. Vol. 33 . No. I I, pp . 1551-1559. 1955.

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GALVANOSTATIC ANODIZATION OF TITANIUM-II .

REACTIONS EFFICIENCIES AND ELECTROCHEMICAL
BEHAVIOUR MODEL
J : L. DELPLANCKE and R . WINANI)

Department of Metallurgy and Electrochemistry, C .P . 165 Universite libre de Bruxelles, Av . F.D.

Roosevelt 50, 1050 Brussels, Belgium

(Received 17 September 1987 ; in revised form 31 March 1988)

Abstract Theefcienciesofthedifferentanodicreactionsobservedduringthegalvanostaticanodizationof
commercially pure titanium in 1 M sulphuric acid between 25 and 75C have been studied . The two
previously observed electrochemical behaviours are characterized by different kinetics for the anodic film
growth, the titanium dissolution, the peroxides formation and the oxygen evolution . Finally, a theoretical
interpretation of the obtained data is proposed.

INTRODUCTION limited to 30 ml and the anode surface to 10 cm' . The

Among the numerous experimental studies devoted to
the potentiostatic or the galvanostatic anodization of
titanium, only a few of them are concerned with the
evaluation of the efficiencies of the anodic reactions
other than the film formation itself. Moreover some
discrepancies are observed in the literature for this film
formation efficiency . Thus, Koyama[l] mentions a
67 % film formation efficiency in aqueous electrolyte
and an efficiency > 100 % in anhydrous electrolyte . By
comparison, Marchenko and Chernenko[2] mention a
value of 20% in a mixture of hydrochloric and
sulphuric acid. Allard and Heusler[3], by studying
aqueous electrolytes of different pH values (between 0
and 13), obtain a film formation efficiency of about
20 % in acidic media (0 5 pH < 3), 10 % in basic media
(10 5 pH C 13) and 50-60% in neutral media (6
< pH 5 8) . In this study, these authors consider three
anodic reactions: the film growth, Ti" ion formation
and oxygen evolution .
The peroxide formation is, as far as we know, not
described in the literature devoted to the anodization
of pure titanium . Nevertheless Kohayakawa et al .[4]
have shown that illuminated TiO 2 monocrystalline
electrodes may oxidize the sulphate anions in per-
sulphate anions by direct transfer of holes from the
valence band of the oxide to the ions in solution .
EXPERIMENTAL
Apparatus
The descriptions of the electrolytic cell, the elec-
trodes, the electrolyte, the power supply and the
electric circuits are given in previous papers[5, 6] . The
design of the electrolytic cell is described in Fig . 1 . It
was adapted to the partial anodic reaction to be
studied . So, in order to measure quantitatively the
titanium ions or the peroxide anions dissolved in the
electrolyte, a small volume of electrolyte and a large
anodic surface are needed. The electrolyte volume was
1551
cooling liquid flow in the coiled tube immersed in the
cell controlled the electrolyte temperature .
For the quantitative measurement of the oxygen
evolution a larger cell (electrolyte volume equal to
500 ml) was used. The gas was collected in a graduated
tube placed above the anode and initially containing
electrolyte.
Analysis
The quantitative analysis of the dissolved titanium
ions was performed by atomic absorption spectropho-
tometry with a Perkin-Elmer 2380 apparatus equip-
ped with a Ti Perkin- Elmer Intensitron lamp . The
studied characteristic wavelength was 365 .3 nm . The
measured concentrations were converted in equivalent
"specific quantity of electricity" (Q .'n )[6] used to
produce these titanium ions (taking into account that
these ions were tetravalent).
To convert the measured volume V of oxygen in
equivalent `specific quantity of electricity" (Qo,) . the
following formula was used (the correction due to the
liquid height in the measuring tube was neglected) :
(P+nH,o.r)To VFn
Q o,=
PoTSV0
where P is the atmospheric pressure, 3rH,o,T the water
vapour pressure at temperature T (in K), S the anode
surface, F the Faraday constant, n the number of
electrons involved in the electrochemical reaction, V o
the volume occupied by one mole of gas measured at
standard conditions and where P o and To are respect-
ively the pressure and the temperature in these stan-
dard conditions . (To avoid oxygen dissolution, the
electrolyte was saturated by bubbling pure oxygen for
at least two hours before anodization .)
The qualitative determination of the peroxides in
