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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
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. 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
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