Surface & Coatings Technology 204 (2009) 829–833

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

High temperature wear behavior of aluminum oxide layers produced by AC micro

arc oxidation
E. Arslan a,⁎, Y. Totik b, E.E. Demirci b, Y. Vangolu b, A. Alsaran b, I. Efeoglu b
a
Erzurum College of Vocational Ataturk University 25240 Erzurum, Turkey
b
Ataturk University, Department of Mechanical Engineering, Faculty of Engineering, Erzurum, Turkey

a r t i c l e i n f o a b s t r a c t

Available online 1 October 2009 Aluminum alloys are becoming increasingly important, especially in the automotive and aerospace
industries. However, these materials tend to have poor wear resistance at atmospheric and high temperature
Keywords: conditions. Aluminum oxide layers are potentially very effective in developing hard, wear-resistant surfaces.
Aluminum alloys The aim of present study was to evaluate the high temperature wear behavior of aluminum oxide layers at
Micro arc oxidation different temperatures by using high temperature pin-on-disc tribo tester and alumina balls as counterfaces.
High temperature The aluminum oxide layers were produced by AC micro arc oxidation (MAO). The structural analyses of the
Wear
layers were performed using XRD and SEM techniques. The hardness was measured using microhardness
tester. The wear rates and friction coefficient was decreased with increasing wear test temperature. The
lowest wear rate and friction coefficient, narrow and smooth wear tracks are obtained at 200 °C.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction increasing interest in fabricating ceramic-like coatings on aluminium,

magnesium and titanium alloys, with the purpose of providing
Aluminum and its alloys are desirable materials due to high corrosion and wear resistance or various functional properties
strength stiffness to weight ratio, good formability, good corrosion [5,14–19]. It is characterized by high productivity, economic efficien-
resistance, and recycling potential for use in automobile industries as cy, ecological friendliness, high hardness, good wear resistance, and
components of internal combustion engines, e.g., cylinder blocks, excellent bonding strength with the substrate [5,20–24].
cylinder heads and pistons [1]. These components are subject to high In the work reported here, a thick, hard layer is produced on
temperature during service. These alloys are susceptible to wear when AA2014 aluminum alloy using MAO at unipolar mode. The structural
matched to harder surfaces under high loads at elevated temperatures analysis of the layers is investigated using X-ray diffraction (XRD).
[2,3]. Some attempts have been made to overcome these problems of Surface morphology and thickness of the layers are examined by SEM.
aluminum and its alloys by means of many surface engineering Tribological tests are carried out at room temperature, 50 °C and
techniques such as chemical vapor deposition (CVD), physical vapor 200 °C. The tribological performances of the layers were evaluated at
deposition (PVD), ion beam assisted deposition, thermal spraying and room and high temperature.
anodizing. Besides these, there has been increased interest to modify
the surface properties of aluminum and its alloys by micro arc 2. Experimental
oxidation (MAO, also named as plasma electrolytic oxidation or
anodic spark oxidation) in the recent years. AA2014 aluminum alloys, whose chemical composition is given in
Micro arc oxidation (MAO) is a potential process to uniformly Table 1, were used as the substrate material. Plate substrates with
synthesize the ceramic-like oxide layers on aluminum by discharging dimensions 25 × 25 × 4 mm were polished to a roughness of
sparks at a high voltage. This technique runs at potentials above the Ra ≈ 0.1 µm, cleaned with acetone, ethanol and distilled water prior
breakdown voltage of the oxide film growing on the surface of an to MAO process. MAO treatment of the aluminum alloys was
aluminum anode by using high voltage, low frequency, AC supply in performed in the MAO-15 system designed and built by Plasma
dilute alkaline electrolytes [4–6]. The oxide layers grown by MAO of Technology Ltd. Aqueous solution of KOH, Na2HPO4 and Na2SiO3 was
aluminum alloys are thick (≈100 µm), hard and adherent to the used as the electrolyte. Deionizing (DI) water was used to prepare the
substrate. The layers consist typically of porous top layer, dense
intermediate layer and thin inner layer [2,7–13]. MAO is attracting Table 1
The chemical composition of AA 2014 substrate.

