenum - rhenium system is shown in Figure 41 a, and a composition
triangle with solubility lines of an a - ternary solid solution of cast alloys
at 1000°C and 1700°C is given in Figure 41 b. It can be seen ( Figure 41b )
157
that the solubility limit of the ternary solid solution in the tungsten
molybdenum - rhenium system / 116 / extends at 1000°C from the maximum
solubility of rhenium in tungsten ( 32% Re ) to the solubility limit of rhenium
in molybdenum ( 46 wt % , 30.5 at . % Re ) and it is somewhat bent toward the
tungsten- rhenium solid solutions . The solubility limit of the ternary solid
solution in cast alloys at 1750°C extends between the corresponding alloys
of the binary system lying on the solubility limit of binary solid solutions, and
they are somewhat bent toward the solid tungsten- molybdenum solution .
A ternary o -phase is formed in the system .
3410 Re 3170
1,° C
30000
Mo
1, ° C
2600
2620 2600
24500 !
2500 2500
2000 1750 ° 2000
1500H H1500
1000 °
1000
w MO
a
60 60
st
Ca
00
wte,
17
R
%
%t
,we
R
1000 % 40
A
20 Boundary of twinning 20
W 20 40 80 Мо
wt % b
FIGURE 41. Rhenium -tungsten -molybdenum system :
a - diagrammatic representation of reactions in system ;
b - composition triangle with solubility limits at
different temperatures.
Deformation twins are formed in alloys which belong to the region of

ternary solid solutions . The " boundary of twinning ' is shown on the diagram
( Figure 41 b ) . The formation of twins is most intense in alloys containing
158
more than 20 at . % ( 25 wt % ) of rhenium . This phenomenon had alreadybeen
noted in binary alloys of rhenium with tungsten, molybdenum , chromium or
vanadium . Apparently, the deformation of alloys in this field may be due
not only to slip , as is the case with metals with a cubic body- centered
lattice , but also to twinning . This problem is discussed in detail in
Chapter XIII .
50
16
$
L
Ro
1,° C
,Rwet
1000-1500 ° 1800
auf
% 10
1400
1000
Pd 20 30
7 ,°C 1000 W , wt %
1400
?
1800
an
2200 L.
2175: 25 °
พ Os
a
b
FIGURE 42. Phase diagrams of ternary systems containing rhenium :

a – rhenium - tungsten - osinium system at 1000 – 1500°C ; b – rhenium -tungsten
palladium system .
Measurement of the solidus temperature showed that in alloys of ternary

solid solutions (up to 30% Re ) with a constant content of rhenium the melting
point of the alloys decreases with decrease in the content of tungsten and
with increase in the content of molybdenum . None of the alloys have a
melting point higher than that of tungsten . Ternary tungsten -molybdenum
rhenium alloys in the region of tungsten- base and molybdenum - base solid
solutions were studied by Sims and Jaffee / 117 /. The variant of the phase
diagram constructed in / 117 / completely agreed with the data in / 116 /.
Rostoker / 114 / constructed two approximate isothermal sections of the
tungsten -molybdenum - rhenium phase diagram at 1000°C and 1500°C , which
agree with the data given earlier /116, 117 ). He used literature data on
binary systems of rhenium with tungsten and with molybdenum , and studied
three ternary alloys only .
Rhenium - tungsten - osmium . An approximate isothermal section
of the tungsten - osmium - rhenium system at 1000 and 1500°C constructed
from literature data and a study of two binary alloys / 114 / is shown in
Figure 42 a . The phase boundaries of both sections are the same , so that
both can be drawn in a single figure.
Rhenium - tungsten - palladium . A phase diagram of the
palladium corner of the rhenium - tungsten- palladium system , constructed
by Tylkina, Polyakova, and Savitskii / 118 /, is shown in Figure 42 b . The
region of palladium- base ternary solid solutions is rather wide . The
159
solubility limit extends from the tungsten + 25 % Re alloy to the palladium
+ 20 % Re alloy of the corresponding binary system , and is little influenced
by temperature .
2. Ternary phase diagrams of rhenium - tantalum and

a third metal
Rhenium - tantalum- vanadium . From literature data on binary

systems and studies on ternary alloys containing from 11 to 70 wt % of
rhenium Rostoker /114 / concluded that after annealing at 1500 ° C all alloys
( except the alloy with 70 % Re ) consist of a single phase (a ); but after
annealing at 1000°C they consist of a TaV2 intermetallic compound and a
TaV2 + a region ( Figure 43 a, b ).
Re Re RE
a b с
attava
Ta Re
V Ta Tove Re V Ta Mb
Re
f
X
7
7
Τα TaCry Cr To Mo Ta os
FIGURE 43. Diagrams of phase regions of ternary alloys containing rhenium :

a , b – rhenium -tanta lum -vanadium system at 1500 and 1000°C , respectively ;
c- rhenium -tantalum -niobium system at 1000 – 1500° C ; d – rhenium -tantalum
chromium system at 1000 – 1500 ° C ; e - rhenium -tantalum -molybdenum system at
1000 – 1500° C ; f – rhenium - tantalum - osmium system at 1000 – 1500° C .
Rhenium - tantalum- niobium . Rostoker ( 114 ) studied two ternary

alloys containing 47 and 64% Re , and concluded that the solubility limit of
tantalum- base and niobium- base ternary solid solutions is a straight line
passing between the solubility limits of tantalum - rhenium and niobium
rhenium binary systems (Figure 43c ) .
Rhenium - tantalum - chromium . A study of two ternary alloys
containing 18 and 35 % Re showed /114 / that both alloys are binary at 1000
and 1500°C (Figure 43d ) .
Rhenium - tantalum - molybdenum . Rostoker / 114 / studied two
ternary alloys , and with the help of literature data on binary systems he
constructed an approximate isothermal section of the tantalum - molybdenum
rhenium system at 1000 – 1500°C ( Figure 43e ) .
160
3170's Re 29000
90 % RC
a b
10 % CO
0
90
00
2.
30
50
Re
wt,
%
27
00
250
00
00
25
27
2300*
)
90 % Os
10 % CO 90 % RU
Os DRU 10 % CO
3050 " 2250 2760 ° Ru wt % 0 2130 °
FIGURE 44. Melting point diagram :

a
- rhenium -osm ium -ruthenium system ; b – section of rhenium -ruthenium - osmium - cobalt
quaternary system with a constant concentration of cobalt equal to 10 %.
Rheniu m - tantalu m - osmium . The literature data on binary

systems , and a study of four ternary alloys containing 5 — 31% Re , were used by
Rostoker /114 / to construct an approximate isothermal section of the
tantalum- osmium- rhenium system at 1000 – 1500°C ( Figure 43f) .
Rhenium - osmium - ruthenium . Savitskii, Tylkina, and Polyakova
/ 119 / constructed a rhenium- osmium- ruthenium phase diagram ( Figure 44 a ) .
Between them these metals form a
continuous series of solid solutions . This
phase diagram is the first example of
Aw unlimited mutual solubility in the liquid and
solid state of three metals with a hexagonal
wte,
f
%
w.wtet
%
R
lattice. The melting point of ternary alloys

decreases smoothly with increase in the
8
with traces
content of ruthenium . The hardness of
of fusion
these alloys decreases with decrease in
1 the content of rhenium . The Os - 20% Re –
20% Ru alloys have the highest hardness
FIGURE 45. Rhenium - zirconium - iron ( 700 kg / mm² ) .
ternary system ( isothermal section ): Savitskii , Tylkina , and Polyakova
1,2 – quenching in water from 1000 and studied a section of the rhenium - ruthenium
from 900 ° C , respectively . osmium- cobalt quaternary system with a
constant concentration of cobalt equal to
10 % . All alloys studied had a hexagonal
close- packed lattice of a quaternary solid solution . The addition of cobalt
to ruthenium- rhenium- osmium alloys leads to a decrease in the melting
point and hardness . The melting point of the alloy decreases from the side
of rhenium- osmium- cobalt toward the ruthenium – 10% Co corner . The
ternary alloy 18% Re – 72% Os — 10% Co has the highest hardness
( 600 kg / mm) (Figure 44b ) .
Rhenium - zirconium - iron . Petrova /120 / studied the stability
of the B- Zr- base solid solutions by X- ray and microstructural analyses of
cast alloys, and found that iron and rhenium, neither of which stabilizes
the ß- zirconium solid solution , do not stabilize it when added together . The
161
continuous and broken lines in Figure 45 separate the phase regions of
(B + w ) or ( B + w + L) which correspond to the isothermal section of these
alloys at 900 and 1000°C .
Rhenium - hafnium - nickel . The existence of an Hf2Ni0.6 Re0 33
compound was found in / 121 /.
3. Ternary phase diagrams of rhenium and nonmetals
Ternary systems with oxygen and metals . The existence

of a ternary oxide of the Mel Mello , type has been reported / 122 / (Table 52 ) .
TABLE 52. Parameters of complex rhenium oxides of the ReMeOxtype

Me A c,Å qa
Titanium 2.85 4.61 1.62

Vanadium 2.76 4.46 1.62
Chromium . 2.75 4.45 1.62
Manganese 2.72 4.38 1.61
Iron 2.71 4.37 1.61
Cobalt 2.69 4.32 1.61
TABLE 53. Phase compositions of tungsten -rhenium -carbon alloys
Composition of charge, mole %

Phase
Re WC
82.4 17.5
75,0 25.0
66.7 33.3 (1
62.2 37.8 a + WC + S!
57.2 42.8 a + WC + SI
46.2 53.8 WC + SI
18.2 8.8 WC + si
For the above compounds 0.4 < x < 1 . It is also believed that for some
of these phases x = 0 , which means that the lattices are free of oxygen .
The isothermal section of the molybdenum- rhenium - oxygen ternary
system given in Figure 46 was assumed / 123 /.
Rhenium - tungsten - carbon . An investigation of the pseudobinary
Re – W2C system was carried out / 124 / on specimens prepared by sintering
in graphite boats . During sintering carbon was absorbed from the boat and
the composition of the alloys shifted towards the pseudobinary Re - WC
system . It was found that alloys containing 46.2 – 75.0 mole % Re melt below
2310 + 20 ° C .
It was found that the system has an a - rhenium - base solid solution and
two intermetallic compounds: WC and an S ' phase, the structure of which
has not yet been determined (Table 53 ) .
162
The tungsten- rhenium- carbon system was studied by microstructural
and X- ray analyses of specimens that had been cast in arc furnaces and
contained up to 40% Re / 125 /.
0
Isothermal sections at 1500 and
2000 ° C were also constructed for
cast alloys ( Figure 47 a , b, c ) . It has
& Reza been found that the system has a
MOO ;8 & ReO₃ continuous series of solid solutions
ReMo0 ,
) n
between rhenium and a -W2C . The

Mo04
Moort & Rel₂

B• eMo
•
substitution of several atoms of

tungsten by rhenium atoms leads to
G& rReMOD
an increase in the parameter a , but

GarieMo
ly
the parameter c remains almost

l
R+emo
unchanged .
2
Oy
M00
**
Preliminary data on the existence

of another low- temperature W2C
Re
modification were also obtained . It
Но амо aM0-6
was found that the system has a
FIGURE 46. Rhenium -molybdenum - oxygen system ternary W3CRe2C carbide (1 - phase )
(diagram of phase areas). with a cubic structure , similar to
that of B - Mn (space group P4.3 – 0?) ,
and a lattice parameter a = 6.859 +
+0.002 Å. According to the authors of / 125 / the s' phase found in /124 / is
apparently a W3ReaC carbide , but it does not exist in a state of equilibrium
with WC , as stated in / 124 /.
Above 2500°C this system contains a ternary carbide (W, Re ) C or w - phase
with a body- centered cubic lattice of the NaCl type (space group Fm3m - 0 );
a = 4.063 + 0.001 Å .
Rhenium - molybdenum - carbon . Two ternary compounds have
been found / 126): Compound MosoRe33.3C 16.7 has a B- Mn type structure
( a = 6.86 + 0.01 Å), analogous to compounds B = (W – Fe --C ), Mo13FeNĄ,
Cr3Ni5Siz. Compound (Mo, Re) C has a Naçi type structure , and a variable
composition up to 40% Re (a = 4.11 + 4.06 Ă ) . MozC and Re form a continuous
series of solid solutions , which decompose if the temperature is decreased .
At 1400°C MozC dissolves 50 at . % Re, and the rhenium- base solid solution
extends up to 20 at . % Mo and 8 at . % C.
Rhenium - silicon- ( iron , cobalt , nickel ) . Isothermal
sections of rhenium - iron - silicon , rhenium- cobalt- silicon , and rhenium
nickel- silicon alloys quenched from 800°C have been constructed /127 / from
the results of X- ray and microstructural analyses .
In the rhenium- iron- silicon and rhenium- cobalt- silicon alloys containing
small amounts of silicon intermetallic compounds are formed with structure
of the u - phase WoFe7 (space group, R3m – Did for compound RefFebSi,
a = 4.67 + 0.01 A , o
25.69 + 0.05 Å , cla = 5.50; for compound RefC05. Si1.3,
a = 4.633 +0.002 A, 6 = 25.514 + 0.005 A, cla = 5.507 ) .
No ternary intermetallic compounds are formed in rhenium - nickel
silicon systems . Rhenium is in a state of equilibrium with binary nickel
silicides .
Ternary systems of rhenium with metals of the iron subgroup and with
silicon differ from analogous manganese systems because of the difference
in the structures of the electron shells of atoms of manganese and rhenium .
163
The formation of intermetallic compounds with a 4 -phase structure in
rhenium- iron- silicon and in rhenium- cobalt- silicon alloys with a low
content of silicon ( about 10 at . % ) can be considered as a " stabilization " of
the unstable binary compounds by silicon . Similar stabilization (of the
o - phase ) is found in the chromium- nickel- silicon systems .
a b
WC
WC
tk WC poc
Wowo Wcop
I'M
sow
*
1 as
м
laß T
ap
as TBS
a1 Q.G 7.6
‫ܤܤܤܤܤܤܣ‬ 7 V让
‫ܩܤܣܫܣܤܩܬ‬
6 of Re W Re
C C
с
1500 ° C
UCZ
WCBC U2C3
WC
UC URECZ
2
WCP
Tarpt
T UCL
as
T 4 +G
lunmampos ‫ܚܣܣܣܤܣܣ‬
พ a a 6 Ġ 11 •6 • 2113- X RE U URCZ Re
x
FIGURE 47. Rhenium -tungsten - carbon system (isothermal sections a , b , c) , and rhenium
uranium -carbon system (d) :
a - cast alloy ; b after annealing at 2000 ° C ; C - after annealing at 1500°C .
Rhenium - uranium - carbon . An isothermal section of this

system at 1500°C has been constructed / 128 /. In this system a ternary
UReC2 intermetallic compound is formed ( Figure 47 d ) .
164
Chapter XII
THE REACTION OF RHENIUM WITH SOME ELEMENTS
In our attempts to clarify the qualitative interaction of rhenium with

other elements of the periodic table / 129 — 131 /, we used the general
conclusions drawn from our own experiments and literature data , and
some other modern views on the physicochemical reaction between elements .
1. Formation of compounds in rhenium - containing alloys

The phase diagrams showing the reactions between rhenium and
transition metals lying to the left of it in the periodic table (group VIII ) ,
and with more complete d- shells and a higher valence than rhenium , are
of the simple type . No intermetallic compounds are formed in these alloys ,
or in other words the system consists of a continuous series of solid
solutions (Re with a - cobalt, ruthenium , osmium ) , or of limited solid
solutions (Re with all other elements of group VIII except iron ) .
With the transition elements of groups III – VI, which lie to the left of
rhenium in the periodic table and have less complete d- shells and a lower
valency than rhenium , rhenium forms a number of intermetallic compounds
with a complex crystal structure and solid solutions of limited concentration .
It is characteristic that intermetallic compounds formed in ternary
rhenium systems are of the same types as those formed in binary ones .
Exceptions are the ternary systems of rhenium with metals that have a
hexagonal lattice and in which no intermetallic compounds are formed . In
binary systems the compounds formed by rhenium with metalloids and with
some transition metals (boron, beryllium , carbon, silicon, germanium ,
nitrogen, oxygen, phosphorus , arsenic , etc. ) have not yet been sufficiently
studied . These compounds have a complex crystal structure . For most
compounds the type of structure has not yet been identified .
In binary and ternary rhenium alloys the intermetallic compounds with
transition metals belong mainly to the o- and X- phases . Alloys with
elements of groups IIA, IIIA, IVA form a Laves phase (a -phase ) . The
temperature of formation , homogeneity range , and crystal lattice
parameters of rhenium compounds in binary systems are given in
Table 51. It should be noted that in alloys containing technetium, which
is an analogue of rhenium , compounds with a structure of the CsCl and
Cr30 types are formed beside the above compounds / 100 /. In ternary alloys
containing oxygen, silicon or carbon , new compounds with complex crystal
structures are formed : hexagonal (containing oxygen ) , cubic of the B - Mn
165
and NaCl types (containing carbon ), and compounds of au - phase W.Fez
type (containing silicon ) . Structures characteristic of systems of rhenium
with transition metals ( o-, x- and X - phases ) will be discussed later in
greater detail .
1.6
-6,7,8
6,1 , HS
1.5
Atomic
radius
15
6.X
%
,Å Nb
1.4
6,X . ‫ی‬.
+
MO Re
6,7 Тc
Mn
13 Cr
15
%
12
-
1
1
D W
FIGURE 48. Influence of the dimensional factor and of the

position of the alloying element in the periodic table on the
formation of o- , X- , and 1 - phases in rhenium systems .
The X- phase which has a structure of the a- Mn type has a body

centered cubic lattice with 58 atoms in the unit cell . It is formed in systems of
rhenium with metals of group III ( aluminum and scandium ) and with
metals of groups IV -VI (titanium , zirconium , hafnium , niobium , tantalum ,
molybdenum , tungsten ) . Technetium , which is an analogue of rhenium ,
forms an X - phase with all these metals , except those of group VIA (tungsten
and molybdenum ) .
The o - phase has the structure of the B- U type, and a complex tetragonal
lattice with 30 atoms in the unit cell . It is formed in alloys of rhenium with
transition elements of groups IV- VIII ( zirconium , hafnium , vanadium ,
niobium , tantalum , chromium, molybdenum , tungsten, manganese , iron ) .
Technetium forms a o - phase with the metals of groups IV VIII / 100 /.
The Laves phase (^ -phase ) has a hexagonal structure of the MgZn2 type
and is formed in alloys with transition metals of group III ( scandium ,
yttrium , gadolinium, erbium, terbium ) , group IV ( zirconium , hafnium ,
thorium ), group VI (uranium, plutonium ), and also of group IIA (beryllium ) .
It should be noted that many of these elements , like rhenium itself,
have a hexagonal close- packed lattice in at least one of their phases .
According to our data, the intermetallic compounds formed by rhenium with
transition metals melt incongruently . The melting points of all compounds
formed by rhenium are lower than the melting point of rhenium itself.
The formation of intermetallic compounds in alloys of rhenium with
transition metals is influenced by a number of factors , such as the
dimensional and electrochemical factors , the difference between the
electronegativity of the elements , change in the electron concentration , etc.
166
We should like to point out the following on the influence of the
dimensional factor on the formation of rhenium compounds : the x- phase is
formed in alloys of rhenium with
transition metals with an atomic radius
a
1. ° C larger than that of rhenium . This means
3090 он
Τα that the dimensional factor is positive
Ta
( Figure 48 ) / 132 /. If the dimensional
Но
2.500 Nb Zr factor is greater than 4% ( aluminum ,
Nb titanium , zirconium , hafnium , niobium ,
2200
Cr Mf tantalum ) the x- phase is formed by a
peritectic reaction in the melt , and if the
MO
Zr dimensional factor is less than 2%
1800 (molybdenum, tungsten ) by a peritectoid
5 10 15 reaction in the solid .
Dimensional factor , %
T, ° C
b
In o - phases the dimensional factor
3000
OX phase To w varies from + 16.50% ( zirconium ) to - 8 %
• 6 -phase ( iron ) .
o Ti
Τα A Laves phase exists in alloys of
MO
2600 Nb
rhenium with yttrium , scandium ,
Nb
gadolinium , erbium , terbium , zirconium ,
Cr
hafnium , thorium , uranium , and
Hf
2200 plutonium because the dimensional
factor of these metals lies within the
3
Zr
range of magnitudes characteristic of
Мо
1800 -phases (10 - 50% ) .
W
There is a certain relationship
between the temperatures of the
FIGURE 49. Dependence of the temperature formation of the o- and X- phases
of formation of o- and X -phases in rhenium
containing alloys on the dimensional factor containing metals of groups IV – VI of
(a) , and on the position of the alloying individual periods and the dimensional
metal in the periodic table (b) . factor . With increase in the difference
between the atomic radiuses of the
metals , the temperature at which the
X- phase is formed increases , and the temperature of formation of the oo- phase
decreases ( Figure 49 a ) .
The influence of the electron structure of elements on the formation of
o- and x- phases between the given element and rhenium is very striking.
For o - phases an electron density of 6.6 electrons per atom is
characteristic /42 ), and for the formation of X- phases an electron density
of 6.0 – 8,0 electrons per atom . The reason for these electron density
values is that o- and x- phases are formed with the participation of transition
elements of groups IV – VI and elements of groups VII – VIII .
It should be pointed out that if an alloy system contains o- and X- phases
formed between rhenium and a metal of group IV – VI, the x - phase is
formed in those alloys that contain more rhenium . This indicates that the
electron density of the X - phase is higher than that of the o - phase .
Figure 50 shows that the content of rhenium in o - phases of the first long
period and in x- phases of the second and third long periods decreases with
increase in the valence of the alloying component. It is clear that if the
valence shells of the alloying element are more complete, less rhenium is
needed to reach an electron density characteristic of these phases . Hence ,
it follows that with reference to the transition elements of the first to third
long periods , rhenium has a high valence .
167
The authors of / 99 , 133 / believe that this is the reason why o - phases
are formed in rhenium- manganese alloys or in rhenium - iron alloys although
neither manganese nor iron satisfies the conditions for the formation of
o - phases . Technetium , which is an analogue of rhenium , behaves similarly
during the formation of o - phases with metals of the first long period /100 /.
However , in the technetium- rhenium o- phase , the concentration of
technetium is higher than that of rhenium .
It should be pointed out that the regularity found during the formation of
o- phases of rhenium with the transition metals of the first long period
(the structure of these phases has not yet been sufficiently investigated ) is
not repeated during the reaction of rhenium with elements of the second and
third long periods . The electron structure of these elements ( zirconium ,
niobium , molybdenum , hafnium , tantalum , tungsten ) is more complex, and
has been little studied . Systems of rhenium with these elements have not
one but two or even three intermetallic phases . If the valence shells of the
elements are less filled , the number of phases formed is greater, and less
rhenium is needed to form a o - phase in the system (Figure 51 ) .
100
Hi,Thar M6,Ta
6 6
V ow , the
TIL V ig
Cr.W.Me
Period
60 AX
,at
%.Ae
% Та Zr Mo
6 27
Zr,Mf VE 1TO
• 6 - phase
ox - phase X - phase 6 - phase
NA ZA VA WA WA U
FIGURE 50. Average content of rhenium FIGURE 51. Dependence of the concentration
in o- and x - phases of systems formed by regions of o- , .- , and x - phases in a rhenium
rhenium with transition metals of sub system on the position of the alloying metal
groups IVA and VIIIA . in the periodic table .
It should be pointed out that in systems with scandium , zirconium , and

hafnium , a Laves phase is formed together with the o- and x- phases . In
binary systems there is usually no Laves phase with the x- phase . Non - phase
has been found in any of the known binary systems containing an x- phase ,
but a o - phase is formed instead. Systems of rhenium with scandium,
zirconium , or hafnium contain all three phases together, which indicates
that the electron effects in the intermediate phases of these systems are
very complex /45 /.
There is a general rule governing the formation of rhenium compounds
as a function of the position of the alloying element in the periodic table
(electrochemical factor ) . Since the structure of the electron shells of the
transition metals becomes more complex as we pass from the first to the
second and third long periods , and the structure of these metals more
closely resembles that of rhenium, which belongs to the third long period,
the number of compounds in the system increases, their concentration
regions become wider (see Figure 51 ), and the temperature of their
formation increases (Figure 49 a, b ) . The temperature of formation of
168
o - phases increases and that of X - phases decreases in systems containing
metals of the second and third long periods as their electron shells become
filled ( Figure 49b ) .
2. Formation of solid solutions in rhenium systems
An interesting property of rhenium, which has a hexagonal close - packed

lattice , is its high solubility; up to 65 at . % in transition monomorphic and
polymorphic metals with a cubic lattice ( BCC : B - Ti, B - Zr , B - Hf, y- U ,
vanadium , niobium , tantalum , molybdenum, tungsten; FCC : nickel,
rhodium, palladium , iridium , platinum ) .
It can be seen from the relationship between the solubility of rhenium in
transition metals of groups IV , V , and VI , and their position in the periodic
table (Figure 52 ) that the solubility
is highest in elements of the first
long period (titanium , vanadium,
Solubility
rhenium
chromium ), while the solubility of

rhenium in metals of the third long
Me
of
,ain
.%t
50
Ta period (hafnium , tantalum , tungsten )
ow is lower , and the solubility of
Nь OMO
40 rhenium in metals of the second long
period ( zirconium , niobium ,
30 molybdenum ) is lowest . Within these
pe ods rhenium has the maximum
solubility in metals of group V
Hfo (vanadium , niobium , tantalum ) , which
Zr0 like rhenium have an odd number of
V VI VII electrons in s td- shells .
The very high dissolving power of
FIGURE 52. Solubility of rhenium in transition metals of the first long period for
metals of groups IV – VI of the periodic table . rhenium agrees well with the fact
that the alloys of rhenium with these
metals form only one intermetallic
compound . The solubility of rhenium is highest in the vanadium - rhenium
system ( 65 at . % Re ), in which the o - phase is unstable at low temperatures .
The solubility of rhenium in metals of the second and third long periods
is lower than in metals of the first long period, and in fact in systems of
rhenium with these metals there are two or more intermetallic compounds .
According to modern theories , the mutual solubility of metals depends
on the existence of isomorphic crystal structures , the difference between
the atomic radiuses (dimensional factor ), the difference between the
electronegativities , and the structure of their valence shells (electrochemical
factor ) .
It is well known that the formation of a wide region of solid solutions is
favored by the presence of isomorphic crystal lattices of the metals . The
continuous series of solid solutions of rhenium with hexagonal close- packed
metals (ruthenium , osmium ) and with the hexagonal modification of cobalt
confirms this theory.
169
As we have already mentioned , the mutual solubility of two metals
depends on the dimensional factor, which is considered favorable if the
difference between the atomic radiuses of the elements does not exceed 15% .
With increase in the dimensional factor , the solubility of rhenium in the
alloying metal decreases , and vice versa . However, there is no linear
relationship between the mutual solubility of metals and the dimensional
factor for any of the periods .
The mutual solubility of elements is greatly influenced by the difference
in their electronegativities , AEn . It is believed that this difference must
not exceed 0.4 for the formation of limited solid solutions , or 0.2 for the
formation of a continuous series of solid solutions /9 ) .
OC
2.5
Electronegativity
ose
Mitare
POR RhRd
U bSb
он OMG
Cr
Os Ir MoRt
2,0 Re
OS bu
r
Sio Nb
Toy /olg oOPE
Bi
osn
Crusoti оса
Coco Hf zr
oße 2n XL oBa
o in
oth
oScom
ola
20 o Cu оса
o Sr
Aug Agoll ολα
1
Kol
1,5 2.0
Atomic radius , Å
FIGURE 53. Influence of the electronegativity of metals

and of their atomic radius on their solubility in rhenium .
The simultaneous influence of the dimensional factor and of the electro

negativity can be found by plotting these magnitudes in the following
coordinates : abscissa , Far , A, ordinate , En . Every element will be
represented by a point ( Figure 53 ). The points representing elements with
a high mutual solubility will lie close to one another . The points representing
elements most soluble in each other are very close to one another . Elements
which form a continuous series of solid solutions with rhenium should lie
on such diagrams within an elipse with semimajor and semiminor axes
equal to 0.2 En and 7% Fre, respectively (cobalt , ruthenium , osmium ) .
Elements forming wide regions of solid solutions (not less than 10% ) lie
within a large elipse with rhenium in the center and with semiminor and
semimajor axes equal to 15% rre and 0.4 En, respectively (vanadium ,
niobium , chromium , molybdenum , tungsten , nickel , rhodium, iridium,
platinum ) . It should be pointed out that the solubility of rhenium in the other
170
elements is also governed by the same law . The points which designate
elements in which rhenium dissolves in amounts of up to 5 % lie within the
large elipse , and points representing elements which dissolve more than
10 % of rhenium lie within the small elipse (Figure 53 ) . According to these
data the experimental results for rhenium agree well with the theoretical
assumptions .
However, the influence of the type of lattice, the dimensional and
electrochemical factors , and the difference in their electronegativities ,
do not explain the high solubility of rhenium in body- centered cubic
B - titanium ( 50 at . % ) and in body- centered cubic vanadium ( 65 at. % ), for
which the above factors are not very favorable (Figure 52 , 53 ) . These
factors also fail to explain why rhenium is more soluble in chromium than
in other metals of group VIA (molybdenum and tungsten ).
It is known / 14 / that the mutual solubility of metals is determined also
by the elastic strain of the distorted lattice of the solid solution , which in
turn depends on the relative difference between the atomic radiuses
( dimensional factor ) , the compressibility, and the modulus of elasticity
in shear. The modulus of elasticity depends on the forces of interaction
between the atoms in the crystal: with increase in these forces the modulus
of elasticity increases and the compressibility in hydrostatic
compression decreases . Pines /134, 135 / found that in a system of two
limited solid solutions the solubility at a given temperature is greater on
the side of the metal with the greater compressibility .
Obviously, other factors being equal , a high compressibility facilitates
an increase in solubility, since the crystal lattice of the metal can become
more deformed without changing its type. Thus , the high solubility of
rhenium in chromium , B - Ti , and vanadium , can be easily explained by the
high compressibility of these metals (compressibility of B- Ti and of
vanadiumis 9.328· 10-9 and 6.057 : 10 , cm "/kg,respectively, andthe
compressibility of chromium is 5.154 • 10-6 cm /kg. The strength of the
interatomic bonds also determines the melting point , the coefficient of
thermal expansion , and some other properties of the metal. Metals with a
high modulus of elasticity and low compressibility are refractory
materials , and as we have already mentioned rhenium has the third highest
modulus of elasticity, and the second highest heat resistance of metals.
In this connection the Pines law was modified in paper /14 / as follows:
at a given temperature the solubility is higher in the metal with the lower
boiling point. This law holds for an evaluation of the mutual solubility of
rhenium and other transition metals . All these ( except tungsten ) have a
melting point lower than that of rhenium , and therefore their solubility in
rhenium is lower than the solubility of rhenium in them .
Obviously , this law can be further generalized as follows : if two metals
have similar electron and crystal structures and reasonably high mutual
solubility, the metal with the weaker interatomic bonds will also have a
higher dissolving power at a given temperature .
In conclusion, we should like to point out that the existence of large
regions of solid solutions of rhenium in metals with a body- centered
lattice (tungsten, molybdenum , chromium , vanadium , niobium , etc. ) and
the considerable changes in the solubility of rhenium in these metals with
temperature , indicate that rhenium alloys are susceptible to aging .
171
Although the experimental data on the processes of decomposition ,
ordering, aging, etc. , are insufficient , the authors nevertheless believe
that these problems are of great theoretical and practical interest , and
should be further investigated .
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127. Gladyshevskii , E.I. and Yu . B. Kuz'ma . Sbornik " Renii,"
p . 170. Izdatel'stvo " Nauka." 1964.
128. Waldorn , M. B. , G. Adam , and B. L. Eyra . 5th Plansee Seminar,
June 1964 (preprint ) .
129. Tylkina , M. A. and K. B. Povarova . Sbornik " Renii , " p . 127 .
130. Savitskii , E.M. and M. A. Tylkina . Rhenium, p . 67. New York -
Amsterdam . 1962 .
131. Povarova , K. B. Avtoreferat dissertatsii " Fiziko-khimicheskoe
vzaimodeistvie reniya s perekhodnymi metallami i svoistva
nekotorykh splavov (Dissertation on the Physicochemical Reaction
of Rhenium with Transition Metals and the Properties of Some
Alloys ) . Moskovskii Institut Stali i Splavov . 1962 .
132. Ageev , N. V. and V.Sh. Shekhtman . Dokl . AN SSSR , 127 , No. 5 .
1959 .
133. Ageev , N. V. and V.Sh. Shekhtman . Dokl . AN SSSR , 135, No. 2 .
1960 .
134. Pines , B. Ya . Fizicheskii Zhurnal, 3 : 309 . 1940 .
135. Pines , B. Ya . Izv . Sektora Fiziko- Khimicheskogo Analiza AN SSSR ,
16:18 . 1943 .
176
Part 4
PROPERTIES AND USES OF RHENIUM ALLOYS
Chapter XIII
PREPARATION AND TREATMENT OF RHENIUM ALLOYS
1. Classification of rhenium alloys
In recent years there has been accumulated a large amount of experimental

data of research on the character of the interaction of rhenium with different
elements , and a number of phase diagrams have been constructed for
binary and ternary systems containing rhenium .
From a theoretical generalization of the data we were able to establish
certain regularities in the reaction of rhenium with elements , depending on
their position in the periodic table , the structure of the crystal lattice ,
and a number of other physicochemical factors ( see Chapters X – XII ) .
If phase diagrams are used as a theoretical basis for selecting alloys ,
it is possible to outline the concentration regions of the most promising
alloys for different purposes and operating conditions / 1 / .
There are three principal groups of alloys of rhenium with transition
metals .
First Group . The most interesting and promising materials are
alloys in the region of solid solutions of rhenium in transition metals of
groups IV – VIIIA . Almost all these metals (titanium , zirconium , niobium ,
tantalum , tungsten , molybdenum , palladium , platinum , etc. ) are extensively
used in industry as constructional materials and as metals which have a
number of specific physicochemical properties .
If these metals are alloyed with rhenium , there is a change in their
physicochemical properties . By controlling the rhenium content , we can
obtain the required properties .
This group of alloys consists of workable materials . Alloys can be
produced in the form of different semifinished products ( sheet , foil, rod ,
wire , pipe, etc. ) .
Alloy compositions have now been developed on the basis of tungsten ,
molybdenum , tantalum , niobium , cobalt , nickel , palladium, titanium and
many other metals together with rhenium , and the technology of production
of semifinished products has been partially worked out / 2 – 87 .
Second Group . The second group of alloys includes those situated
in the central part of the phase diagram . The structure and properties of
these alloys indicate that they are chemical compounds of the type of o- and
X - phases . These alloys are very hard and brittle, and cannot
be turned into semifinished products by ordinary methods . They can be
used in the compact or powder form as materials with specific physical
properties ( cathode , semiconductor , superconductor, catalyst , wear
resisting material , etc. ) .
177
This group of alloys has scarcely been studied , but from the data
available / 9, 10 / we can consider it to be highly promising. If necessary
methods can be developed for the production of semifinished products from
the intermetallic compounds with rhenium by casting and pressing , in the
same way as for intermetallic compounds of other systems / 11 ).
Third Group . The third group consists of alloys in the region of
rhenium- base solid solutions . At present this group of alloys is little
studied . The regions of solid solutions on the rhenium side of phase
diagrams are very narrow for almost all metals , and therefore even small
announts of alloying elements can considerably change the properties of
rhenium . By alloying rhenium it is possible to produce a number of new
rhenium - base alloys with specific physical properties (for example , for
high ohmic resistors , cathodic materials , etc. ) / 1 , 12 ) .
Surface treatment of rhenium is very promising / 13 /. By impregnating
the surface of rhenium with different elements it is possible to obtain any
desired compositions of rhenium alloys in the surface layer of the working
machine part , with different physical properties : low oxidizability , high
wear resistance , corrosion resistance , high reflecting power , special
emission properties , etc. The use of coats of rhenium and its alloys is
also important economically as rhenium is in short supply .
In spite of the great development of research on rhenium alloys , today
we have a relatively small number of widely tested compositions .
The most widely used are alloys of rhenium with tungsten and
molybdenum , as a ductile and weldable constructional heat- resistant
material , for thermocouples, electric vacuum instruments , etc.
Below data on rhenium alloys are systematized with reference to the
applicability of alloys and the specific physicochemical properties which
determine their fields of application .
2. Mechanism of the influence of rhenium on other metals
From Kurnakov's rules , alloying of metals in the region of solid solutions

usually results in an increase in strength and decrease in ductility with
increase in the content of the alloying component . In accordance with this ,
the addition of rhenium to vanadium , niobium , and tantalum , which belong
to group VA and have a high ductility at room temperature or below and a
low ductile – brittle transition temperature , results in much greater strength
of these metals and a decrease in their ductility . A similar phenomenon
occurs if metals of groups VII and VIII are alloyed with Re .
Rhenium has an exactly opposite effect on tungsten , molybdenum , and
chromium , which belong to group VIA, as it increases both their strength
and ductility. Figure 54 shows the influence of rhenium on the strength
and ductility of metals of groups VA, VIA, and VIII . We can expect that
by mastering the industrial methods of thorough purification of tungsten and
molybdenum from interstitial impurities ( zone refining, etc. ), we will be
able to decrease the ductile – brittle transition temperature of these metals
below room temperature , and then by alloying them with rhenium we can
increase their strength and reduce their ductility .
178
We know that transition metals of group VIA with a body- centered
lattice, namely , chromium , molybdenum , and tungsten, are cold- short in
their commercial state, and their ductile – brittle transition température
is high (molybdenum 100 - 200°C , tungsten 350 – 400°C ) .
• W.RE
V gr (V.Nb,Ta )
og
limit y
Solubilit
10 % Re
VI gr (Cr, Mo. )
68
, nd
ao
299Re 47 ° Re
yul gi
68
25 % Re
a 50 % R
ja 6
Me Re , %
a b
FIGURE 54. Variation in ductility when rhenium is alloyed with metals of groups VA , VIA , and VIII:
a - diagram ; b - external appearance of tungsten and molybdenum alloys with varying contents of
rhenium , after hot upset forging .
Recrystallization of wrought tungsten and molybdenum on heating during

service or welding results in brittleness . The combination of these
properties impairs the workability of tungsten and molybdenum (the
preparation of semifinished products , such as sheets and wire ) and their
weldability, and is also a serious drawback during their service / 3 – 5,
14 , 15 / .
The optimum compositions of tungsten- rhenium and molybdenum
rhenium alloys which have a higher ductility, better workability,
machinability, and weldability, than unalloyed tungsten and molybdenum ,
are saturated solid solutions situated near the solubility limit (W with
20 – 30% Re and Mo with 40 – 50% Re ) . * When expressed in at . % , the
rhenium content is approximately the same and is 30 – 35 at . % .
The influence of rhenium on the ductility of tungsten and molybdenum is
illustrated in Figure 54 b . It can be seen that the ingots of alloys with
low rhenium content have cracks at the edges after open- die forging,
Henceforth , all alloy compositions are given in wt %.
179
whereas tungsten alloys with 20 – 30% Re and molybdenum with 40 — 50 % Re
have a high deformability even under these rather drastic forging conditions /2 / .
At present we cannot assume that the reasons for this influence of
rhenium have been completely explained and determined . In a number of
papers attempts have been made to explain the principal mechanisms of the
increase in ductility of tungsten and molybdenum when they are alloyed with
rhenium . Possible reasons for these phenomena are a change in the
composition and properties of oxides , redistribution of oxygen , change in
the solubility of the interstitial impurities , change in the deformation
mechanism , and formation of deformation twins .
Re
W - Ma -R4
FIGURE 55. Deformation twins in rhenium alloys near the solubility limit of rhenium .
In alloys of rhenium with molybdenum and tungsten / 3, 16 / oxygen forms

a complex oxide of the type MoRe04 or WRe04 more readily than MoO2 or
WO, in pure molybdenum or tungsten . MoO2 (WO2 ) exists in the ( grain ]
180
boundaries , because of the low surface tension of these oxides , and because
molybdenum forms a eutectic with MoO2. This impairs the ductility and
workability of molybdenum when the oxygen content exceeds 0.0005 — 0.001% .
a
-198 ° C
126
112
Stress
98 20 ° C
?/k, gm
m
70
200 ° C
56 400 ° C
42
28
1 1
10 12 14 16 18 20 22
Strain , %
84
70
kStress
56
m/, gm
42
28
14
/ 17 / :
a -
htur Strain , %
b
j
FIGURE 56. Stress-strain diagram of the Mo– 50 % (35 at . %) Re alloy
- + 400 °C) ; b
influence of temperature (-196 -
S
successive
loading , unloading, and aging of samples : 1– 21 -hour aging at 20°C ;
2 – sample unloaded and reloaded ; 3 – 1 -hour annealing at 600 ° C .
The double oxide of rhenium with molybdenum has a high surface tension
and does not form on the grain boundaries but as globules inside the grains ,
so that the alloy has a high intercrystalline strength and a large reserve of
plasticity and deformation qualities , even if the oxygen content is 0.03 —
0.05 % . Evidently , the high ductility and good workability of ternary alloys
of tungsten and molybdenum with rhenium are also the result of the
formation of a new phase , e.g. , high- melting oxides of the type (W, Mo)Re04.
Attempts have been made to separate oxides from molybdenum alloys
containing 50 wt % (35 at. % ) Re in order to identify them by the X- ray
method and also to synthesize the oxide /3 /. However, these attempts were
not successful.
181
Oxides in a matrix of this alloy have been studied by an electron micro
analyzer / 17 /. However , not one of the oxide particles was sufficiently
large to absorb the electron beam . The results , which even the authors
consider inconclusive , verify the assumed composition of the MoRe04 oxide .
In alloys containing oxygen , a considerable part of the rhenium is
concentrated in oxides and on the grain boundaries . The rhenium content
of the matrix is only 15 – 20% .
Type A Type B
Twin
b
FIGURE 57. Deformation twins in the Mo -- 500% Re alloy , deformed by bending:
a – twins and extended dislocations; b system of distribution of two types of extended dislo
cations; c – complex network of extended dislocations; d- gaps in twin planes caused by the
growth of the twin in the metal with a high dislocation density; e – gaps in twin planes caused
by the passage through the layer of the twin with the extended dislocations.
A study of molybdenum alloys with varying contents of rhenium /17 /

showed that with increase in the rhenium content in the alloy the amount of
oxides on the boundaries decreases, perhaps owing to a decrease in the
182
oxygen content in the alloy when Re207 evaporates in arc melting . Starting
from 27 – 30 at . % Re , the size of the oxide particles increases also , and
they become more spherical . This indicates an increase in their surface
tension and decrease in wettability .
The formation of deformation twins during cold working or at low
temperatures in binary alloys of rhenium with tungsten and molybdenum
/ 1 , 3 , 18 – 20 / is worth noting . A similar
phenomenon occurs in binary alloys of
700
rhenium with transition metals of group V ,
vanadium , and group VI, chromium , which
have a body - centered cubic lattice /21 , 22 ),
Mym²
600
and in ternary solid solutions of rhenium in
kg
/m
tungsten and molybdenum /23 /. In all cases

500
deformation twins appear in alloys which
1
W are near the solubility limit of rhenium in

400 the solid solution based on the given body
centered cubic metal, and these alloys
MO
300 have the highest ductility . The micro
Cr
structures of some of these alloys are
200 shown in Figure 55 .
Evidently, in alloys with these composi
100 tions deformation is possible not only
through slip , which is characteristic of
metals with a body- centered cubic lattice ,
20 40 but also through twinning, typical of
Re, at . hexagonal metals . This additional
FIGURE 58. Dependence of the hardness mechanism of deformation is caused by the
of cast alloys of molybdenum , chromium , action of considerable amounts of rhenium ,
and tungsten , on their rhenium content . and is exhibited by deformation at low or
high temperatures . It is indicated in / 15 ,
17 / that at low temperatures twinning
occurs more uniformly , and at high temperatures more abruptly . The
author of / 17 / studied twinning during tensile tests on Mo alloy containing
over 50% Re in the range – 196 – + 400° C (Figure 56a ). A series of tensile
tests were carried out , during which the load was removed and reapplied
after varying holding times at room temperature or after annealing at 600 °C
for 1 hour . In Figure 56 b , we show the stress - strain curve ; after every
new load the curve continues in the same direction as it took before the load
was removed .
A noticeable increase in yield strength after annealing at 600°C may
be the result of the precipitation of the o - phase .
The authors of /17 / verify that such a yield strength (see Figure 56 b )
and the serrated stress- strain curve ( see Figure 56 a ) of the Mo – 35 at . %
Re alloy are the result of the origination of a flow of twins during plastic
deformation , and are not due to inhibition of dislocations by the interstitial
impurities . Analogous stress- strain curves were obtained during a study
on twinning of single crystals of a Mo 35 at . % Re alloy /24 /.
An X - ray study of twinning in the Mo 50% Re alloy was carried out in
/24 – 28 /. In /25 / a sample was studied which had been separated from a
single crystal produced by the method of zone melting and deformed to
6% reduction by stretching at 78°K . The X- ray and microstructural studies
established that in the alloy deformation twins form along the planes ( 112 } .
183
The direction of slip in twinning [ 111 ] is in the twinning plane. As deformation
along the planes (112 } in this alloy at room temperature is accompanied by
the same characteristic click and intermittent decrease in stress as in the
formation of twins at 78° K , it is assumed / 25 / that at room temperature
twinning also takes place .
The twinning caused by a 2% reduction produced by stretching at room
temperature Mo 50% Re single crystals , obtained by zone melting, was
studied in /24 /. It has been established that at room temperature twinning
occurs in the alloy along the ( 112 ) plane by means of slip in the direction
( 111 ), which is parallel to the twinning plane , as is the case during deformation
at 78° K /25 / .
Twinning in the Mo 35% Re alloy has been studied by electron
microscope /27 /. The foil made of this alloy was bent . The character of
the distribution of extended dislocations located near the apexes of
deformation twins (Figure 57 a ) was studied , as well as the shape of the
deformation twins . It has been found that extended dislocations related to
deformation twins formed in the systems ( 112 } < 111> frequently combine
into very complex networks, and the twinning planes have a discontinuous
appearance . It was assumed that the intricate dislocation networks originate
as a result of intersection of extended dislocations with other dislocations
during transverse slip of the latter ( see Figure 57c ) .
Gaps in the twin planes ( see Figure 57 e ) form for two reasons . Firstly,
if the growing deformation twin encounters an obstacle, a certain number
of extended dislocations remain near the obstacle and surround it . Here a
gap forms on the twin . If this obstacle consists of dislocations , the extended
dislocations may react with the obstacle dislocations , and complicated
dislocation accumulations form between the fragments of the twin (see
Figure 57 d ) . This phenomenon is probably found in a material with a high
dislocation density even under a continuous load . Secondly, with change in
the direction of the bending load , new twins are created , which interact
with the old twins in such a way that the twin dislocations 1/6 < 1117 on the
boundaries of old twins lead to a decrease in the thickness of these twins if
the dislocations move under the applied stress .
Consequently, many series of extended dislocations may pass through
the old twins and cause local thinning . With a sufficiently large number of
intersecting extended dislocations a gap may form on the plane of the
intersected twin ( see Figure 57 d, e ).
Jaffee /29 / believes that rhenium alloys have a high shear resistance
because the influence of the rate of loading on the yield strength is lower
for these alloys than for nonalloyed metals of group VIA.
A no less important mechanism of the influence of rhenium on the ductility
of metals of group VIA is the change in the solubility of interstitial
impurities . According to the theory proposed by Robins /30 /, a decrease
in the solubility of interstitial impurities in the metals of group VIA is
expected when metals of groups VIIA and VIII are added due to the tendency
to maintain six bound electrons . The addition of rhenium with seven
electrons decreases the solubility of interstitial impurities . One of the
proofs that alloying with rhenium decreases the solubility of interstitial
impurities is the reduction in the hardness of cast alloys of chromium ,
molybdenum , and tungsten containing approximately 5 at . % of rhenium
(Figure 58) /15 /. In later works /29 / Jaffee studied chromium - rhenium
alloys, and assumed that at 400 – 700°C more interstitial impurities are dis
solved in group VIA metals alloyed with Re than in nonalloyed group VIA metals .
5511 184
3. Heat treatment of alloys
The properties of rhenium alloys can be greatly varied by heat treatment .

The presence of large regions of solid solutions of rhenium in almost all
transition metals with a body- centered crystal lattice (vanadium , niobium ,
tantalum , chromium , molybdenum , tungsten, etc. ) , and the appreciable
variation in the solubility of rhenium in them with temperature , indicate
that these alloys can be age hardened . There are no data in the literature
on the heat treatment of rhenium alloys , and this is true not only of rhenium
alloys , but also of most alloys of other high- melting metals .
However , it is quite evident that this problem is topical , and the
application of heat treatment (solution heat treatment , tempering , and age
hardening ) will enable us to control the properties . Many difficulties have
arisen in experiments in this field . These are due to the high temperature
( above 2000°C ) from which the metals must be quenched, the need for
protective atmospheres or a vacuum, the prolonged holding for tempering
because of the low rate of diffusion processes in high- melting metals and
alloys, etc.
The research by the authors in this direction showed that the molybdenum
rhenium ( 50:50 ) alloys are age hardenable . Experiments on quenching
from 2300°C and tempering at 800-1400° C for up to 200 hours were carried
out in vacuo on sheet material produced from cast billets .
Microstructural and X- ray studies , as well as hardness measurements ,
have shown that in the hardened state the alloy consists of a uniform solid
solution with a body- centered cubic lattice . Prolonged tempering leads to
precipitation of dispersed particles of a second phase , which after
coagulation was identified as the o - phase / 1 / .
The group of age - hardenable alloys with rhenium includes the multi
component cobalt- base alloy used in instrument making, which was
developed by the authors together with V. A. Sol'ts . The introduction of
rhenium into the cobalt alloy K40N KHM helped to solve the problem of
increasing the hardness and wear resistance of the alloy, and ensured
reliable service under conditions of vibration and high loads /1 , 7 /.
4. Preparation and deformation of alloys of rhenium

with tungsten and molybdenum
Rhenium alloys can be produced, in the same way as metallic rhenium ,

by powder metallurgy and fusion . Cast alloys of rhenium with different
metals are produced by arc melting with a consumable or nonconsumable
(tungsten ) electrode in a protective gas or in vacuo, or by electron- beam
melting
Ingots weighing up to 0.5 kg can be produced by arc melting with
nonconsumable electrodes , and up to 20 kg by arc melting with consumable
electrodes . The consumable electrode in arc melting consists of either
previously prepared sintered rods of alloys of rhenium with tungsten or
molybdenum of the required composition , or of an electrode made of pure
metals (Re , W, Mo, etc. ) in the required quantities .
185
1. C b
1800
T °C a
1800 1400
0
1400 1000
2
1000 600
600 200
Mo
w 20 40 20 40
Re, at. % Re , at . )
с
60 60
20 " 1000 "
40
♡ 40
Re
at.,
Re,
a%t.
%
20 20
O
W 20 40 60 80 MO w 20 40 60 80 MO
Mo , at. Mo. at.com
DOT o.1 1.II
FIGURE 59. Workability of arc -melted alloys of rhenium with tungsten (a), and molybdenum
(b) , and ternary alloys of rhenium with tungsten and molybdenum (c) /15 /:
1 – good workability limit; 2 – recommended minimum forging temperature ; 3 – recommen
ded annealing temperature ; I – rolling into sheet or rod ; II – forging of ingot; III – possible
de formation to a reduction of not less than 20 % ; IV maximum reduction 1090; V - maximum
reduction 90 % .
The preparation of alloys of rhenium with W and Mo by methods of

powder metallurgy , by mixing tungsten and rhenium powders, results in
nonuniform distribution of rhenium throughout the cross section of the rod .
In the sectors rich in rhenium the hard, brittle o - phase is formed , which
causes disintegration of the rod even during the first stages of pressing .
A much more uniform distribution of components can be obtained by
mixing a solution of ammonium perrhenate with tungstic anhydride /6 /, or
by introducing rhenium in the form of ground ammonium perrhenate into
the tungsten powder / 31 /.
After the necessary treatment the mixture was reduced by hydrogen in
several stages at 300 – 1000°C and pressed into billets . These were
presintered at 1100 – 1800°C in hydrogen or in vacuo , and then sintered at
2400 – 2500 ° C in hydrogen .
The sintered rods of alloys of tungsten with a rhenium content of 5 to
20 wt % /6 / were worked according to the conventional procedures for
tungsten by forging and wire drawing to a certain reduction per pass, and
additional intermediate annealings were carried out at dimensions of
5.0 -0.28 - 0.18 mm .
Ingots of tungsten alloys with a rhenium content of up to 30% are easily
hot worked by various methods /2 , 3, 15 , 16 , 18 /. Alloy billets /2 / were
heated to 1450 – 1500°C in an atmosphere of hydrogen and forged with a
186
hammer to a total reduction of approximately 60% . Upset billets were
rolled after they had been heated to 1200 — 1150°C . Billets were rolled
from 0.6 mm after they had been heated to 500 – 600° C, without any
intermediate annealings . The temperature and compositions of tungsten
rhenium alloys that are easily hot worked are given in /15 / ( Figure 59 a ).
The minimum temperature of good hot workability is 900°C , and the
concentration of Re is 18 — 32 % . We see that the upper concentration
limit of good workability somewhat exceeds the boundary of the single- phase
region of solid solutions of rhenium in tungsten . The inferior workability
at a higher rhenium content is due to increase in the amount of hard, brittle
o - phase in the alloys .
The data of / 15 / on ingots weighing 20 – 40 grams show that the Mo- 50 %
Re alloy can be rolled into sheets at room temperature with a high reduction
(over 90% ) without intermediate annealings . Alloys containing more or less
than 50% Re can be deformed at room temperature to 20% reduction
without cracking . At 1800°C alloys containing 21 — 40% Re show good
workability ( see Figure 59b ) . At 1250 and 1400° C 6 mm diam ingots of
alloys containing 22 – 40% Re were satisfactorily forged into rods or plates ,
but attempts to form Mo — 20% Re alloys were unsuccessful even at
1400 – 1800° C .
The influence of oxygen , carbon , and nitrogen on the workability of
molybdenum- rhenium alloys at high temperatures was studied in /17 /
( Table 54 ) .
TABLE 54. Workability of molybdenum -rhenium alloys with different contents of oxygen , nitrogen , and
carbon /17 /
Impurity , at . % Rolling workability

Forging
Content , at. % workability
carbon at 1400 ° C T , °C reduction , characteristic
oxygen nitrogen %
100 0.0050 20 10 Alloy cracked

1250 15
1
Mo - 20 Re 0.0028 1250 24
Mo - 25 Re | 0.0088 1250 45
0.0355 1200 18
Mo - 30 Re 0.0102 1200 59 Good workability
0.0344 1200 32 Alloy cracked
Mo - 35 Re 0.0050 20 95 Good workability
0.0060 20 95
0.0103 Good worka 1250 80 Good workability
bility
10
0.0140 1250 95
0.0250 1250 95
0.0549 1250 95 Good workability
Mo - 35 Re 0.0060 Alloy cracked
0.0070
80
0.0035**
0.0018**
Normal oxygen content .

