Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 588 (2006) 179–189
www.elsevier.com/locate/jelechem

Aluminium anodising in oxalate and sulphate solutions. Comparison

of chronopotentiometric and overall kinetic response of
growth mechanism of porous anodic films
G. Patermarakis *, K. Masavetas
School of Chemical Engineering, Department of Materials Science and Engineering, National Technical University,
Iroon Polytechniou 9, Zografou 157 80, Athens, Greece

Received 20 December 2004; received in revised form 29 December 2005; accepted 31 December 2005
Available online 3 February 2006

Abstract

Aluminium anodising was performed in saturated and unsaturated H2C2O4 solutions and in H2SO4 and saturated H2SO4 + Al2(SO4)3
solutions at similar temperatures, concentrations and current density to reveal the effect of anions and condensed electrolyte nanoparticle
micelles formed on pore base and wall surfaces on the mechanism of growth of porous anodic alumina films. Chronopotentiometry and
overall kinetics showed that the kinetics and mechanism of growth and nanostructure of films are similar in oxalate and sulphate solu-
tions. But differences also appear, like higher field strength across the barrier layer and much lower pore wall dissolution rate in oxalate
solutions. These are attributed to dissimilar kind of anions, smaller amount of incorporated ones and depth of penetration in barrier
layer and pore walls during the film growth in oxalate solutions and to their participation in a step of oxide dissolution mechanism that
becomes the rate controlling in this case. In saturated solutions the condensed H2C2O4 and Al2(SO4)3 micelles affect the kinetics and
mechanism of film growth, more H2C2O4, allowing a better design of structure. Results promote the knowledge on growth mechanism
and kinetics of anodic films enabling methods to optimise the structure for their many scientific or technological applications.
 2006 Elsevier B.V. All rights reserved.

Keywords: Al anodising; Oxalate/sulphate solutions; Chronopotentiomety; Kinetics; Mechanism

1. Introduction nanoparticle sized ultra active catalysts or supports [11–

Porous anodic alumina films are important materials
applied to improve the mechanical properties of Al [1], as
anticorrosion [2–4] and decorating [2,3] coatings and mem-
branes [5], in magnetic memories [6], catalysis [7–13],
nuclear reactors [14], rechargeable batteries [15], as tem-
plates for synthesising emitters [16,17], fuels cells [18], etc.
Due to the nanometer scale porous structure [2,3,7–13]
and sizes of particles constituting the pore walls [19] they
also found application in nanoscience and nanotechnology,
e.g., forms for electroplating metal nanowires [20–22], tem-
plates for creating C [23,24] or TiO2 [25,26] nanotubes,
*
Corresponding author. Tel.: +30 210 7723099; fax: +30 210 7723184.
E-mail address: gpaterma@central.ntua.gr (G. Patermarakis).
13], etc. Their optimal effectiveness depends on the suitable
design of their porous structure, nature/composition of
pore wall oxide and reactive properties. Porous films form
in phosphoric, oxalic, chromic, and sulphuric acid solutions
[2,3,27,28]. Also, bisulphates [29,30] and H2SO4 + sulphate
salts were used [29,31–36]. The H2SO4, and generally sul-
phate solutions, have been employed most frequently.
The structure of uniformly/regularly grown films is
defined by the surface density, base diameter and shape
of pores. Films grown in H2SO4 have a surface density of
pores of the order 1010 or 1011 cm2 [12,31], depending
solely on, and decreasing with, current density [31,37]
and base diameter, ranging from several nm to a few tens
nm [31], depending on, and increasing with, temperature
and H+ activity at pore bases [29,30]. The pores generally

