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 Journal of The Electrochemical Society, 2021 168 103506

Forming Hard Anodic Films on Aluminum by Anodization in

Oxalic Acid and Alcohol
Hidetaka Asohz and Takuma Sano
Department of Applied Chemistry, Kogakuin University, Hachioji, Tokyo 192-0015, Japan

Porous anodic films have attracted wide attention because of their potential applications in various industrial fields. Reducing their
porosity is expected to improve the hardness. This study focused on evaluating the effect of the electrolyte composition on the
hardness of anodic alumina films formed on aluminum by anodization under mild conditions. In particular, the effect of adding
alcohol (i.e., ethanol and ethylene glycol) to an oxalic acid–based electrolyte was considered. The voltage–time curve, coating ratio
(i.e., film formation efficiency), morphology, and Martens hardness of the resulting anodic alumina films were clearly affected by
the type and amount of added alcohol. Adding alcohol effectively suppressed the chemical dissolution of the anodic film during
anodization without needing to lower the electrolyte temperature, which formed high-strength films with low porosity and thick
pore walls. The Martens hardness of the formed films increased by 18% with the addition of 50 vol% ethanol and increased by 25%
with the addition of 50 vol% ethylene glycol.
© 2021 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ac2ec1]

Manuscript submitted September 7, 2021; revised manuscript received October 2, 2021. Published October 20, 2021.

Porous-type anodic films are generally formed by anodizing aim was to develop an anodization process that can realize high-
aluminum in an acid electrolyte. They have attracted wide attention strength anodic films under mild conditions.
as a host material, template, or mask for the fabrication of various
objects at the nanometer scale.1–7 Many studies have investigated the Experimental
structural features of porous alumina films, especially self-ordered
Pretreatment.—High-purity (99.99%) aluminum sheets with a
pore arrays. In parallel, the formation efficiency of anodic films and
working area of 10 cm2 were used for anodization. Aluminum sheets
the effects of the chemical composition of the electrolyte on their
with a working area of 20 cm2 were used for coating ratio measure-
growth and structure have also been studied extensively.6,8 For
ments to ensure the reproducibility of the results. Prior to anodization,
practical application, an important objective is to improve the
each specimen was degreased in 5 wt% NaOH at 60 °C for 20 s, rinsed
production efficiency of anodic films and properties such as the
in ion-exchanged water, and then immersed in 30 vol% HNO3 at room
hardness, wear resistance, and corrosion resistance.
temperature for 1 min as described in our previous studies.12,13
The properties of anodic porous alumina films are affected by the
dimensions of their structure (e.g., inter-pore distance, pore dia-
Formation of anodic film.—In our previous studies, we system-
meter, pore wall, porosity, and film thickness). Industrially, hard
atically investigated the anodization behavior of a sulfuric acid
anodic films on aluminum are obtained by anodization in a sulfuric
solution containing alcohol.12,13 In this study, we instead selected an
acid solution, which is kept at low temperatures (<10 °C) to avoid
oxalic acid–based electrolyte containing different alcohols. Oxalic
chemical dissolution of the formed oxide film.9–11 Suppressing
acid is a commonly used industrial agent, similar to sulfuric acid.
chemical dissolution of the pore wall is expected to form anodic
The concentration of oxalic acid was set to 0.3 mol·dm−3, which is
films with low porosity, which should improve the film hardness.
typical for obtaining self-ordered porous alumina.2,24 Two types of
In previous research, we focused on adding alcohols to the
alcohols were selected as representative additives based on the
electrolyte to avoid chemical dissolution of the oxide film during
findings of previous studies: ethanol and ethylene glycol. They were
anodization.12,13 For instance, we carried out anodization at a
used to investigate the influence of the type of alcohol on the
constant current of 100 A·m−2 in a sulfuric acid–based electrolyte
formation of anodic porous alumina films and their structural and
containing monohydric alcohol (methanol or ethanol) or polyhydric
mechanical properties.
alcohol (ethylene glycol or glycerol) to investigate the effects of
Anodization was conducted at a constant current density of
adding alcohol on the coulombic efficiency.13 The formation
100 A·m−2, which is the same as the conditions used in our previous
voltage, coating ratio (i.e., formation efficiency of anodic alumina),
studies.12,13 During anodization, the electrolyte was maintained at a
and maximum attainable film thickness all increased with the
constant temperature of 20 °C by a thermostat, and it was gently
amount of alcohol added, regardless of the type of alcohol.13
stirred at 300 rpm by a magnetic stirrer.
Other groups have explained adding alcohol to have the
following effects: the alcohol functions as an antifreeze agent in
Characterization.— Solution properties.—Both the electrical
the electrolyte; the alcohol acts as a cooling agent; and the alcohol
conductivity and viscosity of the mixed solutions of oxalic acid
prevents non-uniform growth of the anodic film (i.e., burning) even
and each alcohol were evaluated at 20 °C. Conductivity and
at a relatively high current density or voltage.14–23 However, these
viscosity were measured by using a multifunction water-quality
studies were primarily focused on preventing burning when fabri-
meter (DKK-TOA, MM-60R) and digital viscometer (ATAGO Co.,
cating ordered porous alumina under high current density or voltage
Ltd., VISCO-895), respectively.
conditions (i.e., hard anodization).
Although adding alcohol to the electrolyte may improve film
Coating ratio.—The formation efficiency of the anodic porous
properties, few studies have focused on the effect on the film hardness.
alumina was evaluated simply and systematically in terms of the
In this study, we focused on the effect of adding monohydric alcohol or
coating ratio, which expresses the conversion efficiency of alu-
polyhydric alcohol to an oxalic acid–based electrolyte on the anodiza-
minum to alumina.8 The coating ratio was calculated as follows:
tion behavior and related characteristics, particularly the hardness. Our

