Surface & Coatings Technology 201 (2007) 7310 – 7317

www.elsevier.com/locate/surfcoat

Influence of the anodizing temperature on the porosity and the

mechanical properties of the porous anodic oxide film
T. Aerts a,⁎, Th. Dimogerontakis b , I. De Graeve a , J. Fransaer c , H. Terryn a
a
Vrije Universiteit Brussel, Department Metallurgy, Electrochemistry and Material Sciences, Pleinlaan 2, 1050 Brussel, Belgium
b
Hellenic Research Centre for Metals, Piraeus Str 252, Athens, Greece
c
KU Leuven, Department Metallurgy and Materials Engineering, Kasteelpark Arenberg 44, Heverlee, Belgium
Received 10 January 2007; accepted in revised form 26 January 2007
Available online 3 February 2007

Abstract

The microhardness and fretting wear resistance of anodic oxide layers, produced on commercially pure aluminium by potentiostatic anodizing
in sulphuric acid under conditions of controlled convection and heat transfer in a reactor with a wall-jet configuration, were evaluated as a function
of the electrolyte temperatures in a wide range from 5 °C up to 55 °C. Additionally, information on the microstructure of the anodic films was
acquired by FE-SEM analyses whereas image analysis of high-resolution surface images yielded quantitative information on the evolution of the
surface porosity as a function of the electrolyte temperature. Hence measured mechanical properties were directly related to the corresponding
microstructure. The microhardness of the anodic films progressively decreased with increasing electrolyte temperatures whereas the wear
resistance remained constant for the lower considered temperatures from 5 °C to 25 °C, followed by a decreasing wear resistance with increasing
electrolyte temperature from 25 °C onwards. Both mechanical properties displayed an important decrease when the electrolyte temperature was
raised from 45 °C to 55 °C. FE-SEM analyses indicated the formation of porous oxides with initially equal pore diameters at the metal-oxide
interface, though pore widening due to chemical dissolution of the oxide by the electrolyte led to films with cone-shaped pores. This phenomenon
became more pronounced with increasing electrolyte temperature and towards the surface of the anodic layer. The deterioration of the
microhardness with increasing electrolyte temperatures could mainly be attributed to the increase of the porosity in the outer region of the oxides
since the rate of microhardness reduction is almost synchronous with the rate of porosity increase. In contrast, the variation of the wear resistance
with increasing anodizing temperature indicates that the degradation of the wear resistance does not only depend on the oxide porosity and is also
affected by other characteristics of the oxide.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Aluminium; Anodizing; Hardness; Wear; Microstructure; Temperature

