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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


in the interface between rubbed surfaces seems to be the
Layered materials such as graphite, MoS2 and WS2 main friction mechanism at low loads, when the shape of
(platelets of the 2H polytype) are used both as solid lu- nanoparticle is preserved. It was found that the beneficial
bricants and as additives in liquid lubricants. Minimum effect of IF nanoparticles increased with the load. Exfoli-
tangential resistance is commonly associated with shearing ation of external sheets of IF nanoparticles was found to
of the weak inter-layer (typically van der Waals, vdW) occur at high contact loads (1 GPa) [7]. The transfer of
bonds in these materials. Over the past few years, inorganic delaminated IF nanoparticles appears to be the dominant
fullerene-like (IF) supramolecules of metal dichalcogenide friction mechanism at severe contact conditions. Thus, one
MX2 (M = Mo, W, etc.; X = S, Se), materials with of the main goals of this work was to study friction and
structures closely related to (nested) carbon fullerenes and wear behavior of the IF nanoparticles under severe contact
nanotubes have been synthesized [1,2]. The main favorable conditions.
benefit of the hollow WS2 nanoparticles was attributed pre- It is known that severe contact conditions, which occur in
viously to the following three effects, named: (a) rolling the mixed lubrication region, indicate the transition to scuff-
friction [3,4], (b) the IF nanoparticles serve as spacer, ing and seizure. Mixed lubrication is an extremely impor-
which eliminate metal to metal contact between the asper- tant regime of liquid lubrication when both fluid film and
ities of the two mating metal surfaces [3,4], and (c) third boundary lubrication take place, see for example the review
body material transfer [5]. IFWS2 nanoparticles appear to paper [8]. Thin lubricant films (1100 nm) are usually ob-
have excellent tribological properties within a definite load tained under mixed lubrication conditions. If the separation
range (PV 150 N m/s) in comparison to typical metal between the contact surfaces is very small, nanoparticles of
full-size cannot be accommodated at the interface. Severe
Corresponding author. Tel.: +972-3-5026616; fax: +972-3-5026619. deformation and fracture of IF nanoparticles are expected
E-mail address: rapoport@hait.ac.il (L. Rapoport). 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- bath with hexane for 30 min. Residue particles from wear
inant over a mixed lubrication regime. The current paper tests were analyzed by transmission electron microscopy
evaluates the effect of IFWS2 nanoparticles under mixed (TEM). The samples were dispersed in n-hexane using an
lubrication conditions. ultrasonic bath, three times for periods of 20 min. After each
It has been speculated for years that third bodies control period of ultrasonic treatment the supernatant was removed
the friction and wear behavior of low friction solid lubricants and a new portion of solvent was added. A drop from the fi-
[9]. Third body in our case can be considered as a mixture nal dispersion was placed on a carbon/nitro-cellulose coated
of oil, solid lubricant nanoparticles and wear particles. The copper electron microscope grid and blotted after 20 s. Inter-
tribological role of the wear particles and powders of solid missions for examination of the rubbed sample with optical
lubricants has been considered in the framework of a third transmission microscope and scanning electron microscope
body lubrication model in the works of Godet (e.g. Ref. (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray
[10]), Berthier (e.g. Ref. [11]), and Heshmat (e.g. Ref. [12]). photoelectron spectroscopy (XPS), and with tip profiler were
It is expected that the interaction between oil, spherical IF made from time to time during the run-in period and the
nanoparticles and the wear particles at the interface between experiment.
the rubbing surfaces determines essentially the friction and XPS measurements were carried out with an AXIS-HS
wear behavior of rubbed surfaces. 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
2. Experimental procedure C 1s line at EB = 284.8 eV. Curve fitting was applied using
GaussianLorenzian line shapes and a Shirley background
The average size of the IFWS2 particles was close to subtraction. Argon ion beam sputtering, which is a destruc-
100 nm (Fig. 1), while that of 2HWS2 was 4 m. Samples tive depth profiling technique, was applied using beam en-
of the 2HWS2 powder were milled for 24 h, leading to ergy of 4 keV and 20 mA emission current. The incident
platelets with an average size of 0.5 m. Pin-on-disk test beam angle was 45 . A large area raster, 4 mm 4 mm, was
was performed at a sliding velocity of 0.6 m/s and loads of used to verify uniformity across the analyzed area. Sam-
100500 N. The materials of disk and flat pin were AISI ples were sputtered at a rate of 3 nm/min as calibrated on a
1050 steel quenched and tempered up to a hardness of 420 Ta2 O5 /Ta reference.
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 3. Results
test. IFWS2 nanoparticles with average size close to 100 nm
were synthesized according to a procedure described in Ref. The time-dependence of the friction force for oil and oil+
[1]. The friction force and wear data were measured in this IF blend at load of 260 N is shown in Fig. 2. The average
experiment. value of the friction coefficient in contact with oil + IF was
In order to evaluate the role of a third body, the wear debris close to 0.014, while it was 0.02 for the sample rubbed with
and solid lubricant particles were rinsed out from the contact the paraffin oil alone. A typical evolution of the friction
surfaces of the samples by treating the sample in ultrasonic force during 5 min cycles of lubricant feeding is presented

Fig. 1. AFM image of IFWS2 nanoparticle on the surface of pyrolytic graphite.


