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04
SOLUTION THERMODYNAMICS
05
!.
TaCx-
I i I
I
0.6 07 0-8 0,9 1,0
C/TQ atom ratio
239
FIGURE 2, The results for the heats of formation of TaCx as a function of composition
(92). The dotted line represents the functional relationship given in the text.
also fts their results for tantalum monocarbide within the experimental error
(Figure 2) .
The connotation of the simple two-term expression for the heat of forma
tion per mole of a nonstoichiometric carbide is that since the heat of mixing
per g
'
atom AHM is given by
(
Xc is the atom fraction of carbon)
and from the standard thermodynamic equation
it follows that if
AHO a + bx then AHc b
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240 ALCOCK
These results therefore i ndicate that the working model for a nonstoi
choimetric carbide or nitride phase over a wide range of composition should
be that the partial molar heats of solution of the components should be
constant. I t has been previously been mentioned that analyses of the thermo
dynamics of phases with a wide range of composition can be made success
fully by means of the grand partition function
.
The variation of the activity
coeficient of each component includes a partial heat of solution which may
be a function of composition. This functional dependence i s related to va
cancy-vacancy i nteraction energies when a defective compound is con
sidered. Thus, Libowitz ( 103) ascribes the dependence of the thermodynamic
properties of hydrides on composition to vacancy i nteraction energies having
the values 4.3 kcal mole
-
1 for DH3
-
o, 1. 5 kcal mole
-
1 for ZrH2
-
o, and 0. 35
kcal ' mole-1 for PdHx. Hoch ( 104) has concluded that the free energy results
for TaCx could be accounted for without such a vacancy interaction term
and thus that the partial heats of solution are constant, which i s consistent
with the calorimetric studies. The values of a obtained from these simpl e
linear expressions for the calorimetric results have no obvious structural
signifcance, and i t wil l be valuable to see if further studies show any relation
ship between IHo and a.
The studies of refractory silicides and borides at high temperatures have
been almost exclusively carried out employing vapor pressure techniques.
This is the obvious consequence of the lack of suitable gas mixtures which can
defne boron or silicon potentials. The silicides of technical importance are
those of high melting point, and the information on the compounds of
Groups IV, V, and VIE is fairly complete. For most of these silicides, Searcy
( 105) lists heats of formation which have been obtained either by second-law
calculations from vapor pressure measurements or by direct calorimetric
measurement ( 106) . Only recently has an electromotive force technique been
applied to the study of silicides, and i n this study ( 107) the thermodynamic
properties of tantal um silicides were obtained by the use of a solid oxide
electrolytes. Levine and Kolodney studied the oxygen concentration cells
wi th electrodes made by suitable combination of the silicide phases (e. g. ,
Pt/Fe, FeO/ThOr Y20
3
/Si02, TaSi2, Ta5Si
3
/Pt) in the temperature range
900-1 100C.
The difculty associated with this study is that the oxide which is in
equilibrium with the mixed silicide phase changes across the Ta-Si composi
tion range and could also change with temperature. Si02 was shown to be
the oxide i n equilibrium with TasSi3-Ta2Si, and Ta20s with Ta2Si-Ta9Si
1
2
Clearly when the oxides of the two components of the silicide have roughly
the same stability and the heat of formation of the silicide is great, the
changing activities of the components in a given mixture could cause the
stable coexisting oxide phase to change from one element, tantal um, to the
other, silicon, across a particular temperature range. The relatively slow
rates of the solid-state reactions associated with this oxygen transfer could
lead to slowly drifting emf.
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SOLUTION THERMODYNAMICS 241
The use of the fuoride electrolyte CaF2 would add extra problems due to
the volatilities of BFa and SiF 9. I t is not surprising then that the only success
ful electrochemical study with borides or silicides has involved a metal which
forms a very stable fuoride. Aronson & Auskern ( l08) measured the free
energies of formation of thori um borides in the temperature range 800-950C
by means of the ceIIs
Th, ThF4/CaF2/ThF4, ThB6, B
/CaF2/ThF4, ThB6, ThB4
/CaFdThF4, ThB, Th(a)
OXIE SYSTEMS
The study of metaIIic oxide single phases, solid solutions, and interoxide
compounds has been a major involvement of high-temperature chemists in
the past decade. The volume of publications and the resulting wealth of
information is much lal-ger than that i n the earlier sections of this article, but
it cannot be said that the state of our knowledge in this area is far in advance
as a result .
. The two most exhaustively studied of the single-oxide systems are un
doubtedly FeOl+X and U02x. These two oxides have major technological
signifcance, and the interests of the steel and nuclear reactor industries have
been weII served in the oxide feld.
The studies of FeOl+x were originated by the classical work of Darken &
Gurry (109) , who used gas-solid equilibration, and one of the most recent is
by Fender & Riley, using solid-state electrochemistry ( 1 10) . The results of a
number of studies between these two temporal and experimental limits
( 1 1 1
-
1 13) appeared to be interpretable in terms of Fe
2
+ vacancies and Fe
3
+
positive holes, or possibly by clusters of interstitial Fea+ ions ( 1 14) . The
ordering of defects however was not contemplated, since the thermodynamic
properties I:H02 and I:S02 appeared to behave uniformly across the whole
phase feld. Fender and Riley' s latest work, however, lends support to the
suggestions of Raccah & Vallet ( 1 15) that there are three regions within the
FeOl+x phase feld which are separated by second-order transitions. These
transitions probably involve the long-range ordering of defects in a char
acteristic manner in each region.