Carbon content in the charge .
187
Oxygen was introduced into the alloys during smelting in the form of
molybdenum and rhenium oxides , nitrogen entered from the atmosphere of
nitrogen and argon during melting , and carbon was introduced in the form
of MoaC . Alloys containing carbon had the lowest workability . They
cracked even during forging owing to the presence of molybdenum carbides
along the grain boundaries .
From Table 54 we see that with increase in the rhenium content to
35 at . % , the amount of oxygen in the alloy can be increased more than ten
times without any deterioration in the workability of the alloy . The nitrogen
content in the alloy with 35 at . % Re must be below 0.006% , and the carbon
content below 0.0018% .
The influence of 0.5% of titanium has also been studied / 17 /. It has
been found that the presence of 0.5% Ti does not affect the workability of
molybdenum - rhenium alloys .
In / 5 , 15 , 16 , 23 / research is reported on ternary tungsten -molybdenum
rhenium alloys . During the construction of the phase diagram of tungsten
molybdenum -rhenium cast alloys, the authors of / 23 / found a " twinning
limit" in the region of ternary solid solutions, i . e . a region of alloys
containing not more than 20 at . % of rhenium, which can undergo
plastic deformation not only by slip, as is characteristic of metals with a
body- centered cubic lattice (tungsten , molybdenum ) , but also by twinning .
We can assume that the mechanism of the influence of rhenium in the
ternary tungsten - molybdenum - rhenium alloys is similar to that in binary
tungsten- rhenium and molybdenum - rhenium alloys . The workability of
tungsten -molybdenum - rhenium 10 – 20 g ingots was studied / 16 / during an
investigation of a region of the ternary phase diagram . Figure 59 c shows
the workability of cast alloys expressed as the reduction in height as a
result of rolling at room temperature and at 1000°C . It can be seen that
molybdenum- base alloys containing 30 - 35 % Re and up to 20 at . % W are
highly ductile at room temperature ( 90% reduction ) ( see Figure 59c ) . At
1000 °C the region of ductile alloys is much wider , and includes tungsten
rich alloys . The rhenium content fluctuates over the range 15 – 35 at . % .
Various semifinished products can be produced from the cast alloys of
rhenium with tungsten and molybdenum / 1 , 2 , 5 , 14, 15 /. In 1963 - 1964 the
authors , together with S. I. Ipatova , V. M. Amosov , V.I. Karavaitsev , V. Kh .
Khaidarov, A.S. Anatienko, T.S. Khudaberdyev , and l . I. Litvinova ,
developed a production technique for 20 u diam wire from cast tungsten
rhenium alloys containing 27% Re . The authors together with V. N. Starkov ,
P. A. Korchagin , L. S. Petrova, and T. 1. Arkusha developed a technology for
making wire and seamless thin- walled tubes from cast molybdenum
rhenium alloys with 47 % Re , and of 20 u thick foil from rhenium alloys
with tungsten and molybdenum of similar composition. The external
appearance of the semifinished products and some of the articles are shown
in Figure 60. The authors together with 2. A. Timofeeva and P.S. Maksudov
developed a technique for making wire and laminas up to 4 u thick .
There is also a report /32 / on the production of seamless tubes 1.9 mm
in diameter with a wall thickness of 0.25 -0.38 mm , and 6.3 mm in
diameter with a wall thickness of 0.63 – 1.02 mm , from a tungsten alloy
with 26 % Re for service at 3000 ° C .
188
lol FIGURE 60. External appearance of semifinished products and articles made of
alloys of rhenium :
a - with molybdenum ; b – with tungsten; 1 – foil down to 20 m; 2 – wire down to
20 u ; 3 – tube (stages of tube manufacture) ; 4 – foil down to 20 W ; 5 – wire down
to 20 u; 6 – heaters , screen ; 7 – spiral (diameter of wire and core 100 W ).
The semifinished products made of rhenium and alloys of rhenium with

tungsten and molybdenum (Figure 60 ) can be used in very many branches of tech
nology as constructional materials and materials with specific physical pro
perties .
5. Production and deformation of rhenium - chromium alloys
In / 15 / it is reported that rhenium increases the ductility of chromium .

The cast alloy with 35 at . % Re was rolled at 1000°C to 90.6% reduction
and showed good ductility during bending at temperatures down to - 196°C .
It is noted that in an attempt to deform alloys with 21.4 — 54 % Re after
homogenizing at 1000°C in an atmosphere of hydrogen, the alloys cracked
at a reduction of less than 20% , which is explained by the contamination of
the ingots with nitrogen from the insufficiently pure hydrogen in the process
of homogenizing .
One of the reasons why alloying with rhenium increases the ductility of
chromium is the change in the mechanism of deformation, analogous to the
change which occurs in other metals of group VIA, tungsten and molybdenum .
189
Deformation twins were observed in alloys containing rhenium near the
solubility limit ( see Figure 55 ) /22 /.
6. Production and deformation of alloys of rhenium with

niobium , tantalum , and vanadium
As we have already mentioned , alloying niobium and tantalum with

rhenium leads to an increase in hardness and strength, and to a decrease in
ductility .
Niobium and tantalum have a high ductility and a relatively high solubility
of interstitial impurities . Therefore , alloying with rhenium does not lead
to a redistribution of oxides from the grain boundaries , or any change in
the structure of the oxides , and any possible decrease of the solubility of
the interstitial impurities by rhenium may have only a negative effect .
When niobium is alloyed with 10 – 15 % Re and tantalum with 10% Re ,
their workability is greatly impaired , and deformation at room
temperature becomes rather difficult / 1 /.
The above refers to the alloys made by arc melting of commercialniobium
and tantalum , and should be verified on alloys melted in a high vacuum .
Highly pure niobium and tantalum prepared by electron- beam melting can
be alloyed with larger amounts of rhenium without loss of their high
ductility at room temperature .
In a study on the influence of rhenium on the ductility of vanadium ,
carbon - reduced vanadium with 0.10 – 0.3% C was used /21 /. It is only
when 65 – 67 at . % Re is added (alloys near the limit of solubility of
rhenium in vanadium ) that the ductility becomes higher than that of the
unalloyed vanadium , and deformation twins are formed ( see Figure 55 ) . In
this case rhenium has the effect of decreasing the solubility of the interstitial
impurities (oxygen, nitrogen, hydrogen , and carbon ), which are present in
vanadium in appreciable amounts . However , the authors were not able to
attain any considerable increase in the ductility of vanadium of the given
degree of purity by alloying it with rhenium .
There is no special necessity for this , since vanadium can be easily
purified and is relatively ductile after electron- beam vacuum refining .
7. Recrystallization of rhenium alloys
There are today a number of papers describing research on the influence

of rhenium on the recrystallization of certain transition metals (tungsten ,
molybdenum , nickel, titanium , etc. ) .
Recrystallization of alloys of rhenium

with titanium
The addition of rhenium as an alloying component considerably
increases the temperature of recrystallization of iodide titanium /33 /
190
( Figure 61 ) . Research was carried out on cast alloys, cold - rolled to
40% reduction . Small additions (up to 0.49 % Re ) have almost no effect on
the temperature of recrystallization, which for iodide titanium increases
from 550° C to 575° C . But further increase in the rhenium content has a
considerable effect on the temperature at which recrystallization begins ;
it increases to 625°C for an alloy with 0.96% Re and then to 800 °C for
an alloy with 5.8% Re (Table 55, Figure 61 ) .
TABLE 55. Influence of rhenium on the recrystallization temperature of certain metals and alloys
Beginning of End of Re , Beginning of End of
Re ,
Base metals
wt %
recrystalli- recrystalli- Base metals wt %
recrystalli recrys.alli
zation , ° C zation , °C zation , ° C zation , ° C
Ni 0 400 500 Ti 0 550

0.5 500 600 0.49 575
2 600 700 0.96 625
Ni -20 % Cr 850 1000 5.8 800
2 850 1000 Μο 0 950
8 1050 1200 50 1350 1700
12 1100 1200 Pd 0 400
W 0 1100-1150 1400 3.44 800
3 1400 1500 8.74 1000
10 1500 1750 11.9 1000
20 1500 1800 Ta 0 1200
30 1500 1900 2.03 1550
Note . Temperatures at the beginning and end of recrystallization were determined by microstructural and
X - ray analyses, and by measurements of hardness after 30 -min annealing.
The hardness of cast and cold -worked alloys is markedly changed by

small additions of rhenium (up to 0.96 wt % ); further increase in the
rhenium content is accompanied by a more uniform increase in hardness
/ 33 / .
Recrystallization of vanadium - rhenium alloys

The influence of small additions of rhenium on the recrystallization
temperature of vanadium was studied on ingots weighing 400 grams, forged
at 1200°C , annealed , and cold- worked to 75 % reduction / 34 /. It was
found that rhenium increases the temperature at which the recrystallization
of vanadium begins from 860°C for pure vanadium to 885°C for alloys with
0.2 - 0.8 % Re . The sharpest increase results from the first 0.15 at . % Re
(Figure 61 ) .
Recrystallization of tungsten - rhenium and

tungsten - molybdenum alloys
The influence of rhenium (up to 20% Re ) on the recrystallization of
sintered tungsten of grade VCh was studied in /6 /, and of grade 218- W
(with additions of potassium, aluminum, and silicon ) in /35 /. The influence
191
of rhenium on the temperature of recrystallization of VCh tungsten was studied
on 280 u diam wire, as shown in Figure 61 and Table 55. The temperature
at the beginning of the recrystallization of tungsten is 1100 – 1150°C and is
increased to 1300 ° C by 1 % Re and
further to 1500°C by 5 % Re . Further
Ta alloying of tungsten by rhenium has
1500 little influence on the temperature at
W
Мо the beginning of recrystallization .
The introduction of rhenium into
1,°C
Ni - Cr
tungsten sharply decreases the grain
size during recrystallization . The
1000 Pd deformation texture is retained in
alloys subjected to higher annealing
TL temperatures /6 /.
1, ° C
900 The influence of alloying with
V
880
rhenium on the recrystallization of
NL tungsten differs somewhat for sintered
500 860
218- W tungsten containing potassium ,
840
aluminum and silicon , and chemically
820
pure VCh tungsten ( Table 56 ) /35 /.
800 After deformation the alloys had a
0,1 02 0,3
Re, wt % fibrous structure .
5 10 15 20
It can be seen that the beginning of
Re, wt % recrystallization of 218- W tungsten is
at 2000 °C ; after the introduction of
FIGURE 61. Influence of rhenium on the tempera 1 , 3 , and 5 % Re the fibrous structure
ture at the beginning of recrystallization of certain is retained up to 2500°C . A higher
metals and alloys / 1 /. rhenium content , up to 10 – 20% , leads
to a lowering of the recrystallization
temperature.
We believe that the introduction of rhenium in large quantities annuls
the influence of additions which inhibit the recrystallization of sintered
tungsten . However, this problem must be further studied .
TABLE 56. Structure of annea led tungsten (218 - W) -rhenium alloys
Annealing temperature, ° C
Re , %
1750 2000 2240 2500 2750 2850 3000
F F-I I r r r
1 F F F F F- r r r
3 F F F F F -I F-I r
5 F F F F- D F-r I
7 -
r
10 F F-I r r r
20 r r r r I
Note : F -- fibrous structure; F-1 – recrystallization less than 50 % complete;

r - recrystallized structure .
We can assume that in cast tungsten - rhenium alloys the nature of the
influence of rhenium on the recrystallization of cast tungsten of various
192
grades will be similar to that of rhenium on the recrystallization of VCh
turgsten . This is due to the partial burning up of impurities during
melting and purification of the tungsten .
The influence of rhenium (over 20% ) on the recrystallization temperature
of pure tungsten ( VCh) /2 / was studied on sintered and cast samples
0.4-0.75 mm thick, deformed at 1200 – 1400°C (below the recrystallization
temperature ) to 85 – 90% reduction . The an ling time was 30 minutes .
b
SOO
hardness
a
Knoop
900
hardness
Knoop
800 100
700
1 7
600 300
5 8
500
9
4
1200 1300 1400 1500 1600 1700 1800

200 1200 1300 1400 1500 1600 1700 1800
Forged Annealing temp. °C Forged Annealing temp. °C
FIGURE 62. Annealing temperature -hardness (500 g load) curve for deformed binary
alloys of rhenium with tungsten ( a) and molybdenum ( b ) (at. % ):
1 - W - 30 % Re ; 2 - W - 27% Re ; 3 – W - 24.5 % Re ; 4 - W - 220% Re; 5 - W - 33.3 % Mo
- 33.3 % Re; 6 – Mo - 35 % Re ; 7 – Mo - 3000 Re; 8 – Mo- 25% Re; 9 - Mo - 22% Re .
The temperature at the beginning of recrystallization is approximately

the same ( 1500 — 1550°C ) for both cast and sintered alloys with 20 and 30% Re .
All samples at temperatures below 1500°C had a clearly marked fibrous
structure . In cast alloys the deformation texture is more clearly marked
and the grain size is 8 d . Recrystallized cast alloys have a coarse- grained
structure . The grain size of the cast W - 20% Re alloy is 364 after
deformation and annealing at 2000° C, and that of the sintered alloy 15u .
The influence of rhenium on the hardness and recrystallization of cast
tungsten and molybdenum after drawing to a diameter of 1.5 mm (reduction
45 – 55% ) has been studied / 15 /. Figure 62 a / 15 / shows the hardness of
W – Re alloys and of the W – 33.3 at . % Mo- 33.3 at . % Re alloy. For all
alloys the hardness decreases gradually with increase in the annealing
temperature to 1600 – 1700°C . Higher annealing temperatures scarcely
affect the hardness of these alloys . The tungsten alloy with 30% Re had the
highest hardness after annealing at all temperatures .
Curves showing the dependence of the hardness of molybdenum alloys
containing 22 – 35 at . % Re on the annealing temperature are given in
Figure 62 b . The hardness of the alloy containing 35 at . % Re is much higher
than that of all other molybdenum - rhenium alloys after annealing at all
temperatures . This is explained by the presence of a certain amount of
o - phase in the Mo – 35 at . % Re alloy, and also in the W — 30 at . % Re alloy.
From a comparison of Figures 62 a and 62 b we see that at all annealing
temperatures the hardness of the ternary alloy W – 33,3 at . %
Mo — 33.3 at . % Re lies between that of the W – 30% Re alloy and Mo –
35 at . % Re alloy, although the ternary alloy contains a larger quantity of
o - phase than either of these binary alloys .
193
In both binary systems the recrystallization temperature increases with
increase in the rhenium content . Other conditions being equal, alloys of
tungsten with rhenium , rolled without intermediate heating, have appreciably
higher recrystallization temperatures . Not one of the tungsten- rhenium alloys
shows signs of the beginning of recrystallization after 500 hours of heating
at 1000°C , whereas the same treatment causes partial recrystallization
in molybdenum alloys with 22 – 30 at . % Re . The presence of the o - phase
limits grain growth . In the W – 33.3 at . % Mo — 33.3 at . % Re alloy the
beginning of recrystallization lies in the 1300 — 1400° C range after holding
at these temperatures for 1 hour / 15 /. In /4, 5 / recrystallization was
studied of ternary tungsten - molybdenum - rhenium alloys with compositions
(in at . % ratios ) of: 1 : 1 : 1 ; 2 : 1 : 1 ; 3 : 3 : 2; 1 : 2 : 1 ; 3 : 1 : 1 ; and 5 : 2 : 2 . Cast
alloys were rolled without intermediate heating to approximately 90%
reduction . The recrystallization was studied by microstructural and X - ray
analyses and by hardness measurements .
600
560
WY
520
k, gm²
480
Hy
/m
440
ol
•2
grain
400
Diam
‫زه‬
.oH, f
360
320
ZO
280
1000 1200 1400 1800 1800 2000

Annealing temp. °C
FIGURE 63. Influence of annealing temperature on the hardness and
grain size of temary W - Mo - Re alloys (wt % (at . % ratios given in
parentheses):
1 - W -20 % Mo - 400% Re (1 : 1 : 1) ; 2 - W -15 % Mo , 290% Re (2 : 1 : 1) ;
3 - W -13% Mo - 25 % Re ( 5 : 2 : 2 ); 4 - W - 12 % Mo - 22 % Re (3 : 1 : 1) ;
5 – W - 24 % M0-31% Re ( 3 : 3 ; 2) ; 6 – W - 340% Mo - 33 % Re (1 : 2 : 1) .
Figure 63 shows that an increase in the annealing temperature to 1500° C

for 1 : 1 : 1 , 2 : 1 : 1 , and 5 : 2 : 2 alloys , and to 1400°C for the remaining alloys,
does not change the hardness perceptibly . A certain decrease in hardness
is caused by a recovery phenomenon. Over the range of recrystallization
temperatures a noticeable decrease in hardness is observed . In the range
of temperatures of secondary recrystallization the hardness decreases less
sharply, and after annealing at the temperatures of 1800 — 2000°C the
hardness remains almost constant and is 480, 400, 390, 380, and 360 kg /mm²
for the 1 : 1 : 1 , 2 : 1 : 1 , 3 : 1 : 1 , 5 : 2 : 2 , 3 : 3 : 2 and 1 : 2 : 1 alloys, respectively .
From data on the variation in hardness , from X- ray analysis , and from
the variation in grain size ( Figure 64 ) it has been shown that the temperature
194
at the beginning of recrystallization of alloys deformed to 90% reduction
or more is 1550°C for alloys 1 : 1 : 1 , 2 : 1 : 1 , and 5 : 2 : 2, and 1450°C for
alloys 3 : 1 : 1 , 3 : 3 : 2 and 1 : 2 : 1 . For alloys deformed to 40 – 50% reduction
the recrystallization temperature is much higher .
The characteristic microstructure of the alloys is shown in Figure 64 .
Deformed alloys have a fibrous structure ; after annealing in the
temperature range of the beginning of recrystallization the fibrous structure
is partially retained, but small new recrystallized grains appear. Alloys
annealed at temperatures at which secondary recrystallization occurs have
a coarse recrystallized grain , and the grain size increases with increase
in the annealing temperature . We should note that for the 1 : 1 : 1 alloy the
fibrous structure is retained even after annealing at higher temperatures
(up to 1700°C ), and grain growth proceeds more slowly than in the
remaining alloys /4, 5 /.
FIGURE 64. Microstructure of a ternary alloy of rhenium with tungsten and molybdenum
( W -20 % Mo - 40 % Re), deformed to 90 % reduction at 1200 ° C , and annealed at different
temperatures:
a – deformed ; b – after annealing at 1600 ° C ; C - after annealing at 1800° C ; d – after
annealing at 2000° C .
The recrystallization has been studied /2 / of a 0.3 mm thick foil of a

molybdenum alloy containing 50 wt % ( 35 at . % ) Re cold- rolled to 70%
reduction . The specimens were held at the annealing temperature for
15 minutes . The recrystallization started at approximately 1300°C when
recrystallized grains 25 u in size appeared . At 1300 — 1500°C primary
recrystallization started and the grain size increased to 50 m ; at
temperatures above 1700°C secondary recrystallization proceeded, and at
195
2100° C the grains grew to 300 u in size . In alloys annealed at temperatures
above 1600 °C , annealing twins appear . The hardness of the cold- worked
foil, 550 kg/ mm², scarcely changes as a result of annealing up to 1000° C .
With further increase in the annealing temperature , the hardness drops
sharply. At temperatures above 1400 — 1500°C the change in hardness is less
marked and up to 2000 - 2100°C a hardness of 330 - 360 kg / mm² is retained.
We know that the recrystallization temperature of cast molybdenum ,
deformed to 70 % reduction , is 950 ° C . The introduction of 50 wt %
(35 at . % ) Re into the molybdenum increases the recrystallization tempera
ture by 350 ° C .
The deformation and recrystallization textures of the Mo 50% Re alloy
have been studied /26 /. The deformation and recrystallization of wire made
from this alloy produces a <110 > texture , which is the same as the texture
produced by drawing other metals with a cubic body- centered lattice /36 /.
Cold rolling of this alloy produces a composite texture consisting of two
main components : ( 111 } ( 110 ) , ( 112 ) ( 110 ) , and two weak components : ( 100 }
( 110 ) , and { 111 } [112 ). This texture differs from that produced by rolling
pure molybdenum / 37 / as it has a stronger (111] [ 110 ] component, and a
weaker ( 100 } [ 110 ] component . This can be explained by the different
mechanisms of plastic deformation . The recrystallization texture of the
cold - rolled Mo 50% Re alloy is described as a composite texture con
sisting of three components: { 112 ) ( 110 ) , ( 100 } ( 110 ) , and {111} ( 110 ) . In
general, this recrystallization texture is retained during annealing up to
1750 ° C .
Recrystallization of alloys of nickel and

chromium with rhenium
Cast nickel alloys with 0.5 and 2 % Re have been studied , as well as the
nickel alloy with 20% Cr and additions of 0.5, 2 , 5, 8 , and 12% Re . The
alloy rods were formed by cold rolling to 37% reduction . The addition of
2% Re to nickel sharply increases the temperature of the beginning of
recrystallization from 400 to 600 ° C . The introduction of up to 2% Re into
the nickel- chromium alloy has almost no effect on the recrystallization
temperature which remains at approximately 800°C . An increase in the
rhenium content to 8 – 12% increases the temperature of the beginning of
recrystallization to 1050 — 1100° C . The recrystallization of the alloy with
2% Re is complete at 1100° C , and of the alloy with 8 – 12% Re at 1200 ° C
( see Figure 61 , Table 55 ) / 38 / .
Recrystallization of palladium - rhenium alloys

In / 39 / the influence of rhenium on the temperature of the beginning of
recrystallization of Pd was studied on 0.8 – 1.0 mm diam wire specimens
made of cast alloys . It was found that the introduction of 3.4% Re increased
the temperature of the beginning of recrystallization from 400° C for pure
palladium to 800° C . An increase in the rhenium content to 8.74 – 11.9 %
increases the recrystallization temperature to 1000°C , i.e. , 600° C above
196
that of pure palladium , and lowers the tendency of recrystallized grains to
grow . Thus , after annealing at 800°C the grain size of pure palladium is
approximately 60 4. In the alloy with 3.4% Re annealed at 1000 ° C the grain
size is approximately 30 y , and in the alloy with 8.74% Re it is 18 – 20h .
Recrystallization of tantalum - rhenium alloys
E. M. Savitskii , M. A. Tylkina, and I. A. Tsyganova studied the influence

of rhenium on the recrystallization of tantalum . They used a cast (arc
melted ) material, deformed at 1000°C to 60% reduction . Even small
additions of rhenium result in a considerable increase in the recrystallization
temperature . The temperature of the beginning of recrystallization
increases from 1200°C for pure tantalum to 1550°C for the alloy with
2.03 Re . Noticeable grain growth begins after annealing at temperatures
above 1700° C .
The results of a study on the influence of alloying a considerable number
of transition high- melting metals and alloys with rhenium show that in all
cases rhenium increases the temperature of the beginning of recrystallization,
and therefore increases the heat resistance of these metals and alloys .
197
Chapter XIV
MECHANICAL PROPERTIES OF RHENIUM ALLOYS
1. Rhenium - tungsten alloys
The mechanical properties of sintered tungsten- rhenium alloys containing

up to 21% rhenium were investigated in /6 / on 350 , 100 , and 50 u diam wire
annealed at 1200 — 1950°C (holding time 20 minutes in an atmosphere of
hydrogen ) . The tensile tests were carried out at room temperature on wire
specimens with a gauge length of 200 mm . The results are given in
Tables 57 and 58. Moreover, these same alloys were subjected to a
technological test : bending to 90° .
TABLE 57. Ultimate strength (kg /mm²) of annealed wire made of tungsten
rhenium alloys /6 /
Content of Annealing temperature, ° C

Deformed
Re , % 1200 1400 1500 1600 1750 1850 1950
100 W 320 220 180 160 140 85 80

0,5 330 220 200 170 130 85 90
2.75 330 220 200 160 150 130 90
4,75 330 220 180 160 150 140 110 90
8.8 330 220 180 170 150 140 110 90
21 370 230 190 180 180 170 170 150
The introduction of rhenium into tungsten of the VCh grade increases its
ultimate strength and elongation in the strain- hardened as well as in the
annealed states . The strengthening effect of rhenium is particularly marked
in alloys annealed at temperatures near 1800 - 2000°C (the ultimate strength
of an alloy with 21 % Re is twice that of tungsten ) . We know that the
elongation of strain- hardened , and , in particular , of annealed (at all
temperatures ) tungsten wire does not exceed 1 - 2% , whereas wire with a
rhenium content exceeding 5 % shows a 15 – 20% elongation after annealing
at 1400 — 1600°C . Among the materials used in the vacuum tube industry,
such high values of elongation are characteristic only of molybdenum wire
and wire made of molybdenum- tungsten alloys , but the ultimate strength of
these wires is much lower . As an example , we give the following comparative
data . Tungsten- rhenium wire , molybdenum wire , and tungsten – 50 % Mo
198
alloy wire with an 8 – 10% elongation have an ultimate strength of 200 -
220 kg / mm² , 115 kg / mm², and 140 kg / mm², respectively .
TABLE 58. Elongation ( s) of wire made of tungsten - rhenium alloys /6 /
Content Diameter Annealing temperature , ° C

of Re , % ofwire, 1200 1400 1500 1600 1750 1850 1950
100 W 100 1.5 1.5 1.5 1.5 0 0 0

0.5 100 1.5-2 1.5 1.5 1.5
2.75 350 8-11 10-12 12-15 8-10 0.1 0 0-1
100 1.5 1.5-2 13-15 6-8 1.5 0
50 1.5 1.5-2 1.5 1.5 1.5 1.5
4.75 350 7-8 16–18 18-20 20-22 14-16 0-1 0-1

100 1.5 1.5 20--23 20-22 10-12 2-4
50 1.5 1.5 1.5 5-10 8-10 2-4
8.8 350 8-9 14-16 14-17 17-20 21-24 2-4 0-1
100 1.5 16-18 16-18 18-20 11-13 3-5 1-2
50 1.5 8-10 16-20 9-11 5-9 1 1-2
21 350 7-9 18-20 17-19 27-29 16-18 6-7 5-6
100 1.5 18–20 17-19 18-23 16-18 6-10 3-4
50 1.5 21-24 22-24 9-10 8-10 7-9 6-8
Note . The elongation of deformed wire for all alloys was not more than 1.5%.
During the bending tests the VCh tungsten wire annealed at 1400 – 1750°C
becomes brittle . Alloys with 2.75 – 4.75 % Re become brittle after annealing
at higher temperatures, and alloys with 8.8 and 21% Re retain their ductility
after annealing at 1400 – 1850°C .
The mechanical properties of sintered alloys of tungsten with 0 – 20% Re
were also studied in /35 /. The alloys were made of 99.99 % pure rhenium
and of tungsten of the following two grades : 1 ) 99.9 % pure , and 2 ) tungsten
containing potassium , aluminum , and silicon (218- W ) . The bars were
worked by the " tungsten" process to 0.203 mm diam wire , at a total
reduction of 99% . The properties of the alloys were studied by tensile testing
at room temperature after annealing at up to 3000°C for 3 minutes ( Table 59 ) .
As we see from a comparison of the data of /6 / and /35 /, the optimum
strength and elongation are attained in pure tungsten ( VCh ) by alloying it
with 20% Re , and in 218- W tungsten by alloying with 10% or less Re . These
data / 35 / require checking .
According to /6 /, the introduction of up to 20% Re increases the strength
of sintered alloys , and also considerably increases their ductility in the
recrystallized state , but the data of /35 / show that the maximum increase
in strength in the recrystallized alloys is obtained by alloying with
5 – 10% Re , and not with 20% Re , and maximum ductility by adding 3 % Re .
Evidently, this difference should be ascribed to the effect of admixtures in
the initial 218- W tungsten (potassium, aluminum , and silicon ) . It is possible
that the rhenium introduced interacts with these admixtures . It is assumed
that the admixtures , as well as rhenium , are located at the grain boundaries
/ 35 /. The amounts of rhenium introduced (over 3 – 5% ) are sufficient to
neutralize the favorable effect of the admixtures on the increase in the
stability of the structure , but they are not sufficient for a full manifestation
199
of the favorable effect of rhenium on the ductility and strength of tungsten .
Very interesting, from this point of view , is a comparison of the properties
of the alloys W - 3% Re (tungsten without admixtures) and 218- W – 3% Re
(tungsten with admixtures ) /35 /. It was found that the 218- W 3 % Re alloy
is ductile after heat treatment , whereas the W – 3% Re alloy is brittle / 35 / .
TABLE 59. Mechanical properties of rhenium -containing 218 - W alloys /35 /
Content Proper - Annealing temperature , °C

Deformed
of Re , ty 2240 2750
1750 2000 2500 2850 3000
0 281 193.3 138,5 135.7 135.7 126.5 114.6

OB
00.2 236.2 189.8 135.0 133.6 135.7 126,5 114,6
8 0.2 0.3 0.5 0.2 0 0 0
HB 544 435 396 391 391
OB 301.3 191.9 179.3 173.6 175.0 163,1 87.9 60.5
Ic
30.3 219.4 186,3 177.9 168.7 169.4 117.4 85.8
1.9 2.2 5.8 12.8 16.7 19.3 1.0
HB 541 524 514 508 490 411
3 323 187.0 168.7 155.4 149.0 144.8 142,7 117.4
OB
00.3 274 182.8 167.3 154.0 145,5 131.5 109.0 98.4
1.8 9.2 18 20 23 25.4 27.6 9
HB 465 464 414 410 407 377

5 OB 337.7 196.8 172.2 163,8 158.2 152,6 154.7 127.9
60.3 274 190.5 169.4 161.7 151.1 132,2 103.3 96.3
8 1.6 5.1 16.3 19.3 18.0 16.0 23.9 11.5
-
HB 503 424 389

7 OB 352 283.8 175.8 170,1 161.7 154.7 142.7 140.6
00.3 270.5 260 156.8 139,2 114.6 108.3 91.4 86.5
2 2.5 17.0 17.5 14.5 13.0 9.0 13.6
III
8
III
10 OB 358.3 187.7 180.0 172,9 172,9 166.6 144.1
00.2 253 182.8 178.6 119.5 108.3 102,6 97.0
8 1.6 18.5 21.5 21.1 17.6 18.2 7.5
-
HB 585 585 585 470 450

20 OB 355.5 189.1 145.5 133.6 130.8 125.1 116.0
003 264.9 146.9 129.4 117.4 113,9 114.6
120.9
8 2.2 14.4 6.2 3.5 2.8 2.3 1.0
HB 594 538 496 490 467 458
Note . OB, 00.2,HB in kg/mm², 8 in % .
The tensile properties of cast tungsten- rhenium alloys ( 20 – 30% Re )

were studied in / 1 , 3 , 15–17 ) .
In /3, 15, 16 / the mechanical properties of tungsten- rhenium alloys were
studied on 1.27 x 1.27 mm wire , produced by hot rolling at 1850°C , and on
round drawn wire .
Data on the ultimate strength and elongation at room temperature of
tungsten- rhenium alloys in the deformed and annealed states /3, 15, 16 / are
given in Figure 65.
In /1 / the authors also investigated the mechanical properties at room
temperature of cast tungsten alloys with 25 and 30% Re produced by arc
melting with a tungsten nonconsumable electrode in an atmosphere of
purified helium . The alloys were deformed by forging after heating to
1400°C , and rolling after heating in hydrogen up to 1200°C . The temperature
at the end of rolling was 800 – 900° C (hot rolling ), and the total reduction was 30% .
200
The tensile properties of alloys at room temperature were tested on
flat samples 0.7 – 1.00 mm thick / 1 / ( Figure 65 ) . From Figure 65 we see
that the data obtained in / 1 , 3 , 15 , 16 / on the ultimate strength agree
well with those for recrystallized alloys , but are very different from those
on deformed alloys . Evidently, this is due to the large difference in the
degree of strain hardening of the deformed alloys , as well as in the shape
of the samples . The degree of reduction of alloys tested in /1 / was
45 – 50% , i . e . , approximately half as high as given in /3 , 15 /.
250 o 1
2
7W - Re (d )
/ m²
200
Do
kg
m
150
W- Re Mo - Re ( d)
100
MO - Re ( r )
50
25
Mo- Re (r)
20
W - Re (d )
10 W - Re ( )
MC - Red )
20 24 28 J2 36
Re , at. %
FIGURE 65. Room temperature values of the ultimate
strength and elongation of cast molybdenum -rhenium
and tungsten -rhenium alloys, deformed and recrystal
lized :
1- according to / 3, 15, 16 /; 2- according to /1 / .
The tensile properties of deformed and annealed wire of various

diameters ( 300 – 20 u ) made of W + 27% Re castings were determined in the
joint work of the authors with N. I. Freze , V. Kh . Khaidarov , A.S.Anatienko ,
T. S. Khudaiberdyev, and N. I. Litvinova. During drawing the wire becomes
much stronger with increase in the degree of deformation . The ultimate
strength of annealed wire of various diameters is approximately 170 –
200 kg / mm² , and the elongation 18 - 22% . Wire deformed to 60 – 65 %
reduction had an ultimate strength of 300 – 350 kg / mm² at various stages
of drawing, and an elongation of only 1 – 3% . In the research the authors
carried out together with Z. A. Timofeeva the strain hardenability of the
tungsten - rhenium alloy was also high . In the transverse direction the
strength of wire or strip made of this alloy and deformed to a reduction of
over 80 % more than doubles, and reaches 450 kg / mm² .
201
Effect of temperature on the mechanical
properties of tungsten - rhenium alloys
The strength and ductility of sintered alloys of tungsten with 1 – 19.2% Re
were determined in the temperature range of 20 – 3000°C in a current of
argon /6 / . The 280 u diameter wire with a gauge length of 150 mm
was heated by an electric current .
The results of tests are given in Table 60. We see that the ultimate
strength decreases sharply with increase in temperature , but at all
temperatures the ultimate strength of the alloy is higher than that of the
unalloyed tungsten . It is interesting to note that at ~ 1200°C the ultimate
strength of W – 19.2% Re alloys is higher than that of unalloyed tungsten .
TABLE 60. Ultimate strength (kg/mm²) of 280 u diam wire made of tungsten -rhenium alloys /6/
Testing Content of Re , % Testing Content of Re , %
tempera temperature,
ture , ° C 0 1.00 2.86 4.9 8.7 19.2 °C 0 1.00 2.86 4.9 8.7 19.2
20 248 247 260 266 280 307 1600 39 35 41 41 41 46
Ultimate strength not 1800 24 17 15 22 25 26

200 200 determined 2000 11 11 11 18 15 14
400 180 The same 2200 9 9 9 12 13 13
81
600 119 2400 7 6 8 9
800 111 2600 4 4 4 7 7 7
1000 74 113 114 131 137 130 2700 2 2 2

1200 51 84 85 123 2800 4 4
1400 42 57 51 63 50 3000 2 2
The maximum testing temperature at which the wire is ruptured by the weight
of the clamp is 2700°C for tungsten and alloys with 1 and 3% Re, and approximately
3000° C for alloys with 10 and 20% Re , i.e. , almost 300°C higher .
As we see from the table , alloying with rhenium up to 20% increases the
ultimate strength of tungsten at high temperatures and its service temperature,
and at the same time increases the ductility of the alloys .
The high- temperature " sagging" tests on sintered tungsten- rhenium alloys
made of 218- W tungsten with 0 – 20 % Re were carried out in / 35 / on
U- shaped samples of 0.2 mm diam wire fastened horizontally in a furnace
filled with hydrogen . The wire was heated for 1 min by an electric current
of magnitude 70% of the melting current , and as a result the alloys
recrystallized . The wire was reheated by the same current for not less
than 5 minutes . A measure of the resistance to sagging was the change in
the horizontal position of the wire .
With increase in the rhenium content the sagging of the free end of the
wire increases :
Content of Re, % . 0 1 3 5 7 10 20
Sagging of the free end of
wire , mm 0-2 0-2 4-5 4-5 10-16 30-50 40-60
The authors of /35 / compared the properties by tests on the sagging of

wire made of alloys containing rhenium ( 3% ) that had been prepared from
pure tungsten and from 218- W tungsten containing admixtures. The wire
202
made of W + 3% Re had a 40 mm sagging deflection as compared with a
4 mm sagging deflection for a wire of 218- W – 3% Re . This indicates that
the properties of alloys prepared from 218- W are affected by the properties
of tungsten, rhenium , and admixtures (potassium , aluminum , and
silicon ) /35 /.
The results of tensile tests on sintered 218 - W +0 – 20% Re ,
carried out at 1400 – 2000°C , are shown in Figure 66 /35 /. As we can see ,
alloys made of 218- W with 3 and 5 % Re
have the highest strength and the
least loss of strength over this temperature
range , whereas the strength of alloys with 10
98 and 20% Re drops rapidly, beginning at
1400°C , and at 2000°C they have an
68.m
ultimate strength of the same order of

g
?/m
70 magnitude as the unalloyed 218- W, or

even lower /35 /. The data of /35 /
disagree with those of /6 /, according to
42
which the highest strength at 2000 –
3000°C is shown by alloys containing
20% Re . Evidently, here we have the
effect of admixtures (potassium , aluminum ,
14
1400 1600 1800 2000 and silicon ) introduced into 218- W to
7.C stabilize the structure .
FIGURE 66. Temperature dependence of the The properties of cast tungsten- rhenium
ultimate strength of alloys of sintered tung- alloys with 20 – 30% Re at high tempera
sten (with admixtures of aluminum , potassium ,
and silicon ) with rhenium :
tures were studied in / 1 , 3, 15 – 17 /.
In / 15, 16 , the authors studied the
1- 218 - W; 2 – 218 - W - 1 % Re ; 3 218 - W mechanical properties of 1.00 mm diam
-30% Re ; 4 - 218 - W - 5% Re; 5 218 - W
10 % Re : 6 -218 - W - 20 % Re /35 /.
and 1.27 mm diam wire at temperatures
up to 1800°C . The mechanical properties
of the tungsten- rhenium alloys at different
temperatures, and in the deformed and
recrystallized states ( 1800°C, 1 hr ) are given in Figure 67. Data on wire
of the same diameter made of unalloyed tungsten /40 / are shown for
comparison .
The curve representing the temperature dependence of the ultimate
strength of the recrystallized alloy has a bend in the range of 500 – 800°C .
The authors of / 16 / believe that this is due to the precipitation of the o - phase
in the alloy. From the graph we see that the highest strength in the
0 – 1200°C temperature range is shown by the deformed alloy, and at
1200 - 1600°C by the recrystallized alloy .
At temperatures above 1800°C the ultimate strength of alloys and of the
unalloyed deformed tungsten is the same . However, the ductility of tungsten
rhenium alloys is very high compared to that of the unalloyed tungsten, and
at 20 – 1500°C the recrystallized W - 27% Re alloy has an elongation of
20 – 30%, whereas pure recrystallized tungsten has an elongation not
exceeding 1-2% .
In / 1 / the mechanical properties of deformed tungsten alloys with 25 and
30% Re at 1500° and 1800°C were tested . The alloys were heated by a
tantalum heater and the tests carried out in vacuo, 10-3 mm Hg, on 0.7 –
10 mm thick cast sheet specimens . The results are given in Figure 67 and
203
Table 61. As we see from the graph, the data of /1 / at 1500 and 1800°C
agree well with those of /16 ), and lie on a continuation of the curve plotted
in / 16 / for the ultimate strength of the deformed alloy .
280
245 01
W - 25 Re ( d )
W - 30 Re (d)
/.kgm²
210
Og
m
W (d)
2R7-
er(
W
W - 30 Re(d )
105 W - 30 Re (r)
,kg8m²
160
70
6601
/m
140
35 W ()
112
84 601
W - 27Re (r)
20
W - 30 Re(d ) 2
W - 30 Re ( r) 60
%P'
8
W ( d) 20
400 800 1200 1600 -200 0 200 400

1, °C T.C
FIGURE 67. Temperature dependence of FIGURE 68. Influence of heat treatment on
the mechanical properties of cast tungsten the properties of the W - 30 % Re alloy at
rhenium alloys after deformation and re -196 to + 400° C :
crystallization :
1 – heating to 1800 ° C , water quenching;
1 - according to data of /15 , 16 / ; 2 – 2 – annealing at 2000 ° C , cooling in vacuo .
according to data of / 1 / .
A study of the effect of temperature on the hardness of cast tungsten

rhenium alloys was carried out in /6 / over the temperature range of
20 – 1000°C and in an atmosphere of argon. The hardness of tungsten and
of alloys from the region of solid solutions with 2, 5, 10, 25, and 75 % Re
( x- phase ) was measured . The change in hardness with temperature in cast
tungsten and its alloys with 2 and 5 % Re is about equal . Alloys containing
10 and 25 % Re have a high hardness at all temperatures ( 350 – 420 kg / mm²
at 20°C , and 200 kg / mm² at 800°C ) .
The hardness of the alloy with 75 % Re decreases sharply from
650 kg / mm² at 20°C to approximately 200 kg / mm² at 800 ° C .
The effect of oxygen, heat treatment , and the testing temperature, in the
range from - 196 to +400°C , on the properties of the W – 30% Re alloy was
studied in / 17 / (Figure 68, Table 62 ) . Ingots of alloys with 0.0042 and
0.0074% of oxygen were deformed at 1400 — 1600°C . The rods formed were
204
heated at 1800° C for 1 hr and quenched in water . One series of samples
with a low oxygen content was also annealed in vacuo ( 2000° C , 1 hr ) before
the test to dissolve the o - phase which appeared after annealing at 1800°C ,
but this attempt resulted only in coagulation of the dispersed o - phase
particles .
TABLE 61. Mechanical properties of alloys of tungsten , molybdenum and tantalum with rhenium at high
temperatures /1 , 5 /*
OB, kg /mm² 8, %
Composition of alloy , wt % annealed deformed annealed deformed
200 20 ° 1500 ° 18000 200 15000 1800 °
W – 30 Re 140 272 34,1 14.3 7.0 5.6

W - 25 Re 119 271 30 15.9 2 6.7 9.0
Mo - 50 Re 95 178 15.2 6.0 4 9.0 25
Mo 40 Re 84 153 13.6 6,2 13.5 16
40 W – 20 Mo – 40 Re ( 1: 1 :1 ) ** 125 185 21 11.8 0 13.5 22
57 W – 15 Mo — 29 Re (2 : 1 : 1) 98 129 26 9.3 7.2 6

45 W - 24 Mo – 31 Re ( 3 : 2 : 2) 90 113 24 8.6 6 8.0 15
33 W - 34 Mo - 33 Re ( 1 : 2 : 1) 92 124 21 9.3 10 7.0 23.5
Ta - 1.5 Re 60 16.9 8.7 5 8.5
Ta- 5 Re 118 23 13.8 2 10.5
The mechanical properties were determined using flat samples 0.7-1.0 mm thick and 50 mm long
(gauge length ).
The data on the ratios of the elements in at . % are given in parentheses .
TABLE 62. Properties of the W - 30% Re alloy during short - time tensile tests /17/
Heat - treatment Strength , kg /mm ? Ductility, %

Testing tem
before the test perature , ° C
00.1 00.2 OB 8
1800 ° C /hr, quenching in 20 132.2 133.04 142.0 5.0 3.8

water 200 100.5 102.04 120.06 12.3 21.0
400 93.71 93.71 110.26 11.3 25.0
-196 135.35 151.1 154.35 0.6 1.0
2000 ° C / 1 hr 20 111.31 111.31 0.6 6.9
400 96.93 93.20 111.38 6.1 22.6
1800 ° C / 1 hr* 20 128.32 130.1 130.1 1.1 1.8
Alloy with 0.0074 % O2, the other alloys contained 0.0042 % O2 .
After the alloy had been quenched from 2000° C the strength and ductility
decreased as a result of the coagulation of the particles of the o- phase .
Increase in the oxygen content decreases the ductility and yield strength,
but has no effect on the ultimate strength / 17 /.
205
2. Molybdenum - rhenium alloys
The mechanical properties of molybdenum - rhenium alloys have been
studied in a number of papers /1 – 3, 15 — 17 /.

In / 3 / it was found that the addition of rhenium to molybdenum increase :
the strength and ductility of the alloys . Figure 65 shows the dependence of
the tensile properties of the cast, deformed , and recrystallized rhenium
molybdenum alloys at room temperature on their rhenium content . The tes
were carried out on 1.06 – 1.27 mm diam wire . Figure 65 and Table 61
show the mechanical properties of molybdenum alloys with 40 and 50 wt %
( 30 and 35 at . % ) Re / 1 /, for cast sheets of deformed and recrystallized
material 0.7 – 1.0 mm thick . The data of both papers agree well, in spite
of the different preliminary treatment and the shape of the samples .
TABLE 63. Properties of foil made of cast Mo - 50 % Re alloy at room temperature /2/
Annealing Microhard Annealing Microhard
OB Grain size , OB Grain size ,
temperature , ness , temperature , ness ,
° C kg /mm² kg /mm2 ° C kg /mm . kg/mm
Deformed 280 550 20 1700 106 360 150

1000 580 20 1800 98 360 150
1200 400 20 1900 101 340 200
1300 183 400 25 2000 103 340
1400 166 360 36 2100 330 300
1600 132 370 51
Foil thickness 0.1 mm .

Foil thickness 0.3 mm .
In /41 / the cast molybdenum - rhenium alloys , which contained up to

30% Re , were rolled at 1250 — 1300 °C in vacuo and annealed at 1400°C for
40 hours . When up to 30% Re is introduced , the hardness and ultimate
strength of the alloys at room temperature increase greatly, but the
elongation and the reduction of area decrease .
The effect of recrystallization annealing on the mechanical properties of
Mo + 50 wt % ( 35 at . % ) Re foil at room temperature was studied in /27. The
foil cold worked from the cast alloy has an ultimate strength of approximately
280 kg /mm². After recrystallization at 1300 - 1600°C the ultimate strength
decreases to 185 – 130 kg / mm², and after annealing at 1700 – 2000°C it
decreases to 100 kg / mm² . In Table 63 we give the results of the measure
ments of microhardness , ultimate strength , and grain size of Mo 50% Re
foil after strain hardening and various annealing processes .
In /42 / the authors studied the mechanical properties of sintered and
electron- beam melted molybdenum - rhenium alloys . The tensile properties
of sintered alloys containing 15 and 30% Re after deformation and annealing
at 1100°C for 5 minutes are given in Table 64. The tests were carried out
with 1 mm thick samples, cut longitudinally and transversely to the directioi
of rolling .
206
TABLE 64. Mechanical properties of sintered alloys of molybdenum with 15 and 30 % Re
Mo - 15 % Re Mo - 30 % Re
Property
deformed annealing , deformed annealing,
1100 °C , 5 min 1100 ° C , 5 min
106 81 127 101

OB
110 78 130 99
100 69 127 87
002
101 64 123 78
8 9 9 12
8
4 7 6 17
24 14 19 16
9 8 12
Note . In the numerator we give the properties of alloys in the longitudinal direction,
and in the denominator in the transverse directions; 0B , 00.2 in kg /mm²; 8 and y in % .
The tensile properties of alloys prepared by electron- beam melting

are given in Figure 69. The sharp increase in strength and ductility is
noticeable in alloys containing approximately 50% Re .
b
a
120
02.2
30
gm²
/k,08.
m
100
%
80
By
o.
Gari 10
60
1
40
20 40 20 40
Re,wt %
FIGURE 69. Mechanical properties at room tempera
ture of the molybdenum - rhenium alloys , prepared by
electron - beam melting /42 /.
Studies of the properties of molybdenum - rhenium alloys were carried

out by the authors together with Timofeeva /43 / ( Figure 70 ) using micro
section specimens (wire with a diameter up to 20 u and strips up to 4u thick ) .
We studied the physicomechanical properties which are important in
materials for the production of elastic elements in instrument building. As
we know , the so- called dimensional factor affects the physicomechanical
properties , especially the mechanical properties . Thus , the strength of
thin fibers in microspecimens is sometimes several times greater than
the strength of the same material shaped into conventional samples of
standard size . The reason for this is not sufficiently clear, but evidently
the character, location, and the shape and the amount of imperfections and
dislocations , and the high surface-to-volume ratio of the metal, are some
207
of the factors which determine these properties of the material . Moreover ,
the very character of the deformation of the material in microsections is
significantly different from that in large volumes .
voor 35000 1200 04
.mm
225
,?wm"/ g
,/P' hm
,kgm²
E,gm²
om
k
og
/m
k/m
1.
%
300 30000 9001 Q3 QZ
14
25000 600 02
100 zopogt 300 QI 0.1

ß
O 15000 0.05
25
Re
FIGURE 70. Influence of the rhenium content in the molyb

denum -rhenium alloy on the ultimate tensile strength
(degree of deformation 85 % ); modulus of elasticity; micro
hardness; elastic lag during torsion; electrical resistivity in
microsections.
The influence of the method of preparation of alloys on the mechanical

properties of thin fibers produced from them is shown in Table 65 .
TABLE 65. Mechanical properties of fibers of molybdenum -rhenium alloys (alloys were prepared by various
methods)
Μο 30 % Re Mo 500 Re
Strength ,
kg /mm2 electron - beam electron -beam
sintered arc -melted sintered
melted melted
OB 300 380 400 280 290

00.2 250 260 290 190 200
Degree of deformation of alloys 84 % .
As we see , the ultimate strength of a fiber of a molybdenum - rhenium

alloy may be as high as 400 kg / mm².
208
1
The mechanical properties of the Mo – 35 at . % Re alloy after electron

beam melting in vacuo ( 10-5 mm Hg) were investigated in /44 /. It has been
found that an alloy deformed to 90% reduction has ob 174 kg / mm² and
8 < 1% ; after annealing at 2000° C for 4 hours of 85 kg /mm², 00.2 = 38 kg / mm²,
= 20% , and its properties differ but little from those of the alloy after arc
melting . The cast alloy has a coarse - grained structure /44 / .
The tensile properties of single crystals of the Mo — 50% Re alloy at
room temperature were studied in /24 /. It was established that the ultimate
strength of a single crystal of the Mo - 50% Re alloy is 65 kg / mm², and the
elongation 7.5 % . Failure occurred by rupture.
The authors , together with N. I. Freze , V. Kh . Khaidarov, A. S. Anatienko ,
K. S. Kanteev, and P.S. Maksudov , developed the technology of making wire
from the Mo -- 47% Re alloy, and determined its mechanical properties . In
the process of drawing, with increase in the degree of deformation, the wire
strengthens greatly. In the annealed state the ultimate strength of wire of
various diameters is 120 – 140 kg / mm², and the elongation 20% . The
deformed wire with a reduction of 70 – 80% at various stages of drawing
had an ultimate strength of 200 – 220 kg / mm², and an elongation of only
2 – 1.5 % ; when the reduction exceeded 90% , the strength ofthe wire , measured
on microsections , was 400 kg / mm² .
Influence of temperature on the mechanical

properties of molybdenum - rhenium alloys
The mechanical properties of rhenium- molybdenum alloys at high
temperatures were studied in /1 , 3, 15 – 17 , 41 / .
The authors of /41 / studied at 1200°C the mechanical properties of
molybdenum- rhenium alloys with up to 30% rhenium content (Figure 71 a ),
obtained by arc melting and rolling at 1250 – 1300° C in vacuo . With increase
in the rhenium content the strength and ductility of the molybdenum
rhenium alloys (up to 30% Re ) increase .
In / 3, 15, 16 / tests were carried out at 0 – 1800°C with 1 – 1.27 mm
diam wire made of cast Mo — 50% Re alloy . The alloys were tested in
the deformed and recrystallized states (Figure 72 ) . For comparison, we
show on the same graph the properties of unalloyed molybdenum under
similar conditions . Molybdenum - rhenium alloys retain their strength and
ductility up to 1000°C . At temperatures above 1000°C the ultimate strength
of all alloys in the recrystallized state falls rapidly and uniformly. The
ultimate strengths of alloys with 22 — 30 at . % Re are close to each other . At
these temperatures the strength of alloys with 35 at . % ( 50 wt % ) Re is
somewhat higher . The delay in loss of strength of the deformed alloys at
temperatures near 800° C is probably caused by age hardening and
precipitation of the o- phase , as in tungsten- rhenium alloys /3, 15 /.
In Figure 72 and Table 61 we give data on the mechanical properties at
1500 and 1800°C of deformed and annealed sheet 0.7 – 1,0 mm thick / 1 /,
made of cast molybdenum alloys with 40 and 50 wt % Re .
As we see from Figure 72, the ultimate strengths according to the data
of / 1 , 3, 15 / agree well, and the data of /1 / could be used to prolong the
curve plotted according to the data of /3, 15, 16 /, although in these last
papers the properties were studied on a wire , and in / 1 / on sheet .
209
a
30 30
/k,Gagm²
Go
m
20 20
Мо 20 30
Re, wt %
с
b 0.4 %
/kgm
0.47 % 60
m
60
Go
/, gm²
HB
kto
80 40 60
m
/k,Oggm²
40
m
1407 .Y . 60 20 40
20
-100 10 20
o
0
S
Nb 1 2 3 нь 1 2 3
Re, wt % Re , wt %
FIGURE 71. Mechanical properties of alloys / 41 /:

a – molybdenum -rhenium alloys at 1200°C ; b and c – niobium -rhenium alloys at 20 and
1200 ° C , respectively.
Properties of rhenium- molybdenum alloys at low temperatures were

studied in / 17 /. As we see from Figure 73 a, the ultimate strength increases
with decrease in temperature , whereas the yield strength and elongation
scarcely change up to the ductile - brittle transition temperature
(approximately - 196°C ), since , according to the authors of / 17 /, the
stresses required for twinning at these temperatures remain constant or
even decrease .
The hardness of cast alloys of the molybdenum- rhenium systems over the
entire concentration range at temperatures from - 196 to + 1150°C was
measured in a current of argon (the temperature of - 196°C was attained by
cooling the samples in liquid nitrogen ) /45 / (Table 66 ) .
The effect of admixtures (oxygen, titanium ), of various heat treatment
processes , and of the testing temperatures on the properties of molybdenum
rhenium alloys were studied in / 17 ). The research was carried out on cast
alloys . Titanium was introduced either in the form of iodide titanium or as
a component of the commercially pure molybdenum containing 0.5% Ti .
Oxygen was introduced as molybdenum and rhenium oxides. The alloys were
forged at 1400°C and rolled at 1000 – 1250°C (the so- called " hot- and - cold
treatment" ). Mechanical properties of the alloys were determined, using
specimens in the deformed and recrystallized states . Moreover, some of
the alloys were tested after the " hot - and - cold " treatment followed by
annealing at 1600, 1800, and 1850°C for 0.25 – 2 hr . The results of short
210
time tensile tests on alloys at temperatures from – 196° to + 1204°C are
given in Table 67. Figure 73a and b shows the dependence of the tensile
properties of the molybdenum alloy with 35 at . % Re on its oxygen and
titanium contents . It was established that the introduction of 0.5 % Ti has
scarcely any influence on the ultimate strength , yield strength, and ductility
of the alloy. An increase in the oxygen content increases the ultimate
strength of the alloy by 10 - 20% .
TABLE 66. Hardness (kg /mm²) of rhenium -molybdenum alloys /45/ *

