Tribological behaviour of MoS

2
/Au coatings
Hsi-Hsin Chien
a
, Kung-Jeng Ma
a,
, SV P. Vattikuti
a
, Chien-Huang Kuo
a
,
Cheng-Bang Huo
b
, Choung-Lii Chao
b
a
College of Engineering, Chung Hua University, No. 707, Sec. 2, Wu Fu Rd., Hsin Chu, Taiwan
b
Department of Mechanical and Electro-Mechanical Engineering, Tam Kang University, No. 151 Ying-Chuan Road, Tamsui, Taipei County, Taiwan 251
a b s t r a c t a r t i c l e i n f o
Available online 10 May 2010
Keywords:
Tribology
MoS
2
/Au
Intralm plastic ow
This study aims to enhance the endurance of MoS
2
coating by applying a thin layer of Au (80 nm) on MoS
2
surface. Experimental results show that the addition of Au lm increases the endurance of MoS
2
/Au over
equivalent coatings without Au. The friction coefcient rapidly decreases to a stable value (0.045) after
about 100 cycles sliding. After more than 15,000 cycles, the friction coefcient gradually increased to a
second stable value (0.15). An average endurance of over 50,000 cycles was measured in this case. The Au
or AuMoS
2
composite layer can effectively prevent oxygen or moisture reaction with MoS
2
and hence
signicantly increases the wear life.
2010 Elsevier B.V. All rights reserved.
1. Introduction
The lubrication mechanisms of a layered solid lubrication lmhave
been thoroughly reviewed by many workers [14]. The endurance of a
solid lubricant lm depends on many parameters such as load,
atmosphere, sliding speed, and type of substrate. There is no general
trend regarding endurance with friction coefcient. Normally, the
friction coefcient decreases with increasing applied load; however, it
results in a decrease in endurance [5].
The simplest way to coat a solid lubricant on a metal surface is by
burnishing of the dry powder of MoS
2
with a soft tissue [6]. Another
approach to produce MoS
2
lm is by bonded coating using organic or
inorganic binders. Recently, sputter deposition provides a convenient
method for MoS
2
achieving good adhesion to most substrates and
good lubrication [7,8]. However, most published results show a low
density columnar morphology, which is susceptible to humidity or
chemical reaction. Teer et al. [9,10] developed fully dense and hard
MoS
2
lms using an unbalanced magnetron sputtering system and
found that the wear life signicantly improved over the low density
columnar MoS
2
. The application of these lms has now been greatly
expanded covering new areas such as cutting tools [11]. More recent
reports show that the tribological properties have been further
improved by the co-deposition of small or large amounts of Ti with
the MoS
2
[1216]. These MoS
2
Ti composite coatings (or called
MoST) produced by closed eld unbalanced magnetron sputtering,
are harder, much more wear resistant, and less sensitive to
atmosphere water vapour than that of MoS
2
coatings. Similar results
regarding MoS
2
metal composite coatings were obtained by other
researchers [1720]. The study of tribological behaviour of the MoS
2

Au composite or multilayer coatings is very limited. Mikhailov et al.

[21] showed that at higher contact pressures the MoS
2
/Au multi-
layers exhibited lower values of friction coefcient (0.120.1) than
comparable pure MoS
2
lms (0.210.31). They also proposed that the
role of metal is most probably associated with a structural
modication of MoS
2
rather than gettering of oxygen during sliding.
Lince et al. [22] studied tribological properties of co-sputtered metal/
MoS
2
solid lubricant lms. The results showed the performance at
different Hertzian contact stresses correlated strongly with Au
content. Both of above mentioned studies are unable to achieve low
friction (b0.05) and high endurance under a high contact pressure at
the same time. This study is devoted to the enhancement of
endurance by the addition of a thin layer of Au adding on pure
MoS
2
coatings. A very low coefcient of friction (0.045) can be
achieved at the same time. The friction and wear mechanisms of
MoS
2
/Au coatings were discussed.
