J O U R N A L O F MA T E R I A L S S C I E N C E 8 ( 1 9 7 3 ) 6 8 8 - 7 0 4

Re v i e w
An o d i c oxi dat i on of t i t a ni um and its al l oys
A. AL ADJ EM
Soreq Research Center, Yavne, Israel
Thi s review deals with the procedures used in the anodic oxidation of ti tani um and its
alloys, the nature and properties of the oxide films, thei r uses, and the trends in
research and development.
1. I n t r o d u c t i o n and hi st or i cal not es
Ti t ani um was discovered in 1791 by W. Gregor,
identified and named in 1794 by H. Kl apr ot h,
and isolated in an i mpure f or m by Berzelius in
1825. The met al was purified in 1910 by Hunt er
(reduct i on of the chl ori de by sodium) but
substantial quantities of metallic t i t ani um
became available onl y aft er t he i ndust ri al
adopt i on of t he Krol l process (reduct i on of
TIC12 by magnesium), in 1949. Hi gh-puri t y
t i t ani um has been pr epar ed in small amount s
since 1925 by t he so-called "i odi de process"
(t hermal dissociation of t i t ani um iodides) [1 ].
Earl y research on the el ect rochemi st ry of
t i t ani um showed t hat it cannot be electro-
deposi t ed (except as an alloy) f r om aqueous
electrolytes; however, many aut hor s have pre-
par ed massive t i t ani um by el ect rodeposi t i on
f r om mol t en salts [2].
In view of its posi t i on in t he peri odi c t abl e
and its electrochemical behavi our, t i t ani um was
classified as a "f i l m- f or mer ", i.e., a met al whose
surface is always covered with a " nat ur al " oxide
film, when exposed t o air, wat er or ot her oxygen-
cont ai ni ng media. Ti t ani um shares t hat classifica-
t i on with many ot her metals, not abl y Ta, Nb, W,
A1, etc. The " nat ur al " oxi de film on t i t ani um
ranges in thickness f r om 5 t o 70 A, dependi ng
on t he composi t i on of t he met al and the sur-
r oundi ng medi um, t he maxi mum t emper at ur e
reached duri ng t he worki ng of t he metal, etc.
[3, 4]. The nat ure of t hat oxi de film is cont r o-
versial; it has been r epor t ed t o consist of TiOz
rutile [I], anat ase [5], or lower amor phous
oxides [1 ]. Di fferent oxides are pr obabl y f or med
under different conditions, and t he oxide
composi t i on may also depend on t he puri t y of
t he metal.
Ti t ani um is a very reactive met al ; nevertheless,
688
it exhibits a high resistance t o corrosi on, which
shoul d be at t ri but ed t o t he prot ect i ve effect of
t he surface oxide films. Such films, and in
part i cul ar TiO2, are i nert with respect t o most
nat ural envi ronment s and many chemicals.
Cor r osi on is believed t o occur t hr ough "weak
spot s" in t he oxide; a forced increase in film
thickness (e.g., by electrolytic or t hermal
oxi dat i on) woul d eliminate such weak spots and
coul d increase t he corrosi on resistance. The
electrochemical behavi our of t i t ani um at t r act ed
at t ent i on as earl y as 1927 [6] and research in
t hat field advanced with t he rapi d expansi on of
t he uses of t i t ani um in part i cul ar aft er the
devel opment of its alloys, combi ni ng a l ow
density with a high strength.
In this review, an at t empt has been made t o
collect and present all available (to t he middle of
1972) dat a on the anodi c oxi dat i on of t i t ani um
and its alloys; the subject has been discussed in
a number of general reviews on t he oxi dat i on of
metals or on t he chemi st ry of t i t ani um [7-13]
but the coverage of the l i t erat ure on t he anodi c
oxi dat i on of t i t ani um in those reviews was onl y
partial. The oxi dat i on of t i t ani um alloys has
received much less at t ent i on t han the oxi dat i on
of t i t ani um; t he available dat a are included in
t he review, t oget her with t he dat a f or t he pur e
metal. Qualitatively, t he anodi c behavi our of t he
alloys and t he propert i es of t he anodi c films are
similar to t hose for t he pur e met al [14]. I t shoul d
be not ed t hat cert ai n t i t ani um compounds (e.g.,
t i t ani um nitride) may also be anodi zed in
aqueous acid solutions, yielding oxide films
whi ch are essentially t he same as t hose f or med
on metallic t i t ani um [15].
2. A n o d i c o x i d a t i o n pr ocedur es
Many electrolytes, under different condi t i ons,
9 1973 Chapman and Hall Ltd.
R E V I E W: A N O D I C O X I D A T I O N O F T I T A N I U M A N D I T S A L L O Y S
have been used f or t he anodi c oxi dat i on of
t i t ani um and its alloys; dat a on t he el ect rol yt e
composi t i ons and the process condi t i ons are
listed in Tabl e I (see t he Appendix). In addi t i on
t o t he electrolytes listed below, special electro-
lytes have been devel oped t o solve cert ai n
specific probl ems, e.g., localized anodi c oxida-
t i on of t i t ani um has been carri ed out t hr ough t he
use of viscous electrolytes and aper t ur ed
t empl at es [16]. In cert ai n cases, mai nl y in pat ent
i nf or mat i on on devices based on anodi zed
t i t ani um, little detail has been r epor t ed on t he
bat h composi t i on and process condi t i ons; in
ot her cases, t i t ani um is ment i oned as one in a
gr oup of metals, wi t hout specific details. In
t hose cases, as well as in a few cases in which
t he original article coul d not be obt ai ned and
had t o be cited on t he basis of some ot her
reference or abst ract , the rel evant listing is only
partial. Except when not ed otherwise, t he
sol ut i ons listed in Tabl e I are aqueous.
We shoul d ment i on here a number of electro-
lytes in whi ch anodi c oxi dat i on of t i t ani um is
not possible; t hose include A1Cla solutions in
et her [17], 0.5 Y HF [18], acid sulphate solutions
cont ai ni ng fluoride [19], t he Jacquet electro-
polishing bat hs (acet at e-perchl orat e solutions)
[20]. In 5 t o 10 N KOH at 25 ~ C [21 ] a passivat-
ing oxi de film may be f or med on t i t ani um, but
active anodi c di ssol ut i on begins aft er a cert ai n
time. Anodi c poIari zat i on in a sol ut i on cont ai n-
ing 16 t o 132 g 1-1 ammoni um sulphate, 15 t o
98 g 1-1 alkali di chr omat e and 10 t o 17 g 1-1 HF
(at 0 t o 100 ~ C, 0.0015 t o 0.7 A cm -2) caused
descaling, r at her t han oxi dat i on of t i t ani um and
its alloys [259]. The addi t i on of chlorides t o non-
oxidizing aqueous electrolytes hi nders t he anodi c
oxi dat i on of t i t ani um and shifts the critical
pot ent i al f or passi vat i on t o mor e positive values
[22], while the addi t i on of cert ai n organi c
i nhi bi t ors (e.g., [p-(HOCH~CH~)2NC~H~O]P(S)
(OEt)~) favours passi vat i on [23].
In most cases, convent i onal d.c. sources with a
cont i nuousl y variable out put range f r om 0 t o
150 V or higher, are used f or t he anodi c oxida-
t i on of t i t ani um; usually, t he equi pment allows
aut omat i c t ransi t i on f r om const ant current t o
const ant voltage, when a preset maxi mum
voltage has been reached. For a descri pt i on of
such equi pment adapt ed t o t he anodi c oxi dat i on
of t i t ani um, see [24]. In cert ai n cases t he use of
a.c. (e.g., in t r i sodi um phosphat e solutions [25])
produces t hi cker oxi de films, as compar ed with
t he use of d.c. anodi c oxi dat i on with pulsed
(20 Hz) current in 20% HC1 at 3 to 10 mA cm -~
[26] produces a passivating oxi de at pot ent i al s
mor e negative t han in t he case of uni nt er r upt ed
d.c.
3. For ma t i on me c h a n i s m, t hi c k ne s s ,
gr owt h r at e and br e a k down of t he
a nodi c f i l ms
3.1. Formati on mechani sm
The f or mat i on mechani sm of anodi c oxi de films,
and in part i cul ar those on aluminiuln and
t ant al um, has been the subject of extensive
research [11]. Al t hough t he general rules
governi ng the anodi c oxi dat i on of t i t ani um are
roughl y t he same as f or ot her "val ve" metals
(i.e., t he i oni c current duri ng anodi c pol ari zat i on
leads t o film format i on, and t he relatively great
cont r i but i on of i oni c current is pr obabl y
associated with t he high heats of f or mat i on of
t he respective oxides [27, 28]), t he cont roversi al
dat a on t he composi t i on and st ruct ure of t he
anodi c films on t i t ani um (see Section 4) lead t o
cert ai n cont roversi es in publ i shed discussions
on the nucl eat i on and growt h of such films.
Accordi ng t o several aut hor s [29, 30] t he
first step in t he anodi c oxi dat i on of t i t ani um
involves t he f or mat i on of an adsorbed l ayer of
oxygen (or some oxygenat ed species) on t he
met al surface, or, mor e accurately, on t he
surface of t he pre-existing " nat ur al " oxi de film.
The nat ur e of such adsor pt i on has not been
elucidated, and Hoa r [31] believes t hat t he
pr obl em of the existence or non-exi st ence of
such an adsorbed l ayer shoul d be regarded
merely as a semantic argument . In any case, t he
exact mechani sm of pr i mar y passi vat i on is
difficult t o establish, and requires f ur t her
clarification [32]. Still, it seems cert ai n t hat t he
f or mat i on of a separat e-phase l ayer is preceded
(or at least accompani ed) by electric charging of
t he doubl e l ayer at t he met al el ect rol yt e inter-
face [33]; this is suppor t ed by dat a indicating
t hat passivity may be repeat edl y lost and acqui red
by switching off and on t he pol ari zi ng current ,
even aft er the bui l d-up of the anodi c film [34].
The presence of oxidizing species is essential f or
oxi dat i on [35]. At low anodi c potentials, t he
rel at i onshi p between t he anodi c cur r ent and t he
electric field across t he oxide film is described
by the following equat i on [36, 37]
i+ = A exp BE
where i+ is t he ionic current , E is t he field
strength and A and B are constants. The half-
689
A. A L A D J E/ v [
wi dt h of the energy barri er f or i on mi grat i on
t hr ough the film on a Ti - Zr alloy (under t he
condi t i ons f or which t he above equat i on is valid)
increases with increasing zi rconi um concent ra-
t i on of t he alloy [36].
Evidence exists t hat the anodi c film on
t i t ani um grows as a result of the t ransfer of
Ti 2+ cations t hr ough the film, i.e., t hat growt h
takes place at the oxide solution i nt erface
[38-40]; however, ot her aut hor s have r epor t ed
t hat t he film grows by oxide ion t ransfer [41, 42].
Thus, it is most pr obabl e t hat bot h Ti 2~ and
02- t ransfer cont ri but e simultaneously t o the
growt h of anodi c films on t i t ani um [43] and it
has been suggested t hat the growt h mechani sm
is similar t o t hat of oxi dat i on in a gas [43].
When a t i t ani um hydri de film is present on the
metal, t i t ani um ions mi grat e t hr ough t hat film
and t he oxide is f or med over the hydri de
[44, 45], but when a t hermal oxide is present t he
anodi c film is f or med beneat h the t hermal [46].
The role of the electrolyte in t he f or mat i on
mechani sm has not been studied in detail.
Al t hough in most cases t here are no diffusion
hi ndrances within the bul k of t he electrolyte [47],
the nat ure of t he anions influences bot h the
initial passivation and subsequent growt h stages
[24, 48-50]; it has been suggested [51] t hat an
anodi c oxide film is f or med only i f the condi t i ons
(including t he nat ure of the electrolyte) f avour
t he f or mat i on of TP + r at her t han Ti a+ ions.
The steady decrease in cur r ent aft er the
est abl i shment of a const ant vol t age (in t he
final stages of oxi dat i on) has been at t ri but ed t o
a gradual decrease in the concent rat i on of Ti a+
ions in t he film [40] or t o an increase in t he
degree of perfect i on of t he film [52]; in bot h
cases t here woul d be an increase in t he appar ent
resistivity of t he film.