1. Introduction in the past and information concerning this matter is available in

The surface properties of anodic alumina films (AAF) render
anodized aluminium products suitable for a wide range of
applications, including use in the packaging, architectural and
aerospacial industries. In many of these applications a key role
is played by the mechanical properties such as the hardness and
wear resistance. Depending on the considered anodizing
conditions these properties can be varied to a wide extent,
hence the influence of the process conditions on the mechanical
properties of the resulting AAF has received extensive attention
⁎ Corresponding author. Tel.: +32 2 629 35 35; fax: +32 2 629 32 00.
E-mail address: taerts@vub.ac.be (T. Aerts).
0257-8972/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.01.044
literature.
Most studies have considered the (micro)hardness or wear
resistance of porous AAF concern oxides formed under hard
anodizing conditions. These conditions, which comprise the use
of low electrolyte temperatures and often special electrolytes,
are used to produce thick anodic oxides (typically thicker than
25 μm) with hardness and wear resistance as their primary
characteristics [1]. Yet even in this field not much work has been
conducted to relate the latter two properties to the electrolyte
temperature [1]. According to Scott [2], who considered
anodizing in a sulphuric acid electrolyte at a constant applied
current density of 4 A/dm2, varying the electrolyte temperature
in the range from − 5 °C up to 15 °C hardly influences the
 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317
abrasion resistance of the resulting AAF. Another study by
Koizumi et al. [3], dealing with galvanostatic anodizing at
current densities from 1 to 8 A/dm2 in a mixed sulphuric acid–
oxalic acid electrolyte at temperatures, varied between − 5 °C
and 20 °C, report an almost constant wear resistance in the
temperature range [− 5 °C to 5 °C], regardless of the applied
current density. In the temperature range [5 °C to 20 °C] on the
other hand, the authors observed a decreasing wear resistance
with increasing electrolyte temperature, with the effect being
more pronounced for the lower applied current densities. This
latter observation should be handled with care, though, since the
anodizing process was always performed for a duration of
45 min, regardless of the applied current density. Hence thicker
oxide films were probably formed and evaluated for the higher
current densities, whereas film thickness influences the wear
resistance and hardness of the AAF [2,4–6].
Anodizing to form thick oxide films in a sulphuric acid
electrolyte at more elevated temperatures than those considered
during hard anodizing often leads to the formation of anodic
oxides with inferior hardness and wear resistance. Porous anodic
oxides with a thickness of 25 μm or more, formed in a sulphuric
acid electrolyte at temperatures between 15 °C and 30 °C (under
different applied current densities from 1 up to 4 A/dm2) are
reported to be characterised by a softer outer layer which reduces
the transparency and wear resistance of the AAF [7,8]. On the
level of the microhardness a similar effect has been observed
across a 25 μm thick AAF grown in a sulphuric acid electrolyte
between 0 °C and 25 °C. Whereas at 0 °C an oxide with a uniform
microhardness was formed, the microhardness of similar films
grown at higher temperatures decreased from the metal base
towards the oxide surface with this declining evolution becoming
more pronounced with increasing temperature [9].
Together with the mechanical properties the process of oxide
formation and the microstructure of the AAF are also influenced
by variation of the electrolyte temperature. With increasing
electrolyte temperature the aggressiveness of the electrolyte
towards the oxide increases accordingly, hence enhancing the
chemical dissolution of the AAF by the electrolyte [10,11].
Under potentiostatic anodizing conditions this increased
aggressiveness leads to higher steady state current densities,
which imply a higher oxide formation rate [12]. Equal
anodizing time and applied potential will induce the formation
of thicker oxide layers as the electrolyte temperature is
increased [12,13], given that the maximum film thickness
under the considered conditions is not reached [14].
Concerning the influence of the electrolyte temperature on
the microstructure of the oxide film formed under potentiostatic
conditions, some authors report an increasing electrolyte
temperature to induce a declining barrier layer nm/V-ratio,
and hence a decreasing barrier layer thickness and pore diameter
[15]. More recent studies on the other hand indicate the barrier
layer thickness to be independent of the electrolyte temperature
Table 1
Applied anodizing times for the different considered electrolyte temperatures
Electrolyte temperature (°C) 5 15 25 35
Anodizing time (s) 8100 4500 2400 1100
7311
Fig. 1. Example of evolution of local anode temperatures on different radial
positions during anodizing at electrolyte temperature of 35 °C.
and to be determined by the applied potential [13,16]. Generally
accepted is the concept of the enhanced chemical dissolution of
the oxide by the electrolyte at elevated temperatures leading to
conically shaped pores with an increasing pore diameter
towards the surface of the AAF [15,17]. Accordingly the
dissolution of material from the pore walls increases the
porosity of the porous oxide film [13,17].
Despite the information available in literature on the
influence of the anodizing temperature on the mechanical
properties and on the microstructure of porous AAF, studies
which consider both aspects and which link the measured
mechanical properties with the observed microstructure are rare.
In this study the influence of the electrolyte temperature on
the microhardness and on the wear resistance of porous AAF
grown in a sulphuric acid electrolyte has been evaluated over a
wide temperature range. In contrast to common anodizing
experiments in a stirred electrochemical cell, anodizing was
performed under conditions of controlled convection and heat
transfer in a reactor with a wall-jet configuration. In addition to
the control of the convective heat transfer, the evolution of the
local electrode temperature during anodizing was measured at
different radial positions on the backside of the aluminium
anodes. The latter features enabled the verification of whether
regular anodizing behaviour, e.g. without the occurrence of
local phenomena such as “burning”, was encountered [12,18].
The microstructure of the formed anodic films has been
observed by plane and cross-sectional FE-SEM analyses,
whereas image analysis performed on high-resolution images
of the surface yielded quantitative information on the evolution
of the surface porosity as a function of the electrolyte
temperature. Hence measured mechanical properties of the
porous oxide films have been directly related to and explained
by the observed corresponding microstructure.
2. Experimental
45 55 For the evaluation of the microhardness and for FE-SEM
570 360
analysis disk shaped AA1050 (99.5% Al sheet 0.3 mm) samples
