Professional Documents
Culture Documents
Greenberg 2004
Greenberg 2004
a
Department of Mechanical Engineering, Technion, Haifa 32000, Israel
Department of Materials and Interfaces, Weizmann Institute, Rehovot 76100, Israel
A study of the tribological behavior of nested inorganic fullerene-like (IF) nanoparticles of WS2, as a potential additive to
base oils is presented. Friction measurement results obtained from three dierent test rigs over a wide range of normal loads
and sliding velocities are shown. Stribeck curves are used to reveal the lubrication regimes where the IF are most eective. It is
found that the addition of IF-WS2 nanoparticles to the base oils results in up to 50% reduction in friction coecient in the
mixed lubrication regime. The mechanism of improved friction and wear behavior with the IF additive is discussed.
KEY WORDS: nanoparticles, friction, lubrication, oil additives, solid lubricants
1. Introduction
Solid lubricants, such as metal dichalcogenide MoS2
or graphite, have been extensively studied and used for
a long time as additives in lubricating oils to reduce
friction and wear of rubbing pairs [1]. The role of
MoS2 powder as a solid lubricant has been discussed
in great detail in Ref. [2]. Fewer studies have been
focused on other metal dichalcogenides such as WS2,
which can also display good lubricating properties [3].
Metal dichalcogenides of the form MX2 (M W, Mo;
X S, Se) have a characteristic anisotropic layered
structure. Strong covalent forces bind M and X atoms
within a lamella, whereas adjacent lamellae interact
through relatively weak van der Waals forces. The unit
cell has a hexagonal symmetry and includes two adjacent lamellae (2H arrangement). This graphite-like
structure is considered to be responsible for the lubricating properties of these materials, because the weak
inter-lamellar bonding facilitates the shear when the
direction of sliding is parallel to the planes of the
material [15].
From the studies of solid lubricants as additives to
lubricating oils, it was concluded that the eectiveness
of the additives was very much dependant on the particle size [6]. Thereby interest in nanoparticles has grown
rapidly during the past decade. The nanometric dimensions of such particles give them unique characteristics,
which cannot be obtained in conventional bulk materials. In the past few years, nested spherical supramole* To whom correspondence should be addressed. E-mail: etsion
@tx.technion.ac.il
180
a Stribeck number gV=P where g is the dynamic viscosity, V is the sliding velocity, and P is the mean contact pressure at the sliding interface. The general shape
of the Stribeck curve depicting the three main lubrication regimes (boundary, mixed, and hydrodynamic) is
common for every lubricated sliding system, but the
Stribeck numbers at which the transition from a certain regime to another occurs are characteristic for
each individual system.
During this research program, tests were performed
with the investigated additive (IF) and results were
compared with baseline data obtained from testing of
pure base oils. Presenting the results by Stribeck curves
helped identifying the lubrication regime with the most
perceivable eect of IF on reduction of friction. Determining such a lubrication regime could also assist in
understanding the lubrication mechanism of IF.
Table 1
Test conditions for the three test rigs.
Test rig concept
Flat-on-at tester
Roller-on-rib tester
Ball-on-at tester
Velocity (mm/s)
0.66
801410
3e-40.11
d = 15, height = 3
disc
AISI 2510/65 HRC
90 16 5 plate
AISI 2510/65 HRC
0.05, 0.1
SN 90, SN 150, bright stock
15
15,000
2.2514.80
Width = 1 mm, length=10
rib
Brass/21 HRC
d = 38, width = 10 roller
Steel/51 HRC
0.22
SN 90, SN 150
5
300
420840
d=5
ball
Bearing steel/64 HRC
90 16 5 Plate
AISI 2510/65 HRC
0.06
SN 90, SN 150
5
400
Figure 1. Schematic
diagram of the
apparatus.
at-on-at
experimental
q
by (see e.g., Ref. [18]) Ra R2a1 R2a2 where Ra1 and
Ra2 are the roughness average values of the two triboelements, respectively was either 102 or 54 nm. The
specimens were demagnetized before the beginning of
the experiments and were stored in polyethylene packs
after dipping in SN 90 oil to prevent corrosion. Both
181
tribo-elements were cleaned immediately prior to testing with acetone in an ultrasonic bath.