Testing temperature , ° C
Content of Re , %
-194 20 400 600 800 1000 1150
100 Mo 370 146 78 80 82 75 73

1 320 154 92 92 93 56 37
3 380 146 102 105 86 47
5 400 152 100 99 103 69 51
10 340 180 113 140 127 96 65
25 370 238 154 140 132 98 80
50 450 282 208 189 196 127 85
75 1120 ** 880 820
90 670 555 392 347 339 235 220
100 400 274 210 208 204 144 134
Hardness measured with conical indenter (90° apex angle) under a 5 kg load .
Microhardness Hy under a load of 200 grams.
168
7
8
/ m²
112
68
kg
m
56
28
20
10
8.
%
400 600 800 1000 1400 1800 2000

T. ° C
FIGURE 72. Temperature dependence of the mechanical properties of
cast molybdenum -rhenium alloys:
1- Mo -35 at. % Re ; 2 - Mo - 30 at. % Re ; 3 - Mo - 25 at. % Re ; 4 -
Mo - 22 at. % Re; 5 – Mo- 20 at . % Re; 6 – deformed ; 7 – recrystallized;
8 - according to data of /3 , 15, 16 / ; 9 – accord ing to data of /1 / .
211
!
TABLE 67. Mechanical properties found by short -time tensile tests in molybdenum -rhenium alloys
Testing 0.01 o
0.1 " 022" CB
Content, at. % State of alloy tempera 8,9%
ture , ° C
kg /mm² kg /mm² kg/mm² kg /mm²
100 Mo /10 / R 20 45.84 57.04 29 21.5

225 21.24 37.65 71.5
450 18.3 30.2 48 81.5
975 12,7 24,25 41 97.5
1100 11.2 17.53 72 97
Mo - 10 Re R -196 95.6 <1 <1
-196 97,7 <1 <1
20 33.7 37.3 47.8 4 6
Mo 20 Re R -196 88.6 101.9 1 2
20 52 54.8 64.7 5 8
Mo - 30 Re R -196 85.8 92,1 116.0 2 3
20 62.6 65.4 90.7 12 47

Mo - 35 Re h.c. t .; annealing -196 35.27 39.47 131.71 13.3 52
- 02 < 0.001 1 hr , 1850 ° C

c.W .; deformation 95 % 20 73.8 151.8 176.5 180.91 1
C.W .; annealing 2 hr, 20 107.6 114.6 114.6 123.7 2

1600 ° C
h.c.t .; deformation , 20 85.8 121.6 128.6 134.65 4 8
60 %
h.c.t .; annealing 20 88,6 91.4 0.6 4
1/4 hr, 1800 ° C { 20 77.3 81.85 101.2 7.7

h.c.t .; annealing 1 hr, 20 48.01 59,1 61.2 135.14 20.0
1800° C 20 40.38 38.7 91.96 27.4 76.0
h.c.t.; annealing 1 hr,
1850° C { 200
400
37.72
39.19
35.55
37.02
65.05
53.54
16.0
20.0
66.3
70.5
h.c.t.; deformation , 982 40.24 56.27 10.0
60 % 1204 8.75 34.05 17.0
Mo - 35 Re h.c.t .; annealing 1 hr, -196 61.41 70.02 149.02 15.4 13
-0.0018 O2 1850 ° C 20 57.95 62.04 100.08 19.1 51
200 47.31 49.2 75.34 17.7 44.9
400 45.21 41.15 67.5 24.0 61.8
Mo - 35 Re h.c.t .; deformation , 20 95.25 114.46 118.24 124.4 10.0 22.4
-
- 0.5 wt % 60 % 982 50.39 61.34 10.9 16.0

Ti **
Μο 35 Pe + h.c. t.; deformation , 20 103,65 116.7 120.2 123.84 8.0 25.6
+0.5 Tit 6007 982 69.32 69.32 18.0 17.9
Mo - 37.5 Re R -196 147.6 1 <1
-196 130.1 140.6 151.8 1 1
R – recrystallized; h.c.t. – "hot -and - cold treatment" ( temperature 1000 — 1250° C ); c.w. - cold worked .
Prepared from iodide titanium .
† Prepared from Mo - 0.5 % Ti.
The long- time strength of a molybdenum alloy with 35 at . % ( 50 wt % ) Re

at 982º and 1093°C was determined in / 17 /. For comparison , tests were
conducted under the same conditions on pure molybdenum and on molybdenum
alloyed with 0.5% Ti . The time to failure was determined for fixed stresses
and temperature ( Table 68 ) . As we see from these data, the molybdenum
alloy with 50% Re has the highest ultimate strength at 982°C . The time to
failure under 28.1 kg / mm2 stress is more than 100 times the time to failure
of molybdenum with 0.5% Ti under 24.6 kg / mm² stress . According to the
212
b
k, gm² g
a
155
602.0
.Ggm2
Bor 155
3
/m
/kg
2
m
126
126
98
98
60
70 70
56 56
60,1 GOLD
40 40
8 o
20 20
%
8,%
0
O 0
-200 0 200 400 200 400 600 800 1000 1200
1 °C Tor
FIGURE 73. Mechanical properties at various temperatures of the cast Mo - 35 at . % Re alloy

containing oxygen (a) and titanium ( b ):
1- less than 0.0010 % Oz; 2 -0.0018 Oz; 3 – without titanium ; 4 – with 0.59% Ti; 5 – with
0.5 % Ti from the Mo - 0.5 % Ti alloy.
TABLE 68. Long -time strength of molybdenum -rhenium and Mo - 0.5 wt % Ti alloys
Minimum creep
Stress , Time to
Composition State of alloy test rate , 8 , W, O
kg/mm² failure , hr
102mm /mm • hr
Temperature 982 ° C
100 %. Mo Annealing 1 hr , 18000 8.4 93.3 0.28 75.2 93.2
10.5 5.5 7.0 54.4 94.5
14.1 0.5 48.8 95.7
Mo - 0.5 wt % Annealing 1 hr , 1340 ° C 19.3 328.7 0.014 22,4
Ti 20.4 82,3 0.32 63.2 89.4
21.8 3.9 5.8 45.6 89.7
24.6 0.35 50.5 92.3
Mo - 35 at . % h.c. t .; annealing 1 hr , 28.1 20.5 1.4 40.0 25.0
Re 1500 ° C
h.c.t .; deformation 60% 28.1 47.1 0.8 56.6 30.2
h.c.t .; deformation 950 28.1 6.1 3.2 38.2
h.c. t . + h.W .; deformation 28.1 72.8 0.5 44.5
60 %
h.W .; deformation 95% 17.6 > 165 0.00034 9.4
1
( test stopped)
Temperature 1093°C
100 Mo Annealing 1 hr, 1800 ° C 8.4 5.3 3.0 41.3 63.0
12.35 0.15 60.1 83.1
Mo - 0.5 wt % 1 hr, 1340 ° C 12,7 > 280 0.023 12.6
Ti
( test stopped)
14.1 221.1 0.11 32.8 88.2
17.6 4.4 6.0 51.7 86.7
21.1 0.3 48.3 89.7
Mo - 35 at . % h.c. t.; deformation 95% 14.1 55.9 0.07 119.0
Re
h.c.t. – hot -and - cold treatment (temperature 1000 – 1250°C ); h.w. - hot worked (temperature 1500 °C ).
213
data of the same paper, at 1093°C the alloy with 50% Re had a lower ultimate
strength than molybdenum with 0.5 % Ti . However, in our opinion , the data
obtained at 1093°C cannot be considered as conclusive in view of the
insufficient number of samples tested .
3. Ternary tungsten - molybdenum - rhenium alloys

Papers /4, 5, 15, 16 , 23 , 46 / describe ternary alloys of the tungsten
molybdenum - rhenium system .
It has been found / 15, 16 , 23 / that the ternary tungsten -molybdenum
rhenium alloys belonging to the region of ternary solid solutions of rhenium
in tungsten and molybdenum have a high ductility near the solubility limit .
The mechanical properties of ternary alloys belonging to the region
between the twinning limit and the limit of solubility of the ternary solution
of rhenium in tungsten and molybdenum were studied in 4 , 5 , 46 / at
room and higher temperatures , using flat specimens 0.7 – 1 mm thick cut
out of a sheet produced by rolling arc- melted ingots .
TABLE 69. Mechanical properties of tungsten -molybdenum -rhenium alloys at room temperature after
annealing at various temperatures
Composition
Deformed
10000 14000 16000 1650° 18000 2000
state
(Weo
alloy
R:M
ratio
at
of
%
8.
1 : 1 : 1 185 4 164 1 140 0 125 0 110 0 112 0
2 : 1 : 1 129 2 118 1 100 2.2 98 2 100 3 94 5
3: 3:2 113 2 104 1.5 98 4 94 7 95 8 93 9.0 87 7
1 : 2: 1 124 98 5 90 9 92 10 98 0.5 67 1
As the high rhenium content of alloys near the solubility limit makes
them much more expensive, an attempt was made to find the optimum
composition nearer the twinning limit, since the alloys in this region have
a high ductility at a minimum rhenium content . The authors of /4 , 5, 46 /
therefore studied the ternary alloys of two sections of the ternary tungsten
molybdenum - rhenium phase diagram ; the section parallel to the tungsten
molybdenum side with a rhenium content of 25 at . % , and the radial section
with a variable content of tungsten and constant molybdenum to rhenium
ratio of 1 : 1 . A study of the dependence of the tensile properties of alloys
at room temperature on the annealing temperature (Table 69 ) /4 / showed
that the curves of ultimate strength og represent the temperature range
of recrystallization of alloys ( Figure 74 ) .
The short- time ultimate strength at room temperature of deformed
alloys of the compositions studied varies from 185 to 113 kg / mm² . If the
annealing temperature is increased to the temperature of the beginning of
recrystallization, recovery takes place and the ultimate strength of the
214
alloys decreases . The greatest decrease in the ultimate strength as a
result of recovery is observed in the 1 : 1 : 1 alloy . In the 1600 – 1650°C
annealing temperature range a sharp decrease in strength occurs in the
1 : 1 : 1 and 2 : 1 : 1 alloys , caused by the process of secondary recrystallization .
With further increase in annealing temperature to 1800 – 2000°C , the
ultimate strength changes little and remains at approximately 95 and
110 kg / mm² for the 2 : 1 : 1 and 1 : 1 : 1 alloys , respectively. The curves of
the annealing temperature versus ultimate strength for the 3 : 3 : 2 and 1 : 2 : 1
alloys have a greater slope , which indicates a lower rate of softening
during annealing. The ultimate strength of these alloys after annealing at
2000°C is 87 and 66 kg / mm , respectively .
200
150
,kgm2
6a
/m
100
01
•2
50 10
* 8
0,1
%
4
2
0
1000 1200 1400 1600 1800 2000
Annealing temperature , °C
FIGURE 74. Dependence of the mechanical properties of ternary
tungsten -molybdenum - rhenium alloys on the annealing temperature:
1 - W - 20 % Mo - 40% Re ( 1 : 1 : 1); 2 - W - 15 % Mo - 29 Re
( 2 : 1 : 1); 3 – W - 24 % Mo - 31% Re ( 3 : 3 : 2); 4 - W - 34 % Mo
33 % Re (1 : 2 : 1) .
Ternary alloys tend toward stress concentration; the reduction of area

of alloys with 25 at . % Re after annealing at 1600°C varies over the range of
20 – 40%, depending on the tungsten to molybdenum ratío .
The elongation of deformed alloys does not exceed 4 % ( 1 calc 50 mm ) .
After annealing, the elongation of 3 : 3 : 2 , 1 : 2 : 1 , and 2 : 1 : 1 alloys increases ,
and reaches 10% for the 1 : 2 : 1 alloy after annealing at 1650°C . An exception
is the 1 : 1 : 1 alloy, which lies on the limit of solubility of ternary solid
solutions , for which a decrease in elongation to 0% is observed as a result
of increase in the annealing temperature above 1400°C . This is evidently
the result of the process of age hardening .
Mechanical properties of alloys at high

temperatures
The tensile properties of ternary alloys at high temperatures were also
studied by testing specimens at 1500 and 1800°C in vacuo /4, 5, 46 ). The
215
tungsten -molybdenum - rhenium alloys have a high ultimate strength at these
temperatures (see Table 61 ), which varies from 21 – 26 kg / mm² at 1500 ° C
to 9 – 12 kg / mm² at 1800°C . This high strength of alloys at elevated
temperatures is due to the great strength of the interatomic bond character
istic of highly alloyed solid solutions of these three high - melting metals .
When comparing the properties of the binary and ternary alloys of
rhenium with tungsten and molybdenum , we should note that binary rhenium
tungsten alloys are stronger than binary molybdenum- rhenium alloys , and
the ternary alloys occupy the intermediate position . The most ductile are
the binary molybdenum- rhenium alloys , and the least ductile the tungsten
rhenium alloys .
The technological characteristics , workability, and temperature of
recrystallization of the ternary alloys , as expected , occupy an intermediate
position between the more ductile molybdenum alloys with 40 — 50% Re ,
which are cold formed and have a lower recrystallization temperature , and
the less ductile tungsten alloys with 25 – 30 Re which have a higher
recrystallization temperature . When determining the optimum compositions
of ternary alloys it should be noted that in the region of ternary solid
solutions of the tungsten- molybdenum- rhenium system the following
regularity is observed: an increase in the rhenium content improves the
ductility and the strength of the alloys with a constant tungsten to molybdenum
ratio ( 1 : 1 : 1 and 3 : 3 : 2 ) . At a constant rhenium content ( in at . % ) the alloy
with a higher tungsten content ( 2 : 1 : 1 as compared to 3 : 3 : 2 and 1 : 2 : 1 ) has
the best mechanical properties .
Therefore , when decreasing the rhenium content in ternary alloys , which
is dictated by economic considerations , it is desirable to increase the
tungsten content in the alloy and decrease the molybdenum content . This
leads to the production of strong alloys which at the same time have
sufficient ductility.
Evidently, the most promising in this respect are the alloys with a
rhenium content of not less than 20 at . % and with a rhenium to molybdenum
ratio of 1 : 1 (in at . % ) /46 /.
4. The ductile – brittle transition temperature of tungsten

rhenium and molybdenum - rhenium alloys
As we have already mentioned , one of the most serious disadvantages of

metals of group VIA (tungsten , molybdenum , and chromium ) of commercial
purity is their brittleness at low temperature . The ductile - brittle transition
temperature is 100 — 200°C for molybdenum , and approximately 350 – 400°C
for tungsten .
Today there are different ideas on the nature of brittleness of these
metals . It is believed that the main reason for brittleness is the presence of
interstitial impurities . Therefore, one of the ways of preventing cold
shortness of metals of group VIA is to free them of interstitial impurities
by refining, or by alloying the metals with elements which neutralize the
effect of impurities .
Rhenium is the only metal which decreases the ductile- brittle transition
temperature of elements of group VIA. The ability of rhenium to decrease
the sensitivity toward interstitial impurities in metals of group VIA, as well
5511 216
as to facilitate plastic slip at low temperatures and twinning, is the reason
why alloying these metals with rhenium decreases the ductile - brittle
transition temperature of the alloys below that of the pure metal. No
substitutes have yet been found for rhenium for increasing the ductility of
metals of group VIA, although work is being carried out in this field /12 /.
The bending test is usually used to determine the " threshold of
brittleness , " that is the temperature at which the specimens fail as a result
of bending at a certain angle ( 8 – 10 °) or around a standard mandrel .
In /3, 5, 15, 16 / the " threshold of brittleness" of binary tungsten- rhenium
and molybdenum- rhenium alloys and of the ternary tungsten -molybdenum
rhenium alloys was determined .
TABLE 70 a . Ductile – brittle transition temperature of recrystallized tungsten, molybdenum , rhenium ,

and rhenium - containing alloys /15 , 47 /
Transition Transition Transition

Alloy , at. % Alloy , at. % Alloy, at. %
tem perature , ° C temperature , ° C temperature , ° C
100 Mo 50 Mo - 30 Re -175 W - 26 Re 75
Mo - 10 RE -35 Mo - 35 Re -254 W 28 Re 75
Mo - 20 Re -90 100 W 335 W – 30 Re 275
Mo - 25 Re -140 W - 22 Re 276 100 Re 25
W - 24 Re 155
Note . The lowest temperature for bending on the mandrel is indicated . The radius of the mandrel is
eight times the thickness of the sample .
Very interesting data are given in / 15 / . The authors studied deformed

and annealed wire made of cast alloys of tungsten and molybdenum with
various rhenium contents . The tests were carried out at room temperature
by winding the wire on the mandrel of a fixed diameter . All the wire
specimens made of an alloy of Mo with 22 – 35 at . % Re and alloys of W with
22 – 27% Re had excellent ductility in the deformed state , and could be bent
to 180° around a mandrel of their own diameter . The ductility of tungsten
alloys decreased somewhat after recrystallization, but they could still be
bent without breaking, whereas wire made of sintered tungsten was
completely brittle and broke during working.
The ductility of the ternary tungsten -molybdenum - rhenium alloy on
bending occupies an intermediate position between that of tungsten and of
the rhenium- rich tungsten alloy . The bending strength of this alloy is the
same as that of the deformed and recrystallized alloys .
In / 15, 47 / bend tests were carried out on recrystallized 0.63 mm thick
sheet specimens made of tungsten- rhenium and molybdenum - rhenium alloys .
The Mo — 10% Re and Mo — 20% Re alloy strips were made by the powder
metallurgy method ( Table 70 a, Figure 75 a and b ) .
With increase in the rhenium content in molybdenum alloys the ductile
brittle transition temperature decreases to - 254°C for an alloy with
35 at . % Re . We should note that a strip made of Mo 35 at . % Re was
solution- heat treated to prevent the precipitation of the o - phase, which
would have decreased the ductility at low temperatures . The ductile- brittle
transition temperature of tungsten decreases from 335°C to approximately
75°C with increase in the rhenium content to 26 – 28 % , i . e . , to the solubility
limit . A further increase in the rhenium content increases the ductile- brittle
transition temperature as a result of the precipitation of the o - phase .
217
Plastic state b
Plastic state а
Minimum
Minimum
bending
bending
radius
radius
M0-35 Re
,of
I
W -126,28) Re
of
,I
Mo-25 Re
M0-30 Re
o OO
Mo - 2 One) W - 24 Rey
12
12
W - 30 Re 100 W
M0-10 Re
100 Mo W - 22Rel
16 16
20 20
Brittle -200 -100 100 Brittle state 100 200 300 400
Bending
a,degrees
state 7°C
angle
30
3 : 1: 1
o
20 O с
2
2 3.3
52. .
1:
20
10
1:11
2 : 1.1
50 100 150 200 250

1. ° C
FIGURE 75. The ductile – brittle transition temperature of cast molybdenum
rhenium ( a ); tungsten -rhenium (b ); and tungsten - molybdenum- rhenium ( c ) alloys /15 /:
T - ratio of the smallest radius of the mandrel to the thickness of the specimens:
1
twinning observed; 2 – no twinning observed .
In / 17 / additional tests were carried out with tungsten- rhenium alloys

quenched from 1800°C in water to hinder the precipitation of the o - phase .
As we see from a comparison of the curves for the tungsten- rhenium
and molybdenum - rhenium alloys , the transition from the plastic to the
brittle state of tungsten- rhenium alloys is less abrupt than that of
molybdenum - rhenium alloys . The authors of / 17 / believe that in
tungsten- rhenium alloys there is no slip which accommodates twinning, and
facilitates subsequent deformation, whereas in molybdenum- rhenium alloys
both slip and twinning are facilitated, and an abrupt transition to the plastic
state is observed at the temperature at which twinning evidently ceases .
These considerations have not been sufficiently verified and must be
confirmed .
In / 5 / tests were carried out by bending 2.5x 5X25 mm specimens made
of cast alloys of rhenium with tungsten and molybdenum, which were
deformed to 70% reduction and recrystallized at 1600°C . The specimens
were tested over the temperature range of – 195 to 350°C on a Gagarin
press . The specimens were fastened in a slotted clamp with a round
opening in the center, so that they could bend . The punch was set up
in the center of the specimen, and touched it with a sharpened edge with a
1 mm radius . Under the action of the load transmitted by the punch , the
sample was bent to a certain angle until the first crack appeared . The angle
218
of bend ,equal to 10° , was assumed to be the threshold of brittleness . It
was shown that the introduction of rhenium appreciably lowers the ductile
brittle transition temperature of these alloys even under very rigid testing
conditions ( Table 70 b , Figure 75c ) .
TABLE 70b . Ductile – brittle transition temperature of tungsten - rhenium and

molybdenum - rhenium alloys during bending
Ductile – brittle Ductile - brittle

transition
Alloy, at. % ratio transition
Alloy , % (W : Mo : Re)
temperature , ° C temperature, ° C
100 W 400 3: 1: 1 50
W-- 25 Re 120 5: 2: 2 120
W- 30 Re 50 2: 1 : 1 200
100 Mo 50 3: 3: 2 200
MO- 50 Re - 200 1: 1:1 300
From a comparison of /5 / and / 15 / we see that there is a certain

disagreement in the results of studies on binary tungsten- rhenium and
molybdenum - rhenium alloys . These disagreements may be due to the
different preliminary working of the alloys , as well as to differences in
the testing conditions (more rigorous in / 5 /) .
For the ternary tungsten -molybdenum - rhenium alloys , the ductile
brittle transition temperature is not intermediate between those of the
corresponding binary tungsten- rhenium and molybdenum - rhenium alloys ,
as might have been expected . As we see from the given studies , the ductile -
brittle transition temperature of the ternary tungsten- molybdenum- rhenium
alloys is the same as that of the tungsten- rhenium alloys , which agrees
with the data of / 15 /.
5. Chromium - rhenium alloys
In / 17 / bending tests were carried out on chromium- rhenium alloys .

In the same way as for molybdenum and tungsten , the authors investigated
alloys from the region of solid solutions of rhenium in chromium , near the
solubility limit , in which an additional deformation mechanism , namely
twinning, is manifest /22 /. The best results are given by a cast chromium
alloy containing 39 at . % Re , rolled at 1000°C to 90.6% reduction . In
Table 71 we give the hardness and ductility in bending of this alloy
after various heat treatments .
The ductility of the Cr — 39 at . % Re alloy in bending of this alloy
with that of the recrystallized Mo – 35% Re alloy . The ductile – brittle
transition temperature for the Cr – 39.at. % Re alloy is - 196°C , and for the
high- purity recrystallized chromium it is 200°C /17 /. In /29 / the authors
give the mechanical properties of the chromium alloy with 35 at . % Re in
the temperature range of - 200°C to +800°C (see Figure 76 ) . As we see from
the graph , the alloy is ductile, and at temperatures above 0°C its elongation
exceeds 20 % . A sharp increase in the ultimate strength and the yield
strength of the alloy was observed below 0° C.
219
603,6g
/,kgm²
140
m
105
68
70
bos
35 8. %
o
-200 200 400 600 800

T. ° C
FIGURE 76. Temperature dependence of the
mechanical properties of cast chrom ium
alloys with 35 at . % Re .
TABLE 71. Hardness and ductility in bending of alloys of Cr with 39 at . % Re / 17 /
Hy, Temperature , Ductility in

Treatment of alloy
kg /mm² C bending, T
Cast 348 20 1.9
Rolling to 90.6% reduction at
1000 ° C 508 20 0
Rolling + annealing, 1200 °C , 1 hr

( in vacuo ) 342 20 0
-196 1.5
Note : T is the ratio of the radius of the mandrel to the thickness of the specimen .
6. Niobium - rhenium and tantalum - rhenium alloys
The mechanical properties at room and higher temperatures of cast

niobium- rhenium alloys containing up to 5 % Re were investigated in /41 /
( see Figure 71 b , c ) .
Alloys of tantalum with rhenium were studied in / 1 /, and in the joint
work of the authors with I. A. Tsyganova . The alloys were arc - melted in a
furnace with a nonconsumable tungsten electrode , then deformed by forging
and either cold rolling or rolling with low preheating . The results of the
tests on the mechanical properties of sheet specimens of alloys containing
up to 5% Re are given in Table 61. The strength of tantalum alloys with 5 % Re
at room temperature is approximately 0.4 -0.5 times that of tungsten
rhenium alloys , but at 1800°C the alloys have almost the same strength .
Alloys of tantalum with rhenium are recommended as a constructional heat
resisting material /48 /. Tantalum alloy rods with 0.5, 0.8, and 2.03%
rhenium , deformed at 1000 ° C to 60% reduction and annealed at 1500° C for
1 hour , had the following properties: 0 8 = 48.4, 59.5, and 75 kg / mm²;
8 = 26.6, 23.8, and 15.0 % ; and y = 66.6 ; 63.5, and 55.5% , respectively .
220
7. Rhenium - titanium alloys
The influence of rhenium on the mechanical properties of iodide titanium

was studied in / 33 / . The alloys were prepared by arc melting with a
tungsten nonconsumable electrode in an atmosphere of argon . The ingots
(weighing 40 grams ) were hot forged at 750 – 800°C to rods with a 7x7 mm
cross section . These were then vacuum annealed at 750 — 850° C in quartz
ampules for 1 hour until a completely recrystallized structure was produced .
The mechanical properties were determined at room temperature using
Gagarin - type specimens with a gauge length of 20 mm (Figure 77 ) .
80
60,2,68,0,4
60
S40
602
2 4 6
Re, %
FIGURE 77. Mechanical properties of titanium -rhenium
alloys at room temperature (og and 0.2 in kg /mm², 8 and
w in % ).
The influence of rhenium on the hot hardness of titanium obtained by the

Kroll process and of its alloys of the VT- 2 grade ( 2 – 3% Cr, 1 – 2% Al )
were studied in /49 /. Measurements were carried out in the 20 – 500°C
range with titanium alloys containing 1 , 5, 10, and 25 wt % Re, and with the
VT- 2 alloy containing 1 , 5, and 3% Re . (The data on the hardness of the
alloy are too high since there was gas contamination of the alloys during
remelting . )
TABLE 72. Mechanical properties of titanium alloys alloyed with rhenium

Content of alloying element, % OB , do .
8, % ak,
Al Nb Mo Re kg /mm² kg/mm² kgm /cm²
III
3 5 77_78 68-72 12-13 51 10-12

3 5 0.05 76-77 67–71 11-12 51 11
3 5 0.1 78-79 74-76 12-15 56-60 11-13
3 5 0.2 79 69–74 10-13 55-56 7-8
3 4 80–81 72-74 14-15 56 10-11
3 4 0.1 90-93 83-85 10-11 55-50 9-10
3 4 0.2 91-92 84-86 10-12 50-51 8-9
In both cases the introduction of rhenium retards the softening of the

alloy . If the temperature is raised to 500°C the hardness of pure titanium
decreases by 50 – 60% , but the hardness of titanium alloys with 25% Re
decreases by only 30% . We should also note that the hardness of titanium
221
alloys with 25 % Re which have a stable B - structure is lower than that of
alloys containing 5 or 10 wt % Re .
The introduction of rhenium into the VT - 2 alloy scarcely changes its
hardness at room temperature , but a temperature rise from 20 to 500°C
decreases the hardness of the VT - 2 alloy by 40% , and of the VT- 2 alloy
containing 3% Re by only 15% . The authors together with L. L. Zhdanova
studied the vacuum - melted titanium alloys with 10, 20, and 30% Re from
which 0.4 mm thick strip and 0.2 mm diam wire were produced . The
Ti – 20% Re alloy has an ultimate strength of 125 kg / mm² .
The authors of /50 / studied the effect of small additions of rhenium on
the mechanical properties of titanium alloys used as electrodes during
welding of titanium alloys (Table 72 ) .
8. Nickel - rhenium alloys
Nickel- rhenium alloys with 1 , 5, 10, and 30% Re were made by sintering
nickel powder (content of impurities : 0.03% C ; 0.06% Fe; < 0.01% Si, 0.03% S ;
0.01% P; < 0.005% Mn; < 0.008% Co ) and rhenium powder of high purity /51/.
The influence of rhenium on the mechanical properties of the alloy at high
temperatures is especially marked in the alloy with 10% Re . The bending
strength was studied at high temperatures . The specimens 0.1 mm thick,
3 mm wide , and 30 mm long were fastened horizontally at one end , and
loaded at the other . The temperatures at which the loaded end of the plates
bent by 1 mm under a 0.9 g load were as follows :
Nickel alloy with 0.15 – 0.25 % Si (" 225 " INCO ) 830
Nickel alloy with 4 % W ( A - 31) 840

Ni – 1% Re . 840
Ni - 50% Re 845
Ni - 10 % Re 920
This type of bending strength tests at high temperatures is very effective

for estimating the applicability of the alloy as a cathode material /51 /.
The authors and E. P. Arska studied arc - melted nickel- rhenium alloys .
From the alloys with a rhenium content of up to 25% , foil up to 100 u thick
and wire with a diameter of up to 200 u were produced by cold forming.
Alloys with a rhenium content of up to 15% can be cold deformed to a
reduction of up to 99 % without any intermediate annealings. The tensile
strength of cold- drawn wire made of alloys with 10, 15, and 20 % rhenium
is 106, 124, and 140 kg / mm², respectively.
9. Ternary nickel- chromium - rhenium alloys

The authors of /8 / studied the influence of rhenium on the mechanical
properties of a nickel- chromium- base alloy with the structure of a
homogeneous solid solution of chromium in nickel of the Nimonic type with
20% Cr . Briquettes of the rhenium powder were added to the molten
chromium- nickel alloy in a high- frequency furnace . Long- time strength
tests were carried out on cast and deformed samples . A 15 mm diam ingot
222
was homogenized , forged , and rolled into 1.8 - 2.0 mm thick sheet at
1100°C with intermediate annealings . After deformation the alloys were
heated to 1000° C and air cooled . Such treatment assured a polyhedral
recrystallized structure . For the alloys containing rhenium the annealing
temperature was raised to 1200°C due to the higher temperature of the
beginning of recrystallization .
600
500
1
failure
,hTime
400
tor
300
50
e
40
failur
Time
200
to
h, r
2
20
100
1 2 3 4 5 6 7 8
Re, wt %
0 1
2 4 6 10
Ni - Cr Re , wt %
FIGURE 78. Dependence of the time to failure of alloys
on their rhenium content :
1- chromium -nickel alloy tested at 800 ° C under a stress

8 kg/mm²; 2 – multicomponent chromium - nickel
alloy tested at 975 ° C under a stress of 20 kg/mm².
The long- time strength of cast specimens 5 mm in diameter , and of

sheet specimens with a 2x10 mm cross section, was tested under static
loads . The curve in Figure 78 (curve 1 ) shows the influence of rhenium on
the long- time strength at 800°C under a stress of 8 kg / mm² (cast samples ) .
If the rhenium content is increased to 8.48% the time to failure of the initial
alloy increases from 55 hr to 530 hr, i.e. , ten times . Figure 79 shows the
results of long- time strength tests on cast alloys with 8.48% Re at 800°,
900° and 1000° C . The columns give the time to failure of the initial Ni - Cr
alloy at 800°C under a stress of 8 kg / mm² , of the alloy containing 8.48% at
800°, 900° and 1000°C under stresses of 8 kg / mm² (additional loading to
10 kg / mm% ) , 4 kg / mm² (6 kg /mm ) and 2.5 kg / mm2 ( 3 kg / mmº ),
respectively . We should mention that the alloys containing no rhenium are
usually not suitable for work at 900° and 1000°C .
223
800 °
500
400
failure
,hTime
tor
kg /mm
300
900 ° 1000 °
200 Jkg /mm ?

kg /mm ?
6-8kg/mm kg/mm
100
kg /mm²
800 ° kg /mm ?
0 % AC 8.48 % Re
Ni -Cr 0
FIGURE 79. Long -time strength of the chromium -nickel
alloy with 8.48 % Re at 800°, 900° and 1000 °C .
In the same work /8 / the authors investigated the influence

of rhenium on the properties of nickel- chromium- base alloys containing
tungsten , molybdenum , titanium, and aluminum , which have a heterogeneous
structure with intermetallic and carbide phases . The long- time strength
of the alloy was studied on cast specimens at 975°C and under a 20 kg / mm²
stress . The results of the tests are given in Figure 78 (curve 2 ) . The
introduction of up to 2.5 % rhenium results in an increase in the long- time
strength, but further increase in the rhenium content decreases the long
time strength. Static compression tests carried out at 20°C showed that the
introduction of up to 10% Re does not reduce the ductility of the alloy.
Microstructural and X- ray spectral analyses have shown that the cause of
the decrease in the long- time strength of rhenium- containing alloys is the
formation of a new , hard ( 1000 - 1200 kg / mmº ) rhenium - rich phase, which
is a complex chemical compound of an almost constant composition
( 67% Re , 19 % W, 4% Mo , 8% Ni ) . In such alloys the matrix becomes
depleted of the carbide- forming elements , tungsten and molybdenum , and
the amount of carbide phase in it decreases .
10. Manganese - rhenium alloys
The influence of small additions of rhenium on the mechanical properties

of manganese- nickel and manganese - copper alloys was studied in /52 /.
Ingots weighing 100 grams were induction melted in an atmosphere of argon,
224
forged at 750° — 800°C into 6 mm diam rods , quenched in water from 800°C ,
and shaped into test specimens . The results of tensile tests at room
temperature are given in Table 73 .
TABLE 73. Influence of small additions of rhenium on the mechanical properties of manganese -copper and
manganese -nickel alloys /52/
Hardness , kg/mm²
OB ?
Alloy, % kg /mm2 8, % 中 , %
quenching, annealing ,
750° C 500 ° C
Mn - Cu (65:35) 40.5 43 34
Mn - Cu - 0.1 Re 43.0 29 32
Mn Ni (75:25) 73.3 16.2 58,2 123 145
Mn — Ni - 0.53 Re 56.2 2.3 72 159 153
Mn - Ni - 1.5 Re 74.8 9.0 35.1 234 227
As we see from the table , rhenium does not have any especially favorable
influence on the mechanical properties of these alloys , and consequently
cannot be recommended as an alloying addition which improves the
mechanical properties of manganese- copper and manganese- nickel alloys .
11. Palladium - rhenium alloys
The mechanical properties of palladium- rhenium alloys were studied in

139 / on 0.8 – 1 mm diam wire made by cold rolling and drawing alloy castings
annealed at 1000°C . The mechanical properties of deformed alloys and of
alloys after annealing at various temperatures were determined at room
temperature .
TABLE 74. Mechanical properties of palladium - rhenium alloys

Content of Re , Microhardness, OBY
State of alloy 8, %
% kg /mm² kg /mm²
Cold deformation 0 110 44,2 2.14
3.4 160 63.0 3.31
8.74 250 75.0 1.5
11.9 254 78.0 0
Annealing at 400 °C , 1 hr 0 106 38.0 1.9

3.4 155 57.6
8.74
11.9 260 78.5 0
Annealing at 500 ° C , 1 hr 0 92 30.4 6.2

3,4 47.8 7.1
-
8.74 4.2
11.9 75.7 0
Annealing at 600 °C , 1 hr 0 82 22.7 12,4

3.4 131 37.8 8.4
8.74 220 47.0 3.6
11.9 250 51.0 0
225
TABLE 74 (Continued )
Content of Re , Microhardness , OBY

State of alloy
kg/mm² kg /mm2
Annealing at 800 ° C , 1 hr 0 81 20.8 14.0

3.4 130 40.1 12.7
8.74 192 42.8 3
11.9 230
Annealing at 1000ºC , 1 hr 0 75
3.4 116
8.74 151
11.9 210
The alloys studied were homogeneous solid solutions of rhenium in

palladium . As we see from Table 74 , an increase in the rhenium content
in the alloys increases their hardness and ultimate strength but somewhat
decreases their ductility . Alloys with a high rhenium content retain their
high strength even after annealing at 800 – 1000°C , whereas for the alloy
with 3.4 % Re and for pure palladium a decrease in strength is observed
after annealing at 400 – 600°C .
12. Iron - cobalt - rhenium alloys
Small additions of rhenium (up to 1.5% ) may be used to alloy magnetically

soft iron- cobalt alloys , containing 35 – 50% Co /53 / . The iron- cobalt
alloys ordered below 730 ° C become brittle , and therefore they are usually
alloyed with chromium or vanadium , which decreases the brittleness, but
also reduces the magnetic saturation , hinders decarbonizing, and reduces the
grain size . This is not desirable in soft magnetic alloys .
TABLE 75. Mechanical properties of iron - cobalt alloys at room temperature
Composition of alloy, % ob , kg /mm ? 8, %
Fe - 50 Co 10 - 12 0.3
Fe - 35 Co 18 0.5
Fe - 50 CO - 1.53 V 19 1.0
Fe – 50 CO -1.0 Cr 21 0.5
Fe — 50 CO - 1.5 Re 65 4.0
сло
Fe - 50 Co - 1.0 Re 58
Fe - 35 Co--1.0 Re 48
The properties of rhenium- containing alloys were studied on 5 – 17 kg

ingots melted in an induction furnace . Rhenium was introduced in the form
of sintered rods . The ingots were forged into 10 – 15 mm thick plates and
hot rolled at 1150 – 1200° C into 1.5 mm thick sheets . These were quenched
226
from 930 ° C and cold rolled to a thickness of 0.35 mm . The mechanical
properties were determined on specimens annealed either in hydrogen or
in vacuo at 920°C . A comparison of the mechanical properties of iron
cobalt alloys containing rhenium , chromium , or vanadium / 53 / is shown
in Table 75 .
From a comparison of the properties we see that rhenium has a greater
strengthening effect on the iron- cobalt alloys than chromium or vanadium .
It increases the strength and ductility of these alloys but does not affect
their magnetic properties .
The hardness of alloys with 35% Co is little influenced by the addition of
rhenium , but the hardness of alloys containing 50% Co increases noticeably
with increase in the rhenium content .
Alloys containing rhenium have an appreciably larger grain size than
those containing chromium or vanadium , which is also a favorable factor
for magnetically soft alloys .
13. Iron - chromium - nickel- rhenium alloys
The influence of rhenium on iron- chromium - nickel alloys ( Table 76 ) was

studied; these alloys are used primarily for the manufacture of elastic
parts such as diaphragms , aneroid barometer boxes , tubular springs ,
bellows, etc. / 54 /.
TABLE 76. Composition of the N36KhTYu alloy containing molybdenum and rhenium (0% ), (balance : iron)
Alloy с Si Mn Ni Cr Ti Al Mo Re
36NKIT Yu 0.05 0.6 1.17 35.58 13.33 2.88 0.85 -
36NKIT YuM5 0.05 0.7 1,17 35.93 12.59 3.06 1.04 4.94
36NKIT YuM5Re 0.05 0.7 1.16 35.93 12.82 3.06 1.08 4.95 7.0
Figure 80 a shows the dependence of the ultimate strength and of the yield
strength of alloys on the annealing temperature . As we see , the rhenium
containing alloy has the maximum strength . The solution heat - treated alloys
consist of a single - phase y - solid solution and are very ductile . They can be
shaped into complex machine parts by cold pressing and deep drawing.
After annealing at 650 ° — 700°C these alloys attain the maximum elastic
properties , since they become strengthened as the result of aging .
For the specialized instrument- building industry these nonmagnetic and
corrosion - resistant alloys must retain their stability and ductility at high
temperatures also ( 500 – 800°C ), so high- temperature tests were performed.
It was established that rhenium increases the strength of the alloy at high
temperatures , as well as the softening temperature . The short- time tensile
tests showed that the ultimate strength of alloys containing rhenium
scarcely changes up to 600° C , whereas that of the 36NKHTYuM5 and
36NKhTYu alloys decreases even at 350 - 400 and 200 – 250°C, respectively
( see Figure 80 b ) . Relaxation stability tests have shown ( Figure 81 ) that
the stress relief in the alloy containing rhenium remained almost stable
after 50 hours of testing whereas in the two other alloys the stress relief
increases continuously.
227
150
m²
/, gm²
Šgas
mkGo
m,k/bĒ
150 130
3
k,/? gm
68
3
m
120 68
2 130
90
2 100
60 3
602
k,/ gm²
120
Ga z
70
m
2 3
100
1 40 80
1
60
200 400 600 800 200 400 600 800
Annealing temperature , °C Annealing temperature , ° C
a b
FIGURE 80. Ultimate and yield strengths of spring alloys containing rhenium :
a - at room temperature after various annealing temperatures; b – at elevated temperatures;
1- 36NKHTYu ; 2 - 36 NKUTYUM5; 3 – 36NKITYUMRe .
80+
60 3
40 1
135 50
Holding time , hr
FIGURE 81. Relaxation curves of spring alloys at
500 ° C ;
1-36NKHTYu ; 2 - 36NKHTYUM5; 3 – NKh

TYUM Re .
14. Cobalt - chromium - nickel - rhenium alloys
The authors of 17 / studied the influence of rhenium on the properties

of the K40NKHM cobalt- chromium- nickel alloy, used for the manufacture
of certain parts of electrical measuring instruments . These alloys must
be antimagnetic and have a high hardness , corrosion resistance , and wear
resistance . For a number of vibration- proof instruments with heavy
mobile parts , cores are required with a Rockwell C hardness of 62 – 64,
and not of 56 — 60 as is usual . This is attained by alloying with rhenium ,
and by appropriate heat treatment . Rhenium was introduced
in amounts of up to 10% into the K40NKLM alloy, which contained
0.11 -0.12 % C ; 0.004 % Se; 0.51% Si; 2.12 % Mg; 16.17% Ni; 21.21% Cr;
6.83% Mo; 12.84% Fe , and 40.18 % Co. The alloys were manufactured by
arc melting with a nonconsumable tungsten electrode in an argon atmosphere .
228
The ingots were forged at 1150 — 1180°C, water quenched from 1180°C,
and cold drawn with intermediate annealings until a 0.5 mm diam wire was
produced with a final reduction of 50 – 80% . Alloys with a rhenium content
of up to 10 % consist of a single- phase solid solution . Alloying with rhenium
leads to the formation of small grains and of deformation twins , especially
in alloys with 7 and 10% Re . Cast alloys have a dendritic structure .
Rockwell C K40NKHM - 7 % Re
64
Rockwell K40NKUM 85 %
с 62
64 80
62 58
° 55
58 54
50
2 4 6 400 500 600 700
Re,wt % Annealing temperature , ° C
а b
FIGURE 82, Influence of rhenium content ( a), degree of deformation , and
the annealing temperature (b) , on the hardness of the K40NKHM alloy .
In the alloy with 15% Re a second phase appears . The effect of the extent
of cold deformation by drawing and of the temperature of subsequent aging
on the hardness and strength of the wire were studied .
280
260
k,/ gm2
4
Go
m
3
240
2
220
200
180
0 200 400 600 800 b
a T, ° C
FIGURE 83. Influence of the annealing temperature on the ultimate strength of

K40NKHM alloys with various rhenium contents (a), and on the external appear
ance of a core with a diameter of 0.5 mm (K40NKhm alloy with 79% Re) (b ):
1 - without rheniurn ; 2 – 3% Re; 3 – 7% Re ; 4 – 100% Re.
It was found that an increase in the rhenium content greatly increases

the hardness and strength of alloys . Wire with a rhenium content of 7 and
229
10% has a Rockwell C hardness of 62 – 64, but that of the K40NKHM alloy
does not exceed 58 ( Figure 82 a) .
The tensile strength of alloys with 7 and 10% Re is up to 265 —
– 275 kg / mm², 10 – 12% more than the maximum ultimate strength of the
K40NKHM alloy (Figure 83 a) .
The influence of the aging temperature on hardness and strength of rhenium
containing alloys is the same as of K40NKLM alloys ; maximum hardness and
strength are attained after annealing at 500 — 550°C .
Figure 82 b, shows the dependence of the hardness of alloys containing
7% Re on the degree of preliminary cold deformation of the wire . The
highest hardness (Rockwell C 63 ) is attained after deformation to a
reduction of more than 80% .
Alloys containing rhenium remain nonmagnetic under all conditions of
heat treatment and machining . The maximum hardness necessary for the
work of wear- resisting machine parts is attained by adding 7 – 10% Re to
the K40NKHM alloy . This addition does not impair the workability of the
alloy . The external appearance of a core is shown in Figure 83b .
15. Wear resistance of rhenium and its alloys
Rhenium and its alloys have a high wear resistance and can be used for
the production of fountain pen tips, axles and mountings of magnetic
indicators , and parts of geodetic instruments . Among pure metals rhenium
has a wear resistance second only to osmium .
Figure 84 shows the relationship of the wear
03 resistance to the position of the element in
100
the periodic table . Metals of group VIIIA
(osmium , ruthenium ) have the greatest
resistance
resistance in each period /55 /.

30 We know of Japanese patents on alloy
Wear
20
he
compositions for fountain pen tips /56 – 57 /:
hu
40 – 75% Re , 20 – 40% Os , 5 — 20% Ta , and
up to 1 % B.
The following industrial method is
nh suggested: the starting metal powders are
Nb PL mixed, melted into a ball by an electric
Pa au current , and ground . The optimum composi
tions are as follows : Re :Os : Ta : B - 60:30 :
0,5
77
10 : 0.5; 75:20 : 5 : 0.5, and 40 : 40 : 20 : 0.5 . The
73 74 75 76 70 79
possibility of using the same alloys without
47 boron is indicated .
FIGURE 84. Dependence of the wear In a German patent it is reported that
resistance on the position of the element spinnerets which are used , for example , in
in the periodic table . the production of viscose can be made of
platinum- base or gold- base alloys with small
additions of rhenium . These alloys differ
from those used before, which contained no rhenium in their fine grain
structure . Alloys containing 0.1% Re have 26,00 – 4550 grains / mm², while
alloys containing no rhenium have only 250 grains /mm /58 /.
230
TABLE 77. Wear of rhenium - osmium alloys
Decrease in volume
Wear Scratch H
Alloy , % during wear, resistance V
hardness
im 3
mm
100 Os 0.060 100 79 438

Os - 25 Re 0.12 53 78 550
Os - 50 Re 0.22 28 59 533
Os – 75 Re 0.24 25 50 356
annealed 0.29 21 32 247
100 Re
{ deformed 0.29 21 36 637
The wear resistance of rhenium- osmium alloys was studied in /55 /.

Table 77 shows data on the wear resistance and hardness of fountain pen
tips made of rhenium- osmium alloys . The wear resistance of osmium is
assumed to be 100. The wear resistance is expressed as the decrease in
the volume of metal as a result of wear .
In /7 / there is a report that rhenium in amounts of up to 7% increases
the Rockwell C hardness from 56 – 60 to 62 – 64, and the wear resistance
of the hard wear- resistant cobalt - chromium- nickel alloy K40NKhM , which
is used in the production of nonmagnetic cores of vibration -proof instruments .
In conclusion it is necessary to point out that further research on the
mechanical properties of rhenium alloys with high- melting and rare earth
metals (vanadium , niobium , yttrium , cerium , etc. ) is very urgently needed .
231
Chapter XV
WELDABILITY OF RHENIUM AND ITS ALLOYS
The production of reliable welded structures from the high- melting

metals , tungsten and molybdenum , is one of the most urgent problems of
modern technology . So far it cannot be considered solved , and this
hinders the wide use of structures made of these high -melting metals .
As weknow the high oxidizability and the tendency toward grain growth
of molybdenum and tungsten during heating , and the high ductile- brittle
transition temperature are the main difficulties in the production of welded
joints with satisfactory ductility at room temperature .
According to the available data , the argon arc welding of commercial
molybdenum and some of its commercial alloys cannot yet produce welds that
are ductile at room temperature . The ductile - brittle transition temperature
was found by static bend tests on welds of these alloys , and is 150 — 200°C .
Joints produced by electron- beam welding have a somewhat higher ductility,
but the zone of the thermal effect remains brittle / 59 /.
By alloying molybdenum with titanium , zirconium , aluminum , and other
metals we can somewhat increase its plastic properties . However , the
plastic properties of the welds of such alloys remain very poor .
Welding either tungsten or tungsten alloys has not yet been mastered .
Alloying molybdenum and tungsten with rhenium is a very effective
means of increasing their ductility at room temperature ( see Chapter XIV).
The use of rhenium for obtaining ductile welds in structures made of
molybdenum and tungsten has developed in two directions : rhenium alloying
of the metal of the welded structures proper , which in practice means
the welding of binary and ternary alloys of rhenium with tungsten and
molybdenum , or rhenium alloying of the metal of the weld . The latter
method is used in welding molybdenum and tungsten alloys.
1. Welding rhenium
A comparative study of the weldability of rhenium by by resistance

welding shows that at the same sheet thickness , current, and compressive
stress , rhenium sheets weld better than molybdenum sheets and almost as
well as tantalum /60 /.
232
2. Welding molybdenum - rhenium alloys
According to the data of /1 / and to the research by the authors with G. N.

