Wear 255 (2003) 785793

Tribological properties of WS2 nanoparticles under mixed lubrication

L. Rapoport a, , V. Leshchinsky a , I. Lapsker a , Yu. Volovik a , O. Nepomnyashchy a ,
M. Lvovsky a , R. Popovitz-Biro b , Y. Feldman b , R. Tenne b
a Department of Science, Holon Academic Institute of Technology, P.O. Box 305, Holon 58102, Israel
b Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel

Abstract
Recently, it has been established that WS2 and MoS2 nanoparticles (inorganic fullerene-like, IF) mixed with oil, and impregnated into
porous matrix of powdered materials appear to enhance the tribological properties of mating surfaces in definite loading range in comparison
to typical metal dichalcogenide solid lubricants. The main results have been obtained under relatively low pressures. It is important to
evaluate the tribological properties of IF when the concentrated contact is obtained. The effect of the IF in oil was studied using pin-on-disk
tester in the regime of mixed lubrication. The interaction between the full film and the asperity contact fractions has been considered and
the time evolution of the friction force was evaluated. The states of the mating surfaces and the nanoparticles before and after the friction
test were studied by transmission electron microscopy (TEM), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy
(XPS). It was established that the IF nanoparticles mixed with oil allow to decrease the fraction of straight asperity contact under mixed
lubrication regime and thus improve their tribological properties. TEM analysis showed that the shape of the IF nanoparticles is preserved
under low loads. It was found that some of the IF nanoparticles were damaged after the friction at the maximal load of 420 N. The IF
nanopaticles appear to form a protective film allowing increased load capacity of the rubbed pairs. The role of the IF solid lubricants as a
part of a third body is discussed in this work. The mechanism of friction and wear of the IF nanoparticles are discussed.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Mixed lubrication; IF nanoparticles; Asperity contact; Friction behavior

1. Introduction dichalcogenides [6]. Sliding/rolling of the IF nanoparticles

Layered materials such as graphite, MoS2 and WS2
(platelets of the 2H polytype) are used both as solid lu-
bricants and as additives in liquid lubricants. Minimum
tangential resistance is commonly associated with shearing
of the weak inter-layer (typically van der Waals, vdW)
bonds in these materials. Over the past few years, inorganic
fullerene-like (IF) supramolecules of metal dichalcogenide
MX2 (M = Mo, W, etc.; X = S, Se), materials with
structures closely related to (nested) carbon fullerenes and
nanotubes have been synthesized [1,2]. The main favorable
benefit of the hollow WS2 nanoparticles was attributed pre-
viously to the following three effects, named: (a) rolling
friction [3,4], (b) the IF nanoparticles serve as spacer,
which eliminate metal to metal contact between the asper-
ities of the two mating metal surfaces [3,4], and (c) third
body material transfer [5]. IFWS2 nanoparticles appear to
have excellent tribological properties within a definite load
range (PV 150 N m/s) in comparison to typical metal
Corresponding author. Tel.: +972-3-5026616; fax: +972-3-5026619.
E-mail address: rapoport@hait.ac.il (L. Rapoport).
in the interface between rubbed surfaces seems to be the
main friction mechanism at low loads, when the shape of
nanoparticle is preserved. It was found that the beneficial
effect of IF nanoparticles increased with the load. Exfoli-
ation of external sheets of IF nanoparticles was found to
occur at high contact loads (1 GPa) [7]. The transfer of
delaminated IF nanoparticles appears to be the dominant
friction mechanism at severe contact conditions. Thus, one
of the main goals of this work was to study friction and
wear behavior of the IF nanoparticles under severe contact
conditions.
It is known that severe contact conditions, which occur in
the mixed lubrication region, indicate the transition to scuff-
ing and seizure. Mixed lubrication is an extremely impor-
tant regime of liquid lubrication when both fluid film and
boundary lubrication take place, see for example the review
paper [8]. Thin lubricant films (1100 nm) are usually ob-
tained under mixed lubrication conditions. If the separation
between the contact surfaces is very small, nanoparticles of
full-size cannot be accommodated at the interface. Severe
deformation and fracture of IF nanoparticles are expected
to occur in this case. Therefore, different friction and wear