3.2. Thickness and growth rates
The thickness of anodi c oxide films is oft en
expressed in t erms of the appar ent growt h rate,
i.e., angst roms per volt of appl i ed voltage.
Most aut hors assume a linear rel at i on bet ween
final voltage and thickness, i ndependent l y of
current density [53]. The met hods used t o
det ermi ne t he thickness include weighing [54-56],
t he Dr ude- Tr onst ed pol ari zed light met hod
(which has shown t hat thickness depends on
subst rat e ori ent at i on) [57, 58], absor pt i on of
alpha-particles in films stripped by dissolution
of the substrate in al cohol i c halid solutions
[59, 60], measurement s of t he oxygen cont ent
690
t hr ough nuclear react i ons [61], i nt erferomet ry
[39, 62], ellipsometry [63] etc. For thickness
measurement s (or f or ot her purposes, e.g.,
transmission el ect ron mi croscopy) the film may
be stripped by scratching the surface and
immersing in 5% Br2 in met hanol [64] or by
dissolving t he subst rat e in a mi xt ure of 350 ml
concent rat ed HC1, 650 ml H20 and 10 g Na F
[651.
The growt h rate is of the order of 20 A V -a,
t he scat t er in r epor t ed values is not t oo great,
beari ng in mi nd the great vari et y of measuri ng
techniques. The r epor t ed values range f r om 18
[63] t o 22 [66] and 23.8 A_ V -~ [39]. The thick-
ness of the oxide film on alloys seems t o be
lower, e.g., on a 50 % Ti-50 % Nb al l oy oxidized
to 100 V in an aqueous t ar t r at e solution, the
thickness reached onl y 1700 A [67].
Accordi ng to Pal ki na [68] t he thickness of the
anodi c film f or med on t i t ani um in 4 N sulphuric
acid at 40 ~ C may reach 0.2 t o 0.3 ~tm, but the
final thickness at any voltage depends on an
equi l i bri um between compet i t i ve growt h and
dissolution processes [69]. The thickness in-
creases with increasing t emper at ur e [55] and the
val ue of about 20 A V -1 refers t o r oom t empera-
ture.
The experi ment al growt h rates are somewhat
l ower t han t he faradai c rates calculated by
assuming t hat t he film consists of TiO~; the
deviations f r om ideality have been at t ri but ed t o
oxygen evol ut i on [70] or to part i al di ssol ut i on
of t he oxide [68]. Thus, t he current efficiency
f or film f or mat i on depends on t emperat ure, the
nat ure of t he electrolyte, and ot her factors. For
anodi c oxi dat i on in weakly-acid aqueous solu-
tions t he efficiency is near 70% [70, 71]; in
aqueous hypochl ori t e solutions the efficiency
depends on pH and has a maxi mum at pH 2 [72].
The assumpt i on of a st oi chi omet ri c (TiO2)
composi t i on is not strictly correct (see Section 4)
and, in addi t i on, the t i t ani um may dissolve
duri ng t he oxi dat i on at a l ower-t han-accept ed
valency [73], so t hat t he efficiency shoul d be
correct ed f or such deviations. The growt h-
dissolution equi l i bri um duri ng anodi c oxi dat i on
(and t hus t he efficiency) coul d be affected by
catalytic phenomena at t he oxi de-el ect rol yt e
i nt erface; it has been r epor t ed t hat t he anodi c
dissolution of t i t ani um in sulphuric acid solutions
is catalysed by hydr ogen [74].
3.3. Breakdown duri ng oxi dat i on
The exact nat ure of the br eakdown of a n o d i c
REVI EW: ANODI C OXI DATI ON OF TI TANI UM AND I TS ALLOYS
oxi de films, which occurs above cert ai n critical
potentials, is cont roversi al , but in all cases it
involves a loss of passivity and in cert ai n cases
it leads t o pi t t i ng of t he metal. In many cases,
e.g., t ant al um, t he br eakdown voltage under a
cert ai n set of condi t i ons is well-defined and
reproduci bl e, and br eakdown is oft en accom-
pani ed by sparki ng (the so-called " a node "
effect). Ti t ani um is different in this respect;
br eakdown voltages are spread over a wide
range, reproduci bi l i t y is poor even i f great care
is t aken t o ensure similarity of condi t i ons, t here
is no sparki ng (except under except i onal
condi t i ons) and br eakdown is generally mani-
fested by a subtle change in the slope of t he
oxi dat i on curve or in t he rate of oxygen evolu-
t i on r at her t han by an abr upt change in cur r ent
or by t hermal effects. Mor eover , in t he case of
t i t ani um t he br eakdown vol t age is strongly
affected by t he nat ur e of t he electrolyte.
In sul phuri c acid solutions t he br eakdown
voltage does not exceed 60 to 70 V [56, 75-78]
(however, a value of 150 V has also been
r epor t ed [57]). I t has been claimed t hat in such
solutions, t he i nt r oduct i on of chl ori de ions has
little effect on t he br eakdown voltage [51];
however, t he addi t i on of sufficient C1- t o H~SO4
must decrease the br eakdown pot ent i al [79].
Al l oyi ng of t he t i t ani um with pal l adi um increases
t he upper limit of pot ent i al s at which t he met al
is still passive [80]. In chl ori de solutions break-
down occurs at 10 t o 12 V [38, 51, 75, 8l ] ; t he
range of passivity of t i t ani um in such solutions
may be wi dened by i nt roduci ng i nt o t he solutions
Cu 2+ or Fe d+ ions [82, 83] or by prel i mi nary
cat hodi c t r eat ment of t he met al surface [84].
In cont act with solid rutile at 1000 ~ br eakdown
duri ng anodi c oxi dat i on occurred at cur r ent
densities above 40 A dm -2 [41]. Accordi ng t o
Ammar [85] t he br eakdown vol t age in aqueous
acid solutions is about 100 V. In t he anodi c
oxi dat i on of t i t ani um in ionized oxygen under
85 mTor r , br eakdown is observed at 83 V [86].
In aqueous solutions of nitric acid t he break-
down vol t age is l 0 V [87]; br eakdown is
accompani ed by oxygen evol ut i on, but t here is
no sparking. In buffered bor at e solutions t he
br eakdown occurs above 100 V [88, 89] and
may even occur above 120 V [34, 90] in t he case
of t he pur e metal, while t he br eakdown voltage
of t he Ti-6 A1-4 V al l oy is somewhat l ower and is
f ur t her l owered i f t he al l oy is heat -t reat ed [34].
Burgers [91] has oxidized t i t ani um in aqueous
bor at e solutions up to 200 V. In non- aqueous
f or mi c acid solutions (cont ai ni ng H~PO~ and
Et3N ) t he br eakdown vol t age is 260 V, but drops
t o 60 to 70 V i f wat er is added t o t he electrolyte
[50]. The breakdown voltage is affected by
agi t at i on of t he electrolyte, i.e., in ammoni um
t ar t r at e solutions its values are 20 and 51 V
wi t hout and wi t h agi t at i on respectively [92]; it
is i mpor t ant t o not e t hat in such solutions
br eakdown starts at flat surfaces rat her t han on
edges.
Yahal om and Zahavi [77] have shown t hat in
sulphuric acid solutions part i al br eakdown occurs
cont i nuousl y duri ng the anodi c oxi dat i on of
t i t ani um, but t here is a noticeable change in
mechani sm above 65 V; the br eakdown in such
solutions leaves a crater-like structure. Break-
down may be associated with film cracking,
caused by i nt ernal stresses in t he oxide [52]. In
his t heor y of dielectric br eakdown of anodi c
films, Sat o [93, 94] at t ri but ed a maj or role t o the
mechani cal pressure P exerted by the electric
field E:
P = [ ( E( ~- l ) E 2 ) / 8 ~ 1 - V / t ,
where 9 is t he dielectric const ant , ~, is the
surface t ensi on and L is film thickness. Sat o did
not deal specifically with t i t ani um but calcula-
tions show t hat f or field strengths of the or der
of 100 to 107 V cm -a (i.e., similar to those existing
duri ng t he oxi dat i on of t i t ani um) the pressure
woul d exceed 1200 kg cm-2; such pressures are
above t he compressive st rengt h of t he oxide and
coul d cause cracking, with a loss of passivity.
The differences between t he anodi c behavi our
of t i t ani um and t hat of t ant al um and ot her
metals (and in part i cul ar t he st rong influence o f
t he electrolyte in t he case of Ti) indicate t hat t he
general theories on the br eakdown of anodi c
films shoul d pr obabl y be modified in or der to
appl y t o t i t ani um. I n t hat case, t here may be
mor e t han a single br eakdown vol t age [77], and
t he br eakdown is pr obabl y associated with a
compl i cat ed rel at i onshi p between part i al anodi c
dissolution of the film, a passivity equi l i bri um
at the oxi de-sol ut i on interface, and phase
changes or mechanical effects caused by t he
field and ot her factors.
4. C o m p o s i t i o n a n d s t r u c t u r e o f t h e
a n o d i c f i l ms
Metallic t i t ani um exists in the close-p~cked
hexagonal ( "al pha- phase") or body- cent r ed
cubic ( "bet a- phase") forms. In alloys, al umi ni um
and tin as well as oxygen and ni t rogen stabilize
691
A. ALADJEM
t he cph structure, while V, Cr, Mn, Fe, Mo, Si,
Zr and Nb stabilize the bcc form. Ti t ani um
di oxi de has t hree known modifications (rutile,
anat ase and brooki t e), and t here are a number
of l ower oxides, not abl y Ti O and Ti2Oa.
Most investigators [27, 39, 72, 95-104, 181]
agree t hat t he anodi c film on t i t ani um consists
of TiO2; however, it has been r epor t ed t hat t he
anodi c oxide is oxygen-deficient [40, 41, 51, 105],
while some aut hors believe t hat oxygen is in
excess [106-108]. In fact, a cert ai n degree of
non-st oi chi omet ry in anodi c films in general is
r egar ded as inevitable [109]. This cont roversy is
widened by report s accordi ng t o which t he anodi c
film is hydr at ed [110, 111 ], or consists of mi xed
oxides including TiO, Ti203 and TiO2 (56, 78,
112]. Accordi ng t o Slomin [113] t he film cont ai ns
also Ti205, while Hal l [38] report s t hat when
t i t ani um is oxidized at low pot ent i al s in neut ral
NaCt solutions, t hree oxygen at oms ar e deposi t ed
on t he surface f or each t i t ani um at om. Accord-
Jng t o Isaacs and Leach [114] a fract i on of the
Ti in t he oxide film may have a valence ot her t han
four.
The above cont roversy has its origins in t he
fact t hat only few of t he aut hor s (and in part i cu-
lar of the earlier ones) have made direct measure-
ment s of the Ti : O rat i o in t he anodi c film; in
fact , in most cases the conclusions concerni ng
st oi chi omet ry have been drawn on t he basis of
st r uct ur al measurement s (e.g., by el ect ron
diffraction), and such measurement s are not very
sensitive t o slight deviations f r om stoichiometry.
Mor eover , it has been r epor t ed [39, 48, 115, 116]
t hat bot h t he composi t i on and the st ruct ure of
the anodi c film depend on t he composi t i on,
:thermal history, etc., of t he metallic substrate.
Thus, it is most pr obabl e t hat t he anodi c film
Js not necessarily st oi chi omet ri c TiO~, and t hat
films studied by different aut hor s had different
composi t i ons (because of differences in t he
materials used, in the condi t i ons of oxi dat i on,
etc. ). Indeed, one of t he most adequat e descrip-
~tions of t he vari at i on in composi t i on has been
provi ded by Huber [98]. Accordi ng t o Huber ,
~the bul k of the film consists of TiO~ (not
necessarily stoichiometric) but t he mi grat i on of
Ti at oms across the met al -oxi de i nt erface
pr oduces an excess of t i t ani um in t he vicinity
of t hat interface, while an excess of oxygen
.exists near t he oxi de-sol ut i on interface. Such an
,excess of oxygen near t he electrolyte woul d be
.consistent with report s accordi ng t o which
oxygen is adsorbed or chemi sorbed on t he anodi c
692
film duri ng its growt h, and subsequently
migrates i nt o t he bul k of t he film [30, 41, 43,
106, 108, 117]. The f or mat i on of at omi c oxygen
is not essential and film growt h may t ake place
even below t he oxygen evol ut i on pot ent i al [118].