0022-0728/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2005.12.021
180 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189
open to the surface due to chemical dissolution of pore
walls by the electrolyte during anodising [2,38–42] similar
to open circuit oxide dissolution [38–42] that is a first order
reaction with respect to H+ activity and is hindered by
incorporated electrolyte anions [29]. Prolonged anodising
may yield a quasi-maximum limiting thickness [2,3,43],
due to pore opening [43,44], reduced with pore density,
temperature and H+ activity.
Al anodising in conditions like low temperatures and elec-
trolyte concentrations and high current densities in which, in
addition, condensed Al2(SO4)3 is not formed inside the
pores, favour the growth of low porosity hard films [2,3]. Sul-
phate additives like Na2SO4, Al2(SO4)3, MgSO4, MnSO4,
(NH4)2SO4 and NiSO4 [31–35] were believed to reduce the
solvent action of electrolyte, thus favouring hard films.
But, actually, their presence may increase H+ activity and
always increases the amount of incorporated anions
[29,30,36]; the first increases the pore base diameter and rate
of pore wall dissolution reaction but the second reduces that
rate. Its reduction can prevail in some cases. Conditions as
above [44–46] and additives like Na2SO4 [31], Al2(SO4)3
and MgSO4 [32], etc., favour pitting, i.e., non-uniform/
abnormal growth of films which thicken locally excessively
[44–46] and acquire non-uniform aspect, thickness, porous
structure, porosity, hardness and roughness and cracks.
Condensed Al2(SO4)3 is formed as colloidal nanoparticle
micelles on pore surface [36]. The field at pore bases and
solid surface of pores catalyse their formation. They are
formed, removed and dissolved, according to a quasi-equi-
librium process and affect the kinetics and mechanism of
film growth by reducing the surface fraction of charge
exchange and diameter at pore bases and the real fraction
of dissolved wall surface. They also enhance the mecha-
nism of regular film growth. Their coagulation is prevented
by their similar charge. Saturated H2SO4 + Al2(SO4)3 solu-
tions exert maximal such effects. Relevant studies [47,48]
revealed many details of the critical role of micelles and
conditions in pores allowing optimisation of films with spe-
cific structural features.
From studies [36,47,48] it appeared that the use of solu-
tions saturated by pore forming electrolyte per se, where
condensed electrolyte micelles must be formed easier, could
further improve their effect on film growth mechanism.
This is possible only for oxalic acid; chromic acid solution
is actually saturated by CrO3, forming on dissolution chro-
mic acid, and not by acid. Thus, the research of Al anodis-
ing in saturated and unsaturated oxalic acid solutions and
in sulphate ones in similar conditions for comparison pur-
poses is interesting enabling predictions for its further opti-
misation, besides that achieved in sulphate solutions
[29,36,37,44,46,48]. This is the new idea of this study. A
combined chronopotentiometric and overall kinetic
method was applied that is an effective tool to enter the
phenomena in barrier layer and pore walls during anodis-
ing [29,36,47] where other methods applied, i.e., to barrier
type films are ineffective, inaccurate or inapplicable due to
the existence of pores.
2. Experimental
Oxalic acid, H2C2O4, 1.53 M electrolyte was decided to
be used for Al anodising, in view of H2SO4 1.53 M (15%
w/v) one often met in the literature, for comparison. But
this solution happened to be saturated. By the method
described elsewhere [36], it was found that 1.53 M is
indeed close enough to saturation concentration while
the solubility increased with temperature. Al was ano-
dised in this solution at current density 15 mA cm2, dif-
ferent times up to a maximum one defined later and
temperature 25 C as well as at temperature 35 C, where
the above solution became unsaturated. For comparison,
Al was also anodised at 25 C in H2SO4 1.53 M solution
and H2SO4 1.53 M + Al2(SO4)3 0.75 M one (that is just
saturated [47]) and H2SO4 1.53 M at 35 C at the same
current density. The amount of H2C2O4 and Al2(SO4)3
at 25 C slightly exceeded the saturation one. The small
amount of precipitate could not appreciably hinder
vigorous bath stirring but always assured saturated
solution.
The pH of solutions was measured that was 0.550, 0.284
and 0.131 for H2C2O4 1.53 M, H2SO4 1.53 M and H2SO4
1.53 M + Al2(SO4)3 0.75 M at 25 C and 0.445 and 60
(indicative value) for H2C2O4 and H2SO4 at 35 C. The
pH measurement after each anodising run showed minor
changes especially in sulphate solutions, which have lower
pH’s. The H+ activities, 10pH, were, respectively, 0.282,
0.520, 0.740, 0.359 and P1 M.
Al sheets 0.5 mm thick and 99.5% pure were used. The
Al composition, shape and dimensions of the Al anodes
and Pb cathodes used and the procedure for washing and
neutralizing Al anodes after anodising to remove the pore
filling solution and contained compounds and drying were
described earlier [36,43].
Al anodising was followed chronopotentiometrically.
During galvanostatic anodising and film thickening, after
some time interval from the start characterised by certain
details (see later), the anodic potential required to keep
constant current remains almost constant in unsaturated
solutions but rises notably in saturated ones [36]. This
potential, determined as previously [49], almost coincides
with the potential drop from the double layer at pore bases
to the oxidejmetal interface [29,36] and is close to anodising
voltage. For convenience the latter was recorded. The volt-
age rise continued up to 50 V for saturated H2C2O4 solu-
tion; then, anodising was interrupted, since higher voltages
could cause large increase of temperature in pores (see
later) notably exceeding that of bulk solution and prohib-
iting a strict control of conditions. In unsaturated solution
anodising took place at various times up to the higher time
in saturated one for comparison purposes. In sulphate
solutions it continued up to higher times, since voltage
was <<50 V. Chronopotentiometric studies were per-
formed up to these higher times.
The mass of film (m) spread over the anodised Al spec-
imen surface (Sg = 30.75 cm2 [43,44]), necessary for the
 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189
overall kinetic study, was determined by the equation accu-
rately applied in sulphate solutions [44]
m ¼ mfi  min þ mAl;F
¼ mfi  min þ jtS g ðAMAl Þð3F 1 Þ; ð1Þ
where min is the initial mass of Al specimen before anodis-
ing, mfi is its final mass after anodising, cleaning and dry-
ing, mAl,F is the mass of Al consumed which obeys
Faraday’s law [43,44], j is the current density, t is the time,
AMAl is the atomic mass of Al and F is Faraday’s constant.
To test its validity in H2C2O4 solution (for reasons given
below) m was also found by oxide dissolution in chromo-
phosphoric acid solution (containing 35 ml H3PO4 85%
w/v and 20 g CrO3 per litre) that dissolves the oxide and
leaves intact Al [3,43]. The thickness of films at an interme-
diate t at each temperature was measured and its unifor-
mity was checked by optical microscope in suitably
formed metallographic specimens as described earlier [43].
The anode and cathodes were observed during anodising
to reveal probable unusual phenomena; after anodising
the Al anodes were examined macroscopically and micro-
scopically as described earlier [45] to verify occurrence or
not of pitting and other phenomena.
3. Results
3.1. General observations for the anodising process, related
phenomena and film morphology. Peculiarities of anodising
process in H2C2O4 solutions compared to that in sulphate ones
During Al anodising in H2C2O4, despite the vigorous
stirring, small rare bubbles, macroscopically observed, were
developed on the surface of anode. Such a gas evolution was
never before observed during Al anodising in sulphate solu-
tions, like H2SO4, H2SO4 + Al2(SO4)3, Al(HSO4)3, KHSO4,
NaHSO4, LiHSO4 and Mg(HSO4)2 [30,43,44,47]. This may
note inaccurate application of Eq. (1) in H2C2O4. If differ-
ences really existed, they should be larger, surely detected,
for films with high m, or thick films. The mass of oxide
was thus determined by its dissolution at the higher t’s. It
was 0.2081 and 0.2721 g at 25 C and t = 60 and 80 min
and 0.2221 g at 35 C and t = 80 min. From Eq. (1) m was
found 0.2078, 0.2751 and 0.2227 g, respectively; the error,
0.14%, 1.10% and 0.06%, is minor. Also the mass of
consumed Al, found by weighing Al specimen before ano-
dising and after oxide removal, essentially coincided with
that of Faraday’s law, as Eq. (1) anticipates. Eq. (1) is thus
valid for H2C2O4 and the gas evolved on the anode may be
not O2 related to Al oxidation.
A quite surprising phenomenon concerning Pb cathode,
not commended heretofore in relevant studies, is that H2
evolution (yielded by the process 2H+ + 2e ! H2) never
occurred, opposite to sulphate solutions where crowded
release of H2 always occurred. Literature search revealed
that cathodic electroreduction of H2C2O4 occurs on high
hydrogen overvoltage metals like Pb [50–52] yielding gly-
oxylic and glycolic acids and glyoxal.
181
The gas evolved on the anode then may be due to oxida-
tion reaction(s), parallel to Al oxidation, of H2C2O4 reduc-
tion product(s) to one(s) embracing gas(es). The volume of
solution, 1 dm3, and total t of each experimental run regard-
ing no participation of products in anodic processes define
minor total concentration; that of participating com-
pound(s) is thus negligible. This may justify why these pro-
cesses do not consume valuable charge thus the measured
and calculated m coincide; but high concentrations might
exert noticeable effects. Also the coincidence of measured
and calculated m may mean that H2C2O4 reduction prod-
ucts participate in chemical, probably catalytic, processes,
as anodic aluminas are strong catalysts [11–13], alone or
together with electrochemical ones. When such processes
compete the Al oxidation one, the spaces of anode and cath-
ode can be separated by proper diaphragm; but here they do
not appreciably affect it and separation was unnecessary.
The H2C2O4 solution films were yellowish more at high
t’s. Such a colouration never occurred in sulphate ones here
or elsewhere [30,43,44,47]. It may be due to products of
H2C2O4 reduction, or other products as above, embodied
in the barrier layer and pore walls. Glyoxal is yellow [53]
and its incorporation may yield colouration.
3.2. Chronopotentiometric study
The anodising voltage (DV) vs. t plots are given in
Fig. 1a. An initial transient stage appears. In a t of the
order of 1 s DV rises rapidly up to a high value. These t
and DV values depend on temperature (T) and electrolyte
kind, are larger at lower T and in H2C2O4, and must mark
the nucleation of pores also in H2C2O4 as in sulphate solu-
tions [49]. During a next transient stage DV drops and
becomes minimum DVm in a time t(DVm) of the order of
1 min where in sulphate solutions a quasi-steady state pore
base diameter, nature/composition of barrier layer and
electrolyte composition in pores is set up that must occur
also for H2C2O4. Then two cases appear:
(i) At T = 25 C and saturated both H2C2O4 and sulphate
solutions DV rises with increasing rate with t. The trend
shows that in H2C2O4 solution the DV rise must be
strongly reinforced with t beyond the higher t
employed; thus DV varies with t similarly as in sulphate
solution. As shown for sulphate solutions [36,47] this
DV rise marks the formation of salt nanoparticle
micelles at least on the pore base surface that causes
the gradual reduction of pore base diameter and free
surface fraction not occupied by micelles both of which
result in the rise of DV. Hence, micelles also form in
H2C2O4 but their nature, condensed H2C2O4, alumin-
ium oxalate, or mixed, is unknown yet.
(ii) At T = 25 C for H2SO4 and at T = 35 C for H2SO4
and H2C2O4 an almost horizontal plateau appears,
met in sulphate solutions when conditions and diam-
eter at pore bases are nearly constant and micelles do
not form [36].
182 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189

