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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.
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
o
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 .
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
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 .
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 .
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 other anodic reaction efficiencies . The influence of the
other
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
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 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
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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