The valence changes of t i t ani um in the oxi de
film are regarded as reversible [119]. The oxide
composi t i on may change with time (during t he
oxi dat i on) even i f condi t i ons are kept const ant .
Accordi ng t o Krasi l ' shchi kov [40] t he film
contains Ti 3+ ions which are responsible f or its
conduct i vi t y, but which mi grat e under t he
influence of t he electric field and whose con-
cent rat i on t hus decreases with t i me; a decrease
in the concent rat i on of excess TP + ions woul d be
accompani ed by a pr opor t i onal decrease in t he
Ti : O ratio.
The differences in composi t i on near the t wo
interfaces of the film (film/metal and film/
electrolyte) agree with the model of Van
Rysselbergh and Johansen [118] for the pot ent i al
dr op across the anodi c films f or med on t i t ani um
in sat urat ed ammoni um bor at e sol ut i ons. Accord-
ing t o t hat model, t he pot ent i al dr op occurs at
t he met al / oxi de interface, across t he bul k oxide,
and at the oxi de/ sol ut i on interface. The above
aut hors [118] report ed also t hat t he residual
current (which is rel at ed t o t he degree of
perfect i on of t he film) at const ant pot ent i al is
not const ant but varies by a f act or of mor e t han
2, as a funct i on of mor e t he puri t y of t he t i t ani um
metal.
In addi t i on to t he vari at i ons in oxygen
st oi chi omet ry, t he anodi c oxide films may
cont ai n vari ous amount s of elements ot her t han
t i t ani um and oxygen, dependi ng on t he com-
posi t i on of the met al and the electrolyte. Thus,
Mn Q is deposi t ed at "weak spot s" in anodi c
t i t ani um oxide films when the anodi c oxi dat i on
is carri ed out in acid electrolytes cont ai ni ng
manganese sulphate [78, 274]. Anodi c films
consisting of TiO2 with variable amount s of Ba,
Ca, Mg, Sr, Li, and ot her oxides (i.e., films
cont ai ni ng alkali or al kal i ne-eart h titanates)
are pr oduced by anodi c oxi dat i on in electrolytes
cont ai ni ng the respective alkali-metal or alkali-
eart h cations [120] or in mol t en alkali carbonat es
[121]. The amount of i ncor por at ed forei gn ions
depends on t he condi t i ons of electrolysis, e.g.,
when t i t ani um is anodically oxidized in sat urat ed
Ba(OH)~ solutions at 24 ~ C a film cont ai ni ng
bar i um (probabl y as the t i t anat e) is f or med at a
c.d. of 70 mA cm -2, but a bari um-free film is
f or med at 5 mA cm -z [122]; t he film cont ai ni ng
R E V I E W: A N O D I C O X I D A T I O N O F T I T A N I U M A N D I T S A L L O Y S
Ba has a rutile st ruct ure, while t he Ba-free film is
anatase. Ani oni c species may also be i ncor por at ed
duri ng anodi c oxi dat i on, e.g., phosphor us-
cont ai ni ng films are pr oduced in an aqueous
sol ut i on of ethyl hydr ogen phosphat e [123]; it is
assumed t hat the P is not t aken- up in t he di oxi de
lattice but f or ms par t of an amor phous phase
[123]. The semi conduct i ng film f or med on Ti in
sul phamat e solutions cont ai ns bot h met al -
oxygen and met al -sul phur bonds [117]. Measur-
able quantities of radi oact i ve sulphur-35 are
i ncor por at ed in t he anodi c film ( pr obabl y as
sul phat e ions) duri ng anodi c oxi dat i on of Ti in
2 0 ~ H2SO4 at 20 ~ C, at 0.6 A dm -2 [56].
The anodi c oxi dat i on of t i t ani um alloys yields
mi xed oxi de films. The oxi dat i on of Ti - 10~ A1
and Ti-9 ~ Cr alloys produces films consisting
of TiO=-A1203 or TiO2-Cr203 [3]. In such alloys,
t he presence of A1 or Cr causes an increase in t he
cor r osi on cur r ent t hr ough the oxide film, in
sul phuri c acid solutions, while mol ybdenum
reduces t he current , i.e., A1 and Cr t end t o
pr oduce less perfect films. The f avour abl e effect
of mol ybdenum is at t ri but ed to a decrease in t he
number of oxygen ( O- ) vacancies in t he oxi de
film. When Ti - Nb or Ti -Ni alloys are oxidized
in 0.1 N KOH, t he Nb or Ni are i ncor por at ed
in t he TiO2 lattice as Nb 5+ or Ni 2+ ions [124].
The cat i on rat i o in t he anodi c oxide on alloys
is not necessarily t he same as in t he met al ; f or
example, anodi c oxi dat i on of a 50 at. ~ Ti-50
at. ~o Nb al l oy in 3 ~ ammoni um t ar t r at e at
pH 2, to 100 V, yielded a 1700 A film in which t he
Nb : Ti rat i o was 6:1 [67].
The t hree crystalline forms of Ti Oz - rutile,
anatase, and b r o o k i t e - as well as amor phous
constituents, have been f ound in t he anodi c
oxide, mai nl y by el ect ron diffraction. An
amor phous (or part i al l y amor phous) st ruct ure
has been r epor t ed by several aut hor s [39, 77, 99,
123, 125]; upon heating, t he amor phous film is
t r ansf or med first i nt o anat ase (at 150 ~ C), t hen
i nt o rutile (above 700 ~ C) [39]. However, most
investigators claim t hat t he oxi de films on
t i t ani um are pr edomi nant l y crystalline. A rutile
st ruct ure has been f ound ei t her by di ffract i on
[5, 123, 126] or by opt i cal or electrical measure-
ment s [109, 127-129], e.g., t he widths of t he
f or bi dden band of the anodi c film f or med on Ti
in 0.1 Y Na OH is the same as t hat of rutile
3.65 eV [128]. On the ot her hand, Sibert [116]
stated aft er a detailed st udy t hat the anodi c
films f or med in aqueous solutions do not consist
of rutile; many ot her aut hor s r epor t an anat ase
st ruct ure [76, 91, 130-134]. Brooki t e was f ound
by Koyama [135] in anodi c films f or med in
non- aqueous electrolytes, and by Yamaguchi
[136] in films f or med in sul phuri c acid. Yama-
guchi not ed t hat reflection t echni ques had a
poor sensitivity since t he resulting el ect ron
diffraction pat t er n indicated an amor phous
structure, while diffraction by t ransmi ssi on o f
" ha r d" (with a wavelength of 0.0272 A) electrons
showed a br ooki t e structure, with a grain size of
5oA.
The different conclusions of vari ous aut hors
on t he st ruct ure of t he anodi c films are most
pr obabl y based on genuine differences in
structure, i.e., t here pr obabl y is no experi ment al
error, but different structures are f or med under
different conditions. Mor eover , in a given
experi ment the structures may change when one
par amet er is changed; f or instance, a gr adual
increase in current density causes a change f r om
amor phous t o anat ase film, and a sponge-l i ke
substance is f or med at high densities [123].
Yahal om [77] has shown t hat amor phous films
are f or med in 0.1 M H2SO4 below 5 V, but
crystalline films are f or med at hi gher potentials.
The differences between t he concl usi ons o f
vari ous aut hor s coul d also be explained by
assuming t hat t he films are composed of t wo or
mor e phases; in t hat case, different measur i ng
t echni ques woul d show different structures (e.g.,
t he result woul d depend on t he dept h of pene-
t r at i on of electrons, t he degree of sophistication
of t he optical met hod, etc.). Indeed, t he presence
of bot h rutile and anat ase has been report ed
[137] f or films f or med in 2 ~o ~ H~SO 4. A stratified
st ruct ure has been observed by Fox et al [138]
in films f or med in mol t en carbonat es at 300 ~ C
and up t o 49 V; t he layer near the electrolyte
had a const ant thickness (200 t o 300 A) and
consisted of anatase, while t he layer near t he
met al consisted of rutile and it al one grew when
t he pot ent i al was increased. The main component :
of a film grown t o 8 V in 4 0 ~ H2SO4 was
anatase, but t here were small amount s of rut i l e
[139].
In addi t i on t o t he differences in composi t i on
and crystalline structure, t here may be differences.
in surface mi crost ruct ure, porosi t y, etc. Mi cro-
pi t t ed films have been obt ai ned aft er anodi c
pol ari zat i on of Ti in chloride [38], f or mi c acid
[140, 141] and ot her electrolytes [142]. Porous.
films are f or med in sulphuric acid [143, 144], in
phosphat e or bor at e solutions at high pH [145],
or in electrolytes cont ai ni ng C1- ions [146, 147].
693
A. ALADJ EM
The porosi t y increases with increasing t empera-
t ur e of oxi dat i on [148]. Accordi ng t o Boddy
[109], anodi c TiO2 films must be por ous or
cracked, since the anodi c leakage current s
depend on t he nat ure of the electrolyte. The
oxide films f or med in acid chloride solutions
cont ai ni ng Cr ~+ or Cr ~+ ions at 85 ~ C are
cracked, because of i nt ernal stresses [52], but
the degree of perfect i on of such films increases
with time. Anodi c pol ari zat i on curves show
t hat even films f or med under relatively mild
conditions (in bor at e- phosphat e solutions) are
not compl et el y i mpervi ous [34]. Vermilyea [149]
also report s t hat such films are not rigid and
uni form.
The crystalline st ruct ure and surface mi cro-
st ruct ure of anodi c TiO2 films are not changed
by i rradi at i on f or up to 60 days with gamma
rays f r om a Co-60 source, at dose rates of 10 as
eV cm -3 rain -1 [161].
Thus, t he anodi c oxi de films on t i t ani um are
rarely, i f ever, st oi chi omet ri c TiO~; in many
cases t he films cont ai n also elements ot her t han
t i t ani um and oxygen. The experi ment al dat a
indicate t hat t he films may be amor phous, or
t hey may consist of any of t he known modifica-
t i ons of TiO2 or mixtures thereof.
9 5 , E l e c t r i c a l a n d o p t i c a l p r o p e r t i e s
The electrical and optical propert i es of t he films
are closely related, and are discussed in t he same
section.
The resistivity of anodi c films on t i t ani um is
either similar t o [150] or l ower t han [151] t he
resistivity of anodi c films on t ant al um; the
resistivity of the film f or med by anodi c oxi dat i on
Jn an oxygen pl asma is 6 1017 f~ cm [86]. The
dielectric const ant of films f or med in mol t en
nitrates is 107 [152], but values f or films f or med
at l ower t emperat ures range f r om 21 t o 47 [39,
135]. The dissipation f act or is 0.01 [86, 102].
Repor t ed values of the capaci t ance range f r om
0.1 gF cm -2 or less [86, 102, 143] t hr ough 1 t o
10 mF cm -2 [87, 152, 153] t o mor e t han
10 gF cm -2 [114]; accordi ng t o Taj i ma [154]
at 400 V the capaci t ance is 40 times t hat of
anodi c films on aluminium. The mean specific
capaci t ance at 1 kHz is 7.6 t o 7.9 gF V cm -~
[39]; it decreases with increasing t emper at ur e
of oxidation. It shoul d be not ed t hat t he values
r epor t ed by Isaacs et al [114] refer to extremely
~hin films; ot her values in excess of 1 ~tF cm -2
cor r espond t o films f or med under r at her unusual
condi t i ons (mol t en salts [152], oxi dat i on to very
694
high voltages [154]), and are not characteristic
of films used in capacitors. The leakage current
in t he case of films f or med in mol t en nitrates is
0.2 laA (~tF V) -1 [152]; f or films tested at 80~o
t he f or mat i on voltage, t hat current is onl y
1 gA cm -~, as compar ed with up to 5 mA cm -2
f or films tested at t he f or mat i on voltage [155].