A typical result is that shown for the composition Fe01.116 in which
I:H1/202 takes the values -61 , 020 460, -64,090 5 10, and -66,090 420
cal g atom
-
1 in the three regions. Koch (1 16) made some high-temperature
X-ray studies with single crystals of FeOI+X which gave results consistent
with the formation of a cubic superlattice having ordered vacancies in octa
hedral sites with clusters of 4Fe
3
+ ions on tetrahedral sites. There is some
evidence, then, to support the idea of defect clustering in this system at
relatively high temperatures, up to 1 350C. It appears that though the
change in partial molar heat of solution of oxygen is small going across these
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242 ALCOCK
ordered structures, the random model of point defects cannot be applied to
FeOl+x
'
The amount of work which must be applied to any metal oxide system to
determine the defect structure appears to have been increased as more de
tailed studies have opened up new problems. The electrochemical studies of
Nb20s-x by Blumenthal, Moser & Whitmore ( 1 17) indicated that the phase
was homogeneous over the concentration range Nb02
4
6
o
to Nb02.496 at
temperatures around 900e. Schafer, Bergner & Gruehn ( l 1 8), however,
concluded from gas-solid equilibrium studies at 1300C that six phases occur
in the composition range Nb02.4
1
7 to Nb02
.
5oo. The annealing times required
in the preparation of these samples were from 15 to 25 hr at 1300C. It thus
appears that the formation of the ordered defect structures could require
treatment at elevated temperatures over a long period of time. Schafer and
co-workers could not analyze their results to give separate partial heats and
entropies of solution since the studies were made at only one temperature,
but they observe that the change in free energy when one of the intermediate
phases was formed from the appropriate mixture of Nb02
.
4
1
7 and Nb02
.
6
QO
had the maximum value of 188 cal mole-
1
of the intermediate phase.
The Ce02-X ( 1 19) phase exists over the range of values of x from 0 to
0.3 at temperatures above 1 100e. At lower temperatures the ordered struc
tures of a series of compounds of general formula Ce,,02n_2 are formed. When
the basic structure is of the fuorite type, in which ordered systems of ox
ygen vacancies are formed, a new system appears for each value of n. The
partial heat of solution of oxygen per g
.
atom IH1(20z
decreases from about
- 1 15 kcal to a minimum at Ce01.6
1
of about -93 kcal and then increases
to -100 kcal at Ce01 . 76 before decreasing again. In the isostructural Pu02
-
X
phase over the same range of composition and in the temperature range 700-
1 140C, the partial heat of solution of oxygen decreases steadily from -120
kcal g atom-
1
at x =0. 02 to -89 kcal at x =0. 35 ( l20) . This range of solid
solutions does not yield a series of compounds analogous to Ce,02n
-
2 on
cooling.
Both partial molar free energies and partial molar heats of solution of
oxygen in the U02 phase have been determined separately between U02
. 000
and U02. 020 ( 121) . The results for the partial free energies have been obtained
by gas
-
solid and emf measurements with reasonable agreement; the results
for the heat (from Gerdanian & Dode 122) were obtained by use of the
Calvet microcalorimeter at 1 100e. The results suggest that between
U02.000 and U02006 the partial molar heat of solution of oxygen changes from
about - 100 to about -30 kcal g. The partial molar entropy of solution of
oxygen changes very rapidly in this region, corresponding to the behavior of
a component in a highly ordered nonstoichiometric system according to the
classical Wagner-Schottky model . The partial heat should remain constant
however i n the dilute solution range, and the calorimetric results are some
what disturbing for this reason.
As a fnal example, Zador and the author (123) found that the dioxide
phase Mo01. 999 to Mo02. 22 showed the behavior expected of a random defect
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SOLUTION THERMODYNAMICS 243
model with no appearance of intermediate phases after lengthy anneals i n
the temperature range 800 to 1050C. The partial molar heat of solution of
oxygen changed from a fairly constant value of -65 kcal g atom-1 in the
metal-rich range to -53 kcal g atom
-
1 in the oxygen-rich range.
The reduction of V02, Ti02, MoOa, and WOa leads not to the formation of
any appreciable range of nonstoichiometry, but to the appearance of a num
ber of intermediate compounds ( 124, 125). These phases, now called Magneli
phases by most authors, have compositions which ft into general formulae
such as (V, Ti)n02n-lJ (Mo, W)nOa
n
-
lJ (Mo, W)nOan
-
2. There have been very
few measurements of the two phase equilibria involving these oxides. but
Ackermann & Rauh (126) have studied some of the tungsten oxide phases,
and Katsura & Hasegawa ( 127) have studied equilibria involving V20a,
Va05, V
4
07, V509, V
6
011, and V02. Both studies were above 1000C, and
hence the establishment of the ordering of the defects should have been com
plete.
Katsura and Hasegawa measured the oxygen potentials of the two-phase
systems at 16000K by means of solid oxide electrolytes and obtained a value
of the free-energy change for the reaction which spans the phase felds of the
Magneli phases, Vn02n-1, i.e. ,
.