L. Rapoport et al. / Wear 255 (2003) 785793 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
Fig. 2. The time-dependences of friction force for oil and oil + IF blend found to be covered by a film. XPS analysis revealed that this
at load of 260 N. 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
Fig. 3. A typical evolution of the friction force during 5-min cycles of
with oil + IF were rougher in comparison to the surfaces
lubricant feeding: (1) paraffin oil; (2) oil + IF nanoparticles. 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
in Fig. 3. It may be seen that feeding of the lubricant to the oil and oil + IF, respectively.
contact region led first to a decrease in the friction force. Analysis of the solid lubricant particles by TEM, SEM
The shape of friction force curves resembles an S-shape and XPS after wear testing showed that the shape of the
with different inclinations for oil and oil + IF lubricants. IF nanoparticles was preserved at loads up to 300 N.
The results of the statistical treatment of these curves at However, some of the nanoparticles were damaged under
definite loads will be presented below. The wear of the pin friction at load of 420 N (Fig. 9). Thin nanosheets of de-
rubbed with oil + IF lubricant was lower in comparison to laminated IF are also observed. Severe damage occurred
the pin lubricated with oil only at all studied loads (Fig. 4). for a few single fullerene-like nanoparticles only. In most

Fig. 4. The effect of load on the wear rate of pin lubricated with oil and oil + IF lubricants.
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- nanoparticles will serve as a part of an efficient transferred
ular sheets of the IF were damaged. This situation might film.
be beneficial for the tribological behavior of the contact, Raw atomic concentrations was analyzed also by XPS
since most of the damaged IF will continue to serve as obtained on the surface, lubricated with pure oil and oil +
solid lubricants, while the exfoliated layers of the damaged 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 oil. The coefficient k varies in the range of 0.61.2 for the
of experiment). The effect of a load on the coefficient B is two lubricants. The results of the statistical treatment of the
shown in Fig. 10. It can be seen that under a low load of experimental data were compared with the theoretical ap-
150 N, the value of B is same for the lubrication with pure proximation (Fig. 11). In order to compare the friction forces
oil and oil + IF. However, for higher loading, B remains un- upon the lubrication with oil or oil + IF, the results are pre-
changed for the oil + IF but, it increased in the case of pure sented as the change in the friction force, F with respect
L. Rapoport et al. / Wear 255 (2003) 785793 791

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 an IF film on the metal surface, protects the contact surface,
the theoretical calculations and the experimental data is ob- restricting the rise of the friction force. On the basis of this
served. The depletion of the oil from the contact leads to a analysis, it may be assumed that the addition of IF nanopar-
quick increase of the friction force, while the formation of 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-
Fig. 10. The effect of a load on the coefficients B for oil and oil + IF pends on the film thickness, the thinner is the film, the
lubricants. 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 surfaces. Identification of WS2 on the contact surface (XPS
to the size of IF nanopowder (low loads) the shape of the and etching); preservation of the undeformed IF nanoparti-
nanoparticles is preserved and sliding/rolling of the spheri- cles (TEM analysis), and formation of rough surface under
cal IF nanoparticles at the interface seems to be the domi- steady friction with load of 420 N, allude to the fact that a
nant friction mechanism. The oil plays a considerable role part of the IFWS2 is preserved undamaged in the valleys of
in this case. When the film thickness is lesser than the size the contact surface, while another part of the IF nanoparti-
of nanoparticles (high loads, mixed lubrication), deforma- cles is delaminated and transferred to the underlying rubbed
tion and destruction of the IF nanoparticles have to lead to surfaces. The IF nanoparticles in the valleys and the de-
formation of the transferred IF film on the contact surface. laminated transferred nanosheets on the surface of contact
It may be expected that with load increasing, the amount of heights decrease the part of straight asperity contact under
delaminated IF nanoparticles increases leading to formation mixed lubrication and thus improves the tribological behav-
of more stable solid lubricant film. In this case, the effect ior of the contact. The decreasing pitting corrosion for the
of oil is decreased. The IFWS2 film protects the contact samples rubbed with the IF nanoparticles (Fig. 6) confirms
surface and thus it enhances the wear resistance of contact 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 793

be expected that the delaminated transferred nanosheets of Acknowledgements


the IF nanoparticles on the surface of the asperity crests de-
crease the part of straight asperity contact under mixed lu- We are grateful to Dr. Rita Rosentsveig for her help with
brication and improves the tribological properties of rubbed the synthesis of the IFWS2 nanoparticles. This work was
surfaces. supported by grants from the Israeli Ministry of Science
Friction behavior of the IF nanoparticles can be under- (Tashtiot) and the USIsrael Binational Science Foundation.
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 References
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