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Journal of Electroanalytical Chemistry 473 (1999) 250 – 255

Formation of Al–Zr composite oxide films on aluminum by

sol–gel coating and anodizing
Keiji Watanabe a, Masatoshi Sakairi a, Hideaki Takahashi a,*, Shinji Hirai b,
Sadae Yamaguchi c
a
Graduate School of Engineering, Hokkaido Uni6ersity, N13, W8, Kita-Ku, Sapporo 060 -8628, Japan
b
Department of Materials Science and Engineering, Muroran Institute of Technology, Mizumoto-cho, Muroran-shi, Hokkaido 050 -8585, Japan
c
Institute for Materials Research, Tohoku Uni6ersity, Katahira-2, Aoba-Ku, Sendai 980 -8577, Japan

Received 31 October 1998; accepted 5 March 1999

Abstract

Al specimens were covered with zirconium oxide film by sol – gel coating using zirconium alkoxide, and then anodized
galvanostatically in a neutral borate solution. The time-variation in anode potential during anodizing was followed, and the
structure and dielectric properties of the anodic oxide film were examined by TEM, EDX, RBS, and impedance measurements.
It was found that the anode potential increases during anodizing, and that the slope of the potential – time curve becomes steeper
with increasing number of dippings in sol–gel solution. An anodic oxide film was formed at the interface between zirconium oxide
and the aluminum substrate during anodizing. This anodic oxide film was composed of an inner Al2O3 layer and an outer Al–Zr
composite oxide layer. The capacitance of anodic oxide films formed after sol – gel Zr-oxide coating and anodizing was about 20%
higher than without Zr-oxide coating. © 1999 Elsevier Science S.A. All rights reserved.

Keywords: Sol – gel coating; Anodizing of aluminum; Zirconium oxide; Al – Zr composite oxide film; Zirconium alkoxide; Electrolytic capacitor

1. Introduction forming anodic oxide films with crystalline oxide.

Barrier type anodic oxide films on aluminum play an
important role as dielectric films in aluminum elec-
trolytic capacitors. The electric capacitance, C, of elec-
trolytic capacitors is expressed by
C = o0oS/d
where, o0 is the vacuum permittivity, o the specific
dielectric constant of the anodic oxide films, S the
surface area, and d the film thickness. Recent develop-
ment of a small electronic devices requires increased
C-values of electrolytic capacitors. To increase the C-
value, increases in o are important in addition to in-
creases in S, and decreases in d [1]. The increases in S
are achieved by electrolytic etching of the aluminum
substrate before anodizing, and the decreases in d by

Presented at the International Symposium on Electrochemistry of
Ordered Interfaces, Sapporo, Japan, 11–12 September, 1998.
* Corresponding author. Fax: +81-11-7067881.
E-mail address: takahasi@icnet.hokudai.ac.jp (H. Takahashi)
Higher crystallinity of anodic oxide films leads to a
lower K value, which is the ratio of film thickness to
film formation potential. Anodizing after hydrothermal
or thermal treatment causes the formation of anodic
oxide films containing g-Al2O3, leading to K-values of
0.8 −1.0 nm V − 1 [2].
(1) Increases in o may be possible by forming Al-valve
metal composite oxide films by incorporating valve
metal oxides as such oxides like TiO2, ZrO2, Ta2O5 and
others have relatively large o values. Previous investiga-
tions of the formation of Al–Ti composite oxide films,
used a pore-filling method [1] and a MOCVD/anodiz-
ing sequential process [3], and found that the parallel
capacitance of composite oxide films is 60% higher than
that of barrier type anodic oxide films on aluminum.
The sol–gel technique is an efficient method for
producing oxide glass, fibers, powders, etc. The process
also offers industrial applications for forming coated
films on different substrates. Coating by the sol–gel
process has several advantages in practical applications:
(1) low temperature processing; (2) the ability to coat

