Preparation and tribological performance of peruoropolyether

derived coatings
Guotuan Gu
a,
*
, Xueqiang Shen
b
, Feng-ling Qing
a,b
a
College of Chemistry and Chemical Engineering, Donghua University, 1882 West Yanan Road, Shanghai 200051, China
b
Key Laboratory of Organouorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, China
Received 17 October 2006; received in revised form 7 February 2007; accepted 8 February 2007
Available online 15 February 2007
Abstract
A series of peruoropolyether (PFPE) functional derivatives terminated with different amide groups (FD-As) were synthesized. The chemical
structures of the FD-As were determined by FTIR,
1
H and
19
F NMR spectra, and the thermo stability was determined by TG analysis. Thin lms of
FD-As were fabricated by strongly adsorbing FD-As molecules on the surfaces of metals such as aluminum plates and steel balls. The thin lms of
FD-As prepared possessed very low surface free energy about 12 mN/m. Tribological performance of these thin lms was characterized using a
UMT-2 model micro-tribometer and a four-ball tribotester using parafn liquid as lubricant. Thin lms of FD-As at both states of UMTand four-
ball tribo analysis can reduce the friction coefcient. And the anti-wear property of the liquid lubricant can also be improved.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Low surface free energy; Functional derivatives; PFPE; Boundary lubrication; Anti-wear coatings
1. Introduction
When two surfaces are rubbed together, lubricants are
generally required to minimize friction and wear. A variety of
liquid materials such as mineral oils, silicones, polypheny-
lethers, esters and uorocarbons have been used through the
years to lubricate surfaces [1,2]. In many applications, uid
lubricant is pressed out by applied load, and the surfaces are
separated by a lubricant boundary layer that may be only a few
molecular dimensions thick. Additives are often mixed into the
lubricants to improve the tribological performance. Wear often
occurs when nonpolar liquid lubricants dewet from metal
surfaces, and results into the failure of lubrication.
Peruoropolyethers (PFPE) are known for their valuable
operation characteristics, wide temperature ranges, high
viscosity indices, as well as chemical and heat-oxidation
resistance [36], and are widely used as lubricants especially in
nano-technology and micro/nanoelectromechanical systems
(MEMS/NEMS) in recent years [710]. The PFPEs with
functional end groups are used extensively to enhance the
absorption on the disk surfaces, which helps the lubricant to be
retained to the disk surface at high temperatures and rotation
rates [11]. Kasai and Raman [12] and Kondo et al. [13] reported
the lubrication behaviors of peruoropolyether with dialkyla-
mine end groups and amine salt end groups for magnetic disk
application, respectively. According to these literatures, amine
and amine salt end groups tightly anchored to the rubbing
surface covers uniformly, which leads to more durability and
better lubricity. Furthermore, PFPE lms have very low surface
free energy and are both hydrophobic and lipophobic, which
makes it useful as an anti-corrosion protective coatings and
lubricant lms. On such metal surfaces coated by PFPE thin
lms with very low surface free energies, most nonpolar
lubricants remained as droplets, while dewetted quickly from
the bare metal surfaces. These phenomena may be helpful to
retain liquid lubricants on the friction surfaces, thus enhance the