G
O 1
600 - 18,000 cal
Ackermann and Rauh represented their results, which were obtained by
vapor pressure measurement, for the standard free energies of formation of
the tungsten oxides by simple two-term equations, and these can be given as
W + 1 .4502 - W02 . 90
(W 20068/20)
W + 1 .3602 -t W02. 72
(W
1
8049/1 8)
.GO - 190,000 + 54. 0T cal mole-1
.GO - 182,200 + 52. 3T cal mole-1
At the mean temperature of the study, 1200C, the diference in stability
between these oxides is therefore 3600 cal mole-1 of oxygen.
DEFECT EQUILIBRIUM CONSTANTS
Within the single-phase nonstoichiometric systems, much efort has been
applied to the elucidation of defect interactions by means of the mass-action
law. What is most surprizing is that in a number of cases one value of the
constant covers a wide range of composition for one system and the use of
the term association prevails. It needs nO stressing here that the situation
is in many respects similar to that in dilute aqueous solutions of simple elec
trolytes, in which it is quite unreasonable to use the mass-action law except
under extreme dil ution. The measurable departures from stoichiometry i n
the high-temperature oxide systems constitute much higher concentrations
of defects than those which should be handled in this way. However, it is of
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244 ALCOCK
i nterest to bring together the successful representations of the experimental
data to see if there is a commonality of behavior.
The transition metal oxides MnO, FeO, CoO, and NiO have all been
studied with respect to nonstoichiometry. The phases all have the NaCI
crystal structure and only show oxygen-excess nonstoichiometry. The ease
of formation of higher-valency cations Ma+ decreases with increasing atomic
number i n this series, and the range of values of x in M01+" is limited by the
formation of the phase M30
4
, except for nickel, in which pressures greater
than one atmosphere of oxygen are required to form the higher oxides.
Manganous oxide was studied by Davies & Richardson ( 128) , who estab
lished the thermodynamics of nonstoichiometry by equilibration of the phase
with CO-C02 mixtures. At temperatures between 1500 and 1650C, the value
of x could be raised to 0.045 at the highest oxygen pressures. The mass
action constant which described the small deviations could be accounted for
by assuming a large intrinsic concentration of positive holes ( 129) and the
higher departure from stoichiometry could be accounted for by means of the
now-standard equation 1/202+2M2+2M3
+
+VM2
+
+0-. The oxygen
pressure dependence of x is thus one sixth power above MnOo
.
olo and one
quarter power below this value.
\\Tustite has been shown to be a complex phase, and the mass-action con
stant data provide very little information which helps to resolve the prob
lem. Swaroop & Wagner ( 130) fnd a one-sixth power dependence of the
vacancy concentration on the oxygen pressure at low defect concentrations;
this changes to one quarter power at higher defect concentrations. It might
be concluded, then, that the defects, the FeH ions, and the vacancies are
fully dissociated at the metal-rich boundary. Brynestad & Flood ( 131) point
out, however, that i n MgO-FeO solid solutions, the one-sixth power law
does not apply, and since the defect concentration is then lower than in
metal-rich FeOI+x, the fully dissociated model should be applicable a for
tiori.
Their alternative suggestion is a "blocking" model based on a fully asso
ciated complex. It is assumed that two Fe3+ ions are always fully associated
with each ferrous ion vacancy, and that each vacancy blocks the nearest
neighbor cation sites from occupation by another vacancy. The mass-action
constant then takes the approximate form
( nFe3+ )3
1
-
_
2nFe2
where ni is the number of ions of the ith kind. This much more complex
expression accounts for the experimental results over the whole composition
range, both i n pure wustite and i n the MgO-FeO solid solutions.
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SOLUTION THERMODYNAMICS 245
The exact structure of the complex has not yet been resolved, but the
alternative suggestion of Roth (132), based on a neutron difraction study,
has most experimental support. The equation for the addition of oxygen to
wustite is
Here Fei3+ is an interstitial ferric iron.
Nickel oxide ( 133) and cobaltous oxide ( 134) both show the simple
p
11
6
0
2 dependence of the departure from nonstoichiometry on oxygen pres
sure which would appear to support the simple point-defect model, but
Brynstad and Flood's model could also be valid here. The deviations from
stoichiometry which have been studied are very small, being limited by the
attainment of one atmosphere oxygen dissociation pressure.
I t thus appears that the ease of formation of the higher-valency ion Mn+
and the insertion of this ion into interstitial sites, which correspond to the
structure of the next-higher oxide Ma04, determines the manner in which the
deviation from stoichiometry in the M0
1
+
x phase depends on the oxygen
pressure. I n this connection it is interesting that the ratio of the oxygen pres
sures for the two-phase equilibria MO-Ma0
4
/M-MO have the values 10
+
2
7,
10+2, and 10+11 at 1000C for manganese, iron, and cobalt, respectively. The
phase Nia04 has not yet been studied. Although the ratio is very much larger
for manganese than for iron and cobalt, the oxidation of Mn' to Mn
a
+
only
occurs substantially over 9 orders of magnitude from MnOl. O05 to Mn01. 05
at 1650C, according to Davies and Richardson.
The oxides Ce02, PU02, and U02 all have the fuorite structure, the frst
two representing the highest valency and U4+ the lowest valency of these
cations in the stable oxide systems. The defects associated with the non
stoichiometric ranges of these oxides appear to occur mainly through the
anions, there being anion vacancies in Ce02
-
X and PuOz--: and interstitial
oxygens in U02
+
x (135) . The heat changes for the reactions
2PU203 + O2 - 4PU02
and
are -197 and - 170 kcal respectively, and the two non stoichiometric phases
have very similar properties with respect to range of existence and partial
heats of solution of oxygen, as was shown earlier.