The band gap is 3.0 eV [156]. The electrical
propert i es of the oxide-electrolyte i nt erface
depend on t he nat ure of t he electrolyte, e.g., t he
capaci t ance of t he doubl e l ayer increases when
fluoride ions are present in t he sol ut i on [157].
The anodi c film is semi conduct i ng in cont act
with an el ect rol yt e (no current passes upon
anodi c pol ari zat i on) [34, 104, 138, 158-161]; f or
films oxidized t o 1000/ ~ in an et hyl ene-gl ycol -
oxalic acid mi xt ure t he rectification f act or is
106 [162]. Rectification occurs at t he fi l m-
el ect rol yt e i nt erface; t he act i vat i on energy f or
cat hodi c current flow t hr ough t he film in cont act
with liquid SO2 cont ai ni ng 0.01 N NaI is 6 t o
16 kcal mo1-1 [163]. The carri er concent rat i on
in t he film duri ng its growt h is 1020 to 10 zl cm -3
[164]; the electric field across t he film at zero
current and at 100 ~tA cm -2 is ,-~2.5 106 and
3.2 106 V cm -1 respectively [165]. The
act i vat i on barri er f or anodi c oxi dat i on of
t i t ani um is A + = 48.5 mAc m -2, B+ = - 1 . 3 3
107 cm mV -1 [105]. The energy of act i vat i on
f or t he di ssol ut i on of t he film (in 10 N HC1 at
25 t o 70 ~ C) is 18.6 t o 22.4 kcal tool -1 (it
decreases at l ower t emperat ures) [273].
The refractive i ndex of the film depends on its
structure, and generally corresponds t o t hat of
t he observed crystalline modi fi cat i on of TiO~.
Koyama [135] report s a val ue of 2.2 t o 2.5.
The film exhibits intense i nt erference col ours,
which depend on t he f or mat i on voltage, t he
composi t i on of t he metal, the f or mat i on
t emperat ure, etc. [34]. The film f or med at 25 V
in 10 ~ ammoni um sulphate is bl ue-purpl e [146].
Kendal l [166] gives t he following col our chart
f or films f or med in HBF4 solutions in di met hyl
f or mami de (the f or mat i on voltages are in
parent heses): indigo (20), dar k blue (30), light
blue (40), green (50), yellow (60), salmon (70 V).
Ther e is an optical absorbance peak at 3.65 eV
and a mi ni mum at 3.8 eV [128]. Phillippi and
Lyon [167] r epor t an asymmet ri c absorpt i on
band at 828 cm -~, composed of superi mposed
modes at 828 and 809 cm -~, f or t hermal oxi de
films on t i t ani um; no such band exists in single-
crystal TiO2, and dat a f or anodi c films are not
available. The t hreshol d wavelength f or phot o-
REVI EW: ANODI C OXI DATI ON OF TI TANI UM AND I TS ALLOYS
conductivity is 290 nm [53]; the maximum
photo emf for 300 A films (formed in ethylene-
glycol-oxalic acid solutions) is 0.53 V (with
ultra-violet or green light) [98]. Illumination of
the Ti-TiO2-electrolyte system with ultra-violet
light reduces the anodic potential [90].
6. Appl i cat i ons of t he anodi c fi l ms
Most actual or proposed uses of anodic films on
titanium are in the fields of electrical or electronic
components (capacitors, resistors, diodes, photo-
electric devices) and corrosion protection. Other
uses include wear- and friction-resistance,
reflective surfaces, preparation for electroplating,
decorative coatings, accelerator targets and
electrophotographic plates.
Although the volume of titanium used in the
manufacture of electrolytic capacitors is small
in comparison with aluminium or tantalum,
titanium compares favourably with those metals
from the standpoint of capacitor properties, and
has important weight and price advantages
[168, 169]; when the oxidation is carried out in
oxalic acid-propanediol solutions the resulting
capacitors are superior to these based on
Ta-Ta205 [170], and the capacitance of films
formed in borate solutions may be up to 40
times that of anodic AlzOa films [154]. The use of
anodic oxidation of titanium for the manu-
facture of capacitors has been studied by many
authors [102, 171-176]; the electrolytes used in
such studies include phosphate [177], borate
[103, 154], nitrate [178], carbonate [179], formic
acid [50] and glycolonitrile [180] solutions.
Several authors have compared the relative
merits of different electrolytes from the stand-
point of capacitor manufacturing [143, 153, 182-
184]; the recommendations differ, but there are
indications that the use of organic electrolytes
(e.g., ethylene-glycol adipate [184]) yields capaci-
tors of improved properties.
Other methods for improving anodized
titanium capacitors include the growth of mixed
oxides such as Ba or Ca titanates [120], deposi-
tion of MnO~ on weak spots of the anodic
oxide [119], nitriding of the metal before
anodizing [ 103 ], pretreatment in nitric acid [152 ],
superposition of a.c. on the d.c. during the
oxidation [143], the use of alloys (e.g., Ti-13~
V-11~ Cr-3~o A1, anodized at 20 to 50 V in
mixed H3PO4-H20-C~H4(OH)~ electrolytes [169 ])
instead of unalloyed titanium, and the use of
two-stage oxidation, in which the titanium was
first anodized in 3 ~ ammonium borate, a layer
of titanium was deposited by vacuum plating
on the anodic film, and the metal was again
anodized [185]. Heating to 700 to 800 ~ C
converts the anodic film from anatase to rutile
and also improves capacitor properties [132].
A few authors have reported that titanium is
an unsatisfactory material for electrolytic
capacitors since the oxide film is non-insulating
[71, 182]. However, it seems that the relation
between capacitance and film properties is
complex, and the exact nature of the layer
responsible for capacitance is not well under-
stood; at least in the case of films formed in
borate solutions [114] the layer responsible for
capacitance is extremely thin (about 1 A) and
the capacity increases with increasing thickness
and is associated with changes in the valence of
titanium in the oxide. Equations for the dielectric
properties of the films used in titanium capacitors
have been presented by Miyata et al [186], and
equations for the shape dependence of the
electrical properties of such capacitors have been
proposed by Nakata and Minami [187].
Other uses of anodically oxidized titanium in
electric components include diodes and rectifiers
[97, 104, 117, 138, 162, 163, 188] and film
resistors [189]; the observed photoelectric [121,
162] and piezoelectric [98] effects could also be
put to use.
The corrosion resistance of titanium and its
alloys in many media, e.g., ammonium sulphate
liquors, sulphuric acid, NaC1 solutions, inhibited
HC1 solutions, chlorinated organic solvents,
bromine, etc., is improved by anodic oxidation
[56, 146, 190-201, 275]. Sealing of the anodic
films with palmitic, stearic and other organic
acids further improves the corrosion resistance
[144].
The effect of anodic oxide films on the stress
corrosion cracking of titanium alloys is difficult
to measure by direct tests, since such tests
usually require the use of fatigue-cracked
samples and anodic oxidation inside the hairline
crack is ineffective [34]; direct comparative
tests with notched (but not precracked) anodized
and non-anodized samples are not very sensitive
[196], but indicate that the anodic oxidation
may have a favourable influence on the resistance
to stress-corrosion cracking. This is confirmed
by indirect studies of environmental and
metallurgical factors [34, 63] which show that
those factors which suppress the anodic activity
of titanium alloys (i.e., reduce the residual current
at a given voltage, increase the breakdown
695
A. ALADJ EM
voltage of the anodi c film, etc.) have at the same
time, an inhibiting effect on stress corrosion
cracking. This favourable effect of anodi c films
is probabl y associated with the fact t hat the
films reduce the r at e of penet rat i on of hydrogen
into the metal (it is considered t hat hydrogen
plays an i mport ant role in the stress corrosion
cracking of t i t ani um alloys in certain environ-
ments [202, 203]. For example, after 7 h of
exposure to 40 ~ sulphuric acid at 60 ~ C the
hydrogen concent rat i on in anodized t i t ani um
remained the same as before the immersion
(11 ppm) while t hat in non-oxidized samples
increased t o 145 ppm [204]. The anodi c oxide
film slows-down the penet rat i on of hydrogen at
500 to 700 ~ C [205], and improves the fatigue
resi stance of t i t ani um alloys [ 144, 206 ]. However,
in general the film on t i t ani um alloys is less
protective t han the film on non-alloyed t i t ani um
[207]; it should also be not ed t hat partially
crystalline films (such as the anodi c films on
t i t ani um and its alloys) are less protective t han
fully amorphous films (such as those on t ant al um)
[2081.
Anodi c oxi dat i on of t i t ani um and its alloys
reduces friction, abrasi on and wear [148, 201,
209] and prevents seizing and galling, e.g., in
cold formi ng [140, 210-213]; this is at t ri but ed
to a micropitted state of the oxidized surface,
which is t hus able to hol d lubricants.
As a result of their strong interference colours,
anodi c films on t i t ani um find use as "col our ed"
coatings [166, 214, 215]. Anodi c coatings have
also been used as intermediate layers in electro-
plating on t i t ani um [216, 217] or as a base for
selective electroplating [215]. Anodizing of
vacuum deposited t i t ani um is a step in the
manufact ure of reflecting surfaces [218]. Electro-
phot ographi c plates have been made by anodi c
oxi dat i on of t i t ani um in a borat e solution [219].
Finally, anodi c oxidation is a convenient met hod
for binding oxygen in the form of TiO2, which
has a high radi at i on stability and may be used
as an accelerator target or in other devices t hat
have to accommodat e high radi at i on fluxes
[601.
7. Tr ends in present research and
concl usi ons
The advances in modern science and technology
have been reflected in the development of
research techniques for the study of anodi c
films on titanium, and the early electrochemical,
capacitance, corrosion, and other measurements
696
are t oday supplemented by a wide use of electron
microscopy and diffraction, ellipsometry, the
use of particle accelerators, etc. The next few
years would probabl y witness the application t o
the anodi c oxidation of t i t ani um of even more
advanced techniques (some of which have already
been applied to the oxidation of other metals)
such as acoustic measurements [220], ion
microprobe mass spectrometry [221], shifts in
X-ray fluorescence lines [222], radioisotopic
tracing [223], aut omat ed ellipsometry [224],
Auger electron spectrometry [225], reflection
[167] and infra-red [226] spectroscopy, optical
studies in electric fields [227], optical absorbance
to infra-red emittance ratios [262] and compu-
terized anodi zat i on control [228]. The maj or re-
maining problems in the anodi c oxidation of
titanium, and in the first place the question of
the exact relation between oxidation conditions
and the composition, structure and properties
of the resulting film, would probabl y be the
subject of more detailed studies. There is still
controversy concerning the nat ure of breakdown,
the mechanism of i o n i c transfer t hrough the
growing film, the growth rate in different elec-
trolytes, and the distribution of the electric field
across the oxide [ 34, 229, 230, 270]. New
oxidizing techniques, including plasma anodiz-
ing [231, 232] and the use of non-aqueous elec-
trolytes [233-235] could be used on a wider
scale, and the range of practical applications
could be extended to optical measuring ins-
truments, medical engineering, nuclear instru-
ment at i on, etc.
In conclusion, it could be said t hat the anodic
oxidation of metals is a true interdisciplinary
field which employs steadily increasing numbers
of physicists, electrochemists and metallurgists
in a search for better underst andi ng of its basic
phenomena and for improving and extending
the uses of the resulting films.
Acknowl edgement s
This review was prepared as a part of work on
the relationship between anodi c behaviour and
stress corrosion cracking of t i t ani um alloys,
which is at present carried out at the Depart ment
of Metallurgy of the University of Paris, Orsay,
France; the aut hor wishes to express his gratitude
to Professor P. Lacombe, Head of the Depart-
ment, for his ki nd hospitality and cont i nuous
help.
It is a pleasure to acknowledge the contribu-
tion of many fruitful discussions with staff of t he
R E V I E W: A N O D I C O X I D A T I O N O F T I T A N I U M A N D I T S A L L O Y S
De p a r t me n t , a n d i n p a r t i c u l a r wi t h Dr M.