tribological performance of liquid lubricants under common
applications.
In this paper, a series of peruoropolyethers (PFPE)
terminated with various amide groups (FD-As) were synthe-
sized. The thin lms of FD-As were fabricated by strongly
adsorbed FD-As molecules on the surfaces of metals such as
www.elsevier.com/locate/apsusc
Applied Surface Science 253 (2007) 69806986
* Corresponding author.
E-mail address: guotuan-gu@henu.edu.cn (G. Gu).
0169-4332/$ see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2007.02.027
aluminum plates and steel balls. The tribology performances of
the thin lms were determined on a CETR micro-tribometer
model UMT-2 without any other lubricants and a MMW-1
four-ball tribotester using parafn liquid as the lubricant,
respectively. Experimental results show that thin lms of
FD-As at both states of UMT and four-ball tribo analysis can
reduce the friction coefcient. And the anti-wear property of
the liquid lubricant can also be improved relative to liquid
parafn.
2. Experimental
2.1. Synthesis and characterization of FD-As
The FD-As were synthesized using peruoropolyetheroyl
uoride to react with N,N-dimethyl ethylenediamine (FD-A1),
urea (FD-A2), thiourea (FD-A3) and guanidine hydrochloride
(FD-A4), respectively. The peruoropolyetheroyl uoride
was synthesized through the ring opening polymerization of
hexauoropropylene oxide (HFPO) according to the literature
[14] and had a number-average molecular weight about 2200
(n = 812). The chemical structures of FD-As were shown in
Fig. 1.
The chemical structures of the FD-As were characterized
by FTIR and
1
H and
19
F NMR. FTIR were recorded on an
AVATAR3600 FTIR (C.E.S.P.) infrared spectrometric analyzer.
1
H and
19
F NMR were recorded on an AV400 nuclear magnetic
resonance detector. To evaluate the heat stability, thermogravi-
metric analysis of FD-As was carried out on an EXSTAR 6000
(Seiko Instrument Inc.) thermoanalyzer.
2.2. Preparation and characterization of FD-As coatings
FD-As coatings were prepared as the following procedure.
Aluminum plates (20 mm 10 mm 2 mm) and steel balls
(12.7 mm) were thoroughly cleaned by ultrasonic washing in
acetone, then dried in a 120 8C drying oven. The cleaned and
dried aluminum plates and steel balls were immediately
immersed into FD-As (1 wt.%) solution of 1,1,2-triuoro-
trichloroethane and kept at 60 8C for 30 min. Then, the
aluminum plates and steel balls were dried at room temperature
for several minutes, and then treated at 120 8C for 1 h to
enhance the adsorption of FD-As molecules on the surface.
A single crystal silicon wafer (10 mm 5 mm 2 mm)
was also used as a substrate to fabricate FD-As thin lms. The
silicon wafer was thoroughly cleaned and dried, and a thin gold
lm was then sputtered onto the surface with a thickness of
about 40 nm. The treated silicon wafer was submerged into FD-
A1 (1 wt.%) solution of 1,1,2-triuoro-trichloroethane at room
temperature for at least 8 h and following by heat treatment as
described above to enhance the adhesion of FD-A molecules
with the gold surfaces. The surface morphology of the gold
surface and FD-As thin lms were observed on a Nanoscope IV
model Scanning Probe Microscopy using AFM mode.
Surface free energies of FD-As thin lms were determined
by contact angle measurements of water and diiodomethane
using a DM300 contact angle tester. Total surface free energy
and polar and dispersive components were calculated by
Fowkess equation as follows [15]:
g
LV
1 cos u
c
2g
d
SV
g
d
LV

