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THE PASSIVATION OF ALLOYS ON TITANIUM BASES

N.D.To~as~ov, G. P. CHERNOVA, Yu. S. Rrrsco~andG.A: AYUYAN


Institute of Physical Chemistry, Academy of Sciences, Leninsky Prospect 31, Moscow, USSR

(Receiued 30 July 1973)

Abstract--Processes of anodic passivation and corrosion behaviour of titanium and binary titanium
alloys in non-oxidising acids at elevated temperatures have been investigated, when the alloy dissolution
in the passive state proceeds at certain rate.
The main control of dissolution in the passive state is determined not by chemical stability of a passive
film (in most alloys it turns out to be of the same order as in pure titanium) but by the value of its ionic
(cationic) conductivity.
For highly-alloyed (MO, Cr, Ta) hardened titanium alloys having a single-phase structure it has been
established that their transition to the passive state is facilitated (smaller passivation currents) in compari-
son with the same alloys in annealed state having a two-phase structure. At the corrosion of two-phase
alloys the surface is enriched with the more stable phase. For Ti-15Ma alloy in the active region of poten-
tials, the P-phase IS accumulated on the surface, a-phase is mainly dissolved. On the contrary, at transpas-
sivation the P-phase (containing greater amounts of Mo) is chiefly dissolved For two-phase Ti&lSCr allay
in transpassivation region. the y-phase. enriched with chromium, is principally dissolved.

The passive films formed on the surface play an impor- of such titanium. The composition and structure of
tant role in corrosion stability of titanium and its alloys are given in Table I. The heat treatment is de-
alloys[I]. The study of electrochemical behaviour of scribed later.
titanium and its alloys in rather aggressive conditions, The folIowing methods were employed:
when a considerable dissolution of metal takes place (1) Electrochemical methods: the measurement of
even in a passive state (as for example, at anodic polat- anodic potentiokinetic curves and chronoampero-
isation in concentrated solutions of sulphuric and hy- metric curves at controlled constant potcntiai value,
drochloric acids at high temperatures) is interesting for the registration of potential change after anodic polari-
the creation of titanium alloys, which are stable in zation has been switched off; (2) gravimetric deter-
aggressive media. mination of corrosion losses at controlled potential
The present studies were carried out with titanium value with simultaneous determination of total
obtained by iodide method and with alloys on the base amount of clecctricity by means of low-resistance iodine

Table 1. The composition and structure of titanium alloys

No. of The composition of alloys


alloys (weight “/:,of additions) Structure

0 Ti, obtained by iodide method (0.0) LX


l-4 Ti-Nb (O-85; 2.1; 5.0; 6.3) a.
s-7 Ti-Sn (@5; 2-2 ; 4-2) c(
8-10 Ti-Mn (0,25; I,3 ; 3,O) a
1 I-14 X-AI (O-45; 1.9; 4-O; 6.1) a
15-18 Ti-Zr (0.4; 2:6; Ll)
19-22 Ti-V(o-4;2;4;6) 19, 20-m; 2;, 22-a + B
23,24-o! ; 25, 26-a -I- ,fJ
23-27 Ti&Mo (0.4; 1.3; 3.4; 6.2; 15.1)
27-8, /3+ w or 8 + tl
28-30-a ;
28-32 Ti-Cr (023:0%7; 48; 5-O: 15) 31-cror a + y;
32-p or OL-I- 1
33 Ti-Cr(SkTa(S) @ora+?
34 Ti&Cr(S)-Tat1 S) Boro:+y
35 TiGNb(20) e+B
36 Ti-Nb(2OtPd(O.l) or+B
37 Ti mNh(2OtPd(0.2) a+B

159
160 N. D. TOMASHOV,
G. P. CHCRNOVA,Yu. S. Rusco~ and G. A. AYUYAN

coulometer; (3) analytical; (4) m&allographic; (5) X- that in our studies not less than 900/, of nonstationary
ray and electron diffraction methods. Some results of current component are spent for direct electrochemical
these studies arc given in present communication. titanium dissolution (reaction 3). If one calculates an
approximate balance for expenditure of total anodic
current he gets the following values for time equal
1. THE CHARACTER OF ANODIC
to 30 min from the beginning of anodic polarisation:
TITANIUM DISSOLUTION
approx 6% of anodic current are spent for the formation
The kinetics and mechanism of anodic dissolution of (thickening) ofpassivefilm(reaction 1); less than 40”/,-
titanium in passive state at constant potential (cp = for the compensation of chemical dissolution of the
+ 1 V) in 40% solution of H,S04 at 80°C was studied. passive film (reaction 2); more than 54x--for direct
In passive region at potentials more positive than electrochemical titanium dissolution (reaction 3) Such
that of complete passivation (rp > rp,,) on titanium and studies and calculations for some titanium alloys: Ti-
its alloys at chosen conditions the anodic current can 5Nb (No. 3); Ti-4*2Sn (No. 8); Ti-@4Al (No. 11); Ti-
be spent for the following processes: i,-the current of 0.4Mo (No. 23); Ti-1.3Mn (No. 9); Ti-0.87Cr (No. 29)
an electrochemical formation (thickening) of oxide have shown that at these experimental conditions the
film, for example, according to the reaction: main part of anodic current is spent for direct electro-
chemical dissolution also for low-alloyed titanium
Ti +- 2H20-+Ti0, + 4H+ + 4e (1) alloys. The same calculations made for different time
&-the current of the film formation according to the intervals of anodic dissolution (10, 15, 30 and 60 min)
reaction (I), but it is spent for a compensation of the have shown that the current expenditure for a direct
chemical film dissolution according to the reaction: electrochemical titanium dissolution prevails. It allows
to make a conclusion that in stationary conditions of
TiO, + 2H+ +TiO”’ + I-I,0 (2) anodic dissolution the main anodic process is a direct
i,-the current of direct electrochemical dissolution of electrochemical titanium dissolution (reaction 3), but
titanium through the passive film. Assuming, that this not a compensation of chemical film dissolution
process in passive state leads to the formation of Ti4+ - (reaction 2).
ions (as titanyl ions) this reaction can be written as fol- The anodic potentiokinetic curves of titanium have
lows been studied at various temperatures (Fig. I). It is seen
that the region of curves in passive state where the cur-
Ti + H,0--*Ti02* + 2H* + 4e. (3) rent density is independent of potential, disappears as
At present time there are no direct methods to deter- the temperature increases. The potentiostatic curve for
mine quantitatively the fraction of the current flowing titanium in 40% H,SO, at 80°C is given in Fig. 2. In
through the passive anode at stationary conditions, order to obtain each point of this curve an every
spent for each of the reactions named above. However, sample was kept from 2 to 8 h until stationary current
the solution of this problem in nonstationary condi- density was achieved at various values of anodic
tions for initial period after the jump increasing of ano-
die potential has been attempted many times for - I-O
example, by Novakovsky[2], Kabanov[3,4] and t