2. Experimental details
M2 tool steel approximately 2520 mm in area and 2 mm
thickness were used as substrate materials. The samples were
polished to Ra=0.03 m roughness and followed by cleaning and
drying process. The MoS
2
coatings were produced using an DC
unbalanced magnetron sputtering system using sintered MoS
2
targets. Sample bias was set to 30 V. The thickness of MoS
2
is
about 0.7 m. After deposition of the MoS
2
, coating, the specimen
was moved into another chamber. RF sputtering system was used to
deposit the Au lm (thickness is about 80 nm) on MoS
2
surface to
form MoS
2
/Au multilayer coatings.
Hardness and elastic modulus of MoS
2
lms were determined
using Nanoindentation tester (MICRO MATERIALS, Nano test 600).
Thin Solid Films 518 (2010) 75327534
Corresponding author. Department of Mechanical Engineering, Chung Hua
University, No. 707, Sec. 2, Wu Fu Rd., Hsin Chu, Taiwan.
E-mail address: ma600229@ms17.hinet.net (K.-J. Ma).
0040-6090/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2010.05.040
Contents lists available at ScienceDirect
Thin Solid Films
j our nal homepage: www. el sevi er. com/ l ocat e/ t sf
Indentation tests were conducted under a depth control mode, i.e. the
loading process was reversed at a pre-set depth of 100 nm, a dwell
time of 10 s was applied to allow for possible time-dependent plastic
deformation. The indentation failure measurements were made using
Vickers microhardness tester over the load range 10500 g. Scratch
critical load Lc was carried out using a Teer Scratch Tester ST-2200
with loading rate dL/dt =100 N/min and the table speed dx/
dt =10 mm/min. Friction and wear measurements were carried out
a pin-on-disc machine, using a 5 mm diameter tungsten carbide ball
as the pin. The normal load is 40 N, the sliding speed was 250 rpm
(the linear speed is 102 m/min), and the friction force was
monitored using a force transducer All the tests were carried out in
air at 20 C, relative humidity was about 4048%.
3. Results and discussion
3.1. Microstructure and mechanical properties
Fig. 1 shows that the DC unbalanced magnetron sputtering system
with a high ion-current density can produce very dense, noncolumnar
MoS
2
layer (0.7 m thickness) on the top of M2 substrates. X-ray
diffraction results show amorphous characteristics. There is a very
thin Au layer (80 nm thickness) on the top of the MoS
2
layer. There
is no obvious structure change in MoS
2
/Au double layer coatings
compared to pure MoS
2
lm. The average chemical composition ratio
of Mo:S in the MoS
2
layer is in the range of 1.41.6 depending on the
coating parameters fromEDX analysis. Small amount of oxygen (b5%)
incorporation was observed in MoS
2
lm. The hardness and elastic
modulus of the MoS
2
layer are approximately 5.20 GPa and 102 GPa as
measured by the nanoindentation test under the maximum load of
7.4 mN, which shows a much higher hardness than conventional
MoS
2
coatings. The adhesion strength of MoS
2
and MoS
2
/Au double
layer coatings in scratch test is over 80 N. Fig. 2 shows that the laminar
structure can be easily formed on the contact surface of MoS
2
/Au
coating under a high contact pressure. The high hardness of the MoS
2
coating can be attributed to its dense structure. The metastable state
in amorphous MoS
2
coatings may favor the formation of the layer
structure with preferred orientation during scratch or wear tests.
3.2. Tribological properties
Experimental results showthat the addition of an Au lmincreases
the endurance of MoS
2
coatings, as shown in Fig. 3. The MoS
2
coatings
exhibit a very low coefcient of friction (0.03). However, it fails
after about 9000 cycles during the pin-on-disc wear tests. Repeat
sliding produces MoS
2
oriented into lamella morphology which
retains low friction. The loss of endurance of MoS
2
is believed to be
related to the reaction with oxygen and counter-face materials, which
change the wear mode of the coating and no longer provide a
lubrication effect. In the case of MoS
2
/Au multilayer systems, a
relatively high coefcient of friction (0.15) was measured during
the initial sliding, which indicates that intralm ow occurs within
the thin layer of Au to accommodate relative movement of the two
Fig. 1. SEM photograph of MoS
2
/Au coating on M2 substrate.
Fig. 2. Surface morphology of MoS
2
/Au coating after scratch test at a load of 300 g.