Klebanov, the binary alloy of molybdenum with 50% Re can be welded by one
of two methods : arc welding with a tungsten electrode in a current of argon ,
or electron- beam welding in vacuo .
Mo -Rez Ma - Re MO
IT
FIGURE 85. External appearance and microstructure of welds of rhenium alloys:

a - weld of the molybdenum -rhenium alloy after rolling; b – bent specimens
of welded joints of a molybdenum -rhenium alloy; c- bent specimens of
welded joints of a ternary tungsten -molybdenum -rhenium alloy ; d micro
structure of various sections of welded joints . x 200. I – cast zone ; II and III -
bend; IV – recrystallized zone .
233
Welding plates 0.3 mm thick in a current of argon showed that the alloy
welds easily to form a solid joint . The welded metal and the weld are
ductile and withstand bending tests to an angle of 180° by free bending in a
vise, or bending around a mandrel with a radius of 31 ( f is the thickness of
the plate tested ). The sample was bent along the weld, which consisted of
coarse equiaxial grains ( Figure 85 ).
a b.
120
30
110
m2
,/Ggo2
25
kGo
100 *
m 90 20H
Go
8.4
80 15
%
70
60.2, 10
60
50 5
1
40 0
10 20 30 40 50 10 20 30 40 50
Re, wt %
FIGURE 86. Mechanical properties of the welds of
molybdenum - rhenium alloys .
Argon arc - welded samples of 1 mm thick sheets of the cast Mo- 50 % Re

alloy were cold - rolled . After three passes the thickness was decreased to
0.3 mm ( 70 % reduction ) , but the weld retained its quality , and no cracks
formed either on the weld or in the thermally affected zone ( see Figure 85 a ).
Electron - beam welding of molybdenum- rhenium alloys in vacuo
( 2.10-5 mm Hg ) was carried out in / 1 , 42 ). In both studies it was noted that
the weld has a solid structure and good mechanical properties .
TABLE 78. Mechanical properties of electron - beam welded molybdenum -
rhenium alloys
Content of 00.2 OB ,
8 ,% 中 ,%
Re , % kg /mm² kg /mm²
47 68 15 20
20
50 64 3.2 7
63 88 13 16
40
61 83 4.8 5
88 106 9 35
50
88 112 15.1 29
Note . The numerator gives the properties of the base metal and the
denominator those of the metal of the weld .
The authors of /42 / studied the weldability of 1 mm thick sheet of
electron- beam melted molybdenum alloys containing up to 50% Re . The
conditions of the electron- beam welding were as follows : voltage 80 kV ,
current strength 7.5 A , rate 18 cm / min . A comparison between the
mechanical properties of the base material and of the material of the welds
of molybdenum - rhenium alloys ( Figure 86 and Table 78) shows that the weld
retains the same strength as the base metal, but it has a somewhat lower
ductility. However , the ductility of the weld is sufficiently great for the
welded alloy with 50% Re to be bent at an angle of 180° /42 ), which agrees
with the data of / 1 /.
234
The hardness of the welded zone for all molybdenum - rhenium alloys
( 10 — 50 % Re ) is lower than that of the base material /42 /.
3. Welding tungsten - rhenium alloys
Welding of binary tungsten - rhenium alloys containing 20 and 30% Re was

studied by the authors of / 1 / and G. N. Klebanov who used specimens 0.4 and
0.7 mm thick for their tests . The welding was done by the argon- arc method ,
and in vacuo by the electron- beam method . For these welded joints a small
grain size in the relatively narrow thermally affected zone is characteristic .
The strong effect of the welding method on the ductility of the weld has been
noted . While after electron- beam welding the tungsten alloy specimens
containing 20% Re could be bent at room temperature to 33° , after argon- arc
welding they could be bent to an angle of 19º only. The welded specimens
always failed along the center of the weld , and this failure was accompanied
by marked local deformation .
We should note that it is very difficult to obtain a welded joint of these
thicknesses (0.4-0.7 mm ) by welding the commercially pure tungsten, owing
to the formation of cracks in the weld zone . When special technological
measures are taken to produce a joint without cracks , the welds of tungsten
are brittle .
4. Welding ternary tungsten - molybdenum - rhenium alloys
Ternary tungsten -molybdenum - rhenium alloy specimens (W - 40 % Re

20 % Mo ) 0.3 and 0.5 mm thick were electron- beam welded in vacuo
( 2 · 10 * mm Hg ) / 1 /. Good welds were produced with a small grain size
in the relatively narrow thermally affected zone . The bending angle of
welded samples at room temperature is 180° (see Figure 85 c and d ) .
5. Rhenium alloying of molybdenum weld metal

The data on the weldability of cast binary and ternary alloys of rhenium
with molybdenum and tungsten indicate that rhenium can considerably
improve the weldability of these two metals .
However, as the scarcity of rhenium does not permit any large scale use
for constructional purposes of sheets of the high- melting tungsten- rhenium
and molybdenum- rhenium alloys which have an excellent weldability , tungsten
and molybdenum should be welded with welding rods made of rhenium or of
its alloys with tungsten and molybdenum .
Welding molybdenum sheet 0.7 – 1., 0 mm thick and VM- 1 alloy sheet
1.0 mm thick with rhenium was studied in / 59, 61 /. The filler metal
was either a 0.5 mm thick strip, or a 1.0 mm diam wire made of Mo - 50% Re
or strips of pure rhenium cut from foil 0.15 mm thick or from sheet 1.2 mm
thick. The specimens were automatically argon- arc or electron- beam
welded in vacuo . During argon- arc welding the specimens were protected
235
from the air in a chamber with a controlled atmosphere, locally under a
portable microchamber , or by supplying argon from a nozzle . The
protective gas was argon of high purity ( 0.01 % N , and 0.005 % O2 ) . The
filler material was fed into the joint between the plates welded , or directly
into the welding bath . The rhenium content in the metal of the weld was
calculated ( 0 – 80 wt % ) . Welding was carried out under conditions which
ensure complete fusion of the edges being welded .
In automatic welding under a controlled atmosphere , when the molybde
num- rhenium alloy filler wire was fed from the side , longitudinal cracks
sometimes appeared in the weld ; these were removed by auxiliary welding .
Argon- arc welding with pure rhenium as the filler sometimes leads to
a certain porosity in the welds . This can be almost completely eliminated
by remelting the metal of the weld .
Welds containing over 50 wt % Re are highly susceptible to cracking
because of the formation of the brittle o - phase .
Welds containing less than 50% Re consist of a solid solution and have
no clearly defined boundary with the affected zone . Welded specimens
containing over 50% Re have a sharply defined fused zone .
The metal of welds containing over 50% Re mixes poorly with the base
metal. Incompletely melted rhenium can be found in such welds due to the
high rate of the welding process . In welds with
a high rhenium content, owing to the nonuniform
3
distribution of rhenium in the molten metal, a
series of structures appear which correspond
,kgm
500
Hv
/m
to phase regions of the composition diagram of

400 the molybdenum - rhenium system .
300
The dependence of the hardness of the welds
on their rhenium content is shown in Figure 87 .
200
A sharp increase in hardness in welds with
2 82% Re is explained by the presence of two phases ,
100 o +B.
Bending tests were performed at room
0
temperature on 50 x 10 mm specimens which were
cut across , as well as along the weld . The
strain hardening of the weld was relieved
FIGURE 87. Hardness of the weld together with that of the base material. The test
was carried out at a constant deformation rate
joint of molybdenum . The weld
was alloyed with rhenium /59 / : ( 18 and 6 mm / min ) . The radius of the mandrel
used in the bending tests was equal to three
1 - molybdenum ; 2 – Mo - 51 % times the thickness of the sheet (Tables 79 and 80 ) .
Re ; 3 – Mo - 820% Re . I - base
material ; II – thermally affec The introduction into the weld of approximately
ted zone ; III – weld . 30 wt % Re increases the ductility of the weld
joint produced by automatic arc welding in a
controlled atmosphere , and by electron- beam
welding in vacuo . This is because in this case the hardness and the strength
of the metal of the weld remain approximately the same as those of unalloyed
molybdenum (or of the VM- 1 alloy ) , whereas its ductility increases
( Table 81 ) .
The maximum ductility of the weld is attained at a 50% Re content . The
metal of such welds, separated from the base metal, can be flattened at
room temperature by bending along the weld . The high ductility of the weld
metal during bending is due to the intensive process of mechanical twinning
236
of the molybdenum - rhenium (50 % ) alloy. Figure 88 b shows the micro
structure of the metal of the weld , containing 50% Mo and 50% Re , after
deformation and rupture . Numerous traces of mechanical twinning are
observed . Figure 88 a shows the metal of the same weld before deformation ,
TABLE 79. Ductility of welded joints of molybdenum and of the VM - 1 alloy alloyed with rhenium /59 /
Content of Re Bending angle, Content of Re Bending angle,
Point of failure Point of failure
in weld , % degrees in weld , % degrees
Base material : molybdenum Base material : VM- 1 molybdenum alloy

0 4 Weld 28 15 Them ally affected
12 2,5 zone
80
30 21 29 32 Weld
10
51 10 Thermally affected 32 31
zone 50 180 Thermally affectea
75 3 The same ( longitudinal zone
sample)
Note . Deformation rate 6 mm /min ; R.mandrel = 35 (S is the sheet thickness ); T = 20° C ; automatic welding
in controlled atmosphere at the rate of 30 m /hr.
TABLE 80. Dependence of the bending angle of welded joints of

the VM- 1 alloy on the rhenium content of the metal of the weld /61 /
Content of Re Bending angle , Point of failure
in weld , % degrees
0 30 Weld
29-34 50 Thermally affected zone
50 180 The same
Note : Deformation rate 6 mm /min; Rmandrel = 3S(S is the sheet

thickness ); T= 20 ° C ; electron -beam welding in vacuo , welding rate =
= 30 m /hr .
TABLE 81. Strength of rhenium -alloyed welds in VM - 1 alloys
Testing temperature , °C
20 1000
Content of Re in weld
OB OB
,
point of failure point of failure
kg /mm² kg /mm²
Unalloyed 56 Weld 33 Weld

30 - 50 % 62 Thermally 34 Base metal
affected zone
Note . Automatic welding in a controlled atmosphere .
The use of rhenium and its alloys as the filler material assures reliable
welding of molybdenum structures . This opens up wide possibilities for
the use of structures made of high -melting metals , and in particular of
molybdenum , at a relatively small consumption of the filler material.
237
FIGURE 88. Microstructure of molybdenum weld
with 50 % Re , X 200 :
a – before deformation ; b – deformation by impact.
With sufficient confidence we can assume that welding tungsten sheets

with a filler material of either rhenium or of its alloys with tungsten or
molybdenum will also assure the reliability of the weld and a high ductility
equal to that of the tungsten- rhenium alloy itself in the cast or deformed
state . The same applies to the ternary tungsten - molybdenum- rhenium
alloys with specific component ratios .
6. Welding titanium alloys
Today, welding of titanium alloys is widely used in various fields of

technology. It is characteristic of titanium alloys that the plastic properties
of the weld are much lower than those of the deformed material, since rapid
cooling leads to the precipitation of large amounts of brittle particles in
the metal of the weld . The authors of / 50 / studied modified cast titanium
filler materials . The base metalwere titanium alloys containing 3 — 5 % Al,
5% Nb , or 3% A1, 4% Mo; rhenium or other metals (boron, zirconium, cerium)
were introduced as the modifying additive .
238
140 180
160
120
140
100
2. 120
80 100
80
40 60
0.05 0.1 Q2 01 0.2

a Re, % b Re , %
FIGURE 89. Dependence of the bending angle of the weld of an alloy on its rhenium
content:
a – Ti - 3 % Al - 59% Nb ; b – Ti - 3% Al - 5 % Mo. 1 - weld ; 2 – base metal.
The addition of rhenium markedly reduces the grain size of the products
of decomposition of the B - phase, but it does not greatly change the structure
of cast alloys .
The weldability was studied on sheet materials , 1–2 mm thick, welded
by the argon- arc automatic method with a tungsten electrode . The
specimens were welded to form a butt joint , without a gap . Bending tests
were carried out on specimens 15 mm wide , and the radius of the punch
was equal to the thickness of the material being tested ( Figure 89 a and b ) .
The data indicate the favorable influence of rhenium on the ductility of the
weld . The addition of 0.05 – 0.1% Re increases the bending angle of
alloys of both series approximately three times . The authors of / 50 /
recommend the following filler alloys for welding titanium alloys : Ti - 3% Al
5% Nb - 0.1 % Re ; Ti - 3% Al — 4% Mo – 0.05 – 0.1 % Re ; Ti – 5% Al — 5% Nb
– 0.05 % Re .
In conclusion we can state with confidence that the use of rhenium in the
welding of high- melting metals deserves attention . Until we find a method
for making reliable welded structures without rhenium, the use of
rhenium for these purposes is highly advantageous .
239
Chapter XVI
ELASTIC PROPERTIES AND THERMAL EXPANSION
OF RHENIUM ALLOYS
We know from design in practice that the applicability of a metal as

constructional material depends on its strength and technological character
istics, and its elastic constants , such as the modulus of elasticity E,
shear modulus G , modulus of cubic compressibility D , and Poisson's ratio k . The
study of the elastic properties of rhenium and its alloys has only just begun .
Rhenium itself has the third highest modulus of elasticity after osmium and
iridium . There is no doubt that rhenium alloys also have a future as
materials with good elastic properties .
A very important characteristic of constructional materials is also their
coefficient of thermal expansion . It determines the stability of the
dimensions and shape of parts during operation, and possible combination
with other materials , which is especially important for machine parts
which operate at high temperatures , and are frequently soldered to glass or
ceramics . Very often the accuracy of instruments permits only an
insignificant distortion in the shape and dimensions of the individual parts .
We should also note that the modulus of elasticity, the internal friction ,
the characteristic temperatures , the coefficient of thermal expansion , the
melting and boiling points, and the hardness characterize the forces of the
interatomic bonds in the metal, and therefore are connected by specific
ratios . Thus , the coefficient of thermal expansion a and the modulus of
elasticity E are related by the following formula :
Cp - Co ga’TEV ,
where cp — Co is the work performed by the expansion of 1 mole of the

substance on heating by 1° C; the coefficient of thermal expansion a is
related to the melting point Tmp by the formula a.Tmp = K (for metals with
a cubic lattice K = 0.02 ) . We should note that for rhenium with a hexagonal
close- packed lattice R - 0.023 , and for the molybdenum alloy with 50% Re ,
which has a cubic lattice , K = 0.017 .
The melting points of alloys and their mechanical and technological
properties are discussed in Chapters X - XV. In this chapter we shall
examine only the very few available data on the elastic properties and
thermal expansion of certain rhenium alloys . In general, these data have
appeared only during the past 2 – 3 years ( 1962 – 1964 ), and relate to the
best studied and known constructional alloys of rhenium with tungsten and
molybdenum .
240
1. Elasticity of molybdenum - rhenium alloys
The elasticity of rhenium -molybdenum alloys was studied in /62 / by the

dynamic method of transverse and longitudinal vibrations to determine the
modulus of elasticity E , and by torsional vibrations to find the shear
modulus G and Poisson's ratio u . The tests were carried out on 1.35 mm
diam wire made of cast alloys and annealed at 2000°C for 2 hours .
TABLE 82. Elastic constants of the Mo - 50 % Re alloy
Material, % E, kg/mm² 6 , kg /mm² u
100 Mo 32,300 12,230 0.324

Mo - 50 Re 34,700 13,500 0.285
Mo - 50 Re 34,600 13,400 0.285
The elastic constants of two specimens made of an alloy containing 50%

( 35 at . % ) Re , and of pure molybdenum are shown in Table 82 .
We see from the table that the introduction of rhenium increases the
modulus of elasticity of the alloy by approximately 5 % and the shear
modulus by 10 % . Poisson's ratio decreases by approximately 10% . A certain
increase in the elasticity is due to an increase in the interatomic binding
forces in this alloy.
?/mm 3
E.10-
38 30 % RE
kg
36 10 % Re
Elastic
torsion
angle
lag
34
,f
o%
of
5% Re 0.3
-
32 0.2
MO
0.1
400 800 1200 20 40

1 , °C Re, %
FIGURE 90. Temperature dependence FIGURE 91. Dependence of the elas

of the modulus of elasticity of molyb tic lag of elastic parts made of mo
denum - rhenium alloys. lybdenum - rhenium alloys on the
content of rhenium .
The modulus of elasticity of cast deformed and annealed molybdenum

alloys containing up to 30% Re was studied in / 41 / at room and at elevated
(up to 1100°C ) temperatures by the resonance method , based on the bending
vibrations of cylindrical samples 75 mm long ( Figure 90 ) . The introduction
of rhenium greatly increases the modulus of elasticity of molybdenum at all
temperatures .
241
The authors of /43 / studied the elasticity of the cold- worked ( 95 — 99
reduction ) molybdenum - rhenium alloys containing up to 50% Re . The
research was carried out on a strip with a minimum thickness of 4 , and
a width to thickness ratio of 10 .
One of the most important properties of materials for elastic parts of
electrical instruments is the characteristic of elastic imperfections of these
materials . The elastic lag of elastic parts made of the sintered molybdenuri
alloy with 5 % Re is equal to 4% of the angle of torsion . An increase in the
rhenium content to 50% decreases the elastic lag to 0.06% of the angle of
torsion ( Figure 91 ) .
The effect of the method of manufacture of the alloy on the elasticity of
elastic parts ( Table 83 ) processed under optimum conditions has also been
studied .
TABLE 83. Elastic characteristics of molybdenum -rhenium alloys

Thermal Elastic lag
Content of Re , coefficient in torsion
Method of preparation E , kg/mm?
% of elasticity , (% of angle
x 10 * .1/ ° C of torsion)
Sintered 32,000 2 0.07

30
Electron -beam melting . 2 0.18
30,000
Sintered 32,000 2 0.06
50 Arc melting 32,000 2.5 0.07
Electron -beam melting . . 30,500 2 0.07
A certain difference in the values of the elastic constants of molybdenum

rhenium alloys ( Tables 82 and 83 ) is evidently due to differences in the
degree of purity of the alloys .
2. Elasticity of tungsten -rhenium alloys

The authors together with Z. A. Timofeeva studied the elasticity of
sintered tungsten- rhenium (up to 20% Re ) wire , deformed to a reduction
of ~ 84% . The diameter of the wire did not exceed 0.1 mm . An increase in
the rhenium content in the alloy from 3 to 20 % results in a 10% increase in
the modulus of elasticity .
3. Elasticity of niobium - rhenium alloys
In /41 / the authors studied cast deformed and annealed niobium - rhenium
alloys with a rhenium content of up to 5% . The modulus of elasticity at 20
to 1300° C was determined by the resonance method , based on the bending
vibrations of cylindrical specimens , with an accuracy of up to 0.2%
(Figure 92 ) . The modulus of elasticity was calculated from the formula :
242
E = 1.6388 · 10-8 (h)* pe, where 1 = 75 mm is the length; f is the natural
vibration frequency, in Hz , d is the density, in g / cm?, G is the weight .
In /41 / it is reported that at temperatures up to 1200°C the modulus of
elasticity of niobium- rhenium alloys is somewhat higher than that of niobium .
5 % RE
12
* gm²
2 % RE
mk/10
Nb
10
400 800 1200
1.C
FIGURE 92. Dependence of the modu

lus of elasticity of niobium - rhenium
alloys on the temperature and the con
tent of rhenium .
4. Characteristic temperature of molybdenum - rhenium

and niobium - rhenium alloys /41 /
The characteristic temperature of molybdenum - rhenium ( 0 – 30% Re ) and
niobium- rhenium ( 0 – 5% Re ) alloys was computed in /41 / from the formula :
1.6818.103 VE
0
A - 6.d ".
where E is the modulus of elasticity; d is the density, and A is the average

atomic weight .
a
8,9 % b
39 485
475 8 , **
1.2 285
35 465
275
33 455
1 1 1
445 1.0 265
MO 20 30 Nb 1 2 3 4 5
Re , wt % Re, wt %
FIGURE 93. Dependence of the characteristic temperature and the modulus

of elasticity of molybdenum -rhenium (a ) and niobium -rhenium ( b) alloys
on their rhenium content.
243
Alloying with rhenium smoothly increases the elastic modulus ( E ) and
the characteristic temperature ( 0 ) of molybdenum and niobium ( Figure 93 a
and b ) .
5. Elasticity of rhenium disilicide
In /63 / it was found that the shear modulus of rhenium disilicide ReSiz
is equal to ( 14.7 + 0.7 ) . 108 kg / mm², i. e . , it is higher than that of
molybdenum disilicide ( 10.74 0.4) · 103 kg / mm².
6. Internal friction of molybdenum - rhenium alloys /64–65 /

The internal friction of molybdenum - rhenium alloys was studied in /64 ,
65 / by means of a torsional pendulum . Research was carried out with
molybdenum alloys containing 50% Re . Specimens 110 – 120 mm long, and
0.6 mm in diameter, were prepared by drawing cast specimens . Tests were
carried out at 105 mm Hg, and an average heating rate of 2°C / min from
20 – 1000°C . The maximum deformation did not exceed 10,5 % , and the frequency
of torsional vibrations was 0.35 – 0.40 Hz .
2.0 p
400 0.120
5
2
300 0.110
200 0.100
6
31
100 0.090
0,080
200 400 600 800 1000
T. ° C
FIGURE 94. Temperature dependence of internal friction
(Q- 1) and of the square of the vibration frequency ( 13) of
molybdenum - 50 % Re alloys with different grain diame
ters /65/:
Internal friction: 1–5 ; 2 – 5 u (repeated heating);
3 — 50 M ; 4 - 200 u. Vibration frequency: 5 - 50 m ;
6 - 200 u ( torsional vibration frequency at 20 °C , 0.3 Hz) .
The temperature dependence of internal friction and of the square of

the vibration frequency (proportional to the shear modulus ) of the samples
of molybdenum alloys with 50% Re is shown in Figure 94 /65 /.
244
As we see from the diagram , the internal friction of the alloy at
temperatures below 700° C is almost uninfluenced by temperature . At
750 – 800°C the internal friction begins to increase . Repeated heating of
the deformed sample results in a similar curve of internal friction, shifted
into the region of high temperatures by 30°C . Recrystallization at 1500°C
for 5 hours ( grains 50 u in diameter ) leads to a decrease in the internal
friction in the region of grain boundary relaxation . At this degree of
relaxation the shear modulus at 900°C is also lower (0.4% compared to 3%
in the transition state ) . After an annealing at 1950°C for 33 hours (the
average diameter of the grains is 200 m ), the internal friction in the
20 – 1000°C range is low (approximately 0.001 ) and scarcely changes , and
the shear modulus does not show signs of relaxation .
1041
I go
400 6 0.118
300 0.108
200 0.080
100 0,070
0,060
0 200 400 600 800 1000
TC
FIGURE 95. Temperature dependence of internal friction
and the square of the vibration frequency of samples in
the initial state (average diameter of grains is 5 W /65 /.
Internal friction : 1 – unalloyed molybdenum ; 2 – Mo
0.13% Zr ; 3 – Mo -50 % Re . Vibration frequency: 4 –
unalloyed molybdenum ; 5 – Mo - 0.13 % Zr; 6 – Mo
50070 Re .
The activation energy of the grain boundary internal friction of the

molybdenum - rhenium alloy in the initial state (degree of deformation 60% )
is 35 kcal / g- atom , and after recrystallization at 1500° C it is equal to
44.3 kcal / g- atom . The authors of /65 / believe that the increase in the
activation energy is due to the transition from the deformed state into a
more stable recrystallized state . Both these values of the activation energy
of the high - temperature internal friction of the molybdenum - 50% Re alloy
are much smaller than that of the self - diffusion of molybdenum in the alloy
containing 20% Re ( 139 kcal / g- atom ) , and of the heterodiffusion of rhenium
in molybdenum ( 94.7 kcal / g- atom ) .
By comparing the temperature dependence of the internal friction of the
molybdenum - rhenium alloy, pure molybdenum, and molybdenum containing
0.13% zirconium (Figure 95 ) the authors of /65 / concluded that the noticeable
increase in the internal friction of the molybdenum - rhenium alloy begins at
a higher temperature (700° C ) than in the other metals ( 600°C ). From 700°C
the molybdenum - rhenium alloy has the lowest internal friction .
245
The absolute values of internal friction at 800°C are as follows :
100% Mo ... 400
Mo - 0.13% Zr 126
Mo - 50 % Re 40
The authors of /65 / consider that the most authentic mechanism appears
to be grain boundary relaxation, which is due to the migration of interstitial
impurities in the intercrystalline zones under the influence of temperature
and cyclic stresses . It is assumed that the addition of 50 wt % Re to
molybdenum noticeably increases the activation energy of internal friction
at the grain boundaries , possibly because of the " perfecting ' of the
intercrystalline zones of the metal, and a decrease in the concentration of
interstitial atoms in the above zones as a result of the increase in the
solubility of these impurities in the bulk of the molybdenum .
From the specific relationship between the processes of creep and
stress relaxation, the authors of /65 / assume that the molybdenum alloy
with 50% Re , which has a higher activation energy of grain boundary
relaxation than molybdenum and the molybdenum alloy with 0.13 % Zr , can
under similar conditions be expected to have the highest resistance to creep
at the grain boundaries .
7. Thermal expansion of molybdenum - rhenium alloys

The mean coefficient of thermal expansion of certain alloys of the
molybdenum - rhenium system was measured using a Strelkov dilatometer
( Table 84 ) at 20 – 900°C. Cast and annealed 4.5 – 7.5 mm thick specimens
were prepared from an alloy developed by K. S. Pridantseva .
TABLE 84. Mean coefficient of thermal expansion (10Ⓡ • 1 / ° C ) of alloys of the molybdenum -
Content
rhenium system
position
Phase
com
alloy
of
Re
Temperature range , o
in
,
State
20-100 20-200 20-300 20-330 20-400 20-500 20-60020-70020-800 |20-900
100 Mol Cast 5.63 5.57 | 5.76 5.88 5.95 5.98 6.04 6.226.43
3 4.62 4.98 5.33 5.50 5.53 5.58 5.61 5.84 5.97
10 a 4.73 5.03 5.20 -
5,43 5.55 5.64 5.66 5.87 | 6.08
60 a +0 5.52 5.55 5,28 4.70 4.85 5.29 5.37 5.53 5.76 5.98
89 Annealed lo + B6.46 6.556.74 6.85 6.87 6.85 6.87 5.92 7.11
at
2000 °
As we see from the table , for all alloys and pure molybdenum there is
a monotonous increase in the coefficient of expansion with temperature . An
exception is the alloy with 60 % Re , that showed an as yet unexplained
transformation , which began in the 300 – 325° C range , and finished at
approximately 340° C . Evidently, this transformation occurs in the o - phase ,
246
large amounts of which are present in this alloy . However , in the alloy
with 89 % Re , which also contains the o - phase , this transformation was not
recorded .
а b
C°1/,:1a0
Mo 20 30 нь 2
Re,wt % Re, wt %
FIGURE 96. Mean coefficient of thermal expansion of rhenium alloys:
a - with molybdenum ; b – with niobium .
The mean coefficient of thermal expansion in the 0 – 1200° C range for

cast deformed and annealed molybdenum- rhenium alloys containing up to
30 % Re was determined in /41 / ( Figure 96 a ) . The introduction of Re in
amounts of up to 30% decreases somewhat the mean coefficient of thermal
expansion from approximately 5.9 · 10-6 for pure molybdenum to
5.1 • 10-61 / ° C for the alloy with 30% Re .
In /43 / the coefficient of thermal expansion of rhenium, molybdenum ,
and of their alloys in the temperature range from 20 to 1000°C was also
studied . The dilatometric curves were recorded with a DR- 49 type
differential dilatometer of the Shevenar system . The mean temperature
coefficient of linear expansion for the molybdenum - 50% Re alloys is
6.1 · 10-6 1 / °C , irrespective of the method of preparation of the alloy
( sintered or after electron- beam melting) /43 /.
8. Thermal expansion of rhenium alloys containing

niobium , tantalum , cobalt , chromium , nickel, and silicon
Niobium - rhenium alloys / 41 / . The mean coefficient of thermal

expansion in the 0 – 1000°C temperature range of cast deformed and
annealed niobium - rhenium alloys with a Re
content of up to 5% was determined in /41 /
18
( Figure 96 b ) . The introduction of rhenium
(up to 5 % ) decreases somewhat the mean
1:«°C/1",0
coefficient of thermal expansion from ~ 8.37 • 10-6
M for pure niobium to ~ 8.13 • 10-6 1 / °C for the alloy

7005-001
with 5 % Re .
600-700
800-900
Cobalt - chromium - nickel - rhenium

20-100
alloys /54 /. The influence of rhenium on the

100E
+
002-
properties of the cobalt- chromium- nickel alloy

1C,°
K40NKHM was studied on 0.5 mm diam wire

FIGURE 97. Variation in the
specimens . Figure 97 shows the variation in the
coefficient of linear expansion coefficient of linear expansion a in the 100 – 900°C
of the K40NKHM alloy with range for the cast K40N KHM alloy with 7 % Re .
7 % Re in the temperature range Rhenium- silicon alloys . In /63 / the
100 – 900 ° C . coefficient of thermal expansion of the ReSiz
247
compound was determined ( 6.6 • 10-6 1 / °C ) and was found to be close to the
coefficient of thermal expansion of wsi, ( 6.25 · 10-6 1 / °C ), but much lower
than that of MoSiz ( 8.25 · 10-6 1 / °C ) .
Tantalum - rhenium alloys . According to the data obtained by the
authors and I. A. Tsyganova , the mean coefficient of thermal expansion in
the 100 – 1000° C range is 6.58 and 6.63 · 10 : 1 / °C for alloys of tantalum
with 0.8 and 2.03% Re , respectively .
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1962 .
36. Barrett , C.S. Structure of Metals . London , McGraw - Hill . 1952 .
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38. Savitskii , E. M. and M.A.Tylkina . – In : Sbornik " Issledovaniya
po zharoprochnym splavam ," No. 4 : 218, Izdatel' stvo AN SSSR .
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39. Tylkina , M. A. and I. A. Tsyganova . - ZhNKh, 8 ( 10 ) : 2346 . 1963 .
40. Kieffer , R. and W.Hotop . Pulvermetallurgie und Sinterwerkstoffe.
- Berlin , Springer- Verlag. 1943 ,
41. Ul'yanov , R. A. and N. D. Tarasov . Izvestiya Vysshikh
Uchebnykh Zavedenii , No. 2 : 140 . 1964 .
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144. 1962 .
43. Timofeeva , Z. A. , M. A. Tylkina , and E. M.Savitskii . In :
Sbornik " Spetsial'nye materialy dlya elektropriborostroeniya ,"

TSINTIEP . 1965 .
44. Sedler , E. , D. Kraut , K. Schlaubitz , and D. Müller . J. Less
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249
45. Savitskii , E. M. and M.A. Tylkina . Renii i ego splavy ( Rhenium
and Its Alloys ) . – In: Sbornik " Issledovaniya po zharoprochnym
splavam , p . 35, Institut metallurgii im . A. A. Baikova . 1956 .
46. Savitskii , E.M. , M.A.Tylkina , and K. B. Pova rova.- Patent
SSSR, No. 165310. 1961 ; Byulleten ' Izobretenii, No. 18. 1964 .
47. Gaines , G. B. In: Rhenium . -Amsterdam -N . Y. , Elsevier Publ . Co.
1962 .
48. Tylkina , M. A. and E. M.Savitskii.- Patent SSSR , No. 634268/22 .
Byulleten ' Izobretenii, No. 6. 1960 .
49. Savitskii , E. M. and M.A.Tylkina . ZhNKA, 3, No. 3. 1958 .
50. Danilova , G. P., M. V. Mal'tsev , M. V.Poplavko, T.M.

Vladimirskay a. In: Sbornik " Renii," pp . 203 — 208 ,
51. Warin , M.P. In: Rhenium , pp . 175 – 180 . Amsterdam N. Y. ,
Elsevier Publ . Co. 1962 .
52. Kopetskii , Ch . V. Fiziko-khimicheskoe vzaimodeistvie margantsa
s perekhodnymi metallami ( Physicochemical Interaction of
Manganese with Transition Metals ) . Author's Summary of Thesis .
- Moskovskii Institut Stali . 1961 .
53. Pshechenkova , S. V. Pretsizionnye splavy ( Precision Alloys ) . -
Trudy TsNIIChM , No. 25 : 227 – 237. 1962 .
54. Sol'ts , V. A. and M. A. Bedretdinova . In: Sbornik " Renii,"
p . 200 , Moskva , Izdatel'stvo Nauka . 1964 .
55. Winkler , 0. – 2. Elektrochem . , 49 : 221 . 1943 ,
56. Japanese Patent No. 4106. 1960 .
57. Japanese Patent No. 4104. 1960 .
58. Holzmann , N. Patent FRG , No. 116966. 1961 .
59. D'yachenko , V.V. , B. P. Morozov , M. A. Tylkina , and E. M.
Savitskii . Svarochnoe Proizvodstvo , No.7 : 1 – 4. 1962 .
60. Kuleshova , T.F. and B. P. Nikonov . In : Sbornik "Renii," p . 186 ,
Moskva , Izdatel'stvo Nauka . 1964 .
61. D'yachenko , V. V. and B. P. Morozov . In : Sbornik " Renii, "
p . 208, Moskva, Izdatel'stvo Nauka . 1964 .
62. T'ao Tsu - ts'ung . Issledovanie plasticheskikh svoistv molibdena
i nekotorykh ego splavov (Research on the Plastic Properties of
Molybdenum and Some of its Alloys ) . Author's Summary of Thesis .
Institut Metallurgii im . A. A. Baikova . 1962 .
63. Samsonov , G. V. , V. A. Obolonchik , V.S. Neshpor , et al .
In: Sbornik " Renii," p . 181 , Moskva , Izdatel ' stvo Nauka . 1964 .
64. Bronfin , M. B. and V. A. Marichev . – In : Sbornik " Protsessy
diffuzii, struktura i svoistva metallov," pp . 52 — 58 , Izdatel'stvo
Mashinostroenie . 1964 .
65. Bokshiein , S. Z. , M. B. Bronfin , S.T.Kishkin , and V. A.
Marichev . In: Sbornik " Protsessy diffuzii, struktura i svoistva
metallov," pp . 40 – 51 , Izd . Mashinostroenie . 1964.
250
Chapter XVII
PHYSICAL PROPERTIES OF RHENIUM ALLOYS
Rhenium alloys are of great interest because of their electrical and

magnetic properties . Some of these alloys can be used for the production
of high- temperature resistors and high- vacuum potentiometers , and
others have semiconductive and superconductive properties .
The production of resistors from rhenium alloys was started only
recently . Literature data are available on studies of the influence of
rhenium on the electrical resistivity of the refractory metals usually used
in electronic and electrical industries (tungsten, molybdenum ), and of some
constructional alloys and noble metals . Only one paper discusses the
influence of alloying elements on the electrical resistivity of rhenium itself.
Studies on the electrical resistivity of rhenium alloys and the construction
of rhenium phase diagrams for the whole range of concentrations , and of
composition - electrical property diagrams , have greatly contributed to the
development of new rhenium alloys .
The electrical resistivity is influenced by alloying , press working, heat
treatment , and particularly by aging , in the same way as the hardness , and
therefore hardness measurements can be used to study these processes .
Alloys with the required electrical resistivity can then be produced by the
correct processes . Unfortunately, it should be pointed out that these
investigations are being carried out haphazardly , and we know of only one
paper which describes a study of the electrical resistivity of rhenium
molybdenum alloys over the whole range of concentrations / 17.
1. Electrical resistivity of alloys of rhenium with

molybdenum and tungsten
The electrical resistivity of molybdenum- rhenium alloys over the whole

range of concentrations was studied at room temperature using cast
specimens ( 2x3x12 mm ) annealed at 2400 and 1600°C (Figure 98 ) . This
method was one of those used in instrumental analysis to confirm the
decomposition of the o - phase and the formation of an x- phase . It was found
that the electrical resistivity of alloys containing molybdenum- base solid
solutions increases with increase in the content of rhenium, and that alloys
containing o- and x- phases have a maximum electrical resistivity one order
ofmagnitude higher than that of saturated molybdenum -base solid solutions / 1 /.
251
u, ohm.cm
300
200
100
Но 20 60 80 RE
Re,wt %
FIGURE 98. Electrical resistivity of cast molybdenum -
rhenium alloys.
1 - annealed at 2400 °C ; 2 – annealed at 1600 ° C .
The influence of various heat - treatment processes on the electrical

resistivity of molybdenum - base alloys containing 22 – 35 at. % Re was
investigated in /2 /, using 14 – 22 u diam wire produced from cast alloys
( Table 85 ) .
TABLE 85. Electrical resistivity of 14 – 22 u diam wire made of cast

tungsten - base and molybdenum- base alloys conta ining rhenium at room
temperature / 2/
Composition Electrical
of alloys , State of alloys resistivity,
at . % uohm · cm
Mo - 22 Re 16.3
Wrought...
Annealed 1550°, 1000 hr 16.1
M10 - 25 Re Wrought . . 17.1
Annealed 2000°, 23 hr 18.7
Mo -30 Re Wrought... 19.0
Anne a led 1500" , 1000 hr 18.6
Annealed 2000°, 39 hr . 28.1
Mo -35 Re Wrought 23.2
Annealed 1500", 1000 hr 22.4
W - 22 Re Wrought 26.2
Annealed 2000" , 1000 hr 24.8
Annealed 2500°, 46 hr 18.4
W - 27 Re Wrought 28.0
Annealed 1500°, 1000 hr 30.1
Annealed 2000º , 1000 hr 28.1
Annealed 2500° , 240 hr 15,4
The electrical resistivity of all alloys decreased after a recrystallization

anneal at 1500°C for 1000 hours . A further increase of the annealing
temperature to 2000° C increased their electrical resistivity, apparently due
to the oxidation of the wire at 2000° C .
The temperature dependence of the electrical resistivity of molybdenum
base alloys containing 30 , 40, and 50 wt % Re ( Figure 99) has been studied
13 /. The measurements were carried out in vacuo on 0.5 – 0.6 mm diam
252
wire specimens (up to 1000°C ) or on 0.1 mm thick foil specimens (above
1000°C ) . The electrical resistivity of an Mo 50 % Re alloy increases from
23 u ohm · cm at 20°C to 60 u ohm · cm at 1000°C , and to 143 u ohm · cm at
1500°C . A decrease in the rhenium content to 30 – 40% decreases the
electrical resistivity of the alloys at all temperatures . The electrical
resistivity of molybdenum wire varies from 6 4 ohm · cm at 20 ° C to
40 4 ohm · cm at 1000°C , and is given in Figure 99.
100 % Re
80+ 27
150
21
8.8
475
100 2.75
W 100 %
50
20
500 1000 1500 300 700 1100 1500

1, °C T, X
FIGURE 99. Influence of temperature FIGURE 100. Temperature dependence
on the electrical resistivity of wire of the electrical resistivity of wire made
made of molybdenum - rhenium alloys : of sintered and cast tungsten - rhenium
1 - 50 % Re ; 2-30 and 409% Re; 3 – alloys .
Mo. The 100 % Re and W - 27070 Re alloys
were cast , other alloys were sintered .
The temperature coefficient of the electrical resistivity of molybdenum

alloys containing 50 and 30 – 40 wt % Re and also of molybdenum over the
range of 20 – 1000°C is equal to 3.7 , 3.6 , and 3.7 · 10-2 1 /° C, respectively .
From 1000 to 1500°C , the increase in the temperature coefficient of the
electrical resistivity of alloys is greater at higher contents of rhenium in
the alloy. Thus , the temperature coefficient of an alloy containing 50% Re
increases four times and is close to 18 · 10-2 1 / ° C . The authors of / 3 /
believe that this is because in alloys with a composition close to the
solubility limit aging occurs at these temperatures .
The electrical resistivity of sintered and cast molybdenum - rhenium
alloys was nieasured (diameter of the wire or thickness of the strip was
10 – 20 u ) . It was found that the resistivity of wire made of sintered alloys
deformed to 84% reduction increases three times if the content of
rhenium is increased from 5 to 50% . Annealing at temperatures up to 900 ° C
has almost no influence on the electrical resistivity of the alloys .
According to / 3 / the method of preparation of molybdenum- rhenium
alloys has no influence on their electrical resistivity .
The electrical resistivity of both sintered and arc- melted molybdenum
base alloys containing 30% Re is 15 4 ohm · cm . The electrical resistivity
of molybdenum -base alloys containing 50% Re is 20 4 ohm · cm irrespective
of whether the alloy was obtained by sintering , arc - melting or electron
beam melting .
253
TABLE 86. Electrical resistivity of sintered tungsten -rhenium alloys at elevated temperatures
(uohm . cm ) /5/ *
Temperature
coefficient
Re
of electrical
content, Electrical resistivity at different temperatures (° K )
% resistivity,
a : 103
( 293-1273W )
O 300 ° 680 ° 920° 1080 ° 1215 ° | 1315° 1410 ° 1490 ° 1570° 1630 °
5,6 15.0 23.0 27.0 31.0 34.0 37.0 40 42.0 44.0 5.77
2,75 300 ° 650 ° 870° 1050 1180° 1230° 1390° 1480 ° 1560 ° 1630 °
8.5 18.7 24.8 30.2 34.6 38.2 41.3 44 45.8 | 48.0 4,10
4.75 300 ° 630 ° 850 ° 10200 1160° 1270 ° 13700 1465° 1540 ° 1615 °
10.4 20.4 27.3 32.4 36.7 40.0 43.2 45.9 48.5 50.5 3.20
8.8 300º 600 ° | 820 ° 10000 1135 ° 1245º 1345° | 1440 ° 1520 1590 °
13,2 23.4 | 30.7 35.8 40.0 43.6 46.4 49.4 51.8 54.3 2.40
21 300 ° 550° 810 ° 980 ° 1120 ° 1250° 1360 ° 1460 ° 1540 ° 1610 °
24,2 34.0 42.0 47.0 51.6 54.6 57.4 59,8 62.6 64.4 1.20
27 ** 293° 676 ° 880 ° 990 ° 1177 ° 1286 °
35 51 59 63 70 73 1.10
The electrical resistivity was measured on a 50 u diam wire .

** The data were obtained by the authors and O. Kh . Khamidov for wire (d = 150 W made of
cast alloys.
The data of /4 / give the electrical conductivity after electron- beam

melting as 5.9 m/ohmmm? for rhenium , 5.5 m /ohmmm for a molybdenum
alloy with 50% Re, and 18 m / ohm · mm² for molybdenum .
The electrical resistivity of cast tungsten- base alloys containing 22 and
27% Re at room temperature after different heat - treatment processes is
shown in Table 85. An increase in the content of rhenium in the alloy leads
to an increase in the electrical resistivity /2 /.
The electrical resistivity of sintered rhenium- tungsten alloys was studied
on 50 u diam wire specimens coated with alundum . Current - potential
characteristics were recorded for radio valve heaters made of this wire / 5 /
at potentials of from 1 to 9 V, and their resistivity was determined at room
temperature . The temperature dependence of the electrical resistivity and
data on the resistivity of cast W - 27% Re alloys are given in Table 86 and
Figure 100. At the same temperatures the electrical resistivity of the wire
increases with increase in the content of rhenium in the alloy. Thus , at
room temperature and at 1000° K the electrical resistivity of W - 21% Re
alloys is 5 times and 2 times that of pure tungsten . The cast alloy
containing 27% Re has an electrical resistivity 7 times that of tungsten.
The data given in Table 86 show that an increase in the concentration of
rhenium in tungsten- base alloys decreases the temperature coefficient of
the electrical resistivity over the range from 20 — 1000°C .
These data show that tungsten- rhenium alloys can be used instead of
pure tungsten to obtain the same filament current on wires of a larger
diameter . This will naturally increase the service life of the wires . Also ,
the temperature coefficient of tungsten alloys containing 20 — 27% Re is
considerably lower than that of tungsten , which is also very important in
service .
254
V. E. Peletskii and V. Yu . Voskresenskii measured the electrical resistivity
of cast W – 27% Re alloys at temperatures of 1200 — 2800°K .
T, K 1400 1600 1800 2000 2200 2400 2600 2800
P , uohm · cm 67.3 73.9 79.9 85.7 91.1 96.8 102.8 109,2
The influence of the rhenium content on the electrical properties of

sintered tungsten alloy wire , used in the U.S. A. in the electric lamp and
electronic industries , has been studied /6 /. This wire is fabricated from
the 218- W alloy containing the alloying elements ( K, Al, Si ) .
At room temperature the resistivity of the 0.2 mm diam wire made of
the 218- W alloy containing rhenium increases with increase in the rhenium
content .
Re content, wt % .. 0 1 3 5 7 10 20
Electrical resistivity , uohm • cm 6.7 7.7 9.7 12.7 14.0 18.8 25.0
2. Electrical resistivity of alloys of rhenium with

noble metals
Noble metals and their alloys are widely used in the production of
instruments and in electronics .
Rhenium - palladium alloys . The electrical resistivity with its
temperature coefficient of two palladium- rhenium alloys are given in
Table 87 /7 / .
TABLE 87. Electrical resistivity and its temperature coefficient of wire made
from cast palladium -rhenium alloys /7 /
Electrical resistivity, wohm .cm Temperature

coefficient of the
Content of Re , % electrical
25° 100 ° resistivity,
1 / ° C (25—100 ° C )
0.35 11.017 13.516 0.003272

2.24 13.048 15,749 0.002965
By alloying palladium with rhenium /8 / its electrical resistivity is

increased . Thus , an increase in the content of rhenium to 11.9 wt % is
accompanied by a fivefold increase in the electrical resistivity and a
decrease in its temperature coefficient from 3.5 · 10-3 to 0.7 . 10-3 1 / °C .
The annealing temperature of palladium and its alloys has little influence
on their electrical resistivity and the temperature coefficient ( Table 88) .
The stability of these properties is a very important positive factor when
these materials are used, particularly in instruments working at varying
temperatures .
The resistivity of ternary palladium- tungsten alloys is given in Table 89
/ 9 /. It can be seen that the electrical resistivity of alloys consisting of
ternary solid solutions with 80 — 85 % Pd decreases appreciably with increase
in the content of rhenium . The temperature coefficient of electrical
255
resistivity remains low in all alloys containing 85 % Pd , and so these alloys
can be used in the production of contacts . The temperature coefficient of
the electrical resistivity of alloys containing 80% Pd increases with increase
in the content of rhenium .
TABLE 88. Dependence of the electrical resistivity of rhenium -palladium alloys on the
heat treatment / 8/
Content of After cold

Tanneal : 0
Re , % working 400 500 600 800 1000
12.14 12.2 11.5 11.85 11.9

0
0.00352 0.0034 0.00312 0.00360 0.00332
21.05 23.5 22.6 22.6 21.6 20.0
3.4 0.00198 0.0026 0.00198 0.00184 0.0029 0.00196
40.4 31.0 38.0 38.4 33.7 33.6
8.74 0.00088 0.00092 0.00088 0.00096 0.00114 0.00097
46.0 49.4 42.0 38.2
11,9
0.0007 0.00071 0.0006 0.0007
Note . The annealing lasted one hour. The numerator gives the electrical resistivity
(in uohm • cm ) at 25 ° C while the denominator gives the temperature coefficient of the
electrical resistivity ( 1 /°C ) at 25 to 100 ° C .
TABLE 89. Electrical resistivity of ternary rhenium -palladium - tungsten alloys /9 /

Electrical Temperature
Chemical composition, %
resistivity coefficient of
Pd W Re
at 25 ° C , electrical resistivity ,
Hohm.cm a ,x10* (25–100 °C )
100 9.96 37.8
95 2.5 2,5 26.94 18.8
90 5 5 42.05 6.76
85 11.25 3.75 69.34 2,4
85 7,5 7.5 57.34 4,452
85 3.75 11.25 40.91 6.983
80 15 5 95.27 0.984
80 12,5 7.5 73,79 2,918
80 10 10 69.32 4.414
80 5 15 62,31 4.712
80 2.5 17,5 58,47 3.78
75 18.75 6.25 62.49 3.569
The electrical resistivity and the temperature coefficient of binary alloys

containing 80 and 75% Pd are almost unaffected by the content of
rhenium / 9 /.
Noble metal alloys containing rhenium have been suggested as a material
for electric resistors , and particularly for potentiometric wire in a
German patent (West Germany ) / 10 / . Instead of the platinum and gold alloys
at present used for the production of wire with a high electrical resistivity,
palladium alloys of the following composition are recommended ( p in
u ohm · cm ) :
256
Pd — 16% Re, p = 51
Pd – 10% Cr - 18% Re p = 95–102
Pd — 5 % V – 17 % Re, p = 95—100
Pd – 7,5 % V – 9 % Re p = 102–110
The best results were obtained with palladium alloys containing

3 — 30% Re . The workability of these alloys can be improved by partially
substituting rhenium by vanadium . The alloys suggested in /10 / have a
low specific gravity, a low thermal emf in contact with copper, a high
tensile strength, and a high electrical resistivity.
3. Electrical resistivity of alloys of rhenium with copper ,

manganese , chromium , iron , cobalt , nickel, or tantalum
Alloys of rhenium with manganese , copper , and nickel .

The influence of small amounts of rhenium on the electrical properties of
alloys of manganese with copper and nickel is shown in Table 90 / 11 /. It
can be seen that rhenium somewhat decreases the electrical resistivity of
both hardened and annealed alloys of manganese with copper or with copper
and nickel . Alloys containing 0.5% Re which have a temperature coefficient
of electrical resistivity close to 0 are very promising .
TABLE 90. Influence of small amounts of rhenium on the electrical properties of manganese
alloys containing copper and nickel
Quenching from 800 ° C Annealing at 4000

Composition of alloys, % P 20 ° P 20 °
a , 1 / °C a , 1 /°C
uohm • cm ( 20-100° C ) uohm · cm (20 – 100 °C )
Cu – Mn (35 : 65 ) 155.0 4.83-10-5 119,7 5.65.10-4

Cu - Mn - 0.1 Re 150.1 8.4.10-5 116.7 3.8.10
Cu - Mn — Ni (16,5 : 63,6 : 19.9) 177,5 0.75.10-5 179.5 -0.75.10-5
Cu - Mn - Ni - 0.5 Re 175.0 174.0
Iron - cobalt - rhenium alloys / 12 / . The influence of small

amounts of rhenium on the electrical resistivity of iron- cobalt alloys has
been studied on cast and on wrought specimens annealed at 920°C in vacuo
or in hydrogen ( Figure 101 ) . Rhenium appreciably increases the electrical
resistivity of alloys containing 25 or 35% Co. Alloys containing 50% Co
have a bend on the resistivity curves at 0.5 Re , which according to the
authors of / 12 / indicates that a new rhenium phase is formed .
Cobalt - chromium - nickel - rhenium alloys / 13 /. The
influence of rhenium in amounts of from 3 to 10% on the properties of
cobalt - chromium- nickel alloys ( K40NKHM ) has been studied / 13 /. The
alloys were arc melted, forged at 1150 – 1180°C , quenched in water from
1180° C , and cold drawn with intermediate annealings . Figure 102 shows
the influence of rhenium on the electrical resistivity of annealed cold- worked
wire . The authors of / 13 / believe that the decrease in the electrical
resistivity as a result of annealing at above 500° C is due to the decomposition
257
of the solid solution and the precipitation of a carbide phase of the CozM03C
and Cr23C6 types , and to recrystallization of the alloy .
• m hm
souo
c
a b с
wyoriwɔ
20
95
'd.
15
10
Cr
0.5 1.0 0.5
Re, %
1.0 0.5 10 15
FIGURE 101 , Electrical resistivity of iron -cobalt -rhenium alloys:

a - 25 % Co; b – 35 % Co ; c – 50 % Co ; 1 – wrought; 2 – after
annealing in hydrogen at 920 ° C for 10 hr and cooling at the rate
of 50 ° C per hr.
85
200 400 600
T
800
'anneal'
FIGURE 102. Dependence of the
°C
electrical resistivity of the K40NKhM

alloy containing rhenium on the
annealing temperature /13/:
1 K40NKAM without rhenium ;
2-3 % Re ; 3 – 7 % Re; 4 – 100% Re .
Tantalum - rhenium alloys . The authors of this work together

with 1. A. Tsyganova determined the electrical resistivity of cast
tantalum- rhenium alloys using a 0.8 mm diam wire annealed at 1500°C .
Tantalum alloys containing 0.5, 0.8, and 2.03% of rhenium have an electrical
resistivity of 16.3 , 17.1 , and 18.5 u ohm · cm and a temperature coefficient
of electrical resistivity over the range of 20 – 100° C of 3.0, 2.74, and
2.70 · 10-3 1 / °C , respectively .
4. Electrical resistivity of rhenium - rich alloys
The influence of alloying elements on the electrical resistivity of

rhenium was studied by the authors of this book together with O. Kh . Khamidov .
The alloys were prepared by arc melting rhenium ( 99.98% pure ) with
titanium , zirconium , hafnium , vanadium , niobium , tantalum , chromium ,
molybdenum , or tungsten in amounts of up to about 10 at . % . The electrical
resistivity of 2x3x20 mm specimens was determined at room and elevated
temperatures (up to 1000°C ) in a vacuum of 10–3 mm Hg ( Table 91 ) .
Table 91 shows that the electrical resistivity of rhenium is increased
least by the addition of molybdenum and tungsten and most by zirconium
and hafnium . Obviously, this increase is due to the influence of the
dimensional factor of these metals in regard to rhenium . The
temperature dependence of the resistivity of alloys at from 20 to 1000°C is
an almost linear function .
258
TABLE 91. Electrical resistivity p (uohm · cm ) and the temperature coefficient of the electrical
resistivity a 25-100X104 1 / C ) of alloys of rhenium with transition metals of groups IV – VI
(at. % )
1% 3 % 5% 7 % 10 %
System P D D
Re - Ti 23.7 | 26.6 33.2 | 15.2 40.5 16.3 48.5 8.2

Re - Zr 24.2 35.7 34.6 24.0 | 47.3 21.1 64.5 11.3
Re- HE 25,8 32.2 37.4 22.2 48.2 18.4
Re - V 23.4 32.0 30.4 26.2 36.3 21.5 42,0 14,7
Re - Nb 25.2 28.3 33.6 24.3 43.0 15.0 55.0 | 11.6 | 77.0 7.8
Re - Ta
Re - Mo
23.2 | 31.0
19.8 41.8
34,5
20.8
25.0 42.2
34.2 24,5
17,557,0 | 12.5
28.6 26.5 22,5 30.0
2.0 / 18.0
Re - W 21,0 42.9 22.2 36,0 25,2 29,5 29.8 23.7 | 32,5 19,4
Note . For pure rhenium = 18.75 uohm • cm , (225-100 = 48.0 • 10-4 1 / °C .
5. Semiconductor properties of rhenium compounds

The interest taken in semiconductor materials for industrial use , and
the development of new semiconductor materials, has increased greatly
during the last years . The well- known semiconductors germanium ,
silicon , and a number of compounds of the AMI BV type, melt at about
1000 – 1500°C . Today, one of the most urgent problems is to develop high
melting semiconductor compounds for operation at much higher
temperatures.
We have as yet very little experimental data on this problem , and the
semiconductor properties of only two rhenium compounds (with silicon and
selenium ) have been studied .
Rhenium disilicide ReSiz / 14 /. The semiconductor properties of
ReSiz have been studied /14 / on specimens prepared by sintering
stoichiometric mixtures of electrolytic rhenium and silicon powders
( 99.99% ) in argon at 1300°C for 3 hr . The rhenium disilicide powder was
pressed into cylindrical specimens with a density of 90% of the theoretical
( 10.8 g / cm°) . The electrical resistivity , the thermal emf, and the Hall
effect were measured on single- phase specimens annealed at 1400°C for ten
hours . Figure 103 shows the temperature dependence of the electrical
resistivity and of the thermal emf of ReSiz at 20 – 1000° C . The log p =
f ( 1 / T ) function shows that rhenium disilicide is a semiconductor with an
activation energy of about 0.13 eV . The electrical resistivity of ReSiz at
room temperature is about 1.102 ohm ?. cm-?. The conductivity caused by
impurities in these specimens is of the hole type, and the conductivity of
ReSiz itself is apparently due to electron movement since above 1000° C the
absolute thermal emf becomes negative .
The Hall coefficient at room temperature is positive , like th thermal
emf. The concentration of the impurity carriers of current is about
1018 cm-3.
It is very interesting to compare the semiconductor properties of
rhenium disilicide with those of disilicides of other transition metals .
Rhenium disilicide has a tetragonal structure, isomorphic with the disilicides
of molybdenum and tungsten, but these have a metallic conductivity and
positive temperature coefficients of electrical resistivity . The MoSi, and
259
WSi, compounds have a p - type conductivity and a' relatively low concentration
of current carriers (1021 cm- ). The disilicides of most other transition
metals have a conductivity of the n - type and a higher concentration of current
carriers , equal to 1023. cm-%, since the conduction band in them is
apparently more than half filled . During a study on the influence of oxidation
1 on the electrical resistivity of rhenium disilicide it was found that
specimens heated in the air at 1400° C for 30 minutes become covered by a
protective film of silicon oxide , but the electrical resistivity remains
unchanged .
Thermal 1.100
3.6 20 2.0 1.2
/°C,uemf
)•u(p,pmohm
240 19
V
clog
160 3.7
2
80 3.5
33
300 500 700 900 1100
1. X
FIGURE 103. Temperature dependence of the electrical
resistivity and of the thermal emf of ReSiz /14/:
1- log ; 2 – thermal emf.
It is interesting that the disilicide of manganese , which is an analogue

of rhenium, has semiconductive properties , too /15 /.
Rhenium diselenide ReSe2 / 16 /. The semiconductive properties
of rhenium diselenide ( ReSez ) were studied in / 16 / on specimens prepared
by sintering a stoichiometric mixture of rhenium powder ( 99 % pure ) and
selenium powder ( 99.9 % pure ) in vacuo at 700°C for 100 hours . The structure
of this compound has not yet been determined , but it was found that it has a
lower degree of symmetry than MoSe2 .
The electrical resistivity and the thermal emf were measured on
compressed specimens . The electrical conductivity of rhenium diselenide
is 6.75 · 10-5 ohm - 1.cm - 1 at 24°C , and 10.7 · 10-5 ohm-? .cm at 64°C . The
positive temperature coefficient of the electrical conductivity and its
magnitude show that ReSe, has semiconductive properties . This is also
confirmed by the high thermal emf of the compound . The thermal emf was
measured by the integral method in a thermocouple with alumel . The
temperature differences between the ends of the specimens varied from
25 to 150 ° C . Under these conditions the thermal emf varied from 1200 to
880 u V / °C . It was found that the hot ends of the alumel became negatively
charged , and hence the authors of / 16 / believe that ReSez is a semiconductor
of the p - type like the disilicides of molybdenum and tungsten .
It is believed / 17 / that compounds of rhenium with nitrogen and
phosphorus may also have semiconductive properties .
260
6. Magnetic properties of rhenium alloys
Little is known on the use of rhenium as a magnetic material, except for

several superconductive alloys containing rhenium that are used in
solenoids . Rhenium has no magnetic properties that make it promising as
a basis magnetic material . However , by alloying magnetic materials with
rhenium a useful material may be obtained .
Hoersted H , versted
20 40 60 80 100 120 120
24 20 40 60 80 100
g8,auss
24
g8, auss
20
2,3
16 16
12 12
FIGURE 104. Magnetization curves of ring FIGURE 105. Magnetization curves of ring
specimens of alloys containing 25 % Co and up specimens of alloys containing 35% Co and up
to 1.09% Re . Thickness of sheet 0.35 mm : to 1% Re /12/ :
1 - 25 % Co, 1% Re , He = 2.13 oersted; 2 - 25 % 1-35 % Co , 1.0 % Re , He = 2.35 oersted; 2 –

