Wear 262 (2007) 1097–1101

Tribological behavior of nanostructured WC particles/polymer coatings

Y. Wang a,∗ , S. Lim b
a Department of Materials Science, Harbin Institute of Technology, Harbin 150001, PR China
b University of Alberta, Edmonton, Alberta, Canada T6G 2G6

Received 4 November 2005; received in revised form 20 October 2006; accepted 13 November 2006
Available online 9 January 2007

Abstract
Tribological and corrosion behaviors of nanostructured tungsten carbide (WC) particles/polymer composite coatings were studied by using
microscratch technology and electrochemical technique. The coatings containing nanostructured WC particles showed a significant increase in
hardness and scratch resistance compared to that of pure polymer coating. The improvement in hardness and scratch resistance is attributed
to the dispersion hardening of nanostructured WC particles in polymer coatings. Corrosion test results showed that the nanostructured WC
particles/polymer composite coatings exhibit better or at least equivalent corrosion resistance to that of the pure polymer coating.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Polymers; Coatings; WC nanostructured particles; Microscratch; Corrosion; Tribology

1. Introduction micrometer-sized particles, nanoparticles are believed to have

The nanostructured materials have long been recognized to
exhibit remarkable and technologically attractive properties due
to their extremely fine microstructure [1]. For a nanostructured
material, there is a tremendous increase in volume fraction of
grain boundaries and triple junctions, as compared to conven-
tional polycrystalline or amorphous counterparts. As a result,
nanostructured materials exhibit several unique physical, chem-
ical and mechanical properties. For example, nanostructured
WC–Co cermets possess high hardness without any appreciable
deterioration in its toughness property [2,3].
Polymers are common materials which are widely used
in industries. However, these are susceptible to damage by
scratching and abrasive wear. Such processes impair the appear-
ance and reduce the mechanical strength by the introduction
of flaws [4]. With advent of new advanced materials, the
use of reinforced polymer composites is becoming more
common. These materials are subjected to abrasive wear in
many applications [4,5]. Recent investigations on inorganic
nanoparticle-embedded polymer composites reveal their signif-
icant potential in producing materials with low friction and/or
high wear resistance [6–12]. In comparison with the widely used
∗ Corresponding author. Fax: +86 451 86413922.
E-mail address: youwang2000@yahoo.com (Y. Wang).
the following advantages [8,9]: (i) the abrasiveness of the hard
microparticles decreases remarkably as a result of a reduction
in their angularity while the mechanical behavior of the bulk
materials remain competitive; (ii) the transferred film can be
strengthened because the nanoparticles would have the capabil-
ity of blending well with wear debris; (iii) the material removal
of nanoparticulate composites would be much milder than that
of conventional composites because the fillers have the same
size as the segments of the surrounding polymer chains.
At present, functional polymer coatings are used in increas-
ingly demanding applications that require good adhesion and
specific resistance to damage. This led to an increasing inter-
est in improving the mechanical properties of polymer coatings,
especially their abrasion, scratch and wear resistance as well
as corrosion resistance. An understanding of abrasion resis-
tance and the associated surface deformation mechanisms is
of primary importance in materials engineering and design
[13,14].
Single pass scratch measurements have been used to map
the scratch resistance of polymers. The single-pass scratch-
ing method is a tribological technique that can be useful in
studying single point abrasive scratching and it may simulate
the deformation conditions of an abrasive process containing
both microcutting and microploughing [15,16]. It also allows
the measurement of the energy dissipated in a scratching event,
along with the normal and tangential forces. Nano/microscratch

0043-1648/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2006.11.013
1098 Y. Wang, S. Lim / Wear 262 (2007) 1097–1101
testing is an attractive technique for the characterization of thin
films or coatings, which overcomes the limitations of both the
classical stylus scratch test (normal force range) and the atomic
force microscope technique (short sliding distances). This tech-
nique can be used to investigate the resistance of a thin film or
coating to scratching, to delamination and to wear [17,18]. Nor-
mal and tangential forces are simultaneously measured during
the scratching process. However, from the existing literature it
is evident that very limited work has been reported on abrasion
or scratch, especially on nano/microscratch studies of polymers
and their composites [14,19,20].