Prior to each test a constant number of lubricant
drops, having a mass of 6 0.5 mg each, was placed
on the plate surface, using a regular 5 mL syringe, to
form a thin lubricating lm of uniform thickness. The
electric motor was turned on to start the sliding
motion and sampling of the friction measurements
started as soon as steady state was reached. By conducting the tests over a range of contact pressures
between 3 10)4 and 0.116 MPa and a range of sliding speeds between 0.6 and 6 mm/s, the Stribeck curve
of the system was constructed, showing the various
lubrication regimes.
The second device is a slightly modied existing
roller-on-block tester, previously described in [19],
where a rotating roller is loaded against a rib to simulate conformal rotational sliding like in journal bearings for example. The unique feature of this test rig is
in keeping the area of contact constant despite the
evolving wear of the tribo-elements. The variation of
the friction force, electrical contact resistance, temperature of the rib, and wear as functions of time were registered continuously during the test duration. The
contact pressures ranged from 2.25 to 14.80 MPa, and
the sliding speeds ranged from 0.08 to 1.41 m/s. The
rib was made of brass of hardness 21 3 HRC to
provide relatively high wear rates and facilitate wear
measurements in reasonably short test times. Steady
friction conditions were maintained by using the aforementioned syringe to regularly place lubricant drops
on the rotating roller at a rate of 1 drop every 10 s.
A third test rig that was used to investigate the IF
under fretting conditions is based on a ball-on-at
contact scheme and is described in more details in
Ref. [20]. Fretting occurs in many mechanical systems
when two contacting surfaces, nominally at rest with
respect to each other, are subjected to deformations
and/or vibrations as a result of the machine work. The
measuring system of this device allows on-line measurements of parameters such as friction force, relative
displacement, contact electrical resistance, frequency
and number of fretting cycles. The mean Hertzian contact pressures in this test were varied in the range of
420 to 840 MPa, the mean sliding speed was 2 mm/s
and the sliding amplitude was 148 lm. One drop of
lubricant was placed, by using the syringe, between the
specimens in the beginning of each test. The drop created a meniscus that kept the ball-on-at contact zone
lubricated throughout the duration of each test.
Prior to the main research program, some preliminary testing was performed on all test rigs to determine
the required test periods and the repeatability of the
three testing devices. It should be noticed that separate
pairs of tribo-element specimens were used for the
experiments with and without the IF to prevent any possible eect of IF traces on the tests with pure base oils.
182
Oil
Viscosity index
17
32
450
3.75
5.3
32
860
860
900
97
98
92
SN 90
SN 150
Bright stock
Figure 4. Stribeck curves from the at-on-at test with bright stock
lubricant.
183
184
TW
L Fn
Figure 7. XPS analysis of rib specimens following tests with pure oil
and with oil + IF.
185
in the Stribeck number was the normal load. Therefore, it seems that there exists a critical normal load,
corresponding to the transitional Stribeck number,
above which some abrupt change occurs in the contact
interface. From the results in gure 9 it seems that this
critical load is unrelated to the presence of IF in the
lubricant, although the presence of IF results in a substantial reduction of about 50% in friction below that
critical load.
Figure 10 presents the contact electrical resistance
behavior in the ball-on-at tests. As can be seen, in
the mixed lubrication regime the contact electrical
resistance in the case of the IF presence is much larger
than that for the pure oil. In this regime the electrical
resistance decreases slightly in both cases as the load
increases due to the reduction in the lm thickness. As
soon as the critical load is exceeded the electrical resistance in the SN 90 + IF case drops sharply and starts
behaving exactly like that in the pure oil case. The
results that are shown in gures 9 and 10 support the
assumption of lubrication mechanism by IF transfer
lm. As a result of the friction process, a transfer lm
forms on the surfaces of the tribo-elements and causes
a decrease in the friction coecient and an increase in
the electrical resistance. Above a certain critical load,
corresponding to the transition from the mixed to the
boundary lubrication regime, the transfer lm is
destroyed, thereby increasing the friction coecient
and reducing the electrical resistance.
The results in gures 9 and 10 show that in the
boundary lubrication regime (above the critical load)
there is still some eect of the IF on the reduction of
the friction coecient but there is no dierence in the
electrical resistance of pure oil or oil + IF. Presumably, some isolated islands of WS2 that still remain on
the surfaces after the transfer lm was destroyed help
reduce the friction but do not aect the electrical resistance.