solution was done by means of the following reactions :
(i) formation of the orange-yellow complex between
hydrogen peroxide (H2 0 2) and titanium (IV) sulphate .
Ozone, sulphuric, persulphuric and Caro's acid do not
1 55 2 J .-L . DFIPIANCKFand R . WINAND
Fig. 1 . Electrolytic cell used to measure the titanium and the peroxides ions dissolved in the electrolyte and
the volume of the evolved oxygen during the galvanostatie anodization of titanium in sulphuric acid .
interfer[7, 8] . (ii) Oxidation in neutral solution
(sodium acetate) of benzidine (4,4'-diaminobiphenyl)
by the persulphuric acid (H 2 S 2 0s ) with formation of a
blue compound[9, 10] . Ozone oxidizes benzidine to a
brown compound[9] . No data were found about the
influence of Caro's acid on this reaction . (iii) Bleaching
of the violet ACVK (1,5-his-(4-methylphenylamino-2-
sodium sulphonate)-9,10 anthraquinone) by
ozone[11 . 12] . Peroxides do not seem to influence this
reaction .
No specific test for the qualitative determination of
Caro's acid (H 2 SO s ) in the presence of H2O,, O,
o
H 2 S 2 s and H,SO, was found in the literature .
The quantitative determination of the total amount
of peroxides present in the electrolyte was done by
iodometry[13, 14J after neutralization by sodium car-
bonate (to avoid iodate formation and oxidation by
the dissolved oxygen) .
According to the fact that the electrochemical
formation of the different peroxides involves two
electrons (see the following reactions), the total
amount of peroxides is converted in the equivalent
"specific quantity of electricity" (Q~) .
O,+2H++2e .0 2 +H 2 O
111 2 0 2 +2H++2e - c 211 2 0
S2 Oa - +2c - -e 2SO; -
SOS - +2H++2e - <aS0 2 +H 2 O
Finally, the thickness of the anodic film% was measured
by three different methods .
The study of the multiple-beam interference colors
shown by the anodized samples[5], by means of an
Applied Color Systems Inc . Spectro-Sensor II ap-
paratus (incidence angle 8') was performed . In this
apparatus the sample is illuminated by white light and
the visible spectrum of the reflected light is recorded . If
the thin film surrounding the metallic substrate is
transparent, interferences between the beams reflected
at the air-oxide interface and those reflected at the
oxide-metal interface occur . Depending on the film
thickness, one wavelength is extinguished and the
complementary one is enhanced . Due to surface
roughness, inhomogeneities in the film thickness, etc,
the recorded spectrum presents a band of low intensity
wavelength centred on the extinguished one and a
band of high intensity wavelength centred on the
reinforced one. That is to say that the spectrum
presents a maximum and a minimum in the recorded
intensity of the reflected light as a function of its
wavelength . If the thickness of the film is between 30
and 150 am, the maximum and/or the minimum are
located in the visible region and the metallic samples
are colored. The determination of the wavelength
corresponding to this extremutn allows calculation
of[5] the thickness of the film if its optical index is
known . The mean value of the optical index of the
anodic film was determined experimentally by varying
the incidence angle of the light in a Leres Trilac
apparatus.
The anodic films were separated from their substrate
by titanium dissolution in a bromine-methanol sol-
ution[6] . The films were deposited on copper grids and
inserted in a transmission electron microscope JEM
200 CX . By focusing the electron beam on the border
of the analysed sample, the film was curved. As is
shown in Fig . 2, the thickness of the film penetrated by
the electrons in the curved part of the film presented a
sharp maximum corresponding to the real thickness of
the film . By recording the image at high magnification
of the curved film and by studying its contrast it was
then possible to measure the film thickness. At least five
measurements on the same sample were needed to
obtain characteristic average values .
Auger profiles were obtained by means of a PHI 32-
060 A SAM apparatus . The same experimental con-
ditions as those used by Mathieu and Landolt[15] for
the sputtering and the Auger analysis of anodic films
on titanium were chosen . As the elemental com-
position of the analysed films and the analytical
experimental conditions were identical, the value of the
sputter rate measured by these authors
(6.1 nmmin - ') was used in our study .