7312 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317
Table 2
Fretting test parameters
Parameter Value
Stroke length 100 μm
Normal load 2N
Test frequency 10 Hz
Number of cycles 25 000
Temperature room
Relative humidity 50% ± 5%
Counter body Corundum ball
of 55 mm diameter were used with the diameter of the active
surface of the working electrode (WE) being 40 mm. Prior to
anodizing samples were alkaline etched in 60 g/l NaOH solution
at 40 °C for 60s, followed by a desmutting treatment consisting
out immersion in a 1:1 concentrated HNO3:H2O solution at
room temperature during 60 s. The samples used for the
evaluation of the wear resistance were electrodes of AA1050
(99.5% Al sheet 1.0 mm) material with a similar geometry,
which prior to anodizing had been mechanically polished.
Anodizing was performed in a wall-jet electrode reactor,
which has already successfully been employed for anodizing
and of which the design and construction are reported else-
where [12,18,19]. In this configuration the electrolyte flow
pattern is due to a submerged fluid jet impinging perpendic-
ularly on the working electrode and spreading out radially, with
the fluid outside the jet being at rest [20]. The characteristics
of the convection are described in literature, for laminar as
well as for turbulent flow [20–23]. As anodizing electrolyte a
145 g/l H2SO4 + 5 g/l Al2(SO4)3.18H2O solution was used.
Thermostatic control of the electrolyte temperature (± 0.1 °C)
was ensured by a Lauda RP845 thermostat that controlled the
flow of H2O through a glass heat exchanger immersed in the 45l
electrolyte reservoir and which was equipped with an external
PT-100 temperature probe. The different considered electrolyte
temperatures were varied from 5 °C to 55 °C in 10 °C steps.
Convection was controlled to a flow condition corresponding to
a Reynolds number of 1500 (based on the nozzle diameter).
Anodizing was performed under potentiostatic conditions
during which a constant potential difference of 17.0 V was
applied between the WE and the aluminium counter electrode
(CE) by a Tacussel power supply. The evolution of the current
and voltage during anodizing was monitored on a Nicolet 310
oscilloscope. Depending on the considered electrolyte temper-
ature different anodizing times were considered in order to
acquire anodic oxide layers with thicknesses in the region of
20 ± 2 μm. They have experimentally been determined for each
electrolyte temperature by trials during which anodizing time
was varied. Corresponding thicknesses of the formed anodic
oxide layers were measured by eddy current measurements
made with a calibrated Fischer Dualscope MP20 (to an accuracy
of ± 1 μm). The oxide thicknesses on the samples for mechanical
testing and FE-SEM analyses were verified in a same manner.
An overview of the anodizing times as a function of the
electrolyte temperature is presented in Table 1.
Local temperatures were measured at the backside of the WE
by five thermocouples (type T), embedded in the sample holder
at 5 different radial positions, these being − 15 mm, − 10 mm,
0 mm, 5 mm and + 15 mm from the centre of the anode
respectively. Fig. 1 depicts an example of a logged evolution of
local anode temperatures during anodizing at an electrolyte
temperature of 35 °C. The advantage of this feature of the
reactor in the framework of this study was the possibility to
verify and guarantee that the anodized electrodes had displayed
a regular anodizing behaviour without occurrence of local
phenomena.
The microhardness of the different oxide films was evaluated
on a Struers Duramin 2 microhardness tester using a Knoop
indenter and a load of 100 gf was applied for 10 s. The optical
transparency of the oxide film hampered the determination of
the indentation length by means of optical microscopy. Hence
FE-SEM images of the indentations were recorded, on which
the indentation length was measured using JEOL SMile View
software for image processing. Corresponding microhardness
values were determined using tables found in [24]. For each
anodizing condition the mean value of a minimum of 30
measurements was considered.
Fretting tests were carried out by using a ball-on-flat
geometry where a corundum of diameter 10 mm (Ceratech,
The Netherlands) acted as the counter body and the anodized Al
substrate acted as flat. The anodized aluminum specimen was
mounted on a translation table and was reciprocated in the
horizontal plane at a frequency of 10 Hz and amplitude of
100 μm by means of a linear ac-servomotor. The displacement
of the table was monitored by an incremental encoder, whose
signal was also sent to the computer via an amplifier. Details of
the fretting test conditions are given in Table 2. After the fretting
experiment, the volumetric wear loss was determined by white
light interferometry (Wyko NT Series, Optical 3D Profiling
Systems).
FE-SEM observations were performed using a Jeol JSM-
7000F FE-SEM. In order to avoid charging effects due to the
non-conductive properties of the oxide, the surfaces of the
samples for FE-SEM analysis were covered with a 1.5 nm Pt/Pd
Fig. 2. Evolution of the microhardness of the anodic oxide layer in function of
the electrolyte temperature.
 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317
Fig. 3. Evolution of the wear volume of the anodic oxide layer (i.e. the volume
removed by the corundum ball during wear testing) in function of the electrolyte
temperature.
layer, applied by a Cressington 208 HR sputter coater equipped
with a Cressington MTM-20 thickness controller.
Image analysis, which enabled to acquire quantitative
information on the porosity of the AAF at the surface, was
performed by using the ImageProPlus software on high-
Fig. 4. FE-SEM images of the surface of porous anodic films formed at electrolyte temperatures of a) 5 °C, b) 35 °C and c) 55 °C. d) converted binary image of b), the
white spots correspond to pore mouths.
7313
resolution images of the oxide surface. The micrographs were
at first transformed to a binary format, whereupon particle
analysis was applied for the estimation of the percentage (%) of
the total surface of the oxide occupied by the pores. Three
micrographs of each oxide were analysed in order to determine
the average value of the porosity.
Information on the microstructure of the porous film at
different depths was obtained by acquiring high-resolution FE-
SEM cross-section images of the oxides at 3 different depths:
the pore base, at a depth of 10 ± 1 μm (i.e. in the middle of the
oxide layer) and near the surface of the oxide. On these images
the diameters of the observed cross-sectioned pores were
measured using the Jeol SMile View software; at every position
the mean value of minimum 20 measurements was considered.
3. Results
3.1. Microhardness measurements
The observed evolution of the microhardness of the anodic
oxide layers as a function of the electrolyte temperature is
depicted in Fig. 2. With increasing electrolyte temperature a
decreasing microhardness, evaluated at the surface of the oxide,
was recorded. The results display a linear decrease in the
temperature range [15 °C to 45 °C], with the microhardness
7314 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317

