Surface Technology, 16 (1982) 153 - 162 153

SELF-COLOUR ANODIZING OF TITANIUM

J.-L. D E L P L A N C K E , M. D E G R E Z , A. F O N T A N A and R. W I N A N D
Unwersitg Libre de Bruxelles -- C P 165, Department of Metallurgy and Electrochemistry,
50 avenue F. D. Roosevelt, B 1050 Brussels (Belgium)
(Received December 2, 1981)

Summary

Relations between the colours and the electrochemical parameters

(current density, quantity of electricity and temperature of the electrolyte)
during the anodization of titanium sheets were studied in a 1 M H2SO4
solution.
Mathematical theories were developed for the kinetics of growth of the
anodic film and for the colours of this film. These theories show that the
relation between the growth and the colour of the film is complicated.
Nevertheless, it was possible to find experimental conditions that led to
uniform and well-defined colours.

1. Introduction

Titanium is a light metal with remarkable mechanical properties. More-

over, this metal is covered by a natural film of oxide that gives it an excellent
resistance to corrosion. This is the reason why this metal is frequently used
in aeronautics and in the chemical industry. Its production is growing
continually. Unfortunately, this metal shows sensitivity to severe corrosion
under specific circumstances. This sensitivity originates mainly from defects
in the surface of the metal.
In order to eliminate the defects, anodizing may be considered. Papers
about the anodization o f titanium are numerous [1]. In some o f them, the
appearance of colours on the surface of the anodized sheets has been
remarked [2 - 10]. In addition, self-colour anodizing of titanium has been
patented [ 11 - 17 ]. Nevertheless, we have n o t found in any of these papers
either a systematic study of the colours obtained after anodizing or a theo-
retical explanation of their appearance. The purpose of this study is there-
fore twofold: on the one hand, to find the conditions that produce, after
anodizing, uniform colours on large area samples and, on the other hand, to
derive theories to explain the phenomena that are responsible for these
colours.

0376-4583/82/0000-0000/$02.75 © Elsevier Sequoia/Printed in The Netherlands

154

2. Experimental details

2.1. Electrodes
Rectangular anodes were prepared by sectioning a sheet o f IMI 115
titanium. The dimensions were 45 m m X 43 mm X 0.9 mm. The anodes were
degreased in trichlorethylene, rinsed with ethanol, dried, and pickled in a
m i x t ur e o f 75 vol.% nitric acid solution and 25 vol.% hydrofl uori c acid
solution as r e c o m m e n d e d in ASTM Standards [18] until red fumes
appeared. Th en the m i xt ur e was quickly diluted with distilled water. T he
o t h e r electrode was an aluminium cathode.

2.2. Electrolyte
Th e electrolyte was a diluted solution of pure sulphuric acid. This
electrolyte was chosen among o t h e r possible solutions because sulphuric
acid is readily available and n o t expensive. The concent rat i on of the solu-
tion was 1.02 M. T he electrolyte was d e o x y g e n a t e d using pure nitrogen.
Experiments were p e r f o r m e d at constant t e m p e r a t u r e by means o f a Haake
thermostat.
Three temperatures were studied: 25, 40 and 60 °C.

2.3. Electrolytic cell and electrical supply

The electrolytic glass cell with a heating jacket was supplied at
constant current. This galvanostatic m e t h o d was chosen for two reasons.
(1) When the voltage is applied in a potentiostatic experiment, the
initial growth o f th e film occurs at a high and u n k n o w n transient current.
(2) During a potentiostatic experiment, a continual decrease in the
current is observed as a result o f the growth o f the film. The kinetics of the
electrochemical growth thus c a n n o t be kept constant t h r o u g h o u t a potentio-
static experiment. Accordingly kinetic study o f the f o r m a t i o n of t he anodic
film is very difficult to carry out.
During o u r e x p e r i m e n t the voltage d r o p between cat hode and anode
and the current intensity in the cell were recorded continuously by means o f
a Servogor 120 BBC Goerz Metrawatt recorder. The a m o u n t o f electricity
was also recorded by means of a Tacussel IG6-N integrator. The electrolysis
was carried o u t at various c ur r e nt densities over periods from 1 s to 1.5 h.