0022-0728/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 9 9 ) 0 0 1 2 1 - 7
 K. Watanabe et al. / Journal of Electroanalytical Chemistry 473 (1999) 250–255 251

substrates with large and complicated surfaces, and (3)
providing unique combinations of film properties with
those of the substrates. In a previous study, one of the
authors investigated zirconium oxide coating on alu-
minum covered with porous-type anodic oxide films by
sol – gel processing and found that alkaline corrosion
resistance of aluminum specimens is improved greatly
by the coating [4].
The present investigation studied the formation of
Al – Zr composite oxide films by sol – gel coating and
subsequent anodizing, and the structure and dielectric
properties of the anodic oxide films were examined.
2. Experimental
2.1. Specimen
Highly pure aluminum (99.99%) foil was used as
specimens (2× 2 cm2 with handle) after electropolishing
in perchloric acid+acetic acid mixture.
2.2. Sol–gel coating
The Zr-oxide coating was applied to the specimen by
sol – gel dip-coating with Zr-oxide sol prepared by mix-
ing zirconium tetra-normal butoxide, diethylene-glycol,
distilled water, and dehydrated ethanol in the manner
shown in Fig. 1. The dipping and heating at 573 K were
repeated two to eight times (n =2 – 8). Further details
of the Zr-oxide sol solution preparation and coating
process is described elsewhere [4].
2.3. Anodizing
Specimens coated with Zr-oxide film were anodized
in 0.5 M H3BO3 + 0.05 M Na2B4O7 solution (pH 7.4) at
Ta = 293 K with a constant current of Ia =1 mA cm − 2,
Fig. 1. Diagram of the procedures for preparing the coated film from
Zr-alkoxide.
and the change in the anode potential (vs. Ag  AgCl)
with time (Ea vs. ta curve) was followed on a digital
multimeter connected to a PC system. Specimens with-
out Zr-coating were also anodized under the same
conditions to determine the effect of Zr-coating on
anodic oxide film formation.
2.4. Characterization of films
Zirconium oxide films and anodic oxide films were
characterized by transmission electron microscopy
(TEM, Hitachi H700 H), Rutherford backscattering
spectroscopy (RBS, High Voltage Engineering 1.7 MV
Tandetron), electron diffraction (ED, Hitachi H-700H),
energy dispersive X-ray analysis (EDX, Jeol JEM-
2000ES), and electrochemical impedance measurements
(ECI, NF-S5720B). In TEM, the vertical cross sections
of specimens were observed by an ultra thin sectioning
technique (Reichert-Nissei Ultra Cuts). In ECI, the
specimens were immersed in 0.5 M H3BO3 + 0.05 M
Na2B4O7 solution (pH 7.4) at 293 K, and 10 mV of
sinusoidal 10 − 2 to 105 Hz voltage was applied. In RBS,
2.0 M eV of He2 + ion were irradiated on the
specimens.
3. Results and discussion
3.1. Growth of the anodic oxide film and its structure
Fig. 2 shows Ea versus ta curves for specimens coated
by the Zr-oxide treatment 2–8 times, and for specimens
without Zr-oxide coating (electropolished). The electro-
polished specimen shows a linear increase in Ea with ta,
while the coated specimens show a 10–15 V-jump at
the very initial stage and then an increase in Ea with ta.
The slopes of the Ea versus ta curves for Zr-Oxide-
coated specimens are much steeper than that without
Zr-oxide coatings, and the slope become steeper with
increasing number of dip-coatings, n, except for n =8.
For n= 8, the slope is very steep initially, but becomes
flatter after 100 s of anodizing.
Fig. 3 shows TEM images of the vertical cross sec-
tions of specimens after Zr-oxide coating with n =4,
without anodizing (Fig. 3(a)) and anodized up to Ea =
100 (Fig. 3(b)), 200 (Fig. 3(c)), 300 (Fig. 3(d)), and 400
V (Fig. 3(e)). The Zr-oxide layer has a uniform thick-
ness of about 200 nm, and the anodized specimens
show two layers between the Zr-oxide layer and the
metal substrate: an outer dark layer and an inner
lighter colored layer. According to the EDX and RBS
analyses, the inner layer consisted of aluminum oxide,
and the outer layer of Al–Zr composite oxide. Fig. 3(f)
shows an electron diffraction pattern obtained from the
Al–Zr composite oxide, and suggests a fluorite crystal
structure. Electron diffraction showed that both the
252 K. Watanabe et al. / Journal of Electroanalytical Chemistry 473 (1999) 250–255

Fig. 2. Change in the anode potential, Ea, during anodizing in 0.5 M

H3BO3 +0.5 M Na2B4O7 solution at 293 K and 10 A m − 2, obtained
for specimens with and without a Zr-oxide coating, where n repre-
sents the number of times dipped in sol-solution.