Electrons

Film

Thickness to measure

I Film
I I

1
Thickness
penetrated
by the electrons

Fig. 2 . Schematic representation of the use ofthe contrast ofa high magnification TEM picture of the curved
part of an oxide film separated from its substrate to measure its thickness .
1554 J : L . DELPLANCKE and R . WINAND
RESULTS
1 . Titanium dissolution
Figure 3 shows the influence of the total "specific
quantity of electricity" (Q') on the "specific quantity of
electricity" related to the titanium dissolution (Qr;)
for two "low" current densities (10 and 20 A M-2 ) and
three "high" current densities (50, 100 and 500 A m -2 )
at 25C .
At "high" current density, Qr, is a growing function
of the electrolysis duration . The ratio Qr 1 /Q', that is to
say the efficiency of the titanium dissolution, is, in this
case, always less than 2' This efficiency increases if
the current density increases . On the contrary, at "low"
current density, after a growth period, Qt stabilizes .
The moment after which this stabilization appears,
corresponds nearly, for a given current density, to the
moment after which the maximum voltage in the
electrochemical evolutions and, thus, the cone struc-
ture appear (points 1, Figure 3) . Here too, the titanium
dissolution efficiency on the one hand, is < 2'v and on
the other hand increases if the current density in-
creases . The same conclusions and the same efficiency
value may be observed at higher temperatures .
Figure 4 shows the influence of the electrolyte
temperature on Qrj for 50 and 500 Am 2 . This
influence is negligible except if the increase in tempera-
ture modifies the electrochemical behaviour ("high"
current density (50 Am - ', 25C) to "low" current
density (50 A m -2 , 50C)).
2. Oxygen evolution
The oxygen evolution is considered in acid elec-
trolytes as the anodic reaction presenting the most
important efficiency . This is only true after a given
quantity of electricity has been fed to the electrolytic
cell . Indeed, the oxygen evolution does not appear
Fig. 3 . Influence of the total -specific quantity ofelectricity" (Q') injected in the electrolyte and of the current
density on the "specific" charge consumed for the formation of Ti" ions (Q};) during galvanostatic
anodization of titanium in I M sulphuric acid at 25"C .
immediately after the beginning of the electrolysis but
well after an induction period . As mentioned ear-
lier[6], this induction period is visualized at "low"
current density, by a stabilization of the cell voltage
followed by a further increase.
The oxygen evolution efficiency is, as represented in
Fig . 5, nearly the same at "high" and "low" current
density and falls between 65 and 81 % .
A careful analysis of the data shows that the oxygen
evolution efficiency on the one hand, for a given
electrolyte temperature, increases if thecurrent density
increases and on the other hand, for a given current
density, decreases if the electrolyte temperature in-
creases . Moreover, at "low" current density, the oxygen
evolution efficiency increases after the appearance of
the cone structure .
3 . Peroxides formation
(a) Qualitative analysis . The qualitative analysis of
the evolved gas and of the electrolyte shows the
following results : (i) small traces of ozone are detected
in the gas phase and in the electrolyte . These traces
have been neglected for the quantitative determination
of the evolved oxygen . (ii) No hydrogen peroxide is
detected immediately after electrolysis but traces are
detected after stabilization of the electrolyte for 2 or
3 h . (iii) Persulphuric acid is detected in the electrolyte.
Moreover, during iodometry, two reactions of
iodide oxidation are detected, the first one proceeds at
high speed and the second one at low speed .
According to the literature[7, 9], the fast reaction
corresponds to the iodide oxidation by the Caro's acid
and the slow one to the oxidation by the persulphuric
acid . The observed traces of hydrogen peroxide may be
the product of the hydrolysis of the Caro's acid
according to :
H2 SO 5 + H 2 O ea H 2 SO 4 + H202 .