1=2
2g
p
SV
g
d
LV

1=2
(1)
where d and p are the dispersion and polar components of each
surface free energy, u
c
the contact angle, and g
LV
and g
SV
are the
interfacial tensions at solidvapor, liquidvapor and solid
liquid interfaces, respectively.
To determine the chemical elements and chemical environ-
ments, X-ray photoelectron spectrum (XPS) analysis was
conducted on a Axis Ultra multi-technique electron spectro-
meter (Kratos, UK), using Mg Ka radiation operating at 250 W
and a pass energy of 29.35 eV. The thickness of FD-As on
aluminum substrate was measured by using the XPS O1s signal
of peruoropolyether and aluminum oxide [16].
AUMT-2model reciprocatingtribotester was usedtoestimate
the tribological properties of the thin lms at ambient conditions
(RH: 4045%). A stationary 3.96 mm GCr15 steel ball was
usedas counterpart. The slidingvelocityandreciprocatinglength
were 1.5 mm/s and 5 mm, respectively. The normal force was
selected as 0.5 N. The coefcient of friction and sliding passes
were recorded automatically. Usually, a relatively low friction
coefcient was recorded at the early stage of sliding and it
rose sharply to a higher stable value after sliding for a certain
passes. It was recognized that the lm failed at this point and
the corresponding sliding passes was recorded as the wear life.
Three replicate tests were carried out for each specimen, and the
average friction coefcients and wear lives of the three replicate
tests were cited in this article.
A MMW-1A model four-ball tribotester was also used to
estimate the tribological performance of the thin lms of FD-As
at ambient conditions (RH: 4045%). The balls (diameter
12.7 mm) used in the test are made of GCr15 bearing steel
(composition: 0.951.05%; C, 0.150.35%; Si, 0.200.40%;
Mn, <0.027%; P, <0.02%; S, 1.301.67%; Cr, <0.30%; Ni and
Cu <0.025%) with HRC 6164. The GGr15 12.7 mm steel
ball was treated as the procedure above to form FD-As thin
lms on the surface of the balls. Parafn liquid was used as
lubricant, which has a boiling point above 300 8C, density
0.8350.89 g/cm
3
, viscosity (at 50 8C) 10.28 mm
2
/s. The Fig. 1. The molecular structure of FD-As.
G. Gu et al. / Applied Surface Science 253 (2007) 69806986 6981
chemical components on the surface of steel balls before and
after tribo-tests were characterized by XPS analysis.
3. Results and discussion
3.1. Synthesis and characterization of FD-As
Peruoropolyetheroyl uoride reacted with slightly excess
N,N-dimethyl hexanediamine (FD-A1), urea (FD-A2), thiourea
(FD-A3) and guanidine hydrochloride (FD-A4), respectively, at
room temperature for several hours, using dry 1,1,2-triuoro-
trichloroethane as the solvent and triethylamine as catalyst.
After the reaction was nished, excess insoluble reactants, N,N-
dimethyl hexanediamine, urea, thiourea and guanidine were
separated from soluble FD-As. Then 1,1,2-triuoro-trichlor-
oethane was removed using a rotatory evaporator. The crude
products were washed thoroughly with deionized water, and
dried by a rotatory evaporator under vacuum.
3.1.1. FTIR and NMR analysis
To determine the structure of FD-As, FTIR,
1
H and
19
F
NMR spectra were recorded.
From the FTIR spectra of peruoropolyetheroyl uoride and
FD-As, the peak at 1885 cm
1
due to C O of C(F) O groups
disappeared in all the FD-As spectra, peaks at 1690 cm
1
due
to C O in CONH (FD-A1), at 1683 cm
1
due to C O in
CONHCONH
2
(FD-A2), at 1689 cm
1
due to C O in
CONHCSNH
2
(FD-A3) and at 1688 cm
1
due to C O in
CONHC(NH)NH
2
(FD-A4) groups appeared.
All the FD-As had the same peruoropolyether chain, so
only
19
F NMR of FD-A1 was recorded using methanol-d
4
as
solvent: d 84.21 to 81.36 (CF
3
), 131.67 (CF
2
), 146.02
to 146.42 (CF) [17].
1
H NMR spectra of FD-As were recorded using mixed
solvents of equivolume of 1,1,2-triuoro-trichloroethane and
CDCl
3
:
For FD-A1: d 1.181.24 (CH
3
), 2.234.02 (CH
2
), 5.77
6.04 (NH).
For FD-A2: d 1.301.37 (NH
2
), 4.354.44 (NH).
For FD-A3: d 1.321.42 (NH
2
), 4.374.47 (NH).
For FD-A4: d 5.78 (CONH), d 3.072.17 (C NH),
d 1.321.19 (CNH
2
).
3.1.2. Thermogravimetric analysis
Thermogravimetric analysis of FD-As were carried out in
air atmosphere with a heating rate of 10 8C/min. The TG/
DTG curves of FD-As were shown in Fig. 2 and all the FD-
As had good heat stabilities. Below 150 8C, all the FD-As
showed almost no weight loss. After that, the weight loss
gradually increased linearly with the temperature increased,
the weight loss of FD-As at elevated temperature may be
Fig. 2. TG/DTG curves of FD-As, at air atmosphere, with a temperature rise speed, 10 8C/min.
G. Gu et al. / Applied Surface Science 253 (2007) 69806986 6982
caused by heat evaporation, this result was similar to Lis
reports [18].
3.2. Preparation and characterization of FD-As coatings