weight of oxide formed

Coating ratio = [1]
z
E-mail: asoh@cc.kogakuin.ac.jp
weight of aluminum consumed
 Journal of The Electrochemical Society, 2021 168 103506

Figure 1. Voltage–time curves for the anodization of aluminum in 0.3 mol·dm−3 oxalic acid with various concentrations of (a) ethanol and (b) ethylene glycol at
a constant current density of 100 A·m−2 and temperature of 20 °C.

The coating ratio was measured at least five times, and the average
value was taken. More details are given in our previous papers.12,13

Film structure.—We measured the thickness of the anodic film

six times for each specimen (three times on each side) by using an
eddy-current coating-thickness tester (Kett Electric Laboratory, LH-
373). The surface structure of the anodized aluminum was directly
observed by field-emission scanning electron microscopy (FE-SEM,
JEOL, JSM-6701F).

Indentation hardness test.—We used an indentation hardness test

to evaluate the hardness of the anodized aluminum. Although the
Vickers hardness test is generally employed to evaluate the hardness
of anodic films,11,25 the size of the impression (i.e., length of the
diagonal) formed by plastic deformation needs to be measured
exactly. For thin films, the shallow indentation depth makes the
impression difficult to observe. The indentation depth should not
exceed 10% of the film thickness. Therefore, we evaluated the films
in terms of the Martens hardness, which can be obtained from
the relationship between the applied load and displacement (i.e.,
load–displacement curve) without requiring observation of the
impression.
The Martens hardness of the anodic films was measured by using
a Dynamic Ultra Micro Hardness Tester (Shimadzu, DUH-211). The
Martens hardness was obtained from the relationship between the
test force and indentation depth during the indentation process, in
accordance with ISO 14577–1 Annex A. An electromagnetic force
was used to press a triangular pyramid indenter with a tip angle of
115° against a specimen. The pressing force was increased at a
constant rate of 4.44 mN·s−1 from zero to the preset test force
(100 mN). The indentation depth was automatically measured as the
indenter was pressed against the specimen. Five positions on each
side of a specimen were tested, and the average value was taken
from three measurements excluding the maximum and minimum
values.
Results and Discussion
Voltage–time curves during anodization at a constant current
density in oxalic acid containing alcohol.—Figures 1a and 1b show
V–t curves for anodization in a mixture of oxalic acid and alcohol at
a constant current density of 100 A·m−2. When the oxalic acid–
based solution was used without alcohol, the voltage sharply
increased at the beginning of the anodization and then decreased.
In the steady state, the voltage was stable and reached approximately
Figure 2. Viscosity and conductivity of a 0.3 mol·dm−3 oxalic acid–water-
–alcohol system as functions of the alcohol concentration: ethanol (EtOH)
and ethylene glycol (EG).
48 V. This type of stable V–t curve is usually observed when stable
porous-type anodic film growth occurs. We previously reported that
adding a monohydric alcohol (e.g., ethanol) or polyhydric alcohol
(e.g., ethylene glycol) to a sulfuric acid–based solution increased the
anodization voltage compared with using sulfuric acid alone.13
Similarly, adding either alcohol to the oxalic acid–based solution
increased the anodization voltage greater than 48 V, and the voltage
increased with the alcohol concentration in all cases. For the
electrolyte of oxalic acid and 50 vol% ethylene glycol, the final
voltage after anodization for 60 min was approximately 100 V,
which was the highest voltage among all cases in this study
(Fig. 1b). Although the voltage increased, no burning was observed
after 60 min of anodization in all cases.
In our previous studies using sulfuric acid–water–alcohol sys-
tems, the influences of the type and concentration of alcohol on the
physical properties of the mixed solution were investigated by
measuring the viscosity and electric conductivity.12,13 The results
clearly demonstrated that the conductivity of the mixed solutions
containing alcohol decreased with increasing alcohol concentration
 Journal of The Electrochemical Society, 2021 168 103506
Figure 3. Relationship between the voltage after anodization for 60 min and
conductivity of the 0.3 mol·dm−3 oxalic acid–water–alcohol system.
Figure 4. Relationship between the coating ratio and alcohol concentration.
Anodization was conducted in 0.3 mol·dm−3 oxalic acid containing 10–
50 vol% of each alcohol at a current density of 100 A·m−2 and temperature
of 20 °C for 60 min.
regardless of the type of alcohol.12,13 In particular, polyhydric
alcohols had a greater effect on the solution properties than the
monohydric alcohols. The same tendency was observed in this study,
as shown in Fig. 2. The viscosity of the oxalic acid–based solution
without alcohol was approximately 2 mPa·s. Adding either alcohol