Galvanostatic anodization titanium-Il 1555

Fig. 4. Influence of the total "specific quantity of electricity" (Q') injected in the electrolyte and of the
temperature of the electrolyte on the `specific' charge consumed for the formation of Ti"ions (Qf j) during
galvanostatic anodization of titanium in I M sulphuric acid at 50 and 500 A M -2 .

say the efficiency of peroxide formation, is, in this case,

0 a o o 0
8 < 12 %. This efficiency decreases if the current density
increases.
. a a At "low" current density, Qa r reaches a maximum
value after an electrolysis duration nearly correspond-
ing to the appearance of the cone structure (point 1).
The peroxide formation efficiency is higher for
"low" current densities than for "high" current densit-
ies but is always < 20 % . The same results are obtained
at higher electrolyte temperature . For a given current
density, as shown in Fig . 7, the peroxide formation
efficiency increases if the electrolyte temperature in-
creases especially when at low temperature the current
density belongs to the "high" current density regime
and at higher temperature to the "low" current density
O I I I I I
10 15 20 25 30 regime.
a-(I0 4C!m 2 )
4. Film formation
Fig . 5 . Oxygen evolution efficiencies as a function of the total
"specific quantity of electricity" (Q ) during the galvanostatic By varying the angle of the incident light on a sample
anodization of titanium at different current densities (5 presenting a second order interference color and by
10A m -2 , 0 20 A m -2 , 50A M-2, 0 100 A M-2) in I M analysing the displacement of the wavelength cor-
sulphuric acid at 25C . responding to a minimum reflectivity in the visible
spectrum, a value of 2 .2 for the optical index of the
anodic films has been found .
This value is in good agreement with the literature
To conclude, two main peroxides are formed during data[16-21] and is less than the value of the optical
the titanium anodization : persulphuric and Caro's index of metallic titanium. Table I shows a comparison
acids . between the thickness of the different samples
measured by colorimetric analysis, by TEM and by
(b) Quantitative analysis, Figure 6 shows the in- Auger profiles . A relatively good agreement is found.
fluence of the total "specific quantity of electricity" Nevertheless, the colorimetric analysis is not ap-
(Q) on the "specific quantity of electricity" related to plicable to very thin films (0-30 am) (no optimum in
peroxide formation (Q* ) for "low" (10 Am -2 ) and the visible spectrum) and on the contrary, the TEM
"high" (50, 100 and 590Am -r ) current densities of analysis is accurate (relative error c 25 %) but not
25"C . applicable to films thicker than 100 not (for a 200 kV
At "high" current density, Q- is a growing function electron microscope).
of the electrolysis duration . The ratio Q ;~,/Q', that is to At "low" current density, the measured film thick-
1556 J . L . DELPLANCKFand R. WINAND

Fig. 6. Influence of the total "specific quantity of electricity" (Q") injected in the electrolyte and of the current
density on the "specific" charge consumed for the formation of S,O ; - and SO',- ions (Qa r ) during
galvanostatic anodization of titanium in 1 M sulphuric acid at 25`C .