Material (wt.%) Cu Mg Mn Si Fe Cr Sn
⁎ Corresponding author. Tel.: + 90 442 2312649; fax: +90 442 2360982.
AA2014 5.0 0.68 0.58 0.83 0.23 0.04 0.03
E-mail address: [email protected] (E. Arslan).

0257-8972/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2009.09.057
830 E. Arslan et al. / Surface & Coatings Technology 204 (2009) 829–833

and cooled to prevent heating over 30 °C. After the MAO process, the
oxidized samples were washed with distilled water and dried at room
temperature.
The fractured cross-sections, oxide thickness and surface mor-
phology of the layers at constant current using unipolar mode were
analyzed by a scanning electron microscope (SEM-Jeol-6400). The
microhardness of the samples was tested using a Buhler Microhard-
ness Tester. The oxidized samples were polished using 0.05 μm
diamond paste, before the measurement of hardness. At least five
indentations at different places on the film surface were measured
and averaged under 10 gf load for each sample.
Tribological properties at high temperatures of the layers were
evaluated by a pin-on-disk tester (CSM high temperature tribo tester).
All the experiments were conducted with Al2O3 ball with the diameter
of 6 mm in sliding contact. The tests were carried out with a load of
2 N at the linear speed of 50 mm/s and in dry sliding condition at
room temperature and at the temperatures of 50 °C and 200 °C in
atmospheric conditions. After the tribological tests, the images of the
wear tracks were analyzed by means of SEM. Surface profiles of the
wear tracks on the layers were measured by a Mitutoyo surface
profilometer. The wear volume was calculated using the profiles
obtained from the wear track cross-section, and thus the wear rate
was attained using K = V / (w · s) equation, where K is the value of the
wear rate, V is the worn volume, w is the normal load, and s is the
distance moved.
XRD scans were performed using a Rigaku 2000 Dmax diffrac-
tometer equipment with a Cu-Kα radiation source before and after
the tribological tests. The measurements were carried out between 30
and 80° scan range, and at the scan speed of 2°/min. Interpretation of
the X-ray results was undertaken using JCPDS files.

3. Result and discussion

The surface morphology and thickness of MAO layers are shown in

Fig. 1. SEM images of a) surface topography and b) cross section of the MAO Al2O3
layers.
Fig. 1a and b, respectively. As shown in Fig. 1a, there were platelets
indicating the formation of molten alumina that are rapidly solidified
due to a quenching effect of the surrounding electrolyte on the surface
aqueous solution. MAO process was carried out at unipolar mode with [25]. Furthermore, the surface micrograph of layer clearly indicated
AC power supply. A unipolar mode at constant current of 1.2 A and the presence of discharge channels forming as dark circular pieces and
100 Hz was applied to substrate for 60 min. The unipolar process was spots dispersed all over the surface. The lamellar circular pieces were
performed at a 50% positive pulse duty cycle. The sample and stainless also around pores like volcano top. The cross-sectional micrography of
steel container walls were used as the anode and cathode, MAO layer is shown in Fig. 1b. The micrography revealed that the
respectively. During the oxidation process, the electrolyte was stirred MAO layer formed at unipolar mode was about 10 μm in thickness.

Fig. 2. XRD multiplot spectra of aluminum substrate and the MAO Al2O3 layers.
 E. Arslan et al. / Surface & Coatings Technology 204 (2009) 829–833 831

The layer/substrate interface was clear, and exhibited a good arc channels increases and sprinkle of melted materials on surface
metallurgical adhesion between layer and substrate. It was deter- leads to high surface roughness [26,27].
mined that the surface roughness increased, as compare to substrate XRD analysis of MAO layers and aluminum alloy are shown in
roughness. The substrate with surface roughness of Ra ≈ 0.1 μm, Fig. 2. The aluminum alloy substrate is composed of Al phases. The
increased to Ra ≈ 0.87 µm after the MAO process. Local melting into MAO layer on Al alloy is consist of α-Al2O3 and γ-Al2O3 phases (see

Fig. 3. The friction coefficients vs. lap, time and distance and the SEM images of the wear track and surface morphology of all the samples.
832 E. Arslan et al. / Surface & Coatings Technology 204 (2009) 829–833