0043-1648/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0043-1648(03)00044-9
786 L. Rapoport et al. / Wear 255 (2003) 785793
mechanisms (not sliding/rolling of IF) may become predom-
inant over a mixed lubrication regime. The current paper
evaluates the effect of IFWS2 nanoparticles under mixed
lubrication conditions.
It has been speculated for years that third bodies control
the friction and wear behavior of low friction solid lubricants
[9]. Third body in our case can be considered as a mixture
of oil, solid lubricant nanoparticles and wear particles. The
tribological role of the wear particles and powders of solid
lubricants has been considered in the framework of a third
body lubrication model in the works of Godet (e.g. Ref.
[10]), Berthier (e.g. Ref. [11]), and Heshmat (e.g. Ref. [12]).
It is expected that the interaction between oil, spherical IF
nanoparticles and the wear particles at the interface between
the rubbing surfaces determines essentially the friction and
wear behavior of rubbed surfaces.
2. Experimental procedure
The average size of the IFWS2 particles was close to
100 nm (Fig. 1), while that of 2HWS2 was 4 m. Samples
of the 2HWS2 powder were milled for 24 h, leading to
platelets with an average size of 0.5 m. Pin-on-disk test
was performed at a sliding velocity of 0.6 m/s and loads of
100500 N. The materials of disk and flat pin were AISI
1050 steel quenched and tempered up to a hardness of 420
and 240 HB, respectively. Five drops of paraffin oil (60
cSt at 30 C) or oil thoroughly mixed with 5% of IFWS2
nanopowder were fed to the contact each 5 min during the
test. IFWS2 nanoparticles with average size close to 100 nm
were synthesized according to a procedure described in Ref.
[1]. The friction force and wear data were measured in this
experiment.
In order to evaluate the role of a third body, the wear debris
and solid lubricant particles were rinsed out from the contact
surfaces of the samples by treating the sample in ultrasonic
Fig. 1. AFM image of IFWS2 nanoparticle on the surface of pyrolytic graphite.
bath with hexane for 30 min. Residue particles from wear
tests were analyzed by transmission electron microscopy
(TEM). The samples were dispersed in n-hexane using an
ultrasonic bath, three times for periods of 20 min. After each
period of ultrasonic treatment the supernatant was removed
and a new portion of solvent was added. A drop from the fi-
nal dispersion was placed on a carbon/nitro-cellulose coated
copper electron microscope grid and blotted after 20 s. Inter-
missions for examination of the rubbed sample with optical
transmission microscope and scanning electron microscope
(SEM), energy dispersive X-ray spectroscopy (EDS), X-ray
photoelectron spectroscopy (XPS), and with tip profiler were
made from time to time during the run-in period and the
experiment.
XPS measurements were carried out with an AXIS-HS
Kratos set-up, using a monochromatized Al K X-ray source
(h = 1486.6 eV) and pass energies ranging from 20 to
80 eV. The energy scale was calibrated, with reference to the
C 1s line at EB = 284.8 eV. Curve fitting was applied using
GaussianLorenzian line shapes and a Shirley background
subtraction. Argon ion beam sputtering, which is a destruc-
tive depth profiling technique, was applied using beam en-
ergy of 4 keV and 20 mA emission current. The incident
beam angle was 45 . A large area raster, 4 mm 4 mm, was
used to verify uniformity across the analyzed area. Sam-
ples were sputtered at a rate of 3 nm/min as calibrated on a
Ta2 O5 /Ta reference.
3. Results
The time-dependence of the friction force for oil and oil+
IF blend at load of 260 N is shown in Fig. 2. The average
value of the friction coefficient in contact with oil + IF was
close to 0.014, while it was 0.02 for the sample rubbed with
the paraffin oil alone. A typical evolution of the friction
force during 5 min cycles of lubricant feeding is presented
 L. Rapoport et al. / Wear 255 (2003) 785793
Fig. 2. The time-dependences of friction force for oil and oil + IF blend
at load of 260 N.
Fig. 3. A typical evolution of the friction force during 5-min cycles of
lubricant feeding: (1) paraffin oil; (2) oil + IF nanoparticles.
in Fig. 3. It may be seen that feeding of the lubricant to the
contact region led first to a decrease in the friction force.
The shape of friction force curves resembles an S-shape
with different inclinations for oil and oil + IF lubricants.
The results of the statistical treatment of these curves at
definite loads will be presented below. The wear of the pin
rubbed with oil + IF lubricant was lower in comparison to
the pin lubricated with oil only at all studied loads (Fig. 4).
Fig. 4. The effect of load on the wear rate of pin lubricated with oil and oil + IF lubricants.
787
This effect becomes more predominant with load increasing,
suggesting that the favorable role of the IF increases with the
load. At a load of 475 N the wear rate of a pin lubricated by
oil was more than six times higher in comparison to oil + IF
blend.
In another series of experiments, the lubricant feeding
was interrupted during the steady state friction regime and
the time interval to a friction force jump was evaluated. It
is seen that while the friction force for pair lubricated with
oil started increasing after 5 min, 35 min passed before a
similar jump occurred in the case of oil + IF nanoparticles
(Fig. 5). The surface of the pin rubbed with oil + IF was
found to be covered by a film. XPS analysis revealed that this
film consisted of WS2 . The loaded pins were subsequently
rinsed carefully in ethanol and etched with 3% HNO3 in
alcohol. The results of this process are presented in Fig. 6.
Considerable pitting corrosion on the surface rubbed with
oil only is clearly observed, while the pin lubricated with
oil + IF exhibited pitting corrosion only in regions, where
the WS2 film was discontinuous.
The IF agglomerates were shown to get compressed and
they penetrate into the surface layers of soft pin (Fig. 7). The
observed ploughing tracks can probably be associated with
the dragging of agglomerated and compressed IF nanopar-
ticles as well as wear debris in the interface, especially at
high loads. As a result of this effect, the surfaces rubbed
with oil + IF were rougher in comparison to the surfaces
lubricated with oil (Fig. 8). The average values of the rough-
ness parameter (Ra ) for the pin under steady state friction
condition under a load of 420 N was 0.28 and 0.32 m for
oil and oil + IF, respectively.
Analysis of the solid lubricant particles by TEM, SEM
and XPS after wear testing showed that the shape of the
IF nanoparticles was preserved at loads up to 300 N.
However, some of the nanoparticles were damaged under
friction at load of 420 N (Fig. 9). Thin nanosheets of de-
laminated IF are also observed. Severe damage occurred
for a few single fullerene-like nanoparticles only. In most
788 L. Rapoport et al. / Wear 255 (2003) 785793