(a) be achieved exceeding slightly or appreciably k00 jtm or k00 jtl

T / oC Electrolyte
[43,44]. The experimental h’s at t = 40 and 60 min and
: 25 H2SO4
50 : 35 H2SO4
T = 25 and 35 C, 18.5 and 28.0 lm, essentially coincided
: 25 H2SO4 + Al2(SO4)3 sat. with those of Eq. (2). Thus Eq. (2) applies also for H2C2O4
: 25 H2C2O4 sat. films. The conformity of film growth simultaneously to
40
: 35 H2C2O4 Eqs. (1) and (2) for both sulphate and oxalate electrolytes
undeniably verifies that the film growth mechanism is identi-
ΔV / V

cal and the characteristic porous, cellular, columnar struc-

ture of anodic films is qualitatively similar for both
30 solutions [43]; this was also verified by SEM, TEM and re-
lated methods [54,55]. For H2C2O4 films all t’s employed
were <tm. But for the H2SO4 ones at T = 25 and 35 C and
20 H2SO4 + Al2(SO4)3 tm  110, 30 and 120 min. Using Eq.
(1) the DV vs. h [h 6 h(tm)] plots were constructed, Fig. 1b,
which resemble those in Fig. 1a up to t = tm.
10 At each T and t or h, DV is higher for H2C2O4 than for
0 40 80 120 160 sulphate solutions. It decreases with T for both kind solu-
t / min tions. For sulphate solutions DV is initially higher in pure
(b) 60 H2SO4 but beyond a t or h the trend is reversed.
T / o C Electrolyte
: 25 H2SO4
The chronopotentiometric study shows that the mecha-
: 35 H2SO4 nism of film growth is common for both H2C2O4 and sul-
50 : 25 H2SO4 + Al2 (SO4)3 sat. phate solutions. Though the DV vs. t or h plot implies the
: 25 H2 C2O4 sat.
formation of micelles on the pore base surface also in sat-
: 35 H2C2 O4
urated H2C2O4 solution, further undeniable evidence is
40 given below by the overall kinetic study.
ΔV / V

3.3. Overall kinetic study

30
The m vs. t plots are given in Fig. 2a. The m vs.
h[h 6 h(tm)] plots are given in Fig. 2b. In sulphate solutions
20 at each j and for regular film growth and constant pore
base diameter (Db), met when Al2(SO4)3 micelles are not
formed at pore bases and conditions around them are con-
10
0 20 40 60
stant or change imperceptibly with t [36], the DV vs. t plot
at t > t(DVm) shows an almost horizontal plateau [45]; then
h / µm
the kinetic model [44,45]
Fig. 1. Variation of the anodising voltage, DV, with time, t, (a) and film
thickness, h[h(t(DVm)) 6 h 6 h(tm)], (b) at current density j = 15 mA cm2, A ¼ ðkjt  mÞð41 pS g d c k 0 tÞ1 ¼ A0 þ A1 t þ A2 t2
temperatures T = 25 and 35 C and in H2C2O4 and sulphate solutions.
¼ 4p1 p; ½A0 ; A1 ; A2 > 0 and tðDV m Þ 6 t 6 tm ; ð3Þ

Pitting was not observed and thus films were regularly/
uniformly grown. The uniformity of film thickness was also
checked by optical microscope [43] and satisfactorily veri-
fied for both electrolytes. The thickness of uniformly/regu-
larly grown films in sulphate solutions, or the average one
of irregularly grown films, (h) is given by
applies, irrespective of pore shape [43,44], where A is a
dimensionless factor, k is a constant resulting from Fara-
day’s law, dc is the density of compact pore wall oxide
(3.42 g cm3) [43], A0 ¼ nD2b where n is the surface pore
density, A1 and A2 are parameters determined by j and T
and p is porosity (v/v). From Eqs. (2) and (3)

h ¼ k 0 t ¼ k 00 jt; ðt 6 tl Þ; ð2Þ A ¼ A0 þ A01 h þ A02 h2 ¼ 4p1 p; ½A0 ; A01 ; A02 > 0

where k00 is a constant 3.09 · 106 cm3 mA1 min1 and tl is
the time up to which h increases linearly with t [43]. The tl is
identical to, or slightly higher than, tm at which the maximum
average diameter of pores at a position along them, usually
at or near film surface, approaches first the cell width and
surface sight starts to change from a shiny, transparent
and similar to Al metal to a mat, milky one [43–45]. For
t > tl h increases with retarded rate with t up to a t = tc where
it may become 0; then a quasi-maximum limiting h (hc) may
and h½tðDV m Þ 6 h 6 hðtm Þ. ð4Þ
1
For t = 0 the model (3) gives A0 = 4 p p but initially
only a barrier layer exists with zero p. Thus, it applies after
the t of pore nucleation, which is of the order of 1 s [29],
i.e., negligible compared to t’s employed. The limitation
t(DVm) 6 t 6 tm always satisfies this condition. The A (or
p) is related to basic features like n, Db, etc., and magnifies
the m differences permitting detailed/accurate studies of
regular film growth [29,37,44].
 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189 183

(a) 0.4 (a) 0.7

T / oC Electrolyte
: 25 H2SO4
: 35 H2SO4
: 25 H2SO4 + Al2(SO4)3 sat. 0.6
: 25 H2C2O4 sat.
0.3
: 35 H2C2O4

0.5
m/g

A
0.2
0.4
T / oC Electrolyte
: 25 H2SO4
0.1
0.3 : 35 H2SO4
: 25 H2SO4 + Al2(SO4)3 sat.
: 25 H2C2O4 sat.
: 35 H2C2O4

0.0 0.2
0 40 80 120 160 200 0 40 80 120 160
t / min
t / min
(b) 0.4 (b) 0.7
T / oC Electrolyte
: 25 H2SO4
: 35 H2SO4
: 25 H2SO4 + Al2(SO4)3 sat. 0.6
0.3 : 25 H2C2O4 sat.
: 35 H2C2O4

0.5
m/g

0.2
0.4
T / oC Electrolyte
: 25 H2SO4
0.1
0.3 : 35 H2SO4
: 25 H2SO4 + Al2(SO4)3 sat.
: 25 H2C2O4 sat.
: 35 H2C2O4
0.0 0.2
0 20 40 60 0 20 40 60
h / µm h / µm
Fig. 2. Variation of the film mass, m, with time, t, (a) and film thickness, h Fig. 3. Variation of the dimensionless factor A with time, t, (a) and film
[h(t(DVm)) 6 h 6 h(tm)], (b) at current density j = 15 mA cm2, tempera- thickness, h[h(t(DVm)) 6 h 6 h(tm)], (b) at current density j = 15 mA cm2,
tures T = 25 and 35 C and in H2C2O4 and sulphate solutions. temperatures T = 25 and 35 C and in H2C2O4 and sulphate solutions.