2.4. Colour analysis

In order to describe accurately the colours o f our samples, an objective
criterion was chosen: t he colour o f each sample was characterized as a d o t
in the X - Y diagram o f the International Commission of Lighting according
to the m e t h o d described in t he IES Lighting Handbook [ 1 9 ] .
Knowledge o f the distribution o f the luminous intensity reflected by
the sample for wavelengths in the range 380 - 760 nm for 5 nm increments
and o f the same distribution for the light source is needed. These data are
obtained b y means o f a Zeiss RA3 s p e c t r o m e t e r coupled with the reflective
device M40. The results are analysed by means of an HP 21 MX com put er.
 155

3. Results

3.1. E l e c t r o c h e m i c a l results
Figures 1 - 5 s h o w the anode-to-cathode voltage drop versus the a m o u n t
of electricit:~ for five current densities. At a given current density no differ-
ence between the curves should be observed provided that the p h e n o m e n o n

70'
70 V[V)

aO

50
50

~0 /.0

3O

20 20

10 10

I0 20 3b ~0

Fig. 1. A n o d e - t o - c a t h o d e volta.~e d r o p V as a f u n c t i o n o f t h e a m o u n t Q o f e l e c t r i c i t y f o r
a c u r r e n t d e n s i t y o f 4 0 . 5 A m - ( t e m p e r a t u r e , 25 °C).
Fig. 2. A n o d e - t o - c a t h o d e v o l t a g e d r o p V as a f u n c t i o n o f t h e a m o u n t Q o f e l e c t r i c i t y f o r
a c u r r e n t d e n s i t y o f 32.4 A m - ~ ( t e m p e r a t u r e , 25 ° C ) .

70" v{v)

60

50
V{V)
40 z,O

30 30

20

10 10

~Q 2p ~ &o s9 o(¢)

Fig. 3. A n o d e - t o - c a t h o d e voltage d r o p V as a f u n c t i o n o f t h e a m o u n t Q o f e l e c t r i c i t y
f o r a c u r r e n t d e n s i t y o f 24.3 A m - 2 ( t e m p e r a t u r e , 25 °C).
Fig. 4. A n o d e - t o - c a t h o d e voltage d r o p V as a f u n c t i o n o f t h e a m o u n t Q o f e l e c t r i c i t y
for a c u r r e n t d e n s i t y o f 16.2 A m - 2 ( t e m p e r a t u r e , 25 °C).
156

(V3

30

20 ~
10

q~ 2; ____?o_ 4o ~o 6;) ~lc)

Fig. 5. Anode-to~athode voltage drop V as a function of the amount Q of electricity

for a current density of 8.1 A m - 2 (temperature, 25 °C).

is highly reproducible. This is approximately true at 40.5 and 8.1 A m-2.

For the intermediate values, the curves, similar at the beginning, diverge
rapidly.
The voltage drop measured at the end of the electrolysis for each
sample m a y be plotted v e r s u s the amount of electricity, whatever the current
density is. This plot is shown in Fig. 6. Two types of behaviour, one called
"high" current density, the other one called " l o w " current density, may be
distinguished. They break up at a b o u t 9 V. Nevertheless, the aspect of all
the curves is the same: an initial fast increase in the voltage drop followed
b y a region of much slower increase. This aspect has already been observed
b y Ammar and Kammal [20] and by Jouve e t al. [21] respectively for
current densitites lower and higher than ours. Figures 1 - 5 show also that
each curve, whatever the current density, presents an inflexion point at
a b o u t 9 V. A potentiostatic study shows that gas evolution is observed at
this voltage at the surface of the anode.

FI o.i
Figures 7 and 8 show the influence of the temperature of the electro-
lyte on the overall voltage drop for current densities of respectively 40.5 A

x ~

10

4o ~o 6o ~ Ic)

Fig. 6. Anode-to-cathode voltage drop Ve at t h e end o f e l e c t r o l y s i s as a f u n c t i o n o f t h e

a m o u n t Q of electrmity for various current d e n s i t i e s (temperature, 25 °C): +, 40.5 A m-2;
o, 32.4 A m - 2 ; x, 24.3 A m-2;m, 16.2 A m - 2 ; e , 8.1 A m -2.
 157