Fig. 5. The effect of interruption of oil and oil + IF feeding to the contact on friction force under steady state friction.

of the damaged nanoparticles only a few external molec-
ular sheets of the IF were damaged. This situation might
be beneficial for the tribological behavior of the contact,
since most of the damaged IF will continue to serve as
solid lubricants, while the exfoliated layers of the damaged
nanoparticles will serve as a part of an efficient transferred
film.
Raw atomic concentrations was analyzed also by XPS
obtained on the surface, lubricated with pure oil and oil +
IFWS2 under load of 420 N pins are presented in Table 1.

Fig. 6. The surfaces of the pins after friction with the load of 420 N ((a) oil; (b) oil + IF) and after etching with 3% HNO3 in alcohol ((c) oil; (d) oil + IF).
 L. Rapoport et al. / Wear 255 (2003) 785793 789

Fig. 7. Penetration of the IF nanoparticles and their agglomerates into the surface layers of the soft pin.

Table 1
Surface concentrations (at.%) of the steel pins after friction under load of 420 N with paraffin oil and paraffin oil + IFWS2
Lubricant Elements and binding energies (eV)a

W 4f S 2p Fe 2p O 1s C 1s

33.2 WS2 35.8 WO3 163 WS2 169 SO2 710 Fe oxide 530.6 284.9

Pure oil 0 0.06 0.1 0.2 7.4 38 52.55

oil + IFWS2 0.1 1.35 0.2 0.96 2.24 25.5 69.6
a Most likely compound for the corresponded chemical state.