Au c o u t u r i e r , wh o a l s o r e a d a n d c o mme n t e d o n
t h e ma n u s c r i p t .
T h e a u t h o r i s g r a t e f u l t o P r o f e s s o r F. Ab e l e s ,
He a d o f t h e De p a r t me n t o f Op t i c s a t t h e
Un i v e r s i t y o f Pa r i s , Qu a i St . Be r n a r d , wh o
c l a r i f i e d c e r t a i n p o i n t s c o n c e r n i n g t h e o p t i c a l
p r o p e r t i e s o f t h e a n o d i c f i l ms , a n d t o P r o f e s s o r
L. L. Shr e i r , wh o s e v a l u a b l e s u g g e s t i o n s a n d
c o mme n t s h e l p e d t h e a u t h o r wr i t e a b e t t e r p a p e r .
Appendix
T AB L E I Anodi c oxidation procedures
Electrolyte composi t i on Operat i ng condi t i on and References
remarks
1. 10 N sulphuric acid Use of a.c., 10 to 10 000 H2. [29, 26]
Oxide film formed only at low
frequencies
2. 22 ~ H~SO~, with small amount s of AI, Cu and Zn 0 to 60 ~ C, 5 to 80 V, AI [214]
salts cat hode
3. Solutions of borate, phosphate, succinate, citrate or Various [236]
tartrate in organic acids, alcohols or esters
4. 54. 6~ met hanol - 3 1 . 6 ~ adipic a c i d - 9 . 7 ~ sodi um
adipate, 5.1 ~ water
5. 2 ~ HNO3
6. Buffered borat e solutions
7. 8% H2C204
8. 3 ~ ammoni um t art rat e
9. l t o 5 ~ Na OH
10. Mixed nitrates (sodium-calcium)
11. Sulphuric aci d (various concentrations, from 0.2 y
to concentrated)
12. 5 ~ tartaric acid, or 20 ~ HzPO4, or 5 % oxalic acid
13. Di l ut e HCI (2 g 1-1) cont ai ni ng Cr ~+ (175 g 1 1) and
Cr ~+ (15 g 1-1) ions
14. 2 N Na2SO4 + 0.1 N H2SO~
15. Di l ut e HC1, with organic inhibitors
16. 1 ~ CrO3 in dilute H2SO4 or HsPO~
17. 1 5 ~ H2SO~ 4 0 ~ HzPO~
18. HsPO4 (50 g l 1) _ Na F (930 g 1-1)
19. Concent rat ed ( > 350 g 1-1) Na OH or KOH
20. Sul phami c acid in formami de
21. 450 g 1-1 CrO3, small amount of HF
22. 8 ~ HsPO4 in tetrahydrofurfuryl alcohol
23. Various sulphuric-phosphoric acid mixts.
24. 5 to 20 ~ ammoni um sulphate
25. 1 Y sodi um sulphate
26. 1 0 ~ oxalic acid
27. 0.1 to 11.0 M HC1
28. Hot concentrated HCI
29. Saturated oxalic acid
3.5 V, 3 10 -6 Ac m 2 [237]
4 V, ambient temp.
At pH 6.7 to 12.5
0 to 60 ~ C, 5 to 80 V
pH 7, 10 mA cm -2
Ambi ent temp. , 4 V
348 ~ C, up to 50 V
1 to 20 mA cm -2, various
temps, up to 100 ~ C
1 . 5 to 7.5 mA cm -~, up to
130 V
p H 1.0, 85 ~ C
11 to 14 V, form unstable films
20 mi n at 5 Af t -~
1 A d m - ~
30 to 80~ 25 to 80V,
5 to 60 sec
Room temperature
250 mA cm -~, 3 min
2 mA cm -~, 50 to 150 V
up to 100 ~ C
40 to 50 ~ C
1 0 8 Am -2, 10 to 4 0 V
25 to 75 ~ c
Solutions in met hanol with
1 0 ~ H~ O
Up to 9 V
25 to 60 ~ C, 5 to 6 0 mAc m
[216]
[145]
[214]
[92, 151]
[212, 216]
[152, 178]
[3, 43, 44, 55, 56, 68, 75,
77, 136, 137, 139, 142,
190, 193, 198, 201,202,
213, 217, 238, 241,255,
257, 260, 265, 267, 269,
276]
[142]
[52]
[164, 247]
[81,248, 249]
[250]
[251]
[46]
[215, 252]
[234]
[119]
[97]
[1471
[204]
[129]
[207, 253]
[1151
[258]
[105]
697
A. ALADJ EM
El ect rol yt e composi t i on Oper at i ng condi t i on and References
r emar ks
30. 0.1 M HC104
31. Mol t en 1: 1 NaNO3:Ca(NOa)= mi xt ur e
32. 5 N H=SO, wi t h 1 mol 1-1 KI
33. 1 : 1 mi xt ur e of ethylene-glycol and sat ur at ed oxalic
acid
34. Oxygen-free HC1 cont ai ni ng > 0.115 mol 1 1
t r i val ent Fe
35. 0.12 N Na F i n 5 ~ sul phuri c acid
36. Borax i n di et hyl ene glycol
37. 1 8 ~ HCI
38. 2 t o 8 ~ Na OH or KOH, 1 t o 3 ~ EDTA or ot her
compl exant s (gl uconat e, ni t ri l oacet at e)
39. 5 N H~SO4 wi t h i nhi bi t or s (e.g., p- ni t r oani l i ne)
40. 4 0 ~ H2SO4, up t o 0.186 g 1-1 t i t anyl i ons
41. 3.0 t o 3 . 5 ~ NaC1
42. HF 11.5, H20 6.2, t et r ahydr of ur an 15, et hyl ene
glycol 67.3
43. 1 0 ~ NH4 bor at e i n et hyl ene-gl ycol
44. 8 t o 40 oz ga1-1 Na OH or KOH, 3 t o 10 oz gal i
NAF
45. Ethylene-glycol 100 ml, H20 100 ml , H3PO4 10 g
46. Mi xed (e.g., Na- ammoni um) phosphat es, 70 g 1 1
47. Na OH 214.5, Na2SiOa 18.75, TiO2 15.0, act i vat ed
car bon 3.75 g 1-1
48. Vari ous sol ut i ons (0.01 t o 0 . 4 ~ NaF, KF, NH4F;
1 t o I 0 ~ NH4HB4OT, KHzPO4, H3PO~; or i n
0.1 t o 5 . 0 ~ NH~BF4, (NH~)~SiF~, SnF2, ZnF2,
CdF~ dissolved i n wat er wi t h glycerol, met hanol ,
f or mami de, et hanol ami ne)
49. 0.1 N KC1
50. 0.5 N Na2S or HC104
51. 0.05 M NaaBO4
52. Et hyl hydr ogen phos phat e
53. 2 0 ~ NHO8 + 3 ~ HF
54. 2 0 ~ sul phur i c acid sat ur at ed wi t h H~
55. 0.5 ~ a mmoni um hydr ogen phos phat e
56. Di l ut e HCOOH sol ut i ons
57. 70 ~ glycolonitrile
58. Var i ous electrolytes ( compar at i ve st udy): nitric,
sul phuri c, phosphor i c, bori c, oxalic, t ar t ar i c, citric
acids, K2Cr207, Na2MoO~, (NH~)~S~Os, Na~WO~,
NH4HSO~
59. 10 par t s et hyl hydrogen phosphat e, 5 par t s 85
H3PO4, 20 par t s glycerol, 65 par t s H20
60. Two step anodi zi ng:
I : 100 ml ethylene-glycol, 100 ml H20, 10 g
phosphor i c acid
I I : 1 0 ~ H3BO3
61. 7 ~ a mmoni um car bonat e
[2391
300 ~ C, AI cat hode [1381
Above 1 mA cm -~ [261 ]
12 V [98, 162]
35 ~ C; di ssol ut i on of Ti occurs
i f t he Fe concent r at i on is
reduced
Use of a.c., 50 Hz 5000 A m -z
20 t o 40 mi n, 10 t o 12 Af t -~
150 t o 212 ~ F
0.4 mA cm -~
30 t o 55 ~ C, i nt er r upt ed
cur r ent (500 Hz)
12 t o 85 ~ C, up t o
200 mA cm -~
35 t o 40 V, 5 mi n
Fi r st at 200, t hen at 4 t o 8
mA i n -2
pH 3 t o 12
pH 13 t o 14, 66 t o 68 ~ F,
10 Af t 2 Pb cat hode
50 t o 80 ~ C, 10 mi n,
80 t o 200 V
[83]
[1891
[256]
[2151
[196]
[254]
[491
[63, 191]
[263]
[2641
[1131
[132]
[199]
[206]
[246]
12 V [1111
25 t o 65 ~ C [18, 269]
1 mA cm -2, 30 mi n [268]
In aqueous sol ut i ons [123]
[266]
Room t emp, above [101 ]
140 mA cm -2
85 V [218]
200 t o 250 V, 5 t o 20 A ft -2, [140, 141]
0 t o 40 ~ C
90 mi n at 75 V [180]
24 V, 18 t o 20 ~ C [181]
250 V, 10 mA cm -~, 30 rain [102]
2 0 0 mA i n -~
Cons t ant vol t age, t o a resi dual
cur r ent of 1 mAi n -~
[2721
[1791
698
REVI EW: ANODI C OXI DATI ON OF TI TANI UM AND I TS ALLOYS
El ect rol yt e composi t i on Oper at i ng condi t i on and References
r emar ks
62. Vari ous electrolytes (NH4HB~Ov, NH4 mol ybdat e, [183 ]
citrate, t ar t r at e, succinate, or borax, NH4H~POa) i n
organi c sol vent s ( met hanol , et hanol , pr opanol , glycol,
glycerol, pr opi oni c acid, di et hyl ami ne, et hyl ene glycol,
pyridine, Ac20)
63. 0.1 N Na B Q [1341
64. HCOOH cont ai ni ng 2 ~ phos phor ous acid, 5 to [50]
10 ~ H20, 400 t o 700 ppm HE
65. Et hyl ene-gl ycol adi pat e [184 ]
66. 2.5 ~ H3BO8 wi t h 0.05 ~ bor ax 150 t o 250 V [219]
67. Eut ect i c mi xt ur e of mol t en al kal i car bonat es 600 to 800 ~ C [ 1 2 1 ]
68. 3 % a mmoni um bor at e [185]
69. Mi xed Li - Na- K car bonat e [2711
70. Sat ur at ed Ba(OH)~
71. 7 0 ~ HNO3
72. Solid rut i l e
73. Distilled H20
74. Ammoni um bor at e sol ut i on, cont ai ni ng s t ar ch-
i odi ne
75. 1 t o 43 ~ HBF4 i n di met hyl f or mami de
76. Di l ut e cyani de sol ut i ons
77. 3 ~ a mmoni um t ar t r at e
78. Sat ur at ed H3BOz or di l ut e CrO3, Li OH, KOH,
ci t rat e or t ar t r at e
79. Mi xed HsPO4-Ho.O-C2H~(OH)z sol ut i on
80. 50% C2HsPO2(OH)2 - 5 0 ~ H20
81. Sat ur at ed a mmoni um bor at e
82. 0.01 M Na2SO4
83. 0.1 N KOH
84. Oxygen pl asma i oni zed at 800 V
85. 20 vol conc. HNO~ + 80 vol conc. H2SO~
(electrolyte " SN" )
86. Di l ut e sol ut i ons of organi c acids
87. Mi xed chl or at e electrolytes
88. 2 ~ HaBO ~ q- 0.5 ~ (NH4)~B~OT.4H20
89. Sat ur at ed oxalic acid, wi t h 1-2-propanedi ol
90. 5 N H2SO4, > 0.01 mol 1-1 SbCI3
91. NaC1, or K di chr omat e, or K phos phat e sol ut i ons
92. J) i l ut e H3BO3
93. Aci d met hyl -et hyl phos phat e sol ut i ons (5 t o 25 ~ )
94. 1 0 ~ Na CN, or al kal i ne K- Ti oxal at e
95. 5 ~ HF, or 7 0 ~ HNO3
96. 5 t o 1 0 ~ oxalic-citric-lactic acid, or 5 ~ Na2HPO~
97. Ar nmoni acal t ar t ar i c acid sol ut i ons
98. 3 ~ HsPO~ + 1 ~ H3BO3
99. Mol t en HNO~ or HNOa
1.0 t o 5.0 mA in -~
60 t o 70 V (or 260 V i n
absence of wat er)
600 t o 700 ~ C, above
10 -3 A cm 2
25 ~ C, 5 t o 70 mA cm -2
25 ~ C, 10 V, 1 mA cm -2
900 t o 1000 ~ C, up t o
40 A dm 2
Boi l i ng
4 t o 5 V
10 t o 60 sec, 20 t o 7 0 V
p H2 , 100 V
50 t o 2000 V, bel ow 100 ~ F
20 t o 50 V, sui t abl e for alloys
300 t o 400 mA dm -~ t o 150 t o
400 V, t hen at cons t ant vol t age
t o bel ow 10 mA dm -2
(resi dual cur r ent )
25 ~ C, 100 mA cm -2
29 ~ C, 12.5 mA cm -2, to 70 V
85mTor r , 8 0 V
40 ~ C
1 0 V
p H9 t o 1 0 , 6 0 V
pH 0.4, 14 mA cm -~, up to
400 V
10 V ( maxi mum voltage)
20 V ( maxi mum vol t age)
Up t o 300 t o 400 V
Room t emp. , up t o 110 V
315 ~ C, cons t ant cur r ent
4 mAc m -2
[1221
[871
[41 ]
[240]
[88]
[166]
[244]
[67]
[201]
[169]
[176]
[J541
[1311
[124]
[86]
[39]
[277]
[245]
[149]
[170]
[242]
[243]
[114]
[143]
[1431
[1431
[143]
[66]
[341
[278, 2791
699
A. ALADJ EM
Ref erences
1. P. PASCAL, " No u v e a u Trai t 6 de Chi mi e Mi ne r a l e " ,
14 ( Ma s s on & Ci e, Par i s 1963).