60: 6O Ve (V}

Ve•
SO. 50

~0

20
J
/ -
'IO 10

O(F_) O(C)
10 2o 30 10 20 30

Fig. 7. Anode-to-cathode voltage drop Ve at the end of the electrolysis as a function of

the amount Q of electricity for various temperatures (current density, 40.5 A m-2):
- - , 20 °C;- - -, 40 °C;-- - --, 60 °C.
Fig. 8. Anode-to-cathode voltage drop Ve at the end of the electrolysis as a function of
the amount Q of electricity for various temperatures (current density, 16.2 A m-2):
- - , 20 °C;- - - , 40 °C;-- - --, 60 °C.

m - 2 and 16.2 A m - 2 . A n increase in t e m p e r a t u r e greatly decreases t h e

voltage at t h e e n d o f t h e electrolysis at high c u r r e n t d e n s i t y and o n l y slightly
at l o w c u r r e n t d e n s i t y . H o w e v e r , in this case at high t e m p e r a t u r e a s t e a d y
value o f t h e voltage d r o p m a y be o b t a i n e d .

3.2. Results o f the study o f the eolours

T h e t i t a n i u m a n o d e s s h o w e d c o l o u r s t h a t c h a n g e d d u r i n g t h e process
o f electrolysis. In o r d e r t o establish a relation b e t w e e n these c o l o u r s and t h e
e l e c t r o c h e m i c a l d a t a , seven samples, each o f w h i c h was representative o f o n e
o f t h e seven d i f f e r e n t c o l o u r s o f t h e visible s p e c t r u m , were selected.
Figure 9 shows t h e d i s t r i b u t i o n o f t h e l u m i n o u s intensities o f these
samples versus t h e wavelength.

bSO'D~l~

08

06

Fig. 9. Absorption of the light reflected by samples as a function of the wavelength X:

curve 1, yellow; curve 2, light brown; curve 3, brown; curve 4, violet; curve 5, dark blue;
curve 6, sky blue; curve 7, green.
158

Figure 10 shows the reduced trichromatic coordinates of these samples

in the diagram o f the International Commission of Lighting.
For each current density, samples with the same reduced trichromatic
coordinates were selected and plotted as functions of the electrochemical
observations (Fig. 11).

G8. ,~-.q,~o
'5~o ~o
07. x~.~o

06, "~o $7o

05, s00 ~5~0
y . .7.zx%sgo
0~ ~ .6" ~ I~;3"~600

02
01 ~80~ J

0136o02 03xOL~ 05 06 07

Fig. I0. Reduced trichromatic coordinates: point 0, light source, point I, yellow; point
2, lightbrown; point 3, brown; point 4, violet;point 5, dark blue; point 6, sky blue;
point 7, green.

a
'704Ve (V) ~ b

60 . . . . . . . . . . . ,

4O

30 ..

2O

10

lc, 2.0 a9 L..o s.o 60 Q{()

Fig. 11. Relation between the colours of the samples (- - -~ and the electrochemical
parameters (--) (temperature, 25 °C): curve a, 40.5 A m-2; curve b, 32.4 A m-2; curve
c, 24.3 A m-2; curve d, 16.2 A m-2; curve e, 8.1 A m-2; curve I, yellow; curve 3, brown;
curve 4, violet,curve 5, dark blue, curve 6, sky blue; curve 7, green.
 159