The amount of carbon on the surface lubricated with IFWS2 dynamic full film regions and asperity regions [8]:
is found to be higher than on the surface rubbed with paraf-
f = X h fh + X A fA (1)
fin oil. It is expected that the rougher surface rubbed with
IF nanoparticles can be a main cause of this effect. Substan- where fh , fA are the friction coefficients of the hydrody-
tial amount of tungsten and sulfur oxides is found on the namic and asperity contact and Xh , XA are the fractions of
surface of the sample treated with IFWS2 . Traces of WS2 the total contact load supported by fluid and by asperities,
are found as well. Depth profiling via Ar ion sputtering in- respectively. The fraction of the friction force (F ), which
dicates mostly the following order of the layers. The top- is raised due to increasing asperity contact mode is
most layer consists mostly of a film of physisorbed carbon
and oxygen. Beneath this layer one finds a layer enriched F F F0
= = F (2)
with non-volatile sulfuroxygen species, and further down Fmax Fmax
tungsten oxide, tungsten sulfide and finally iron oxide. The It may be seen that the kinetics of the friction force changes
thickness of the layers containing tungsten and sulfur oxides with time. For oil and oil + IF lubricants this curve forms an
calculated using an attenuation approach was about 2 nm. S-shape curve, Fig. 3, which can be described by Avraami
equation [13] as
4. Discussion F = 1 exp(B k ) (3)

It is known, the mixed lubrication regime may be de- where B is the coefficient which depends on the formation
scribed by two types of friction generating regions: hydro- of asperity contact during oil depletion, k the coefficient of
790 L. Rapoport et al. / Wear 255 (2003) 785793

Fig. 8. The surface of the pins after friction with (a) oil and (b) oil + IF. Load P = 420 N.

the exponent, and the the time (5 min in present series
of experiment). The effect of a load on the coefficient B is
shown in Fig. 10. It can be seen that under a low load of
150 N, the value of B is same for the lubrication with pure
oil and oil + IF. However, for higher loading, B remains un-
changed for the oil + IF but, it increased in the case of pure
oil. The coefficient k varies in the range of 0.61.2 for the
two lubricants. The results of the statistical treatment of the
experimental data were compared with the theoretical ap-
proximation (Fig. 11). In order to compare the friction forces
upon the lubrication with oil or oil + IF, the results are pre-
sented as the change in the friction force, F with respect
 L. Rapoport et al. / Wear 255 (2003) 785793
Fig. 9. TEM picture of the IFWS2 nanoparticles after the friction test with load of 420 N.
to their maximal value Fmax . A good agreement between
the theoretical calculations and the experimental data is ob-
served. The depletion of the oil from the contact leads to a
quick increase of the friction force, while the formation of
Fig. 10. The effect of a load on the coefficients B for oil and oil + IF
lubricants.
791
an IF film on the metal surface, protects the contact surface,
restricting the rise of the friction force. On the basis of this
analysis, it may be assumed that the addition of IF nanopar-
ticles to oil allows to decrease the fraction of straight asper-
ity contact and thus to improve the tribological properties
of pin-on-disk contact pair under mixed lubrication. It may
be expected that the feeding of a lubricant provides origi-
nally a continuous full film contact and low friction force,
Fig. 3. The thickness of the lubricant film decreases with
time leading to an increase of the asperity contact and thus
to increasing the friction force. It may be assumed that the
applied load under the pin-on-disk test is shared between
full film lubrication and straight asperity contact and thus a
mixed lubrication is the dominant friction mechanism under
these conditions. When the thickness of the film becomes
smaller than the characteristic size of the IF nanoparticles,
IFWS2 nanoparticles have to delaminate and/or they can
be preserved in the valleys of roughened surfaces. The de-
gree of deformation/delamination of the nanoparticles de-
pends on the film thickness, the thinner is the film, the
larger is the fraction of delaminated nanoparticles. It may
792 L. Rapoport et al. / Wear 255 (2003) 785793