2. J. MELLOR, " k Compr e he ns i ve Tr eat i s e on
I nor ga ni c a n d Theor et i cal Ch e mi s t r y " , 7 ( Long-
r oans, Lo n d o n 1960).
3. v . ANDREEVA a n d v . KAZARI N, " Pr oc . I I I
I nt e r na t . Conf . Met . Cor r os i on. 1966" ( " Mi r " ,
Mo s c o w, 1969) pp. 464-472.
4. v . ANDREEVA a n d N. SHISHAKOV, Z. Fiz. Khim.
32 (1958) 1671.
5. s. MORIOKA a n d A. UMEZONO, Nippon Kinzoku
Gakkaishi 20 (1956) 403.
6. E. BOTTS a n d v. KRASNKOPF, J. Phys. Chem. 31
(1927) 1404.
7. M. NAGAYAMA, Boshuko Gijutsu 19 (1970) 490.
8. N. WATANABE a n d Y. KANAYA, Denki Kagaku, 39
(1971) 139.
9. D. VADACHKORIYA a n d A. SHONIYA, " Av t o ma t .
i Me k h a n . Pr ot s . Na ne s e ni ya Pokr yt i i " ( TNI I I TEI ,
Mo s c o w, 1969).
10. c . DELL' OCA, D. PULEREY, a n d L. YOUNG,
Physics of Thin Films 6 (1971).
11. L. YOUNG, " An o d i c Oxi de Fi l ms " ( Ac a de mi c
Pr ess, Ne w Yor k, 1961).
12. rI. RI CHAUD, Corrosion et Anticorrosion, 4 (1957)
400.
13. T. NEUMANN, " Pa s s i vi e r e nde Fi l me u. De c k-
s c hi c ht e n Anl a uf s c hi c ht e n" ( Vor t r age, Fr a nkf ur t -
a m- Ma i n , 1955).
14. v. ORLOVA a n d N. SHKATOVA, Pr oc e e di ngs Si xt h
Conf . o n Che m. , Met al l ur gy a n d Us es o f Ti t a ni um
[In Rus s i a n] 19-24, Mos c ow, 1965.
15. G. BIANCHI, F. MAZZA, a n d s. TRASATTI, Z.
Physik. Chem. (Leipzig) 226 (1-2) (1964) 40.
16. Br i t i s h Pat . 1062026 (1966) t o St a nda r d Tel eph. &
Cabl es Lt d.
17. A. JOHNSON a n d L. SHREIR, Corrosion Science 5(4)
(1965) 269.
18. B. RIVOLTA, Met . Ital. 50 (1958) 173.
19. L. ZHI LI NA, Zh. Priklad, Khim. 33 (1960) 2526.
20. P. JAQUET, Met al Treatment 18 (1951) 176.
21. E. FAI ZULLI N a nd D. BAITALOV, Zashchita
3~Ietallov 4(1) (1968) 11.
22. T. SHIMOZE, A. TAKAMURA, a n d H. HIROSE,
Boshoktl Gijutsu 14(2) (1965) 60.
23. A. BRYNZA, L. GERASYUTI NA, a ndT. KRYACHEK,
Ukr. Khim. Zhurnal 28 (1962) 396.
24. R. LAMOUREUX, AD 266358 (1961).
25. E. CHERNENKO, L. YANOV, a n d v . CHERNENKO,
Elektrokhimiya 7(9) (1971) 1374.
26. M. FOKIN a n d v . TIMONIN, Zashchita Metallov
4(2) (1968) 185.
27. A. VHH, Electroehimica Act a 14 (1969) 921.
28. D. FRANZ a n d H. GOEHR, Ber. Binsenges. Physik.
Chem. 67(7) (1963) 680.
29. Y. TOMASHOV a n d N. STRUKOV, Dokl. Akad.
Nauk S S S R 152 (1963) 1177.
7OO
30. G. KOSSYI, V. NIVAKOXISKII, a n d YA. KOLO-
TYRKIN, Zashchita Metallov 5(2) (1969) 210.
31. T. P. HOAR, " Pr oc . I I I I nt e r na t . Conf . Me t .
Cor r os i on 1966" ( " Mi r " , Mos c ow, 1969) pp. 88-98.
32. s. AKULI NI N a nd M. SHCHEVELEV, " Di f f uz.
Po l u p r o v . " , 1967, 196-200 ( Publ . 1969). ( Ca 75:
102444.)
33. E. KHAIRY a nd M. EL-KHATIB, J . Chem. United
Arab Rep. 4(1) (1961) 13.
34. A. ALADJEM, M. AUCOUTURI ER, a n d P . LACOMBE,
t o a ppe a r i n J. Mater. Sci. 8 (1973).
35. M. STERN, Jr. Electrochem. Soc. 105 (1958) 638.
36. K. NAKATA a n d v . I I DA, Denki Kagakg Oyobi
Kogyo Bulsuri Kagaku 37(5) (1969) 366.
37. A. GUNTHERSCHNIZE a n d H. BETZ, Z. Phys. 92
(1934) 367.
38. c . HALL a n d N. HACKERMAN, J. Phys. Chem. 57
(1953) 262.
39. F. COVER a n d M. MUSSELIN, Thin Sol i dFi l ms 2(3)
(1968) 211.
40. A. KRASIL' SHCHIKOV, " Pr oc . I I I I nt er . Conf . Met .
Cor r os i on 1966" ( " Mi r " , Mos c ow, 1968) pp. 327-
335.
41. w. DORNELAS, Thesi s, Uni ver s i t y o f Par i s, 21
De c e mbe r , 1967.
42. R. TYLECOTE, CNRS Symp. No. 122 (1963). Publ .
Par i s 1965, pp. 241-7.
43. v . NOVAKOVSKII a n d v . OVCHARENKO, Zashchita
Metallov 4(6) (1968) 656.
44. N. TOMASHOV, V. MODESTOVA, L. PLAVI CH, a n d
A. AVERBUKH, " Ko r r o z i y a Met al l ov i Spl avov
1965", ( " Me t a l l ur gi ya , " Mos c ow, 1965) pp. 80-102.
45. A. SUKHOTIN a n d L. TUNGUSOVA, Zashchita
Metallov 4(1) (1968) 8.
46. A. BOGOYAVLENSKII a nd v . GORBACHEVA, Tr.
Kazan. Aviats. Inst. 108 (1969) 80.
47. N. TOMASHOV, YU. RUSKOL, a nd G. AYUYAN,
Zashchita Metallov 7 (1971) 272.
48. A. BOGOYAVLENSKII, Tr. Kaz. Aviats. Inst. 90
(1966) 3.
49. I. TOMASHOV a n d w. MATVEEVA, Zashchita
Metallov 7 (5) (1971) 189.
50. D. CHESELDINE, J. Electrochem. Soc. 111(8) (1964)
1005.
51. J. COTTON, " Pr oc . I I I I nt er nat . Conf . Met .
Cor r os i on, 1966" ( " MW' , Mos c ow, 1969) pp. 334-5.
52. E. LETSKIKH, A. KOMORNI KOVA, V. KUYAZHEVA
a nd YA. I~OLOTYRKIN, Zashchita Metallov 6(6)
(1970) 635.
53. A. TSUNESABURO a n d H. ITO, Mere. Inst. Sci.'Ind.
Res. Osaka Univ. 22 (1965) 77.
54. T. MATVEEVA a n d v. PAVLOVA, " Ko r r o z i y a
Met al l ov i Spl avov 196Y' , ( Met al l ur gi zdat , Mos c ow,
1963) pp. 208-11.
55. N. TOMASHOV a n d T. MATVEEVA, " An o d .
Za s hc hi t a Me t a l l ov" ( Ka z a n. Avi at s. I nst , Ka z a n ,
1964) pp. 544.
56. A. BOGOYAVLENSKII a n d s . BORODINA, ibid,
pp. 440.
R E VI E W: ANODI C OXI DAT I ON OF T I T ANI UM AND I TS AL L OYS
57. V. ANDREEVA, Corrosion 20(2) (1964) 35t.
58. P. HAYFI ELD a n d G. WHI TE, Nat. Bur. Stand.
Misc. PubL No . 256, (1963) 157.
59. A. ALADJ EM~ D. BRANDON, J . YAHAL OM, a n d
J. ZAHAVI , I n t e r n a t . Conf . El e c t r on Mi c r os c . ,
R o me 1968.
60. A. AL ADJ E M a n d o . B R ANDON, Jr. Vac. Sci .
Technol. 6 (1969) 635.
61. G. AMSEL a n d D. SAMUEL, J. Phys. Chem. Solids
23 (1962) i 707.
62. F. KOVER, The s i s , Un i v e r s i t y o f Pa r i s (1967).
63. J. GREEN a n d A. SEDRI CKS, Met . Trans. 2(7)
(1971) 1807.
64. N. TOMASHOV, R. AL' TOVSKI1, a n d M. KUSH-
NEREV, Zavod. Lab. 26 (1960) 298.
65. D. LAI NER a n d M. TSYPI N, Zavodsk. Lab. 25 (1959)
1209.
66. G. HASS, VacUum 11 (1952) 331.
67. s . KHOO, G. WOOD, a n d D. WHI TTLE, Electro-
chimica Act a 16 (1971) 1703.
68. N. PALKI NA a n d A. SHATALOV, Elektrokhimiya
7(1) (1971) 96.
69. t . AMMAR a n d I. KAMAL, Electrochimica Acta 16
(1971) 1555.
70. M. KOYAMA, Ri kagaka Kenkyusho Hokoku, 38(5)
(1962) 546.
71. ldem, ibid 38(5) (1962) 645.
72. I. FLIS a n d I. VOROB' EV, " Z a s h c h i t a Me t a l l o v i
Oks i d. P o k r . " ( AN SSSR, Mo s c o w, 1965) pp.
312-16.
73. P. BROUILLET, I. EPELBOIN, a n d M. FROMENT,
J. Electrochem. Sac. 106 (1959) 534.
74. R. AR MS T R ONG, J . HAR R I S ON, H. THI RSK~ a n d
R. WHI TFI ELD, i bm 117(8) (1970) 1003.
75. YA. KOL OT YR KI N a n d v . S T R UNKI N, Zashchi t a
Metallov 6 (1970) 511.