Heusler [5,6] and also in our studies[7]. A certain


conclusion on the current distribution between the
processes of film thickening and processes of titanium
dissolution after constant potential achieved could be
made when the mass of titanium anode was con trolled
beginning from lo-min exposition and the amount of
electricity was determined by microcoulometer of spe-
cial constructionC8J. The treatment of experimental
results and calculations for anodic polarization time
equal to 30 min have shown that in nonsteady current
interval a main part of electricity (94%) is spent for the
transition of titanium into solution (reaction 2 + 3)
and only a small part is spent for a thickening of oxide
film (reaction 1). If we assume that the rate of chemical
dissolution of oxide film (reaction 2) does not depend
on the potential and that the rate of this reaction can
not exceed a steady current density, the ratio of
amount of electricity, spent for titanium dissolution, to
a nonstationary component of current, but not to total 1, PA/cm'
amoupt of electricity can be estimated (ie, maximum Fig. 1. Anodic potentiokinetic curves for titanium, obtained
possible current for the compensation of chemical dis- with a sweep speed 4 V/h in 40% H2S04 at various tempera-
solution of the film should be excluded). It appeared tures: l-25”; 2-50”: 3-70”: 4-80”: 5-90°C.
The passivation of alloys on titanium bases 161

an electrode(Q) and an amount of electricity, spent for


titanium dissolution (Q,), Table 2 says that in condi-
tions similar to those of Fig. 2 the more positive the
potential the thinner the films formed on the titanium.
This is confirmed by the colour change of anodic tilms,
the colour changes from brown at ‘p = 0.7 V, yellow at
cp = 1.0 V to yellowish at cp = I.4 V and higher.
The self-activation time of samples with anodic film
(r,), formed in the same conditions, after the current of
potentiostatic polarisation is switched off, grows as the
polarisation potential increases, as can be seen from
Table 2. Thus, the films formed on the titanium at rp =
0.7 V being more thick, were activated faster and were
less protective than films formed at rp = 1-4 V.
This discrepancy can be explained by assumption of
double-layezity of anodic films on titanium, formed in
giver conditions as it was found by Koizumi and Nak-
ajama for similar conditions[9]. According to these
workers the passive film on titanium, prepared in
H,SO, solutions, consists of continuous barrier layer,
I I
IO 100
next to the metal and noncompact external layer. Bar-
rier layer is amorphous at low temperatures and has
i I+ v fd /cm2 an anatase structure at higher temperatures.
Thus, it can be assumed that the electrochemical
Fig. 2. The part of stationary anodic potentiostatic curve
for titanium in potential range 0.14-2.2 V (40% H,SO,, behaviour of passive titanium in experimental condi-
80°C). tions is determined by a thickness and properties of
compact barrier layer, but not by the properties of
potentials, beginning from complete passivation more thick porous surface formations, which do not
potential (rp,,). As it can be seen from Fig. 2, the prevent the high rate of titanium dissolution at less
stationary current density for titanium decreases by positive anodic potentials. The thickness of barrier
two orders when potential changes from cpo = + oxide layer, as it will be shown later, grows when ano-
0.14 V to cp = 1.4 V and only at potentials beginning die potential of the formation in&eases, though the.
from 1.4 V the current density does not depend on the mean thickness of the whole film, determined coulome-
potential. Such behaviour of titanium can be related trically can decrease since the thickness of porous sur-
with the change of properties of anodic films which are face layer of the film diminishes.
formed on titanium at various potentials. To investi- To estimate the thickness and ionic conductivity of
gate the properties of passive films and their role in dis- barrier layer the volt-ampere curves of anodic films,
solution of passive titanium the studies on the deter- formed at different potentials, have been measured
mination of thickness and structure of the formed films (Fig. 3). The curves have been obtained by the follow-
have been performed, the V-A curves for titanium elec- ing way. The titanium electrode was dipped into the
trode with passive film, formed at different potentials, solution (40”/, H,S04, 80°C) at potentials 07; I.0 or
have been measured also. 1.4 V and was kept there until stationary current was
Experimental results on the determination of thick- achieved. After that the potential has been changed by
ness of the films, formed on titanium during 3 h anodic some value Aq to less positive value, after 20 s the cur-
polarisation are given in Table 2. The determination of rent was registeredand potential was restored to initial
film thickness was made by measuring of amount of value. As soon as the current reached the initial value,
electricity, spent for the passiSe*film formation (Q,). On the cycle was repeated for another value and so on.
the other hand, Q, was determined as a difference This procedure allows to suggest that the measurement
between a total amount of electricity, passing through of curve was performed with practically unchanged

Table 2. Experimental results on the thickness determination of the films, stationary formed on
titanium in 3 h at different potentials (40% H,SO,, 80°C)