It is known that the pore/cell ordering in film surface is

poor, following metallurgical texture [54,56,57]. But the
inherent to film growth mechanism of their self-organisation
gradually yields a hexagonal ordering towards the metalj
oxide interface [58–65]. Thus at t P t(DVm) where exactly
Eqs. (3) and (4) apply, excluding only a thin surface layer
of poor ordering, in the rest thicker film part better ordering
and uniformity are assured, i.e., within each Al grain domain
when cell width is much smaller than grains size [56] (e.g., at
low j’s) or along larger areas or all surface when cell size is
comparable to, or larger than, grains size (e.g., at high j’s).
When DV increases drastically at t P t(DVm), a scatter
of points usually occurs in the A vs. t[t(DVm) 6 t 6 tm]
and h [h[t(DVm)] 6 h 6 h(tm)] plots which, irrespective of
pitting growth or not, obey the equation [36]
A  A0 þ A1 t þ A2 t2 ¼ A0 þ A01 h þ A02 h2 ;
where A0, A2 and A02
are >0 while A1 and are usually >0
at low j’s and become <0 at higher j’s and minima appear;
colloidal Al2(SO4)3 nanoparticle micelles form at least on
the pore base surface affecting the mechanism of film
growth. The average Db and the average rate of wall disso-
lution decrease with t or h [36] more at low A1 (or A01 ) due
to the rise of surface fraction occupied by micelles. Reduc-
tion of p with h can only thus occur.
The A vs. t and h plots are given in Fig. 3a and b. The
parameters A0, A1, A2, A01 and A02 appear in Table 1. Figs.
1 and 3 show that micelles are not formed in H2SO4 and
H2C2O4 solutions at T = 35 C. At T = 25 C they show
formation of micelles in saturated H2C2O4, while Fig. 1
shows formation of micelles in saturated sulphate solution
but this is not so strongly manifested by Fig. 3. However,
micelles also form in this case since as j rises A1 and A01
decrease and at j > 15 mA cm2 they become <0 [36], con-
ð5Þ
sistent to Fig. 1. Thus, both the mechanism of film growth
A01 and overall kinetic responses in these two kind solutions
resemble. The plots in Fig. 3 shift upwards with T for both
184 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189

Table 1
Values of parameters A0, A1, A2, A01 and A02 and of correlation coefficient, COR, derived from fitting Eqs. (3) and (4) or (5) to the experimental results, and
estimated values of the anodising ratio, a.r. = 21(DcDb)(DVm)1, and the average filed strength across the barrier layer, E  (a.r.)1
Electrolyte T/C 104A0 104A1/min1 106A2/min2 104 A01 =lm1 106 A02 =lm2 COR Db/nm (h ! 0 for a.r./nm V1 E/V nm1
saturated solutions)
H2SO4 1.53 M 25 3255 13.34 8.81 28.77 41.00 0.9997 16.02 0.52 1.92
H2SO4 1.53 M 35 4228 22.44 130.36 48.41 606.79 0.9987 18.25 0.61 1.64
H2SO4 1.53 M + 25 3585 3.16 7.95 6.81 37.00 0.9893 16.81 0.54 1.87
Al2(SO4)3 0.75 M
(saturated)
H2C2O4 1.53 M 25 4029 19.91 21.34 42.96 99.37 0.7556 17.82 0.18 5.71
(saturated)
H2C2O4 1.53 M 35 4336 1.97 15.54 4.17 72.63 0.9967 18.48 0.23 4.33