The defect equilibrium constant for PuOz--x depends upon the minus one
sixth power, according to the results of Markin & Rand (120) . Atlas &
Schlehman (136) , who studied this system at a higher temperature, found
the dependence to be of the minus one fourth power in the same range of
nonstoichiometry, The defect formation reaction could be written
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246
ALCOCK
or
depending on the formation of interstitial metal ions or oxygen vacancies.
The oxygen pressure dependence can then be related to the concentration of
defects and the power will be "determined" in the case of the interstitial
species by the extent to which the electrons are trapped to form Pua+ ions.
The results of Bevan & Kordis (1 19) for Ce02z and of Tetenbaum &
Hunt (137) for UOH, show behavior very similar to Pu02
-
z, the power de
pendence of the defect concentration on the oxygen pressure being about one
ffth. Over the wide range which was covered by Bevan and Kordis, the
change of slope of the log p02/log x plot can be clearly seen.
There is no analogous region for cerium and plutonium oxides correspond
ing to U02
+
" and it must sufce here to remark that Aukrust, Forland &
Hagemark (138) interpreted the results for this oxide by a defect equilibrium
which associates two US ions in a complex with an oxygen interstitial ion
2 UH + 1/2 O2 -2 UH Oi
Willis (135) showed by means of neutron difraction that the structure
was more complex than this, as far as the oxygen interstitial ion is concerned.
I t appears that these results must be interpreted as showing that there are
two types of oxygen ion, 0' at (0. 5, 0. 38, 0. 38) and 0" at (0. 41, 0. 41, 0. 41)
rather than at the (0. 5, 0. 5, 0. 5) position which would normally be antici
pated. These ions occur in equal numbers to one another and an equal num
ber of vacant sites are on the oxygen lattice. Such an arrangement of oxygen
ions is found in the U
4
09 lattice. This evidence, together with the defect
equilibrium constant found by Hagemark, suggests that the 2U. Oi "com
plex" is the progenitor of U
4
09, which is the phase which is next formed on
oxidation of U02.
The oxides V02, Ti02, Nb02, and Mo02 are all of the rutile structure with
slight modifcation in the latter two systems. It was mentioned earlier that
no metal-rich region of nonstoichiometry in V02-
x has yet been observed,
but the other three oxides have been successfully prepared in the metal-rich
composition range. The defect equilibrium constants for the reduction may
be written either as
with the formation of oxygen vacancies, or as
In the latter case, where an interstitial ion is postulated, the charge of the
interstitial ion may be reduced to Ma+ by the trapping of one of the electrons,
or MS
+
ions can be formed on normal lattice sites. In the Magneli phases
which are formed in both V02-: and Ti02z, the shear planes contain MS+
ions with the twelvefold oxygen coordination typical of the hexagonal close
packing of the M203 phases. If it were assumed that the defect structure in
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SOLUTION THERMODYNAMICS
-7o r-
-90
'
.
t
-10
0
-1
1
0
-
1
20 !. g g g g g
g
CPITION X IN M
2-X
247
FIGURE 3. The relationship between chemical potential and atom fraction of oxygen
in Ti02_z, according to a number of separate studies (148) ,
the homogeneous range Ti01
.
99c Ti02
.
000 is the Ti
a
+
ion which takes up a posi
tion corresponding to the oxygen coordination of the shear planes in the series
Tin02n
-
l , the defect equilibrium constant would involve the oxygen partial
pressure to the minus one fourth power. The value obtained from a number
of studies is closer to the minus one ffth power which corresponds to the un
trapped electron and Tii
4
+
interstitial ion.
In the other oxides Nb02-x and Mo02-x in which a signifcant range of non
stoichiometry has been found, the defect equilibrium constant only involves
the minus one half power of the oxygen pressure. It is therefore concluded
that the number of electrons which are released by reduction at this early
stage are small compared with the intrinsic concentration.
The difculties that are inherent in the study of mass-action constants
are well represented by the collection of results shown in Figure 3, which
summarizes the studies made on substoichiometric Ti02
SOLID SOLUTIONS OF OXIDES
The Hume-Rothery rule that solid solution can take place to a great
extent between species whose radii do not difer by more than 15 percent is
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248 ALCOCK
well exemplifed in the literature. In relation to oxide solid solutions, this
rule holds weJl when the oxides have the composition close to stoichiometry,
but the introduction of nonstoichiometry adds a new chemical dimension
which afects the working of the rule.
The near-stoichiometric solid solutions show a smaJl departure from
Raoult's law and measurements of FeO-MgO in equilibrium with iron have
been made, with excellent agreement, by a number of workers (139-141).
The results of Hahn & Muan ( 142) for the NiO-MgO and NiO-MnO solid
solutions in equilibrium with nickel were made with H2-C02 gas mixtures in
gas-solid equilibration. These results have been confrmed by Seetharaman
& Abraham ( 143) , ( 144) , who used solid oxide galvanic cells. The thermo
dynamic data for these systems do not provide very much information except
when the results suggest phase separation at low temperatures.