Fig. 11. The results of statistical treatment and theoretical approximation of the friction force data during 5-min cycle.

be assumed that under friction with a film thickness close
to the size of IF nanopowder (low loads) the shape of the
nanoparticles is preserved and sliding/rolling of the spheri-
cal IF nanoparticles at the interface seems to be the domi-
nant friction mechanism. The oil plays a considerable role
in this case. When the film thickness is lesser than the size
of nanoparticles (high loads, mixed lubrication), deforma-
tion and destruction of the IF nanoparticles have to lead to
formation of the transferred IF film on the contact surface.
It may be expected that with load increasing, the amount of
delaminated IF nanoparticles increases leading to formation
of more stable solid lubricant film. In this case, the effect
of oil is decreased. The IFWS2 film protects the contact
surface and thus it enhances the wear resistance of contact
surfaces. Identification of WS2 on the contact surface (XPS
and etching); preservation of the undeformed IF nanoparti-
cles (TEM analysis), and formation of rough surface under
steady friction with load of 420 N, allude to the fact that a
part of the IFWS2 is preserved undamaged in the valleys of
the contact surface, while another part of the IF nanoparti-
cles is delaminated and transferred to the underlying rubbed
surfaces. The IF nanoparticles in the valleys and the de-
laminated transferred nanosheets on the surface of contact
heights decrease the part of straight asperity contact under
mixed lubrication and thus improves the tribological behav-
ior of the contact. The decreasing pitting corrosion for the
samples rubbed with the IF nanoparticles (Fig. 6) confirms
the presence of IF film on the contact surface. Thus, it may

Fig. 12. The scheme of third body under friction with IF nanoparticles.
 L. Rapoport et al. / Wear 255 (2003) 785793
be expected that the delaminated transferred nanosheets of
the IF nanoparticles on the surface of the asperity crests de-
crease the part of straight asperity contact under mixed lu-
brication and improves the tribological properties of rubbed
surfaces.
Friction behavior of the IF nanoparticles can be under-
stood better by making use of a third body model. The
scheme of a third body under friction of contact pair lubri-
cated with oil+IF lubricant is shown in Fig. 12. It is expected
that under severe contact conditions, when the thickness of
the lubricant film is lesser than that of the size of the IF
nanoparticles, the third body consists not only of the oil and
wear debris, but also of the delaminated nanosheets of IF
nanoparticles. The straight asperity contact is limited by the
presence of IF nanoparticles, which are partially confined in
the valleys of the contacting surfaces and by the transferred
films of IF at the asperity crests. It is expected that the first
bodies covered with the IF nanoparticles (in valleys or as
transferred films) facilitate the shearing of the third body. IF
nanoparticles can be furnished from the valleys to the con-
tact surface, improving thereby the friction behavior.
5. Conclusions
1. The IF nanoparticles showed the best tribological prop-
erties in comparison to pure paraffin oil.
2. The application of IF nanoparticles allows to decrease
the fraction of straight asperity contact in comparison to
lubrication with oil only and thus to improve tribologi-
cal properties of a pin-on-disk contact pair under mixed
lubrication.
3. The surface of the pin rubbed with oil + IF was found to
be covered by a film. The friction coefficient remained
at low values over long periods of time after interruption
of the lubricant supply.
4. The observed ploughing tracks are associated with the
shear of agglomerated and compressed IF particles as
well as wear debris in the interface, especially at high
loads.
5. The contacting surfaces were found to be rougher in the
case of oil + IF than in contact with pure oil only. It is
expected that at very high loads, improvements in the
friction response can be associated with the transfer of
thin delaminated nanosheets.
793
Acknowledgements
We are grateful to Dr. Rita Rosentsveig for her help with
the synthesis of the IFWS2 nanoparticles. This work was
supported by grants from the Israeli Ministry of Science
(Tashtiot) and the USIsrael Binational Science Foundation.
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