kind solutions while at each T those of sulphate and
H2C2O4 solutions intersect each other at t’s or h’s reduced
with T. Despite the higher acidity of sulphate solutions,
quite amazingly, p is smaller at low t’s or h’s. The span
of A or p variation, for comparable large t or h ranges, is
smaller for H2C2O4 plots.
3.4. Approximate estimation of structural features and of the
average field strength across the barrier layer
In sulphate solutions, the pores may nucleate in pre-
formed small cracks created by mechanical stresses [29]
appearing in the initial flat barrier type oxide in the sub-
layer adjacent to the Aljoxide interface and directed to
the surface. Oxide is formed, actually in that interface
[49,66], Fig. 4, at the same rate in both kind solutions.
Thus, the number of active cracks and nucleation of pores
Dc
pore wall oxide
x pore
Dx Al2O3
cell boundaries
h
attached layer
Db
double layer
barrier layer
metal / oxide interface
Al
Fig. 4. Schematic representation of a section parallel to the pore axis of an
elongated, columnar cell of a porous anodic alumina film. The pore, the
pore base diameter Db, the pore diameter at a position x along the pores
Dx, the cell size Dc, the pore wall oxide and the hemispherical shell shaped
barrier layer are distinguished. Also, the metaljoxide interface and cell
boundaries are shown. The pore generally broadens towards the film
surface as a result of the pore wall chemical dissolution reaction by the
electrolyte inside the pores during the film growth.
must be affected primarily by j and secondarily by the kind
and concentration of electrolyte and anions, though the
pores can really start to develop at different time or thick-
ness of initial barrier type film. The anions are embodied in
a sublayer of barrier layer adjacent to its surface where the
concentration of, e.g., sulphate, anions strongly drops
towards the interface [29,30]. After the formation of pores
and at t P t(DVm) the anions thus embodied cannot affect
the production of oxide in the interface and n. These must
be valid also for oxalate anions, which are embodied in
much less amounts than sulphates [27] (see also later).
Since n is of the same order for various electrolytes
[2,3,12,55], it depends almost solely on j in sulphate ones
[31,37] varying slightly with j, the oxide is formed only in
the oxidejAl interface [49,66] and the pores nucleate by
the above mechanism, n in H2C2O4 and sulphate solutions,
though probably not coinciding, must be comparable and
qualitatively alike depending on j. This is valid despite that
appreciable differences may appear in the literature due to
different conditions of anodising, usually performed at con-
stant DV where j (and n) changes with electrolyte kind and t
and to the measurement methods usually based on TEM;
the determination of n is based on the measurement of a
small number of pores in a limited surface area and thus
it is usually inevitably accompanied by errors. Since at
j = 15 mA cm2 n = 1.269 · 1011 cm2 [12], the average
Dc, obeying nD2c ¼ 4=3 [49], is Dc  32.4 nm that must be
also roughly comparable to that in H2C2O4 solution at
identical j. The average Db’s, Db = (A0/n)1/2, Table 1, are
also of nm scale where these values are close to the real
ones for sulphate solutions and approximately valid for
oxalate ones; as noted earlier the Db’s are almost indepen-
dent of t or h in unsaturated solutions but these Db’s are
true for h ! 0 in saturated solutions where micelles grow
at t > 0 gradually reducing Db.
The anodising ratio (a.r.), i.e. DVm/[barrier layer thick-
ness = 21(DcDb)] and the average field strength across
the barrier layer (E)  (a.r.)1 are given in Table 1. E is
much higher in H2C2O4 films. For both kind solutions E
drops with T. Irrespective of the accuracy of adopted n,
and thus of Dc, Db, a.r. and E’s, information is taken for
their relative values.
The phenomena in barrier layer, on pore wall surface
and inside the pores during Al anodising are complex,
 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189
determining each other, and greatly affect the mechanism
of film growth. For a satisfactory discussion and interpre-
tation of results, given below, the processes and conditions
inside the pores must be first discussed.
4. Discussion
4.1. Overall processes occurring inside the pores during the
film growth
The mass balance of anodic processes shows that H2O is
consumed yielding oxygen for oxide production in
amounts corresponding to pore walls around pore bases
[29], Fig. 4, and H+ ions are released in the pore base
region [67] (2Al + 3H2O  6e ! Al2O3 + 6H+). For sul-
phate solutions Al2(SO4)3 forms by the ‘‘field assisted’’
pore base oxide dissolution [2,3,31,33–35,68–70], through
the rejection from surface and then hydration of Al3+
and migration of O2 inwards the barrier layer [29], and
by the chemical pore wall oxide dissolution [2,38–42]
(Al2O3 + 3H2SO4 ! Al2(SO4)3 + 3H2O). It enters the pore
filling solution which contains Al2(SO4)3, besides H2SO4.
Similar processes must occur in H2C2O4 electrolyte and
Al2(C2O4)3 and/or Al(HC2O4)3 are thus formed.
The heat evolved during Al anodising mainly around the
pore bases, which increases with j and DV, is dissipated to
the bath solution mainly through the pore filling solution,
which has higher thermal conductivity than the pore wall
oxide. A gradient of temperature is set up along the pores
[43]. The temperature around the pore bases (Tb) is >T and
that at position x, Fig. 4, (Tx) increases with x. The Tx  T
rises with decreasing T and average Dx and increasing x, j
and DV [43]. The acid and salt concentrations secondarily
affect Tb and Tx. After transient phenomena end, at each
t and x a quasi-steady state is attained for the mass, charge
and heat transfer.
4.2. Conditions inside the pores during the film growth
4.2.1. Steady state conditions inside the pores in unsaturated
solutions
The quasi-steady state transport phenomena inside the
pores were studied [45,67] considering regular film growth
and Tx = T in H2SO4 solutions up to concentrations
(ca,0) = 15% w/v and in H2SO4 + Al2(SO4)3 solutions at
similar acid concentrations and salt concentrations (cs,0)
up to that at which micelles do not grow on pore base sur-
face, where transport analysis was possible [45,46]. The
dependence of acid concentration at pore bases (ca,b) and
position x, Fig. 4, (ca,x) and of salt concentration at pore
bases (cs,b) and position x (cs,x) on h, x, j, T, ca,0 and cs,0
is generally complex especially for ca,x and ca,b. But cs,x
increases with x and j, decreases with T and faintly changes
with ca,0 [45]. However, always and especially for denser
baths, the ca,x and cs,x for x 6 150 lm examined did not
appreciably differ from ca,0 and cs,0. To a tolerable approx-
imation, ca,x  ca,0 and cs,x  cs,0. Although such a trans-
185
port analysis for H2C2O4 (that must be also complex
enough) is absent, a more or less similar situation is
expected. Thus in both kind solutions the H+ concentra-
tion and activity in bath bulk solution (cHþ ;0 , aHþ ;0 ), at posi-
tion x along the pores (cHþ; x , aHþ; x ) and at pore bases (cHþ ;b ,
aHþ ;b ) must follow ca,0, ca,x and ca,b which are close each
other. At each h, Tx  T must be larger in H2C2O4 than
in sulphate solutions due to the higher DV’s.
4.2.2. Steady state conditions inside the pores during
anodising in saturated solutions
In saturated sulphate baths at ca,0 = 15–95% w/v super-
saturation dominates in pores during film growth enlarged
on increasing x and j and decreasing Tx [47]. The ca,x varies
slightly and cs,x rises with x. The unlike dissociation con-
stants of acids and concentrations and mobilities of anions
[71] and the saturation of H2C2O4 solution by acid and of
sulphate one by salt may affect transport phenomena. The
acid and salt concentrations and their distributions along
the pores thus may differ in the two kind solutions. But
despite differences the situation must be roughly similar.
Supersaturation in sulphate solutions favours the growth
of Al2(SO4)3 micelles on pore base and wall surfaces; the
rise of Tb and Tx acts oppositely [36,47]. These must occur
also for H2C2O4.
4.3. Comparison of pore wall chemical dissolution rate
during film growth in sulphate and H2C2O4 solutions. Effect
of electrolyte anions incorporated in pore wall oxide and