increased the solution viscosity. The viscosity particularly increased
with the addition of ethylene glycol; the mixed solution containing
50 vol% ethylene glycol exhibited a high viscosity of 4 mPa·s. In
contrast, the conductivity decreased with an increasing amount of
either alcohol. The conductivity of the oxalic acid–based solution
without alcohol was 5.5 S·m−1, which was used as the standard
value for comparison. Adding up to 50 vol% ethanol or ethylene
glycol decreased the conductivity to 0.9 and 0.8 S m−1, respectively.
Figure 3 shows the relationship between the voltage after
anodization for 60 min and electric conductivity of the mixed
solutions depending on the alcohol content. The final voltage clearly
increased with decreasing electric conductivity. The rate of voltage
increase was clearly higher with ethylene glycol than with ethanol.
The final voltage was higher with 50 vol% ethylene glycol (100 V)
than with 50 vol% ethanol (85 V). Moreover, the rate of voltage
increase was clearly higher when the electric conductivity was less
than 3 S·m−1 (i.e., more than 10 vol% alcohol) in both cases. The
increased voltage can be attributed to the high solution resistance of
the electrolyte used for anodization, which was a consequence of the
high viscosity and low ionic conductivity as shown in Fig. 2.
Coulombic efficiency of alumina formation in terms of coating
ratio.—Figure 4 shows the influence of the ethanol or ethylene
glycol concentration on the coating ratio. Anodization was con-
ducted for 60 min at a constant current density for all cases (i.e., the
electric charge was the same). The coating ratio was 1.35 with oxalic
acid alone and increased approximately 3% (from 1.35 to 1.39) with
50 vol% ethanol and approximately 8% (from 1.35 to 1.46) with
50 vol% ethylene glycol. Although the coating ratio increased
with the alcohol concentration regardless of the type of alcohol,
the coating ratio was significantly higher with ethylene glycol than
with ethanol.
If the same amount of alumina is formed by the same electric
charge, a higher coating ratio implies that the chemical dissolution of
alumina into the electrolyte during anodization was effectively
suppressed by the addition of alcohol. In our previous study,13 we
attributed the increase in the coating ratio to the alcohol suppressing
the chemical dissolution of the oxide film. In this study, adding
ethylene glycol suppressed the chemical dissolution of the oxide film
more effectively than adding ethanol, which yielded a higher-mass
alumina film at the same electric charge. Adding different types of
alcohol had similar effects regardless of the base acid (i.e., sulfuric
acid or oxalic acid).
Film thickness.—If anodization is conducted at a constant
current density for the same amount of time (i.e., the same electric
charge), the mass of the formed alumina (i.e., amount of oxidation
reaction) should be the same according to Faraday’s law. To
evaluate the film formation efficiency, we also measured the film
thickness.
In all cases, the films were 16–18 μm thick after 60 min of
anodization. Adding alcohol to the electrolyte did not appear to have
any particular effect on the film thickness. This indicates that the
growth rate of the anodic film (i.e., the anodic reaction itself) is
independent of the addition of alcohol. The fact that the coating ratio
changed even as the film thickness stayed the same strongly
indicates the difference in dissolution behavior of the formed
alumina films in the electrolyte. A higher coating ratio implies that
the formed alumina film had lower porosity and a thicker pore wall.
Surface structure of the anodic films formed in oxalic acid
containing alcohols.—Figure 5 shows surface SEM images of
alumina films formed with oxalic acid and 10–50 vol% ethylene
glycol. In this study, we used one-step anodization rather than two-
step anodization to obtain an ordered porous structure.2 Therefore,
the surface morphology of the anodized aluminum was strongly
affected by the surface texture of the aluminum pretreated in NaOH.
Alkaline etching is usually applied to remove rolling features (e.g.,
scratches and crack-like defects) on the aluminum surface.26
Because alkaline etching proceeds relatively rapidly, the surface is
less flat than with electropolishing. After alkaline etching, the
topography of the aluminum surface was roughly divided into two
areas: preferentially pore-generating (scallops) and relatively protu-
berant (ridges). The scallops were typically a few hundred nan-
ometers to a few microns in size. Each scallop was surrounded by a
network of continuous ridges.
 Journal of The Electrochemical Society, 2021 168 103506
Figure 5. SEM images of the surface of anodized aluminum specimens prepared in 0.3 mol·dm−3 oxalic acid containing ethylene glycol at 100 A·m−2 and 20 °C
for 60 min under different conditions: (a) without ethylene glycol; (b) with 10%, (c) 20%, (d) 30%, (e) 40%, and (f) 50% ethylene glycol. Lower images show