30 .000

o,a00

10 .000

0 . ICm ')

Fig. 7. Influence of the total "specific quantity of electricity" (Qt) injected in the electrolyte and of the
temperature of the electrolyte on the "specific" charge consumed for the formation of S,Oa and SOS - ions
(Qa r ) during galvanostatic anodizatiun of titanium in 1 M sulphuric acid at 50 and 500 Am -

ness is limited to 110 rum . A "high" current density
films as thick as 1 .5 m may be obtained . From the
thickness measurements, a film formation efficiency
may he deduced but this one is only significant if the
films are homogeneous and present an uniform thick-
ness. This determination is then limited at "high"
current density to films before sparking (microporous
structure) and at "low" current density to films before
oxygen evolution (whisker growth) . For other elec-
trochemical experimental conditions, the film forma-
tion efficiency is deduced from the measurement of the
other anodic reaction efficiencies . The influence of the
other
electrolyte temperature on the film thickness is rather
limited .
All these results are summarized in Fig . 8 at 25C for
typical "low" and "high" current densities .
DISCUSSION
The present study confirms the results of Allard and
Heusler[3] . Indeed, in I M sulphuric acid, the ionic


Galvanostatic anodization titanium-11 1557

Table 1 . Comparison of the thickness measured by colorimetric analysis, TEM

analysis and Auger profile for reference samples anodized in t M sulphuric acid
Current Cell voltage Calorimetric
density at the end of analysis TEM analysis Auger profile
(AM -2) anodization (V) mm) mm) (nm)
IO 7 16+3 10
10 11,5 50 35++9 31
50 20 56 41+5
_44
10 15,5 62 47+7 42
10 25 74 74+16 60
10 37,5 105 9310 85
50 58 141 105+55 112

Film formation
QOxygen evolution
_Titanium dissolution
V (VI Peroxides formation

100

50

Fig. 8 . Influence of the electrochemical parameters on the anodic reactions efficiencies during galvanostatic
anodization of titanium in I M sulphuric acid at 25`C .

conduction of the film, associated with the thickening
of the anodic film represents, for all the obtained films,
approximately 15 5 % of the total conduction . But,
the electronic conduction of the film (85 5 % of the
total current) is responsible not only for the oxygen
evolution and titanium dissolution (as mentioned by
these authors) but also for peroxide formation .
Some correlations may be observed between the
kinetics of the different anodic reactions and some
typical structures of the anodic films .
Thus, the cone structure may be correlated with the
decrease of the efficiency of persulphate formation, no
further increase in the concentration of Ti" ion in the
electrolyte and the increase of the efficiency of the
oxygen evolution . The stabilization of the Ti4 ` con-
centration suggests a mechanism of oversaturation of
the electrolyte in the pits observed in the oxide film and
percipitation of TiO 2 around these pits (cone struc-
ture) . How this mechanism is coupled with per-
sulphuric acid destruction and oxygen evolution is not
yet clear.
Another correlation may be observed between the
microporous structure and the decrease of the effic-
iency for persulphuric acid production . As proved by