contained in pore filling solution on that rate
The rate of chemical dissolution (length/time) of pore
wall oxide by the electrolyte, or that of pore radius
increase, at each surface position x, Fig. 4, (rd,x) obeys
the equation
rd;x ¼ k d;x aHþ ;x ð1  hx Þ; ð6Þ
where kd,x is the local rate constant, depending on the nat-
ure/composition of surface oxide and hx is the local frac-
tion of surface occupied by micelles [36]. As discussed
aHþ ;x  aHþ ;0 . In unsaturated pore filling solution hx = 0
[36]. The local rd,x and kd,x cannot be found but the average
ones along the pores (rd,a, kd,a) obey the equation
n1=2 rd;a ¼ fA0 þ ½ð4=3ÞA  31 A0 1=2 g½ð4=3Þt1
1=2
¼ n1=2 k d;a aHþ ;0 ; ðt 6 tm Þ; ð7Þ
where A are Eq. (3) fitting the results [29], Fig. 3. It has a
strict physical meaning for constant Db. Experimental tech-
niques directly revealing the nature/composition of barrier
layer during the film growth are unknown [72]. Only indi-
rect methods can be applied. The mechanism of porous
layer growth predicts that the nature/composition of oxide
across the barrier layer is impressed across the adjacent
pore walls and for sulphate solutions films it is extrapolated
on pore surface of a h = hc thickness film [29,30]. Its discov-
ery along that surface reveals it across the pore walls and
186 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189
barrier layer. For sulphate solutions the increase of anions
concentration in a thin layer on pore walls (or surface con-
centration) reduces rd,x [29,30]. Thus rd,a and kd,a decrease
with the average anion concentration along the pores or
across the pore walls [29]. The relative kd,a’s in common an-
ion, e.g., sulphate, solutions inversely represent the relative
average anion concentrations.
To avoid inaccuracies in determining rd,a’s probably aris-
ing from the adoption of an n value from the literature [12],
n1/2rd,a was used since n is almost constant for sulphate
solutions and neighbouring (or even close enough) to that
in oxalate solutions. The n1/2rd,a vs. t plots appear in
Fig. 5, excluding the saturated solutions, where for H2C2O4
n1/2rd,a’s < 0 (unacceptable) and for sulphate one the real
n1/2rd,a’s must differ from those of Eq. (7), since Db decreases
with t due to the effect of micelles. Always n1/2rd,a increases
with t (or h) or along the pores towards the film surface.
For aHþ ;x  aHþ ;0 n1/2kd,a thus increases across the pore walls
and barrier layer and towards the cell boundaries and
Aljoxide interface, Fig. 4. These concern both kind solutions.
For t ! 0, rd,a ! rd,a,0 and kd,a ! kd,a,0, where rd,a,0 and
kd,a,0 are the local rd,a and kd,a on walls at pore bases. This
variation of n1/2rd,a and n1/2kd,a with t even for t 6 t(DVm)
is valid since the A vs. t plot results, Fig. 3, were treated for
t > t(DVm) where a quasi-steady state in nature/composi-
tion across the barrier layer and adjacent pore walls is set
up. The kd,a,0 concerns this region surface in steady state
at t > t(DVm) or at t  0 supposing absence of transient
stage at t 6 t(DVm). The n1/2rd,a’s for h ! 0, n1/2rd,a,0’s,
Fig. 5, and aHþ ;0 ’s show that kd,a,0 increases with T for sul-
phate solutions, obeying Arrhenius law, and at constant T
it is much lower in H2C2O4 than in sulphate solution that is
valid also for rd,a or kd,a at each t or h. The reduction of
n1/2kd,a on decreasing h shows that the embodied oxalate
5 and hb decrease with Tb [37] reducing DV. The Tb and
T/˚C Electrolyte
: 25 H2SO4
: 35 H2SO4
4 : 35 H2C2O4
-1
r d,a / min
3 (DVm), the employed j and T = 25 C, the equation [29]
1/2
10 n
2
3
1 T and aHþ ;0 reducing DV. This combined effect holds also
0 at low t’s or h’s. The hb ( 0 for t or h ! 0) rises with t
0 40 80 120
t / min
Fig. 5. Variation of parameter 10 n1/2rd,a with time, t, at current density
3 solutions plots, T = 25 C, is thus justified.
j = 15 mA cm2, temperatures T = 25 and 35 C and in unsaturated
H2C2O4 and H2SO4 solutions.
anions also retard the oxide dissolution. The anticipated
much lower n1/2kd,a in H2C2O4 than in sulphate solution
for high h ! hc, where n1/2kd,a approaches the local
n1/2kd in the free of anions regions of cell boundaries or
oxidejAl interface [29], shows that the kd of pure oxide is
much lower in H2C2O4 films. The oxide dissolution mech-
anism embraces [29]: (i) hydroxylation of surface by disso-
ciative adsorption of H2O on Al3+ and O2 sites; (ii)
protonation of hydroxylated surface yielding H2O on
Al3+ while anions are adsorbed on surface that is the rate
controlling step in sulphate solutions [29]; (iii) solvation
of Al3+ and their rejection in pore filling solution assisted
by adsorbed anions and H2O. Step (iii) must become the
rate controlling in H2C2O4 solutions.
4.4. Interpretations of chronopotentiometric and overall
kinetic response of growth mechanism of porous anodic
alumina films in sulphate and oxalic acid solutions
4.4.1. Interpretation of DV vs. t or h plots, their relative
positions and of DV change with T and solution kind
As already noted the variation of DV is due almost
exclusively to potential drop from the solutionjoxide inter-
face at pore bases to the oxidejAl one; DV strongly depends
on the thickness of barrier layer, 21(DcDb), and pro-
cesses in this region [29]. For saturated sulphate solutions
at ca,0 = 15–95% w/v and t P t(DVm) the DV vs. t or h plots
generally show an accelerated rise of DV [36,47]. The
increase of cs,b with h enhances the growth of micelles that,
in turn, increases the pore base surface fraction occupied
by them (hb). The field strength on this surface (Eb) and j
exert similar effects. The rise of Tb acts oppositely [36].
Supersaturation in pores favours maximal growth of
micelles at each h but the low Db, or high 21(Dc  Db),
and hb > 0 require high DV even from the early stages nota-
bly rising Tb. At each j, Db increases while 21(Dc  Db)
cs,b increase with h. The effect of rising Tb is lower than that
of cs,b. These concern also H2C2O4. The plateaus in plots in
unsaturated solutions are due to weak changes of Db and
conditions inside pores with h.
In sulphate solutions and quasi-steady state, t P t
1
ðnD2b Þ ¼ 0:3947a1
Hþ ;b þ 2:2645; ð8Þ
applies showing that Db increases with aHþ ;b (or aHþ ;0 ); it is
easily verified that the present results obey it. Db increases
also with Tb or T [37]. 21(Dc  Db)1 decreases with both
for H2C2O4, Fig. 1. For sulphate solutions and constant
T the higher aHþ ;0 of saturated ones justifies the lower DV
or h reducing Db [36,47] and enlarging DV that gradually
exceeds DV in unsaturated solution; the section of sulphate
Assuming DV affected only by 21(Dc  Db)1, the com-
parable Dc and slightly different Db’s (h ! 0 for saturated
 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189
solutions) and thus 21(Dc  Db)1 for both kind solutions
cannot justify high DV differences, especially for identical
Tb where they must be even larger. The anions embodied
in barrier layer play an important role.
The double layer on the pore base surface consists of
fixed layer containing mainly SO2 4 in sulphate solutions
[29] and diffuse layer containing all ions. The penetration
of anions occurs through microcrevices among the nano-
particles constituting the barrier layer the surface density
and void space of which drop towards the oxidejAl inter-
face [29]. The field drives the anions from the fixed layer
to crevices. As higher is the charge and smaller is the size
of anions, as higher is the amount of embodied ones and
depth of penetration. The size of tetrahedral SO2 4 , with
charge located in two adjacent O atoms, is smaller than
that of lengthy C2 O2 4 , with charge spread in two edges.
This is valid also for HSO 
4 and HC2 O4 . The first dissoci-
ation of H2SO4 is complete but the second dissociation
constant at T = 25 C is 1.2 · 102 [71]; the first and second
dissociation constants of H2C2O4 at this T are 6.5 · 102
and 6.1 · 105 [71]. At comparable acids concentrations
those of HC2 O 4 and C2 O4
2
are much lower than those
 2
of HSO4 and SO4 . The conditions in the double layer
probably promote dissociations to SO2 4 and C2 O24 . But
 2
the concentrations of HC2 O4 and C2 O4 in double (and
fixed) layer are still much lower than those of HSO 4 and
SO24 . The concentration of SO 2
4 in H 2 SO 4 + Al 2 (SO 4)3
solution is even higher. The incorporation of anions is thus