The study of the oxidation of solid solutions can provide very interesting
information in connection with solution models, since it is possible to dilute
one species in a proposed complex simply by the addition of a chemically
stable species. Thus, in FeO-MgO solid solutions, it is only the ferrous ion
which can be oxidized, and it is of considerable interest to discover whether
the heat of oxidation of the ferrous iron is the same in the solid solution as in
pure wustite. According to Iyengar & the author (145) the partial heat of
solution of oxygen in these solutions is independent of the Fe/Mg ratio
from 3. 2 to 20 mole percent wustite, and the value is the same, within experi
mental error, as that in pure wustite -67.25 kcal g atom
-
1 to within
5 kcal.
Aronson & Clayton ( 146) showed that the partial heat of solution of oxy
gen in (VI Th
1
-!)02- solid solutions remained constant ( 2.5 kcal g
. atom-I) from y =1 to y=0. 29, and Roberts & Markin ( 147) report that the
partial heat of solution of oxygen in (UIPUl-)02
+
" solutions remains sensibly
constant until the average Pu valency is reduced to 3. 1 .
All of these results suggest that the defect mechanism which operates in
the pure oxide, is also responsible for the oxidation behavior of the solid
solutions.
These studies of nonstoichiometry in oxide systems show yet again that
the sol ution problems of the materials scientist in metallic and ceramic
systems remain largely unresolved. In many cases, it is not the gross thermo
dynamic properties which are now of major signifcance, and if we are to
pursue the business of correlating thermodynamic properties with atomic
models, then the materials which are investigated must be defned with re
spect to chemical composition in the most rigorous way, both before and after
the measurement. The techniques which we use at present, and which give us
thermodynamic results to 200 cal on the average, are still not sufciently
precise since all too frequently the balance of stability hangs on a few calories.
The choice of a preferred atomic model out of a number of suggested models
is becoming increasingly difcult as the art of fashioning new models pro
gresses. When a sufcient number of parameters is available. a number of
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SOLUTION THERMODYNAMICS 249
models can be ftted to the same imprecise data, but at least the confict
should lead towards some more defnitive experiment. Recent years have seen
an increasing use of more than one technique in investigating a given system.
Thus, the use of free-energy and calorimetric techniques in tandem seems to
be more readily accepted as the desirable modus operandi. It seems clear,
however, that structural information such as high-temperature X-ray and
neutron difraction data will be required to an increasing extent as model
building is pursued. Because of the radical changes which might be brought
about by the presence of relatively minor impurity levels, it would seem de
sirable that thermochemists working in this feld seek an alliance with their
structural colleagues so that their measurements may be made on equally
well-defned substances in the physical as well as the chemical sense.
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250 ALCOCK
LITERATURE CITED
1. Kubaschewski, 0., Evans, E. LJ., A
cock, C. B. 1967. Metallurgical
Thermochemistry. London: Perga
mon 4th ed.
2. 1967. Proc. Brit. Ceram. Soc. No. 8
3. Rapp, R. A. Ed. 1970. Physicochemi
cal Measurements in Metals Re
search, Vo!' 4. New York; Inter
science
4. Rizzo, F. E., Bidwell, L. R., Frank,
D. F. 1967. Trans. Met. Soc. AIME
239; 1901
5. Cater, E. D., See Ref. 4, Part I, 21
6. Wriedt, H. A., Darken, L. S. 1965.
Trans. AIME 233; 1 1 1 , 122
7. Lange, K. W., Schenck, H. See Ref. 4,
Part I, 267
8. Markin, T. L., Bones, R. J., Wheeler,
V. J. See Ref. 2, 51
9. Fromm, E., 1970. J. Less-Common
Metals 22 : 139
10. Allen, N. P., Kubaschewski, 0., von
Goldbeck, O. 1951. J. Electrochem.
Soc. 98; 417
11. Kubasehewsk, 0. , Deneh, W. A.
1953. J. Inst. Metals 82; 87
12. Ibid 1955. 84;440
1 3. Komarek, K. L., Silver, M. , 1962.
Thermodynamics of Nuclear Ma
terials, 774. Vienna: IAEA
14. Isenberg, I. , Phys. Rev. 79: 736 1950
15. Wagner, C., 1944. Z. Phys. Cher.
A 193:386
16. Mott, N. F., 1936. Proc. Cambridge
Phil. Soc. 32: 281
1 7. Herzfeld, K. F., Goeppert-Mayer, M.
1934. Z. Phys. Chem. B 26:203
18. Friedel, J. 1952. Phil. Mag. 43: 153
19. Ebisuzaki, Y., O'Keefe, M. 1967.
Progr. Solid-State Chem. 4: 187
20. McQuillan, A. D. 1967. Phase Stabil
ity in Metals and Alloys, 375.
New York: McGraw-Hill
21. Hoare, F. E. 1963. Electronic Struc
ture and Alloy Chemistry of the
Transition Elements, 29. New York:
Interscience
22. Lacher, J. R. 1937. Proc. Roy. Soc.
A 161 ;525
23. Fowler, R., Guggenheim, E. H. 1949.
Statistical Thermodynamics. Cam
bridge Univ. Press
24. Hoch, M. 1964. Trans. AIME 230: 138
25. Mallett, N. W., Koehl, B. G. 1962.
J. Electrochem. Soc. 109:61 1
26. Brodowsky, H. A. 1965. Z. Phys.
Chem. N. F. 44: 129
27. Brodowsky, H. A., Schaller, H. J.
1969. Trans. Met. Soc. AIME 245 :
1015
28. Gallagher, P. T. , Oates, W. A. 1969.
Trans. Met. Soc. AIME 245 : 179
29. Ricca, F., Giorgi, T. A. 1967. J. Phys.
Chem. 71 :3627
. .