QP ?a*
k/cm2 d min

0.7 o-2924 O-2710 0.0214 46.1 9.2


1.0 o-1521 O-1368 0.0153 33.0 21
1.4 O-1036 0.0926 0~0110 23.7 24

* It was determined after 5 h anodic polarisation at the same conditions


162 N. D. TOMASHOV, G. P. CHERNOVA, Yu. S. KWCOL and G. A. AYUYAN

0.3
20 set I-

>

a” 0.2

0 I IO 100

11 pA /cm2

Fig. 3. The dependence of logarithm of anodic current density on electrode potential for titanium elec-
trode with a stationary passive film, formed at various potentials (0.7; 1.0; 1.4 V) in 40’%,H,SO, at 80°C.

film. Thus, the curves of Fig. 3 represent the dependence electrode; 6 is the film thickness and 1 is the part of
of ionic current, passing through the unchanged pas- whole potential drop, localised in film
sive film on the potential shift from stationary poten- The tentative value of thickness of barrier layer can
tial of the film formation, which is equal to 0.7; 1-Oand be calculated according to the equation (5) with some
1.4 V respectively. The logarithm of current density assumptions. From the experiment (Fig. 3)
(In i) linearly depends on the anodic potential (cp).
It was found by Giinterschulze and Betz[ll] that kT6
ionic current i and field strength in film E are related m = B
as follows
isequal to013;0.14 and 017 for potentials offilm for-
i = AexpBE (4) mation 0.7; 1.0 and 1.4 V respectively. At 80°C the kT
value is equal to 0.03e V ; Z = 4; a according to [37]
where A and B are constants and E is field strength in
does not depend on pY of solution and is equal to
film. The observed linear dependence of logarithm of
O-9 + 1.4A (take a = 1 A). It is assumed now that the
anodic current on electrode potential (Fig. 3) enables
main portion of potential drop for passive Ti-anode is
us to suppose that in studied region of passive poten-
tials the field strength in the film depends linearly on localised in the film eg in [38] the potential drop in
the electrode potential, similar to that as it was shown film in I N Na,SO, was shown to be 60 + SOo/,.Thus,
for passive titanium in alkali solution[14]. Taking this 1 can be assumed to be 0%. The calculation for poten-
fact and later studies[12,13] into consideration one tials 0.7; 1.0; 1.4 and l-8 V gives the following values
can represent the equation (4) in the detailed form: of thickness of barrier films (6): 14.1 ; 15.0; 18.5; 23.2 A
respectively. Thus, the thickness of barrier layer grows
as potential increases and is considerably less than the
W za. [(cp - %) mean value of the total thickness of passive film (Table
i = 2an vcxp
( > -kTexpkT 6 (5)
2).
The barrier layer formation at potentiostatic
where a is activation distance, n is the number of titanium passivation takes place at the first minutes of
mobile interstitial ions in a volume unit; I/ is the polarisation, similar to the formation of anodic films
vibration frequency of interstitial ions; W is the acti- on titanium in another condition[l& 163. This is sup-
vation energy of ion; Z is the charge of ion; q is elec- ported by the experimental fact that the slope of the
trode potential: q, is the potential of reversible oxide curves at each potential of film formation (Fig. 3) does
The passivation of alloys on titanium bases 163

Cr,Mn.Sn.Nb.Mo,”
not depend on the time of electrode anodic polarisa-
tion (of the film formation) before the curve measure-
ment and this slope is a function of potential of the film
formation.
The electron diffraction studies of titanium surface
after the anodic polarization for 5 h (40% H,SO,,
SOOC)at various potentials have shown that the anodic
films consist of titanium dioxide of two modifications:
rutile and anatase, and than the higher the potential of
film formation the greater the relative percentage of
anatase in comparison with rutile. IT we compare the
composition and structure of anodic films, formed in
sulphuric acid of moderate concentration at anodic
polarisation[9] and the composition and structure of
the films formed in diluted boiling solutions of sul-
phuric and hydrochloric acids in self-passivation pro-
cess[ 101 with our studies results we can conclude that
at uur conditions the barrier oxide layer consists of
anatase, but a rutile forms a porous part of the film and
appears as a result of some secondary processes. The
similar structure composition of the barrier layers,
formed at different potentials, does not allow to
explain a considerable decreasing of anodic currents Alloymg component , wt %
(almost by two orders) at the increasing of anodic Fig. 4. The dependence of stationary current density of ano-
potential from +O-14 to + 1.4 V (Fig. 2) as a result of die titanium and alloys dissolution at potential q = I.0 V
chemical stability change of these layers. This is sup- (40% H,SQ4, 8O”C, r = 5 h) and self-activation time on
ported also by a rclativcly small increasing of chemical alloying additions percentage.
stability of passive films, formed at different potentials,
the chemical stability is estimated by self-activation
time (2,) (see Table 2). The main reason of stationary The stationary rates of anodic dissolution of low
anodic current decreasing is the lowering of ionic con- alloyed titanium alloys in passive state at mentioned
ductivity of passive films during their formation at conditions are given in Fig. 4. One can see that Al, V,
more positive potentials because of the lowering of MO, Zr and Nb increase the rate of anodic dissolution
their defectness, but the effect of the rate difference of of titanium alloy from the passive state, Cr and Mn
the chemical dissolution of the passive films on the rate diminish this rate and Sn does not influence it.
of anodic dissolution can be neglected Tt can be Proceeding from the experimental data on the main
thought that the defectness of anodic films decreases as expenditure of anodic current for direct electro-
the anodic potential increases up to some value (q = chemical titanium dissolution it is unlikely to suppose
1-4 V). beginning from this value the defectness does that the change of the rate of titanium anodic dissolu-
not change significantly. For example, up to 1.8 V the tion at alloyage is determined by the change of rate of
barrier layer thickness still increases, though station- chemical dissolution of passive oxide. An approximate
ary current does not decrease already (Fig. 2). The conclusion on the effect of alloying elements on the
curve bend (Fig. 2) takes place near the equilibrium rate of chemical dissolution of the passive films for
potential of oxygen electrode (1.23 at pH = 0). It can studiid alloys was drawn on the base of self-activation
be supposed that the activity of adsorbed oxygen in- time (se) of the electrode at the same conditions (40”/,
creases as the potential approaches the equilibrium H2S04, 80°C) after anodic polarisation has been
oxygen electrode potential and this is apparently the switched off.
cause of decreasing of films defectncss and of current The self-activation time data measured by the time
lowering of titanium anodic dissolution. of sharp change of potential to negative values after the
anodic current was switched off are given in Fig. 4. As
it can be seen from Fig. 4 all studied alloys besides Ti
2. THE EFFECT OF ALLOYING COMPONENTS Al and Ti-Zr have the same self-activation time (close
ON THE ANODIC DISSOLUTION OF
to the t, of titanium) irrespective of that whether they
TITANIUM ALLOYS IN PASSIVE
increase or decrease the rate of anodic dissolution.
STATE
Proceeding from the classical conception of film passi-
The study of the effect of alloying components on vity[13], according to which Ihe steady anodic current
the anodic dissolution of the titanium alloys in passive is equal to the chemical dissolution rate it could be
state was carried out for low-alloyed titanium alloys l- assumed that the alloys having the anodic currents
24 and 2X-30 (see Table 1) at the same conditions (40% lesser than those for titanium, would have the greater
H2S0,, 80°C p = 1 V). self-activation time.
164 N. D. TOMASHOV, G. P. CHERNOVA, Yu. S. RUSCOL and G. A. AYUYAN