Tungsten carbide (WC) is a technologically important mate-
rial and has been widely used as cutting tools, rock drills,
punches and wear-resistant coating materials [21]. Bulk WC is
known to exhibit excellent friction characteristics and improved
wear resistance. Since the resistance to mechanical and chem-
ical damage of the composite coatings is highly desirable,
nano-sized WC particulates in polymer composite coatings
should also provide the polymers with improved corrosion
and tribological properties. The present paper discusses scratch
behavior and improved corrosion resistance of nanostructured
WC particle–polymer composite coatings.
2. Experimental procedure
2.1. Materials
The nanostructured tungsten carbide particles, about 40 nm
grain size, were obtained from Inframat Corporation, USA. Par-
ticles size was about 200 nm. The particles were washed in
acetone and then with water to remove any contaminants in a
50 ml centrifuge tube. The particles were separated from the
liquid by gravity centrifuge (IEC HN-SII Centrifuge) at speed
of 21,000 rpm for approximately 20 min. The supernatant was
poured off from the tube and sediment was left in the tube to be
dried in a desiccator’s for more than 2weeks.
The polymer incorporate was obtained from Solomon Coat-
ings, Edmonton, Alberta. It is known as Xylan 1810/D1864
commercially and is known to be a useful coating material as
dry lubricant and exhibits good corrosion resistance because
of the PTFE compound in the blend. However, the polymer
does not have appropriate abrasion or erosion resistance. The
product contains about 34% solids by weight and the density is
1.13 kg/dm3 .
2.2. Substrate preparation
The base metal used in this experiment was a 1018 grade
carbon steel cut into small pieces with a working surface area
of 1.95 cm2 . Steel specimen substrates were polished up to
13–16 ␮m and the pure polymer or mixture of polymer with
WC particles were coated on the substrates by spin coating
method. The thickness of coatings is controlled by the centrifu-
gal force that is perpendicular to the coating surface. At low
rotation speed, the coating solution spreads out on the substrate,
and at high rotation speed (generally 2000–4000 rpm) thin films
are formed [22].
Fig. 1. Schematic view of the substrate with the coated material.
Table 1
List of prepared samples
Sample First layer Second layer
A Polymer Polymer
B Polymer 10% solids mixture
C Carbon steel –
D Polymer 20% solids mixture
The WC nanoparticles were blend with the Xylan polymer
at solids content of 10 and 20% particles by weight. To ensure a
good dispersion of the powders in the polymer, the mixture was
ultrasonically stirred before spin coating. Due to fast sedimen-
tation of the particles, the coating was performed immediately
after the preparation the suspension. To completely seal the sub-
strate by the polymer, the polymer without particles was first spin
coated at 2000 rpm for about 40 s. The coated sample was baked
in an oven at 360 ◦ C for 20 min. After then, the thickness of first
layer is about 40–50 ␮m. When the first layer was set, a second
layer of coating by WC polymer suspension was deposited on
the substrate by the same mechanism. The sample was baked
again under the same condition as in the first layer coatings. The
total thickness of the coatings is about 80–100 ␮m. The coated
substrate is schematically shown in Fig. 1. The details of the
samples prepared are summarized in Table 1.
2.3. Hardness and scratch tests
The hardness of different polymer coatings with and with-
out embedded nanostructured WC particles was measured by
Vickers microhardness tester. The applied load is 50 g and the
loading time is 15 s for the hardness testing.
The resistance of the coatings to scratching was evaluated
using a universal microtribometer (CETR), which had a mechan-
ical testing probe made of tungsten carbide. The shape of the
probe is illustrated in Fig. 2 [18]. The microscratch test was per-
formed in two different manners, i.e. constant loading scratch
Fig. 2. Shape of the indenter used for scratch test.