Zr-oxide and inner aluminum oxide layers were amor-

phous oxides. It is clear from Fig. 3 that the thickness
of the inner layer, da, increases with ta (or Ea), and that
the thickness of the outer layer, dc, increases initially
with anodizing potential(time), and that it decreases
after a maximum.
Fig. 4 shows the changes in the thicknesses of the
inner, dc (Fig. 4(a)), and outer layers, da (Fig. 4(b)),
with anodizing time, ta, for specimens coated by Zr-ox-
ide with different n and for aluminum without a Zr-ox-
ide coating (solid line in Fig. 4(b)). The film thickness
Fig. 4. Changes in thickness of the outer, dc and inner layers, da, with
ta, for Zr-oxide coated specimens. Conditions for anodizing as in Fig.
2.
for the specimen without Zr-oxide coating shows a
linear increase with ta, but the time variation in da for
specimens coated by Zr-oxide is complicated, and varies
with n. At the initial stage, all the da versus ta curves
show a slope similar to that of the specimen without
Zr-oxide coating. Later, the slope becomes flatter for

Fig. 3. Transmission electron micrographs of vertical cross sections of specimens anodized up to Ea =(a) 0; (b) 100; (c) 200; (d) 300 and (e) 400
V after Zr-oxide coating. Electron diffraction pattern of Al–Zr composite oxide layer is shown in (f). Conditions for anodizing as in Fig. 2.
 K. Watanabe et al. / Journal of Electroanalytical Chemistry 473 (1999) 250–255
n= 2 specimens, while the slope becomes steeper for
specimens with n= 4, 6 and 8. The upward deviation
in the slope becomes more remarkable with increasing
n.
At this point it may be informative to consider the
growth mechanism of anodic oxide films on Zr-oxide-
coated aluminum. Fig. 5 shows a model of the for-
mation of an anodic oxide film during anodizing of
Zr-oxide-coated aluminum. It is considered that the
Zr-oxide layer has a network structure of micro-pores
and cracks, and that the micro-pore network is more
developed near the surface of the Zr-oxide and on
specimens with smaller n. The micro-pore network
may be formed by the evaporation of organic com-
pounds during heating of the sol precursor film, and
filled partly with Zr-oxide during the subsequent coat-
ing cycles. In the heat treatment, a thin thermal alu-
minum oxide film may also be formed at the interface
between the Zr-oxide and metal substrate [2].
When the Zr-oxide coated specimen layer is im-
mersed in anodizing solution, water and electrolyte
penetrate into the micro-pore network, and the Zr-ox-
ide layer is unable to sustain an electric field. The
jump in Ea at the very initial stage of anodizing (see
Fig. 2) may be due to the aluminum oxide layer
rather than the Zr-oxide layer. This is partly sup-
ported by the fact that the jump in Ea is independent
of n. A similar jump in Ea has been observed in the
anodizing of aluminum after heat treatment in air [4].
During anodizing after Zr-oxide coating, O2 − ions
dissociated from water at the bottom of the Zr-oxide
layer transport inwards across the anodic oxide film
to form pure aluminum oxide at the interface be-
tween the inner Zr-oxide layer and metal substrate.
The outward transport of Al3 + ions forms the com-
posite oxide by filling micro pores at the interface
between the outer layer and Zr-oxide layer with alu-
minum oxide. In addition to the formation of oxide
at the two interfaces, a conversion of composite oxide
to aluminum oxide may occur at the interface be-
tween the outer and inner layers, due to the outward
Fig. 5. Model of the formation of the dual layer structure of anodic
oxide films during anodizing of Zr-oxide films.
253
transport of Zr4 + or ZrO2 + ions in the composite
oxide layer.
Assuming that the transport number of Al3 + and
2−
O ions remains constant during anodizing, the
mechanism of the growth of the outer and inner lay-
ers can be explained as follows. The downward devia-
tion in the da versus ta curve for the specimen with
n= 2 from that for the specimen without Zr-oxide