1558 J .-L . DELPLANCKE and R . WINAND

sparking and by the formation of the high temperature

stable allotropic form of TiO 2 (rutile) in the micropor-
ous films, a high temperature is observed on the surface
of the anode during breakdown . Thermal decompo-
sition of the persulphuric acid and unsaturation of the
electrolyte by Ti 4 ' ions may be explained by this
thermal effect .
The correlation between the kinetics of the anodic
reactions and the "epitaxial" films is more complex .
During the initial growth of these films, no oxygen
evolution is observed . Assuming that the electrolyte is
saturated with oxygen before anodization, this means
that electronic transfers between the energy levels in
the electrolyte and in the oxide film are impossible and
then, the current is completely consumed for film
growth . During the anodization process, as pointed
out earlier[ 61, an electrical breakdown accompanied
by oxygen evolution occurs . The anodic potential at
which this breakdown occurs is reported in Fig . )3 of
the preceding paper[6] for the different studied cur-
rent densities . This potential increases slightly with the
current density at "low" current density and increases 0 10 50
more sharply at "high" current density . It is possible to Vax(V)
correlate the values of the breakdown potentials with
the thickness of the films at these potentials . It appears Fig . 9 . Relationship between the thickness of anodic films
that the film thickness is nearly constant for all these reproducing the titanium substrate and the cell voltage
potentials and is equal to 50 10 nm . It is interesting (V AiC)
to note that this value of 50 nm is very similar to that
mentioned by Jouve et al (25-70 nm)[20, 22, 23] .
These authors consider that for this thickness, micro- increase of the film thickness could only be possible if
cracks appear in the oxide film . The study by TEM of defects like oxygen vacancies appear . Electron trans-
medic films thicker than 50 nm, even at high magnifi- fers from the energetic levels in the electrolyte to these
cation ( x 508, 500) does not reveal such microcracks . It defects could then occur and promote oxygen
is proposed then that for this thickness electronic evolution .
transfers could occur and oxygen evolution could As the field strength is higher for higher current
appear . As the potentials needed to produce the 50 nm density, when the defects appear, a higher current
thick film increase with increasing current densities, efficiency is expected for the oxygen evolution . This
this means that the field strengths in the oxide films phenomenon is indeed observed experimentally .
increase too with increasing current densities . Is this The mechanism of ionic conduction could be as-
field strength constant during anodization at a defined sociated at "high" current density with an increase of
value of the current density? Due to structural changes the film temperature (as observed by Jouve and
at "low" current densities and due to incertainties in Leach[28]) that could promote the "epitaxial"
the measurement of the voltage drop[6] at "high" growth[29] .
current densities, the relationship between the forma- More experiments for current densities between 50
tion potential and the film thickness was only de- and 500 Am -2 at 25'C are needed to estimate more
termined for a current density of 50 Am -2 at 25' accurately the influence of the current density on the
(Fig . 9). A linear relationship, in agreement with the field strength, to correlate this with the reaction
Mott-Cabrera theory is observed . The proportionality efficiencies and then to confirm the proposed
coefficient (2 .4 nm V `) is similar to those mentioned explanation .
in the literature[18, 19,24] and corresponds to a
constant field strength of about 4 .2 10 s V/m .
So, the obtained results are in agreement with a CONCLUSIONS
growth of the oxide film under a constant field
strength . This film strength increases with increasing The purpose of this study was to analyse qualitat-
current densities used during galvanostatic ively and quantitatively the different anodic reactions
anodization . occurring during the anodization of titanium . Beside
What is responsible then for the breakdown of the the "classical" reactions (film formation, oxygen evol-