Co , 0.5 % Re, He = 1.74 oersted; 3 – 25 % Co , 35% Co , 0.5% Re , He = 16.1 oersted ; 3 – 35 %
0.2 % Re , He = 1.63 oersted. Co , 0.2 % Re , Ho = 1.48 oersted .
, oersted
20 40 60 80 100 120
24
4
8,gauss
Z
3
20
16
12
FIGURE 106. Magnetization curves of alloys

containing rhenium , after annealing in hydro
gen at 920 ° C for 10 hours and cooling at the
rate of 50 ° C per hour:
1-50 % Co, 1.59% Re , He = 3.9 oersted ; 2
50 % CO , 1.0 % Re , He = 2.3 oersted; 3 – 50 %
Co , 0.5 % Re, Hc = 1,0 oersted ; 4 – 50 % Co ,
0.297 Re , Ha = 0.73 oersted; 5 - 50 % Co ,
without rhenium , He = 0.53 oersted .
261
Iron - cobalt - rhenium alloys / 12 / . Soft magnetic alloys
( iron- cobalt ) containing 35 – 50% Co have the highest magnetic saturation,
and therefore are used to produce magnetic conductors in transformers and
other electromagnetic devices . Below 730°C these alloys become brittle as
a result of the ordering of their structure .
In order to decrease the brittleness of these alloys small amounts of
alloying elements ( Cr , W, Re ) are added . The influence of rhenium on the
magnetic and mechanical properties of these alloys was studied / 12 /.
Figures 104 — 106 show the magnetization curves of ring specimens of cast
and wrought alloys annealed at 920°C ( 25, 35, and 50% Co and 0.2 - 1.5 % Re ) .
An increase in the content of rhenium up to 1.5 % has almost no influence on
the magnetic saturation of the alloys , but it appreciably improves their
mechanical properties /12 /.
Alloying magnetically soft iron- cobalt alloys with small amounts of
rhenium is very promising .
7. Superconductive rhenium alloys
Alloys of rhenium with superconductive transition metals are of great

interest .
Since the structure of the electron shells influences the superconductivity
of metals and alloys , we shall discuss the alloys of rhenium with some
elements in the order of their location in the periodic table .
Subgroup II A
Beryllium . According to / 18 / the Be Re compound has superconductive

properties at temperatures above 1.68° K .
Subgroup III A
Yttrium . The Re2Y compound has a he onal structure of the
MgZn, type, and a transition temperature Tc- 1.83°K / 19 /.
Subgroup III B
Boron . The structure of the Re2B compound is unknown , but it may

possibly be tetragonal of the Me2B5 type (y - phase ). The temperature of
transition into the superconductive state is 2.8°K /20 /.
Aluminum . According to /21 / the Re24Als compound (a - Mn ) has
Tc = 3.35°K, and 6.33 valence electrons per atom .
Subgroup IVA
Titanium . The influence of rhenium on the Tc of titanium has been

studied in /22, 23 ). In /22 / the Tc of arc -melted, wrought and annealed
alloys was determined by measuring the mutual inductance.
262
It has been found that the addition of rhenium stabilizes the solid solution
with a body- centered cubic lattice and increases the temperature of transition
to the superconductive state to 2.7° K ( Ti - 10 at . % Re ) . The Re24Tig
( x - phase ) with an a - Mn type lattice has Tc = 6.6° K /23 /. It was found /21 /
that the X - phase of the titanium- rhenium system has about 6.47 valence
electrons per atom and Tc = 5.1 ° K .
Zirconium . The Re Zr compound has a hexagonal structure of the
MgZn , type (Laves phase ), Tc = 6.0° /24 / and 5.9 ° K /18 /. The Re24Zr5
compound ( x- phase with a structure of the Q - Mn type) has Tc - 9° K /23 /.
It was found / 21 / that the X -phase of the zirconium - rhenium system which has
6.5 valence electrons per atom has Tc ~ 7.4° K . According to Alekseevskii
/ 18 / the Re24Zrs compound has T. - 3 ° K .
Hafnium . The HfRe, compound with a hexagonal lattice of the MgZn2
type ( Laves phase ) has T.- 4.8°K /19 /. It was found /21 / that the X- phase
of the hafnium- rhenium system (a - Mn type) has Tc = 5.8 — 5.9° K, and about
6.58 valence electrons per atom .
Subgroup VA
Vanadium /21 /. The V24Re 76 compound (VRez ) has a o - phase structure

and Ic = 4.52°K ( 6.52 valence electrons per atom ) .
Niobium . The superconductivity of the o- (ß - U ) and x - la - Mn ) phases
formed by rhenium with transition metals has been studied /25 /.
specimens were arc melted, homogenized , and annealed at 1500°C for
100 – 150 hours in vacuo ( 3 · 10-6 mm Hg ), and then quenched in water after
annealing. The phases were identified by X- ray analysis . The starting
materials for the preparation of the alloys contained less than 0.1% of
metallic and gaseous impurities . The temperature of the transition into
the superconductive state of the Nb – 50 at. % Re alloy (NbRe , o - phase ) is
2°K /25 /, and of the Nb – 82 at . % Re alloy ( x -phase ), it is 9.89° K according
to /25 /, and 9.7°K according to /23 /.
TABLE 92 /21 / . Some thermodynamic characteristics of rhenium compounds
Number of
y , mjoule / Ces ( TC )
valence
Compound Structure
electrons Tc , K (degrees ) . Y (TC)
male
per atom
Nb38 Reas a-Mn 6.24 2.43 2,35 2.65

NbspReni a-Mn 6.42 5.60 3.58 2.85
NbzoReso a -Mn 6.60 6.83 5.00 3.16
M042Rese 6.58 6.35 3.31 2.83
MozaRego a-Mn 6.77 9.25 3.80 2,77
W50Reso 0 6,50 5.12 2.69 2.91
Crao Reso 6.60 2.15 4.18
Several niobium- rhenium alloys with an a - Mn structure ( x- phase ) have

been studied /21 /. The authors determined the transition temperature Tc ,
the factor of the electron contribution to the specific heat y , and the
relationship between the electron contributions to the specific heat in the
superconductive state Ces (Tc), and in the normal state riTc) (Table 92 ). The
263
same authors also found that the X - phase in niobium- rhenium alloys has
Tc ~ 8.8° K and ~ 9.5°K , and 6.4 valence electrons per atom .
Tantalum . The temperature of the transition to the superconductive
state of the alloy Ta- 50 at . % Re (TaRe , o - phase ) is equal to 1.3°K /25 /, of
the RezTa compound ( x- phase ) it is 6.78°K /25 /, and of the alloy Ta – 64% Re
( Re2Ta, X - phase ) it is 1.46°K /23 /. According to the authors of /23 / these
differences in Tc of x- phases are due to differences in the number of valence
electrons , which is 6.5 valence electrons per atom for TaRe3 and 6.3
valence electrons per atom for Ta36Re24 . For the x- phase of the tantalum
rhenium system T. ~ 1.7 ° K, and ~ 6.27 valence electrons per atom /21 /.
Subgroup VB
Nitrogen . The No.34Re ( ReNo.43- x) compound has a face - centered cubic

lattice and a transition temperature of 4.0 ° K 26 /.
Subgroup VI A
Chromium . It has been found that the Cr2Rez (o - phase ) has Tc = 2.15° K
( Table 92 ) /21 /.
The superconductivity and the antiferromagnetism of chromium - rhenium
alloys containing 70 at . % Re have been studied /27 /. It can be seen from the
figure that the maximum temperature of transition into the superconductive
state ( Ic) is about 5° K for alloys in the vicinity of the boundary of
homogeneous solid solutions of rhenium in chromium . In this system the
regions of alloys with superconductive and antiferromagnetic properties
overlap one another . During measurements of the anomaly of the electrical
resistivity of chromium- base solid solutions it was found that the Néel
temperature is almost doubled over a very narrow range of concentrations .
Thus , for alloys containing about 20 at . % Re the transition into the super
conductive state and the electrical resistivity anomaly occur simultaneously .
A considerable increase in the specific heat also takes place at this critical
concentration of rhenium, which according to the authors of /27 / is due to
the sudden transition from the magnetic into the superconductive state .
Molybdenum . The superconductive properties of molybdenum
rhenium alloys have been studied more than those of other rhenium alloys .
The great interest taken in molybdenum - rhenium alloys is partly due to
their good workability and mechanical properties , so that they can be
shaped into wire and strip .
A molybdenum + 25 at . % Re alloy was studied /28 / in order to produce
a superconductive solenoid for service at low temperatures in a field of
15 kgauss . The studies were carried out on 70 u diam wire . The wire was
prepared by cold drawing two bars that had been electron- beam melted
from rods of rhenium and molybdenum . The dependence of the critical
magnetic field on the current for short pieces of 70 u diam wire in two
directions of the external field at 1.5 and 4.2° K is shown in Figure 108 .
The critical field for a 0.025 mm diam wire made of an alloy containing
15 at . % of Re is 2 kgauss higher than for a 0.12 mm diam wire made of
the same alloy . It was found that the dependence of the critical
magnetic field on current is also influenced by the method of preparation of
264
the wire , and the differences between different batches can reach several
kgauss . A solenoid 3 cm long with an internal diameter of 0.3 cm and an
external diameter of 2 cm was made of gold - coated 0.07 mm diam wire
produced from an alloy containing 25 at . % Re . The gold coating served as
an insulator between the turns . The individual layers of turns were
separated by a thin layer ( 0.01 mm ) of insulating material. The solenoid
had 20,000 turns . The experiments were carried out with allthe coils switched
in and three sections connected in parallel ( Figure 109 ) . The shape of
the curves for the conditions of each test is such that the horizontal lines
marked at the ends represent the average magnitude of the field over the
corresponding range . The parallel connection between part of the layers
permits considerable currents to pass through the outer coils where the
field is considerably weaker, and to produce a more intense field in the
center of the solenoid .
temperature
Ica
1
Neel
,ØTK
600
SOO THн sot

10
400
300 3
0.01
2006 2
100
b.c.c.
0.0011
20 60 2 6 10 18
Re , at . % Ha, kgauss
FIGURE 107. Temperature of the FIGURE 108. Dependence of the
transition into the superconductive critical magnetic field on the
state and the Néel temperature for electric current passed through
chromium - rhenium alloys /27/ . wire made of molybdenum +25 at.
% Re (MozRe) for two directions
of the external magnetic field at
1.5°K and 4.2% (70u diam wire)
/ 28/:
0-1.5 ° K ; A-- 4.2K ; continuous
line - H Ilc ; dashed line Hllc .
Molybdenum alloys containing 3, 10 , and 50 wt % Re were studied by

I.N. Goncharov, L. I. Litomskii , and N. S. Khukhareva . They used wire
specimens 0.2 -0.3 mm in diameter and 60 mm long , and measured the
temperature of the transition into the superconductive state ( Tc ) from the
electrical resistivity and the field current ( 1 = f(u) ) characteristic at 4.2° K .
The current- field curve for a Mo 50% Re alloy is shown in Figure 110 .
With specimens containing 10% Re the following measurements were made :
H = 0, ; = 1.1 · 103 A / cm?; at H = 1 koersted , j = 0.3 · 103 A / cm². These
measurements show that in an identical magnetic field , a decrease in the
content of rhenium in the alloys leads to a decrease in the current density .
265
Molybdenum alloys with 3% Re have a temperature of transition into the
superconductive state below 4.2°K . For molybdenum alloys containing
50% Re Tc = 10.9° K .
1.10 .
c/Aj,m²
kH,gauss
15
1.10
Center
End
1 11
1.10
-1.5 -10 -05 o 0.5 10 1.5 o 20 30
Distance along axis of solenoid , cm H, koersted
FIGURE 109. Dependence of the magnetic FIGURE 110. Dependence of the critical
field of a solenoid made of MogRe wire on magnetic field on current for Mo – 35 at .
its position with reference to the axis of % Re alloys at 4.2° K .
another solenoid made of molybdenum
+ 25 at. % Re wire at 1.59K . The coils are
connected in series (continuous curve) or
partially in parallel (dashed curve) . Dia
meter of wire 70 H.
1
According to /20 /, for the MozRe alloy Tc- 10°K . The Mo Rez compound
(o - phase ), whose exact composition has not been given in this work, has
T. = 6.0°K /25 /. The MoRez compound ( x - phase , a- Mn ) has T. - 9.89° K /25 ).
The temperature of transition of binary alloys of the molybdenum
rhenium system into the superconductive state was studied over the whole
range of concentrations of alloys arc melted in a furnace with a
nonconsumable tungsten electrode in an inert atmosphere , and annealed at
1500 – 2500 ° C for 50 – 100 hours in an induction furnace in a vacuum of
about 3 • 10-8 mm Hg /29 /. Figure 111 a shows that alloys on the boundary
of solid solutions of rhenium and molybdenum have the highest Tc. The
compositions of alloys which do not become superconductive down to 1 °K
are designated by points with a vertical arrow pointing downwards and the
letter N (normal). The maximum transition temperature corresponds
approximately to an electron density of 6.4 electrons per atom. The tempera
ture of transition of o- and x - phases is considerably lower and agrees with
previous data. Two cast molybdenum - rhenium alloys consisting of
Mo42Re58 (u - phase ) and MO23Re 77 ( x - phase ) were studied in /21 /. The
characteristics of these alloys are given in Table 92 . It should be pointed
out that the MO23Re 77 alloys quenched from the molten state have a wide range
of transition temperatures ( Tca 10.25° K ) . After they have been annealed
for 100 hours at 1800° C these same alloys have Tc = 9.25° K, and the range
of transition temperatures narrows appreciably /29 /.
266
T, ° C
3000
2500
1.6 a
2000
2400
พ Re
1400 ta
400
12 ♡
Took
10 O
6 2
1 1 N
2
1
0
MO 20 40 60 80 RC W 20 60 80 Re
R!, at. % Re , %
a b
FIGURE 111. Temperature of transition into the superconductive state of

molybdenum -rheniurn ( a ) and tungsten - rhenium (b) alloys / 29/.
Tungsten . According to I. N.Goncharov, L. Litomskii , N.S.

Khukhareva , tungsten alloys containing 3 , 10, and 20% Re have no
superconductive properties above 4.2° K .
For the Rew (o - phase ) compound Te = 5.2° K 25 /, the RezW ( x- phase )
compound T. - 9.00°K / 18 / , and the RegW, (o -phase) compound To = 6.00 ° K / 20 /.
It is stated in /20 / that the addition of tungsten to rhenium increases
the temperature of the transition into the superconductive state , but the
maximum Tc is not given in this paper . The temperature of the transition
into the superconductive state of binary rhenium - tungsten cast alloys
annealed at 1500 – 2500° C for 50 – 100 hours has been studied over the
whole range of concentrations /29 /. The maximum transition temperature
is shown by an alloy with an electron density of approximately 6.6 electrons
per atom .
The properties of the W 50Re50 (o- phase ) alloy have been studied in /21 /
( Figure 92 ) . For this alloy the value of Tc = 5.12° K agrees well with the data
given in /25 /.
Subgroup VIII A
Manganese . The o - phase of the manganese - rhenium system has

Tc < 1 ° K at ~ 6.9 electrons per atom /21 /.
Group VIII
Osmium . In the ternary rhenium system the temperature of transition

into the superconductive state is 5.74° K for the ReTiOs alloys ( 32 ), and
2.0° K for the ReYOs alloys /30 /. There is little data on the superconductive
properties of rhenium alloys , but attempts can be made to systematize
existing data so that further research can be planned .
267
12
. 6 - phase HO MO .
o X -phase No 8 MOO
Zrоооль °
NO " MO
Tc
,K
ozr
TL 3 Mo
6 Noo Hf oow
Tt ooW
.V
-
4 AL
Mbo o2r
Nb • Cr
2
Ta Ta o ºota
Mng
11 1
9.7 5,9 6.1 6.3 6.5 67 6.9

Number of electrons per atom
FIGURE 112. Dependence of the transition of o and x
phases in alloys of rhenium with transition metals into the
superconductive state on the average number of valence
electrons per atom .
The data of different authors on the relationship between the transition

temperature into the superconductive state of o- and X - phases of rhenium
systems / 19, 21 , 23, 25 ), and the average number of valence electrons per
atom calculated from the true composition of the compounds , are shown in
Figure 112. The boundaries of the enclosed area were determined /25 / for
phases with a structure of a - Mn , B - U, and B - W . For all phases with a
structure of the B - U (o ) and a - Mn ( x ) types the maximum temperature of
the transition into the superconductive state corresponds to ~ 6.5 – 6.7
valence electrons per atom . This differs from the number of 7 valence
electrons given in /31 /, but agrees well with the data of /32 /. Figure 112
shows that the o- and x- phases of rhenium systems conform to the same
regularities .
We should like to mention the two regularities that we found for compounds
formed in alloys of rhenium with transition metals . They concern the
position of the alloying metal in the periodic table, and therefore the
structure of its electron shells (Figure 113 ) .
The relationship between the Tc of a rhenium compound with a structure
of the o- , , - , or X - phase types and the position of the alloying element in
the periodic table (we took the maximum known values of Tc in each phase )
shows that on passing from elements of group III A to those of group VI A
with less electrons than rhenium , that is on approaching the number of
s + d electrons characteristic of rhenium , the transition temperature
increases. This can be seen well in compounds with a structure of the same
type, and formed by metals belonging to the same period . Thus , the Tc of
phases with an a - Mn structure ( x- phase ) increases as we pass from
zirconium to niobium and farther to molybdenum in the second long period,
and from hafnium to tantalum and tungsten in the third long period . 0 - Phase
compounds of the first long period are exceptions , probably because of the
coincidental ferromagnetism characteristic of these metals (chromium,
manganese ) .
268
No
12 olto
• 6 - phase 2r o Wพ
ox.phase Но
xd - phase
TO
T!
zr เพ
KT.o HF
V
xHf
Cr
Y No
Нn
Ta
I 7 WI
Group of periodic table
FIGURE 113. Dependence of the temperature of transition

of rhenium compounds into the superconductive state on the
position of the alloying element in the periodic table .
The same regularity has also been found for phases with a - phase
structure (Y - Zr in the second long period ) and the o - phase structure
(Nb – Mo in the second long period , and Ta– W in the third long period ) .
It should be pointed out that Tc for o - phases in systems of rhenium with
elements of group IV A ( zirconium and hafnium ) have not yet been investigated
but it can be shown that the o - phases in these alloys will have no super
conductive properties .
The second regularity on the structure of electron shells of the alloying
element is that in compounds with the same type of crystal structure Tc will
be higher for compounds formed by rhenium with a metal with a less
complex electron shell . This means that the Tc of an alloy of Re with a
metal of the second long period will be higher than that of an alloy of Re
with a metal of the third long period (for example , Tc for o - , .- and x- phases
in the alloys of rhenium with zirconium , niobium, and molybdenum will be
higher than that for the same phases in the alloys with hafnium , tantalum ,
and tungsten ) .
The influence of the number of valence electrons in the compound on its
transition temperature into the superconductive state is appreciable, which
agrees with the conclusion reached in /25 /. If a o- and an x- phase are
formed in the same alloy between rhenium and an element of groups III A –
VI A , the number of valence electrons in these phases increases with
increase in the content of rhenium in the phase . The phases can be
arranged in order of increase in the valence electron number as follows :
0- , - , and x- phases . Figure 113 shows that for metals of the same
period Tc of the x- phase is higher than Tc of the 2 - phase or o - phase, which
means that to increases with increase in the valence electron number .
The dependence of the Tc of rhenium compounds on the position of the
alloying element in the periodic table should be checked . This is possible
by further research on rhenium alloys and by determining the Tc of other
rhenium compounds . However , we believe that by systematizing data on
other elements of the periodic table it should be possible to find compounds
with the required Tc (obviously, with a certain error ) .
269
8. Thermal conductivity and optical properties of
rhenium alloys
V. E. Peletskii and V. Yu . Voskresenskii measured the thermal conductivit

of the W – 27% Re alloy at temperatures of 1400 — 2800°K .
T" , K 1400 1600 1800 2000 2200 2400 2600 2800
1 ,watt.m - 1. degree ? 54.4 56.3 58.2 60.1 62.0 63.9 65.8 67.7
The same authors also found & for white light and en for monochromatic
light , the relative blackness of a tungsten - 27% Re alloy at temperatures
of 1600 – 3000° K .
T, K 1600 1800 2000 2200 2400 2600 2800 3000

e 0.211 0.231 0.251 0.270 0.290 0.310 0.329 0.347
€ (at 1 = 0.65) 0.434 0.429 0.425 0.420 0.415 0.411 0.406 0.402
Bibliography for Chapter XVII

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17. Samsonov , G. V. , V. A. Obolonchik , V.S.Ne shpor , T.S.
Verkhoglyadova , I. L.Vereikina , and T.I. Mikhlina .
Sbornik " Renii," p . 181. Moskva, Izdatel' stvo " Nauka. " 1964 .
18. Alekseevskii , N.A. and N.N.Mikhailov . ZhETF , 43,
No. 6 ( 12 ) : 2110 . 1962 .
19. Compton , V.B. and B. T.Matthias . Acta crystallogr . , 12 : 651 .
1959.
20. Hulm , J.K. Phys . Rev., 98 , ser . II, No. 5 : 1539. 1955 .
21. Bucher , E. , I. Busch , F. Heiniger , and J. Müller . Zürich ,
Verlag Laborat . für Physik den Werkstoffen . 1963 .
22. Matthias , B.T. , V. B. Compton , H. Suhl , and E. Corenzwit .
Phys . Rev., 115 : 1597 . 1959.
23. Matthias , B.T., V. P.Compton , and E.Corenzwit . J. Phys .
Solids , 19 : 130 – 133. 1961 .
24. White , G.K. and S. B. Woods . Can . Phys ., 35 : 892 . 1957 .
25. Blaugher , R. D. and J. K. Hulm . - J. Phys . Chem . Solids , 19 : 134 –
138. 1961 .
26. Matthias , B. T. and W. H. Zachariasen . J. Phys . Chem . Solids ,
7:98 . 1958 .
27. Bucher , E., F.Heiniger , J. Muheim , and G. Müller . - Rev.
Mod . Phys ., 3 ( 1 ) : 1461. 1964.
28. Kunzler , I. H. , E. Bucher , F.S. L.Hsu , B. T. Matthias , and
C.Wahl . J. Appl. Phys ., 32 : 325. 1961 .
29. Hulm , J.K. and R. D. Blaugher . Phys . Rev. , 123 ( 5 ) : 1569 . 1961 .
30. Matthias , B. T. J. Appl . Phys . , 31:23 . 1960 .
31. Matthias , B.T. Progress in Low - Temperature Physics . Vol. II.
Amsterdam , North Holland Publ. Co. 1957 .
32. Roberts , B.W. General Electric Res . Lab ., Techn . Rept, No. 61 – RL
- 274411. 1961 .
271
Chapter XVIII
USE OF RHENIUM AND ITS ALLOYS IN ELECTRONICS

AND ELECTRICAL ENGINEERING
One of the most promising fields of application of rhenium is electronics .

In this field of technology, more than in any other , all the physicochemical
properties of rhenium and its alloys can be used most fully. As the
instrument parts are small the consumption of rhenium is low, which is
especially important due to the scarcity of rhenium .
The interest shown in rhenium as a material for electronic instruments
has recently been shown by extensive development of work in this direction .
In the literature a number of review papers have appeared / 1 – 3 /.
1. Rhenium as an electron emitter
Emission characteristics of rhenium . Today the most

widely used metals for thermionic cathodes are tungsten and tantalum , which
at a sufficiently high working temperature have satisfactory emission
properties and a low evaporation rate .
The material for making a thermionic emitter, i.e. , a cathode , must
have certain properties , but one of the most important is the work function .
TABLE 93. Properties of cathodes made of pure metals / 3 -5 /
Rate of
Metal To, °K (16= 3 A /cm? vaporization at To.
Хуар
ug /cm².se
. sec
W 0.54 2780 0.043

Ta 0.51 2585 0.043
Mo 0.61 2580 0.42
Re 0.59 2955 0.13
Note : Q is the work function ; ava is the heat of vaporization of

atoms ; js is the density of the saturation current.
Tables 93 and 94 show certain properties of cathodes made of pure

tungsten , tantalum , molybdenum , and rhenium /3 – 13 /.
We know that different crystal faces have different work functions , and
consequently the effective work function of a material depends also on the
state of its surface , the method of preparation , and the heat treatment .
272
TABLE 94. Properties of cathodes made of pure metals
Work Richardson's
Cathode Cathode , method of preparation
material and treatment
function , constant Å , Reference
4 , eV A.cm ?. degree -2
W 4.52 14 /
Polycrystalline
Ta 4.12 /4 /
Mo 4.27 14 /
Re Precipitation on tungsten wire from gaseous
phase 5.1 200 16 /
Rhenium deposited electrolytically on
tungsten wire ; annealing for 250 hr at
1500 °C ; for 50 hr at 1800 ° C .... 4,74 720
Rhenium - coated tungsten , as in /6 / ;

experimental tube with guard anodes ;
50 y layer of rhenium on 0.3 mm diam
tungsten wire 4.89 195 14 /
Rhenium on tungsten 4.77 350 18 /
4.8 52 19 /
Sheet rhenium 4.6 / 10 /
Rhenium on tungsten wire; autoelectron
-
emission 5.0 / 11 /
Rhenium deposited electrolytically on
tungsten wire 4,75 700 / 12 /
Rhenium . 4.85 66 1131
Use of rhenium as a thermionic emitter . From a

comparison of the thermionic emission properties of rhenium with the
properties of other high - melting metals ( see Tables 94 and 95 ) , we see that
on the average the work function of rhenium is higher , and therefore the
density of the thermionic emission current at temperatures similar to those
of tungsten, tantalum , and molybdenum is somewhat lower .
However , rhenium has a number of advantages over tungsten . Rhenium
has a smaller tendency to take part in the " water cycle ." * It is thus
advantageous to use rhenium , for example , in hydrogen gas - discharge
devices /9 /. Moreover , rhenium has better mechanical properties at room
and elevated temperatures .
In contrast to other high- melting metals rhenium does not form any
carbides , which is very important , for example , when carbon cathodes are
used in mass spectrometer guns / 14 /.
Mass spectrometers with tungsten filaments are very gas- sensitive , and
their readings depend on the composition of the gases which had already
been studied in the mass spectrometer . Moreover , during operation an
insulating film of WO3 formis on the filament . Rhenium does not have these
disadvantages , as its oxide films are conductors . In / 14 / in a mass
spectrometer used for the analysis of samples containing a large percentage
of aromatic hydrocarbons, the tungsten emitter was replaced by a rhenium
one . During operation of the rhenium emitter for 4 hours , the change in
The "water cycle" is a term given to the process occurring in vacuum bulbs. It is due to the reaction of
insignificant amounts of water vapor present in the tube with the metal, with the formation of a metal
oxide on the hot element ; the oxide vaporizes and is condensed on the colder tube walls, where it is reduced
to metal; the water vapor released returns, and the cycle is repeated. The "water cycle " is the cause of
the burning out of tungsten heating elements and the darkening of the internal walls of the tube is due to
the deposition of metal on them .
273
the filament current was only 0.05 A , compared to several tenths of an
ampere for the tungsten emitter . The emission of rhenium emitters is more
stable in time, and does not depend on the composition of the previously
examined samples . Thus , for the rhenium emitter the current source was
adjusted twice in three months , whereas for the tungsten emitter several
times a day. The life of the rhenium emitter is much longer than that of
the tungsten emitter, the reading is more accurate, and the authors of / 14 /
recommend that the rhenium emitter be used for work in analytical mass
spectrometers .
10 .
FIGURE 114. Photomicrograph of a point made of cast

rhenium .
Avtoelectronic emission / 11 , 15 /. At present the possibility

of using rhenium in superhigh frequency (SHF ) instruments as autoelectronic
emitters is being considered; extremely high densities of emission currents
can be taken off these emitters .
In / 15 / rhenium emitters were produced by the electrodeposition of
rhenium on tungsten wire . After readjustment of the emitter the following
is observed in the operation : the six- fold axes of symmetry are perpendicular
or almost perpendicular to the axis of the emitter, and the other crystallo
graphic directions are disordered . Faces with low indices give a smaller
density of the emission current than other faces at the same voltage . In the
opinion of the authors of /15 / this is due to the higher than average work
function of these sections .
In / 11 / research on autoelectronic emission was carried out with points
made of cast rhenium , and with tungsten points coated with a rhenium
electrodeposit (see Figure 114 ) . * The emission picture accurately shows
the hexagonal structure of the lattice and the basal plane (0001 ) . Dark
spots are situated along the crystallographic bands , and the planes of the
( 2120 ) type with large nonemitting faces alternate with the planes of the
[ 1100) type with smalldark sections . This is not in complete agreement with
the data of /15 /.
In the emission pictures produced by the point readjusted under the
operating conditions at ~ 1100°C , the dark spots were large and the emission
came mainly from the edges between the faces . The temperature and the
time of readjustment are approximately similar to those of tungsten .
The emission picture of the rhenium - coated tungsten shows that the layer
of rhenium on tungsten, approximately 0.5 u thick, consists of a single
crystal. The emission picture is similar to that of pure rhenium .
The samples of cast rhenium were prepared in our laboratory.
274
Research on the resistance of rhenium to ion bombardment / 11 / was
carried out with rhenium points in autoelectronic diodes and in a Muller
projector. Mercury vapor was fed from a special ampule into the
thoroughly evacuated chambers, the
a
vapor pressure was regulated by
100
changing the temperature of liquid
mercury . The anode- cathode voltage
( u ) curves were plotted as a function of
սիսը
time ( 1 ) at a constant emission current

%
90
,
i and at temperature of the emitter of

800 – 900° C ( Figure 115 ) . The decrease
80 in u = f(t) indicates the sharpening of
2 18 26 32 the emitter due to cathode sputtering
b T, min caused by mercury ion bombardment .
100 -5
A rapid drop in voltage is seen on
the voltage versus temperature curve
90
( see Figure 115 a and b ), which is the
natural criterion of the stability of the
ulu
%
emiiter material against ion

,
bombardment .
80
For rhenium the time interval
preceding the rapid pressure drop is
70
greater but the drop itself is smaller
than for tungsten . Thus , rhenium is
five or six times more stable than
8 24 32
T, min tungsten .
FIGURE 115. The u = f ( T) curves for the
Rhenium and rhenium - coated tungsten
nium (a) and tungsten ( b ) plotted at diffe have a weak adsorption capacity for
rent pressures of mercury vapor , with a hydrocarbons , and are resistant to
stable current i = 30 4A and T = 800 ° C . oxygen adsorption /11 , 15, 16 /.
The emission properties of rhenium
Rhenium Tungsten (Figure 116 ) / 11 / begin to deteriorate,
No. No and the thermionic emission drops
p.104 , u.k V (r = 0) p.10 u ,kVT = 0) sharply when the oxygen pressure is of
mm Hg mm Hg
the order of 10-6 mm Hg, whereas the
19.3 5 1.1 6.6
2 3,2 22.0 6 5.0 16.2
tungsten cathode becomes poisoned
6.5 22.5 7 6.5 7.0 even at a pressure of 10-8 mm Hg, i. e . , it
4 20.0 30.0 8
9
6.5
10
17.0
15.5
is less reliable and stable in operation .
The emission properties of rhenium
coated tungsten are stabilized by
high- temperature annealing. The authors of /8 / believe that this leads to
the formation of a W -- Re alloy at the boundary between the tungsten and
rhenium .
From the given data it follows that if relatively small currents are
required thermionic cathodes made of rhenium are preferable to tungsten
cathodes . In particular , such cathodes can be advantageously used in
ionization manometers / 17 /.
Considering that rhenium points are more stable than tungsten points
and have a lower susceptibility to cathode sputtering and the adsorption of
residual gases, and considering that rhenium cathodes show good stability when
high currents are being drawn from them, rhenium can be recommended
for autoelectronic cathodes .
275
secondar
Coeffici ent
y
1.50
of
emission
electron
3
19/10 1.00
10
0.50
Re
-2
w
-3
10-8 107 106 105 10-4 200 400 600 800 1000
Poz. mm Hg Primary energy flux , VA
FIGURE 116. Influence of oxygen FIGURE 117. Coefficient of secondary electron
on the thermionic emission of emission of rhenium (1 ) , tungsten (2 ) , and the tung
tungsten and rhenium when Tw = sten + 25 % Re alloy ( 3).
= 1500 °K , and T ,' Re 1440 ° K .
Secondary emission properties of rhenium /18 - 25 /.

/ 18 / rhenium was studied in a tube from which air was continuously
evacuated by a diffusion oil pump . Rhenium was heated to red heat . The
maximum value obtained for the coefficient of secondary electronic emission
was 1.3 .
In / 19 / the maximum coefficient of secondary emission is 1.6 ; rhenium
was heated at temperatures of over 2200° C in a vacuum ( less than 10-8 mm Hg ) .
According to the data of 20 /, the secondary electron emission of rhenium
scarcely differs from the secondary electron emission of tungsten
( Figure 117 ) .
The emission properties of rhenium (decrease in the work function and
the increase in the coefficient of secondary electron emission ) can be
improved by alloying it with metals such as titanium , zirconium , hafnium ,
or tungsten .
The problem of the use of alloys of high- melting metals as a new and
effective source of thermionic emission has been discussed in 21, 22 /,
and as a source of secondary electron emission in /23 /.
The emission properties of alloys of rhenium with tantalum , titanium ,
and tungsten were studied in /20, 24, 25 /. In /24, 25 / the dependence
of the work function and the maximum coefficient of secondary electron
emission at 1600, 1700 and 1900 ° K on the alloy composition was studied .
According to the data of /20 /, the tungsten alloy containing 25% Re has a
lower coefficient of secondary electron emission than tungsten or rhenium .
However , the coefficient of secondary emission of the alloy is still too high
(it differs little from that of tungsten ), so that if a cathode with a really low
coefficient of secondary emission is required , the wire should be coated
with a suitable material .
Rhenium- barium and other cathodes . Recently, the vacuum
tube industry has started to use porous metallic film cathodes on a wide
scale . In /16 , 20, 26 – 28 / research on the properties of barium- rhenium
cathodes is described . The maximum emission of Ba - Re cathodes is
somewhat lower than that of the tungsten- barium cathodes , and it is reached
at temperatures 250 – 300° higher than in the case of tungsten cathodes .
276
Some results of the tests are given in Table 95. A comparison of the
characteristics of cathodes coated with rhenium sponge and ordinary tungsten
has shown that the emission characteristics of these two types of cathodes
differ very little .
TABLE 95. Emission properties of barium -rhenium and barium -tungsten cathodes /3,20,26 – 28 /
Saturation Saturation
current, A /cm ?, current , A / cm ,
Type of cathode % at the brightness Type of cathode at the brightness
temperature of temperature of
1060 ° C 1060 ° C
0.5CaO : 3Ba0 : 03 9.5 2-3 10.5 CaO • 3BaO •Al2Oz 10 1

Re 90 Re 90
Α1 0.5 0.5 Cao3BaO+Al2O • 0.5 SiO2 10 0.4-0.5
0.5 Ca0 : 3Bao.WCB 9.5 4-6 Re 90
90 0.5 CaO • 3BaO •Al2O3.0.5 SiO2 10 2-4
Al 0.5 W 90
Sintered aluminate and alumosilicate cathodes which do not contain

reducing agents in the working mixture coated with rhenium sponge showed
much better emission characteristics than cathodes coated with tungsten
sponge . According to the data of /20 /, the pressed aluminate cathodes
containing a reducing agent and coated with tungsten sponge have a low
work function ( 1.2 eV ) and a high emission ( 6 — 3 A / cm² ) . The authors of
/20 / also tested cathodes with a matrix containing molybdenum , rhenium ,
and tungsten in equal ratios by weight. These cathodes have analogous
emission properties and a long service life .
The important characteristic of sintered cathodes is the rate of
vaporization of free barium and barium oxide ; the service life of the
cathode and its electron emission depend on the rate of vaporization of
barium .
The authors of / 12 / studied the properties of porous barium - tungsten
rhenium film cathodes . Rhenium was electrodeposited on the tungsten
îilament and barium was sprayed onto the cold rhenium surface . The
dependence of the electron emission of the filament on the rate of
vaporization of barium from its surface was then measured .
TABLE 96. Work function and Richardson's constant for thoriated
Re and w
Richardson's
Work function
Material constant Å ,
'I eV
A /cm² • degree?
Thoriated rhenium . 2.52 1.4
Thoriated tungsten . 2.63 3.0
The rate of vaporization of free barium and barium oxide from the
filamentary pressed cathodes coated with tungsten and rhenium sponge was
also measured in /29 /. It was shown that the rates are approximately the
same, and vary from 1 to 6 .10-10 g / cm² / sec at 1200° C .
277
Data on the rhenium- barium (rhenium- barium- tungsten) cathode system
and the standard cathode (barium- tungsten ) / 12 , 29 / show that the sintered
cathodes coated with rhenium sponge do not have any special advantages
with regard to the emissive characteristic over cathodes coated with
tungsten sponge . However , in /30 / the authors note that rhenium has an
advantage over tungsten, since rhenium does not form any stable compounds
with the material of the coating. In other words , rhenium does not form
the high- resistance intermediate layer which produces a parasitic cathode
resistance in tungsten cathodes .
Data has also been given on the work function and the value of
Richardson's constant for thoriated rhenium and tungsten (Table 96 ) / 10, 31 ).
In / 10, 31 / the authors give the activation temperatures of thoriated
cathodes : for rhenium 1100 – 1300°C and tungsten 1600 — 1900°C .
2. Rhenium as cathode material for a thermionic

transducer (TIT )
Recently, due to the great development of research on the direct

conversion of thermal energy into electrical energy, a new field has opened
up for rhenium and its alloys.
It has been recognized that under specific conditions materials with a
high work function have good heat emission properties in alkaline metal
vapors . There is a simple relationship between the work function of a
material in vacuo and its effective work function in cesium vapors : other
conditions being equal a high work function in vacuo corresponds to a low
effective work function . This is due to the better adsorption of cesium
vapor by materials with a high work function and a higher ability to generate
positive ions of cesium , etc. /32 , 33 /.
The use of rhenium as a cathode material for thermionic transducers
is mentioned in /32 , 33 / and also in a number of other works , for example
/ 34 - 39 /
The much greater current density, specific power, and efficiency of
conversion of rhenium emitters in comparison with other emitters in the
range of the average cathode temperatures ( 1300 – 1700°C ) stimulated new
research . Besides direct measurements of the current- voltage character
istics of conversion, the authors studied the following: emission properties
of various faces of the rhenium single crystals /40 /; emission properties
and characteristics of various alloys containing rhenium /24, 41 /; the
reactivity of certain oxides used as high- temperature electric insulation
materials in contact with high- melting metals (including rhenium ) /39 /; the
properties of rhenium compared to other materials of various geometric
shapes and surface porosities , etc. /42 – 44 / as ion generators in cesium
vapor at various temperatures .
From this research we can conclude that rhenium and its alloys are
promising material for producing TIT cathodes , and that it is most
important to search for rhenium - base alloys which have work functions in
vacuo higher than that of rhenium , sufficiently high melting points, good
mechanical properties , and a slight affinity to insulators and alkaline metals .
278
The density of the emission and ion currents of rhenium single crystals
in cesium vapor was measured in /63 /. The author measured two strongly
emitting planes of single crystals
( 1000 ) ( 1011 ) and two weakly emitting
1024 planes ( 1221 ) ( 1231 ) (Figure 118 ). The
Electron
work function was determined from
current
measurements of the density of the ion
current . The author found that the
Current
c?A/,density
current
stability of a rhenium emitter which had

Ion
m
operated for two years was higher than

that of a W- emitter .
In /39 / the author studied materials
for thermionic transducers operating
at 2000'C . The physical properties
(melting point , vapor pressure,
105 coefficient of thermal expansion ) of
tungsten , rhenium , and tungsten
rhenium alloys are satisfactory, so
10-64 that these materials can be used as
o 1
cathodes and in the production of TIT .
o 2
Research was also carried out on
. 3
the compatibility of high- melting metals
104 a 4
(tantalum, niobium, molybdenum ,
1.0 1.5
tungsten and rhenium ) with oxides of a
number of metals ( rare earth metals ,
3:10 aluminum, thorium, hafnium ),
FIGURE 118. Density of the electron and ion considered possible materials for
currents in cesium plasma for the emitting insulators . Tests were performed in
surfaces of a rhenium single crystal /63 /: a vacuum of the order of 10-4 - 10-5 mm
1- density (1010); 2 - (1000) ; 3 – (1271 ) ; Hg at 2400°C . The reactivity of pure
4- (1231 ) . oxides with high- melting metals
increases in the following order :
thorium oxide , hafnium oxide , yttrium
oxide , aluminum oxide , erbium oxide , and holmium oxide . The high- melting
metals can also be placed in the following order according to the increase in
the reactivity with these oxides : tungsten, rhenium , niobium , molybdenum ,
and tantalum .
However , the problem of the nature of the interaction of oxides with
metals is not yet clear, and by methods of microstructural and X- ray
diffraction analyses it was difficult to determine the boundaries of either
the reaction layers or the diffusion layer . The photographs obtained by
means of an electron microscope show the presence of oxide precipitates
on the twinning planes of rhenium ( Figure 119 ) . The compatibility tests
carried out at 2000 ° C have shown saturation of metallic components with
oxygen and in particular the formation of an intermediate phase between the
emitting metal and the oxide insulator in the rhenium - yttrium oxide system .
One of the interesting uses of the thermionic transducers is the conversion
of nuclear energy into electrical energy. In /45 /, there is a description of
the method for using high- temperature , heat- releasing elements made of
UC – Me type cermets . Cermets have a higher strength and thermal
stability than metal carbides . Cermets containing 80% by volume of UC and
20 % by volume of one of the high -melting metals (tungsten, rhenium ,
279
Boundary
ТНО,
Re
Y203
Twins
Re
Y203
FIGURE 119. Precipitation of thorium and yttrium oxides on the

twinning planes of rhenium ( electron photomicrograph x 24,000 ) /45 /:
a – mixture of Re - Thoz, 2445 °C /1hr, vacuum 1.10 - mm Hg;
b- mixture of Re - Y2O3, 2445 °C / 1hr, vacuum 2 • 10-5 mm Hg.
5511 280
molybdenum , niobium ) have been studied . The research showed that
the reactivity of the metallic matrix for UC at 1700°C decreases in the
following order : niobium , molybdenum , tungsten , and rhenium . Thus , the
cermet UC - Re is the most stable fuel material for use in transducers , and
has been recommended . The finished fuel elements consist of a core made
of UC Re cermet and a niobium can . As a diffusion barrier between the
core and the can a tungsten foil was used . Niobium was chosen as the
material for the cans for cermet discs . The authors of /45 / point out that
it would be very desirable to use rhenium as a material for cans (emitter ) ,
however, this metal has fundamental disadvantages such as a large thermal
neutron capture cross section, complicated manufacture , and high cost .
3. Rhenium as the base of high - temperature cathodes
The properties of rhenium as a material for the bases of high - tempera

ture oxide (coated ) cathodes were studied in /46 – 49 /. The necessity of
increasing the operating temperatures of cathodes compels us to reject the
nickel usually used for oxide ( coated ) cathodes because of the high rate of
vaporization of nickel . However , high- melting metals such as tungsten ,
molybdenum , and tantalum react actively with the coating material, cause
a deterioration of the emission properties and shorten the service life of
the cathode / 3, 46 /.
Moreover, metals such as nickel and platinum are not sufficiently strong
at temperatures above 900 – 1000°, and the base walls of the cathode have
to be thicker . This results in an increased time of heating of the cathode
(the time after switching on before the tube functions). Communications
which have appeared on the use of rhenium- nickel alloys /47 / and of pure
rhenium /46 / for the bases of oxide cathodes are of interest . If we
consider that the specific heat of nickel ( 1.06 cal / mole ) is higher than the
specific heat of rhenium , the decrease in the thickness of the base walls
of cathodes if rhenium is used should result in an even greater reduction
in the heating time of the cathode /46 /.
For filamentary oxide cathodes of economical tubes , where 8 – 10 u diam
tungsten filaments are often faulty, it is advisable to use wires made of
pure rhenium or rhenium- tungsten alloys . These are more ductile and
stronger, and have a higher electrical resistivity , and therefore the wire
can have a larger diameter for the same filament current .
One of the favorable properties of rhenium for use in vacuum tube
technology is its high corrosion resistance under specific operating
conditions , for example , in contact with ceramic tubes made of aluminum
oxide / 1 / ( Figure 120 a and b) . Rhenium is also compatible with certain
other materials (for example, carbides ).
Research on the emissive properties of the alkaline - earth metal oxides
deposited on rhenium cores was carried out in /30, 46 – 48 /.
In /46, 48, 49 / the authors studied oxide coated rhenium cathodes
shaped as caps 4 mm in diameter, 2 mm in depth, and welded to a
molybdenum stand . To create a more developed surface and improve the
adhesion of the oxide coating to the base, 5–8 mg of rhenium powder with
a grain size of 40 – 70 u were applied to the base . Emission substances of
281
various compositions (strontium carbonate , or a mixture of strontium
carbonate with calcium carbonate ) were rubbed into the rhenium sponge
obtained after sintering at 2000° C in hydrogen . Figure 121 /48 / shows the
dependence of the rate of vaporization of strontium oxide from various metals
(platinum , tungsten, tantalum , or rhenium ) on the temperature in the
1000 – 1300° C range . From the diagram we see that the rate of vaporization of
strontium from rhenium at the initial moment (curve 1 ) is approximately
five – eight times higher than from platinum . But after the vaporization of
1 – 2% of the substance ( approximately 10-5 mg / cm² ) the rate decreases
(curve 2 ) , and approaches the rate from platinum (curves 3 and 4 ) .
FIGURE 120. External view of rhenium ( a) and tungsten (b) heating elements wound on
ceramic tubes made of aluminum oxide ( alundum) , after 7000 hr of operation at 1750 °C
( x15 ) , and the view ( c ) of evacuated U - shaped tubes with rhenium ( on the left ), and
tungsten (on the right) heaters. These show the relative resistance of these materials to the
" water cycle " / 1 / .
The authors /48 / assume that the reason for this regularity may be that
the rhenium sponge or the rhenium base may contain a small amount of
reducing impurities . Also strontium oxide may possibly be reduced by
rhenium itself. From Figure 121 we see that at 1000 — 1100°C the rate of
vaporization of strontium from molybdenum is approximately 60 – 80 times
higher and from tungsten 20 – 40 times higher than from rhenium /48 /.
Research on the emission characteristics of rhenium cathodes coated
with alkaline - earth metal oxides showed that the cathodes are satisfactorily
activated and their emission characteristics are analogous to those of
nickel cathodes with a coating of the same composition (Figure 122 ), but
considerably higher than the characteristics of molybdenum - base cathodes
/49 /. Somewhat later analogous results were obtained in /50 /.
In / 50 / the authors worked with standard diodes and compared the
properties of rhenium cathodes coated with a ternary carbonate to the
properties of nickel- base cathodes containing an activating addition of
silicon and magnesium .
The authors of /49 / studied the conditions for activating and conditioning
rhenium- base cathodes , and determined the optimum composition of coatings
for such cathodes . They also investigated the stability of the thermal and
secondary- emission characteristics .
282
vaporization
2.
00
Rate
.sec
,g/cm²
of
15
10-11
0.55 0.6 0.65 0.7 0.75 0.8
103/ 1,0 %
FIGURE 121. Temperature dependence of
the rate of vaporization of strontium from
various materials /48 / :
1 – rhenium , initial moment; 2 – rhenium ,
after vaporization of 1-2 % of strontium ;
3,4 - platinum ; 5 – tungsten ; 6 – molyb
denum .
a
Emission
current
b
function
,A m²
30
Work
/c
,eV
2.5
2.0
1.5
Sr20, 20 40 60 80 cal Sreb , 20 40 60 80 Сао
C20, % C20 , %
6,41 02
FIGURE 122. Dependence of the emission current (a ) and the work
function (b ) on the composition of the coating :
1 – nickel core ; 2 - rhenium core .
The chemical composition of emission coatings is given in Table 97 /46 /.