favoured more for SO2 2
4 than C2 O4 ; penetration of HSO4

and HC2 O4 practically does not occur due to their lower
charge and larger size. The lengthy C2 O2 4 must be sub-
jected to the highest possible effect of field to enter the bar-
rier layer or it must be adjusted parallel to the surface,
which, in turn, inhibits its penetration. The amount of
embodied sulphate anions and penetration depth are thus
larger [27], irrespective of Tb. The geometry of oxalate
anions, spread of charge and low concentration must be
responsible also for the slow solvation of Al3+ during pore
wall dissolution, despite the higher Tb favouring that.
In sulphate solutions Eb rises with j and hb and drops with
Tb while j alike affects the required local field strength in oxi-
dejAl interface (Ei) [36]. The local field strength rises towards
this interface and the average one in the sublayer enriched by
anions is lower than in the rest [29]. Thus Eb < E < Ei. The
barrier layer is slightly thicker in H2C2O4 solutions due to
slightly lower Db’s. The sublayer enriched by anions is thin-
ner. Thus the free of anions sublayer near oxidejAl interface
is notably thicker. Though Tb is larger in H2C2O4 solutions
reducing Eb and E, the higher hbP0, thinner first sublayer
and thicker next one justify the higher E and DV.
4.4.2. Interpretation of both the relative positions of A vs. t
or h plots and their plot profiles
The higher A0 in saturated than in unsaturated sulphate
solution is due mainly to the larger average Db in the first
for h ! 0, owing to the higher aHþ ;b or aHþ ;0 , Eq. (8). The
Dx, Fig. 4, increases with h due to pore wall dissolution;
187
thus the pores generally broaden towards their mouths.
In saturated solution the Db decreases with t or h. The
higher aHþ ;0 in this solution increases and hx > 0 decreases
rd,x and rd,a; the second effect together with that of anions
embodied in larger amounts dominate and rd,a becomes
lower. Hence, the average gradient of A vs. t or h plot
and the span of A variation are lower in saturated solution
and the plots at T = 25 C intersect.
In saturated H2C2O4 solution, the formation of micelles
is strong, stronger than in sulphate one, probably due to (i)
higher E and thus Eb favouring their growth [36] and (ii)
easy formation suggesting that they rather consist of acid
molecules, favouring epitaxy. The Db strongly decreases
with h, rd,a is low and thus p decreases up to  25 lm
and then rises. As noted, p can diminish with h only in sat-
urated solutions for j’s greater than a limit [36,47] that is
lower in H2C2O4. Due to the strong decrease of Db with
t, low rd,a and appearance of minimum in the A vs. t or h
plot, though it meets A axis at a value larger than in sul-
phate solutions at T = 25 C it sects their plots at low h’s.
The smaller span of A variation up to high h’s in saturated
H2C2O4 is thus explained.
In unsaturated H2C2O4 and H2SO4 solutions, the almost
constant Db and increase of Dx with t or h justify the valid-
ity of Eqs. (3) and (4) and the A vs. t or h plot profiles in
both T’s. The shift of plot of unsaturated H2SO4 solution
upwards with T is due to the increase of Db, rd,x and rd,a
causing, at each h, rise of A (or p). This holds also for plots
of both saturated solutions compared to those of unsatu-
rated ones at T = 35 C due mainly to the large T varia-
tion. The differences in profiles of A vs. t or h plots and
their relative positions are thus justified.
Eq. (8) gives for H2C2O4 nD2b ¼ 0:2728 that is <0.4029,
Table 1. This may mean that Eq. (8) does not truly apply
in H2C2O4; but most probably this is mainly due to the
higher A0’s for H2C2O4 than for both sulphate solutions,
despite the lower acidity of H2C2O4, owing to the larger
DV, rising real Tb (and Tx) and Db.
5. Conclusions
1. The mechanism of growth of anodic films is similar in
both oxalic acid and sulphate pore forming electrolytes.
Saturated solutions also show similar behaviours. But
differences also appeared like: (i) higher field strength
across the barrier layer requiring larger voltage that
results in higher real temperature around pore bases
and along the pores which, in turn, increases the pore
base diameter and rate of pore wall dissolution in
H2C2O4; (ii) despite this, the pore wall dissolution is
much slower in H2C2O4, not justified by the lower acid-
ity and higher temperature along the pores; (iii) much
stronger formation of H2C2O4 than Al2(SO4)3 micelles
in saturated H2C2O4 and sulphate solutions that, in
turn, affects more strongly the mechanism and kinetics
of film growth despite the higher temperature inside
the pores.
188 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189
2. These differences are due to the different kind of electro-
lyte anions resulting in: (i) much lower amount of
embodied anions [27] and depth of penetration in the
barrier layer and pore walls in H2C2O4 films requiring
higher field strength on pore base surface, Eb, and aver-
age one across the barrier layer; (ii) different rate of pore
wall dissolution mainly due to participation of anions in
the step of process mechanism of Al3+ solvation and
rejection from the surface that becomes the rate control-
ling in H2C2O4 solutions; (iii) easier and stronger growth
of micelles in H2C2O4 due to their common nature with
electrolyte and higher Eb owing to reasons noted in (i).
3. H2C2O4 solutions thus favour uniform diameter along
pores, thick films and high total real surfaces more than
sulphate solutions and retaining low p’s even at high h’s,
as well as reduction of p with h, etc., in saturated ones.
4. The H2C2O4 anodic films predominate compared to sul-
phate ones when e.g. clearer material, high h, low p, high
total real surface, etc., are desired that extends the opti-
misation of Al anodising achieved in sulphate solutions
[36,37,44,47,48]; it is noted that the larger DV is not pro-
hibitively high for industrial scale units.
5. The results may contribute to a change of trends of rel-