40%H,SO,. 80°. rp=f,OV. r-5h

0.6

i. pA /cm2
Fig. 5. The dependence of togarithm of anodic current density on electrode potential for titanium and
alloys with passive film, formed preliminary at potential q = 1.0 V.

The small dependence of the rate of chemical disso- method described when the Fig. 3 was discussed. The
lution of passive films on the titanium alloyage by the data are give in Fig. 5. It is seen that for all alloys the
small additions of studied elements is also supported electrode potential depends linearly on the current
by the data on the anodic polarisation curves of stud- density logarithm in a wide range of current densities.
ied alloys and on the structural analysis of formed pas- It should be noted that a slope of curves
sive films.
It appeared that passivation potential (p,,) and com-
tgy=kT!?
plcte passivation potential (cp,,,) in studied conditions Za 1
are equal to -0.21 V and +014 V respectively for all
studied alloys and they are slightly effected by alloying in equation (5) is the same for different alloys. The
additions. The last fact is an indirect indication of an values Z and a do not change significantly at alloyage
identity of passivating layers of titanium and its low- and can be assumed to be constant. Then the con-
alloyed cc-alloys. stancy of rgy for different alloys means that the poten-
The electron diffraction study of structure of oxide tial gradient (field strength)
films formed on the low-alloyed alloys at cp = 1.0 V in
40% H2S04 at 80°C at 5 h exposition (ie, at the steady
anodic dissolution) has shown that the films of identi-
cal composition-X0, with structures of rutile and
anatase are formed on the surface of all alloys like a (in equation 5) is unchanged, though the thickness of
pure titanium. Obviously, the main effect of alloying harrier layer of the passive film changes in some extent
element on the anodic current of dissolution of because of the alloyage. Obviously, if the field strength
titanium alloy from the, passive state is determined not in the film, ie, potential drop for the film thickness
by the change of chemical stability of passive film, but unity, is constant, then the ionic current value is deter-
by the change of defectness of oxide film and therefore mined by specific properties of oxide only, ie, by a spe-
of its ionic conductivity when alloying component cific ionic conductivity. The difference of steady cur-
atoms enter the oxide lattice. rent values on titanium and alloys is explained by an
It was interesting to determine the character of the alloyage effect on pre-exponential factor of equation
change of ionic conductivity of passive films depending (5) by means of the change of mobile ions con-
on the titanium alloyage by various components. This centration nand the activation energy of ion W. Taking
was made by a measurement of V-A characteristics for this into consideration the substantiated assumption
passive films, formed on the studied alloys at poten- can be made that the diff‘erence of steady anodic cur-
tial + 1,OV in solution of 40”,, H ,SO, at 8O’C by rents for studied titanium alloys can be explained not
The passivation of alloys on titanium bases tl55