The compounds studied are intended for service over a wide temperature
range from 800 – 1000°C , where nickel- base cathodes are not suitable .
In Figure 123 a /46 / we give the typical underheat characteristics of
three types of rhenium cathodes , from which we see that the emission
characteristics of cathodes with an ordinary coating of triple carbonate
are quite satisfactory (curve 1 ) , and in practice are similar to those of
nickel- base cathodes with the same coating /51 /. The cathodes coated with
283
triple carbonate containing 16% BaCO3 can operate at this takeoff of the
current at 850 — 900°C only (curve 2 ), and cathodes coated with a double
carbonate at 950 – 1000°C only ( curve 3 ) .
TABLE 97. Composition of emission coatings (in % )

Material BaCO3 SICO, Cacoa son CI “ NO Fe3 + Na +
Triple fine - grained

carbonate . 52 41 7.5 0.01 Not 0.01 0.001 0.01
found
Triple carbonate with
16 % BaCO3 .... 16 45 38 Not 0.001 0.0001 0.03
found
Double carbonate
( CaS) CO , 0.08 48.66 Not Not 0.29 0.0003 0.05
51
found found
In Table 98 /46 / we give the work functions of various types of cathode

coatings at a constant value A. = 120 A / cm² . degree ? The table shows the
lowest temperature at which a current takeoff of the order of 50 mA / cm² is
possible .
TABLE 98. Work function of rhenium -base cathodes
Temperature , o
Temperature ,
Cathode coating 9. eV at la =
°C
- 50 mA /cm²
(Ba , Sr , Ca ) Coz 600 1.6-1.7 650
(Ba , Sr , Ca ) CO3 + 10% BaCO , 700 1.8-1.9 760
(Ca , Sr) CO2 750 2.0-2.2 950
Figure 123 b /46 / shows the temperature dependence of the anode

current of a number of cathode coatings on rhenium under pulse operating
conditions ( 1 = 1 – 3 u sec, n = 50 pulses / sec ) at 850 — 1100°C .
The best results were obtained with cathodes coated with the usual triple
carbonate . A current takeoff of the order of several tens of amperes / cm²
is possible even at 800 — 850°C , i.e. , at the same temperatures as with the
ordinary nickel oxide - coated cathode .
TABLE 99. Maximum service life of calcium - strontium cathodes

with a rhenium base
Vaporization time Vaporization rate

of Sr from a
1.10 -' g /cm² Sr, rhenium base , Temperature, ° C
hr
g /cm².se
100 3.10-9 1220
1000 3.10-10 1120
10,000 3.10-11 1030
284
current
/cAnodic
density
a
,mm² A
20
400 600 800 1000 T. ° C
b
current
density
c/Anodic
850 °
,mm²A
30
1100 °
1100 *
1000
1000 °
900 °
10
Anodic potential , 3/2 kV
FIGURE 123. Typical underheat characteristics (a ) , and variation
in the anode current ( b ) of three types of cathode coatings on a rhe
nium base /46 /:
1 - triple carbonate ; 2 — triple carbonate 16 % BaCO3; 3 double

carbonate , curve at 850 ', triple carbonate; all other curves: triple
carbonate with 16% BaCO3.
The authors of /46 / computed the maximum service life of rhenium

oxide- coated cathodes from data on the vaporization of the coating
components , assuming that only temperature affects the loss of strontium
oxide ( Table 99 ) . It was found that cathodes have a satisfactory service life
at temperatures below 1100 ° C only. The density of the current of
thermionic emission of such cathodes under continuous and pulse operating
conditions is not great , so that the authors of /46 / consider that these
cathodes can be operated under conditions of combined takeoff of current
from thermionic and secondary electron emissions in instruments of the
magnetron type. We should note that service life tests on rhenium cathodes
with different coatings at various working temperatures showed that the
experimental data agreed well with the calculated . The data of tests on
various batches of optimum- activated cathodes are given in Table 100 .
Table 101 /46 / shows the values of the coefficients of secondary electron
emission of cathodes with various coating compositions at temperatures
when there is a noticeable thermionic emission current . These values do
not differ from those obtained for the double and triple barium oxides (52 ),
285
are one- and- a- half to two times greater than for the thorium and yttrium
oxides / 52 ), and also depend on the degree of activation .
TABLE 100. Results of service life tests on rhenium -base cathodes
Current density , Time , hr

Composition of coating Temperature, ° C
mA /cm²
950 1000
(Ca, Sr , Ba) CO3 + 16 % BaCO3
100 1050 150
1150 50
(CaSr) CO , 100 1050 500

1100 300
300 1150 100
(CaSI) COZ
1250 30
When thermionic and secondary- emission cathodes are used under pulse
operating conditions with a current takeoff of several tens of amperes / cm²,
the electrical conductivity of the oxide layer becomes of considerable
importance . A large current decrease can lead to a considerable potential
drop on the layer, which in its turn can result in a breakdown of the tube
( sparking ) /46 /. The measurements carried out during operation showed
that at possible temperatures of the cathodes of 1000 — 1100°C, the electrical
conductivity of strontium and calcium oxides is 5 .10-5 and 5 · 10-4 ohm -1.cm ?
respectively, i . e . , of the same order as for barium oxide at the operating
temperatures of usual oxide cathodes / 54 /.
TABLE 101. Coefficients of secondary electron emission of various oxide

coated rhenium -base cathodes
Coefficient of
Cathode coating Temperature, ' C secondary electron
emission
(Ba , Sr , Ca) COZ 600 4.5-5.5

(Ba , Sr , Ca ) CO3 + 16% BaCO3 600 4.5-7.0
(CaSr) CO , 800 4.5-6.5
In addition to the usual oxide coatings of alkaline- earth metals , cathode

coatings on the basis of thorium , yttrium , and rare earth metals /3 / are
also widely used .
According to the data of /53 /, the densities of emission currents with
coatings made of ThO2 and Y203 on a rhenium base are somewhat higher
than those with a tantalum base , and almost equal to those with a
molybdenum base . The emission constants for such cathodes are given
in Table 102 .
The thermal stability of ThO2 and Y203 coatings on a rhenium base ,
determined from the time of disappearance of the coating at 2250°K, is not
lower than on a tantalum base . At 2000°K the thermal stability of La203
and of Eu205 coated on rhenium is four and four to five times , respectively, highei
than the thermal stability of these oxides coated on tantalum .
286
TABLE 102. Values of the thermionic emission constants of optimum
activated thorium and yttrium oxide -coated cathodes on rhenium and
tantalum bases
According to the
According to the Richardson
line Richardson
Dushman equation
Active coating
and material
Q. eV at T =
of the base
, ev
A , amp / = 1400K , A =
/cm ?.degree? = 120 A /cm ?.
• degree?
Tho - Re 2.21 0.2 2.99
Th02- Ta 3.04 89 3.08
YzOz - Re 2.41 0.6 3.09
Y2O3 – Ta 2.48 1.7 3.03
In / 10, 31 / it was found that the reduction temperature of thorium coated

on a rhenium base is 2300 - 2600° C , i.e. , the same as for a tungsten base .
Optimum temperatures of the thermally activated rhenium base cathodes
are much higher than those of a number of cathodes with other bases
(Table 103 ) /56 /.
TABLE 103. Optimum temperatures of thermal activation of high-melting oxides coated on rhenium
and tantalum bases , and values of the coefficient of secondary electron emission
Coefficient of Coefficient of
Active coating Activation Active coating Activation
and material secondary and material
secondary
temperature, temperature ,
electron electron
of the base K of the base K
emission emission
Thoz - Re 2200--2300 2.4-2.5 LaqOz - Re 1750-1900

Tho - Ta 2100 2.6-2,8 LazOz — Ta 1650-1750 2.4
YzO3 - Re 2150-2250 2.25 -2.35 Eu2O5 - Re 1650-1800
Y2O3 - Ta 2050 2.3-2,4 EuqO5 - Ta 1400-1450
We should also note the lower temperature sensitivity of thorium oxide

and yttrium oxide coatings on a rhenium base . Overheating to 400 ° above the
optimum temperature of activation does not decrease the emission power of
cathodes with rhenium bases .
This increases the stability of their characteristics and indicates the low
reactivity of rhenium toward these coating materials /3 /. Therefore , it is
possible to use rhenium as a base for thorium oxide- coated cathodes of
powerful oscillation tubes , in which the cathodes operate with a current
takeoff of several hundred milliamperes per cm² at 1900 – 2000°C /3 /.
A study of the effect of oxygen on thermionic electron emission / 55 /
showed that the cathode with a rhenium base recovers its properties, as
in the case of a molybdenum base , but in contrast to a tantalum base .
However, the good mechanical properties of rhenium alloy /3 / bases coated
with thorium oxide are also promising for cathodes .
287
Cathodes of this type are used in magnetrons /3 ), where secondary
emission is of great importance ( Table 103 ) . Secondary emission was
measured during pulse operation at 1200° K after activation at optimum
temperatures. Thorium - yttrium , thorium- lanthanum , and yttrium
lanthanum oxide coatings , which have a high coefficient of secondary
emission /56 /, on a rhenium base will make highly efficient emitters /3 /.
Thus , rhenium and its alloys can be advantageously used as bases for
oxide - coated cathodes , especially in vibration- proof instruments , and for
bases of thorium oxide - coated cathodes of powerful oscillation tubes and
instruments of the magnetron type /3, 46 /.
Of a certain interest is the attempt to improve the existing oxide- coated
nickel cathodes by the introduction of rhenium into the nickel alloy /30 /.
In the USA nickel alloys are used as bases of alkaline- earth oxide - coated
cathodes . These alloys contain 2 – 4.5% W, and are designated 202
( International Nickel Co ) , and A- 31 , A- 32 , and P- 51 ( Superior Tube Co. ) .
Sintered nickel alloys are produced with 1 , 5, 10 , and 30% Re . The impurity
content in the alloy is 0.03% Ca; 0.06% Fe; < 0.01% Si; 0.03 % S; 0.01% P;
< 0.005% Mn ; and < 0.008% Co.
Circular plate bases were made of these alloys for the indirectly heated
cathodes of diodes . A mixture of carbonates consisting of 50% BaCO3,
44% SrCO3, and 6% CaCO3, was used for the coatings . In spite of the
absence of reducing agents in the alloy , the activation or stabilization of
the cathodes was attained at 850° , i.e. , at a lower temperature than for the
original alloys containing no rhenium /30 /. The activation time of oxide
coated cathodes with nickel- rhenium alloy bases /30 / was as follows
( in min ) :
225 nickel alloy , made by INCO , 0.15-0.25 % Si 75-90

Nickel alloy A - 31 -40
Ni - 1 % Re 50-60
Ni - 5 % Re ~40
Ni - 10% Re 20-30
100% Re . 5-10
In a comparative estimate of the emission properties of oxide- coated

cathodes with nickel and nickel- rhenium bases it was found that oxide - coated
cathodes with nickel- rhenium bases ( 1 – 10% Re ) are almost twice as
effective as cathodes with a base made of the 225 nickel alloy ( 0.15-0.25 % Si )
and better than those with the A- 31 alloy . The nickel- rhenium alloys have
been patented in France and the USA / 57 /.
Numerous tests on the above alloys were carried out in amplifier tubes
of the PTT- 216 type made by the Postes et Télécommunications ( P.T.T. )
of France . Pentodes with directly heated cathodes were built . The filament
current was 0.3 A and the voltage 6.3 V; the average mutual conductance
was 12.5 mA /V, with 150 V on the plate and screen, and an average plate
current of 12.3 mA . The guaranteed life is 8000 hours , and the density of
the emission current is 50 mA / cm² /30 /.
The Compagnie Generale de Telegraphie Sans carried out comparative
tests on a batch of 100 tubes with oxide- coated Ni – Re cathodes ( 1 – 10% Re ),
and tubes with oxide - coated nickel + 4 % W (type P- 51 ) cathodes . The nickel
rhenium cathodes had superior properties during evacuation and activation .
The activation can be carried out at lower temperatures , which decreases
288
the danger of deformation of the cathodes /30 ). For the group of tubes of
the RTT- 216 type with nickel bases containing 10% Re the heating voltage
can be reduced , with a corresponding reduction in the heating power of
approximately 30% .
The average life of oxide - coated cathodes with nickel cores containing
10% Re at a heating voltage of 6.3 V , for a 21 - tube batch , is 21,400 hours ,
and for one - third of the tubes it is 26,500 hours .
A decrease in the slope of the current- voltage curve (transconductance )
was observed for two tubes only after 12 , 800 and 21,000 hours of operation / 30 / .
Thus , we can assume that the introduction of up to 10% Re into the
nickel base increases the cathode life to several thousand hours, and makes
it possible to produce stable cathodes at relatively low temperatures . This
is of special importance for cathodes operating for a very long time .
Moreover , the nickel- rhenium cathodes are relatively simple to
fabricate compared to cathodes made of more complex alloys containing
zirconium and cerium as reducing agents /30 /.
4. Rhenium and its alloys in structural elements in

vacuum tubes and other devices
The use of rhenium and its alloys with tungsten and molybdenum in the
structural elements of electronic vacuum devices is due to a number of
factors . An important role is played by their high strength and ductility
at both low and elevated temperatures , by their high recrystallization
temperature , by the lower tendency for grain growth than in the case of
tungsten, which is normally used for the same structures, and by their
ductility after recrystallization .
As we have already mentioned , one of the valuable and very important
properties of rhenium is that , unlike tungsten, it does not take part in a
water cycle." The rate of vaporization of rhenium in the presence of water
vapor is only a fraction of that of tungsten ( Table 104, Figure 120 c ) /2 /.
TABLE 104. Rate of vaporization of rhenium and tungsten in the "water cycle "
Test temperature Loss after
Material 7800 hr ,
initial final mg/cm2
Tungsten 1300 1275 1.5
1750 1660 8.25
Rhenium 1300 1200 0.65
1750 1660 0.98
Tungsten coated with 1300 1310 0.48
rhenium 1750 1700 0.57
Figure 120 c / 2 / contains the view of an evacuated tube in which

rhenium and tungsten were tested for the " water cycle " under the
same conditions .
289
The loss from tungsten coated with rhenium is smaller than that from
pure rhenium . This is due to the higher degree of finish of the surface of
the coated sample .
Cathode preheaters . Today heating elements made of tungsten
rhenium alloys are widely used, and tests are being carried out on heating
elements made of rhenium and its alloys with molybdenum .
In Table 105 /2 / we give the results of bench tests of the service life of
14 – 22 udiam wire made of cast alloys of rhenium with molybdenum and
tungsten . Tests were carried out in vacuo by direct heating .
TABLE 105. Service life of alloys of rhenium with tungsten and molybdenum
Alloy Service
Alloy Temperature Service
Temperature
composition , life , hr composition life , hr
at . %
of specimen , ° C at. %
of specimen , ° C
Mo - 25 Re 2000 23 100 W 2500 27
Mo - 30 Re 2000 39 W - 22 Re 2500 46
Mo - 35 Re 2000 160 W - 27 Re 2500 240
It can be seen that the service life of a heating element increases with
increase in the rhenium content in molybdenum- base and in tungsten- base
alloys .
Another series of experiments was performed with special elements /27.
Five elements made of pure tungsten (of the Associated Electric Company ) ,
and five elements made of an alloy of tungsten with 26% Re (of the Associated
Electrical Industries , Ltd. ) were heated to 2500 ° under similar conditions .
The average service life of tungsten elements was 37 hours , and of the
elements made of tungsten with 26% Re 51 hours /27.
The high strength , good ductility in the recrystallized state, and the high
electrical resistivity of rhenium and its alloys with tungsten, which is several
times higher than that of tungsten , made it possible to obtain the same
filament current and voltage of the heating element with wires of a larger
diameter for heating elements of the same shape . This , combined with the
high strength of the wires , assures a better retention of the shape used,
for example , under conditions of vibration .
The service life of cathode heaters is also determined by the rate at
which the material of the heater interacts with the insulating materials ,
usually aluminum oxide ( alundum ), at the operating temperatures . Tests
on rhenium and tungsten in contact with alundum under similar operating
conditions ( 7000 hr at 1750°C ) /2 / showed that rhenium is much more inert
than tungsten , and can work successfully in contact with alundum under
conditions when a tungsten preheater would disintegrate (see Figure 120 ) .
Heaters made of rhenium or its alloys with tungsten increase the
reliability and durability of electric vacuum instruments . This is verified
in practice by the present experience of the introduction of heaters made of
rhenium - tungsten alloys into a number of instruments , in particular
receiving - amplifying tubes /58 /. The firm Varian Asso (USA ) found that the
replacement of tungsten heaters by rhenium heaters increases the life of many
instruments working in vacuo in the presence of NH3 vapors hundred
fold (three months compared to one day ) /59 /. In the USA the heating
elements of certain electric valves are made of tungsten - rhenium alloys
290
/2, 60 ). In /61 / the author reports on the use of heating elements made of
rhenium wire in the very sensitive vacuum tubes for radar devices in
airplanes, in photographic projection lamps, and in railroad signal lamps .
2
b
100
intensity
Radiatio n
10 % Re
90
%.
80
5 % Re
70
02 Re
60
50
100 200 500 1000 2000 5000 10000
Number of times switched on с
FIGURE 124. Views of a diagnostic X - ray tube ( a ), a combined anticathode ( b) , and

variation in the intensity of the X- ray radiation with variation in the rhenium content
in the anticathode ( c ):
1- Mo ; 2 - W - Re.
We also know of the fabrication of filaments of flash lamps for photography,

from rhenium and tungsten- rhenium alloys . These alloys increase the life
of the bulb, and also make it possible to decrease the power of the electric
source /60, 62 /.
There is a report on the building of a device for the X- ray study of
materials at temperatures above 2000°C in which a rhenium heating element
is used . For temperatures below 2000°C a tantalum heater is possible /63 /.
Materials for the parts of electric vacuum devices .
Due to mastering of the production of semifinished articles of rhenium and
its alloys in the form of foil, flat and round wire , it is possible to
manufacture instrument parts such as klystron grids , oscillation tube
anodes , and others which operate at high temperatures . Especially
important and promising for electric vacuum devices is the mastering of
the manufacture of semifinished products of rhenium and its alloys with
tungsten and molybdenum made by the vacuum smelting method . If these
materials are used in instruments it is possible to increase the vacuum
and the reliability of operation more than when semifinished products made
of cermet materials are employed .
In / 3 / it is noted that the higher resistance of rhenium against ion
bombardment may be very important in powerful devices of superhigh
frequency and in X - ray tubes . In a number of cases it is advisable to
291
rhenium - coat parts , for example , tungsten electron tube control grids ,
molybdenum spirals for traveling -wave tubes, copper rods of magnetrons , etc. ,
to protect them against ion bombardment , the effect of the water- cycle ,
the influence of carbon .
Rhenium does not interact with carbon , and therefore it can be used as
an insulation layer between graphite (or a carbon- containing medium ) and
the carbide- forming high- melting metal of the main structure.
In /65 / the possibility is discussed of using tungsten - rhenium alloys as
constructional materials for making the cans of Po210 fuel slugs in
nuclear rocket engines of space craft . The operating temperature of the
can is 2200 ° — 1600°C and operating time is 3 months .
Rhenium- tungsten alloys have also been used in diagnostic X - ray tubes
/64 / where the rotating anticathode was formerly made of tungsten
( Figure 124 a ) . This permits high power to be produced at a small focus .
The path heated by electrons creates a temperature gradient of several
thousand degrees per millimeter . Owing to the nonuniform expansion , the
surface of the tungsten anticathode becomes rough and cracks . This results
in a weakening of the intensity of the X - ray radiation with time . For
anticathodes the Siemens Co. (West Germany ) used tungsten alloys with 5
and 10% Re as a coating for the tungsten disc (a two- layer anticathode )
( see Figure 124b ) . Figure 124c shows that anticathodes of this design lose
only 11 – 20% of the initial intensity of radiation after switching on
10,000 times , whereas the losses with pure tungsten are 50% . Thus the
power and the life of the X- ray tubes can be increased .
Conclusion
The data given show that rhenium and its alloys with tungsten and
molybdenum have in many cases advantages over other high- melting metals
used today in electronics , and radio- and electrical technology . Because
of the specific physical properties of rhenium and its alloy's necessary for
modern electronics combined with its good mechanical properties (strength
and ductility ) , good workability, processability, weldability , corrosion
resistance , etc. we can confidently state that the use of these metals is a
new step in the development of electronics . By employing these alloys the
quality of the instruments can be improved , and their reliability and
service life increased under rigid operating conditions as to temperature,
voltage , vibration , etc.
Especially effective is the use of semifinished products made of these
new materials produced from cast blanks . In recent years the methods of
arc and electron- beam melting of high- melting metals have been extensively
used . These greatly increase the purity of metals and alloys . In instruments
with parts made of semifinished products of rhenium , or of its alloys with
tungsten or molybdenum , produced by methods of vacuum melting, it is
possible to increase the vacuum greatly .
However, we should note that these new materials have not yet been
sufficiently tested, and work in this direction should be extended especially
for the accumulation of technical and economic data . If we consider the
great scarcity of rhenium, its use can be recommended only in those
instances when it cannot be replaced by tungsten or molybdenum without
292
impairing the quality of the instruments . It is clearly more profitable to
use in place of pure rhenium its alloys with tungsten , molybdenum , niobium ,
and other high- melting metals .
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295
Chapter XIX
THE USE OF RHENIUM AND ITS ALLOYS

IN THERMOCOUPLES
The development of high -temperature technology and the increasing use

of high- melting metals has made the measurement of temperatures of
2000° C or higher a problem of special
interest and urgency .
35
Today, optical pyrometers of various
30
types, as well as thermocouples made of
Temf
6 various alloys , are used to measure high tem

, v
m
25 peratures , depending on the range studied .

Thermocouples of the platinum group of
20 S types Pt – 10% Rh / Pt ; Pt – 13% Rh / Pt;
Pt – 30% Rh / Pt — 6% Rh have a relatively
15 high stability and accuracy of readings , do
not require any protective atmosphere,
10 and can operate a long time at up to 1200
1500° C , and for a short time at 1700 -
5
1800°C (Figure 125 ) /1 /.
Tungsten- molybdenum thermocouples
-2 of type W /Mo or W / Mo – Al are used at
500 1000 1500 2000 2500 temperatures above 2000°C in a reducing
1 C
FIGURE 125. Thermoelectromotive
or neutral medium or in a vacuum , but they
force of thermocouples: have great disadvantages: after prolonged
operation at high temperatures , the
1- Pt - 10 % Rh / Pt; 2 - Pt - 13 % Rh /
Pt - 1% Rh ; 3 – Pt - 30 % Rh /Pt - 6 %
thermoelectrical properties of these
Rh ; 4 – W /Mo; 5 – W / Mo -0.5 % Al ; thermocouples change, and the metal of
6 - W - 37 Re / W - 15 % Re ; 7 - W the thermocouple becomes brittle . This
5 % Re / W -20 % Re . impairs the operation and reduces the
accuracy of the readings .
The search for new high - temperature
electrode materials resulted in the appearance of numerous papers on the
subject of the thermoelectrical properties of rhenium alloys .
1. Thermocouples made of rhenium coupled with noble metals

In /2 / data are given on the thermoelectromotive force (temf) of several
alloys of platinum with rhenium coupled with platinum .
296
а 15
Coupled with Ir
20 b
RC
28
24 5
20
Temf
,Temf
20 0
,mV
Temf
V
V
m
,m
16 Ir
40
Coupled with w 5
12 Re
3 30
-2 20
200 600 1000 14.00 300 600 900 1, °C 100 SOO 1000 1500 2000 2500
1, ° C T, ° C
, egree
dTemf
12
/u V
85 % Pd 80 % Pd 75 % Pd
1 1
0
5 10 15 5 10 15 20 5 10 15 20 25
Re, wt % Re,wt % Re,wt %
d
FIGURE 126. Thermoelectromotive force of the thermocouples:
a platinum - rhenium ; b - platinum and palladium alloys with rhenium , coupled with platinum : 1 – Pt
4.2 % Re; 2 – Pt - 0.12 % Re; 3 – Pd - 2.24 % Re ; 4 – Pd -0.35% Re; c – iridium -rhenium alloys coupled with
iridium and tungsten: 1 – Ir - 60 % Re; 2 – Ir– 70% Re; 3 – Ir - 90 % Re; 4 – Ir - 50 % Re; 5 – Ir - 30 % Re;
d- palladium -tungsten -rhenium and palladium - rhenium alloys coupled with copper (to 50 ° C ).
More extensive research was carried out in /3 /. The temf was studied
for the rhenium / platinum couple ; the thermocouple 457 mm long made of
0.5 mm diam wires was calibrated over the 0 – 1000°C temperature range
against a Pt / Pt – 10% Rh thermocouple . The tests were performed in a
tubular furnace with a hydrogen atmosphere . Figure 126 a shows the shape
of the temf curve of the platinum- rhenium thermocouple . The temperature /
temf ratio is well described by the equation E = 1.56 – 0.90 · 10-2 T +
+ 1.29 • 10-6 T ?, where E is expressed in millivolts (mV ), and T in °K . The
first derivative gives the sensitivity of the thermocouple: p = -0.9 . 10-2 +
+ 2.58 · 10-57 ( in mV / degree ) . With increase in temperature the differential
temf (sensitivity of thermocouple ) increases , and consequently the accuracy
of the measurement increases also .
In /4 / the temf of palladium containing 0.35 and 2.24 wt % of Re coupled
with platinum was measured in the 0 – 900°C temperature range . The temf
of the Pt / Pd – 2.24 % Re couple is not large, and does not exceed 2.23 m V
at 813° C; the temf of the Pt / Pd – 0.35 % Re couple is negative, and is
-6.65 mV at 813°C . Moreover , in the same work the absolute temf of cast
nondeformed palladium- rhenium alloys was measured on specimens
297
containing up to 45 wt % Re and annealed at 1000°C for 72 hours . With the
addition of rhenium to palladium the absolute temf increases , reaches a
maximum ( 9.85 u V ) at 28.65% Re , and then begins to drop . Evidently, the
shape of the curve is caused by the presence of a considerable amount of a
second phase in alloys containing 40 – 45 % Re .
TABLE 106. Thermoelectromotive force of rhenium -palladium and rhenium - tungsten alloys coupled with copper
Temf when Temf when
Chemical composition, % coupled with
Chemical composition , % coupled with
W copper , W Re
copper ,
Pd Re Pd
uV /degree HV /degree
100 -7.01 80 10 10 + 10.76

95 2.5 2.5 +4.2 80 7.5 12.5 + 10.86
85 11.25 3.75 +12.72 80 2.5 17.5 +9,21
85 7.5 7.5 +12.32 75 18,75 6.25 + 5.55
85 3.75 11.25 +10.03 75 12.5 12,5 + 8.71
80 15 5 +10.06 75 6.25 18.75 + 8.01
80 12.5 7.5 +10.71
In the literature there are data on the temf of binary platinum- rhenium
15 /, iridium- rhenium /6 /, and palladium - rhenium /7 / alloys , and of
ternary palladium- tungsten- rhenium alloys /8 /. Figure 126 b shows the
results of measuring the temf of the platinum - palladium- rhenium alloys
/ 5, 8 /, coupled with platinum at temperatures from 0 to 800 — 1000°C . The
variation in the temf with temperature is smooth and almost linear, and
the temf of the platinum- rhenium alloys is much higher than that of the
palladium - rhenium alloys over the same temperature ranges . The temf of
palladium containing 0.35 % Re is negative, the other alloys studied have
positive values of the temf. The nature of the temperature dependence of
the temf of these alloys makes these materials suitable for thermocouples .
For use as thermocouples operating in the temperature range above
2000°C , iridium - rhenium alloys have been studied over the entire range of
concentrations , coupled with either tungsten or iridium /6 /. The results
are given in Figure 126 c . The character of the change in temf, and the
results of X - ray diffraction studies enabled the authors to recommend the
following as thermocouples : Ir / Ir - 60% Re and Ir / Ir – 70 % Re , suitable
for work up to 2450°C .
The authors of /8 / studied the absolute temf of the palladium- rhenium
and palladium - tungsten - rhenium alloys coupled with copper (see Figure 126d ).
It was found that even small additions of rhenium sharply change the sign of
the temf of palladium . The value of temf in the palladium - rhenium system
reaches a maximum on addition of 5 wt % Re , and further increase in the
rhenium content results in an insignificant decrease in the temf. In the
palladium- tungsten- rhenium system the temf reaches a maximum in alloys
situated in the section with a constant content of Pd of 85 % . Even small
amounts of rhenium noticeably increase the temf of the palladium- tungsten
alloys .
The thermoelectromotive force of rhenium alloys containing palladium
and tungsten coupled with copper is given in Table 106 /8 /.
298
2. Thermocouples made of rhenium coupled with tungsten ,
molybdenum , or their alloys / 6 , 9-20 /
In /9 / it was found that rhenium coupled with molybdenum or tungsten

gives a high electromotive force , and these thermocouples may be used up
to very high temperatures . These couples were also studied in /6 , 10, 11 /
( Figure 127 ) . The electromotive forces produced by tungsten- rhenium
thermocouples are higher than those obtained in /9 /.
-
32
W / Re
Temf
V
28
,m
24
20
16 Mo/Re
12
o
Re /Mo -50 % Re
-4 RB/ w -30% Re
-8
1 1
400 800 1200 1600 2000
T. ° C
FIGURE 127. Thermoelectromotive forces of the W /Re , Mo / Re,
Re / W - 30 % Re , and Re /Mo -50 % Re thermocouples:
1 - according to Sims and Jaffee; 2 - according to Haase and
Geschneider; 3 – according to Rouse ; 4 according to Lachmann ,
A control te of the work of these thermocouples was carried out / 12 ) , and

the reproducibility of the results verified . The temf of the Re / W – 30% Re
and Re / Mo – 50% Re thermocouples was also studied .
The electromotive force was measured for thermocouples placed in a
vacuum chamber ( 10-4 mm Hg ) . To obtain a hot junction the ends of the
wire made of rhenium , tungsten , molybdenum , or alloys , were welded in
helium. Up to a temperature of 1600°C the thermocouples were calibrated
against a Pt – 10% Rh / Pt thermocouple , and above 1600°C , the temperature
of the internal wall of the chamber was measured by an optical pyrometer .
In Figure 127 we give the temf of the tungsten - rhenium and molybdenum
rhenium thermocouples according to the data of the authors . The results of
/6 , 9 – 12 / agree well . The differential temf of the rhenium- tungsten couple
is high , at least up to 2200°C . The differential temf of the molybdenum
rhenium couple increases to 1400°C only. With further increase in
temperature , the temf decreases rapidly. The temperature dependence of temf of
the Re / W – 30% Re and Re /Mo - 50% Re couples is shown in Figure 127 .
The addition of rhenium to either tungsten or molybdenum almost completely
eliminates the high temf created by the unalloyed couples of rhenium with
tungsten and molybdenum .
299
The temperature dependence of the temf is determined by equations / 12 /
of the type :
E = a + bt * + cf * + d + es + ft' ( E in mV, T in °C ) .
Values of the coefficients for the metal couples are given in Table 107 .
TABLE 107. Coefficients of equations for the thermoelectromotive force
Metal couple a . 100 . 10 ° c.10 d . 1046 1.105
Re/W 2.28 3.58 -42.9 30.0 -11.5 1.75

Re/Mo 3.71 13.2 -3.51 3.79 1.28
ReN - 30 % Re 3.53 -0.0240 -3.56 0.853
Re/Mo -50 % Rel 4.05 0.987 -3.19 0.735
Note : The maximum temperature of measurement is 2200°C ; for the Re /Mo - 50 % Re

couple it is 2100 ° C .
In addition, it has been calculated / 9 / that the W / W – 30% Re and

Mo / Mo - 50% Re thermocouples give a high temf.
We know that one of the most important characteristics of a thermocouple
is the stability of its readings with regard to temperature and time. The
experiments performed with wire made of pure tungsten and pure rhenium
/19 - 20 / showed that the scattering of readings in a circuit composed of a
number of welded tungsten or rhenium wires increases with temperature .
However , for the commercially pure tungsten , the scattering of readings
of the temf at 2000°C does not exceed the permissible scattering for copper
of 99.999 % purity at 650°C , but for rhenium the scattering is much greater,
and at a temperature of the order of 2000 – 2200° C the error is 14.4 % .
Another, no less important drawback of these thermocouples is that at
temperatures near 1400° C their temf begins to decrease , and the sensitivity
drops .
All these facts spurred us to study thermocouples made of alloys of
tungsten with various rhenium contents .
3. Thermocouples made of tungsten coupled with a

tungsten - rhenium alloy, or of two tungsten - rhenium alloys
Thermocouples made of rhenium- tungsten alloys are used in the following

combinations : tungsten coupled with a tungsten- rhenium alloy, or a couple
of two tungsten alloys containing various amounts of rhenium .
Thermocouples made of unalloyed tungsten coupled with an alloy have
been studied / 13 – 14, 17 , 20 — 23 /.
These thermocouples have a number of advantages over all other types
of high - temperature thermocouples : 1 ) a high temf up to 2900°C ; 2 ) high
melting point , above 3000°C ; 3 ) chemical stability at high temperatures in a
protective atmosphere (hydrogen, inert gas , vacuum ) ; 4 ) relatively low
vapor pressure of components; 5 ) good machinability and workability of
tungsten - rhenium alloys .
300
a b
20
7
,\V/ egree
dTemf
6
20
Temf
,mv
10 3
3
0
1000 2000 1000 2000

T, ° C T. ° C
FIGURE 128. Characteristics of certain tungsten - rhenium thermo
couples:
a – Temf; b – sensitivity: 1 – W /W -1% Re ; 2 – W /W - 3% Re;
3 – W / W – 5 % Re; 4 – W /W - 8.8% Re; 5 – W / W - 13.5 % Re; 6
W / W - 150% Re; 7 – W / W - 20 % Re ; 8 – W - 3% Re / W - 15 % Re ;
9 - W - 5 % Re / W -20 % Re .
In / 1 , 13, 20 / the values of the temf were found for tungsten- rhenium
thermocouples , either tungsten coupled with tungsten - rhenium alloy, or
two tungsten - rhenium alloys with a
rhenium content of up to 20% ( see
Figure 128 a ) , and also the values of the
sensitivity of thermocouples ( dE / dt)
30
6 ( Figure 128 b ) as a factor of the
temperature over the range of 0 to
2000° C . The wire for the thermocouples
was made of sintered alloy blanks . It can
Temf
be seen from Figure 128 a and b that the

,mV
20
temf and sensitivity of thermocouples
made of tungsten coupled with tungsten
rhenium alloys increase with increase in
10
the rhenium content in the alloy. However ,
these thermocouples made of tungsten
coupled with tungsten- rhenium alloys have
one great drawback, namely the tungsten
element of the thermocouple becomes very
0
1000 1500 2000 250 brittle at high temperatures .
1, " C The replacement of the tungsten
FIGURE 129. Thermoelectromotive force element by an element made of W — 3% Re ,
of certain tungsten -rhenium thermocouples: W – 5 % Re , or W – 10% Re / 1 , 13 – 17 ,
1 - W /Re; 2- W – 50% Re / W - 20 % Re ; 3 . 20 , 24 / alloys eliminated this drawback.
W - 5 % Re / W - 26 % Re ; 4 - W - 10 % Re /W The temperature dependence of the temf
- 20 % Re; 5 - W - 3% Re / W - 15 Re . of the W — 5 % Re / W – 26% Re; W 5 %
Re / W – 20% Re; and W – 10% Re / W – 20%
Re thermocouples is shown in Figure 129.
The temf values of these thermocouples have a higher stability than those of
the best thermocouples with a tungsten element /1 , 21 /.
301
In Table 108 we give the values of the temf and sensitivity of two types of
thermocouples /14 / at various temperatures .
TABLE 108. Properties of tungsten -rhenium thermocouples

Type of Temf , mv Sensitivity, uV / ° C
thermo
couple -196 ° 1000 10000 1500 ° 20000 -196 ° 100 ° 10000 15000 20000
BP5/ 20 -1.59 1.4 16.2 23.3 29.4 8.0 14.0 16.0 13.0 11.0
BP10/ 20 -1.15 1.0 10,7 15.3 18.9 6.0 10.0 10.0 8.0 7.0
Calibration of tungsten - rhenium thermocouples . One of the difficult

problems encountered when using high - temperature tungsten- rhenium
thermocouples is their calibration in the high- temperature range . Up to
1600° C tungsten- rhenium thermocouples can be calibrated against a
platinum- rhodium thermocouple; at higher temperatures they must be
calibrated against an optical pyrometer / 15 /. Tungsten- rhenium can be
accurately calibrated against pure metals , for example, the W – 5% Re / W
20% Re thermocouples /25 /. The data of /25 / show that there are some
inaccuracies in the readings of these calibrated thermocouples , which are
very dependent on the batch of the metal . The authors of /25 / believe that
it is not yet possible to use a tungsten- rhenium thermocouple as a standard
for the calibration of other tungsten- rhenium thermocouples .
Stability of tungsten - tungsten -rhenium thermocouples. There are a
number of reasons for the instability of the readings of a thermocouple .
The main ones are the presence of stresses in the metal and the variation
in chemical composition along the wire . The mechanical stresses can be
relieved by annealing , so that the principal factor is the effect of the
chemical composition . The change in the chemical composition of the
thermocouple metal, and consequently the reproducibility of its readings,
can be affected by the conditions of the preliminary heat treatment and the
operating conditions of the thermocouple . In /20, 22, 24, 26 / the effect of
these factors on the stability and reproducibility of readings of the tungsten
rhenium thermocouple materials is discussed .
The effect of annealing in a vacuum of the order of 104 mm Hg at
temperatures of up to 2100° C were studied in / 22 / , and in hydrogen at
1500°C in /20 /. The wire was annealed in hydrogen at 1500°C for 15 seconds
by the method of " rewinding" through the furnace. It was found that such
annealing conditions were sufficient for the production of a homogeneous
wire of the prescribed tolerance within one coil (+ 0.05 mV ) .
A wire made of alloys of tungsten with 5, 10, and 20% Re was heated by
an electric current for from 5 min to 25 hours . The thermocouple made of
such an annealed electrode and of an electrode made of the same metal but
not annealed developed a maximum temf of approximately 0.32 mV for the
W – 5 % Re ( annealed ) / W – 5 % Re (not annealed ) couple ; 0.316 mV for the
W – 10% Re ( annealed ) / W – 10% Re (not annealed ) couple ; and up to
0.875 mV for the W – 20% Re (annealed ) / W – 20% Re (not annealed ) couple ;
i.e. , the reading error caused by a change in the electrode characteristics
due to annealing did not exceed about 2 – 3% at 2100°C for the W — 5 % Re / W
- 20% Re couple. This change could have been caused by the loss of tungsten
302
as the result of the " water cycle" process , which is possible under the
given annealing conditions .
When the annealing was carried out in a vacuum with heating by a
tungsten heater to temperatures near 2100°C for 5 minutes to 25 hours /22 /,
the following maximum temfwere observed : for the W – 5% Re ( annealed ) /
W – 5% Re (not annealed ) couple, 0.563 mV ; for the W - 10% Re (annealed )/
W – 10% Re (not annealed ), 0.322 mV; and for the W – 20% Re ( annealed ) /
W – 20% Re (not annealed ) couple , 0.066 mV, i . e . , the maximum error of
measurement of the temf by the W – 5 % Re / W – 20% Re thermocouple at
1500°C would not exceed 2 - 2.5 % /22 /.
When electrodes with an aluminum oxide cap were annealed in a reducing
atmosphere in a current of dry hydrogen in a graphite furnace up to 1700°C
for 5 min to 25 hours , it was found that at 1500°C the change in the temf
did not exceed 0.25 mV for the W — 5 % Re (annealed ) / W – 5 % Re (not
annealed ) and the W -20% Re (annealed ) / W – 20% Re (not annealed ) couples ,
and 0.15 mV for the W – 10% Re ( annealed ) / W – 10% Re ( not annealed )
couple , i.e. , the error of measurement at this temperature is small, and
not more than 1 – 1.5% .
Research on the heterogeneity (inhomogeneity ) of the tungsten- rhenium
wire along the coil, as well as in coils of one batch or different batches , was
carried out in 20, 24 /. For the annealed wire the heterogeneity inside one
coil attained 0.1 mV . Annealing in hydrogen at 1500° C for 15 sec decreased
the inhomogeneity to the admissible level, but did not eliminate hetero
geneity between the batches . It was found that for a more complete
stabilization of the thermoelectrical properties it is advisable to anneal the
wire in hydrogen at 1500 — 1600°C for 5 – 10 minutes /20 , 24 /.
The stability of the readings of tungsten- rhenium thermocouples during
operation in a reducing medium of hydrogen up to 2200 – 2300°C was also
studied /26 /.
The temf developed by the thermocouple at 1000°C was determined before
the tests , as well as after various operating times at high temperatures .
After 240 hours of operation at 2200 — 2300°C the discrepancy AT at 1000°C
and at an initial temf of 16.037 u V did not exceed 4 % ; such a discrepancy is
insignificant for operation in the above temperature range .
As we see from the data of /22 , 26 /, which agree with one another ,
tungsten- rhenium thermocouples can be successfully and widely used in
industry for operation at temperatures near 2300°C in vacuo , as well as in
inert and reducing media .
In / 1 , 20 , 24 / to determine the characteristics of the stability and
mechanical strength of the thermocouple material, the authors studied the
effect of the medium, temperature , and duration of operation of thermo
couples under industrial and similar conditions .
In particular , the thermocouples were operated under the following
conditions :
1. The thermocouple was held in the working space of the graphite
heater of a high- temperature furnace for 10 – 12 hours at 1600 — 1650°C .
The wires were protected by alumina two- channel 3.5X2X0.7 mm tubes ,
and by an alumina pole tip fastened in the working space of the furnace.
2. The thermocouple was held in a vacuum furnace for 2 – 3 hours at
1800 – 2400° C .
Two - channel tubes made of alumina were used to insulate the wire when
the furnace was heated to 1800°C . For operation at up to 2200°C one - channel
303
beryllium tubes were used , and for operation up to 2400 – 2500° C the wires
were not sheathed , because no suitable refractory material could be found .
3. The thermocouples were held in high- temperature furnaces (at
1000 — 16 50° C ) in a hydrogen and argon medium continuously for over 20 days .
4. Thermocouples were used to measure the temperature of steel in
electric - arc and open- hearth furnaces , and in crucibles of induction
furnaces by the method of short insertion . The temperature measured was
1600 – 1900° C , and up to 40 or more measurements were taken with a single
junction . The divergence of the thermocouple readings did not exceed + 4°C .
Up to 45 readings were made in the crucible of the induction furnace , and
up to 25 in the electric- arc furnace with a single junction . The thermo
couples were then checked for the stability of their thermoelectric properties .
5. Thermocouples were used to measure the temperature of the wall of
the electric - arc furnace during melting .
In measurements of the temperature of the electric - arc furnace lining
during melting, the thermocouple of type W – 3% Re / W – 15% Re was used,
which was later replaced by a more stable thermocouple W – 10% Re / W
20% Re / 14, 24 /.
All the tests showed that the thermocouples studied have a high mechanical
strength (the wire near the junction after operation under various conditions
remained ductile ) with a sufficiently high stability of the thermoelectric
properties (especially the thermocouple of the W - 10% Re / W -20% Re type).
In /27 / the authors studied the causes of brittleness in tungsten- rhenium
thermocouples operating in a carbon- containing atmosphere. It was found
that the brittleness is due to the formation of a ternary carbide , which is
stable from the melting point up to at least 800°C , i.e. , over the temperature
range in which tungsten- rhenium thermocouples operate .
The authors of /18 / also studied the behavior of a number of thermo
couples , w / Re , W / W – 25% Re , Re / W – 25 % Re , C – Re , C – Ir, in a
carbon - containing medium . The results show that the unsheathed
thermocouples W / Re and W / W – 25% Re can be successfully used for a
short time (about 15 sec ) in an atmosphere of hydrocarbons up to 2300°C .
At present / 14, 16, 20, 24 / thermocouples of the W – 5% Re / W – 20 % Re
type are used at the Elektrostal' Plant for measuring the temperature of the
lining of electric - arc furnaces, as well as in devices for the periodic
measurement of the temperature of liquid steel . During 1959 – 1960 over
100 thousand measurements were performed at this plant with these
thermocouples . These thermocouples can be used in various media: argon,
nitrogen, helium , hydrogen, and a vacuum . If appropriately protected they
can be used in atmospheres containing carbon and ceramic dust or in contact
with graphite , solid solutions , etc.
Thermocouples are also used to measure the temperature of a still
gaseous medium , of high - velocity gas jets , and under vibration conditions .
They enable us to measure temperatures up to 2500°C reliably .
Tungsten - rhenium thermocouples of the W / W – 26% Re type can be used
in nuclear reactors /28 – 30 /. They are employed to measure temperatures
up to 2760°C in the center of fuel slugs made of UO2 (BOR AX - V ). However,
if the wires are sheathed in a tantalum tube with beryllium oxide and
magnesium oxide insulation, the maximum temperature which these
thermocouples can read accurately is 2200°C , since at a higher temperature
the tantalum tube begins to react with the beryllium oxide /28, 29 /.
304
The same thermocouples can measure the temperature of the hydrocarbon
atmosphere in reactors of the Kiwi- A and Kiw- A3 types . To measure the
temperature of gases emerging from Kied reactors , two types of W / W –
25 % Re thermocouples are used . One type is fitted with a molybdenum tube
and a beryllium oxide insulation, and the other type has a tungsten block
and an insulation of boron nitride and copper and magnesium oxides /30 /.
4. Thermocouples made of molybdenum - rhenium alloys

Molybdenum - rhenium alloys (up to 50 wt % Re ) are very promising as
thermoelectrodes at high temperatures in carbon- containing media . Molyb
denum is carburized less actively than tungsten, and rhenium does not form
carbides . The alloys have a high strength and are highly ductile / 17 /.
The highest temf and sensitivity are shown by thermocouples made of
the Mo — 20% Re / Mo — 50% Re and Mo – 20% Re / Mo — 40% Re alloys
( Table 109 ) .
TABLE 109. Properties of molybdenum -rhenium themocouples

Type of Temf, mv Sensitivity , uV / ° C
thermo
100° 10000 15000 18000 1000 10000 1500 ° 1800°
couple
MP20 / 50 1 9.8 13.6 15.5 10.C 9.5 7.4 4.8

MP20 / 40 0.5 9.5 10.5 11.8 5.0 9.0 6.0 4.0
The thermoelectric properties of wire after annealing in hydrogen at

1500°C are already well stabilized, and further annealing at 1750 °C does
not change them . Studies showed that in vacuo the wire becomes brittle
in direct contact with graphite . The protection of the wire from direct
contact with graphite by means of aluminum oxide tubes considerably lengthens
the service life ( 5 – 7 hours without protection, and over 350 hours in
protective tubes at 1500°C ) /17 /.
5. Rhenium - carbon thermocouples
It is reported / 18, 31 / that a thermocouple of rhenium coupled with

graphite of the highest purity has been constructed . The thermocouple can
be used in an inert or reducing atmosphere . The hot ends of the thermo
couple are connected by a movable clamp, and no diffusio of
material between the electrodes is observed . The graphite is strong enough
to support the thermocouple in a gas stream of waste reactor gases / 31 /.
6. Manganese - nickel base alloys with rhenium

The data given below /32 / show that the introduction of very small
amounts of rhenium into a manganese- nickel alloy increases the temf of a
thermocouple of this alloy and copper very little :
305
75% Mn - 25 % Ni ... 1.85
(Mn - Ni) - 0.53% Re . 1.96

(Mn - Ni) – 1.57 Re 1.94
Very small additions of rhenium do not prevent the use of this alloy for
constructional elements which come in contact with copper in a number of
instruments .
7. Thermoelectromotive force of molybdenum - rhenium

alloys coupled with copper and aluminum
When these alloys are used in electrical devices as stay wires and torsion
suspension wires, in addition to the favorable combination of a number of
physical and mechanical properties , they must
satisfy one important condition, namely, their
differential temf with reference to the
constructional alloys of copper or aluminum
used in the instruments should not exceed
0.1 4V / degree.
,uegree
d/Temf
The thermoelectric properties of tension

V
wires made of molybdenum - rhenium alloys

coupled with either copper or aluminum have
AL /MO-RE been studied /33 /.
In Figure 130 we give the dependence of the
temf of annealed and cold- worked specimens
of molybdenum alloys with different rhenium
contents coupled with copper and aluminum .
Cu /mo -Re Cold working materials changes the value of
the temf insignificantly , but this value is very
20 40
dependent on the alloy composition . The temf
Re, % of the specimens with coupled aluminum
FIGURE 130. Themoelectromotive
decreases from 10 to 0.2 u V /degree if the content
force of wires made of molybdenum
of rhenium in the alloy increases from 5 to
rhenium alloys with a varying content
50 % . The curve showing the dependence of
of rhenium coupled with copper and temf on the rhenium content of molybdenum
aluminum : alloys coupled with copper passes from the
1 and 3 annealed wire; 2 and 4 - region of positive values of temf to the region
degree of deformation 84 % . of negative values . Thus , the alloy with a
rhenium content of approximately 30% has an
insignificantly small temf with reference to
copper (0.14 V / degree ) .
A change in the tempering temperature of the alloys from 100 to 900°C
has scarcely any effect on the thermoelectric properties of the thermo
couples studied . In Table 110 we give the temf of alloys of molybdenum
with 30 and 50% Re after heat treatment , and show the methods of alloy
preparation .
Thus , alloys of molybdenum with 30 and 50% Re have the most favorable
thermoelectric properties with reference to copper and aluminum for
electric - instrument building .
306
TABLE 110. Thermoelectromotive force (uV / degree) of rhenium -molybdenum alloys
Method of preparation of alloy

Alloy, % electron -beam
sintering arc melting
melting
Mo - 50 Re -2.5 -2.5 -2.5

0.25 0.15 0.2
Mo - 30 Re -0.1 -0.7
2.5 2
Note : In the numerator , temf of the alloy coupled with copper; in the denominator ,
temf of alloy coupled with aluminum .
Conclusion
The data given in this chapter show that rhenium - containing alloys are
very promising materials ior thermocouples operating at high temperatures
( of the order of 2000°C or more ) . They have a number of advantages over
other materials used today . As already mentioned , wires made of tungsten
rhenium alloys are now widely used in industry . We can state with
confidence that the compositions studied do not exhaust all the possible uses
of rhenium alloys as material for thermocouples . To create new
compositions for thermoelectrode couples , alloys of rhenium with high
melting transition metals of groups IV – VIII are very promising in the
region of solid solutions based on these metals . These alloys have a high
melting point , are stable, have good mechanical properties , and good
workability, and can be shaped into wires . Of special interest are ternary
compositions of rhenium alloys .
307
Chapter XX
RHENIUM AND ITS ALLOYS FOR USE AS ELECTRIC CONTACTS
It is known that materials used for electric contacts must have a number
of specific properties . Today, to evaluate the possible use of a certain
metal as a contact material, it is necessary to determine a large number of
properties and characteristics , such as the contact resistance , current
voltage characteristics of the arc , minimum values of thecurrent and voltage
of arc formation , current and voltage of bridge formation, the erosion
factor under various conditions , etc.
It is very difficult to produce a contact material which has the complete
set of necessary properties , because in most instances a low contact
resistance is inherent in materials with low hardness and density, whereas
low erosion factors under arc conditions usually occur in hard and rigid
materials with high melting and boiling points , as in these materials the
interatomic bonds are stronger . The erosion resistance is also affected
by the metal structure and a number of other factors . The most wear
resistant are high melting and hard materials .
Therefore, the materials should be selected according to the conditions
of use , namely, the voltage and current in the commutated circuit, and
the length and frequency of switching on . The environment , i . e . , the
temperature and humidity of the air, and the degree of its contamination by
corrosive impurities , etc. , must also be considered .
Of the high- melting metals tungsten is used most frequently for the
production of contacts . However , this metal is susceptible to corrosion .
In operation and even during storage an oxide film forms on it, which
breaks the contact .
In a number of studies in the Soviet Union and abroad , scientists
determined the specific characteristics of rhenium and its alloys , as
possible material for electric contacts in place of tungsten and other metals .
Rhenium and its alloys with tungsten, molybdenum , and silver , were studied
most .
We know that rhenium and its alloys with high- melting metals have high
boiling and melting points , high recrystallization temperatures , and high
electrical resistivity, density, hardness , and strength . Rhenium oxides
are volatile . The highest oxide Re2O7 sublimes at 362°C, but tungsten
trioxide sublimes at a temperature above 800°C . The electrical resistivity
of rhenium is higher than that of tungsten , and its electrochemical potential
is more electropositive .
This set of properties makes rhenium and its alloys potential and
promising material for contacts . In /34 / it was suggested for the first time
that rhenium be used for contacts .
308
Sims 35 – 37 / indicates the high wear resistance of rhenium contacts
against high - voltage dc arcs . This is because the oxide film on rhenium
impedes the transfer of metal and the welding of contacts . The film
thickness does not increase owing to the volatility of the oxides , so that the
film does not disturb the contact conductivity . Rhenium contacts for heavy
current contact breakers are more erosion resistant than tungsten . It is also
pointed out that rhenium is corrosion resistant in magneto- contacts of marine
engines .
Contact materials of rhenium and its alloys are prepared by various
methods, such as sintering, casting, and impregnation .
Rhenium contacts are made from forged rods of sintered or cast rhenium .
Contacts made of tungsten - rhenium alloys are manufactured from forged
rods, produced from either sintered or cast blanks of these alloys . The
rhenium- silver and rhenium- copper compositions are prepared by various
methods / 38 - 39 /.
As we know , alloys of rhenium with silver and copper do not react mutually in
the liquid or solid state . An impregnation method was used which consists
in making a porous rhenium blank with a prescribed 10 — 40% porosity by
successive sintering of the compressed contact alternating with pressing.
The porous shell formed was impregnated by either molten copper or silver
in a hydrogen atmosphere / 38 /.
The authors of /39 / studied the same compositions for silver- rhenium
contacts, as in /38 /. The contacts were manufactured according to methods
developed by the authors of /39 /. Rhenium and silver are dissolved
separately in nitric acid and the solutions mixed in the prescribed ratio .
Silver perrhenate and excess silver are precipitated from the solution . The
filtered and dried mixture of precipitates is reduced by hydrogen at 300° C
for 2 hours . The light- gray mixture of silver and rhenium powders of
10 – 20 u particle size is pressed into contact blanks with a silver sublayer .
The contacts are sintered in hydrogen at 900°C for 3 hours , and then
pressed for the last time under a 5 ton /cm²pressure . These compositions
consist of a mixture of fine silver and rhenium particles , which are the
two components of the pseudo- alloy.
1. Contact resistance
The contact resistance of rhenium and of a number of its alloys has been
studied in /40 – 49 /.
The contact resistance of contacts made of cast alloys of rhenium with
metals of groups IV – VI ( Table 111 ) was determined as the mean value of
four measurements at a 100 A dc current, and under a load at 0.5, 4.5,
and 13,6 kg. The table shows that the lowest contact resistance is shown by
contacts made of alloys of rhenium with vanadium , chromium, molybdenum ,
and tungsten /40 /, so that these alloys are evidently promising contact
materials .
The contact resistance of rhenium and its alloys with tungsten / 38 , 41-42/
was determined under loads of up to 400 gram, and at a current of 1 and
2 A, using freshly cleaned contacts , contacts that had been exposed to air
for 14 days , and contacts after 10,000 operations under load .
309
TABLE 111. Contact resistance (mohm / cm ) of some alloys of rhenium with transition metals /40/
Alloy Load , kg
Note
base
Re , % 0.5 4.5 13.6
metal
1 Ti 50 6.45 6.08 5.90 Excess heat caused erosion of the contact point (pitting),
90 4.49 4.20 4.14 other sections of the contact surface did not become
oxidized , the contact resistance is unstable
Zr 30 3.95 3.64 3.87 Contact surfaces became hot , red , and oxidized , the
50 13.20 14.00 solder of the positive contact melted
90 6.35 3.93 4.64
Hf 90 3.16 2.80 2.70 Highly oxidized
V 10 2.10 1.70 1.10 No oxidation of specimens noted ; a small mark appeared
30 2.20 1.80 1.30 at the contact point
50 2.50 1.90 1.30
3.10 2.70 2.60
Nb 30 3.44 3.44 3.04 A shiny red oxide appeared on the contact surface of the
50 6.40 6.00 5.36 alloy with 90% Re, other contacts did not become
90 4.80 3.86 3.70 oxidized , but marks appeared at the contact point
Ta 30 11.20 8.50 9.80 Specimens with 90% Re became highly oxidized ; spark
50 11.30 10.30 discharge on the surface of contacts with 50% Re on
90 3.30 2.63 2.64 switching on of the current ; contacts with 30 % Re
cracked and broke on switching on of the current
Cr 50 4.06 3.13 1.84 No oxidation
90 1.83 1.46 1.05
Mo 1.50 0.50 0.20 No oxides on the surface . Small red spots at contact
10 1.60 1.10 0.80 point
30 2.20 1.30 1.15
50 1.90 1.50 0.90
90 . 3.30 2.25 1.76
W 30 3.40 2.60 2.00 Contacts made of alloy with 85% Re became oxidized ;
55 4.50 4,10 4.20 the oxide film is blue with a light -red spot at the center.
89 4.20 3.20 2.70 The alloy with 55% Re was little oxidized and turned
100 1.70 1.40 0.96 dark at the contact point. The alloy with 30% Re was
scarcely oxidized, except at small points at the point of
contact
The contact resistance of cleaned rhenium contacts ( Figure 131 a ) has

almost the same value as that of tungsten .
During operation the contact resistance of rhenium changes little
( increases 1.5 times ), whereas under the same operating conditions for
the same time the contact resistance of tungsten contacts increases
16 times . This phenomenon occurs under a 200 gram load, as well as
under other loads . The contact resistance of rhenium contacts covered by
a thick black- brown film after 10,000 operations under arcing conditions
is only 2.5 times higher than that of the clean contacts , but for tungsten
contacts it is 50 times higher .
For reliable operation ( low and stable contact resistance ) the authors
of /38, 42/ recommend a load of not less than 50 gram.
The results of measuring the contact resistance of alloys are shown in
Figure 131 a . The contact resistance of alloys is many times that of pure
metals, and is approximately 30 times higher than that of tungsten with a
200 gram load . However, the contact resistance of alloys changes very
little with time, and sometimes even decreases . It is also little influenced
by operation under arcing conditions.
310
a
Rc, mohm
b
500 Rc , mohm
200 10
2
100
3
5
50
2
20 311
10
3
10 31
2 0,5
5 11
2
2
2 0,2
20 100 300 500 24 100 200 400