30. Ricca, F. See Ref. 29, 3632
31. Pan, S. S. , Webb, F .. J. 1965. Nuc!.
Sci. Eng. 23: 188
32. Darken, L. S., Smith, R. P. 1946.
J. Am. Chem. Soc. 68: 1 1 72
33. Ban-ya, S., Elliott, J. F., Chipman,
J. 1969. Trans. Met. Soc. AIME
245 : 1 199
34. Speiser, R., Spretnak, J. W. 1955.
Trans. A m. Soc. Metals 47 :493
35. McLellan, R. B., Gerrard, T. L. ,
Horowitz, S. J., Sprague, J. A.
1964. Trans. Met. Soc. AIME
239: 528
36. Powers, R. W., Doyle, M. V. 1959.
Trans. Met. Soc. AIME 21 5:655
37. Gibala, R. , Wert, C. A. 1966. Acta
Met. 14: 1095
38. Hultgren, R., Orr, R. L., Anderson,
P. D. , Kelley, K. K. 1963. Selected
Values of Thermodynamic Proper
ties of Metals and Alloys. New
York; Wiley
39. McCabe, C. L., Schadel, H. M., Jr.,
Birchena1l, C. E. 1953. J. Metals
5 : 709
40. Trumbore, F. A., Wallace, W. E. ,
Craig, R. S. 1952. J. Am. Chem.
Soc. 74: 132
41. Blandin, A. , Deplante, J. L. 1963.
Metallic Solid Solutions. New York;
Benjamin
42. Fuchs, K. 1935. Proc. Roy. Soc. 151 :
585
43. Hardy, H. K. 1953. Acta Met. 1 :202
44. Blair, G. R., Downie, D. B. 1970.
Metal Sci. J. 4: 1
45. Orr, R. L. , Argent, B. B. 1965. Trans.
Faraday Soc. 61 : 2126
46. Weibke, F. 1937. Z. Anorg. Chem.
232 :289
47. Samson-Himmelstjerna, H. O. 1936.
Z. Metallk. 28: 197
48. Korber, F. , Oelsen, W. , Mitt, K. W.
1937. Inst. Eisenforsch. 19:207
49. Kleppa, O. J. 1956. J. Phys. Chem.
60:842
50. Kleppa, O. J., King, R. C. 1962. Acta
Met. 10: 1183
51. Friedel, J. 1954. Advan. Phys. 3;446
52. Freedman, J. F., Nowick, A. S. 1958.
Acta Met. 6: 1 76
53. Kubaschewski, O. 1968. Thermody
namics of Nuclear Materials, 685.
Vienna: IAEA
A
n
n
u
.
R
e
v
.
M
a
t
e
r
.
S
c
i
.
1
9
7
1
.
1
:
2
1
9
-
2
5
2
.
D
o
w
n
l
o
a
d
e
d
f
r
o
m
w
w
w
.
a
n
n
u
a
l
r
e
v
i
e
w
s
.
o
r
g
b
y
M
i
d
d
l
e
E
a
s
t
T
e
c
h
n
i
c
a
l
U
n
i
v
e
r
s
i
t
y
o
n
0
2
/
1
3
/
1
2
.
F
o
r
p
e
r
s
o
n
a
l
u
s
e
o
n
l
y
.
SOLUTION THERMODYNAMICS 251
54. Alcock, C. B. , Kubik, A. 1969. Acta
Met. 1 7:437
55. Bidwell, L. R., Rizzo, F. E., Smith,
J. V. 1970. Acta Met. 18: 101 3
56. Goodenough, J. B. 1966. Magnetism
and the Chemical Bond. New York:
Interscience
57. See Ref. 51
58. Kleppa, O. J. 1955. Acta Met. 3:255
59. Crangle, J. 1963. Electronic Structure
and Alloy Chemistry of the Transi
tion Elements, 51. New York: Inter
science
60. Taylor, R. W., Muan, A. 1962. Trans.
Met. Soc. AIME 224:500
61. Schwerdtfeger, K., Muan, A. 1965.
Trans. Met. Soc. AIME 233: 1904
62. Myles, K. M., Darby, ]. B. 1968.
Acta Met. 16:485
63. Landolt, C., Muan, A. 1969. Trans.
Met. Soc. AIME 245 : 791
64. Leach, ]. S. Ll. See Ref. 3, 199
65. Kubaschewski, O. 1959. Nat. Phys.
Lab. Symp. No. 9, Pap. 3C. H. M.
Stationery Ofce
66. Laves, F. 1956. Theory of Alloy Phases,
1 24. Cleveland, Ohio: ASM
67. Pauling, L. 1960. Nature of the Chem
ical Bond. Ithaca, New York:
Cornell Univ. Press. 3rd ed.
68. King, R. C., Kleppa, O. J. 1964. Acta
Met. 12: 87
69. Alcock, C. B. , Grieveson, P. 1961-
1962. J. Inst. Metals 90:304
70. Alcock, C. B., Cornish, ]. B. , Grieve
son, P. 1966. Thermodynamics, 1 :
211. Vienna: IAEA
71. Brewer, L., 1967. Phase Stability in
Metals and Alloys, ed. P. S. Rud
man, J. Stringer, R. I. Jafee, 39.