high–magnification images of each specimen.
When pretreated aluminum was anodized in the oxalic acid–-
based solution without alcohol, the usual porous-type anodic film
formed on the aluminum surface. Nanopores were generated in the
scallops, and very few were generated on the ridges (Fig. 5a). The
small amount of pore generation on the ridge areas was attributed to
the relatively thick barrier oxide that initially formed because of the
higher electrostatic fields present on protuberances.27 Similarly,
nanopores were observed in the scallops even when alcohol was
added to the electrolyte (Figs. 5b–5f). The pores that formed in the
initial anodization stage had smaller diameters than the main pores
that formed in the steady state.28 However, the ratio of the pore
diameter to inter-pore distance in the films clearly decreased with the
addition of alcohol. Moreover, the pore wall thickness and ridge
width increased with the alcohol concentration. These SEM images
clearly show that the chemical dissolution of the outer surface of the
anodic films was suppressed by the addition of alcohol. The
relationship between the porosity α, inter-pore distance dint, and
pore diameter dpore is given by
α = (d pore/d int) 2 × 100 [2 ]
Therefore, if α = 10%, then dpore/dint ∼ 0.32. The SEM images in
Fig. 5 indicate that the porosity of the outermost surface should be
less than 10% for all cases. Among these cases, the lowest porosity
should be for the anodic film formed in oxalic acid containing
50 vol% ethylene glycol. Although using only the outermost surface
morphology of the anodic films to evaluate the porous film structure
is not strictly appropriate, the images do appear to indicate that the
film porosity was reduced by the addition of ethylene glycol.
As discussed in our previous studies,12,13 the dielectric constant
of a water–alcohol system varies from 80.37 (H2O) to 50.38 (50 wt%
ethanol) and 64.92 (50 wt% ethylene glycol) at 20 °C.29 In terms of
the degree of acid dissociation, ethanol has a low dielectric constant
and may suppress dissociation of the acid in the mixed solvent well,
which should in turn suppress the chemical dissolution of the oxide
film in an acid solution. In contrast, ethylene glycol has a higher
dielectric constant than ethanol, so it may be expected to suppress
acid dissociation not as strongly. However, the results were opposite
of what was expected. Despite having a higher dielectric constant,
ethylene glycol effectively suppressed the chemical dissolution.
Therefore, we concluded that the influence of alcohol as an additive
on the chemical dissolution of the oxide film cannot be explained
only in terms of the degree of acid dissociation or the dielectric
constant of the mixed solution. Because the effects of adding alcohol
on the chemical dissolution of the oxide film has not yet been fully
elucidated, it is also necessary to consider the hydration and/or the
intermolecular interaction such as a hydrogen bond in the oxalic
acid–water–alcohol systems.
Indentation hardness test.—In our previous studies using sulfuric
acid as the base electrolyte, adding ethylene glycol resulted in anodic
films with low porosity (<10%) owing to the effective suppression of
chemical dissolution.13 Adding ethylene glycol (polyhydric alcohol)
was more effective than adding ethanol (monohydric alcohol) at
improving the film formation efficiency and maximum film
thickness.13 In this study, where we used oxalic acid as the base
electrolyte, the same tendency was confirmed as shown in Figs. 4 and
5. Therefore, the mechanical properties (e.g., hardness, wear resis-
tance, and elasticity) of anodic films should also be indirectly
improved by the addition of alcohol to the electrolyte.
Figure 6 shows typical load–displacement curves for anodized
aluminum specimens at a maximum applied force of 100 mN. The
hold time at the maximum load was 5 s. The curves for indentation
were similarly sharp in all cases. The slope of the loading curve
increased gradually with increasing load (test force). The indentation
depth of each specimen was clearly affected by the composition of
the electrolyte used for anodization.
Figure 7 summarizes the influence of the alcohol content on the
load–displacement curves. A typical curve for each condition is
shown for comparison. Regardless of the type of alcohol, the
indentation depth at the maximum load decreased as the amount
of alcohol increased, which suggests that the hardness of the film
increased. For the anodic film formed in oxalic acid alone, the
indentation depth at maximum load and the penetration depth at
unloading were 1.05 and 0.75 μm, respectively. When 50 vol%
ethylene glycol was added to the electrolyte, this resulted in the
shallowest indentation depth at maximum load and penetration depth
at unloading of 0.88 and 0.62 μm, respectively.
Figure 8 shows the average values of the Martens hardness
(HM115), which is calculated as follows:
 Journal of The Electrochemical Society, 2021 168 103506