3.2.1. Surface morphology characterization
The AFM surface morphology of the gold-coated silicon
wafer and FD-As thin lms are shown in Fig. 3. The surface of
FD-A1 coated gold-coated silicon was smoother than the
surface of gold-coated silicon wafer, which indicated that the
FD-A1 molecules formed a very thin lm on the gold particles
accumulated on the surface of silicon wafer.
3.2.2. Surface free energy measurement
Contact angles were measured at room temperature with a
horizontal microscope with a protractor eyepiece. Droplets
were placed at ve different positions on one sample and the
average value was adopted as the contact angle. Contact angles
of PFPE (CF
3
CF
2
CF
2
O((CF
3
)CFCF
2
O)
n
CF
2
CF
3
, with a num-
ber-average molecular weight about 3000) treated Al substrates
using the same procedure aforementioned were also measured
for compare. As shown in Table 1, all the FD-As coated
aluminum plates were hydrophobic and oleophobic, while
PFPE treated substrate was a little hydrophilic. This means that
the functional derived PFPE of FD-As showed a different lm
formation compared with PFPE. The polar end groups anchored
at the surface of substrates and formed continuous lms, while
PFPE formed discontinuous lms [13]. This may be the reason
for the different wetting behaviors of FD-As treated substrates
with PFPE treated substrates. Thin lms of FD-A1 on gold
surface showed bigger CA for water than that on surface of Al
slides, this might be due to smoother surface of FD-As lm on
sputtered gold coating on silicon wafer.
Surface free energy is an important factor for frictional
performance of solid surfaces. Low surface free energy may
lower the friction force dramatically. The surface free energy
and dispersive (d) and polar (p) components of the thin lms of
FD-As on Al slide were calculated from the contact angle of
water and diiodomethane [19], which were listed in Table 2.
Surface free energies of thin lms of Zdol 2000 and Zdol
4000 were reported by Izumisawa and Jhon [20]. The g of FD-
As calculated were a little higher (for FD-A1 13.59 mN/m, FD-
A2 11.8 mN/m, FD-A3 12.2 mN/m and FD-A2 12.2 mN/m)
than that of Zdols (for Zdol4000 10.6 mN/m, Zdol2000
10.7 mN/m). This may be caused by the more polar amide end
groups of FD-As compared with that of Zdols, which had
CH
2
OH end groups. The very low surface free energy of FD-As
coating on aluminum plate showed that FD-As could form a
thin lm on the surface of substrates.
3.2.3. XPS analysis
To determine the chemical composition and structure of the
FD-As thin lms, the surface of FD-A2 thin lm was analyzed
using an Axis Ultra multi-technique electron spectrometer
(Kratos, UK) with an Al Ka X-ray source and an pass energy of
40 eV. The Al anode voltage was 15 keV and the lament
current was 20 mA. The pressure in the spectrometer during
analysis was typically in the 10
9
Torr range. XPS spectra were
Fig. 3. Top AFM images of gold-coated silicon wafer (left) and FD-A1 coated gold surface (right).
Table 1
Contact angles for water and diiodomethane on different surfaces
CA for water CA for diiodomethane
FD-A1 105 89
FD-A2 102 101
FD-A3 101 98
FD-A4 101 98
PFPE 83 45
FD-A1 on gold surface 113 93
Table 2
Surface energy (g), dispersive (g
d
) and polar (g
p
) components of thin lms of
FD-As of PFPE derived from water and diiodomethane (unit, mN/m)
g
d
g
p
g
FD-A1 10.6 2.99 13.59
FD-A2 3.9 7.9 11.8
FD-A3 4.8 7.4 12.2
FD-A4 4.8 7.4 12.2
G. Gu et al. / Applied Surface Science 253 (2007) 69806986 6983
recorded automatically. Using a least-square curve-tting
program installed in the spectrometer, the C 1s for the self-
assembled FD-A2 monolayer thin lm surface was split into
several sub-peaks of functional groups, and the concentrations
of functional groups for the thin lm surface were obtained.
A typical splitting of the spectrum of C 1s was shown in
Fig. 4A. The peaks in the spectra could be ascribed to groups as
follows [19], CF
3
at 292.4 eV, CF
2
at 290.2 eV, CF at 288.9 eV,
CONHat 287.7 eV, HNCONH
2
at 286.3 eVand Cat 284.8 eVto
contaminant carbons. From the C 1s spectrum of the complex
lmsurface, about 73%Catoms were CF (estimated according
to the ratio of the areas of the peaks), indicating the thin lm
consisting of PFPE main chains, which was in accordance with
the chemical structure of FD-A2 molecules very well. The F 1s
spectrumis also shown in Fig. 4B. XPS spectra of other adsorbed
FD-As thin lms were similar to that of FD-A2.
3.2.4. Thickness of thin lms of FD-A2 on aluminum
substrate
Generally, there is an aluminum oxides layer on the out layer
of the aluminum substrate. According to literature [16], the
thickness of PFPE lubricant thin lm could be calculated by the
following equation:
d l
1
ln