New York: McGraw-Hill
72. Engel, N. 1949. Kem. Maanedsbl.
30:53, 75
73. Brewer, L. 1967. Acta Met. 15 : 553
74. See Ref. 71, 566-67
75. Robinson, P. M. , Bever, M. B. 1967.
Intermetallic Compounds, ed. J. H.
Westbrook, 38. New York: Wiley
76. Mott, N. F. 1937. Proc. Phys. Soc.
London 49:258
77. Harrison, R. ]. , Paskin, A. 1963.
Metallic Solid Solutions, Paper V,
ed. Friedel, Guinier. New York:
Benjamin
78. Mullikan, R. S. 1934. J. Chem. Phys.
2 : 782
79. Varley, J. H. O. 1954. Phil. Mag. 45 :
887
80. Hillert, M. See Ref. 77, Paper XLVII
81. Grieveson, P. 1967. Proc. Brit. Ceram.
Soc. No. 8, 137.
82. Naoumidis, A., Stocker, H. J. 1968.
Thermodynamics of Nuclear Ma
terials, 287. Vienna: IAEA
83. Sano, T., Katsura, M. , Kai, H. See
Ref. 82, 301
84. Leitnaker, J. M. See Ref. 82, 317
85. Steele, B. C. H. , Javed, N. A. , Alcock,
C. B. 1970. J. Nucl. Mater. 35: 1
86. Potter, P. E. See Ref. 82, 337
87. Belton, G. R. , Fruehan, R. J. 1967.
J. Phys. Chem. 71 :1403
88. Balducci, G., Capalbi, A., DeMaria,
G., Guido, M. 1969. J. Chem.
Phys. 51 : 2871
89. Balducci, G., DeMaria, G. , Guido, M.
See Ref. 88, 2876
90. DeMaria, G. , Balducci, G., Capalbi,
A., Guido, M. 1967. Proc. Brit.
Ceram. Soc. No. 8, 127
91. Cuthbert, ]., Faircloth, R. L. , Flowers,
R. H. , Pummery, F. C. W. See Ref.
90, 155
92. Storms, E. K. 1967. The Refractory
Carbides. New York: Academic
93. Alekseev, V. I. , Panov, A. S. , Fiveiskii,
E. V., Shvartsman, L. A. See Ref.
82, 446
94. Kleykamp, H. 1969. Ber. Bunsenges.
Phys. Chem. 73:354
95. Richardson, F. D. 1953. J. Iron Steel
Inst. 1 75:53
96. Worrell, W. L., Chipman, ]. 1964.
Trans. Met. Soc. AIME 230: 1682
97. Mah, A. D. , Kelley, K. K. 1961. US
Bur. Mines, Rep. No. 5858
98. Mah, A. D. 1963. US Bur. Mines
R.I. 6177
99. Morozova, M. P., Khernburg, M. M.
1966. Zh. Fiz. Khim. 40: 1125
100. Kornilov, A. N. , Zaikin, I. D. ,
Skuratov, S. M. , Shveikin, G. P.
1966. Zh. Fiz. Khim. 40: 1070
101. Huber, E. J., Jr., Head, E. L. , Holley,
C. E., Jr., Storms, E. K., Krikorian,
N. H. 1961. J. Phys. Chem. 65 :
1846
102. Huber, E. J+ , Jr., Head, E. L. , Holley,
C. E., Jr., Bowman, A. L. 1963. J.
Phys. Chem. 67: 793
103. Libowitz, G. G. 1963. Non-Stoichio
metric Compounds, Advan. Chem.
Ser. No. 39 74
104. Hoch, M. , Juenke, E. F., Sjodahl,
L. H. 1968. Thermodynamics of
Nuclear Materials, 497. Vienna:
IAEA
105. Searcy, A. W. 1970. Chemical and
Mechanical Behaviour of Inorganic
Materials, ed. A. W. Searcy, D. V.
Ragone, U. Colombo, 51 . New
York: Interscience
106. Robins, D. A., Jenkins, I. 1955. Acta
Met. 3:598
A
n
n
u
.
R
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v
.
M
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S
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i
.
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1
:
2
1
9
-
2
5
2
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o
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s
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o
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2
.
F
o
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s
o
n
a
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u
s
e
o
n
l
y
.
252 ALCOCK
107. Levine, S. R., Kolodney, M. 1969. J.
Electrochem. Soc. 1 16: 1420
108. Aronson, S., Auskern, A. 1966. Ther
modynamics, 165. Vienna: IAEA
109. Darken, L. S., Gurry, R. W. 1945. J.
Am. Chem. Soc. 67: 1398
1 10. Fender, B. E. F., Riley, F. D. 1969.
J. Phys. Chem. Solids 30:793
1 1 1 . Haufe, K., Pfeifer, H. 1953. Z.
Metallk. 44:27
1 12. Rizzo, F., Smith, J. V. 1968. J. Phys.
Chem. 72 :485
1 1 3. Kleman, M. 1965. Mem. Sci. Rev.
Met. 62: 457
1 14. Richardson, F. D. 1948. Discuss.
Faraday Soc. 4: 256
1 15. Raccah, P., Vallet, P. 1961. C. R.