evant technology also towards oxalate baths since better
optimisation of regularly grown films as regards the
desired nature/structure and certain properties is
possible.
References
[1] S.L. Leach, F. Neufeld, Corros. Sci. 9 (1969) 225.
[2] J.W. Diggle, T.C. Downie, C.W. Goulding, Chem. Rev. 69 (1969) 365.
[3] L. Young, Anodic Oxide Films, Academic Press, London, 1961.
[4] L.L. ShreirCorrosion, vol. 2, Newnes-Butterworths, London, 1976.
[5] A.W. Smith, J. Electrochem. Soc. 120 (1973) 1068.
[6] S. Kawai, I. Ishiguro, J. Electrochem. Soc. 123 (1976) 1047.
[7] K. Rai, E. Ruckenstein, J. Catal. 40 (1975) 117.
[8] Y. Chu, E. Ruckenstein, J. Catal. 41 (1976) 384.
[9] S.K. Ihm, E. Ruckenstein, J. Colloid Interf. Sci. 61 (1977) 46.
[10] S.K. Ihm, E. Ruckenstein, IEC Prod. Res. Dev. 17 (1978) 110.
[11] G. Patermarakis, C. Pavlidou, J. Catal. 147 (1994) 140.
[12] G. Patermarakis, K. Moussoutzanis, J. Chandrinos, Appl. Catal. A:
General 180 (1999) 345.
[13] G. Patermarakis, N. Nikolopoulos, J. Catal. 187 (1999) 311.
[14] X.D. Bai, C. Heming, C.L. Ma, D.Q. Peng, D. Duo, D.X. Zhong,
J.F. Lu, B.H. Guo, Z. Xin, G.M. Bai, J.L. Guo, Rare Met. Mater.
Eng. 33 (2004) 300.
[15] A. Mozalev, S. Magaino, H. Imai, Electrochim. Acta 46 (2001) 2825.
[16] E.R. Holland, Y. Li, P. Abbott, P.R. Wilshaw, Displays 21 (2000) 99.
[17] N.V. Gaponenko, I.S. Molcham, G.E. Thompson, P. Skeldon, A.
Pakes, R. Kudrawiec, L. Bryja, J. Misiewicz, Sens. Actuator. A 99
(2002) 71.
[18] P. Bocchetta, G. Chiavarotti, R. Masi, C. Sunseri, F. Di Quarto,
Electrochem. Commun. 6 (2004) 923.
[19] G. Patermarakis, P. Kerassovitou, Electrochim. Acta 37 (1992) 125.
[20] Z. Zhang, D. Gekhtmann, M. Dresselhaus, J. Ying, Chem. Mater. 11
(1999) 1659.
[21] Z. Wang, M. Kuok, S. Ng, H. Fan, D. Lockwood, K. Nielsch, R.
Wehrspohn, Mater. Phys. Mechan. 4 (2001).
[22] T. Gao, G. Meng, J. Zhan, Y. Wan, C. Lian, J. Fa, L. Zhan, Appl.
Phys. A 73 (2001) 251.
[23] J. Li, C. Papadopoulos, J.M. Xu, M. Moskovits, Appl. Phys. Lett. 75
(1999) 367.
[24] G. Che, B. Lakshmi, E. Fisher, C. Martin, Nature 393 (1998) 346.
[25] A. Michailowski, D. Almawlawi, G. Cheng, M. Moskovits, Chem.
Phys. Lett. 349 (2001) 1.
[26] D. Gong, C. Grimes, O. Varghese, W. Hu, R. Singh, Z. Chen, D.
Dickley, J. Mater. Res. 16 (2001) 3331.
[27] G.E. Thompson, R.C. Furneaux, G.C. Wood, Corros. Sci. 18 (1978)
481.
[28] R.C. Furneaux, G.E. Thompson, G.C. Wood, Corros. Sci. 18 (1978)
853.
[29] G. Patermarakis, K. Moussoutzanis, J. Chandrinos, J. Solid State
Electrochem. 6 (2001) 39.
[30] G. Patermarakis, J. Chandrinos, K. Moussoutzanis, J. Electroanal.
Chem. 510 (2001) 59.
[31] G.C. Wood, J.P. O’ Sullivan, Electrochim. Acta 15 (1970) 1865.
[32] Y. Fukuda, T. Fukushima, Electrochim. Acta 28 (1983) 47.
[33] R.B. Mason, J. Electrochem. Soc. 103 (1956) 425.
[34] S. Tajima, Y. Umehara, Plat. Surf. Finish. 68 (1981) 54.
[35] S. Tomita, Alutopia 11 (4) (1981) 15.
[36] G. Patermarakis, K. Moussoutzanis, J. Solid State Electrochem. 6
(2002) 475.
[37] G. Patermarakis, K. Moussoutzanis, J. Electrochem. Soc. 142 (1995)
737.
[38] M. Nagayama, K. Tamura, Electrochim. Acta 13 (1968) 1773.
[39] M. Nagayama, K. Tamura, Electrochim. Acta 12 (1967) 1097.
[40] M. Nagayama, K. Tamura, H. Takahashi, Corros. Sci. 10 (1970) 617.
[41] J.W. Diggle, Electrochim. Acta 18 (1973) 283.
[42] J.W. Diggle, T.C. Downie, C.W. Goulding, Electrochim. Acta 15
(1970) 1079.
[43] G. Patermarakis, P. Lenas, Ch. Karavassilis, G. Papayiannis,
Electrochim. Acta 36 (1991) 709.
[44] G. Patermarakis, D. Tzouvelekis, Electrochim. Acta 39 (1994) 2419.
[45] G. Patermarakis, K. Moussoutzanis, Corros. Sci. 43 (2001) 1433.
[46] G. Patermarakis, K. Moussoutzanis, Corros. Sci. 44 (2002) 1737.
[47] G. Patermarakis, K. Moussoutzanis, J. Solid State Electrochem. 9
(2005) 205.
[48] G. Patermarakis, J. Solid State Electrochem., in press, first electronic
publication, DOI: <doi:10.1007/s10008-005-0665-7>.
[49] G. Patermarakis, K. Moussoutzanis, Electrochim. Acta 40 (1995) 699.
[50] F. Goodridge, K. Lister, R.E. Plimley, K. Scott, J. Appl. Electro-
chem. 10 (1980) 55.
[51] E.V. Tilak, N.L. Weinberg, Technique of Electroorganic Synthesis,
Part III, Wiley, New York, 1982.
[52] Y.L. Zhou, X.S. Zhang, Y.C. Dai, W.K. Yan, Chem. Eng. Sci. 58
(2003) 1021.
[53] R.C. Weast (Ed.), Handbook of Chemistry and Physics, sixtieth ed.,
CRC Press, Boca Raton, 1980, p. C-323.
[54] Th. Skoulikidis, G. Patermarakis, Aluminium 65 (1989) 185.
[55] C.R. Martin, Chem. Mater. 8 (1996) 1739.
[56] A.P. Li, F. Müller, A. Birner, K. Nielsch, U. Gösele, J. Vac. Sci.
Technol. A 17 (4) (1997) 1428.
[57] P. Bocchetta, C. Sunseri, R. Masi, S. Piazza, F. Di Quarto, Mater.
Sci. Eng. C 23 (2003) 1021.
[58] A.P. Li, F. Müller, A. Birner, K. Nielsch, U. Gösele, J. Appl. Phys.
84 (11) (1997) 6023.
[59] O. Jessensky, F. Müller, U. Gösele, Appl. Phys. Lett. 72 (10) (1998)
1173.
[60] L. Zhang, H.S. Cho, F. Li, R.M. Metzger, W.D. Doyle, J. Mater.
Sci. Lett. 17 (1998) 291.
[61] O. Jessensky, F. Müller, U. Gösele, J. Electrochem. Soc. 145 (1998)
3735.
[62] A.P. Li, F. Müller, U. Gösele, Electrochem. Solid State Lett. 3 (3)
(2000) 131.
[63] H. Masuda, M. Yotsuya, M. Asano, K. Nishio, M. Nakao, A.
Yokoo, T. Tamamura, Appl. Phys. Lett. 78 (6) (2001) 826.
[64] K. Nielsch, J. Choi, K. Schwirn, R.B. Wehrspohn, U. Gösele, Nano.
Lett. 2 (7) (2002) 677.
 G. Patermarakis, K. Masavetas / Journal of Electroanalytical Chemistry 588 (2006) 179–189 189

[65] H. Pan, J. Lin, Y. Feng, H. Gao, IEEE Transac. Nanotechnol. 3 [69] J. Siejka, C. Ortega, J. Electrochem. Soc. 124 (1972) 883.
(2005) 462. [70] P. Neufeld, H.O. Ali, J. Electrochem. Soc. 120 (1973) 479.
[66] S. Ono, H. Ichinose, N. Masuko, J. Electrochem. Soc. 138 (1991) 3705. [71] D. Dodos, Electrochemical Data, Elsevier, Budapest, 1975.
[67] G. Patermarakis, J. Electroanal. Chem. 447 (1998) 25. [72] G. Patermarakis, K. Moussoutzanis, N. Nicolopoulos, J. Solid State
[68] J.P. O’Sullivan, G.C. Wood, Proc. R. Soc. (London) Ser. A 317 Electrochem. 3 (1999) 193.
(1970) 511.