P. 8 P.8
FIGURE 131. Contact resistance of rhenium - tungsten
alloys (a ) , and compositions of rhenium with silver ( b )
/ 38/ :
1- W ; 2 Re ; 3 - W -30% Re ; pure ;
after holding in air ; - after operation ;
1 ' – Ag; 2 ' – Re ; 3 ' – Ag - 50% Re: - pure :
after holding in air .
The mechanical load for alloys should be rather high. If the recom
mended load for tungsten contacts is 100 – 250 gram, for the tungsten
rhenium alloys it is in the region of
a 300 – 400 gram , i . e . , double that
R.mohm for tungsten .
According to the data of 43 – 45 /
0,8 an increase was observed in the contact
resistance of an alloy of tungsten with
0,6 15 % Re during prolonged operation as a
contactor at a current of more than 22A .
0,4
Kirillova / 50 / studied alloys of
2 6 tungsten with 15, 16 , and 20% Re , and
R.mohm I, A tungsten and rhenium (produced by
b
sintering ) as materials for contact
breakers of ignition systems .
24 These alloys and the widely used
platinum - iridium alloys were tested
under the same conditions . It was
shown that alloys of tungsten with 20% Re
have much better contact properties
12 than either the alloy of platinum with
1
2 5 % Ir or pure tungsten .
02
0,6 The contact resistance of contacts
10 30 50 70 Pig made of an alloy of tungsten with 20% Re
FIGURE 132. Dependence of the contact resis is very stable . Here the necessary
tance of silver -tungsten and silver- rhenium condition for good operation is an
contacts on the current ( a ) and on the load ( b ): annealing of the contacts at 1800°C for
1- AWS -50 ; 2- ARS - 50 ; 3 – ARS -30 ; 30 minutes . Comparative tests under
- AWS -30 . the same conditions of the contact
311
resistance of contacts made of rhenium and tungsten showed that the contact
resistance of rhenium after operation does not change and remains low , but
tungsten loses its conductivity completely after operation .
The contact resistance of silver- rhenium alloys was studied in /38 — 39,
42 / . The composition of rhenium- silver alloys was as follows : ARS – 30,
30% Ag and 70% Re ; ARS – 50 , 50% Ag and 50% Re; RS , 70 – 82% Ag and
30 – 18% Re . The Re · Ag specimens were shaped like rivets and were soldered
to copper bases . The contact surface was spherical with a 20 mm radius .
The contact resistance ( Figure 131 b ) of rhenium- silver alloys lies
between that of silver and rhenium . Here , with increase in the silver
content in the alloy, the resistance decreases . Holding in air has little
influence on the contact resistance of silver- rhenium and tungsten- rhenium
contacts . A stable resistance is attained under a load of 100 – 150 grams /38/.
The contact resistance of the ARS- 30 and ARS- 50 silver- rhenium and
other alloy contacts depends on the current and the load ( Figure 132 a and b )
/39 /. The contact resistance was measured by the ammeter- voltmeter
method . When the load was increased from 0 to 70 gram, the value of the
resistance of the ARS- 30 alloy at 3A changed from 26 to 0.8 uohms . A
further load increase had little influence on the contact resistance of this
alloy . A load increase from 0 to 30 gram changed the contact resistance
of the ARS- 50 alloy from 1.3 to 0.4uohms . For the silver- tungsten
compositions with the same silver content an analogous change in the
contact resistance takes place . However, the value of the contact resistance
is somewhat higher .
The change in the current under a constant load of 50 g has almost no
effect on the contact resistance of silver- rhenium contacts , which agrees
well with the data of /46 /.
2. Volt - ampere characteristics
The volt- ampere characteristics of the arc between rhenium contacts are
much lcwer than those of the arc between tungsten contacts /38, 42 /. In
Figure 133 a we give the volt- ampere characteristics for two lengths of
the gap between contacts made of alloys of tungsten with 3, 5, 15, and 20% Re .
The minimum values of currents and voltages of arc formation lo and U.
for rhenium, tungsten, and their alloys , are given in Table 112 .
TABLE 112. Minimum values of voltages and currents of arc formation
Material , % U .. V 1.. A Material , % U .. V 1 .. A
Re 12 0.30 W – 15 Re 17 0.26
18.5 0.24 W - 5 Re 17 0.26
W - 20 Re 17 0.26 W – 3 Re 18 0.23
The volt - ampere characteristics of alloys (see Figure 133 a ) for a

distance between the contacts of 1.5 mm coincide almost completely with
those of tungsten. When the distance between the contacts is 0.5 mm , the
5511 312
characteristics of the alloy approach those of tungsten as the rhenium
content in the alloy decreases .
a
U. V
80
1.6 mm
0.5 mm
4 J, A
U. V b
80
40
1.6 mm
0.5 mm
20
1.0 2.0 3.0 4,0

1, A
FIGURE 133. Comparative volt- ampere characteristics of rhenium , tung
sten , and their alloys (a ) , and rhenium , silver , and their alloys ( b ):
1 – W — 3 % Re ; 2 – W - 5% Re ; 3 – W - 15 % Re ; 4 - W -20 % Re :
5 - silver; 6 rhenium : 7 - Ag - 50% Re ; 8 -
– Ag - 30 % Re.
The minimum values of the current lo and voltage U, of arc formation,

given in Table 112, show that for tungsten and its alloys the minimum
values of the voltage are similar ; with decrease in the rhenium content in
the alloy, these values approach those for tungsten .
TABLE 113 . Results of arc formation tests /47–49 /
Arc
Increase in the
Material, %
contact resistance
Length , mm arcing time, sec
100 Re 1.4 5.3

100 W 0.05 0.2
W - 5 Re 0.08 0.3
W – 15 Re 0.5 1.8
W 20 Re 1.35 5.1 30 times
Mo - 10 Re 0.35 1.3
Mo - 18 Re 1.9 7.1
Mo 40 Re 2.7 10.3 20 times
Ag – 22 Re 2.3 8.7 40 - 200 times
Cu 21 Re 2.1 8.0 4 times
Pd - 7 Re 0.03 0.1
The volt- ampere characteristics of rhenium- silver alloys accordingto the

data of /38, 42 / are given in Figure 133b . From the comparative data it follows
that the volt- ampere characteristics of the investigated compositions
313
are higher than those of rhenium, and close to those of silver . With increas
in the distance between the contacts , the difference in the characteristics
increases .
The minimum values of the currents and voltages of arc formation are
somewhat higher for alloys than for pure metals .
In /47 – 49 / the authors studied the duration of contact arcing and its
effect on the contact resistance of rhenium and its alloys . The contacts
were slowly (at a rate of 0.265 mm / sec ) drawn apart, and the length of the
arc formed between the contacts was measured with an indicator . Re was
determined by closing the contacts and measuring the voltage drop across
them . A dc arc was formed 15 times , the voltage being 110 V, and the
current, 1.5 A. The contacts were not cleaned between each arcing . The
results obtained are given in Table 113 .
From Table 113 we see that the arc length for tungsten is much less than for
rhenium , but no impairment of contact was observed in rhenium . For tungsten
alloys with low rhenium content the arc length corresponded to that of pure
tungsten, and in alloys with 15 or 20% Re it reached values near those for
pure rhenium . The arc between the molybdenum - rhenium contacts was
lengthened to 0.37 — 2.7 mm . An increase in resistance caused by arcing
was observed in rhenium compositions containing silver and copper .
3. Erosion resistance
The erosion resistance of contacts made of rhenium and its alloys has
been studied in a number of works .
In / 38, 42 / the erosion resistance was studied at a frequency of
switching on of 5 per sec , a load of 150 g, and a 0.5 mm gap between the
contacts . The erosion caused by break was studied at 30 V and 2 A and 5 A.
The number of work cycles for tungsten and alloys of tungsten with rhenium
was 1 million , for alloys of rhenium with silver, 200 – 500 thousand . In
another variant the tests were carried out at 15 V and 2.5 A, with a 0.5 mm
gap between contacts , and under a load of 150 g . The number of cycles was
10,000 . The contacts were weighed on analytical scales , and the mean
change in weight was determined for one operation, as the wear of the
contacts in one operation under arcing conditions is proportional to the
amount of electricity passing through the arc . In the first case, the load
was ohmic and in the second inductive .
The nature of the erosion of rhenium during the processes studied , is
completely different from that of tungsten . The results of testing contacts
made of rhenium, tungsten , and their alloys are given in Table 114 .
From the table we see that in all cases in tungsten contacts wear of the
cathode and transfer of metal to the anode occur , whereas in rhenium
contacts both electrodes are worn, the anode to a greater extent. An exception
is the arc produced at 30 V and 5 A, when the anode is worn and metal
transferred to the cathode . In long arcs ( in a circuit with an inductive load )
the wear of the cathode when the contacts are of rhenium is double that
occurring when they are made of tungsten, and the anode in rhenium
contacts is worn five times more rapidly than the cathode .
314
TABLE 114. Mean change in weight (10- mg) per operation
Ohmic load Inductive load
Material , % 30 V , 2 A 30 V , 5 A 15 V , 2,5 A
anode cathode anode cathode anode cathode
100% Re -1.8 -1.2 -4.6 + 1.5 -3270 -624

100% W +0.2 -0.5 +2.5 -25.3 + 12 -300
-
W- 20 Re +1.5 -0.8 +0.6 -1.5 -802 -254
W - 15 Re +0.1 -1.1 + 0.5 -5.8
W- 10 Re -200 -192
W – 5 Re +0.2 -2.7 +0.3 -1.5 +9 -225
In long arcs produced at 30 V and 5 A the metal removed from both

rhenium and tungsten contacts comes from the greater part of the contact
surface . At the same voltage and with a current of 2 A, the wear of
rhenium contacts is again distributed over the contact surface , while in the
case of tungsten contacts , the cathode becomes pitted and metal is
deposited in blisters on the anode .
In the case of a long arc produced at 15 V and 2.5 A, immediately after
the operation the contacts are covered by oxidation products in the form of
blackish- brown flakes, grayish scales, or a grayish- brown film .
The erosion factor y for rhenium is many times greater than for tungsten .
As both contacts are worn, y is computed for the cathode as well as for the
anode , but the values are not comparable with y for tungsten .
Erosion tests at high alternating currents were carried out with sintered
rhenium ( 3.17 – 9.52 mm in diameter and 0.30 – 1.27 mm thick ) in
laboratory -type contactors at 2500 A and 230 V in air and in transformer
oil . The contacts showed a high resistance to erosion, and their surfaces
were bright and free of oxides . The erosion characteristics of rhenium
alloys with tungsten /38, 42 / ( Table 114 ) determined at 30 V and either
2 or 5 A show that the direction of metal transfer for alloys is the same as
for tungsten, i.e. , from the cathode to the anode .
In long arcs the nature of the metal wear changes . In an alloy with 5 % Re
the wear observed is similar to that in the case of pure tungsten, whereas
in alloys with 10 and 15% Re both contacts wear like rhenium contacts , and
the anode is worn more rapidly. The wear values of the alloys occupy an
intermediate position between those of pure tungsten and rhenium . After
10,000 operations with a long arc all the contacts become sooty, all
the anodes are pitted and covered by a grayish film , and the surfaces of the
cathodes are tarnished / 38 / .
The addition of rhenium to tungsten changes the character of operation
of the contacts /42 /. Contacts made of tungsten alloys with 15 % Re are
operable for a long time at breaking currents 18 = 2 A. The entire contact
surface is covered uniformly by an oxide layer and has no noticeable pits
or metal build-ups . The authors of /42 / believe that the oxide films which
form during operation are current conductors . It is also possible that
" self- cleaning" of the contact surface from oxide films takes place due to
the volatility of the oxides formed . After tests , the working surface of tungsten
rhenium contacts is uniformly worn, whereas on tungsten contacts under
the same operating conditions metal transfer on restricted areas is observed .
315
The mean values of the wear of contacts made of the W – 15 % Re alloy,
tungsten, and rhenium after 180 million operations under various
operating conditions are given in Table 115 .
TABLE 115. Mean wear of contacts under various operating conditions
Mean wear of
Contact contact pair after Frequency of Breaking
material, % 180 million opera operations , Hz current , A
tions , mg
100 W 28.7 50 3.0 - 3.2

W - 15 Re 12.7 50 3.0 - 3.2
100 W 12.0 100 2.3 - 2.5
W 15 Re 12.4 100 2.3 - 2.5
100 Re 84.5 100 2.3 - 2.5
It can be seen from the table , that the wear of rhenium contacts is
approximately three times that of tungsten , but for tungsten- rhenium
contacts it is less .
Tungsten- rhenium alloys / 50 / as materials for contactors were
compared with platinum- iridium alloys , which are extensively used under
these conditions . It was shown that the former have appreciable advantages .
Alloys with 20% Re have a high erosion resistance to arc and spark .
Tests under arcing conditions were performed with a 6 A current , which
was interrupted 50 times per second . The circuit contained inductance of
0.037 henry; a voltage of 27 V was used , and the test was continued for 1 hour .
In the spark test the testing time was 2 hours , the capacitance 0.45 u F ,
and the working voltage 3 kV .
TABLE 116. Changes in weight of the rhenium -silver contacts per operation ( 10-6mg)
1= 2 A 1= 5 A
Contact designation
anode cathode anode cathode
Ag -12.8 +0.6 -40 + 7.0

ARS - 50 -12.4 -3.8 - 26 -- 52.0
ARS -30 --- 12.6 -4.4 -30 - 59.0
RS -18.7 + 5.4 - 104 + 16.0
Re -1.2 -1.8 + 1.5 -4.6
Tungsten- rhenium alloys erode quite differently from alloys of noble

metals . For platinum and palladium alloys under the same operating
conditions it is the cathode that loses material (the cathode material is
transferred to the anode ), but the anode and the cathode of tungsten- rhenium
alloy contacts incur losses , and the anode loses more metal than the
cathode . This phenomenon is explained by the oxidizability of the alloy at
the high temperatures of arcing . During the test under arcing conditions.
the anode loses 4 – 6% of the initial weight of the material, and the wear is
uniform over the entire contact surface . In tests on the resistance to
arcing there was not a single case of sticking of the contacts .
316
Rhenium alloys gave better results than platinum - iridium alloys in the
spark resistance tests also . The anode losses in spark tests are 1 - 2% of
the initial weight of the contacts ; the wear is uniform .
The erosion characteristics of rhenium- silver alioys /38, 42 / are given
in Table 116 .
In contacts of the ARS- 50 and ARS- 30 types we do not observe transfer
of metal in any specific direction , as in the case of silver, i.e. , both
contacts are worn . In contacts of the RS type the direction of transfer is
the same as for silver, but the wear is twice as high .
In /47 – 49 / erosion was tested with de and ac on a vibrator
with a 50 Hz frequency, a breaking current of 1 A, a voltage of 48 V, and
a total number of switching on of 120,000 . The ac had a frequency of
500 Hz , and the other parameters were the same as above .
Tests with dc (Table 117 ) confirmed that wear of rhenium contacts is
greater, and occurs in a different direction than in tungsten contacts . The
erosion of rhenium (crater on the anode and a build up on the cathode )
differs from the uniform erosion of tungsten cathodes . Under the same
conditions , but with a spark arrester , there is scarcely any erosion
of rhenium contacts .
TABLE 117. Erosion of rhenium alloys (mg)
DC (without spark extinguishing) DC ( without spark extinguishing)

Material , % Material, %
anode cathode anode cathode
100 Re -16.2 + 2.2 Ag - 22 Re -68 -17

-28.7 +2.1 Cu - 21 Re -64 -20
100 W + 0.2 - 2.6 I + 6.2 -11.1
Pd – 7 Re
W - 5 Re +0.2 -1.2 II - 2.6 -14.4
W - 20 Re + 0.2 - 2.9
The authors of /47 – 49 / also tested rhenium compositions with 8 and

18% Ag for sticking at 50-300 A , 60 V , and 50 Hz . The contacts were
closed 50 times under current and opened with the current switched off.
Contacts of all compositions showed no sticking or deterioration of
contact conductivity at all currents ; however , the contacts were strongly
burnt and covered by oxide flakes ; sputtering was observed .
4. Corrosion of contacts
In /40, 47 – 49 , 51 / contacts made of rhenium , tungsten, and alloys

of rhenium with tungsten and molybdenum were tested for the effect of
moist air and high temperatures .
According to the data of /47 – 48 , 51 /, contacts made of rhenium,
tungsten, and alloys of rhenium with tungsten and molybdenum were tested
for contact resistance (by the voltmeter - ammeter method ) under a
700 gram load at 4 A and 6 V , in the initial state and after holding in a
thermostat at 100 – 110° C for 7 hours and in an electric furnace at 500,
700 , and 1000°C for 5 minutes .
317
In Table 118 we give the mean data of the measurements /47 /.
TABLE 118. Dependence of the contact resistance of contacts (mohm ) on heating

Heating temperature, °C
Material , %
before test 100 – 110 500 700 1000
100 Re 4 22 27 1.1 8.3

11 56 37 4.3 11.2
100 W 31 460 550 1038 bc
W - 5 Re 19 38 54 600 - bc bc
W – 15 Re 210 524 1650 bc
W - 20 Re 25 157 576 bc bc
Mo – 10 Re 2.2 9.1 300 bc bc
Mo 18 Re 1.9 3.4 300 bc
Mo - 40 Re 6.8 5.6 185 1000
Ag - 22 Re 2.5 4.1 0.3 0.5
Cu - 21 Re 4.5 23.0 12
Pd – 7 Re 8.4 7.9 318 522 2.4
Note . For rhenium two parallel tests were carried out ; bc is the breakdown of conductance.
In Figure 134 we show a graph of the dependence of the contact

resistance of tungsten and rhenium contacts on heating. We can clearly
see the advantage of rhenium contacts, which showed a low contact
resistance on the contacts subjected to heating to 1000°C , owing to the
vaporization of the oxides formed on the surface .
Tungsten and its alloys with 5, 15, and 20 % Re have an inadequate
corrosion resistance under high temperature conditions , a nonconducting
film forms on them , the resistance increases ,
Amohm
and conduction through the contacts is

impaired at temperatures above 500 – 700°C .
Conduction through contacts made of
molybdenum - rhenium alloys is also impaired
at 500 – 700° C , and at 1000°C , the contacts
become very burnt .
The rhenium- silver composition heated
to 700° C retained a low contact resistance
60
whereas the rhenium - copper composition
showed a considerable increase in resistance
at 500°C owing to oxidation of copper .
Re In /46 / it is noted that owing to the high
500 1000 volatility of rhenium oxides heating the
1.00 silver- rhenium composition with 10 % Re to
FIGURE 134. Contact resistance of 900°C increases its electrical resistivity much
tungsten and rhenium contacts after less than in the case of compositions with
heating to various temperatures tungsten and with molybdenum . The contacts
made of the composition with 10% Re was
tested by direct current ( 36 V and 4 A) and
no considerable increase in the contact resistance was found . However ,
the wear of the contacts was even greater than that of silver- nickel contacts .
318
The author of the article took into consideration the high cost of rhenium,
and believes that rhenium does not have any technical advantages over the
known compositions of silver and nickel .
FIGURE 135. External appearance of contacts after tests in a

humid medium :
a - rhenium contact after 50 days of testing; b – tungsten
contact after 30 days of testing.
The inadequate corrosion resistance of tungsten during operation of

contacts at a high humidity also results in a breakdown of conductivity.
Tests performed in humid atmospheres on the resistance /51 / of contacts
made of rhenium and tungsten showed that rhenium is more corrosion
resistant than tungsten . In Figure 135 we show the external appearance of
contacts made of rhenium and tungsten after tests in a humid atmosphere
( 95+ 3% ) . After 50 days the surface of the rhenium contacts did not change ,
but remained smooth and bright . On the other hand , after 30 days the
surface of the tungsten contacts was covered by a thick layer of oxides .
TABLE 119. Mean contact resistance (mohm ) of contacts /47 / made of alloys of rhenium with
tungsten and molybdenum
Testing conditions
Material, tropical corrosion

cleaned contacts
2 days 3 days 35 days
100 Re 2.3 86 118

100 W 5.0 191 bc
W – 15 Re 5.6 bc
Mo – 10 Re 2.2 207 bc
Mo - 18 Re 1.9 408 bc
Mo -
40 Re 6.8 121 bc
In /47 / contacts were tested in moist air, under conditions simulating

the operating conditions of contacts in the tropics ( t = 45°C , air humidity
95 — 98% ) , for 8 hours . During the remaining hours of the day the contacts
were kept at room temperature, and in the process of cooling they became
covered by dew . In tests for 35 days the rhenium contacts retained their
brightness, but the tungsten contacts became tarnished after two days, and
319
after 35 days they were completely covered by corrosion products . Contacts
made of alloys of rhenium with tungsten and molybdenum behave analogously
to tungsten contacts ( Table 119 ) .
According to the BBC program, USA / 40 /, rhenium contacts were tested
in highly humid and corrosive media . In tests in a highly humid medium
for two weeks (humidity 90 — 95% and temperature 25 – 65°C ) rhenium
contacts did not corrode, whereas the surface of tungsten contacts was
covered by corrosion products even after 24 – 48 hours ; this is confirmed
by the data of / 51 /.
Tests in the spray of a 20% solution of salt at 35° C showed that rhenium
contacts do not corrode even after 300 hours , but corrosion products appear
on tungsten contacts after 72 — 96 hours /40 /.
5. Reliability of operation
Electric contacts are an integral part of any electric system . Statistics

show that most equipment failures are due to contact breakdowns /52 /. An
analysis of contact failures shows that they are caused by incorrectly
selected contact materials , parameters , and modes of operation . Therefore,
the problem of increased reliability of contact equipment is of great
importance . The term " reliability of an electric contact" implies that it is
capable of trouble - free performance of its functions with preservation of
its fundamental characteristics under the given operating conditions for a
given number of work cycles and a given period of time . In /52 / the
authors describe a detailed examination of the physicochemical processes
occurring in contacts during various periods of their service lives which
cause breakdowns . The data on tests under operating conditions of new
contact materials which have a low contact resistance , high corrosion
resistance , and other necessary properties are of interest . Research on
the possible use of rhenium contacts in magneto ignition systems showed
that in the operation of magnetos under the conditions of 3000 rpm there
was very little misfiring, and after 400 hours of operation at 600 rpm , the
number of cases of misfiring was satisfactorily low .
After a 500 hour operation the operating properties of contacts were
quite satisfactory . Rhenium contacts withstand six- fold overloads of the
nominal current well .
The effect of oxidation of a rhenium contact surface paired with a gold
contact on the reliability of operation was tested at 0.065 V; each contact
operated 200 times . Heating in the air for 15 minutes at 400°C results in
the formation of an oxide film on tungsten; on rhenium no noticeable film
is formed and the contacts work well . After 30 min heating to 450°C all
rhenium contacts gave 100% operation, whereas in the tungsten contacts
from 2 to 27 failures were observed . After rhenium had been heated in an
oxidizing flame, causing the appearance of oxide film , rhenium contacts
also gave 100% performance /40 /.
In tests on contacts made of alloys of rhenium with titanium , zirconium ,
hafnium , vanadium , niobium , tantalum, chromium , molybdenum, and
tungsten, for the operation reliability in pairs with gold contacts at 0.065 V,
and an 8 g load, in the course of 200 operations it was established that
alloys of rhenium with titanium, zirconium, vanadium , niobium and
320
tantalum are not suitable for use as contact material owing to the high
percentage of breakdowns ( 2 – 40% ) /40 /.
The good operating characteristics of rhenium contacts in electric tests
and the high corrosion resistance make rhenium contacts suitable for use
in medium power magnetos for outboard motors and for motors used during
certain seasons .
A number of companies in the USA have conducted tests which show that
rhenium contacts can be successfully used in relays operating under the
following conditions: 6 V , 30 g load , current 1 – 1.4 A, number of
operations 8.5 · 106 per hour , as well as in sealed relays in reactive
ignition systems (jet engine ignition ) /40 /.
One of the automobile firms of the USA tested rhenium contacts paired
with rhenium or platinum- ruthenium contacts in magneto systems . For
platinum- ruthenium contact parts the mass transfer amounted to 0.33 mm
in 50 hours , whereas the mass transfer in rhenium contacts operating with
platinum- ruthenium was only 0.006 mm per 100 hours of operation /40 /.
Alloys of palladium with rhenium (from 1 to 20% Re ) as material for
weak current electric contacts have been patented in West Germany / 53 /.
In the patent it is also noted that up to 50% Re in the alloy can be replaced
by tungsten . Compared with the palladium alloy containing 15 % Cu , which
is at present used for the same purposes , alloys of palladium with rhenium
show only approximately 1 / 100 of the wear , especially under high electric
loads . Consequently , they have a longer life .
Conclusion
It has been shown that rhenium and its alloys are good materials for
current- carrying vibratory contacts under certain operating conditions . The
working parts (contacts ) are small in size , and the electrophysical and
mechanical properties of rhenium materials are well utilized .
The data collected on the contact properties of rhenium and its alloys
show that pure rhenium has advantages over tungsten as a contact
material , mainly because of the stability of the contact resistance in
operation under adverse conditions of atmospheric and tropical corrosion ,
high temperature, and long arcs , and during storage in corrosive media.
Therefore , rhenium can be used to replace tungsten in contacts when failure
is due to corrosion , i.e. , during the operation in a tropical atmosphere , or
in contact with sea water . Under these conditions rhenium contacts assure
high stability of operation .
Alloys of rhenium with tungsten also have a number of advantages over
pure tungsten . Even a small amount of rhenium in the alloy increases the
stability of the contact resistance many times . The erosion resistance of
alloys subjected to short- duration arcs is high . Therefore, alloys of
rhenium with tungsten are recommended for operation in equipment which
provides for a load in the range of 200 – 250 grams and is intended for
conditions of short- duration arcs /38 /.
It has also been found that contacts made of alloys of tungsten with
15 – 20% Re have advantages over the tungsten contacts in voltage regulators
and ignition devices /50 / .
321
Rhenium and its alloys with tungsten have a good workability . They are
cut and ground according to the procedures adopted for tungsten, and
contacts are easily soldered onto copper, brass , and steel mountings by
the methods used for soldering tungsten contacts /47 /.
Moreover , rhenium can be readily impregnated by copper and silver,
and can serve as a base for compositions obtained by impregnation or
coprecipitation from solutions .
Some authors / 38 / believe that contacts made of rhenium- silver alloys
have no advantages over pure silver or silver- nickel compositions .
However, the authors of /39 / believe that since erosion resistance of
silver- rhenium contacts is higher than that of silver contacts , the intermediate
resistance is also lower than in tungsten- silver contacts , and even more
important, there is no transfer of metal from one contact to another ,
contacts made of silver- rhenium compositions can be used to replace silver
and tungsten- silver contacts under demanding operating conditions .
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324
Chapter XXI
DIFFUSION TREATMENT OF RHENIUM . RHENIUM AND

RHENIUM ALLOY DEPOSITS
This chapter deals with two problems : the production of diffusion layers
on rhenium and rhenium coating of other metals (by electrodeposition,
vapor phase deposition , etc. ) .
We know that all high- melting metals , including rhenium, are not
sufficiently heat- resistant, and oxidize at elevated temperatures . Oxygen
from the surface diffuses readily into the metal . One of the methods of
increasing the heat resistance of high- melting metals is the production
of protective coatings by various methods (diffusion treatment, electro
plating, vapor phase deposition, etc. ) . However , the resistance of the
coatings is very dependent on the interdiffusion of the alloy components
and of the protective coating . Therefore, research on the diffusion
processes in heat- resistant rhenium alloys is of special importance .
In the literature there are few data on coating rhenium and diffusion in
rhenium alloys . Research in this direction has only begun, and is
qualitative rather than quantitative . The diffusion treatment of rhenium is
the subject of only one paper, by A. N. Minkevich et al . / 1 /.
Rhenium can be deposited on metals by various methods , the principal
ones being electroplating and vapor phase deposition .
As we have already mentioned , rhenium has a number of unique
properties, and a considerable part is played by its high corrosion resistance
in a number of corrosive media (molten metals , solutions of certain acids ,
salts , and alkalis ) , as well as its stability in very humid media, the
absence of any tendency to take part in a " water cycle ," inability to form
carbides , etc. Rhenium is thus a very valuable constructional material
for chemical and vacuum tube industries , and in certain other branches
of technology, where materials with a high corrosion resistance are
required .
However, rhenium is rare and expensive , and the preparation of
complex- shaped parts from rhenium is difficult . Therefore , if the surface
properties of articles are of main importance, it is not necessary to make
the article from rhenium or its alloys , but to limit these metals to suitable
coatings . This method is extensively used in electronics and other
technological fields .
1. Diffusion in rhenium - molybdenum alloys

Self - diffusion of molybdenum in molybdenum - rhenium
alloys . The self - diffusion of molybdenum was studied for alloys of
325
molybdenum with 10 and 20% Re . Cylindrical samples 14 mm in diameter
and 5 mm high were made from ingots melted in an arc furnace, and
annealed at 2000 ° C for 10 – 15 hours in a vacuum of 10-4 mm Hg to obtain a
coarse- grained stabilized structure . The samples were electroplated with
the radioactive Mo" isotope . The activated samples were diffusion annealed
at various temperatures in the 1700 – 2100°C range in a vacuum of 10-4 mm
Hg . After the diffusion annealing, metal layers were removed successively
from the activated surface of the samples , and the integral radioactivity of
the remainder of the sample was measured . The self - diffusion parameters ,
which can be found from the equation for the diffusion coefficient
of molybdenum in solid solutions with rhenium, D = 20 expo (-V/RT) cm / sec ,
TABLE 120. Self - diffusion parameters of molybdenum in alloys with rhenium
Pre -exponential factor, Activation energy ,

Alloy , % cm²/sec cal/ g -atom
100 Mo 4.52 113,300 200
Mo - 10 Re 2.88 · 103 141,000 + 1800
Mo - 20 Re 4.24 - 103 139,000 1500
The addition of rhenium increases the activation energy of the self

diffusion of molybdenum .
This effect of rhenium is explained by possible localization of the
admixture atoms in the paths of the high diffusion conductivity of the solvent
(boundary grains and mosaics, dislocations , and the surfaces of oriented
microcavities ) . Moreover, it is assumed that the addition of such significant
amounts of rhenium as 10 - 20 wt % ( 6 — 12 at . % ) can lead to a certain
change in the interatomic forces , the lattice constants , and the equilibrium
concentration of the vacancies .
The diffusion of rhenium in the bulk of molybdenum .
The diffusion of rhenium in molybdenum was studied by
186the method of shifting
the activity curve by adding the radioactive isotope Re
The diffusion coefficient of rhenium in molybdenum has the following
values :
Temperature , C .. 1700 1800 1850 1950 2000 2100

Diffusion coefficient, x 1011 cm /sec . 0.28 1.3 1.4 4.7 8.4 17.10
The temperature dependence of the diffusion coefficient of rhenium in

molybdenum was found:
D = 9.68.10-* exp ( - (94.700 + 1500)/RT ] cm ? / sec.

Due to the lower value of the activation energy the diffusion of rhenium
in molybdenum proceeds approximately twice as rapidly as the self - diffusion
of the atoms of molybdenum over the temperature range studied . The
difference between the activation energies of diffusion of the base metal
and impurity atoms , which in the given instance is approximately
19 kcal / g- atom , is evidently caused by local lattice distortions due to
326
dimensional discrepancy , and by the difference in the charge of the solvent
and admixture ions .
A microstructural examination of the diffusion taking place in rhenium
plated molybdenum heat- treated at 800°C in vacuo was carried out in /2 /;
on heating to 1100°C no diffusion of rhenium in molybdenum was observed .
2. Diffusion in rhenium - tungsten alloys
The diffusion of rhenium in tungsten and of tungsten in rhenium was

studied in / 3 / by the method of microstructural analysis and by hardness
measurements . Rhenium coatings 250 – 300 u thick were applied to tungsten
sheet 6 mm thick . The grain size of the rhenium coating was 1 – 24. The
specimens were subjected to a vacuum diffusion annealing at 2000°C for
up to 600 hours . Before the annealing, a sharply defined boundary was
observed between the base metal and the coating . The coating was compact,
without any micropores or cracks . The difference in the coefficients of
thermal expansion of tungsten and rhenium leads to the formation of cracks ,
situated at an angle of 45° to the axis of the specimen , but the coating itself
remains solid . After the annealing , a transition diffusion zone was
observed , which consisted mainly of two sections : a j - phase on the tungsten
side , and an x- phase on the rhenium side . The microhardness of tungsten ,
transition layers , and rhenium , is given in Figure 136. The characteristic
microstructures of diffusion layers are shown in Figure 137 a and b .
2000
1600
/k, gm2
My
m
Ae พ
300 200 100 100 200 300

Diffusion layer , u
FIGURE 136. Microhardness of the diffusion layer of a tungsten -rhenium bimetal

after diffusion at 2000 ° C :
1- diffusion time 100 hours; 2- 200 hours; 3 – 500 hours (the boundary between
the o- and x - phases is taken as the zero point of the diffusion layer).
With increase in the holding time an increase in the thickness of the

transition diffusion layer ( Figure 138 a ) is observed , and the growth of the
thickness of the layer is governed by the law of proportionality to the
square root of the diffusion time ( Figure 138b ) .
The authors of / 3 / note that the diffusion in the tungsten- rhenium
system at 2000°C proceeds more slowly than the diffusion in the rhenium
molybdenum , rhenium- niobium, niobium - tungsten , and tungsten - tantalum
systems .
327
Re RE
FIGURE 137. Characteristic microstructures of diffusion layers of the tungsten -rhenium

bimetal after diffusion at 2000C :
a — diffusion time 200 hr , X500 , polarized light; b – diffusion time 500 hr, X150 ,
polarized light.
80
,ulayer ion
60
Width
diffus
a
= 40
of
20
0
100 200 300 400 500 600 700
Chr
100
80
60
b
40
x
20
0
5 10 15 20 25 30 35
Vc
FIGURE 138. Increase in the width of the

transition diffusion layer of a tungsten
rhenium bimetal plate after diffusion at
2000 ° C :
a – dependence of the width of the diffusion
layer on the diffusion time ; b – dependence
of the width of the diffusion layer on the
square root of the diffusion time .
5511 328
In /2 / the diffusion of rhenium electrodeposits into the nickel and steel
base was studied and it was found that rhenium does not diffuse into nickel
and steel at temperatures up to 1100°C , and even a deterioration in the
quality of the plates and of their adhesion to the base is observed . The
author /2 / believes that this is due to the difference between the coefficients
of thermal expansion .
3. Diffusion treatment of rhenium
The diffusion treatment of rhenium , by means of which we can modify

the physicochemical properties of the surface layers of rhenium in the
desired direction, was studied by A. N. Minkevich, M. A. Tylkina, L.N.
Rastorguev, and G. P. Rodionova .
Of greatest interest are types of diffusion treatment of rhenium such as
boronizing, siliconizing, calorizing , and chromizing . With these elements
rhenium forms a number of high- melting compounds. Rhenium cannot be
carburized , since it does not form carbides .
Boronizing /1 /. Deformed and annealed sintered rhenium was
boronized by two methods : in a bath with molten borax and boron carbide
powder ( 30% ) at 1000 and 1200°C; or with boron carbide powder in vacuo
( 5 · 10-5 mm Hg ) at 1400°C . The change in hardness of the boronized
rhenium layer after these two methods is given in Figure 139 a and b . The
depth of the boronized layer was approximately 0.06 – 0.15 mm , depending
on the method, the temperature , and the time of boronizing .
The hardness of the layer depends on the method , time , and temperature
of boronizing . After boronizing in a borax melt ( 1000 – 1200°C , 3 hours )
the hardness varies over the range of 1890 – 2160 kg / mm² , and after
boronizing with boron carbide powder in vacuo ( 1400 – 1500°C , 2 – 6 hr2 ) ,
the hardness is 2580 — 2900 kg / mm², i.e. , approximately 700 kg /mm
higher . This indicates a different composition of the surface layers .
We know three boride phases , namely, RezB , Re7B3, and ReB3 /4, 5 /
in the boron- rhenium system .
By X- ray structural analysis of boride layers on rhenium / 1 / it was
found that the surface layer produced by boronizing in vacuo with boron
carbide at 1400°C consists of two boride layers : a thin upper layer with a
hexagonal close- packed structure , and a ReB3 boride lattice , and an
underlying extensive textured layer of hexagonal boride Re7B3, isomorphous
with Cr7B3, with a = 7.5036 kX and c = 4.8512 kx , which corresponds to the
data of /5 /. A microstructural analysis also showed the presence of two
boride layers ( Figure 140 a ) . There are no literature data on the micro
hardness of rhenium borides . The phase composition of the surface layer
obtained by boronizing in borax has not yet been studied . It is possible that
the difference between the microhardness of these two layers cannot be
explained only by the different amounts of boron in the borides formed,
but may be due to the formation of ternary compounds of rhenium with
boron and carbon, or alloying of rhenium borides with carbon .
Siliconizing . Rhenium was siliconized /1 , 6 / at 1000 and 1100°C
for 8 hours in a mixture containing approximately 40% powdered fireclay,
60% silicon powder , and 3 % ammonium chloride . The change in the
microhardness of the surface layer ( see Figure 139 c ) showed that the depth
5511 329
of the surface layer is little dependent on the temperature of siliconizing
and is approximately 0.15 – 0.20 mm . However , the hardness of the surface
layer is very dependent on the temperature of siliconizing. Thus ,
siliconizing at 1000°С produces a hardness of approximately 920 —
– 1000 kg / mm² . After siliconizing at 1100°C the microhardness on the
surface is 1400 kg / mm², at a depth of 0.02 – 0.09 mm it is approximately
1800 kg / mm², and at a greater depth it decreases to 1670 kg /mm².
According to the authors of /1 /, the nature of the variation in the hardness
of the surface layer , siliconized at 1000 and 1100° C , indicates the formation
during siliconizing of not less than two compounds . The boundaries of
these cannot be established by a microstructural method (see Figure 140 c ) .
Microhardness
a b
3000
,kgm²
EF
/m
1200-3 hr
1400-2 hr
2000
1400° 4hr
1000th
1000
1400 6 hi
Microhardness
0.05 0.10 0.15 0 0.05 010 0.15 0.20

2000
,kgm²
/m
1100-8 hr
1500
1200-8 hr
1000
1100-8 hr 1000-8 hr
500 21
1000-8 hr
0.30 0.60 0 0.10 0.20 0.30

Distance from the surface, mm
с d
FIGURE 139. Hardness of the diffusion layers of rhenium specimens:

a – boronizing in molten borax containing boron carbide powder ( 30 % )
at 1000 and 1200 ° C ; b – boronizing with a boron carbide powder in
vacuo (5. 10-4 mm Hg) at 1400 ° C ; C- ca lorizing at 1000 , 1100 , and
1200 °C ; d – siliconizing at 1100 and 1000 ° C .
X- ray structural analysis showed /1 / that the surface layers of rhenium

specimens treated at 1100° C consisted of two silicides: ReSiz with a
tetragonal crystal lattice and constants a = 3.12 kx , c = 7.66 kX, and ReSi
with a cubic lattice and a = 4.6 kx which approximately agrees with the
330
available literature data 17 /. The authors of / 1 / believe that it is also
possible that rhenium silicide has a considerable silicon deficiency, since
its lattice constants are somewhat lower than those given in /8 / for an
equilibrium composition .
FIGURE 140. Microstructure of diffusion layers of specimens

of diffusion - treated rhenium :
a – boronizing (1400 °C /2hr),X 200 ; C -chromizing (1100 °C /
8 hr), x 135; c – calorizing (1200°C / 8 hr), x 135 ; d – sili
conizing ( 1100 °C / 8 hr) , x135.
Calorizing / 1 /. Rhenium was calorized at 1000 , 1100, and 1200° C

for 8 hours in a powdered mixture containing approximately 40% fireclay,
60 % aluminum , and 3% ammonium chloride . In Figure 139c and 140 c data
are given on the depth and hardness of the surface layer . No X - ray
structural analysis of the calorized layer was carried out . After comparing
the microhardness versus depth relationship of the calorized layers with
data of the Re – Al phase diagram /8 /, the authors of / 1 / assume that
calorizing at 1000 and 1100° C produces a surface layer which consists of
Al2Res, with approximately 90% Re , and a microhardness of approximately
800 kg / mm² /8 /, and after calorizing at 1200°C the aluminum content in
the layer increases to a AlzRe composition, with a microhardness of
1000 kg / mm² /8 /. However, these assumptions require further verification.
331
Chromizing / 1 /. After chromizing it was found that in most cases
the hardness of the surface layer either decreases somewhat or remains
unchanged . Microstructural analysis showed that the external corrosion
resistant chromized layer ( see Figure 140 b ) is separated from the core
by a wide dark zone , which indicates the formation of a new phase during
chromizing . However, judging by the microhardness value of the chromized
layer, which is 330 — 550 kg / mm², this is not the o - phase which forms in
the Cr - Re system /9 / (its hardness is 1500 – 1600 kg / mmº ), but a
chromium base a - solid solution .
Research on diffusion treatment of rhenium is of interest for creating
a protective surface layer on rhenium, which will prevent oxidation and
also have the special physical properties , such as wear resistance ,
emission properties , etc. For research on oxidizability, see page 347 .
4. Electroplating with rhenium and its alloys
Rhenium plating . The electroplating method of applying rhenium

coatings was used for the first time in 1934, when Fink and Deren / 10 , 11 /
reported on the production of a shiny, mirror- like rhenium surface.
Rhenium was deposited from a sulfuric acid solution of potassium
perrhenate (pH = 1.01 0.1 , current density 10.8 A / dm² ) at room temperature .
In / 12 / there is also a report on the preliminary research during which
a hard and brittle rhenium deposit was produced . The author of / 12 /
believes that this brittleness of the deposit was caused by the evolution of
hydrogen . The deposition of rhenium on rhodium is accompanied by a
smaller hydrogen overvoltage , which favors the deposition of rhenium .
In / 13 / the authors report on the production of a satisfactory coating
from a sulfuric acid solution, and on the study of possible deposition of
rhenium from citric acid solutions .
The author of / 14 / studied the application of rhenium deposits , 20 – 25 u
thick, on various high -melting metals . Thick deposits were obtained by the
deposition of 1-2 u layers in succession, with annealing at 1000°C after
each deposition , in order to transform the deposit from the amorphous into
the crystalline state .
However , the deposits produced in these studies had poor mechanical
properties and were brittle .
An attempt to improve the properties of rhenium deposits and to produce
ductile tungsten - rhenium alloy on the surface of tungsten wire was made in
/ 15 /. The deposit was plated from a bath which consisted of ammonium
perrhenate and sulfuric acid at pH = 1.0 — 1.3 . Better deposits were
obtained by plating for 6 minutes at room temperature and a current density
of 10.8 A / dm². The specimens were annealed in hydrogen at 900 – 950°C
for 15 minutes in order to reduce the oxides present in the coating . This
cycle was repeated many times . After two cycles a coating 0.024 mm thick
was produced . After annealing in hydrogen the coating remained bright
for a long time in the air . However, in an atmosphere contaminated by
vapors of chemical reagents (acids , alkalis , salts , etc. ), oxidation occurred
within a short time .
332
a
b
FIGURE 141. Rhenium electrodeposits / 16 ):

a – on tungsten , 40 min , 32 °C , 21 A /dm² , X500 ; b- on tungsten, four depositions,
each for 20 min at 20 ° C , 17.8 A / dm², X500 ; C – on nickel , 10 min , at 21 ° C ,
16.2 A /dm², x 100 ; d - on tungsten , coagulation of pores in the diffusion zone after
annealing, 8 hr at 2000 ° C , X 500 .
Of special practical interest are rhenium deposits on tungsten . Rhenium

plated tungsten is promising as a contact material and material for electric
vacuum devices . A rhenium- plated layer is also promising as a diffusion
barrier between tungsten and carbon in the operation of tungsten parts in
carbon - containing atmospheres.
The authors of / 16 / used a bath of the following composition : ammonium
perrhenate 24 g / liter, sulfuric acid 87 g / liter, ammonium hydroxide
25 g / liter , at pH 1 , with a platinum anode . The temperature of the bath
was 21 – 88°C, and the current density from 10.8 to 280 A / dm ? The
presence in the bath of other metallic ions is not desirable . The baths
containing ammonium nitrate were also studied . The deposits obtained are
unstable in the air and in humid media . It is assumed that rhenium is
deposited under these conditions as rhenium hydride . In order to dissociate
the hydride and obtain rhenium , the articles were annealed at 950 – 1000° C
in hydrogen .
333
A 12 h thick electrodeposited layer of rhenium can be obtained by
alternately depositing and annealing; a continuous process is not possible
because of the fall in the hydrogen overvoltage during deposition of rhenium
hydride . The deposited layer has a discontinuous structure (Figure 141 b ) .
The authors of / 16 / believe that the base metal has a strong effect on
the rate of deposition of rhenium . For tungsten this rate is 4.70 1.2 mg Re /
100 A . min / dm ?, and for nickel it is 18.54 2.5 mg Re / A. min / dm². The
rhenium deposit on nickel ( Figure 131 b ) was produced at a smaller current
density than on tungsten (Figure 141 a ) .
The preparation of the tungsten surface consists in rinsing in acetone ,
pickling at 60°C , rinsing in water , and treating with 3.6 N H2SO4 for
30 minutes . The nickel surface before rhenium coating is rinsed in 1.2 N
sulfuric acid .
The hydrogen overvoltage also affects the rate of deposition of rhenium .
Electrolytic polishing of the surface of tungsten wire on which rhenium is
to be deposited reduces the rate by a factor of 1.4. Increase in temperature
from 21 to 88° C , as well as an increase in the current density from 10.8 to
18 A / dm², increases the rate of deposition 1.3 times . The plating rate
scarcely changes with time .
The production of tungsten - rhenium alloys by the method of diffusion
annealing was studied in /16 /. Rhenium was deposited on tungsten wire and
the wire was annealed in hydrogen first at 900°C , and then at 2000°C to
complete the diffusion process and the production of the tungsten- rhenium
alloy . Bending tests on such specimens at room temperature were carried
out by winding the wire on mandrels of various diameters . The measure of
brittleness was the mandrel radius to wire radius ratio . Ductile wire can
be wound on mandrels with smaller diameters without failure .
The ductility of the wire after diffusion annealing for 4 and 6 hours is
the same as that of the tungsten- rhenium alloy. The wire can be wound on
a mandrel with a radius of 17 – 18 radiuses ofthewire to be bent. Annealing
for 2 hours was clearly insufficient for completion of diffusion , and the wire
behaved like recrystallized tungsten , was very brittle , and could be wound
on a mandrel of a much larger radius only, equal to 41 radiuses ofthewire .
Time of diffusion annealing at 2000 ° C , hr 1 2 4 6 8
Mandrel radius to wire radius ratio 68 41 18 17 30
The hardness of the surface layer of the wire is 2000 kg / mm², which
indicates the formation of a o - phase on the surface layer . The hardness of
the diffusion zone is 650 kg /mm², and of the wire, 550 kg / mm² . Evidently,
the diffusion zone is a tungsten- base solid solution / 16 /. These data agree
well with those of /3 /, in which the processes of diffusion in rhenium
coated tungsten were studied .
The o - phase which forms on the surface has no effect on the ductility of
the wire, since it forms a discontinuous layer / 15 /. The decrease in the
wire ductility after diffusion annealing for 8 hours is caused by the
coagulation of pores in the diffusion zone ( Figure 141 d ) . The formation of
these was also noted in / 3 /.
In / 17 , 18, 24 / it is shown that rhenium should be deposited on various
metals (tungsten and molybdenum wire , titanium , graphite , copper, nickel,
and other materials ) from electrolytes containing 12 g / liter KRe04 and
35 g / liter H2SO4, at a cathode current density of 50 - 100 A / dm ?, and at
temperatures of 25 – 60 ° C .
334
To obtain deposits with a thickness of more than 5d , it is necessary to
complete several " deposition- annealing" cycles . Depending on the base
metal, rhenium- plated specimens can be annealed in vacuo or in a hydrogen
or argon atmosphere at a temperature of 500 – 1000 ° C / 18, 24 /.
The quality of rhenium deposits was checked by mechanical methods
( hammering, 180° bending to failure; wire wound on a mandrel ), by chemical
tests for porosity, and by the metallographic method . Metallographic
investigations have shown that only thin layers of rhenium adhere strongly
to the base , and that the thick deposits crumble .
From /19 / we learn of the use of rhenium electrodeposits for lining the
internal walls of fuel tanks .
Rhenium alloy coatings . Electrodeposition of various
compositions of rhenium alloys greatly increases the possible production of
articles with specific properties of the surface layer .
Nickel- rhenium coatings . The electrodeposition of rhenium- nickel alloys
is described in /10 , 20, 21 , 23, 33 /.
In /21 / the authors indicate the possibility of producing rhenium- nickel
alloys with varying nickel contents , depending on the concentration of
rhenium in the electrolyte , at a high current efficiency ( approximately 100% ) .
The nickel- rhenium deposits were plated from nickel- plating solutions
containing potassium perrhenate . A new bath was also developed, which in
the past was used for the production of a rhenium deposit , with the addition
of nickel sulfate . The rhenium content in the coating was up to 85% .
In /23 / rhenium - nickel coatings were applied to copper and chromium
nickel rods , after chemical pickling .
Rhenium- nickel alloys /23 / were deposited from three baths , developed
in / 21 / . The optimum composition of the solution for the production of
bright and dense deposits of nickel alloys with 14 – 89 % Re was as follows :
225 g / liter crystalline NiSO3 · 6H20 , 45 g / liter crystalline Nici · 6H20,
70 g / liter citric acid , 30 g / liter boric acid, and 0.4 – 30 g / liter KRe04.
The properties of the nickel coatings formed are given in Table 121 .
According to the data of / 18 / in order to deposit Re – 20% Ni alloy
coatings on titanium, an electrolyte of the following composition /33 / can
be successfully used : 15 g / liter KRe04, 5 g / liter NiSO4 · 6H20 , 50 g / liter
(NH4)2SO4, and pH 2.5 – 3.0 . The electrolysis conditions are : current
density 4 A / dm”, temperature 70° . The articles were annealed in vacuo or
in argon at 700 – 800° C for 30 minutes . The rhenium- nickel alloy deposit
can be produced up to 30 u in thickness , without any intermediate annealing,
as is necessary for rhenium coatings /18 /. Nickel- rhenium alloy coatings
produced under these conditions are uniform , compact , and not brittle
( Figure 142 a ) .
Cobalt - rhenium coatings. The possibility of producing cobalt- rhenium
coatings with a varying content of rhenium (up to 85 % ), depending on the
electrolyte composition, was studied in /22 /. To produce the cobalt
rhenium coatings an electrolyte of the following composition was used :
6 – 60 g / liter CoS04 · H20, 66 g / liter citric acid, and ammonia to pH 7 ,
current density 1 – 10 A / dm?, and 1 – 10 g / 1 KRe04.
In /23 / a cobalt- rhenium alloy coating was deposited from an electrolyte
of the same composition as in /22 /. The rhenium content in the alloy
depended on the concentration of potassium perrhenate in the electrolyte.
The cathode current density was 5 A / dm?, and the temperature of the
electrolyte 70°C . The properties of cobalt- rhenium coatings plated on
335
copper and nickel- chromium alloys are given in Table 121 /23 /. During
electrolysis no diffusion penetration into the surface layer of the copper or
the chromium- nickel was observed ( see Figure 142 b ) .
TABLE 121. Properties of rhenium alloy coatings / 23 /