Acad. Sci. 253 :2682
1 16. Koch, F. 1967. PhD thesis. North
western Univ.
1 1 7. Blumenthal, R. N., Moser, J. B.,
Whitmore, D. H. 1965. J. Am.
Ceram. Soc. 48:61 7
1 18. Schafer, H., Bergner, D. , Gruehn, R.
1969. Z. Anorg. Chem. 365 : 31
1 19. Bevan, D. J. M., Kordis, J. 1964. J.
Inorg. Nue!. Chem. 26: 1509
120. Markin, T. L., Rand, M. H. 1966.
Thermodynamics, 1 :145. Vienna:
JAEA
121. IAEA 1965. Thermodynamics and
Transport Properties of UO. Tech.
Rep. Ser. No. 39. Vienna
122. Gerdanian, P., Dode, M. 1968. Ther
modynamics of Nuclear Materials,
41. Vienna: IAEA
123. Zador, S., Alcock, C. B. 1970. J. Chem.
Thermodynam. 2 :9
124. Andersson, S., Jahnberg, L. 1963.
Ark. Kemi 21 :413
125. Hurien, T. 1959. Acta Chem. Scand.
13:365
126. Ackermann, R. J. , Rauh, E. G. 1962.
J. Phys. Chem. 67:2596
127. Katsura, T., Hasegawa, M. 1967.
Bull. Chem. Soc. Jap. 40: 561
128. Davies, M. W., Richardson, F. D.
1959. Trans. Faraday Soc. 55 :604
129. Smyth, D. M. , 1961. J. Phys. Cher.
Solids 19: 167
130. Swaroop, B. , Wagner, J. B. 1967.
Trans. Met. Soc. AIME 239: 1215
131. Brynestad, J. , Flood, H. 1958. Z.
Elektrochem. 62 :953
132. Roth, W. L. 1960. Acta Crystallogr.
13:140
133. Tret'yakov, Vu. D., Rapv, R. A. 1969.
Trans. Met. Soc. AIME 245 : 1235
134. Gleitzer, C. 1962. Bull. Soc. Chim.
Fr. Vol. 75
135. Willis, B. T. M. 1963. Nature 197: 755
136. Atlas, L. M. , Schlehman, G. J. 1966.
Thermodynamics, 2:407. Vienna:
IAEA
137. Tetenbaum, M., Hunt, P. D. , 1968.
J. Chem. Phys. 49:4739
138. Aukrust, E., Fj!rland, T., Hagemark,
K. 1962. Thermodynamics of Nu
clear Materia/s, 713. Vienna: IAEA
139. Hahn, W. C., Muan, A. 1962. Trans.
Met. Soc. AIME 224: 416
140. Schmahl, L. G., Frisch, B., Stock, G.
1961.Arch. Eisenhuettenuw. 32 :297
141. Shashkina, A. V., Gerasimov, Va. 1.
1953. Ser. Fiz. Khim. 27 :399
142. Hahn, W. C., Muan, A. 1961. J. Phys.
Chem. Solids 19:338
143. Seetharaman, S. , Abraham, K. P.
1968. Indian J. Technol. 6: 123
144. Seetharaman, S., Abraham, K. P.
1968. Trans. IMM C 209
145. Alcock, C. B., Iyengar, G. K. 1967.
Proc. Brit. Ceram. Soc. No. 8 219
146. Aronson, S. , Clayton, J. C. 1960. J.
Chem. Phys. 32: 749
147. Roberts, L. E. J., Markin, T. L. 1967.
Proc. Brit. Ceram. Soc. No. 8 201
148. Alcock, C. B. , Zador, S. , Steele,
B. C. H. 1967. Proe. Brit. Ceram.
Soc. No. 8 231
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CONTENTS
STRUCTURAL CHARACTERIZATION OF MATERIALS BY USE OF ELECTRON
MICROSCOPY AND SPECTROSCOPY, Victor A. Phillips and Eric
Lifshin 1
DEVELOPMENT AND ApPLICATION OF THEORETICAL TECHNIQUES TO
PROBLEMS IN MATERIALS SCIENCE, J. C. Phillips 93
ANOMALOUS PROPERTIES OF THE VANADIUM OXIDES, John B. Good-
enough
101
THE STRUCTURE OF DEFECTS IN SOLIDS, J. H. Crawford, Jr., and L.
M. Slifkin 139
MODELS OF THE GEOMETRICAL, ELECTRONIC, AND VIBRONIC STRUC-
TURES OF IDEAL CLEAN SOLID SURFACES, C. B. Duke 165
SOLID-STATE PHASE TRANSFORMATIONS, C. M. Wayman 185
SOLUTION THERMODYNAMICS IN METALLIC AND CERAMIC SOLID SyS-
TEMS, C. B. Alcock . 219
CRYSTAL GROWTH, R. A. Laudise, J. R. Carruthers, andK. A. Jackson. 253
SOLID THIN FILMS, E. Kay 289
PHYSICS OF STRENGTHENING MECHANISMS IN CRYSTALLINE SOLIDS,
William D. Nix and Ricardo A. Menezes. 313
ELECTRONIC AND OPTICAL PHENOMENA IN SEMICONDUCTORS, M. E.
Jones and R. T. Bate 347
CORROSION SCIENCE, 1970, David A. Vermilyea 373
AUTHOR INDEX
399
SUBJECT INDEX
411
vii
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