In i - l/T appeared to be the same for titanium and


studied alloys and was equal to 19.4 kcal/g-atm (Fig.
6). The constancy of activation energy for titanium and
itsalloys does not agree with an assumption of the dif-
ference of chemical stability of the films on titanium
and alloys, the high value of the activation energy
points out that diffusion processes in solution are not
rate-determining for dissolution of titanium or alloy.
However, the mechanism of alloying components
effect on the character of defectness change and ionic
conductivity of passive films on titanium is not clear
yet. In any case the experimental results can not be
explained by the theory of valency induction of Farvey,
Wagner, Hauffe[l7]. According to this theory 3-valent
chromium ions being in oxide film of TiO, with elec-
tronic conductivity type should increase an ionic cur-
rent, but the 5-valent ions should decrease it, ie, the
effect should be just opposite to that found in our
studies (Figs. 4 and 5). If we assume a hole type of con-
ductivity(it is less probable) we should remove this dis-
crepancy, but even in this situation the contradictions
remain. The radical distinctions of the ionic conducti-
vity changes of TiOa, caused by the additions of cer-
Fig. 6. The dependence of logarithm of anodic current den- tain elements of the same valency (Sn4+ and Zr4+) or
sityon inverse absolute temperature for electrodes, made of of the lower valency (Al3 + and Cr”+) are not explained
titanium and two alloys with passive film, preliminary also.
formed in the same electrolyte (40% H2S04, 80”) at cp=
1 V. + = 5 h.
3. THE EFFECT OF TITANIUM ALLOY
by alloying component effect on the chemical stability STRUCTURE ON ITS ELECTROCHEMICAL
of the film but by the change of its defectness and ionic AND CORROSION BEHAVIOLJR
conductivity. Therefore, for studied low-alloyed These studies were carried out on the alloys Ti-
titanium alloys the main process of anodic dissolution 15Mo (No. 27) (Table I), Ti-Cr (Nos. 31 and 32), and
in passive state, like a pure titanium, is a process of di- Ti-Cr-Ta (Nos. 33 and 34).
rect electrochemical transition of titanium ions into
the solution, ie, reaction (3). (a) The Ti-15MO ulloys
The conclusions on the preferential role of reaction The Ti- 15Mo alloys had a p-structure after harden-
of direct electrochemical dissolution in anodic process ing from 850” and subsequent tempering at 400” for
at the steady anodic current on titanium and studied 14 h, /? + w-structure after hardening from 850” and
alloys are supported by the results of the study of tem- subsequent tempering at 400” for 14 h and fi + JX-
perature effect on the steady anodic current through structure after hardening from 850” and tempering at
passive film, formed at constant conditions (40”/, 550”for 50 h[18]. The study of these alloys was carried
H,SO,, 80°C. cp = 1.0 V, z = 5 h). Pure titanium and out in 40% H,SO, at different temperatures. A con-
alloys Ti+SCr and Ti-6.3Nb have been studied, The siderable increasing of dissolution rate was found as
experiment was carried out in the following way: the one goes from pure /?-structure to B + w- and /?+ c1-
steady anodic current was registered at mentioned structures, as it can be seen in Fig. 7, where the depen-
conditions, then an electrode was transferred into 40% dence of logarithm of the corrosion rate on the inverse
H,SOI having a lower temperature at v = 1.0 V, after absolute temperature (l/T) is given. It was found that
30 s anodic current was registered, then an electrode the alloy of pure &structure dissolves uniformly (40%
was transferred back to 40% H,SO, at 80°C. rp = H,SO,, 9O”C), and a ratio between MO and Ti in solu-
I.0 V and kept at these conditions until previous tion is approximately the same as in alloy. If the alloys
steady current was achieved. When this previous cur- with p + c+structure dissolves at these conditions, the
rent value was settled the cycle was repeated at another fine-dispersed dark layer, identified as pure B-phase, is
temperature. It was assumed that when an electrode accumulated on the surface of the sample, cl-phase
was placed in 40% H,SO, solutions of lower tempera- passes into the solution mainly and a MO content in
tures the film did not undergo any considerable dissolved metal does not exceed 3.3% of dissolved
changes. Thus, the temperature dependence of anodic metal quantity. As the fine-dispersed /?-phase having a
current on the titanium or alloy with a film, formed at lower hydrogen overvoltage[19] accumulates on the
the same conditions, was obtained. The activation surface the hydrogen depolarisation process is facili-
energy of this process, calculated by the slope of curves tated and that leads to the current increasing of anodic
LAVol. i9No.4-B
166 N. D. TOMASHOV, G. P. CHERNOVA, Yu. S. RUSCOL and G. A. AYUYAN

tion. For example, in 40% H,S04 at 90°C at 4 =


+ O-l V the corrosion rates of/$ /j’ + w and p + c( alloys
were equal to 0.28; 0.48; 0.99 g/m’ h respectively; but
at cp = +0,74V and T = 80°C the corrosion rates of
the same alloys were equal to 1.17; l-65 and
1.81 g/m’ h, meanwhile in active state the corrosion
rates of these alloys (as it can be seen in Fig. 7) at the
same temperatures differed more than an order. It was
found that at the corrosion in the range of potentials
of transpassivation for molibdenum (cp = 0.74 V) the
surface of p + u-alloy is enriched with an a-phase
layer, in solution a percentage of molibdenum becomes
higher than that in alloy.
(b) Ti-Cr-Ta alloys
The binary Ti-5Cr and Ti-15Cr alloys and triple Ti-
Fig. 7. The dependence of logarithm of corrosion rate at 5Cr-5Ta and Ti-5Cr-15Ta alloys (Nos. 31-34, Table
steady potentials (in active state) for Ti-15Mo alloy with 1) have been studied in 5% HCl solution at lOO”C[22].
various structure in 40% H,SO, on the inverse absolute The structure effects of these alloys on the corrosion
temperature (l/T). rate are given in Table 3. It is seen that two-phase
alloys LY+ y (annealing at hOO”C, 25 h, cooling in fur-
process and alloy dissolution rate, since the passiva- nace) have a corrosion_rate in 5% HCI at IOWC, 2-10
tion potential is not reached. times greater than single-phase alloys a’ or /s of the
An alloy with j3 + w-structure (4O’x H,SO, YOOC) same composition (hardening from 1000”, exposure 4 h,
is covered at the dissolution with a more dense dark cooling in water). The increasing of corrosion rate of
film, which could not be identified by X-ray technique. a + y alloys in comparison with p-alloys is explained
It can be assumed that this film is a phase, enriched by a lowering of overvoltage of hydrogen evolution on
with MO, since the analysis of solution indicates a low- the cathode for two-phase alloys in comparison with
ered content of molibdenum (.5.5-8*5°k of dissolved single-phase alloys, that was supported by a measuring
metal quantity) in comparison with its content in alloy. of cathode polarisation curves. Together with an over-
It takes place because w-phase which contains a less voltage lowering of cathode process in two-phase
quantity of MO, dissolves in the first turn[20]. The fol- alloys the rate of anodic dissolution increases. This can
lowing empirical activation energies were obtained for be explained by the fact, that the phase TiCr, or
alloys with the structures fi + 01, @ + ~1, and p: 10.6; (TiTa)Cr, in alloys without tantalum or with a low
19.4 and 20.6 kcal/g-at. respectively. In spite of the tantalum percentage undergoes more intense cor-
similar values of activation energy of alloys with p- and rosion, it leads to the increasing of true surface and to
p + w-structures the corrosion rates of p + w-alloy the formation of structure defects.
are considerably higher than those of alloy with a pure The study of alloys structure effect on their anodic
p-structure. This can be explained by the formation of behaviour has shown (Fig. 9a), that the passivation
the greater number of the active centres on the surface current increases as the chromium percentage grows
at selective dissolution of o-phase and as a result, by for two-phase alloys in great extent than for single-
a considerable increasing of pre-exponential factor in phase ones. The passivation current decreases as tan-
Arrhenius equation for p + o-alloy. It is known[21], talum percentage in TiLSCr-Ta alloys increases. ‘pp
that a total square of the active centres on the surface
of a solid phase is included in the pre-exponential fac-
tor of Arrhenius equation for heterogeneous reactions.
As it is seen from anodic polarisation curves for
these alloys, given in Fig. 8, at potentials of active dis-
solution the correspondence between currents and
therefore between the dissolution rates of alloys with
various structures is the same as in corrosion exper-
iments, discussed above. In addition, the potentials of
the beginning of passivation and complete passivation
do not depend almost on the structure changes and are
(1
equal to ‘pP z -0.14 V and qPepz to.1 V respectively. 2-O