thicknesses. Considering the surface of the AAF formed at

55 °C, as is presented in Fig. 4c, it could be noted that at some
locations the oxide walls between neighbouring pores had
completely been dissolved, inducing a merging of the involved
pore mouths. For all the considered electrolyte temperatures
similar images, yielding qualitative information, were converted
into binary images suitable for image analysis with the latter
providing quantitative information on the observed features. As
an example the binary image corresponding to Fig. 4b is
depicted in Fig. 4d, in which the white spots correspond to the

Fig. 5. Evolution of the porosity, determined at the oxide surface, in function of

the electrolyte temperature.

values of the aluminium electrodes anodized at 5 °C and 55 °C

slightly deviating from this tendency. The former electrodes
possessed a higher microhardness than found by extrapolation
of the linear trend line, whereas on the 55 °C anodes a lower
microhardness than deduced from the linear evolution was
measured.

3.2. Wear resistance

In contrast to the microhardness, the fretting wear resistance

of the anodized electrodes exhibited a different relation as a
function of the electrolyte temperature. Fig. 3 illustrates the
evolution of the wear volume of the anodic oxide layer (i.e. the
volume removed by the corundum ball during wear testing) as a
function of the electrolyte temperature. Within the margins of
the error bars, a similar value for the wear volume was measured
for the lower of the considered temperatures up to 25 °C,
whereas from this electrolyte temperature on the wear volume
increased with the electrolyte temperature. Like microhardness
the increase in wear volume displays a linear trend in the
temperature range [25 °C to 45 °C], though it is followed by a
pronounced increase between 45 °C and 55 °C. Hence the wear
resistance of the anodic oxide layers (which is inversely
proportional to the wear volume) remained constant from 5 °C
to 25 °C, then subsequently decreased with increasing
electrolyte temperature, first linearly from 25 °C to 45 °C and
finally significantly from 45 °C to 55 °C.