Figure 7. Load–displacement curves for indentation tests of specimens

prepared in 0.3 mol·dm−3 oxalic acid with various concentrations of
(a) ethanol and (b) ethylene glycol.

Figure 6. Load–displacement curves for indentation to a maximum load of

100 mN: (a) anodized aluminum in oxalic acid alone, (b) anodized aluminum
in oxalic acid containing 50 vol% ethanol, and (c) anodized aluminum in
oxalic acid containing 50 vol% ethylene glycol.

1, 000 × F
HM115 =
26.43 × h 2
F is the load (mN), and h is the indentation depth at maximum load
(μm). For the anodic alumina film formed in oxalic acid alone, the
average HM115 was 3412 N·mm−2. In contrast, HM115 increased
with the amount of either type of alcohol added to the electrolyte.
With ethanol, the average HM115 varied from 3343 N·mm−2
(10 vol% ethanol) to 4025 N·mm−2 (50 vol% ethanol). Thus, adding
ethanol increased the film hardness 1.18 times compared with the
reference specimen.
[3]
Figure 8. Relationship between the Martens hardness (HM115) and alcohol
concentration.
A similar effect was confirmed when ethylene glycol was the
additive. The highest and average values of HM115 with 50 vol%
ethylene glycol were 4352 and 4251 N·mm−2, respectively. Thus,
adding ethylene glycol increased the film hardness 1.25 times
compared with the reference specimen. It is considered that the
increase in Martens hardness was influenced not only by the
 Journal of The Electrochemical Society, 2021 168 103506

Table I. Data obtained from the indentation hardness test. strategy for preparing hard anodic films with low porosity under
mild anodization conditions to prevent burning.
HM115/N · mm—2
Composition Acknowledgments
Maximum Minimum Average
The authors thank Shimadzu Corporation for technical support
Oxalic acid 3,518 3,210 3,412 with the indentation hardness test. This work was partly financed by
+ 10% EtOH 3,509 3,252 3,343 the Light Metal Educational Foundation of Japan.
+ 20% EtOH 3,809 3,691 3,735
+ 30% EtOH 3,660 3,343 3,549 ORCID
+ 40% EtOH 3,858 3,617 3,772 Hidetaka Asoh https://orcid.org/0000-0003-0722-9994
+ 50% EtOH 4,056 4,008 4,025
+ 10% EG 3,699 3,451 3,595 References
+ 20% EG 3,519 3,344 3,445
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