 Y. Wang, S. Lim / Wear 262 (2007) 1097–1101
with an applied normal force of 20 g and increasing loading
scratch with a load ranges from 0.05 to 25 g.
Morphologies of the coating surfaces and the scratch tracks
were observed using an optical microscope.
2.4. Corrosion test
The potentiodynamic study was carried out in a typical
three-electrode arrangement with the coated sample as working
electrode, a platinum coil as the counter electrode and a standard
calomel electrode as the reference electrode. The aqueous cor-
rosion behavior of the coated and uncoated 1018 carbon steels
was measured in 3 wt.% sodium chloride solution at room tem-
perature by using a computer-assisted potentiostat (Solartron).
Potentiodynamic polarization measurements were conducted by
sweeping the electrode potential from −0.25 to 0.25 versus
open circuit potential (OCP) at a 1.66 mV/s scan rate. Dur-
ing the experiments, except for the area of interest, the sides
of specimens were sealed with epoxy. The potentiodynamic
measurements were taken after 2 h.
3. Experiment results and discussion
3.1. Structure and hardness of coatings
Fig. 3 shows an optical micrograph of a polymer coating
mixed with 10 wt.% nanostructured WC particles. It can be seen
that WC particles were not evenly dispersed in the polymer coat-
ing as isolated particles, but often remained as aggregates. We are
searching a method to disperse the particles well in the polymer
coatings.
Although material properties determining resistance to wear
and erosion are not well defined and hard to predict, materials
with high hardness, rapid work hardening rate and good oxida-
tion and corrosion resistance, in general, exhibit an enhanced
wear and erosion resistance [23,24]. In polymeric materials, a
certain degree of rigidity and hardness is essential to improve
resistance to mechanically induced surface damage.
Fig. 3. Typical micrograph of coating containing 10 wt.% nanostructured WC
particles; (dark areas) WC and (light areas) polymer.
1099
Fig. 4. Hardness results of different polymer coatings with and/or without n-WC
particles.
Fig. 4 shows the microhardness results for the polymer coat-
ings with and without embedded nanostructured WC particles.
The average hardness is seen to increase with increasing amount
of nanostructured WC particles in polymer coatings. The differ-
ence between the measured maximum and minimum hardness
values also increases with increasing the amount of nanostruc-
tured WC particles in polymer coatings.
3.2. Scratch resistance
The scratch resistances of different polymer coatings with
and without nanostructured WC particles were measured and
the results are shown in Fig. 5 and Table 2. Fig. 5 shows the
results of scratch test obtained under increasing loading condi-
tion. In general, the tangential force, FX , which refers to scratch
resistance or abrasion resistance, would increase linearly with
increasing the normal force, Fz , if there are no damage induced
by severe plastic deformation and no fracture during increasing
loading. When coating material is damaged during increasing
loading, the FX would no longer be linear with increasing nor-
mal force. The failure load of a coating can be recorded based
on the normal force, Fz , corresponding to the on-set point of the
FX fluctuation.
It can be seen from Fig. 5a that the FX for pure polymer
coating departure from the linear relationship at the FX about
2.5 g, indicating that the pure polymer coating has damaged
at this load (Fz is about 14 g). In contrast, the FX for the
nanostructured WC particles/polymer composite coatings, FX
is still linearly increasing with increasing the Fz up to testing
limit of 25 g, as shown in Fig. 5b. The FX value in this test is
recorded to be 10 g for the nanostructured WC particles/polymer
Table 2
Scratch resistance of different coatings
Sample Average FX (g)
A 1.6132
B 3.7379
D 6.9269
1100 Y. Wang, S. Lim / Wear 262 (2007) 1097–1101
Fig. 5. Results of scratch tests obtained from: (a) polymer coating and (b) 10%
n-WC particles/polymer coating.
composite coatings. That means nanostructured WC parti-
cles/polymer coatings exhibit higher scratch resistance. The
scratch resistance of the nanostructured WC particles/polymer
coatings is at least three times higher than that of the pure
polymer coating. As mentioned above that the failure load for
the pure polymer coating is about 14 g, while the failure load
of the nanostructured WC particles/polymer coatings can not
be measured in the test load range (maximum 25 g).