76. A. AL ADJ E M, D. B R ANDON, J . YAHAL OM, a n d
J. ZAHAVI , Electrochimica Act a 15(5) (1970) 663.
77. J. YAHALOM a n d J. ZAHAVI , ibid 15(9) (1970) 1429.
78. L. DZ HAP AR I DZ E , D. OT I AS HVI L I , A. S HAKA-
RI S HV1 LI , V. P R UI DZ E , a r i d R. C HAGUNAVA,
Pererabotka Margan. Polimet. Rud. Gruz. (1970) 130.
79. I. DUGDALE a n d J. COTTON, Corrosion Science 4
(1964) 397.
80. N. T OMAS HOV, G. C HE R NOVA , a n d R . AL ' T OVS KI I ,
Zh. Fiz. Khim. 35 (1971) 1068.
81. M. BREI TER, Electrochimica Act a 15(7) (1970) 1195.
82. M. LEVY a n d G. S KL OVE R , J. El ect rochem. Sac.
116(3) (1969) 323.
83. S. YOS HI Z AWA, F. HI NE , a r i d s . S HI BAMORE ,
Denki Kagaku 35(1) (1967) 54.
84. Y. TOMASHOV, G. CHERNOVA, a n d R. AL' TOVSKH,
Z. Physik. Chemie 214 (1960) 312.
85. I. AMMAR a n d L KAMAL, Eleetrochimica Act a 16
(1971) 1539.
86. o . HUSTED, L. GRUSS, a n d T. MACKUS, 3..
Eleetrochem. Sac. 118 (1971) 1989.
87. R. MISCH a n d w. RUTHER, ibm 100 (1953) 531.
88. G. KLEI N, i bm 113 (1966) 345.
89. D. MCLEAN, N. S C HWAR T Z , J . WE R NE R , a n d
M. GRESH, Bel l Te l e p h o n e La b . AD 232690 (1960)
pp. 14-15.
90. T. RUPPRECHT, Naturwiss. 47 (1960) 127.
91. w. B UR GE R S , A. C L AAS E N, a n d I . Z E R NI KE ,
Z. Physi k 74 (1932) 593.
92. G. WOOD a n d c . PEARSON, Corrosion Science 7(2)
(1967) 119.
93. N. SATO, Electrochimica Act a 16 (1971) 1683.
94. N. SATO, Nippon Kinzoku Gakkaishi 34 (6) (1970)
105.
95. A. SUKHOTI N a n d L. TUNGUSOVA, Zashchita
Metallov 7 (1971) 259.
96. D, BAI TALOV a n d v . EAI ZULI N, Issled. Elektro-
khim. Magnetokhim. i Elektrokhim. Metody Analiza
2 (1969) 121.
97. F. HUBER, Solid State Electronics 5 (1962) 410.
98. Idem, J. Electrochem. Sac. 110(7) (1963) 846.
99. R. HARRI NGTON a n d H. NELSON, Te c h. Pu b l . 1158
( AI MME , I ns t . o f Me t a l s ) 1940.
100. E. KHAI RY a n d M. EL- KHATI B, Egypt J. Chem. 1
(1958) 47.
101. M. STERN a n d n . WI SSENBERG, J. Electrochem.
Sac. 106 (1959) 755.
102. s . CALLAHAN, U. S. Pa t . 3262867 (1966).
103. A. DE RUDNAY, U. S. Pa t . 2960642 (1960).
104. r . HUBER a n d M. ROTTERSMAN, J. Applied Phys.
33 (1962) 3385.
105. v . LAVRENKO a n d A. CHEKHOVSKI I , Ukr. Khim.
Zhurna130(8) (1964) 788.
106. A. BRYNZA a n d v . EEDASH, Zashchita Metallov
4(3) (1968) 252.
107. V, VE S E L OVS KI I , T. BORI S OVA, A. YAKOVL E VA,
a n d s . I ZI DONOV, Electrochim. Act a 10(3) (1965)
325.
108. G. KOSSYI, V. NOVAKOVSKI I , a n d YA. KOLO-
TVRKI N, Zashchita Metallov 6(3) (1970) 317.
109. P. BODDV, J. Electrochem. Sac. 115 (1968) 199.
110. E. SATO, Denki Kagaku 35(11) (1967) 831.
111. R. OTSUKA, Kol l oi dZ. 153 (1967) 59.
112. T. MARCOVI C a n d J. J o v I c , Werkstoffe Corros.
18(7) (1967) 582.
113. G. SLOMI N, U. S. Pa t . 2934480 (1960).
114. H. ISAACS a n d J. LLEWELYN LEACH, J. Electro-
c.~em. Sac. 110 (1963) 680.
115. I. MENZIES a n d A. AVERI LL, Electrochimica Act a
13(4) (1968) 807.
116. M. SIBERT, AD 262706 (1961).
117. A. VIJH, Electrochimica Act a 16 (1971) 1427.
118. H. J OHANS E N, G. ADAMS , a n d P. VAN RYS S EL-
BERGHE, J. Electrochem. Sac. 104 (1957) 339.
119. H. ISAACS a n d J. LEACH, J. Inst. Metals 91 (1962)
80.
120. A. HULTQUI ST a n d M. Sl BERT, NAS A C R 364
(1966).
121. i . OZERVANAYA, T. MANUKHI NA, a n d ~ .
SMIRNOV, Zashchita Metallov 8(1) (1972) 128.
122. M. YAMAZAKI a n d H. NOZAKI , Kogyo Kagaku
Zasshi 74(6) (1971) 1265.
701
A. AL ADJ E M
123. M. TECOTZKY, AD 265215 (1961).
124. i . ROZENFEL' D, A. AKI MOV, a n d E. OSHE,
" Ko r r o z . Za s h c h . Me t a l l o v " ( Me t a l l ur gi ya , Mos c ow,
1970), 202-6.
125. R. HARRI NGTON a n d H. NELSON, Trans. AIME
137 (1940) 62.
126. s . FISHELEVA a n d P. ME L ' NI KOV, " Sb o r n i k Na u c h
T r u d . " ( Me k h . - Te k h . Fa k . , Sver dl ovs k, 1969) 54.
127. A. FROVA, P. BODDY, a n d v . CHEN, Phys. Rev.
157 (1967) 100.
128. A. AKIMOV a n d I . ROZENrEL'D,ZashchitaMemllov
6(6) (1970) 640.
129. I . ROZENFEL' D, A. AKIMOV, a n d E. OSHE, ibm
5(2) (1969) 217.
130. D. BRANDON, J. ZAHAVI , A. ALADJEM, a n d
J. YAHALOM, J. Vael#im Sei. Techn. (6) (1969) 783-7.
131. g. ALADJEM, D. BRANDON, J. YAHALOM, a n d
J. ZAHAVI , I AE C Re p o r t (1969) 1189.
132. E. WAI NER, U. S. Pat . 2943031 (1960).
133. s . HI ROTA, H. CHI BA, T. TANAKA, a n d H. NOAKE,
Oyo Butsuri 26 (1957) 651.
134. H. C mB A, Denki Kagaku 28(1) (1960) 5.
135. MASASHI KOYAMA, Rikagaku Kenkyasho Hokoku
39(1) (1963) 21.
136. s . YAMAGUCHI , J. Electrochem. Soc. 108 (1961)
302.
137. T. KOI ZUMI a n d T. NAKAYAMA, " Pr oc . I I I I n t e r n a t .
Conf . Me t a l l i c Co r r o s i o n ( 1 9 6 6 ) " ( " Mi r " , Mo s c o w,
1968) pp. 454- 68.
138. M. FOX, R. HANSON, a n d B. MUNRO, Brit. J. Appl.
Phys. 16(8) (1965) 1213.
139. N. TOMASHOV, R. AL ' T OVS KI I , a n d M. KUSH-
NEREV, Doklady AN SSSR, 141 (1961) 913.
140. L. SHREIR a n d R. PI GGOT, Bri t . Pa t . 962904 (1964).
141. A. R. PI GOTT a n d L. L. SHREIR, Nature 189 (1961)
216.
142. N. TOMASHOV a n d E. ZALI VALOV, Zh. Priklad.
Khim. 42(11) (1970) 2474.
143. M. SIBERT, J. Electrochem. Soc. 110 (1963) 65.
144. I. KRAMER a n d c . BURROWS, U. S. Pa t . 3510411
(1970).
145. n . BAI TALOV, V. MAKAROV, a n d F. FAI ZULI N,
Issled. Elektrokhim., Magnetokhim. i Elektrokhim.
Metody Analiza 2 (1969) 127.
146. E. MANTON a n d M. TURNER, I n: " T h e Sci ence,
Te c h n o l o g y a n d Ap p l i c a t i o n s o f T i t a n i u m" ( Per -
g a mo n Pr ess, Oxf or d, 1970).
147. G. CHERNENKO, N. MARCHENKO, a n d A.
ROMANOV, Soci et Pat . 197540 (1968).
148. s . BORODI NA a n d D. EVSEEVA, Trudy Kazan.
Aviats. Inst. 96 (1966) 56.
149. D. VERMILYEA, J. Electroehem. Soc. 110 (1963) 345.
150. N. BABA, K. EUJ I WARA, a n d s . TAJI MI , Denki
Kagaku 39 (1971) 42.
151. G. WOOD a n d c . PEARSON, Nature 208 (5010)
(1965) 547.
152. A. YAMASHITA a n d H. HAGI WARA, J. Electrochem.
Soc. 112(3) (1965) 279.
7 0 2
153. v . SAVOSHCHENKO, Radiotekhnika, No . 6, (1968)
84.
154. s . TAJIMA a n d T. MORL J. Electrochem. Soc. Japan
22 (1954) 174.
155. K. NAGASAKI a n d H. I SHI DA, Keikinzoku 8 (1958)
60.
156. A. E UJ I S HI MA, K. HONDA, a n d s . KI KUC HI ,
Kogyo Kagaku Zasshi 72(1) (1969) 108.
157. E. KHAI RY a n d M. EL- KHATI B, Egypt. J. Chem. 1
(1958) 75.
158. K. SCHWABBE, " Pr oc . I I I I n t e r n a t . Conf . Met al l i c
Co r r o s i o n , 1966" ( " Mi r " , Mo s c o w, 1969) pp. 52-72.
159. J. COTTON a n d A. WOOD, Trans. Inst. Chem. Eng.
41(11) (1963) 354.
160. D. BAI TALOV, T. GORBUNOVA, a n d v. EAI ZULLI N,
Issled. Elektrokhim., Magnetokhim., Elektrokhim.
Metody Analiza 3 (1970) 132.
161. g . ALADJEM, J. Radiation Eng. 3, (1973).
162. r . HUBER, J. Electrochem. Soc. 115(2) (1968) 203.
163. e . SCHMI DT, r . HUBER, a n d R . SCHWARTZ, Phys.
Chem. Solids 15 (1960) 270.
164. v . OVCHARENKO a n d v . NOVAKOVSKI I , Zashchita
Metallov 6(2) (1970) 201.
165. P. VAN RYSSELBERGHE a n d H. JOHANSEN, J.
Electrochem. Soc. 106 (1959) 355.
166. E. KENDALL, U. S. Pat . 3616279 (1971).
167. c . PHI LLI PPI a n d s . LYON, Phys. Rev. B 3(6) [3],
(1971) 2086.
168. H. HAGI WARA, A. YAMASHI TA, A. MATSUDA,
a n d T. SUZUKI , Matsushita Tech. Rep. (Osaka) 8
(1962) 251.
169. F r e n c h Pat . 1310006 (1962) [ To T h o ms o n - Ho u s t o n
F r a n c e Co. ]
170. Phi l co Cor p. Re p o r t AD 231587 (1959).
171. H. RUDENBERG, J. HOHNSON, a n d L. WHI TE,
Pr oc. El e c t r o n i c Co mp . Conf . (1962) p. 90.
172. R. MARTI N, Ge r ma n Pa t . 1205192 (1964).
173. s . MI NAMI , W. NE YAGAMAS HI , a n d A. NOMURA,
U. S. Pat . 3359191 (1967).
174. A. MIYATA a n d M. KOYAMA, Rikagaku Kenkyusho
Hokoku 37 (1961) 290.
