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

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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

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



Thickness to measure

I Film

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 immediately after the beginning of the electrolysis but

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

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 .

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
. 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
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-

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


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



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 further increase in the concentration of Ti" ion in the
of the anodic film represents, for all the obtained films, electrolyte and the increase of the efficiency of the
approximately 15 5 % of the total conduction . But, oxygen evolution . The stabilization of the Ti4 ` con-
the electronic conduction of the film (85 5 % of the centration suggests a mechanism of oversaturation of
total current) is responsible not only for the oxygen the electrolyte in the pits observed in the oxide film and
evolution and titanium dissolution (as mentioned by percipitation of TiO 2 around these pits (cone struc-
these authors) but also for peroxide formation . ture) . How this mechanism is coupled with per-
Some correlations may be observed between the sulphuric acid destruction and oxygen evolution is not
kinetics of the different anodic reactions and some yet clear.
typical structures of the anodic films . Another correlation may be observed between the
Thus, the cone structure may be correlated with the microporous structure and the decrease of the effic-
decrease of the efficiency of persulphate formation, no 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 1559

based on the transformation of an only lightly defect- 12 . W . J . Masschelein and G . Fransolet, J. Am. Wat . Wks Ass.
ive TiO 2 film into an oxide film containing numerous 69, 461 (1977).
defects is proposed . 13 . 1 . M. Koltholif R . Belcher, V . A. Stenger and G .
Matsuyama, Volumetric Analysis, Vol. III, Interscience,
New York (1957).
Acknowledgements-One of the authors (JLD) is indebted to
14 . A . 1. Vogel, A Textbook of Quantitative Inorganic
the National Fund for Scientific Research of Belgium for a Analysis . Theory and Practice, Longman. Harlow (1948) .
four years research assistant grant that resulted in a Ph .D .
15 . H. J . Mathieu and D. Landoll, Proceedings of the 7th
thesis[30] . The authors wish to thank Drs W . Masschelein,
M . Degrez and A. Fontana for profitable discussions and Mrs International Vacuum Congress, Vol . 3, pp. 2023 6
Vanhelden for the colorimetric analysis . (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
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