A single phase alloy had a best corrosion stability, two- /I (


2.4
phase /? + oc-alloy had a worst corrosion stability in
the range of passive state potentials and in the range 10 102 103 IO4

of potentials of transpassivation for molibdenum. i. PA/cm

However, the difference in corrosion rate of alloys of Fig. 8. AnodicpotentiokineticcurvesofTi-I5 MO alloy with
various structures was not so great as at active dissolu- various structure in 40% H*SO, at 90°C.
The passivation of alloys on titanium bases 167

Table 3. The effect of composition and structure of titanium alloys on the corrosion rate in
5% HCI at 100°C. z = 3 h

Single-phase Two-phase

Corrosion rate, Corrosion rate,


Alloy Structure g/m’ h Structure g/m’ h

Ti r I@0
Ti-5 Cr x’ lo.0 a+Y 133.0
Ti--15Cr 28.6 X-tY 230.0
Ti-SCr-STa 9.7 x+Y 79.0
Ti-5 Cr- 15Ta 5.8 x+Y 11.0

and pcpcp for single-phase alloys do not depend on chro- The value of anodic loop in Ti-15Cr alloy is consider-
mium percentage in alloy (Fig. 9). For two-phase alloys ably greater and wider than that for alloys with So/,Cr.
with lSo/, Cr q,, is slightly shifted to more positive The difference of anodic curves for single-phase and
values. two-phase alloys in the range of transpassivation for
Since the rate of curves measurement influences the chromium we explain in the following way. In cr + y
current value in passive state, the stationary values of alloys the preferential dissolution of y-phase, enriched
anodic currents have been measured at qP = 0.55 V with chromium in the surface layer of ahoy takes place
(Table 4). when the potential of chromium transpassivation
The results say that the structure does not influence + 1-2 V is attained. It is supported by the fact that this
considerably the anodic dissolution current in passive loop is absent at the reverse motion of the anodic curve
state, meanwhile when the Cr percentige grows up to and at slow sweep potential speed.
15%. the current also increases, but when Ta percent- Single-phase hardened Ti-Cr-Ta alloys slightly
age grows up to 15% the current decreases. differ from Ti-Cr alloys in anodic hehaviour in trans-
A certain increasing of current is observed at anodic passivation region of chromium. There is a current de-
curves for single-phase alloys at potentials of transpas- creasing at the increasing of Ta percentage in alloy in
sivation for chromium (about 1.2 V) and more positive, active field. Two anodic loops are observed for two-
for two-phase alloys at these potentials the maximum phase Ti-SCr-5Ta alloys (Fig. 10). The first loop at
of anodic current (anodic loop) (Fig. 9) is observed. potential + 1.25 V corresponds to the maximum of
The loop value at the anodic curve depends on alloy anodic current for Ti-Cr alloys, and the second loop
composition and the rate of the curve measurement. is observed at more positive potentials. As the perccnt-
age of Ta increases up to 15% only one loop is
observed, hut at more positive (+ 1.45 V) potentials.
5 % HCL. IOO”C. 24V/h
Such difference in behaviour of Ti-Cr and Ti-Cr-Ta
alloys is explained by difference of electrochemical
behaviour of y-phase, which contains Ta in Ti-Cr-Ta
alloys. The study of anodic behaviour of TiCr, and
TaCr, compounds has shown that the dissolution rate
of TiCr, is considerably higher than that of TaCr,,
though in transpassivation region they begin to dis-
solve at the same potential + l-2 V. This explains the
maximum shift of anodic current to positive values as
Ta is added into Ti-Cr alloy. However, a certain
amount ofa’-phase, supersaturated with chromium, can
remain in alloy with a relatively small Cr and Ta per-
centage (P-stabilisers). Because of this when the maxi-
mum of anodic current, determined by a low dissolu-
tion ofy-phase, enriched with Ta, is shifted, the current
for the dissolution of oc’-phase, enriched with Cr is not
shifted and thus the current maximum for Ti-5Cr-5Ta
alloy biphurcates.
The conservation of a-phase becomes unlikely in Ti-
iv mA/cd 5Cr-15Ta alloy, ie, when the percentage of P-stabi-
Fig. 9. Anodic potentiokinetic curves for TiGCr and Ti- lizers is high, therefore the first current maximum at
Cr-Ta alloys in 5% HCl at 100°C. The sweep speed 24 V/h. + 1.25 V disappears.
(a) The effect of composition and alloy structure on passiva- The effect of the composition and structure of alloys
tjon current. on the anodic dissolution rate and the components
I68 N. D. TOMASHOV, G. P. GERNOVA, Yu. S. RIJSCOL and G. A. AYLJYAN