n
2
l
2
I
1
n
1
l
1
I
2
1

(2)
where d is the thickness of the FD-A lm in angstrom, I
1
and I
2
the photoelectron intensities of the FD-A layer and Al
2
O
3
layer,
l
1
and l
2
are the average mean free path of O 1s in peruor-
opolyether and in Al
2
O
3
, which are 16 A

[16] and 16.7 A

[21],
respectively. The numerical density n
i
of type i atoms is given
by the following equation: n
i
= r
i
N
A
/M
i
, where M
i
is the
molecular weight, N
A
the Avogadros number and r
i
is the
density. The density n
1
of the oxygen atoms in FD-A2 is given
by r
1
N
A
/166, and the density n
2
of the oxygen atoms in Al
2
O
3
is
given by r
2
N
A
/102. The value of (n
2
/n
1
) can be calculated as
3.34 by using these values and the densities (1.9 10
3
kg m
3
for peruoropolyether and 3.9 10
3
kg m
3
for aluminum
oxide). Eq. (2) was converted to Eq. (3), with which the
peruoropolyether lm thickness can be easily calculated:
d 16 ln

3:5

I
1
I
2

(3)
The XPS O 1s spectra of FD-A2 on aluminum substrate was
shown in Fig. 5, peaks at about 537.5 eV can be attributed to
oxygen atoms in peruoropolyether of FD-A2, has a signal area
ratio of 40.7%, peaks at about 534.5 eV are oxygen atoms of
aluminum oxides, has a signal area ratio of 59.3%. Then the
thickness of the thin lm of FD-A2 could be calculated as
19.6 A

