Materials Chemistry and Physics 82 (2003) 370374

Preparation and self-lubrication treatment of ordered porous anodic

alumina film
Yanchun Zhao, Miao Chen , Weimin Liu, Xiang Liu, Qunji Xue
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
Received 19 December 2002; received in revised form 3 April 2003; accepted 25 April 2003

Abstract
Carbon nanofibers were applied into the pores of the porous anodic oxide film (AOF) on aluminum to improve the wear properties of the
alumina film. This encompassed an initial formation of an ordered porous AOF by re-anodizing in oxalic acid and a subsequent development
of the carbon precursors within the pores via the polymerization of acrylonitrile within the pores of AOF. After polymerization, a series of
heat-treating conditions convert the polyacrylonitrile (PAN) polymer structure into a quasi-graphic structure. The sliding wear and friction
properties of self-lubrication films were measured by means of a ball-on-plate apparatus using a steel ball as a counterface. The results
showed that self-lubricating treatment could improve the wear properties of porous anodic film more efficiently.
2003 Elsevier B.V. All rights reserved.
Keywords: Porous anodic alumina film; Polymer; Carbon fibers; Tribology and wear

1. Introduction porous structure of the AOF [3]. It is also recognized that

The high strength to weight ratio of light metals and
their alloys is the key requirements for new applications
in various machinery and transportation system especially
in aerospace and automobile products. Aluminum based
materials, owing to their advantage of high strength to
weight ratio, good corrosion-resistance, and lightweight,
have been finding many applications. However, some short-
comings of aluminum materials including low hardness,
high friction coefficient and difficulty to lubrication limited
the extended application. Various surface treatments such
as physical vapour deposition (PVD), laser irradiation [1,2]
have been applied to aluminum-matrix materials to improve
their generally poor tribological properties. Traditional and
relatively simply anodizing process has also been used to
confer good wear resistance to aluminum and its alloys.
However, hard anodic oxide film (AOF) surfaces have high
friction coefficients when sliding against metal. On the
other hand the endurance life cannot meet the increasing
demands. It has been found that the friction coefficient of
anodic oxide film of aluminum was effectively reduced and
its lubricating performance was improved considerably by
synthesizing or depositing lubricating phase in the regular
Corresponding author. Tel.: +86-931-8277533;
fax: +86-931-8277088.
E-mail address: miaochen@lsl.ac.cn (M. Chen).
porous anodic alumina films are potentially advantageous
as lubricant reservoirs, although they have only received
limited preliminary study on tribology [46].
In this paper, ordered porous alumina film were obtained
on aluminum by re-anodizing in oxalic acid and the carbon
nanofibers were synthesized in the ordered porous anodic
oxidized aluminum film in order to improve the tribolog-
ical properties of the film. The tribological property of
self-lubricating films is also discussed briefly.
2. Experimental
2.1. Anodization
Specimens of 99.999% purity aluminum of dimensions
30 mm 20 mm 0.15 mm were employed prior to anodiz-
ing. The aluminum foils were annealed under nitrogen at-
mosphere at 500 C in order to enhance the grain size in the
metal and to obtain homogeneous condition for pore growth
over large areas. Subsequently, the foils were degreased in
5% NaOH at 60 C for 30 s, rinsed with deionized water
and then electropolished in a 1:5 (v/v) mixture of HClO4
and C2 H5 OH. Anodization was carried out under a constant
potential of 60 V in a 0.3 mol l1 oxalic acid solution for
3 h at 1 C. The alumina formed was then removed with a

0254-0584/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0254-0584(03)00265-7
 Y. Zhao et al. / Materials Chemistry and Physics 82 (2003) 370374 371

Fig. 1. The SEM image of a regular alumina film prepared by two-step

anodization method and clarified in phospholic acid solution. (a) Top
surface structure view of AOF, (b) cross-section view of the resultant
highly ordered nanochannel AOF. Fig. 2. The SEM image of carbon nanofibers after dissolution of the
alumina film.