Table 4. Current density dependence on the composition and structure of alloys in 5% HCI
at 100°C at cp= 0.55 V

Single-phase state, Two-phase state,


hardening from IWO” annealing 600”, 25 h
Alloys
composition Structure mAjcmZ Structure mA/cm’
Ti cl 8,1 - -
Ti-5Cr 9.1 NfY 6.9
Ti-15Cr ; 14.4 z+Y 14.3
Ti-SCr-5Ta 62 r+Y 8.8
Ti-K-15Ta 3.3 a+Y 3.9

5% HCL, IOO’C 24V/h region the corrosion rates are considerably less, but the
corrosion rate of two-phase alloys is greater than that
for single-phase ones. The ratio of Cr to Ti + Cr quan-
tities in solution is considerably greater than that in
alloy. It is characteristic in great extent for two-phase
alloys than for single-phase ones.
The maximum corrosion rate and maximum pre-
dominance of dissolution rate of the component or
phase, less stable at given conditions, are observed at
initial period of polarisation. The increasing of Cr per-
centage in solution in comparison with that in alloy in-
dicates that in the range of Cr transpassivation the
selective Cr dissolution from alloys is possible: both
from the solid solution of Ti-Cr homogeneous alloys
I.2 and from two-phase alloys even in greater extent. Such
---_-_=,
preferential Cr dissolution for hetcrogcneous alloys is
determined firstly by a preferential dissolution of
y-phase with increased Cr percentage; for the homo-
geneous alloys it is determined by a volume diffusion
of Cr atoms from surface layers of solid solution in the
process of anodic dissolution[24-261.
The results obtained in the study allow to conclude
iI mA/Cm2 that the measurement of anodic potentiodynamic
curves with high sweep speed is a good method of
Fig. 10. Anodic curves (24 V/h)for single-phase (a) and two-
registration of anodic processes, related with the
phase (b) Ti-Cr-Ta alloys, 5% HC’I, 100°C.
change of surface metal layers.

ratio in corrosion solution for active region and for (c) TiGNbPd alloys
transpassivation region has been studied.* The sam- The considerable increasing of corrosion stability of
ples were polarised at potentials -0.3 ; +- 1.5 and 2.0 V, some passivating metal materials by their alloyage
then corrosion rate and the ratio between Ti and Cr with the small quantities (0.1L0.5°~) of cathode addi-
quantities, passing into solution, were measured analy- tions (Pd, Pt, Cu. Re, Ru etc.) was shown by numerous
tically by means of photocolorimetric analysis[23] studies at the Institute of Physical Chemistry of the
(Table 5). Academy of Sciences of the LJSSR[27-301 and further
In active potentials range the corrosion rate for two- studies at many laboratories[31,32 et al.]. It was found
phase alloys is considerably greater than that for that this happens because of a strong decreasing of
single-phase alloys. The alloys dissolution takes place cathode process overvoltage at the accumulation of
approximately in accordance with the weight propor- cathode component on alloy surface and the potential
tion of components in alloy irrespective of alloy struc- shifting of alloy corrosion to passive state region.
ture, possibly at some predominance of Ti (more active The most important positive effect of cathode
component in active state than Cr). In transpassivation alloyage was found for titanium. This is a consequence
of not only the great tendency of titanium to passiva-
tion, but also is a consequence of passive state stability
* The sensitivity of chemical method of Cr/Ti + Cr ratio in the presence of Cl--ions and that of the absence of
determination in passive region in solution was not suffi- tendency to transpassivation. Owing to their high abi-
cient. lity to passivation and high corrosion stability in acidic
4
Table 5. Dissolution rate (K) at g/m2 h of Ti-5Cr and Ti-15Cr alloys at anodic polarisation and Cr/Ti f Cr ratio in solution 5% HCl loO”C,7 = 60 min z
BW
Single-phase alloys Two-phase alloys %.
(hardening) (annealing) d
c.
s
5% Cr 15”’ Cr 5% Cr 15%~r %
(a’) ;;I (a + y) (a + Y) E
Potential 5
of anodic Cr/Ti t Cr Cr/Ti + Cr Crfli + Cr Cr/Ti + Cr x
polar&ion K in solution K in solution K in solution K in solution 5
g/m2 h o/ g/m2 h o/ 0’ 2.
(PHV ,0 /0 g/m’ h % g/m2 h /k g
z.
-03 260 4.0 27.0 13-5 53-o 4.4 182-O 14.0 2
3
tl.5 0.06 14.2 0.2 17.0 @OS 30.0 Q-7 39-O
t2.0 0.05 24.0 0.16 26.0 009 26.4 04 50.0 $
1
170 N. D. T~MASHOV, Cr. P. C‘HERNOVA,YIJ. S. Rusco~ and G. A. AVUVAN