The results shown in gures 9 and 10 are typical;
very similar results were obtained with the SN 150 oil.
The only dierences were a slightly lower friction coefcient levels and a higher transition Stribeck number,
at about 7.5 10)11 m, compared to the SN 90 oil. A
few experiments were conducted with SN 90
oil + 2H-WS2 additive. The results showed lower friction coecients in the mixed lubrication regime compared to the pure SN 90 oil however, the improvement
was only half of that with the IF additive.
4. Conclusion
186
Acknowledgments
This research was supported in parts by the Fund
for the Promotion of Research at Technion and by the
Israel Ministry of Science. The authors gratefully
acknowledge help of Dr. R. Rosentsveig in the synthe-
References
[1] F.J. Clauss, Solid Lubricants and Self-lubricating Solids
(Academic Press, New York and London, 1972).
[2] I.L. Singer, in: Fundamentals of Friction: Macroscopic and
Microscopic Processes, eds. I.L. Singer and H.M. Pollock (Kluwer, Dordrecht, 1992).
[3] S.V. Prasad and J.S. Zabinski, J. Mater. Sci. Lett. 12 (1993)
1413.
[4] G.W. Stachowiak and A.W. Batchelor, Engineering Tribology
(Elsevier, Amsterdam, 1993).
[5] T. Hisakado, T. Tsukizoe and H. Yoshikawa, J. Lubricat. Technol. 105 (1983) 245.
[6] W.J. Bartz, ASLE Proc. Int. Conf. Solid Lubrication (1971) 335.
[7] R. Tenne, L. Margulis, M. Genut and G. Hodes, Nature 360
(1992) 444.
[8] R. Tenne, M. Homyonfer and Y. Feldman, Chem. Mater. 10
(1996) 3225.
[9] R. Tenne, M. Homyonfer and Y. Feldman, Adv. Metal Semicond. Clusters 4 (1998) 227.
[10] D.J. Srolovitz, S.A. Safran, M. Homyonfer and R. Tenne, Phys.
Rev. Lett. 74 (1995) 1779.
[11] L. Rapoport, Y. Feldman, M. Homyonfer, H. Cohen, J. Sloan,
J.L. Hutchison and R. Tenne, Wear 225 (1999) 975.
[12] L. Rapoport, Yu. Bilik, Y. Feldman, M. Homyonfer, S.H. Cohen
and R. Tenne, Nature 387 (1997) 791.
[13] S.R. Cohen, Y. Feldman, H. Cohen and R. Tenne, Appl. Surf.
Sci. 144 (1999) 603.
[14] Y. Golan, C. Drummond, M. Homyonfer, Y. Feldman,
R. Tenne and J. Israelachvili, Adv. Mater. 11 (1999) 934.
[15] Y. Golan, C. Drummond, J. Israelachvili and R. Tenne, Wear
245 (2000) 190.
[16] U.S. Schwarz, S. Komura and S.A. Safran, Phys. Rev. Lett. 85
(2000) 1671.
[17] M. Chhowalla and G.A.J. Amaratunga, Nature 407 (2000) 164.
[18] H. Czihos, Tribology (Elsevier, Amsterdam, 1978).
[19] G. Dehm, B. Medres, L. Shepeleva, C. Scheu, M. Bamberger,
B.L. Mordike, S. Mordike, G. Ryk, G. Halperin and I. Etsion,
Wear 225229 (1999) 18.
[20] M. Varenberg, G. Halperin and I. Etsion, Wear 252 (2002) 902.
[21] T. Mathia and F. Louis, Powder Technol, 37 (1984) 155.
[22] S. Qiu, J. Dong and G. Chen, Lubricat. Sci. 12 (2000) 205.
[23] M. Shen, J. Luo and S. Wen, Tribol. Trans. 44 (2001) 494.
[24] Y. Feldman, G.L. Frey, M. Homyonfer, V. Lyakhovitskaya,
L. Margulis, H. Cohen, G. Hodes, J.L. Hutchison and R.
Tenne, J. Am. Chem. Soc. 118 (1996) 5362.