mixture of phosphoric acid and chromic acid, and the spec-
imen was anodized again under the same condition for 6 h
as mentioned above.
To clarify the pore configuration, the specimen was dipped
in a 5 wt.% phospholic acid solution at 30 C for 30 min for
pore-widening treatment after the anodization.
2.2. Self-lubrication treatment
The porous alumina specimens after pore-widening
treatment were immersed into a 26 ml aqueous solu-
tion of 1.3 mol l1 acrylonitrile. Polymerization reaction
was achieved through the addition of 12 mL of 15 mM
(NH4 )2 S2 O8 , 13 ml of 20 mM NaHSO3 , and a drop of
0.5 mol l1 sulfuric acid, this polymerization was carried
out at 40 C for 2 h. All solutions were purged with nitrogen
prior to and during the reaction. After polymerization, the
specimen was removed from the reaction and allowed to
dry. The composite film was heated at 250 C in air for a
minimum of 1 h for stabilization of the polymer chain, then
the composite was heated at 700 C under argon in a quartz
tube for 1 h for partial graphitization of the polymer.
2.3. Tribological tests
The tribological behavior of the self-lubrication alumina
films was evaluated using a range of dry, reciprocating
pin-on-plate tests on a DF-PM Tribometer (GCr15 steel pin
of 3 mm diameter, wear track of 50 mm length, load of 3 N).
2.4. Analysis
The films and synthesis results were mainly examined
by scanning electron microscopy (SEM, JSM 5600LV) and

(c)
transmittance (arb. units)

(b)

(a)

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )
Fig. 3. FT-IR spectra of PAN fibers with the background alumina film removed (a) after polymerization, (b) after stabilization at 250 C, (c) after
carbonization at 700 C.
372 Y. Zhao et al. / Materials Chemistry and Physics 82 (2003) 370374

Fourier transform infrared spectroscopy (FT-IR, Bio-Rad). 16

X-ray photoelectron spectroscopy (XPS, PHI 5702) was em- (a) C1s
14
ployed to examine the chemical state of carbon fibers/film
composite and confirm that the pores are full of carbon fibers. 12
The sample was obtained as following: after the heat treat-
ment at 700 C, the surface of composite film was polished 10

by sand paper and then ultrasonically cleaned in water to

KCPS

8
eliminate the contaminants.
6

4
3. Results and discussion
2
3.1. Scanning electron microscopic analysis
295 290 285 280 275

Fig. 1a shows the SEM images of an ordered porous alu- Binding Energy(eV)
mina film consisting of a hexagonal close-packed array of
80 nm diameter channels with a density of approximately
1010 cm2 formed by the two-step anodization process and 5
(b) Al2p
clarified in phospholic acid solution. Fig. 1b depicts the
cross-section of the AOF with pores parallel to each other 4

and perpendicular to the surface of the film. This film en-

able one to make thin cylinders of uniform dimensions with 3
KCPS

controlled diameter as small as few tens of nm. As a result,

fibers can be obtained in the host film. Fig. 2 shows SEM
2
images of carbon nanofibers structure prepared in the regular
porous alumina films. It can be clearly seen that the carbon
1
fibers are of equal diameter and have a highly ordered array.
The exposed carbon nanofibers retain the size and shape of
the pores in the AOF template. 0
85 80 75 70 65

Binding Energy(eV)
3.2. Fourier transmission infrared and X-ray
photoelectron spectroscopy results
40
(c) O1s
In order to determine if the polyacrylonitrile (PAN) within 35

the alumina membrane was converted to quasi-graphic ma- 30

terial, the FT-IR spectra were collected after each process-
25
ing cycle. Fig. 3 indicates changes in the FT-IR spectra of
KCPS

PAN fibers after the initial polymerization, stabilization at 20

250 C and carbonization at 700 C, respectively. All spec-

15
tra were obtained after dissolving the porous alumina films.
On the FT-IR spectra of the PAN fibers after polymer- 10