3.3. Microstructure

FE-SEM images clearly displaying the pore structure at the

surface of the porous oxides formed at different temperatures
were captured at high magnifications. Fig. 4a, b and c represent
pictures of the porous anodic oxides formed at electrolyte
temperatures of 5 °C, 35 °C and 55 °C respectively. The surface
of the oxide formed at 5 °C possessed a dense structure with
small pores and separated by thick pore walls, whereas with Fig. 6. FE-SEM images of a cross section of a porous anodic film formed at
increasing electrolyte temperature the structure became more electrolyte temperatures of 55 °C a) at the pore base b) at a depth of 10 ± 1 μm
open with increasing pore diameters and declining wall and c) near the surface.
 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317
Fig. 7. Evolution of the pore diameter, determined at the pore base, at a depth of
10 ± 1 μm and near the oxide surface, in function of the electrolyte temperature.
observed pore mouths. The calculated porosity as a function of
the electrolyte temperature is displayed in Fig. 5. With
increasing anodizing temperature an increasing porosity at the
surface of the AAF was recorded. This inclining evolution
became more pronounced for the higher electrolyte tempera-
tures, leading to an increase in porosity from 4% for the
electrode anodized at 5 °C up to 32% for the corresponding
anode formed at 55 °C.
The pore structure of the AAF was studied by FE-SEM
analyses on cross sections of the oxide films at the 3 previously
mentioned positions: the pore base, in the middle of the anodic
layer and near the surface. An example of these observations is
presented in Fig. 6a–c, which display FE-SEM images at these
three positions of a cross sectioned oxide formed at 55 °C.
Based on these images, which allowed accurate measuring of
the diameter of the observed pores, the in-depth evolution of the
pore diameter of the oxide films was determined, and is
presented in Fig. 7. In general, for all considered temperatures
the pores became wider with decreasing depth, i.e. from the
pore base towards the oxide surface. At the pore base a constant
pore diameter of 10 ± 1 nm was observed, regardless of the
electrolyte temperature. Over the entire film thickness the pore
diameters observed on electrodes anodized at 5 °C and at 15 °C
displayed similar values, whereas in the temperature range from
15 °C to 55 °C the pore diameters in the middle of the oxide and
near the surface increased with increasing electrolyte temper-
ature. The latter phenomenon was seen to take place on a
moderate level from 15 °C to 35 °C, though became more
noticeable as temperature increased from 35 °C to 55 °C.
Additionally the widening of the pores with increasing
temperature was more pronounced near the surface of the
AAF than at half film thickness.
4. Discussion
4.1. Influence of electrolyte temperature on microstructure
All anodizing experiments, performed at the different
electrolyte temperatures, were executed under potentiostatic
7315
conditions during which an equal potential difference of 17.0 V
was applied. During steady state anodizing the pore diameter of
the porous anodic oxide (as well as barrier layer thickness and
cell diameter) is known to be directly related to the applied
potential [15], hence porous oxides with similar pore diameters
should have been formed. Near the pore base indeed a constant
pore diameter, regardless of the electrolyte temperature, was
found (cf. Fig. 7). In contrast, at the other positions in the oxides
– which contrary to region near the pore base already had been
exposed to the electrolyte – different pore diameters were
observed as a function of the position in the film as well as a
function of the electrolyte temperature. For all the considered
electrolyte temperatures the pore diameter increased towards the
oxide surface leading to cone-shaped pores. Since the oxide
formation process occurs at the regressing metal-oxide
interface, the oxide at the surface being most recently formed,
i.e. near the pore base, the described phenomenon of pore
widening increases with increasing time of exposure to the
electrolyte and its dissolving action. The constant pore diameter
found near the pore base, where the oxide is freshly-formed and
has not yet been exposed to the aggressive electrolyte for a
significant time, confirms that originally porous oxide films
with similar pore diameters were formed, regardless of the
electrolyte temperature. Hence in a specific electrolyte for a
wide temperature range the pore diameter at the pore base only
depends on the anodizing voltage that determines the electrical
field distribution. Hence the observed differences in micro-
structure of the formed oxides originate from differences in the
aggressiveness of the electrolyte towards the oxide induced by
varying the electrolyte temperature. And thus is most striking in
the near-surface area where the oxide dissolution is greatest due
to the longest exposure time. For example, at an electrolyte
temperature of 55 °C, after an exposure time of 360 s, the pore
structure near the surface of the 20 μm thick oxide was to a large
extent dissolved. Only thin cell walls, at some locations already
“perforated” (Fig. 6c) combined with occasional coalescence of