coating (see Fig. 4(b)) may be explained by the distri-
bution of micro-pores, and be due to the conversion
of composite oxide to aluminum oxide. This would
imply that the specimen with n= 2 has the most de-
veloped micro-pore network structure especially at re-
gions near the surface, and so has the slowest
conversion, causing the downward deviation. With
n] 4, there are fewer micro-pores and the conversion
becomes faster as n increases, leading to the upward
deviation in the da versus ta curves (see Fig. 4(b)).
The net rate of increase in dc is obtained by sub-
tracting the conversion rate of the composite oxide
layer at the interface between the inner and outer
layer from that of the formation rate of the com-
posite oxide layer at the interface between the outer
layer and the Zr-oxide layer. Here dc shows a maxi-
mum at intermediate periods of anodizing (see Fig.
4(a)), and this may be explained by the decrease in
the formation rate of the composite oxide layer with
ta, due to a larger porosity at the outer region of the
Zr-oxide layer.
3.2. Dielectric properties of the anodic oxide films
Fig. 6 shows Bode diagrams from impedance mea-
surements of specimens coated by Zr-oxide with n=4
and anodized to Ea = 0, 100, 200, 300, and 400 V. All
the impedances, Z, are about 2×103 V m2 in the low
frequency range to around 1 Hz, and log Z then
decreases linearly with a slope of − 1 between 1 and
103 Hz, and the slope become slightly flatter for f\
103 Hz, With increasing Ea the curves shift to high
frequencies. With increasing frequency, f, the phase
shift, u, decreases, and after a minimum of about 90°
u increases again. The equivalent circuit of all the
specimens can be expressed by the series combination
of a parallel resistance, Rp, and a parallel capacitance,
Cp, with a solution resistance, Rsol, (see inset in Fig.
6); the parallel capacitance, Cp, depends on Ea. More
complicated equivalent circuits could be expected
since the anodic oxide films formed on the Zr-oxide
coated specimen are composed of an outer Al–Zr
composite oxide layer and an inner Al2O3 layer, as
shown in Fig. 3. This simple behavior seems difficult
to explain, but may be due to a very high capacitance
of the outer layer, compared with the inner layer.
254 K. Watanabe et al. / Journal of Electroanalytical Chemistry 473 (1999) 250–255
Fig. 6. Bode diagram for unanodized specimen and specimens an-
odized to 100, 200, 300, and 400 V after Zr-oxide coating with four
immersions in sol-solution. Conditions for anodizing as in Fig. 2.
Fig. 7 shows the relationship between the reciprocal
of the parallel capacitance, 1/Cp, of anodic oxide films
and anode potential, Ea, for specimens with and with-
out Zr-oxide coating. The value of 1/Cp for the speci-
men without Zr-coating is proportional to Ea, as could
be expected from Eq. (1). The dielectric constant of the
anodic oxide film can be calculated from the slope of
Fig. 7. Changes in reciprocal capacitance, 1/Cp, with anode potential,
Ea, for Zr-oxide coated specimens. Conditions for anodizing as in
Fig. 2.
Fig. 8. Thickness of the outer, dc and inner Al2O3 layers, da versus Ea,
for Zr-oxide coated specimens with (a) n =2 and (b) n =6. Condi-
tions for anodizing as in Fig. 2. Broken line represents aluminum
without Zr-oxide coating.
the straight curve and film thickness, and is about 9.5
for the specimen without Zr-oxide coating. Specimens
coated by Zr-oxide with nB 6 show flatter slopes, more
so with increasing n. The specimen with n= 8 shows a
large 1/Cp at Ea = 0 V, and 1/Cp initially increases
rapidly and then more slowly at about 150 V. This is
due to the poor development of the micro-pore net
work structure in the Zr-oxide layer.
Consequently, the capacitance of anodic oxide films
formed after Zr-oxide coating is at most about 20%
higher than without Zr-oxide coating.
Fig. 8 shows the changes in the da and dc with anode
potential, Ea, obtained for specimens coated by Zr-ox-
ide with n= 2 and 6. The change in thickness of the