. Thickness of other FD-As lms are similar with that of

FD-A2. This indicated that the functional derived PFPEs
formed continuous lms with thickness about 2 nm.
3.3. Tribological performance
The variation of friction coefcient (COF) as a function of
sliding passes recorded using the UMT-2 Micro-Tribotester is
shown in Fig. 6. It was indicated that all FD-As thin lms
reduced the friction coefcient greatly, for FD-A1 from
substrates 0.73 to about 0.19, FD-A2 to about 0.15, FD-A3 to
about 0.17 and FD-A4 to about 0.15. This means that FD-As
thin lms as prepared may be used as lubricant thin lms.To
evaluate the tribological performance of FD-As thin lms under
lubrication of a liquid lubricant, a MMW-1A model four-ball
tribotester were used to estimate the tribological performance
Fig. 4. C 1s (A) and F 1s (B) XPS spectra of FD-A2 monolayer thin lm as
prepared.
Fig. 5. XPS O 1s spectra of FD-A2 on aluminum substrate, signal area ratio
(%): atoms at binding energy of about 537.5 eV, 40.7%; atoms at binding energy
of about 534.5 eV, 59.3%.
G. Gu et al. / Applied Surface Science 253 (2007) 69806986 6984
of thin lms of FD-As. FD-As coated GGr15 12.7 mm steel
balls and liquid parafn were used in this article.
The variation of COF with time increasing under a load of
300 N, rotation speed of 1450 rpm and duration of 30 min was
shown in Fig. 7. Clearly, the thin lms of FD-As on the surface
of steel balls could reduce friction force dramatically. The COF
was reduced from 0.090.11 to 0.060.07 for FD-A1, to 0.04
0.05 for FD-2, to 0.060.07 for FD-3 and to 0.050.06 for
FD-A4, respectively.
The variation of wear scar diameter (WSD) under different
load was shown in Fig. 8. At every load, WSD of FD-As coated
balls were smaller than that of bare balls. Under lower load, for
example, 196 N, the WSD of FD-As coated balls reduced from
0.642 mm for balls to 0.512 mm for FD-A1, to 0.525 mm for
FD-A2, to 0.371 mm for FD-A3 and to 0.536 mm for FD-A4,
respectively. Even under higher load of 392 N, the WSD of FD-
As coated balls still reduced from 0.735 mm of bare iron ball to
0.656 mm for FD-A1, to 0.667 mmfor FD-A2, to 0.657 mmfor
FD-A3 and 0.685 mm for FD-A4. This means that FD-As thin
lms can improve the anti-wear property of parafn liquid.
It indicated that boundary lubrication occurred under above
state of four-ball friction experiments. When boundary
lubrication lms failed under severe friction conditions, wear
would take place. When nonpolar liquid lubricant was
contacted with steel, the liquid would dewet from the surface
quickly, weak boundary lubrication lms formed, lubrication
was easy to be failed under such conditions. This may be the
main reason for not so good anti-wear property of liquid
parafn wax. The FD-As thin lms described above had very
low surface free energy, which made it lyophobic. When the
liquid was contacted with the surface, wetting would be
difcult, and droplets of liquid lubricant were formed sitting on
the surface of iron balls. This may be helpful to prevent the
dewetting of lubricant molecular thin lms under boundary
lubrication and improve the tribological properties of nonpolar
liquid lubricants during rubbing. As a matter of fact, during the
experiments, when steel balls were observed under a magnier,
a lot of small droplets of liquid parafn were actually found on
the surfaces of treated steel balls, but no liquid droplets were
found on bare steel balls surfaces. On the other hand, the
adsorbed FD-As thin lms may work as an effective boundary
Fig. 6. Variation of friction coefcient of FD-As thin lms, using Al slide as substrate. Conditions: room temperature (RH: 4045%); load, 0.5 N; sliding velocity,
1.5 mm/s; sliding span, 5 mm.
Fig. 7. Variation of coefcient of friction (COF) with friction time. Conditions:
load, 392 N; rotation speed, 1450 rpm; duration time, 30 min.
Fig. 8. WSD of FD-As coated steel balls under different load. Rotation speed,
1450 rpm; parafn liquid as base lubricant; duration time, 30 min.
G. Gu et al. / Applied Surface Science 253 (2007) 69806986 6985
lm and reduce the friction and wear. Furthermore under severe
friction conditions, the main chain of FD-As will decompose to
form uorides such as FeF
2
or FeF
3
[22], which are anti-scratch
components. This was conrmed by the XPS spectra on the
worn surfaces (Fig. 9a and b). The F 1s peak of FD-As lm
before friction is at 688.2 eV, and the F 1s spectrum of the worn
surface was at 688.5 eV (68.1%) and 690.2 eV (31.9%), which
were corresponded to CF and FeF
2
and FeF
3
, respectively.
4. Conclusions
A series of PFPE terminated with different amide groups
were synthesized. Using the afnity between the polar end
groups and metal surfaces, thin lms of FD-As can be formed
by adsorption of FD-As molecules on surfaces of metals. Thin
lms of FD-As as prepared have very low surface free energy,
which can reduce coefcient of friction of substrates greatly
when measured by UMT tester. And under a lubrication of
liquid lubricant, FD-As thin lms can help to keep lubricant as
small droplets on surfaces of metals, which can improve the
tribological performance of liquid lubricant. This tribological
behavior of FD-As thin lms may be useful in wide variety of
applications.
Acknowledgements
The authors would like to thank Ms. Zonghui Li and Dr.
Jingwei Zhang for the XPS analysis and helpful discussion,
Jisheng Zhang for the UMT-2 tribology analysis. The authors
are also grateful to the National Postdoctoral Science
Foundation of China (Grant no. 2005038411) for the nancial
support.
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Fig. 9. XPS spectra of F 1s of FD-As coated steel ball surface (a) and worn
surface (b).
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