pore mouths at the surface, remained (Fig. 4c). The near-surface
region of the 20 μm thick anodic oxide formed at 5 °C on the
other hand still displayed a dense oxide structure with relatively
narrow pores and thick cell walls even after an exposure time of
8100 s.
The effect of enhanced oxide dissolution with increasing
electrolyte temperature that leads to a more porous oxide
structure near the surface was considered quantitatively through
the determination of the porosity by image analysis. When the
evolution as a function of the electrolyte temperature of the
determined porosity at the surface (Fig. 5) and the observed
evolution of the pore diameter near the surface (Fig. 7) were
compared, a similar trend was discernable. In both graphs more
or less similar values were found for the oxides formed at
electrolyte temperatures 5–15 °C and 25–35 °C, with higher
measured values of the pore diameter and porosity for the latter
rather than for the former one, followed by a pronounced
increase between 35 °C and 55 °C. This strong increase in
porosity (and pore diameter) with increasing electrolyte
temperature for the higher electrolyte temperatures suggested
an accordingly enhanced oxide dissolution rate under these
7316 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317
anodizing conditions, certainly when taking into account the
reduced anodizing times.
Related to the electrolyte temperature another parameter of
importance in relation with the properties of the anodic oxide
film is the local electrode temperature. Anodizing of aluminium
is a process during which heat is produced, the main heat source
being the Joule heating of the oxide-covered anode by electrical
power dissipation. This heat, which is mainly produced in the
vicinity of the aluminium anode, can effectively be removed by
electrolyte convection [12]. Hence, anodizing under conditions
of insufficient convective heat transfer will lead to a local
accumulation of the produced heat near the anode, accompanied
by a rise of the electrode temperature. Due to the latter effect
local phenomena, such as burning, are likely to arise and oxide
films with a locally modified (micro)structure will be formed
[12,18,19]. Therefore the monitoring of the local anode
temperatures during anodizing not only yields valuable
information concerning the temperature of the electrode itself,
but also provides a tool for verification whether the considered
conditions of convective heat transfer are appropriate to avoid
the occurrence of local anomalous oxide growth. In this study
the observed change in local electrode temperatures, as for
example shown in Fig. 1, indicated normally evolving electrode
temperatures for all the different considered conditions. As a
result, the selected (and controlled) conditions of convection
ensured sufficient heat removal during anodizing at all the
considered electrolyte temperatures, thus producing anodic
oxide films which really have the microstructure (and cor-
responding mechanical properties) representative for the chosen
condition.
4.2. Influence of electrolyte temperature on mechanical
properties and relation with microstructure
The thermally enhanced effect of oxide dissolution by the
electrolyte is most pronounced in the near-surface region.
Therefore the mechanical properties of the outer region, near the
oxide surface, are known to differ from the corresponding
properties in the bulk of the anodic film [2,8,9,25]. Nonetheless
for this study it was deliberately decided to evaluate the
microhardness and the wear resistance of the outermost region
of the oxide since for many applications the behaviour of this
upper layer is of interest. Moreover, concerning the evaluation
of the wear resistance the techniques for assessing this property
of the outer region are well understood for anodic film thinner
than 25 μm, since for these oxide films the measured layer is a
significant part of the oxide [25].
The decreasing microhardness with increasing electrolyte
temperature was an expected trend that was in line with the
observed porosity increase with temperature. The higher the
porosity of the anodic layer the less material present in the oxide
film to resist the indentation load, hence the softer the anodic
film was expected to be. Though however the recorded decline
in microhardness did not completely match the degree to which
the porosity increased. The decrease in microhardness upon the
increase in electrolyte temperature from 45 °C to 55 °C,
exceeding the reduction deduced by linear extrapolation, could
be linked to the observed significant growth in porosity and to
the highly dissolved oxide structure formed by the anodizing
process at the latter temperature. On the other hand, the
evolution of the microhardness in the remaining temperature
range differed from the corresponding observed change in
porosity. Considering the evolution of the porosity as a function
of the electrolyte temperature small deviations between 5 °C
and 15 °C, and between 25 °C and 35 °C were observed,
whereas the microhardness displayed almost equal differences
between successive temperatures in the range [15–45 °C] and
even an increased difference between the anodic layers formed
at 5 °C and 15 °C. Apparently, beside the porosity and oxide