media, containing Cl--ions, the Ti-O.2Pd alloys find a assume that only a-phase dissolves at given conditions
wide application in industry. (this is close to real situation) the calculations indicate
At the last time the good results on the cathode that the percentage of Pd in a-phase was equal to
modification of some titanium alloys, possessing of 0.018% at mean concentration of Pd in alloy equal to
high strength characteristics were obtained[33]. 0.2%. Because of that the self-activation of Ti&ZONb-
Recently[34], some peculiarities of cathode alloying Pd (0.1 and 0.2%) alloys is hampered and this leads to
addition effect on heterogeneous, two-phase alloys on increasing of their corrosion rate in comparison with
titanium base were found. The effectiveness of cathode single-phase Ti Pd alloys, having the same mean Pd
alloyageofalloy is determined by the amount ofcathode percentage (Table 6).
addition, accumulated on the alloy surface at the initial It can be supposed that if a cathodic addition intro-
period of corrosion. Therefore, at the corrosion of two- duced in c( + p titanium alloys dissolves mainly in the
phase alloys with Pd when only one phase dissolves, less corrosion stable a-phase the accumulation of cath-
only the fraction of Pd which is in preferentially dis- odic addition on the surface and transition of alloy to
solving phase will be accumulated on the alloy surface. passive state will occur with a more high rate.
This was the case for Ti-Nk Pd alloys[34], containing
20% of Nb and 0.1 or O-2% of Pd and having a two-
phase structure CL+ 8’ (annealing at 8WC, exposure CONCLUSIONS
I h, a slow cooling with a furnace) at their corrosion
in HCl and H,S04 solutions. The passivity and corrosion behaviour of titanium
The formation of powdery layer on the surface was and some alloys on titanium base in corrosion-active
observed at the corrosion of two-phase Ti-IONb and media have been studied.
Ti-2ONh alloys in sulphuric and hydrochloric acids. X- 1. It has been found that in 40% H,SO, at 80°C an
ray analysis of such powder has indicated that it is anodic polarisation of titanium at Q = 1 V the direct
practically pure /?-phase. At the corrosion of two-phase electrochemical transition of titanium ions (as TiOzf)
Ti-Nb alloys, modified with Pd, the preferential disso- in corrosion solution is a preferential anodic process.
lution of or-phase only will be observed at the initial The interval of polarisation curves for titanium in 40%
period of active corrosion. It is known that the Pd H,S04, where the current density (in passive state) is
solubility in a-phase with hexagonal lattice is consider- independent of potential, disappears gradually as tcm-
ably lower (-5%) than that in D-phase with cubic pcrature increases from 25 to 90°C. The total thickness
body-centrcd lattice (45-50%)[35,36]. Because of that of passive films, formed at more positive potentials (+
the amount of Pd, accumulated on the alloy surface at l-4 V), is less than that of films formed at less positive
the corrosion in active period will be considerably less potentials (+ O-7 V), though the protective properties of
than that, calculated by the corrosion value proceeding latters are worse. This is explained by two-layer struc-
from the total Pd percentage in alloy. The relative pcr- ture of the films. The barrier film layer next to metal
centage of p-phase will increase, as Nb percentage in inhibit the metal dissolution. The protective properties
alloy increases, while the amount of a-phase, undergo- of barrier layer increase if the layer is formed at more
ing a corrosion will decrease. Therefore, in triple Ti positivepotentialsnotonlyattheexpenseofits thickness
Nb Pd alloys with high percentage of Nb (10 and 20%) increasing, but mainly at the expense of its defectness
the total amount of Pd in cc-phase will decrease in com- decreasing and of decreasing of ionic conductivity. The
parison with its amount in double Ti-Pd alloys. The electron diffraction studies have shown that anodic
accumulation of Pd on the surface of Ti-NbPd alloy titanium film has a mixed anatase and rutile structure.
will be more slow than that on the Ti-Pd alloy with the The anatase fraction increases when film is formed at
same Pd percentage in alloy. Actually, at the corrosion positive potential. It can be supposed that the barrier
of Ti-ZONbO.2Pd alloy in 20% H,SO, at 100°C for layer has an anatase structure, the outer porous layer,
5 h it was found that only about 9% of calculated formed apparently owing to secondary crystallisation,
amount of Pd is accumulated on the surface. If we has a rutile structure.

Table 6. Corrosion stability (g/m’ h) of Ti&NbPd alloys in solutions of sulphuric and hydrochloric acids

Concentration of H,SO, Concentration of HCl


“/, “/,
Temp.
Alloys “C 20 30 40 10 15 20

Ti-2ONb 25 - 0.35 0.84 - o-14 0.59


Ti-2ONbXl.l Pd 25 0.49 I-03 O-028 0.51
Tia.1 Pd 25 0.027 0.16 O-025 0.07
TikZONb 100 26 - 130 225 7-8 88
Ti-20NLO.2 Pd 100 23 120 0.52 7.0 9.0
TiGO-2 Pd 100 1.9 10.7 0.12 o-4 2.8
The passivation of alloys on titanium bases 171

2. The alloying components effect on the anodic dis- takes place in accordance with their weight percentage
solution of a-titanium alloys in passive state has been in alloy. In Cr transpassivation region the ratio
studied. It was found that additions of AI, V, MO, Zr, Cr/Ti + Cr in solution is considerably higher than
Nb to titanium increase, the additions of Cr, Mn de- that in alloy. The preferential dissolution of Cr is noti-
crease, those of Sn do not effect on the dissolution rate ceable for two-phase alloys especially. The dissolution
of low-alloyed titanium alloys though the rate of rate of less stable at the experimental conditions com-
chemical dissolution of passivating oxide for majority ponent or phase prevails at the initial period of dissolu-
of alloys (excluding Ti-Al and Ti-Zr) does not change tion.
from the small additions of studied elements. 5. It was found that in Ti 20NbOn2Pd alloys with
The passive film structure on the studied low-al- two-phase /-I+ a structure a greater part of Pd is in b-
loyed r-titanium alloys appeared to be identical to that phase which is more stable with respect to H2SOd and
of passive film on pure titanium (anatase + rutile). The HCl solutions because of high Nb percentage. There-
potentials of passivation and complete passivation do fore, the rate of Pd accumulation on the surface at the
not change appreciably. The steady currents difference initial period is lowered very much and the transition
in passive state on different alloys is explained by the of alloy into passive state and a stability increasing
change of deftx;tness degree of passive film, when alloy- when Pd is added, are hampered in contrast to pure LX
ing component atoms enter its lattice and therefore by or pure /3structures.
the change of its ionic conductivity. It was supposed that if a cathodic addition dissolves
The direct electrochemical process of titanium disso- mainly in the less corrosion stable phase this addition
lution is a main process at anodic dissolution in pas- should be more optimum cathode addition for alloyage
sive state for low-alloyed a-titanium alloys and for of two-phase-titanium alloys.
pure titanium.
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