4. Discussion

4.1. Electrochemical aspects

Our results have been used as a basis for an a t t e m p t to explain theoret-
ically the kinetics of the growth of the anodic film on titanium. The
different kinetic steps o f growth of an anodic film in general have been
presented by Vermileya [22] as follows: nucleation of the anodic film;
growth of the crystals;possible formation of a continuous film;thickening
of the film; limitation of the film thickness.
As a result of our experiments, these steps have to be changed in the
case of titanium. The first three steps may be withdrawn because there is,
before anodization, a natural continuous oxide film. The last two steps must
be changed as follows: thickening of the natural oxide film; oxygen evolu-
tion; dissolution of the film in sulphuric acid.
The discharge of oxygen, observed during our experiments, has also
been observed by Jouve et al. [21] but has not been observed by Ammar
and Kammal [ 2 0 ] , probably because they did n o t reach a high enough value
of the voltage drop between the electrodes and thus of the anodic potential.
The dissolution of the titanium oxide film in sulphuric acid is thermo-
dynamically possible [23] and was experimentally observed by Sinigaglia
et al. [24]. From a theoretical point of view, there are only two phenomena,
diffusion and migration, t h a t may be responsible for the thickening of the
film.
A quick calculation shows that diffusion is not of great importance
because the speed o f the growth" by diffusion at 25 °C in the solid state is
at most about 0.1 A s-1 . We considered, as some workers do [2 - 4], t h a t
Ti 4+ ion migration in a strong electric field in an ionic conductor that may
eventually show some electronic conduction (this allows oxygen evolution
to occur) is responsible for the film growth.
Mott and Cabrera's theory [25] of growth by migration, already
developed for anodizing aluminium, can be used in our case.
If there is no discharge of oxygen at the surface of the anode and if
the dissolution o f the film in sulphuric acid may be neglected, the variation
in the voltage V as a function o f the current density J, the time t and the
initial thickness 60 will be as follows (in standard units):
V = A(5.4 X 1 0 - n J t + 60) ln(BJ)
where A and B are constants. This formula was used for the linear part of
the curves in Fig. 3 between 0 and about 10 V and for a current density of
24.3 A m -2. We obtained for ~0 a value of about 30 A, which is in agree-
m e n t with literature values [26]. If there is oxygen evolution at the anode
at a partial current density J+ and if A5 = kt" is the law of dissolution of
the film in sulphuric acid, where A5 represents the variation in the thickness
during dissolution, the above formula will become
15.4 × l O - 1 1 ( j - - J ÷ ) - - k n t " - i 1
V = A{5.4 × 1 0 - n ( J - J+)t + 5o -- kt n} In 5.4 X 10-11/B
160

The values of each parameter in this formula would have to be experi-

mentally determined by further studies.

4.2. Coloration of the films

Two theories have been proposed to explain the colour of the anodized
titanium sheets.

o ,,b A,A,b

Fig. 12. Multiple-beam interference.

(1) The colours could be due to stoichiometric defects in the composi-

tion of the film [10].
(2) Interference phenomena may cause the coloration [ 12, 13, 15, 17 ].
Figure 12 illustrates the second theory, which is called the "multiple
beam interference" theory.
If the incident beam 1 is a beam of white light, the reflected beam,
which is formed by the interfering beams 2, 5, 8, 11, ..., will be coloured.
This colour will be the one reinforced by the interferences and will thus be
the complementary colour of the extinguished colour. The value of the extin-
guished wavelength will be dependent on the thickness of the oxide film.
This theory has been described in several books [27 - 29].
Table 1 shows the conditions for the extinction and reinforcement of
wavelengths in ideal conditions, i.e. a transparent oxide film (index of
refraction, n2) with a constant thickness on an even and perfectly reflecting
surface of titanium (index of refraction, n3). When the value of the thickness
d introduced in this formula is increased, a succession of colours is obtained.
Th~s theoretical succession is exactly the same as the succession that we have
observed experimentally, i . e . yellow, brown, dark blue, sky blue, green,
yellow. Figure 10 shows that a range of wavelengths is absorbed instead of
only one wavelength. This can be attributed to non-uniformity in the thick-
ness of the oxide layer. Nevertheless, the value of the most strongly absorbed
TABLE 1
C o n d i t i o n s for t h e r e i n f o r c e m e n t and e x t i n c t i o n o f w a v e l e n g t h s under ideal c o n d i t i o n s

Reinforcement Extinction

47/ 4~/
n2 < n3 -- n 2 d c o s 12 = 2k~" -- n2d c o s 12 = ( 2 k + 1)71
k

4y 4~
n2 >n3 -- n2d cos t2 = ( 2 k + 1)~" -- n2d cos z2 = 2kTr
k k
 161

wavelength increases with the thickness of the oxide film, i.e. with the
duration of anodization at constant current. We therefore think that the
p h e n o m e n a o f interference are responsible for the colours of the films. It
may, however, be possible that for thick crystallized films these colours are
a consequence o f stoichiometric defects.