thickness other parameters, which were unaccounted for,
influenced the microhardness. In order to exclude a possible
difference in composition of the oxide layers (e.g. a difference
in sulphate concentration in the anodic film), EDX analyses
were performed in plan view on the different oxide layers. No
compositional differences were detected in the analysed volume
of the outer 3.0 ± 0.5 μm3.
For the higher temperatures in the range [25–55 °C] the
evolution of the wear resistance of the anodes as a function of
the electrolyte temperature almost matched the corresponding
evolution of porosity. In this temperature range where the
increased aggressiveness of the sulphuric acid electrolyte
produces an increasingly porous film especially in the near-
surface oxide region exposed to an increasing extent of
chemical dissolution, appeared to play a key role in the
deterioration of the wear resistance of the anodic layer. When
considering the lower electrolyte temperatures from 5 °C up to
25 °C, no influence of the electrolyte temperature on the wear
resistance of the anodic film was observed. This result was in
line with the data of Scott [2] who saw a limited influence of the
electrolyte temperature on the abrasion resistance of the anodic
film in the range from − 5 °C up to 15 °C. Though care must
taken when making this comparison as in Scott's study the wear
resistance was determined by considering an abrasive jet test
which yields a bulk property, whereas the in this study
considered fretting wear test tends to give information about
the wear resistance of the outer part of the oxide layer [8,25].
The observed effect of increased pore widening towards the
surface, which became more pronounced with increasing
temperature, could be accounted for by the formation of anodic
films with inferior wear resistance and hardness towards the outer
regions of the oxide (a softer outer layer), and which are reported
to be obtained by anodizing at more elevated temperatures than
those considered during hard anodizing [7–9].
5. Conclusions
In this study the microhardness and wear resistance, as well
as the microstructure of porous anodic oxides, produced by
anodizing of 99.5% pure aluminium electrodes under controlled
conditions while varying the electrolyte temperature in the wide
range from 5 °C to 55 °C, were evaluated.
The microhardness of the anodized electrodes progressively
decreased with increasing electrolyte temperatures. The wear
resistance of the anodic oxide films, evaluated by means of
 T. Aerts et al. / Surface & Coatings Technology 201 (2007) 7310–7317
fretting wear tests, remained constant for the lower considered
temperatures from 5 °C to 25 °C, whereas from 25 °C on an
increasing electrolyte temperature led to the formation of anodic
films with reduced wear resistance. Both mechanical properties
displayed an important decrease when the electrolyte temper-
ature was raised from 45 °C to 55 °C.
FE-SEM analyses of the oxide films showed that under the
considered potentiostatic anodizing conditions initially porous
oxides with equal pore diameters were produced at the metal-
oxide interface, though chemical dissolution of the oxide by the
electrolyte induced the formation of cone-shaped pores. Hence
in a specific electrolyte for a wide temperature range the pore
diameter at the pore base only depends on the anodizing voltage
that determines the electrical field distribution. On the other
hand, due to the thermal enhancement of the chemical
dissolution of the oxide by the electrolyte the increase of the
pore diameter towards the oxide surface becomes more
pronounced with increasing electrolyte temperature. On the
account of this effect the porosity of the oxides at the surface,
quantitatively determined by image analysis, increased from 4%
at 5 °C up to 32% at 55 °C.
The decrease of the microhardness of the anodic oxide with
increasing electrolyte temperature was in line with the increase
of the porosity with temperature. The wear resistance of anodic
oxide films also degraded with increasing electrolyte temper-
ature, though this tendency did not completely match to the
observed increase in porosity with temperature. Hence the
deterioration of the microhardness with increasing electrolyte
temperatures was mainly attributed to the increase of the
porosity in the outer region of the oxides. In contrast, the
observed variation of the wear resistance with increasing
electrolyte temperature could not solely be related to the oxide
porosity and was apparently also influenced by other charac-
teristic(s) of the oxide, as for instance the degree of hydration.
Overall this paper highlights the important influence of the
electrolyte temperature on the microstructure and mechanical
properties of the anodic film and further emphasizes the
significance that electrolyte convection and heat transfer of the
anodizing process have in terms of influence on the mechanical
properties of the anodic oxide film.
Acknowledgements
The authors acknowledge the support from the Instituut voor
de aanmoediging van innovatie door Wetenschap & Technolo-
7317
gie in Vlaanderen (IWT, contract nr. SBO 040092). M. Peeters
(KULeuven, dept. MTM) is greatly acknowledged for the
performed wear tests.
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