ization (Fig. 3a), the stretching vibration modes of CN 5

(2240 cm1 ) and CH (2950 cm1 ) and the bending vibra-
tion modes of CH (1447 cm1 ) are clearly visible. During
0
540 535 530 525 520
the heat treatment at 250 C in air, the various reactions Binding Energy(eV)
expected in this process, such as cyclization, dehydrogena-
tion, and oxygen uptake occur almost simultaneously [7]. Fig. 4. XPS spectra of C 1s (a), Al 2p (b) and O 1s (c) for carbon
The most prominent changes observed are the decrease and fibers/alumina film composite.
elimination in the CN stretching mode, CH stretching and
bending vibration mode after heating to 250 and 700 C. for nanofibers [10,11]. The binding energy is mainly as-
The detail vibrational structure changes have been shown in cribed to sp2 CC bonding and the spectra include a small
previous work and are indication of quasi-graphitization of peak in the vicinity of 288 eV originated from the CO
the PAN precursor [79]. bonding which derivated from the process of stabilization at
Fig. 4a shows the C 1s regions of typical XPS spectra. The 250 C [8]. Fig. 4b and c shows the Al 2p and O 1s regions of
peaks of binding energy of C 1s are approximately 284.6 eV typical XPS spectrum, the peak of binding energy of Al 2p
 Y. Zhao et al. / Materials Chemistry and Physics 82 (2003) 370374 373

1.0 (a)
Friction Coefficient

0.5

(b)

0.0
0 100 200 300 400 500 600

Sliding cycles

Fig. 5. The variation of the friction coefficient with sliding cycles before (a) and after self-lubrication treatment (b).

and O 1s is approximately 74.2 and 531.4 eV, respectively,
corresponding to characteristic regions of alumina.
3.3. Mechanical properties of self-lubricating film
Fig. 5 shows the test results of measurements described in
Section 2.3. Compared with porous alumina film, a signifi-
cant decrease of friction coefficient is obtained by the forma-
tion of composite film. After self-lubricating treatment, the
mechanism of friction process can be explained as follows
[5]. At the beginning of friction, most of the carbon fibers
are stored in the pores of porous alumina films, only a small
proportion of carbon fibers are present on the surface of the
film. After sliding, carbon fibers in the pores are brought
to the friction surface and thus the friction is reduced be-
tween the film and the steel ball, so the friction coefficient
rapidly decreases to 0.23 (Fig. 5). From the SEM picture
(Fig. 6a and b) of the wear tracks on the hard alumina film,
we find that the wear track turned from rough to smooth
after self-lubrication treatment. This indicates that the car-
bon fibers in the pores of AOF reduce the wear of the steel
ball. Comparing the friction coefficients before and after
self-lubrication treatment, the reduction is about 0.65, which
shows that the lubricating effect of carbon fibers is obvious.
Since the porous alumina film consists of a large number
of close-packed hexagonal cells with regular round pore in
the center of each cell, and the pores pass through the coat-
ing from the bottom to the surface. Most of the load is borne
by the anodic oxide film. As we know, the anodic oxide
film is a fragile material and much harder than the Al sub-
strate, so most cracks will probably be generated in the hard
alumina film [12]. The cracks spread along the direction
perpendicularly to the sliding direction. When the cracks
spread to a certain degree some cracks will meet together
and produce some pieces separated from the hard alumina
film (Fig. 6a). Then the pieces are peeled off under the action

Fig. 6. SEM photograph of the wear track on the hard alumina film (a) anodic oxide film, (b) self-lubricating anodic oxide film.
374 Y. Zhao et al. / Materials Chemistry and Physics 82 (2003) 370374
of sliding. After self-lubricating treatment, the pore is
full-filled with carbon fibers. This lead to the brittleness of
the composite film varied and cracks spreading will be hin-
dered, thus spreading rate of cracks are lowered (Fig. 6b).
So the wear rate of the steel ball decreases and the specimen
shows higher endurance life.
4. Conclusions
A self-lubricating anodic film has been formed on alu-
minum by re-anodizing in oxalic acid and a subsequent de-
velopment of the carbon precursors via the polymerization of
acrylonitrile within the pores of alumina film. SEM, FT-IR
and XPS techniques are applied to characterize the synthesis
results of carbon fibers. Pin-on-plate reciprocating tribolog-
ical tests reveal a significant reduction in the coefficient of
friction after the self-lubricating treatment on ordered porous
anodic alumina film.
Acknowledgements
We acknowledge the National Natural Science Founda-
tion of China (Grant No. 50275142) and Ministry of Science
and Technology (Grant No. 2202AA302609) for financial
support and Top Hundreds Program of Chinese Academy
of Sciences. The authors would like to thank researcher
Jia-Zheng Zhao of Lanzhou Institute of Chemical Physics
of the Chinese Academy of Sciences for enthusiastic help.
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