5. Conclusions

It may be concluded that the t w o theories that we have developed,

the one a b o u t the kinetics of growth of the oxide film and the other about
the coloration o f these films, have a c o m m o n point, the thickness of the
film. Accordingly, the colours of the samples and the electrochemical
parameters can be related to one another. Further experiments should be
performed in order to characterize more precisely the films formed by
anodizing and to determine the limits of validity of our theories.
From a practical point of view, we have found a surface treatment that
leads to uniform colours and the experimental conditions necessary for good
reproducibility of a given colour. These data may be employed for the
following industrial uses: ornamental effects in jewelry; the colouring of
titanium sheets for architectural purposes; local "printing" b y anodizing
instead of b y painting, which does n o t adhere very well to the normal
titanium surface; automatic choice of a titanium piece from among others
according to its colour instead of its dimensions.

Acknowledgments

The authors want to express their gratitude to a number of colleagues

in the university who helped to achieve this work, either b y fruitful
discussions or b y allowing them the use o f the facilities o f their laboratories:
in particular, t h e y are grateful to Professors R. Poncelet, O. Goche and F.
Bouillon.

References

1 J.-L. Delplancke, Anodisation autocolor~e du titane, Travail de Fin d'Etudes en Vue

de l'Obtention du Grade d 'ingdnieur Civil Chimiste, Universit~ Libre de Bruxelles, 1981
2 F. Kover and M. Musselin, Rev. Gen. Elect., 76 (1967) 793.
3 F. Kover and M. Musselin, Thin Solid Films, 2 (1968) 211.
4 F. Kover, Thdse de Doctorat d'Etat, Facult6 des Sciences de Paris, 1967, enregistre-
ment CNRS A.O.1088.
5 A. Aladjem, J. Mater. Sci., 8 (1973) 688.
6 G. Darnault, MetaUurgie (Mons), 12 (1972) 146.
7 H. Richaud, Rev. Mdtall. (Paris), 54 (1957) 787.
8 P. Pedeferri and R. Pionteili, Electrochim. Met., 3 (1968) 211.
162

9 N. P. Peksheva, Zashch. Met., 14 (1978) 74.

10 I. Rozenfel'd, A. Akimov and E. Oshe, Zashch. Met., 5 (1969) 217.
11 E.W. Kendall, U.S. Patent 3,616,279, 1971.
12 P. Derouwaux and E. Spycher, Swiss Patent 513,012, 1971.
13 P. Derouwaux and E. Spycher, Swiss Patent 522,516, 1972.
14 J. B. Cotton and P. C. S. Hayfield, Br Patent 1,175,355, 1969.
15 F . W . Lewis and J. H. Clayton, Br. Patent 1,319,542, 1973.
16 Hi-Shear Corporation, Br. Patent 1,100,912, 1968.
17 J. Weigel, Ft. Patent 1,398,453, 1965.
18 A S T M Stand. B481-68, Part 7, 1971.
19 J. E. Kaufmann and J. F. Christensen (eds.), IES Lighting Handbook, Illuminating
Engineering Society, New York, 5th edn., 1972.
20 I. A. A m m a r and I. Kamal, Electrochim. Acta, 16 (1971) 1539.
21 G~ Jouve, A. Politi, P. Lacombe and G. Vuye, J. Less-Common Met., 59 (1978) 175.
22 D. M. Vermileya, Adv. Electrochem. Electrochem. Eng., 3 (1963) 211.
23 M. Pourbaix, Atlas d'Equilibres Electrochimiques d 25 °C, Gauthier-Villars, Paris,
1963.
24 D. Sinigaglia, G. Taccani and B. Vicentini, Werkst. Korros., 24 (1973) 1027.
25 J. Bernard, L'Oxydation des Mdtaux, Vol. 1, Gauthier-Villars, Paris, 1962.
26 V. Andreeva and V. Kazarin,Proc. 3rd Int. Conf on Metallic Corrosion, 1966, Mir,
Moscow, 1969, p. 464.
27 M. Born and E. Wolf, Principles o f Optics, Pergamon, Oxford, 1965.
28 J. P. Mathieu, Optiq ue, Vol. 1, Optiq ue Electro magndtiq ue, Soci~t~ d'Edition d 'Ensei-
gnement Sup~rieur, Paris, 1965.
29 S. Tolansky, Multiple-beam Interference Microscopy o f Metals, Academic Press, New
York, 1970.