film? Assuming that stoechiometric titanium dioxide is ution and titanium dissolution), new anodic reactions
an excellent insulating material with an energy gap of (persulphuric and Caro's acids formation) have been
3.2 eV[25] and that non-stoechiometric titanium observed. Moreover the efficiency of the peroxide
dioxide presents oxygen vacancy levels near the con- formation is important (10-20%) for the studied
duction band, responsible for its n-type semiconductor experimental conditions. Taking into account an
behaviour[26, 27], it is proposed that during the initial oxygen evolution efficiency of about 65-81% . the
growth of the oxide film, a low defective oxide could be anodic film growth and thus the ionic conduction are
formed until a thickness of 50 rim is reached . A further rather limited . An interpretation of the observed data
 Galvanostatic anodization titanium II
based on the transformation of an only lightly defect-
ive TiO 2 film into an oxide film containing numerous
defects is proposed .
Acknowledgements-One of the authors (JLD) is indebted to
the National Fund for Scientific Research of Belgium for a
four years research assistant grant that resulted in a Ph .D .
thesis[30] . The authors wish to thank Drs W . Masschelein,
M . Degrez and A. Fontana for profitable discussions and Mrs
Vanhelden for the colorimetric analysis .
REFERENCES
1 . M . Koyama, Rikagaku Kenkyusho Hokoku, 38, 546
(1962) .
2. N . A. Marchenko and G . G . Chernenko, Metal. Nemetal.
Pakrytiya Legk . Metal. Splavov, pp. 104-8 (1972) .
3 . K . D . Allard and K . E. Heusler, J. electroanal. Chem.
Interfacial Electrochem . 77, 35 (1977).
4. K . Kohayakawa, T. Yamaha, A . Fujishima and K . Honda,
Nippon Kagaku Kaishi 10, 1351 (1978) .
5 . L L . Delplancke, M. Degrez, A. Fontana and R. Winand,
Surf. Technol. 16, 153 (1982) .
6. J. L. Delplaneke and R. Winand, Electrochim . Acre 33,
1539 (1988).
7. F. Ephmim, P. C . L. Thome and E . R . Roberts, Inorganic
Chemistry, Gurney & Jackson, London (1948) .
8. W. Massehelein, M . Denis and R . Ledent, Wat. Sewage
Wks, 69 (1977) .
9 . G . Chariot, Les Reactions Chimiques en Solution.
L'Analyse Qualitative Mindrale, 6th Edition, Masson,
Paris (1969).
10. A .!. Vogel, Textbook of Macro and Se,n imicro Q ua litative
Inorganic Analysis, 5th Edition, Longman, Harlow
(1979).
11 . W . J . Masschelein, Ozonlzation Manual for Water and
Wastewater treatment, Wiley, New York (1992).
1559
12 . W . J . Masschelein and G . Fransolet, J. Am. Wat . Wks Ass.
69, 461 (1977).
13 . 1 . M. Koltholif R . Belcher, V . A. Stenger and G .
Matsuyama, Volumetric Analysis, Vol. III, Interscience,
New York (1957).
14 . A . 1. Vogel, A Textbook of Quantitative Inorganic
Analysis . Theory and Practice, Longman. Harlow (1948) .
15 . H. J . Mathieu and D. Landoll, Proceedings of the 7th
International Vacuum Congress, Vol . 3, pp. 2023 6
(1977).
16. G . Blondeau, M . Froelicher, M . Froment and A . Hugot-
Le Goff, J . Phys .. Colloq. 5, 157 (1977).
17. F . Di Quarto, K. Doblhol'er and M . Gerischer,
Electrochim . Acts, 23,195 (1978) .
18. A. Gagnaire and J . Joseph, C .r . scant. Acad . Sci . ser. II
293, 357 (1981).
19. J . Joseph and A . Gagnaire, Thin Solid Films 103, 257
(1983).
20. G . Jouve, A . Politi, P . Lacombe and G . Vuye, J . less-
common Metals 19, 175 (1978) .
21 . A . Politi, G . Jouve and P . Lacombe, J . lesscomnsan Metals
56, 263 (1977) .
22 . G . Jouve and N . E . Dermdji, J . less-common metals 86,
161 (1982).
23. G . Jouve and C . Severac, Titanium Science Technology,
Proceedings of the 5th International Conference on, Vol .
4, pp- 2589-94 (1984) .
24 . R . Olier, P. Clechet, C . Martelet, 1 . It. Martin and A .
Cachard, J. less-common Metals 69, 73 (1980) .
25 . S. Trasatti, Electrodes of Conductive Metallic Oxides,
Parts A and B, Elsevier, Amsterdam (1980).
26 . J . F . Baumard and F. Gervais, Phys. Rev . B 15, 2316
(1977) .
27 . R. N. Blumenthal, J . Baukus and W . M. Hirthe, J .
electrochem. Sac, 114, 172 (1967) .
28 . G. Jouve and J. S L . Leach, Thin Solid Films 110, 263
(1983) .
29 . J . Benard, L'Oxydatton des Mdtaux, Vols 1 and 2,
Gauthier-Villars, Paris (1962) .
30. J : L . Delplancke, Ph .D. Thesis, Universitd Libre de
Bruxelles (1987).