anodic oxide films formed on aluminum without a
Zr-oxide coating is plotted as a dotted straight broken
line with slope 1.5 nm V − 1.
For n= 2, da increases with Ea, and the rate of
increase in da decreases with Ea. The dc increases with
Ea, and shows a maximum at Ea = 300 V before it
decreases above this potential. The total thickness of
the anodic oxide film, da + dc, is lower than the film
without a Zr-oxide coating, and this becomes more
remarkable as Ea increases. Assuming that the electric
field sustained by the inner layer is the same as that
sustained by anodic oxide films on aluminum without a
Zr-oxide coating, the outer composite oxide layer of the
n=2 specimen can sustain higher electric field than the
inner layer.
The n= 6 specimen which shows a linear relationship
between da + dc and Ea, and the slope is similar to that
 K. Watanabe et al. / Journal of Electroanalytical Chemistry 473 (1999) 250–255
Fig. 9. Changes in da, dc and the apparent dielectric constant oapp
with repeated dip-coatings in sol-solution, n, for specimens anodized
up to Ea = 400 V after Zr-oxide coating.
of the specimen without Zr-oxide coating. This suggests
that the outer composite oxide layer can sustain an electric
field similar to that sustained by the inner layer. The
differences in electric fields of the outer layer between the
n= 2 specimen and n =4 specimens can be explained by
differences in the Al3 + ion content in the outer layer and
crystallinity.
The value of da, dc, and the apparent dielectric constant,
oapp ( = Cp × (da +dc)/o0), for specimens anodized up to
400 V after Zr-oxide coating are plotted against n in Fig.
9. The value of da shows a minimum at n = 2, and then
increases to reach a maximum at n = 6. The dc increases
slightly with n until n =4, and it increases appreciably
above n= 6.
The oapp of the anodic oxide films formed on specimens
coated by Zr-oxide with n= 6 is larger than that on the
specimen without Zr-oxide, while the specimen with n = 2,
4, and 8 show smaller values. The high value of Cp for
specimens with n=6, can be explained by its high oapp
value.
4. Conclusions
The formation of Al – Zr composite oxide films on
aluminum by sol–gel coating and subsequent anodizing
255
was attempted to increase the capacitance of anodic oxide
films. The following conclusions may be drawn.
(1) Galvanostatic anodizing of aluminum coated with
Zr-oxide films by sol–gel processing leads to the forma-
tion of oxide film, which consist of an outer Al–Zr
composite oxide layer and an inner Al2O3 layer at the
interface between the Zr-oxide layer and the metal
substrate.
(2) The thickness of the inner layer, da, increases with
time, and the rate of increase in da increases with the
number of dip-coatings, n.
(3) The thickness of the outer layer, dc, initially
increases, and after a maximum decreases. This is more
remarkable for specimens with larger n-values.
(4) The change in the dc and da with time can be
explained by an outward transport of Zr4 + ions and
micro-pores in the Zr-oxide coating.
(5) With nB 6, the capacitance of the anodic oxide
films formed by the Zr-oxide sol–gel processing and
subsequent anodizing is at most 20% larger than that of
oxide films formed on Al without a Zr-oxide layer, while
with n\ 8 it is smaller.
Acknowledgements
The authors wish to thank K. Nishinaka and K. Dohjun
at Muroran Institute of Technology for experimental
assistance with the sol–gel coating, and Dr K. Takahiro
.
and Dr S. Nagata at Tohoku University for the RBS. The
work was supported financially by the Light Metal
Education Foundation of Japan, and the Ministry of
Education, Science, Sports and Culture, Japan with a
Grant-in-Aid for Scientific Research on Priority Areas for
‘Electrochemistry of Ordered Interfaces’ (No. 10131204).
A part of this work was carried out under the Visiting
Researcher’s Program of the Institute for Materials
Research, Tohoku University.
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