The average FX values can be automatically given by the
microtribometer under a constant loading condition. Table 2
shows the average FX values for different polymer coatings
scratched under a constant loading condition. It can be seen
that the average FX increased with increasing the amount of
Fig. 6. Typical scratch tracks on different polymer coatings: (a) pure polymer coating and (b) 10% n-WC particles polymer coating.
nanostructured WC particles in polymer coatings, indicating
an improved scratch resistance with increasing WC particles
in polymer coatings.
Frictional coefficient (CO) of different polymer coatings can
also be recorded during the scratch testing. It can be seen from
Fig. 5 that the frictional coefficients of nanostructured WC parti-
cles/polymer composite coatings are higher than that of the pure
polymer coating. Perhaps, the higher friction is attributed to poor
dispersion of nanostructured WC particles in polymer coatings.
Some clusters of WC particles were exposed on the coating
surfaces after baking due to the shrinkage of the polymer. It is
anticipated that by imposing the dispersion of nanostructured
WC particles in polymer matrix, frictional coefficients of the
nanostructured WC particles/polymer coatings would be similar
to that of the pure polymer coating.
3.3. Scratch surfaces
Morphologies of scratch tracks on coating samples were
examined using an optical microscope. The obtained micro-
graphs are shown in Fig. 6. Fig. 6a shows a scratch track on a pure
polymer coating created during scratch test. Fig. 6b for nanos-
tructured WC particles/polymer composite coating, the scratch
track is not clearly visible. It can be concluded from Fig. 5 that
the scratch track of nanostructured WC particles/polymer coat-
ing is more scratch resistant than that of pure polymer coating.
Also shown are the fragments at the edge and at the bottom of the
scratch track on the pure polymer coatings, while such fragments
were not observed on the nanostructured WC particles/polymer
composite coatings.
3.4. Hardness and scratch resistance
Scratch resistance is not uniquely defined, poorly understood,
and difficult to measure. For instance, it may be used to describe
abrasion, adhesion and erosion, and evaluated in terms of gloss
reduction, weight loss, color change or magnitudes of defor-
mation [25]. Furthermore, contact mechanics depend on both
material and surface properties of the two solids in contact,
and the exact contact geometry; thus, the relationship between
contact conditions and deformation is complex [26]. There is
limited understanding of the link between intrinsic properties of
polymers and scratch resistance. This is not a single parameter
 Y. Wang, S. Lim / Wear 262 (2007) 1097–1101
Fig. 7. Relationship between the scratch resistance and hardness of different
coatings.
Fig. 8. The condition of the substrates after 2 h immersion in 3 wt.% NaCl.
relation but different for polymers, with responses ranging from
glassy and ductile to rubbery [27].
Fig. 7 shows the relationship between the scratch resistance
and the hardness of different polymer coatings. It can be seen
that the scratch resistance of the polymer coatings is strongly
dependent on their hardness which depend on the amount of
nanostructured WC particles embedded in the coatings.
The results in Figs. 5–7 demonstrate that nanostructured
WC particles can remarkably strengthen polymer coatings and
improve their hardness and scratch resistance, or abrasion resis-
tance. It was suggested that the remarkably improvement in
hardness and scratch resistance should be related to the strength-
ening of nanostructured WC particles in polymer coatings.
3.5. Corrosion resistant
The potentiodynamic curves in Fig. 8 show a distinctive dif-
ference between the three different coatings. Coating B shows
higher corrosion resistance than the other two samples after 2 h
of immersion in NaCl solution. The corrosion current for coat-
ing A and coating B are similar to each other because both have
the polymer layer as base coatings. However, open circuit poten-
tial for coating A is about 300 mV less than that of the coating
B which indicates that it is more susceptible to corrosion. For
1101
sample C (bare carbon steel), the open circuit potential shows a
significant higher current density than the rests.