175. I. SATO, J a p. Pa t . 4438 (1959).
176. M. SIBERT, U. S. Pat . 3085052 (1963).
177. Fr e n c h Pa t e n t ( De ma n d e ) 2022610 (1970), t o
Ma t s u s h i t a Co, J a pa n.
178. n . HAGI WARA a n d A. YAMASHI TA, U. S. Pa t .
3239436 (1966),
179. Y. I SHI KAWA, Y. SAZAKI , a n d E. OKAMOTO,
J a p. Pat . 8384 (1958).
180. A. SALOMON a n d J. CARSON, U. S. Pat . 3255389
(1966).
181. P. SCHM1DT, U. S. Pa t . 3410776 (1968).
182. A. MIYATA a n d M. KOYAMA, Rikagaku Kenkyusho
Hokoku 38 (1962) 152.
183. s . MIYATA a n d M. KOYAMA, J a p. Pat . 5816 (1958).
184. M. BUBEMCEK, Czech. Pa t . 115823 (1965).
185. I. SATO, J a p. Pa t . 5029 (1959).
186. A. MIYATA a n d A. E UR NI C m, Scientific Papers,
Inst. Phys. Chem. Res. Tokyo 5 4 (1960) 184.
REVI EW: ANODI C OXI DATI ON OF T I T ANI UM AND ITS ALLOYS
187. K. NAKATA a n d s . MINAMI, Denki Kagaku 34(7)
(1966) 511.
188. F. HUBER, Syr up. El ec. Rect i f . Co n d . Mech.
An o d i c Fi l ms ( Da l l a s 1967), pp. 162-77.
189. R. QUI NN, U. S. Pat . 3180807 (1965).
190. CHUK CHI NG- MA a n d E. PERES, [lid. Eng. Chem-
istry 43 (1951) 675.
191. H. BOMBERGER, F. BEEK, a n d M. FONTANA, dr.
Electrochem. Soc. 102 (1955) 53.
192. v . KAZARI N a n d v . ANDREEVA, Ko r r o z i ya
Me t a l l o v i Sp l a v o v 1963, pp. 156-66.
193. N. TOMASHOVa Bd G. CHERNOVA, Khim. Mashino-
stroenie, No . 3 (1961) 30.
194. J. COTTON, Chem. Eng. Progress 66(10) (1970) 57.
195. A. BRYNZA~ L. GERASYUTI NA, a n d v . FFDASI-I,
Ukr. Khim. Zhurna136(4) (1970) 397.
196. M. SOUFFRANT, Corrosion (France) 19(6) (1971)
353.
197. N. FEIGE a n d R. KANE, Chem, Eng. Progress 66(10)
(1970) 53.
198. N. TOMASHOV, R. AL' TOVSKI I , a n d A. ARAKELOV,
Doklady A N SSSR, 121 (1958) 885.
199. K. BECK, U. S. Pa t . 294911 (1960).
200. H, B6HM, Metalloberfliiche 11 (1957) 197.
201. L. MCGRAW a n d a. STOCKDALE, U. S. Pat . 3075896
(1963).
202. A. VASSEL, Pr i va t e Co mmu n i c a t i o n ( F r o m P h . D.
The s i s ) Un i v e r s i t y o f Par i s , 1972.
203. M. BLACKBURN, J. FEENEY, a n d x. BECK,
Boe i ng Re s e a r c h La b . , D1- 82- 1054 (1970).
204. F r e n c h Pat . 1521286 (1968) [t o I C I. Lt d . ]
205. YU. ZVEZDI N a n d v u . BELYAKOV, Optimizarsiya
Met . Protesssov 4 (1970) 394.
206. T. POCHI LY a n d w. I ' ARKER, U. S. Pat . 3338805
(1967).
207. I. MURGULESCU, O. RADOVI CI , a n d s . C1OLAC,
" Pr oc . I I I I n t e r n a t . Conf . Me t a l l i c Co r r o s i o n ,
1966" , ( " Mi r " , Mo s c o w, 1968) pp. 440- 7.
208. N, HACKERMAN, Z. Electrochem. 62 (1958) 632.
209. M. CHEVALI ER, J. MOISSAN, a n d R. MOLIN1ER,
Surfaces 10(59) (1971) 90.
210. P. MI LLER, a n d :4. PRAY, MetalProgress 69 (1956)
61.
211. T. POCHI LY, AD 633986 (1966).
212. H. PRAY, P. MI LLER, a n d R. JEFFREYS, PB Re p.
147158 (1961).
213. R. CHEVI GNY a n d H. RI CHAUt ) , Fr e n c h Pat .
1117264 (1956).
214. j . WEI GEL, F r e n c h Pa t . 1398453 (1965).
215. R. PI ONTELLI a n d P. PEDEFERR[, J. Eleetrochem.
Soc. 115(10) (1968) 1046.
216. F. SCHMI DT, U. S. Pat . 3207679 (1965).
217. YA. ALEKSANDROV, Trudy Kaz. Aviats. Inst. No.
108 (1969) 70.
218. M. VALIDOV a n d A. MASLOVETS, Sovi et Pat .
161482 (1964).
219. s . RAETHER, Ge r ma n Pat . 1165407 (1964).
220. z . w. GOMES a n d r . CARDON, dr. Sol i dSt at e Chem.
3(1) (1971) 125.
221. R. PAWEL, J. PEMSLER, a n d c . EVANS J UN. , J .
Electrochem. Soc. 119 (1972) 24.
222. c . SHENBERG, p r i v a t e c o mmu n i c a t i o n (1971).
223. F. WORMWELL a n d J. THOMAS, Soc. Chem.
Industry, No . 28, (1968) 365.
224. R. GREEF, Review Sci. Instr. 41 (1970) 532.
225. K. MUELLER, Microchimica Act a Suppl. 4 (1969) 1.
226. F. BOZON- VERDURAZ, J. Catal. 18(1) (1970) 12.
227. w. I~RANZ, Z. Naturforsch 13 (1918) 484.
228. Ge r ma n Of t e n 1938608 (1971) [to El e c t r o c h e m,
En g i n e e r i n g Gmb H] .
229. A. MAKRI DES, J. Electrochem. Soc. l l l 187C
( Me e t i n g Ab s t r a c t ) (1964).
230. j . DEWALD, d r. Electrochem. Soc. 102 (1955) 1.
231. G. TIBOL a n d R. HULL, ibid l l l (1964) 1368.
232. a. O'HANLON, dr. Vacuum Sci. Tech. 7 (1970) 330.
233. I. DIRMEII,:, Corrosion 25(4) (1969) 180.
234. I. MENZIES, G. MARSHALL, a n d G. GRIFFIN,
Corrosion Sei 9(4) (1969) 287.
235. M. TURPI N a n d M. TESTERMAN, J. Eleetrochem.
Soc. 109 (1962) 168,
236. K. MASASHI, Rikagaku Kenkyusho Hokoku 38
(1962) 321.
237. A. TSI NMAN, E. KOVSMAN, a n d v . KUZUB, Ukr.
Khim. Zhurna131(9) (1965) 923.
238. E. KUZNFTSOVA, T. BORISOVA, a n d v . VESE-
LOVSKI I , Elektrokhimiya 4(2) (1968) 167.
239. D. VERMILYEA, J. Phys. Chem. Solids 26(1) (1965)
133.
240. j . DRALEY, F. DEBOER, a n d c . YOUNGDAHL,
J. Electrochem. Sop. 108 (1961) 622.
241. N. TOMASHOV, V. MODESTOVA, L. PLAVI CH, a n d
A. AVERBUKH, Pr o c e e d i n g s Si xt h Conf . o n Ch e m. ,
Me t a l l u r g y a n d Us e s o f T i t a n i u m ( I n Ru s s i a n ) ,
Mo s c o w 1965 p. 130.
242. I. ANOSCHENKO, A. ZORCHENKO, a n d G.
LUK'YANOVA, Zashchita Metallov, 6 (1970) 443.
243. G. DUMMER a n d FI. NORDENBERG, I n : " F i x e d
a n d Va r i a bl e Ca p a c i t o r s " , ( Mc Gr a w- Hi l l , Ne w
Yo r k , 1960).
244. E. E~CE a n d J. MARCOLI N, J. Metals 6 (1954) 346.
245. I . ELIS a n d v . ZOLOTUKHIN, Trudy Leningrad.
Tekh. Inst. Tsellyuloz. Bumazh. Prom. No. 13 (1964)
78.
246. w. MI ZUSHI MA a n d Y, I I OA, U. S. Pat . 3502552
(1970).
247. v. OVCHAREN KO a n d v . NOVAKOVSKI I , Zashchita
Metallov 6(3) (1970) 320.
248. H. TOGAKO, H. SASAKI , a n d y u . KANDA, Nippon
Ki nzoku Gakkaishi 33(1 I) (1969) 1280.
249. v . GRI GOR' EV a n d I. GERSHANOVA, Zh. Prikland.
Khim. 42(9) (1969) 2135.
250. A. MORRI S, U. S . Pa t . 3488269 (1970).
251. A. BOGOYAVLENSKI I , V. GORBACHEVA, a n d
P. LANTSMAN, Tr. Kazan. Aviats. Inst. 108 (1969)
75.
252. R. PI ONTELLI , F r e n c h Pat . 1522637 (1968).
253. o . RADOVI CI a n d s . CI OLAC, Rev. Roum. Chim.
13(1) (1968) 31.
703
A. ALADJ EM
254. A. BRY~qZA, V. rEr)asrl , and v. SOTNXKOVA,
Zashchita Metallov 4(2) (1968) 189.
255. J. PETERS, AD 639419 (1966).
256. F. KOVER and M. MUSSELIN, Rev. Gen. Electricite
76(6) (1969) 793.
257. M. L~VY, Corrosion 23(8) (1967) 236.
258. r. MAZZA, ibid, 23(8) (1967) 223.
259. L. COVINGTON, German Pat. 1187884 (1965).
260. o. RUDI GER, W. FISCHER, and w. KNORR, Z.
Metallk. 47(11) (1956) 599.
261. A, MURTAZAEV and L. ~r Doklady Akad. Nauk.
Uzbek SSR 22(2) (1965) 35.
262. J. JANSSEN, ASD-TR-61-147 (1961).
263. w. RICHESON and M. EISENBERG, J. Electrochem.
Soc. 107 (1960) 642.
264. M. MIZUSHIMA, ibid 108 (1961) 825.
265. T. MATVEEVA, M. TYUKI NA, V. PAVLOVA, and
N. TOMASHOV, Titan i ego Splavy, No. 6 (1961),
211.
266. H. RtCnAUD, Rev. MOt. 54 (1957) 787.
267. H. RIC~AUI), Sixieme Congress Internat. de Fabric.
Mech., Paris 1956.
268. ri. CHXBA, Jap. Pat. 9556 (Nov 9, 1956).
269. B. RIVOLTA, Met . Ital. 50 (1958) 255.
270. L. STOLBIKOV and G. TURCHANINOV, Elektro-
khimiya 7(6) (1971) 899.
271. I. OZERYANAYA, T. MANUKmNA, and I.
SMIRNOV, Fizi-Khim. Elektrokhim. Rasplav. Solei
Shlakov 2 (1969) 245.
272. E. WAINER, U.S. Pat. 2874102 (1959).
273. v. KUCERA, P. NOVAK, F. FRANZ, and J. KORITTA,
Collection Czech. Chem. Commun. 32(6) (1967) 2049.
274. s. MINAMIandJ. OAGAWA, U.S. Pat.3454473 (1969).
275. E. ROSS and B. CHAMBERS, U.S. Pat. 3400058
(1968).
276. M. MANDRY and G. ROSENBLATT, J. Electrochem.
Soc. 119 (1972) 29.
277 r. HUBER and J. BLOXON, IRE Trans. Components
Parts, June 1961.
278. K. HIRATA, H. YONEYAMA, and n. TAMURA r
Electrochim. Act a 17(5) (1972) 793.
279. Idem, ibid 17(5) (1972) 805.
Received 20 April and accepted 21 November 1972.
704