Table 2 morphology and wear track of layer and substrate after the
The changes in the friction coefficients of the MAO coatings at different temperatures tribological tests are given in same Fig. 3. Besides, Table 2 shows the
and aluminum substrate.
minimum, maximum, mean and standard deviation of the coefficient
Sample Start Minimum Maximum Mean Std.dev. of friction for all the samples. It was obviously seen from Fig. 3 that the
AA 2014 substrate 0.12 0,12 0.83 0.74 0.04 friction coefficient of AA 2014 aluminum substrate was considerably
Wear test at room temperature 0.18 0.18 0.62 0,55 0.07 unstable and approximately µ = 0.74. The unstable behavior of the
Wear test at 50 °C 0.22 0.19 0.50 0.45 0.04 friction coefficient for the substrate was related to fracture of passive
Wear at 200 °C 0.25 0.24 0.52 0.39 0.03
oxide layer under load. The graphs at room temperature and 50 °C
show that the friction coefficient started low and then gradually
Fig. 2). In the spectra, reflection (214)α and (400)γ with strong increased during test. However, the friction force started similarly low
diffraction intensities was identified as the diffraction peaks of α- and then remained constant with time at 200 °C. After initial stage, the
Al2O3 and γ-Al2O3, respectively. The reflection of (110)α, (211)α and increase in friction coefficient for room temperature and 50 °C
(222)γ at relatively low intensity were also detected on layers. The resulted from abrasive effect of hard α-Al2O3 phases. The stable
microhardness of the layer was measured as 1200 HV. The high trend in friction of coefficient of sample at 200 °C can be explained
hardness value was related to the distribution and intensity of the with the re-modification of the surface topography, low shear force
hard α-Al2O3 phases. involved during sliding and the formation of a solid lubricant due to
The tribological tests of MAO layers were performed at room the introduction of wear debris. The change of surface topography for
temperature and 50 °C and 200 °C. After the tribological tests, each this temperature can be seen in Fig. 3. The pores dispersed
sample was analyzed to evaluate the change on the surface morphology homogeneously on the surface were obtained for 200 °C tests. On
and phases by XRD and SEM. The wear tracks were also observed using the other hand, no significant changes were seen on the surface
SEM. The graphic showing the relationship between the friction morphologies of the specimens which were tested at room temper-
coefficient and the lap, the surface morphology and the wear tracks of ature and at 50 °C. Besides, it was determined that the wear test
all MAO layers and aluminum substrate are given in Fig. 3. temperatures changed surface roughness of the layers. The variations
Evolution of the friction coefficient with wear time, lap, and on surface roughness are given in Fig. 4. There were not considerable
distance for the aluminum substrate and MAO layer sample under dry differences at the peaks in XRD studies after the tribological tests at
friction condition against Al2O3 ball is shown in Fig. 3. The surface room temperature, 50 °C and 200 °C, as seen in Fig. 5. But the peaks

Fig. 4. The wear rates and surface roughness of all the samples and an example wear track profile.

Fig. 5. XRD multiplot spectra of the layers after tribological tests.

 E. Arslan et al. / Surface & Coatings Technology 204 (2009) 829–833 833

were relatively shifted to low angles with increasing of the wear test friction tendency and stable friction behavior was observed at
temperature. The SEM was used to compare the wear track 200 °C. The wear rates decreased with increasing temperature. The
morphology after the tribological test at room temperature, 50 °C lowest wear rate and narrow and smooth wear tracks are obtained
and 200 °C (see Fig. 3). The stable and unstable behaviour of the at 200 °C.
friction coefficients were also supported by the wear track images and
wear rate. Depending on the test temperature, different values were
obtained for the wear rates. The wear rates decreased with an Acknowledgments
increasing temperature. An example wear track profile and the wear
rates as a graphic at different temperatures are presented in Fig. 4. The The authors would like to thank the Scientific and Technological
lowest wear rate was determined for the tests performed at 200 °C. Research Council of Turkey for funding the project by grant no:
The wear track images at different temperatures are given in Fig. 3. It MAG107M313.
was observed that the wear tracks at room temperature and at 50 °C
were quite rough, abrasive particles and debris. On the other hand, the References
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