4. Conclusion
Nanostructured WC particles can be blended with polymer
to make composite coatings with high performance. The nanos-
tructured WC particles/polymer composite coatings exhibit
higher hardness and higher scratch resistance than the pure poly-
mer coating. The scratch resistance of the nanostructured WC
particles/polymer coatings is at least three times higher than that
of the pure polymer coating. It is suggested that the improve-
ment in hardness and scratch resistance is related to the particle
strengthening of nanostructured WC particles in polymer coat-
ings. From the electrochemical test, the nanostructured WC
particles/polymer composite coatings exhibit better or at least
equivalent corrosion resistance compared to the pure polymer
coating.
Acknowledgements
The authors would like to thank Dr. D.Y. Li and X.Y. Wang
for allowing and assisting the use of nano/microscratch tester.
References
[1] L.L. Shaw, et al., Surf. Coat. Technol. 130 (2000) 1–8.
[2] K. Jia, T.E. Fischer, Wear 200 (1996) 206–214.
[3] K. Jia, T.E. Fischer, Wear 203–204 (1997) 310–318.
[4] M.J. Adams, et al., Wear 251 (2001) 1579–1583.
[5] K. Friedrich, Friction and wear of polymer composites, in: K. Friedrich
(Ed.), Composite Material Series 1, Elsevier, Amsterdam, 1986, pp.
233–287 (Chapter 8).
[6] Q. Wang, J. Xu, W. Shen, W. Liu, Wear 196 (1996) 82–86.
[7] C.B. Ng, L.S. Schadler, R.W. Siegel, Nanostruct. Mater. 12 (1999) 507–
510.
[8] C.J. Schwartz, S. Bahadur, Wear 237 (2000) 261–273.
[9] M.Z. Rong, et al., Ind. Lubric. Tribol. 53 (2001) 72–77.
[10] B. Wetzel, et al., in: Y. Zhang (Ed.), Proceedings of the ICCM-13, Wan
Fang Digital Electronic Publishing, Beijing, China, 2001, p. ID1021,
doi:10.1007/0-387-26213-X 3/b.Polymer Composites.2005.12.
[11] F. Li, K. Hu, J. Li, B. Zhao, Wear 249 (2002) 877–882.
[12] M.Q. Zhang, et al., Macromol. Mater. Eng. 287 (2002) 111–115.
[13] V. Jardret, H. Zahouani, J.-L. Loubet, T. Mathia, Wear 218 (1998) 8–14.
[14] V.A. Soloukhin, et al., Polymer 43 (2002) 6169–6181.
[15] B. Lamy, Tribol. Int. 17 (1984) 35–38.
[16] Y.N. Liang, S.Z. Li, D.F. Li, S. Li, Wear 199 (1996) 66–73.
[17] Y. Xie, J.A. Williams, Wear 162–164 (1993) 864–872.
[18] X.Y. Wang, D.Y. Li, Mater. Sci. Eng. A 315 (2001) 158–165.
[19] R. Consiglio, N.X. Randall, B. Bellaton, J. von Stebut, Thin Solid Films
332 (1998) 151–156.
[20] D. Rats, V. Hajek, L. Martinu, Thin Solid Films 340 (1999) 33–39.
[21] Z.G. Ban, L.L. Shaw, J. Mater. Sci. 37 (2002) 3397–3403.
[22] H.J. Kim, et al., Korea-Aust. Rheol. J. 14 (2002) 71–76.
[23] Y. Wang, W. Chen, J. Mater. Sci. Lett. 22 (2003) 845–848.
[24] M. Johnson, D.E. Mikkola, P.A. March, R.N. Wright, Wear 140 (1990)
279–289.
[25] D.C. Evans, J.K. Lancaster, The wear of polymers Treatise on Materials
Science and Technology, vol. 13, Academic Press, New York, USA, 1979.
[26] K.L. Johnson, Contact Mechanics, Cambridge University Press, Cam-
bridge, UK, 1985.
[27] A. Krupicka, M. Johansson, A. Hult, Prog. Org. Coat. 46 (2003) 32–48.