Mean thickness of
Coating Time of Hardness of
Base layer , u
composition , metal
deposition , layer , Properties of layer
% min kg/mm²
measured computed
Ni - 20 Re Cu 40 19.0 155 Compact , does not peel,

thickened at some places
Ni - 33 Re Cu 50 . 19.0 10 Not Compact , very uniform ,
measured does not peel
-
Ni - 13 Re Ni - Cr 20 6.6 460 Compact , wavy , does
not peel
Re - 80 Co Cu 20 14.2 12.3 250 Some regions are covered
by a discontinuous, un
even coating, which
peels
Re - 17 Co Cu 20 10.9 8.0 245
Re - 30.8 Co Ni - Cr 20 23.2 460 Good , compact , rough ,
does not peel
Re - 37 Co Ni - Cr 20 23.8 640 Good , even , compact ,
does not peel
Re -1 Cr 5 16.1 15.3 720 Compact , cracks formed
Cu in the preparation of
ground microsection
7 28.4 22.4
Ni - Cr 5 19.0 100 Discontinuous, even , peels
in some regions
Re - 5.4 5 10.0 7.5 Compact , uneven , cracks
Cu
Cr - 13.3 Ni { 10 20.0 12.4 formed during operation
Ni - Cr 15 31.4 600 Discontinuous, rough , does
not peel
Cobalt -rhenium alloy coatings produced on titanium ( 18 / by the same

method were compact, uniform, and ductile , and adhered well . The
thickness of the layer formed without any intermediate annealings was
up to 30 h . The final annealing was carried out at 700 – 800°C in argon
or in vacuo for 30 minutes .
Rhenium - lead coatings. During a study on rhenium coatings the Re - 1%
Pb alloy coating was produced /18/ using anodes made of the Pb – 8 % Sb
alloy. This coating was more compact and uniform than that of pure
rhenium . Nearer the titanium base a sublayer was discovered which
indicates that diffusion processes take place between the coating and the
base metal (see Figure 142c ) .
Rhenium - chromium coatings . Rhenium- chromium alloys were deposited
23, 24, 34 / on copper and chromium- nickel alloys from a solution of the
following /23 / composition : 50 g / 1 KRe04; 40 g / 1 (NH4)2SO4; 75 g / 1 H2SO4,
and 15 g / 1 Cros. The electrolysis was carried out at 75º and at a cathode
current density of 100 A / dm² . Bright compact Re – 1% Cr alloy coatings
were produced ( see Figure 142 d ) . The properties of these alloys are
given in Table 121 .
336
FIGURE 142. Rhenium alloy electroplating /23/:
a – rhenium -nickel; b – rhenium -cobalt ; c – rhenium - lead ; d – rhenium - chromium ,
Rhenium - chromium - nickel coatings. The high- quality rhenium

chromium - nickel alloy coating on copper and chromium- nickel alloys was
produced from a bath /23, 34 / containing 50 g / 1 KRe04; 40 g / 1 (NH4)2SO4 ;
75 g / 1 H2SO4 ; 15 g / 1 CrO3, and 45 g / 1 NiSO4. The temperature of the
electrolyte was 75°C , and the cathode current density was 100 A / dm². The
properties of the coating are given in Table 121. No diffusion penetration
of the alloy into the surface layer of the base metal was observed .
Iron - rhenium coatings. The electrodeposition of iron- rhenium coatings
containing up to 85 % Re /22 / was studied .
Tungsten - rhenium - cobalt coatings. In / 18 / there is a report on the
electroplating of W – Re – Co alloys with a rhenium content of up to 30%
from an electrolyte containing 12 g / 1w (as WO3); 7 g / 1 Re (KRe04);
2 g / 1 Co ( COSO4.7H2O ) ; 25 g / 1 (NH4)2SO4 40 g / 1 NH4OH ; and 10 g / 1 NaOH .
The plating was carried out at 10 A / dm and at a temperature of 60° C .
In a number of papers there are reports on the production of rhenium
coatings on graphite, tungsten, molybdenum , tantalum , nickel, brass ,
copper, and other base metals / 18, 25, 26 / .
Rhenium coatings have good protective properties in outer space, but
more exact data are not given . There is also a report on the use of rhenium
and rhenium- alloy coatings as undercoats for the prevention of diffusion
between the base metal and the metal of the protective coating . Thus ,
tungsten - rhenium alloys are used as undercoats between tungsten and
graphite. The strength of such a coating is 37 kg / mm² at 20°C and 12.9
kg /mm² at 2200 °C . The coating has a good resistance against thermal
shock . Undercoats of alloys of rhenium with tungsten, tantalum,
molybdenum , or niobium are used to reduce interdiffusion between
tungsten (molybdenum ) and the protective coatings against oxidation , in
particular, chromium coatings /25, 26 /.
337
5. Rhenium coatings from the gaseous phase
Production of rhenium coatings by the

method of thermal dissociation of rhenium
carbonyl vapor
Rhenium carbonyl is produced by a reaction between potassium or

ammonium perrhenate and carbon monoxide at 250 — 270 °C under a
pressure of 350 – 500 international atmospheres /27 /.
Rhenium carbonyl prepared by this method contains the following
impurities : 0.0005 % Zn; 0.0012% Cu; 0.0015 % Al; 0.0003 % Mg; 0.00006% Mn;
0.01 % Si ; and 0.0025 % Fe .
The decomposition rate constant of rhenium carbonyl is K = 2.12 · 10-6 exp
F- 18,630 /RT ) for the 250 – 420 °C temperature range /27 /.
The degree of decomposition of carbonyl over the 250 – 315°C
temperature range is x = 1 -exp (-2.12 . 10-6.1.exp ( -9390 / T ) .
Rhenium is deposited on a tungsten filament by the following method: the
wire surface is heated for 3 min to 900 – 1000° C in a current of moist
hydrogen . The coating is applied when the temperature of the wire is
500 – 600°C . The rate of deposition depends on the pressure and the
molar percentage of rhenium carbonyl . At pressures of approximately
46 – 47 mm Hg the mean rate of deposition is 5. 2 / hr ; at 30 – 33mm Hg
the rate is 6.3 / hr ; and at a pressure of 14 - 18 mm Hg it is
approximately 10.3u / hr .
In /27 , 28 / an industrial continuous -action installation for rhenium
coating of tungsten wire is described . The wire feed rate is 13 m / hr .
Coatings produced by the above method are up to 10 u thick, which is
approximately equal to the diameter of the initial tungsten wire, so that in
fact a bimetallic wire is produced . The strength of the wire decreases
somewhat due to the brittleness of the surface layer .
The high- temperature properties of rhenium- coated filaments were
studied in / 27 / . The heat resistance of the rhenium layer was investigated
in a vacuum of the order of 2 · 10-6 – 6 · 10-6 mm Hg at 2500 — 2600°K . The
thickness of the dense rhenium coating decreased as a result of heating,
and the rate of vạporization of rhenium under the above conditions is
0.3 – 0.4 \ / hour .
The strength of rhenium- coated tungsten filaments which have been
heated for a long time is higher than that of tungsten filaments after the
same treatment, but not rhenium coated .
Testing rhenium- coated tungsten filaments directly during operation of
the tubes is the most exact method, which can immediately solve the
problem of whether the use of rhenium- coated tungsten wire in electron
tubes instead of ordinary tungsten wire is advantageous .
The wire was used for the production of filaments in the form of loops
( Figure 143 a ) and of heaters for the electron tube cathode as spirals,
single for monofilar heaters , and double for the bifilar heaters
( Figure 143b ) .
A comparison of the blackening of filament lamps ( see Figure 143 a ),
one with a rhenium- coated and the other with an uncoated tungsten filament
( after forced incandescence to 1700° K and holding for 150 hours at this
temperature ) , showed that the lamp with the uncoated filament was much
more blackened .
338
FIGURE 143. Comparison of operation under high -temperature
conditions of rhenium coated (2 and 4) and uncoated ( 1 and 3 ):
a - incandescence lamp filaments; b – bifilar cathode

heaters /27 /.
In tests of electron tubes with bifilar heaters for 30 hours at 1800° K

a considerable darkening of the uncoated bifilar heater was observed
( see Figure 143b ) . This indicates that disintegration occurs . The rhenium
coated bifilar heater did not change /27 /.
Production of rhenium coatings by the

thermal dissociation of rhenium chlorides
Of the known halides of rhenium , of practical interest for the deposition

of metals by thermal dissociation are the chlorides ReCl3 and ReCls, as
well as rhenium oxychloride ReOC14 /29 – 32 ).
The production of rhenium coatings by the method of thermal dissociation
of rhenium pentachloride was studied in the 900 – 1750°C temperature range
of rhenium precipitation . The temperature of the vaporizer was 200°C ,
and the flow rate of the gas carrier ( argon ) was 10 liters / hour . In the
900 – 1200°C range the degree of utilization of chloride increases with the
temperature of the base layer , and in the 1200 — 1750 °C range it is almost
constant and amounts to 50 – 53% . Under these conditions the maximum
precipitation rate of rhenium is 10.5 mg / hr . cm ? The optimum tempera
ture of the vaporizer is equal to 200°C .
It was also established /29 / that the precipitation rate of rhenium in
vacuo is three times that under atmospheric pressure , but does not exceed
30 mg / hr · cm . Moreover, the complicated design of the vacuum
apparatus annuls the advantage of a vacuum .
The production of rhenium coatings by the thermal dissociation of
rhenium trichloride was studied at a temperature of 1200° of the base layer
and 500 — 550°C of the vaporizer . It was established that the principal gas
component when ReCl3 is heated to 500 – 550° C is the product of its
339
disproportionation , i.e. , rhenium pentachloride , from which the precipitation
of metallic rhenium occurs on the hot surface of the base layer . The
precipitation rate of rhenium is the same , but the degree of utilization of
chloride is lower than in the case of ReC15. Therefore , the authors of /29 /
consider it inadvisable to use rhenium trichloride for the production of
rhenium coatings .
The production of rhenium coatings by the thermal dissociation of ReOCY
was studied in the 900 – 1500° C temperature range at a constant concentration
of ReoCl4 in the gas phase of 0.2 g / l, which corresponds to the vaporization
temperature of ReoCl4 ( 95°C ) and an argon flow rate of 5 1 /hour . At
900 – 1250° C the degree of utilization of ReoCl4 increases with the
temperature of the base layer, but at a higher temperature it remains
constant ( 60% ) and near the theoretical ( 66% ) . The maximum value of the
precipitation rate of rhenium under the above conditions is 22 mg / hr · cm² .
The concentration of ReOC14, equal to 0.2 g / 1 , is the optimum concentration
for the utilization of ReOC14. At 25° C the optimum flow rate of argon is
4 – 12 1 / hr . The precipitation rate of rhenium is directly proportional to the
concentration of ReOC14. At a 1.4 g / l concentration the rate is 145 mg / hr .
.cm?, and can be expressed by the following relationship : a = 0.324.c .g / hr .
The authors of /29 / believe that ReOC14 for the production of rhenium
coatings from the gaseous phase has a number of advantages over ReCl5 .
ReoCl4 does not dissociate in the gaseous phase up to 650°C , so that we
can use it at any concentration, but ReCl, dissociates even at 190 — 200°C
into Cl2 and the slightly volatile ReCl3 , so that the possibilities of
obtaining high concentrations of ReCls are limited, and the precipitation
rate of rhenium does not exceed 10 mg / hr · cm² . With ReOC14 the
precipitation rate of 145 mg /hr · cm² is not the maximum and can be
increased . Moreover, the process of dissociation of ReoCl4 is characterized
by a higher metal yield ( 60 – 61% compared to 50 – 53% for ReC15 ), and a
stability over a wider range of process parameters , and it can easily be
regulated .
ReoCl4 can be purified from admixtures by simple refining, which will
yield a highly pure product , whereas the refining of rhenium pentachloride
is hindered by its dissociation .
The structure and quality of rhenium coatings produced by the dissociation
of ReCl, and ReoCl4 are approximately the same . If the temperature of the
base metal is below 1200°, finely crystalline coatings are formed . With
increase in the temperature the size of the crystals increases . According
to the authors of / 31 /, the density of the coatings is almost equal to the
theoretical density of rhenium .
The adhesion of rhenium coatings to tungsten and molybdenum is good,
as in all cases in bending tests , twisting to failure , and oblique shearing
tests , no peeling or cracking of the coatings was observed .
The same authors developed a technique for continuous rhenium coating
of 30 — 200 u diam tungsten wire by the method of rhenium precipitation
from the gaseous phase through the dissociation of oxytetrachloride. The
output of the device is up to 100 m / hr or higher, and the layer is 4u
thick / 33 / .
However , the method for the production of coatings on tungsten filaments
by thermal dissociation of rhenium compounds requires further improvement .
The high temperature to which the tungsten filament must be heated in the
process of rhenium precipitation causes the recrystallization of tungsten,
which results in brittleness of the wire .
340
Bibliography for Chapter XXI
1. Minkevich , A.N. , M. A.Tylkina , L.N.Rastorguev , and G. P.

Rodionova . In: Sbornik " Renii," p . 221. Moskva, Izdatel'stvo
Nauka . 1964 .
2. Sominskaya , 2. M. and A. A.Nikitina . In: Sbornik " Renii,"
p . 96. Moskva , Izdatel'stvo Nauka . 1964 .
3. Kirner , K.- Planseeber . Pulvermetallurgie , 9 ( 3 ) : 151 . 1961 .
4. Samsonov , G. V. and K.N. Portnoi . Splavy na osnove tugoplavkikh
soedinenii ( Alloys on the Basis of High- Melting Compounds ) , p . 167 .
Oborongiz . 1961 .
5. Aronsson , V. Acta chem . scand . , p . 733. 1960 .
6. Minkevich , A.N. Metallovedenie i termicheskaya obrabotka,
No. 8 : 9 – 15. 1961 .
7. Knapton , A.G. In : Plansee Proceedings , 1958 , p . 412. London ,
Pergamon Press . 1959 ,
8. Savitskii , E. M. , M. A. Tylkina , and K. B. Povarova . ZhNKh ,
6 , No. 8. 1961 .
9. Savitskii , E. M. , M.A.Tylkina , and K. B. Povarova . ZhNKA ,
4 (8 ): 873. 1959 .
10. Fink , C.G. and P. Deren . - Trans . Electrochem . Soc . , 66 : 471 .
1934 .
11. Fink , C.G. and P. Deren . U.S. Patent, No. 2 : 138573 , 29 November
1938 .
12. Young , C.B. Metal Ind . , 34 : 176 . 1936 .
13. Netherton , L. E. and M. L.Holt . Trans . Electrochem . Soc . ,
95 : 324 . 1949 .
14. Levy , R. German Patent No. 805213 , 10 May 1951 .
15. Sims , C. , G.Craighead , R.Jaffee et al . Investigation of
Rhenium . WADC - Rep . , No. 54 — 371 : 117 . 1954.
16. Root , G.S. and J.G. Beach . Electroplating of Rhenium . - In :
Rhenium , Amsterdam - N. Y. , Elsevier Publ . Co. 1962 .
17. Sklyarenko , S.I. , Z.M.Sominskaya , 0.V.Zenkevich , and
G. L. Miroshnichenko . Trudy Gosudarstvennogo Instituta
Redkikh Metallov, No. 1 : 301, Metallurgizdat . 1959.
18. Sominskaya , Z. M. and A. A.Nikitina . In : Sbornik " Renii,"
p . 90 , Moskva , Izdatel'stvo Nauka . 1964 .
19. Schreiter , W. Neue Hütte IX, 2 ( 9 ):559 — 567. 1967 .
20. Joynd , C. – Metal Ind . , 34 : 176 . 1934 .
21. Netherton , L. E. and M. L.Holt . J. Electrochem . Soc . , 98 : 106 .
1951 .
22. Netherton , L.E. and M. L.Holt . J. Electrochem . Soc . , 99:44 .
1952 .
23. Sominskaya , Z. M. , A. A.Nikitina , M.A.Tylkina , S.I.
Sklyarenko, and E.M.Savitskii . In: Sbornik " Renii, " p . 209,
Moskva , Izdatel'stvo AN SSSR . 1961 .
24. Sklyarenko , S.I. , Z. M. Sominskaya , A. A. Nikitina , and
1.1 . Lavrov . - In: Sbornik " Redkie metally i splavy, " p . 111,
Metallurgizdat. 1960 .
25. Armstrong , J.R. and R. A. Long . Nucl . Sci . Abstr . , 17 ( 9 ) :
14776. 1963 .
26. Amer . Met . Market ., 70 (60 ) : 11. 1963 ,
341
27. Ginzburg , A. A. – Trudy Instituta " Gipronikel ' , " No. 12:35 . 1962.
28. Ginzburg , A. A. – In: Sbornik " Renii," p . 87 , Moskva, Izdatel'stvo
Nauka . 1964 .
29. Zelikman , A. N. and N. V.Baryshnikov . In : Sbornik " Renii, "
p . 102, Moskva , Izdatel'stvo Nauka . 1964 .
30. Zelikman , A. N. and N. V. Baryshnikov . Voprosy Radioelektro
niki, Seriya Elektronika, No. 8. 1962 .
31. Zelikman , A.N. and N. V. Baryshnikov . – Izvestiya Vysshikh
Uchebnykh Zavedenii, Seriya Tsvetnaya Metallurgiya, No.2 . 1963 .
32. Baryshnikov , N.V. Issledovanie i razrabotka tekhnologii
polucheniya renievykh pokrytii metodom termicheskoi
dissotsiatsii khloridov reniya ( Investigation and Development of
Methods of Rhenium Coating by the Thermal Dissociation of
Rhenium Chlorides ) . Author's Summary of Thesis . Moskovskii
Institut Stali i Splavov . 1963 .
33. Korovin , N.V. and M.N.Ronzhin . ZhPKH , 23 ( 12) : 2734. 1960 .
34. Sklyarenko , S.I. , Z. M. Sominskaya , A. A. Nikitina , and
I.I. Lavrov . In : Sbornik "Renii," p . 152, Izdatel'stvo AN SSSR .
342
Chapter XXII
CORROSION RESISTANCE OF RHENIUM AND ITS ALLOYS
There are few data in the literature on the corrosion resistance of

rhenium and its alloys in various corrosive media at room and at elevated
temperatures . The most interesting and important in practice are investiga
tions of the oxidizability of rhenium, at elevated temperatures .
1. Oxidation of rhenium
As we have already mentioned , rhenium , as well as certain other high

melting metals , have good high- temperature strength . Their other
distinctive feature is rapid disintegration
T, ° C
due to intense oxidation at high temperatures ,
1400 1000 700 particularly in the case of molybdenum and
Ae MO rhenium .
Os The temperature dependence of the
relative oxidation rate of all high- melting
metals during one -hour tests is given in
/hcChange
102
weight
N6 Figure 144 / 1 /. Here, the lowest stability

,mrm²
in g
-Та was shown by rhenium /2 /, and the highest

RU by tungsten /3 ), but all these metals
W cannot operate without protection at high
temperatures . When heated above 600°C
à
rhenium vigorously reacts with oxygen

to form rhenium heptoxide /4 /.
Data on the oxidizability of cast rhenium
HI in the air at various temperatures are
102 pcr
given in Table 122 / 5 /.
Rh The kinetics of the oxidation of rhenium
1034
was studied in detail in /6 /, with sintered
rhenium ( 99.93 % pure ), in the deformed
1
10 1
state upon 40 – 50% reduction, and in the
6 104
recrystallized state . The temperature
range of oxidation of recrystallized and
FIGURE 144. Oxidation of high -melting cold - worked samples was 350 — 725°C , and
metals /1 / . the tests lasted up to 50 hours . Corrosion
Data for molybdenum , rhenium , osmium , was determined gravimetrically, by the
ruthenium , iridium , and rhodium are weight loss of the sample . The weight loss
given as the weight loss . was related to the surface area of the
343
sample, which was measured after each reading because of the intensity
of the oxidation . In Figure 145 we give the results of the oxidation of
recrystallized and cold- worked rhenium at temperatures of 350 – 725°C .
a b
3500 3500
Weight 3000 3000

2
m²
°,g/loss
5
c10
2000 2000 !
1000 1000
500 500
11 10
100
10 20 30 40 50 20 30 40
T, hr T, hr
FIGURE 145. Oxidation of recrystallized ( a) and cold -worked ( b )
rhenium at temperatures (° C ) of /6 /:
1- 725 °; 2 – 650 °; 3 - 625°; 4 - 600 °; 5 - 575°; 6 – 525°; 7 –520° ;
8 - 500°; 9 - 475 °; 10 - 400°; 11 –
- 3500.
Cold working greatly influences the oxidation rate . For rhenium the
linear oxidation law holds in all cases , which indicates the complete
absence of protective action by low melting and volatile oxides ReO3 and
Re2O7. During the sublimation of rhenium heptoxide the authors of /6 /
observed crystals in the form of monoclinic prisms and thick fibrous
crystals growing in light - yellow clusters . For each temperature two linear
rates are normally observed, the second of these characterizes the
stabilized oxidation process (Table 123 ) .
TABLE 122. Oxidation rate of rhenium
Testing tempera- Testing time, Oxidation rate ,

ture , ° C hr g /cm²/hr
300 1 -0.0005
600 1 0.0117
900 1 1.17
1200 0.5 2.56
1500 0.25 5.24
From the temperature dependence of the constants of the linear oxidation

rate /6 ), the values of the apparent activation energy were computed, and
also the pre - exponential factor of the Arrhenius equation . Equations
characterizing the oxidation process were obtained : K = 1.151 · 103 .
exp -17320/Rt for the oxidation of recrystallized rhenium at 400 — 725°C,
and K = 3.29 · 103 exp-18060 /RT for the oxidation of cold- worked rhenium at
400 - 650 °C .
344
TABLE 123. Constant of the linear law of the oxidation rate of rhenium
Oxidation
K , g/cm² .hr . 10-3 Oxidation
K , g /cm².hr . 10-3
temperature tem perature
recrystallized cold -worked recrystallized cold - worked
350 4,44 575 53.5 64.2

400 2.67 5.0 600 58.2
475 8.15 18.7 625 61.1 93.8
500 23.7 650 102.7 233.3
525 22.7 55.0 725 173.5
Rhenium reacts with oxygen in the following stages /6 /: 1 ) diffusion of

oxygen molecules to the surface ; 2 ) primary chemical reaction of rhenium
with oxygen (O2 ); 3 ) adsorption and ionization of the gas on the film surface;
4 ) electrochemical reaction of scale formation, accompanied by secondary
oxidation - reduction reactions in the Re - system ; 5 ) vaporization and
desorption of volatile oxides; and 6 ) diffusion of products from the surface .
From the values of the apparent activation energy the authors of /6 /
assume that the slowest , and therefore the rate - determining stages , are
the fourth and fifth , which kinetically are inseparable in linear oxidation .
The electrode process on the rhenium anode also has a marked influence
on the operation of the high- temperature galvanic cell Me ( MeO )o, and the
kinetics of the total oxidation process , since the film of molten Re207
present on the surface of the sample is a strong electrolyte .
From the values of the oxidation rate constants the authors of /6 /
conclude that at the final temperatures the electromotive force ratio , i . e . ,
the ratio of the reaction energies for the Me ( MeO )O circuit of the high
temperature galvanic cell of the cold - worked and recrystallized rhenium ,
is approximately equal to two .
In /7 / it is also noted that the oxidation of rhenium proceeds at the grain
boundaries and on the surface of the grains . The oxidizability of rhenium
at the grain boundaries on heating in the air causes intergranular failure
during hot working .
We should note that sintered and cast rhenium do not tarnish on heating
in the air to approximately 300°C , and can be stored in the air for a long
time. Rhenium produced as a galvanic coating /7 / tarnishes rather rapidly
in the air . To avoid tarnishing the rhenium should be preheated in a hydrogen
atmosphere to complete reduction of the oxide residues present in the
electrolytic rhenium .
2. Corrosion resistance of rhenium alloys
Oxidation of molybdenum - rhenium alloys . The oxidation

of molybdenum - rhenium alloys was studied on cast and deformed alloys of
molybdenum with 50% Re and on metal of molybdenum welds alloyed with
different amounts of rhenium (up to 50% ) .
The formation and the behavior of oxides differ for molybdenum and
rhenium on heating . When molybdenum is heated oxide formation begins at
400 – 450°C or higher . At 777 °C the MoO3 – M0O2 eutectic begins to melt .
345
For rhenium oxide formation starts even at 160° C , and at a temperature
of approximately 300°C the lowest-melting rhenium oxide Re2O7begins to melt .
Consequently, alloying the weld with rhenium will change the oxidation
process .
In /8 / the oxidation of welded joints was studied on specimens cut from
sheet molybdenum and Mo — 50% Re alloy, and on welded joints with various
rhenium contents . The specimens were
heated in air for 10 minutes at 300 , 500,
A6 /F, mg/cm ?
90 and 800°C . The oxide films formed on
the surface of the heated samples were
80 removed by pickling . The results of the
experiment are given in Figure 146. On
70 the Y - axis we show the ratio of the
weight of oxides ( in mg ) to the surface
60 area (cm² ) . The surface of the weld is
30 — 40% of the surface of the sample .
The rhenium content has little influence
50
on the rate of oxidation of welded joints
40
up to 500°C . This rate differs little from
that of the base material. At a tempera
ture of 800 °C the oxidation increases
30
sharply . With increase in the rhenium
content the rate of oxidation of the metal
20 of the weld increases .
Oxidation of tungsten - rhenium
10 alloys . In /9 / the authors studied the
1 2 3 4 5 oxidation at 650° C for 7 hours of sintered
0
300 500 800 1 ,° C alloys made of 218- W (tungsten with an
admixture of potassium , aluminum , and
FIGURE 146. Oxidation of alloys of molyb silicon ) and 0 – 20% Re in a current of
denum with varying rhenium contents in the dry air ( flow rate 600 cm3 / min ) . The
air at high temperatures : results of the oxidation tests (given as
weight gain ) are shown in Table 124 and
1 – molybdenum as base material ; 2 -
molybdenum as weld joint; 3 – weld con and Figure 147 .
taining 250% Re ; 4 – weld containing 50 % Re; The table shows that the addition of
5 – alloy of molybdenum with 50 % Re as rhenium decreases the oxidizability of
basis material, tungsten by a factor of 6 – 7 .
The vaporization of sintered alloys of
tungsten 218- W with 0 – 20% rhenium
was studied in / 9 / . It was found that alloying with rhenium ( less than 20% )
decreases the rate of weight loss of the material in a vacuum of 1 – 10 mm
Hg at 2800 – 3000°K (Table 124 ). It is also noted that the initial erosion
under such testing conditions includes oxidation , since there are residual
gases in the chamber .
In /26 / it was found that alloys of tungsten th 5 and 26% Re can operate
in contact with Al2O3, BeO, MgO, Y203, and Tho of commercial purity at
temperatures of the order of 1500°C for 1000 hours without corroding. Some
data /27 / on the corrosion resistance of rhenium and its alloys with tungsten
in contact with alundum ( Al2O3 ) and in the presence of water vapor
("water cycle " ) are given on pages 281 , 289.
346
TABLE 124. Oxidation of alloys of tungsten with rhenium
Rhenium content , Increase in
%
Weight loss , %
oxidation , %
218 - W alloy
(without rhenium ) 15.3 2,18
1 7.8 1.38
3.5 1.4
2.5 1.3
-
-
7
10 1.8 1.63
20 2.1 2.4
Protective coatings on rhenium were studied in /10, 11 ). Due to

the high oxidizability of metallic rhenium and its alloys , protection is
necessary during operation at high
temperatures . Coatings were produced by
25
methods of diffusion treatment : boronizing,
chromizing, siliconizing, and calorizing
(page 329 ) .
Weight
2 Tests on the resistance of the boronized

,gain
%
layers to scaling were carried out at 950°C

for 24 hours in the air ; it was found that
the surface of boronized metals is in a
better state than that of untreated metals ,
and is covered by a compact thin vitreous
700 900 1100 film / 10, 11 /. Only reddish - brown films of
1, ° C the untreated rhenium were left after 10 hours
FIGURE 147. Temperature dependence of heating at 1000° in the air , whereas
of oxidation in the air of 218- W ( 1) under the same conditions the boronized
and the alloy of 218 - W with 3% Re ( 2 ) rhenium loses only 288 g / m² . Thus , the
(given as weight gain ) /9/. stability of boronized rhenium to oxidation
increases almost five times . In Figure 148
we show the resistance of rhenium to scaling
at 800°C . Chromizing also resulted in a striking increase in the resistance
of rhenium to oxidation ( see Figure 148 ) /11 /. The calorized and siliconized
rhenium specimens show almost as low a resistance to scale formation as
untreated rhenium / 11 / ( Figure 148 ) . The oxidation products ofthe calorized
and siliconized layers consist of a grayish ash.
Data on the resistance of siliconized specimens to scaling agree well
with those obtained by studying the oxidation rate of alloys of rhenium with
silicon .
Alloys of rhenium with silicon were studied in /12 /. It was found that
the oxidation rate of rhenium decreases with increase in the silicon content ,
but remains considerable until the ReSiz compound is formed . The ReSiz
compound becomes completely oxidized at 1000°C in oxygen in the course
of 90 hours .
In / 13 / tests were carried out on the heat resistance of nickel- chromium
rhenium alloys ( 20% Cr ) . Cylindrical specimens 8 mm in diameter and 12
12 mm high were heated in the air at 1200°C for 50 hours . The heat
resistance was determined by the weight gain . It was found that rhenium
347
in amounts of 5 – 8% is a useful alloying addition to chromium- nickel alloys ,
and considerably increases the heat resistance and the long- time strength ,
but does not decrease the ductility or workability.
2000 50
Cr Cr
0 0
B
Change
2000 50
B
in²
m,g/wt
4000 100
6000 150
AL Re
8000 200
Re si
10 000 250
13 100 g/m² after 6.5 hr
12000 300
2 4 6 8 10 2 6 8 10
Duration of test , hr
FIGURE 148. Oxidation of menium at 800 ° C after different diffusion treatments /11/ .
3. Corrosion of rhenium in acid and alkaline solutions
The reaction of rhenium with various reagents depends greatly on the

state of the rhenium, the particle size of rhenium powder or the method
of production of the compact material, and the degree of purity .
The corrosion resistance of rhenium and its alloys in acids and alkalis
was studied in / 14, 15 /.
Cast rhenium is most resistant to corrosive media, sintered rhenium
is less resistant , and rhenium powder least . The activity of rhenium powder
depends on the completeness of the reduction of rhenium . Rhenium which
has not been completely reduced is very hygroscopic, and absorbs water
readily . This leads to the formation of perrhenic acid HRO4. Metallic
rhenium powder reduced from either ammonium or potassium perrhenate
should therefore be stored in glass jars with a ground glass stopper , sealed
with paraffin .
Compact metallic rhenium is slightly soluble in concentrated hydrochloric ,
sulfuric , and hydrofluoric acids / 14 /, and in organic acids such as the
oxalic , acetic , or citric . Rhenium is slightly attacked by hot sulfuric acid .
In nitric acid it dissolves vigorously .
On prolonged holding at room temperature ( for not less than several
hours ) rhenium reacts with alkalis , especially in the presence of potassium
ferricyanide . Rhenium reacts actively with fused alkalis /14 /. The
authors of / 15 / found the effect of hot concentrated acids and of fused
alkalis on ReGez . Only hot concentrated sulfuric acid and fused sodium
hydroxide react with this compound .
The authors of / 16 / studied the corrosion resistance of rhenium and
its alloys with molybdenum prepared by sintering and by arc and electron
beam melting. They investigated their stability in dilute boiling acid solutions .
These solutions were freshly prepared every day and had a constant pH .
348
8
0.3
resistance
corrosion
a
/yLinear
,mearm
4
0.1
21 28
0.5
0.3
0.1
O 7 21 28
Exposed to corrosion , days
FIGURE 149. Corrosion resistance in a 20 % solution of

H2SO4 ( a ) and in a 30 % solution of Hci (b ) of molyb
denum - rhenium alloys / 16 /:
1 - rhenium , electron - beam melted ; 2 – Mo - 50 % Re ,
electron - beam melted ; 3 - Mo - 40 % Re , electron
beam melted; 4 – Mo - 20 % Re , electron - beam melted;
5 – Mo - 30 % Re , sintered and deformed; 6 – Mo - 30 %
Re , sintered , deformed , and annealed at 1100° (5 min );
7 - Mo - 10 % Re , electron -beam melted ; 8 – Mo
15 % Re, sintered and deformed; 9 - Mo- 15% Re ,
sintered , deformed and annealed at 1100 ° C (5 min ) .
In a 30% solution of nitric acid cast specimens corroded in the course

of a few minutes , but in a 20% solution of sulfuric acid (Figure 149a ) , and
in a 30% solution of hydrochloric acid ( Figure 149b ) the sintered and cast
specimens were tested for up to 28 days , and the corrosion rate either
decreased or remained the same during the process of testing . Sintered
specimens had a better corrosion resistance than electron- beam melted
specimens ( except the alloy containing 10% Re ) . Under these conditions
pure rhenium had the highest corrosion resistance . The presence of the
o - phase in the alloy of molybdenum with 50% Re did not impair its
corrosion resistance in boiling dilute acids . These data require checking .
4. Effect of molten metals on rhenium
It has been found that rhenium does not react with liquid gallium at
800 °C /17 /
349
The corrosion resistance of compact (cast and sintered ) rhenium and
of rhenium powder to gallium at high temperatures was studied in /18 /.
It was found that if rhenium is heated in liquid gallium at 800°C and 1100°C
for 50 hr it scarcely dissolves and does not change its external appearance .
Suitable tests were also carried out in liquid gallium with molybdenum ,
steel, and nickel plates, electroplated with rhenium on all sides / 18 /. For
comparison , molybdenum, steel, and nickel plates without rhenium
coatings were also tested under the same conditions , molybdenum at
1100°C , nickel and steel only at 300°C (as at a higher temperature they
dissolve ) . A metallographic analysis of the coatings showed that rhenium
coatings are sufficiently dense and do not have any continuous pores .
| However, at higher temperatures gallium penetrates under the coating
and corrodes the base metal . This is explained by the formation of cracks
in the coating at these testing temperatures ( 1100°C ) . However, in all cases
rhenium retards the corrosion process . Under the same conditions the
corrosion proceeds deeper in uncoated specimens , and the content of the
metal being tested in gallium is also higher . Evidently, a stronger adhesion
of the rhenium coating to the base metal ( for example, in rhenium - plating
of high- melting metals ) increases the protection against corrosion in
gallium .
Rhenium corrodes , and partially diffuses, in molten lithium /19 /. We
also know that rhenium dissolves only slightly when heated in lead at
300° C for 1 hour, and in zinc at 520 ° C for 1 hour . Rhenium is insoluble in
molten silver (at 1060°C ) and copper ( 1180°C ) , but is completely soluble in
molten nickel (at 1550°C ) and iron (at 1640°C ) /20 /. Rhenium forms an amalgam
with mercury /21 /. When heated to 300°C in a reducing atmosphere
rhenium does not react with mercury /22 /.
Rhenium reacts vigorously with and is completely soluble in molten
titanium , zirconium, hafnium, vanadium, tantalum , niobium, chromium ,
molybdenum , tungsten, iron, nickel, cobalt, ruthenium, rhodium,
palladium, osmium, iridium , and platinum /23 /.
Rhenium is almost insoluble in molten gold, so that it can be used in
contact with molten gold /24 /.
The authors of /25 / also studied the corrosion of rhenium in lithium .
They found that rhenium has a high resistance against corrosion in molten
lithium at 538 — 1000°C under static conditions . The authors of /25 / placed
metals according to decrease in corrosion resistance in lithium in the
following series : beryllium , chromium , cobalt, niobium , iron, molybdenum ,
rhenium, tantalum , titanium, tungsten, vanadium, and zirconium .
Bibliography for Chapter XXII
1. Jaffee , R.I. , D.J.Maykuth , and R.W.Douglass . Refractory

Metals and Alloys , pp . 383 — 463. – N. Y. , Interscience Publishers.
1961 .
2. Sims , c.T. et al. Investigation of Rhenium . – Progr.Rept. to
Aeronaut . Res . Lab .WADC ., Contract AF- 33 ( 616 ) 323, Battelle
Memor . Inst . Columbus . 1955 — 1956 .
3. Levine , D.J. and R. G. Frank . ( Private Communication in Paper by
J.M. Pugh ) . – J. Metals , 10 ( 5 ) : 335 – 340. 1958 .
350
4. Congina , 0. A. Redkie metally ( Rare Metals ) . - Metallurgizdat .
1955 .
5. Shelton , R. A. J. Brit.J. Metals . 1957 .
6. Frantsevich , I. N. and V.A. Lavrenko . In : Sbornik " Issledo
vaniya po zharoprochnym splavam ," 4 : 323 – 339, Izdatel'stvo AN
SSSR . 1959 .
7. Sims , C.T. , C. M. Graighhead , and R. I. Jaffee . J. Metals ,
7 : 169 - 179 , 1955 .
8. D'yachenko , V.V. , B. P. Morozov , M. A. Tylkina , and E. M.
Savitskii . Svarochnoe Proizvodstvo , No. 7 : 1 – 4. 1962 .
9. Pugh , G.W., L.H. Amra , and D. T. Hurd . Trans . ASM, 55 ( 1 ) :
451 - 461. 1962 .
10. Minkevich , A.N. – Metallovedenie i Termicheskaya Obrabotka ,
No.8 : 9 – 15. 1961 .
11. Minkevich , A.N. , M. A. Tylkina , L. N. Rastorguev , and G. P.
Rodionova . In : Sbornik " Renii," p . 221 , Moskva , Izdatel ' stvo
Nauka . 1964 ,
12. Knapton , A.G. Plansee Proceedings . 1958. p . 412 . London,
Pergamon Press . 1959 .
13. Tylkina , M. A. and E. M. Savitskii . – In: Sbornik " Redkie metally
i splavy," p . 80 , Metallurgizdat . 1959.
14. Sims , C.T. In : Rhenium . Van Nostrand ( editor ) . Amsterdam
N. Y. , Elsevier Publ . Co. 1962 .
15. Searcey , A.W. , R. A. McNees , and J. M. Criscione . J. Amer .
Chem . Soc . , 76 : 5287 . 1954 .
16. Class , J. and G. Böhm . – Planseeber . Pulvermetallurgie , B10 ( 3 ) :
144. 1962 .
17. Wilkinson , W.D. - J. Inst . Met . 1954 ; Met . Abstr . , June , 881 , U.S.
Atomic Energy Commission Publ . ( ANL- 5027 ) . 1953 .
18. Sominskaya , Z.M. and A. A.Nikitina . – In: Sbornik "Renii,"
pp . 90 – 96, Moskva, Izdatel ' stvo Nauka . 1964 .
19. Gresse , A. V. Naturforsch . , 8 : 533 — 536 , 1953 .
20. Sims , C.T. and R.I.Jaffee . J. Metals , 8 (8 ) : 913 – 917. 1956 .
21. Holmann , S.H. Z. anorg. Chem . , 202 : 277 – 291. 1931 .
22. Heyne , G. and K. Moers . Z. anorg . Chem ., 196 : 157. 1931 .
23. Tylkina , M. A. and K. B. Povarova . - In: Sbornik " Renii," p . 127 ,
Moskva, Izdatel'stvo AN SSSR . 1961 ,
24. Halland - Nell , U. and F. Sauerwald . - Z. anorg . Chem . , 276 : 155 .
1945 .
25. Hoffman , E. E. Corrosion of Materials by Lithium at Elevated
Temperatures . Oak Ridge Natn . Lab . Tenn . March 23, 1959; Nucl .
Sci . Abstrs . , 6570. 1963 .
26. Fornwalt , D. E. , B. R. Gourley , and A. V. Manzione . A Study
of the Compatibility of Selected Refractory Metals with Various
Ceramic Insulation Materials.- Presented at Electron Microprobe
Symposium of Electrochemical Society Meeting, Washington D. C. ,
October 1964 .
27. Gaines , G. V. Rhenium in Electronics . In : Rhenium, p . 139,
Amsterdam - N.Y., Elsevier Publ . Co. 1962 .
351
Chapter XXIII
CATALYTIC PROPERTIES OF RHENIUM
In the Soviet Union, East Germany, and the USA, research is being
carried out on the catalytic properties of rhenium and its compounds . In
East Germany this is mainly in order to replace platinum catalysts in
certain processes . In the literature there are several reviews on rhenium
catalysts / 1-4 /.
The catalytic properties of rhenium were first studied in the hydrogenation
and dehydrogenation of hydrocarbons /5-7 .
Rhenium sulfides have a high catalytic activity in the dehydrogenation of
alcohols to aldehydes and ketones . Platonov et al . /8 – 15 / found that in
the dehydrogenation of methyl, ethyl, and isopropyl alcohols in the presence
of rhenium sulfides it is possible to produce formaldehyde, acetaldehyde,
acetone , and other products in good yields .
Balandin et al . developed certain theories on the catalytic effect of
rhenium / 1 , 16 — 19, 23 /. On the basis of the multiplet theory, Balandin
foretold the dehydrogenating properties of rhenium for six- membered
cyclic hydrocarbons . This was verified by experiment : rhenium deposited on
activated carbon proved to be an active catalyst for the dehydrogenation of
cyclohexane and its homologues / 16 – 18 /. Catalysts were tested on various
carriers prepared by different methods . Rhenium was deposited on activated
carbon in the form of ammonium perrhenate , or as a complex of rhenium
heptoxide with dioxane / 16 /. Balandin , Karpeiskaya, and Tolstopyatova / 19 /
studied the kinetics of the dehydrogenation of cyclohexane, methylcyclo
hexane , and ethylcyclohexane , on the rhenium - dioxane catalyst . The reaction
rate decreased , but the activation energy increased with increase in the
molecular weight of the hydrocarbon / 1 , 19 ). The same catalysts can be
used in the dehydrogenation of side chains of alkyl- aromatic hydrocarbons ,
dehydrocyclization of paraffins , and the production of y- butyrolactone from
butanediol- 1,4 / 1 /.
The properties of rhenium as a hydrogenation catalyst were studied in
/20 — 24 /. It was found that in the colloidal state rhenium can dehydrogenate
maleic and cinnamic acids at room temperature /20, 21 /. The authors of
/23 / studied the hydrogenation properties of the rhenium catalyst produced
from the dioxane complex with rhenium heptoxide , as well as of the
skeletal catalyst prepared for the first time by leaching the rhenium
aluminum alloy ( 50% rhenium ) . These two catalysts are effective in the
hydrogenation of compounds containing a double bond , carbonyl and
carboxyl groups , and an aromatic nucleus .
352
Broadbent et al . /24-27 ) thoroughly studied rhenium sulfides and oxides
as catalysts . In the presence of these catalysts it is possible to reduce
unsaturated compounds and compounds containing carbonyl and nitro groups ,
without breaking the carbon- sulfur, carbon- halogen , or carbon- nitrogen
bonds .
Ryashеntseva, Minachev , Kalinovskii , et al . showed that it is possible
to produce secondary amines of the thiophene series by the reduction of
the corresponding azomethines , as well as the products of alkylation of
p -phenylenediamine with acetone in the presence of rhenium heptasulfide /42/.
Today rhenium is considered promising as a catalyst of the following
processes : hydrocracking, alkylation, and reforming.
Hydrocracking . Rhenium catalysts have a high activity in the
hydrocracking of heavy hydrocarbon fractions into light ones . These
properties of rhenium catalysts were first described in a German patent
128 / and in a number of papers /29 – 33 /. Hydrocracking was carried out
using refined medium oils under medium or high pressures of hydrogen
( 50 and 275 atmospheres ) at temperatures of 400 – 370°C for 7, 24, and
48 days /29 /. Under high pressures catalysts of the following composition
were used : 10% tungsten sulfide applied on activated clay which had been
impregnated with HF (the catalyst normally used in industry ) with the
addition of 1 ) 3 g Re per liter of catalyst with 5 % MoO3; and 2 ) 10 g Re per
liter of catalyst . With rhenium catalysts a much larger yield of the liquid
product ( 82 – 87% instead of 81 % ) was obtained, and the octane number
increased to 72.7 instead of 70.9 . For industrial use of the rhenium
catalyst , 3 – 5 kg of rhenium are required per mº of the catalyst .
At medium pressures catalysts of the following composition were tested :
Al2O3 + 12% MoO3 (catalyst normally used in industry ) and the experimental
catalysts : 30% SiO2 + 70% Al2O3 + HF + Re ( 3 g / 1 ); 30% SiO2 + 70% Al2O3 + Re
( 3.2 g / 1) . Rhenium catalysts had advantages over industrial catalysts : a
higher total yield of the liquid product ( approximately 90% instead of 78% ),
a higher octane number of the naphthene fraction at temperatures below 180° C
( 74 – 75 instead of 60 ), and a higher cetane number at temperatures above
180° C ( 45–47 instead of 19 ) . Research workers believe that for practical
use in hydrocracking under medium pressures , rhenium catalysts must be
produced with a higher stability, with a longer life before it need be
regenerated /29 /.
Dealkylation . Preliminary experiments on the possible use of
rhenium catalysts for dealkylation of toluene to benzene were carried out
in East Germany /32 /. A catalyst containing 2 g Re or platinum per liter
of catalyst was used . The reaction proceeded at 600 ° C under atmospheric
pressure . On the rhenium catalyst benzene forms at high flow rates only .
Research workers believe that the further development of work in this
direction is promising .
Reforming . A large number of papers by Soviet and German
scientists describe rhenium catalysts in the transformation of hydrocarbon
mixtures under pressure of hydrogen / 16 , 28, 40 /.
The rhenium- alumina catalyst treated with hydrogen sulfide and containing
20 % Re /30 / is highly active . At 500°C and at a hydrogen pressure of
5 atmospheres (H2 : HC = 5 : 1 ) it is possible to produce up to 76% benzene
from cyclohexane , and 52.5 % benzene from methylcyclopentane /30 , 40 /.
However , this catalyst becomes less active with time (approximately
353
200 hours ) . Certain authors /4 / believe that the introduction of 20% Re
into the catalyst is excessive . A German patent /34 / is proposed for a
reforming catalyst containing 3 — 40 g Re per liter of catalyst . However,
this catalyst is less active than the industrial platinum catalysts used for
reforming.
As rhenium today is still rather expensive , in the Soviet Union research
has been carried out on the use of rhenium as an additive to aluminum
palladium catalysts . A rhenium- aluminum- palladium catalyst , containing
1 % Re , 1% Pd on fluorinated ( 0.4% F ) aluminum oxide , treated with hydrogen
sulfide /40 /, was found to be an active and sufficiently stable catalyst in the
dehydrogenation of cyclohexane and methylcyclohexane , the dehydroiso
merization of methylcyclopentane , and the isomerization of p - hexane. The
benzene yield from cyclohexane is 87% , and from methylcyclopentane it is
61.2% /40 /. The toluene yield from methylcyclohexane is 90%, and the
isohexane yield from p- hexane is 52% /38 /. The introduction of 1% Re into
the aluminum-palladium catalyst increases its stability during benzene
reforming almost 4 times / 39 /. This catalyst also had a high activity under
conditions of reforming the 71 – 102°C fraction of the Karadag benzine in a
fluidized bed of the catalyst . As a result of reforming, it is possible to
increase the aromatic hydrocarbon content in the reformed benzine to
5 times that in the initial fraction. After 100 hours of operation the catalyst
is regenerated, and its activity is completely restored /41 /.
A method has been developed for the separation of rhenium from the
rhenium- alumina / 35 / and rhenium- sulfide- alumina catalysts /37 /.
CONCLUSION
Rhenium catalysts are not yet used in industry because of the high cost
of rhenium . Rhenium catalysts have not been sufficiently widely studied in
various reactions . However , even today the trends in the use of rhenium in
catalysts as a promoting addition to certain catalysts have been outlined .
Small amounts of rhenium greatly increase the catalytic effect /42 /. The use
of small amounts of rhenium in the palladium- rhenium catalysts is also
feasible /40 /. We should also note that rhenium is the only metallic catalyst
which does not become poisoned by sulfur, selenium, and arsenic .
The authors wish to express their gratitude to M. A. Ryashеntseva and
E. I. Karpeiskaya for their valuable advice in the writing of this chapter .
Bibliography for Chapter XXIII
1. Balandin , A. A. and E.I.Karpeiskaya . – In : Sbornik " Renii,"

2. Blom , R. H. , V. Collonisch , and C.H. Kline . Ind . Eng . Chem .,
54:16 . 1962 .
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i analiticheskoi khimii ( The Use of Rare Elements and Titanium
in Chemical Industry, and Analytical Chemistry) . Survey. -
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– Zh Kh, 6 : 1059 . 1936 .
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- ZhoKh , 6 : 855 . 1936 ,
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1937 .
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7 : 2895 . 1937 .
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Doklady AN SSSR , 122 : 227 . 1958 .
17. Balandin , A. A. - Uchenye Zapiski MGU , No. 175 : 97. 1956 .
18. Balandin , A. A. , E. I. Karpeis kaya , and A. A. Tolstop yatova .
– Izvestiya AN SSSR , OKhN , pp . 1365, 1529. 1959 .
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– ZhFKh , 33 : 2471 . 1959.
20. Zenghelis , C. and E. Stathis . Chem . Abstr . , 33 : 8081 . 1939 .
21. Zenghelis , C. and E.Stathis . - C.r. , 209 : 797 . 1939 .
22. Ni , P.F. and D.V.Sokol'skii . Izvestiya AN Kaz . SSR , Seriya
Khimicheskaya, No. 1 ( 3 ) . 1946 , 1958 .
23. Balandin , A. A. , E.I.Karpeiskaya , and B. D. Polkovnikov .
Doklady AN SSSR , 139 ( 5 ) : 1101. 1961 .
24. Broadbent , H.S. , G.C.Campell , W.J. Bartley , and J.H.
Johnson . J.Org . Chem ., 24 : 1847 . 1959.
25. Broadbent , H.S. and J.H.Johnson . J. Org. Chem . , 27 : 4400 ,
4402. 1962 .
26. Broadbent , H.S. , L.Slaugh , and N. L. Jarvis . – J. Am . Chem .
Soc . , 76 : 1519 . 1954 .
27. Broadbent , H.S. and G.W.Whittle . - J. Am . Chem . Soc . , 81 :
3587. 1959 .
28. Drescher , K. , H.Hummel, G.Rossmanith , and H.Sander .
Patent of the G. D. R. , No. 17295. 1959 .
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Izvestiya AN SSSR , OKN, p . 147. 1960 .
31. Minachev , Kh . M. , M. A. Rya shentseva , and V. A.Petukhov .
– Izvestiya AN SSSR , OKEN , p . 1307. 1961 .
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Leuna -- Merseburg, 3 : 329 . 1960 — 1961 .
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Leuna – Merseburg, 2 : 465 . 1959 – 1960 .
34. Hummel , O. Patent of the G. D. R. , No. 11796. 1956 .
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1960 .
355
36. Minachev , Kh . M. and M. A. Rya shentseva . Izvestiya SSSR ,
OKEN , pp . 103, 107. 1961 .
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— Izvestiya AN SSSR , OKUN , p . 1673. 1961 .
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Literature on the Analytical Chemistry

of Rhenium
Lebedev , K. B. Renii (Rhenium ) . – Metallurgizdat . 1960 .

Obolonchik , V. A. Renii (Rhenium ). Kiev , Izdatel'stvo AN USSR .
1961 .
Sbornik " Metody opredeleniya i analiza redkikh elementov, " Izdatel ' stvo
AN SSSR . 1961 .
Sbornik "Renii," pp . 214 - 274 , Izdatel'stvo AN SSSR . 1961 .
Sbornik " Renii," pp . 231 — 254, Izdatel'stvo Nauka . 1964 .
Tarayan , V.M. and S. V. Vartanyan . Zavodskaya Laboratoriya ,
No. 11 : 1301 . 1964 .
Rabchikov , L. W. and L.W.Borisova . Talanta , 10:13 . 1963 .
Rhenium , p . 191 . Amsterdam New York . 1962 .
356
EXPLANATORY LIST OF ABBREVIATED NAMES OF USSR INSTITUTIONS,
JOURNALS , ETC. , APPEARING IN THE BIBLIOGRAPHIES
Abbreviation Full name (transliterated) Translation
DAN SSSR Doklady Akademii Nauk SSSR Proceedings of the Academy

of Sciences of the USSR
Izd . AN SSSR Izdatel'stvo Akademii Nauk Publishing House of the

SSSR Academy of Sciences of
the USSR
Izv . AN SSSR Izvestiya Akademii Nauk SSSR Bulletin of the Academy

of Sciences of the USSR
Izv . AN KazSSR Izvestiya Akademii Nauk Bulletin of the Academy of

Kazakhskoi SSR Sciences of the Kazakh
SSR
IL Izdatel'stvo Inostrannoi Li Foreign Literature Publishing

teratury House
IONKh Institut Obshchei i Neorgani Kurnakov Institute of

cheskoi Khimii imeni General and Inorganic
N. S. Kurnakova Chemistry
ONT Otdel Normirovaniya Truda Department of Labor Norms
ONTI Ob" edinenie Nauchno Association of Scientific

Tekhnicheskikh Izdatel'sty and Technical Publishers
SPb Sankt - Peterburg St. Petersburg
TSIINTsvetmet Tsentral'nyi Institut Informatsii Central Information Institute

Tsvetnoi Metallurgii of Nonferrous Metallurgy
TSINTIEP Tsentral 'nyi Institut Nauchno Central Institute of Scientific

Tekhnicheskoi Informatsii and Technical Information
Elektrotekhnicheskoi Pro of the Electrical Engineer
myshlennosti i Priborostro ing Industry and Instrument
eniya Makers
Ukr SSR Ukrainskaya SSR Ukrainian SSR
357
Abbreviation Full name ( transliterated ) Translation
ZhETF Zhurnal Eksperimental'noi i Journal of Experimental and

Teoreticheskoi Fiziki Theoretical Physics
ZhFKh Zhurnal Fizicheskoi Khimii Journal of Physical Chemistry
ZhNKh Zhurnal Neorganicheskoi Khimii Journal of Inorganic Chemistry
ZhPKh Zhurnal Prikladnoi Khimii Journal of Applied Chemistry
358
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Translated from Russian

Published for the U.S. Department of the Interior

Translated from Russian

Israel Program for Scientific Translations

Translated by Ch . Nisenbaum, Chem . Eng .

Printed in Jerusalem by IPST Press

Chapter 1. Sources of Rhenium 8

2. The geochemistry of rhenium . 8

Chapter II. Industrial Sources of Rhenium 10

1. Molybdenum concentrates and the products of their treatment 10

2. Copper concentrates and products of their processing 11

Chapter III. Extraction of Rhenium 12

1. Extraction of rhenium from molybdenite concentrates and

2. Extraction of rhenium from copper concentrates and from

4. Extraction of rhenium from solutions by cementation 14

5. Ion exchange and sorption 14

6. Chlorination of dust with sublimation of rhenium chlorides . . 15

Chapter IV . Production of Metallic Rhenium 20

1. Reduction of potassium perrhenate by hydrogen 20

3. Reduction of ammonium and potassium perrhenates by

4. Electrolytic production of rhenium 23

5. Thermal decomposition of rhenium compounds 24

6. Methods for the production of very pure rhenium 24

Chapter V. Production of Metallic Rhenium . 27

Chapter VI. Plastic Deformation of Rhenium 33

Chapter VII . Chemical Properties of Rhenium . 52

3. Compounds of rhenium with carbon O . 59

7. Compounds of rhenium and nitrogen . 64

10. Thermodynamic characteristics of compounds of rhenium with

12. Melting and boiling points 71

13. Crystal structure of rhenium compounds 71

15. Magnetic properties of rhenium compounds . 74

Bibliography for Chapter VII . . 75

Chapter VIII . Physical Properties of Rhenium 80

3. Boiling point and vapor pressure 83

12. Optical properties . 96

Chapter IX . Mechanical Properties of Rhenium 99

Chapter X. Binary Phase Diagrams 110

Chapter XI. Ternary Phase Diagrams . 154

1. Ternary phase diagrams of rhenium - tungsten and a third

Chapter XII . The Reaction of Rhenium with Some Elements . . 165

1. Formation of compounds in rhenium - containing alloys 165

Bibliography for Chapters X – XII 172

4. Preparation and deformation of alloys of rhenium with

6. Production and deformation of alloys of rhenium with niobium ,

Chapter XIV . Mechanical Properties of Rhenium Alloys • 198

10. Manganese -rhenium alloys 224

Chapter XV . Weldability of Rhenium and Its Alloys 232

4. Welding ternary tungsten -molybdenum -rhenium alloys 235

5. Rhenium alloying of molybdenum weld metal . 235

6. Welding titanium alloys . 238

Chapter XVI . Elastic Properties and Thermal Expansion of Rhenium

4. Characteristic temperature of molybdenum - rhenium and

7. Thermal expansion of molybdenum - rhenium alloys 246

Chapter XVII. Physical Properties of Rhenium Alloys . 251

1. Electrical resistivity of alloys of rhenium with molybdenum

7. Superconductive rhenium alloys 262

Chapter XVIII. Use of Rhenium and Its Alloys in Electronics and

3. Rhenium as the base of high - temperature cathodes 281

1. Thermocouples made of rhenium coupled with noble metals 296

3. Thermocouples made of tungsten coupled with a tungsten