Fig. 3. Comparison of the endurance of the coatings during the pin-on-disc wear test; using a 5 mm dia. WC/Co ball as the pin, and the sliding speed was 150 rpm.
7533 H.-H. Chien et al. / Thin Solid Films 518 (2010) 75327534
surfaces. Repeated sliding allows the Au to pile up at the edge of wear
tracks, thinning the Au layer. The MoS
2
layer gradually becomes
involved in the plastic ow process if the shear stress developed is
above the shear strength of the MoS
2
coatings. The friction coefcient
rapidly decreases to a stable value (0.045) as MoS
2
shears.
Continued sliding allows the Au to combine with the orientated
MoS
2
to form a very thin AuMoS
2
composite layer (Fig. 4(a)). The
transfer and detachment alternately of layered AuMoS
2
wear debris
occur at this stage. It can be observed that Au or AuMoS
2
composite
wear debris smear and adhere on the crack crevices of MoS
2
under-
layer (Fig. 4(b)), which can effectively delay oxygen reaction with
MoS
2
lm. In this stage, both intralm plastic ow within orientated
MoS
2
and AuMoS
2
composite layers and interlm sliding between
the Au and MoS
2
composite wear debris are thought to involve the
friction process. It is believed that the orientated MoS
2
most probably
dominates the energy dissipation process and results in a very low
friction coefcient (0.045), approaching the value of pure MoS
2
. This
result is quite different compared with the other researchers [21,22].
It is believed that the intralmow occurs within the thin layer of Au
in their MoS
2
/Au multi-layers, and dominates the whole plastic ow
or energy dissipation process. The intralm plastic ow within
orientated MoS
2
was depressed. This can explain why a relatively
higher coefcient of friction (0.12) was obtained in their multilayer
coatings. Further increasing the applied load may favor intralm
plastic ow within orientated MoS
2
and decreasing the coefcient of
friction.
After more than 15,000 cycles of sliding, the MoS
2
layer totally
combines Au to form a AuMoS
2
composite layer, the plastic ow and
interlm sliding will occur in the AuMoS
2
composite layer to
accommodate shear and normal stresses. The friction coefcient
gradually increased to a second stable value (0.15). The gold
contents on worn region after about 1000 and 15,000 cycles are
12.31% and 10.30 wt.% respectively, from EDX analysis. The oxygen
content was increased with the sliding duration. It is believed that the
Au or AuMoS
2
composite layer can effectively delay oxygen or
moisture reaction with MoS
2
and hence signicantly increase the
wear life. The stable value of friction 0.15 is maintained up to
50,000 cycles. It is estimated the lifetime is over 50,000 cycles.
A smaller coefcient of friction of 0.040 was obtained at the Au top
layer of 30 nmafter 80 cycles wear test. However, this lowfriction can
last only to 11,000 cycles and then the coefcient of friction was
gradually increased to a higher value (0.140.15) with the duration.
The estimated lifetime is up to 38,000 cycles in this case.
4. Conclusions
The loss of endurance of MoS
2
is believed to be related to the
reaction with oxygen and counter-face materials, which changes the
transfer and wear mode of the coating and thus no longer provides a
lubrication effect. Applying a very thin layer of Au on the MoS
2
layer
can signicantly avoid humidity or tribochemical effects on the MoS
2
layer and hence signicantly increase the wear life.
Acknowledgement
The authors are grateful toDr. D.G. Teer for the provisionof specimens
and helpful discussion.
References
[1] C. Donnet, M. Belin, T. LeMogne, J.M. Martin, in: D. Dowson, et al., (Eds.), The Third
Body Concept, Elsevier, Amsterdam, 1996, p. 289.
[2] E.W. Robert, W.B. Price, in: L. Pope, L. Fehrenbacher, W. Winer (Eds.), New
Materials Approaches to Tribology: Theory and Applications, Materials Research
Society Symposium Proceeding, 140, 1989, p. 251.
[3] W.O. Winer, Wear 10 (1967) 422.
[4] T. Spalvins, J. Vac. Sci. Technol. A5 (1987) 212.
[5] I.L. Singer, R.N. Bolster, J. Wegand, S. Fayeulle, B.C. Stupp, Appl. Phys. Lett. 57
(1990) 995.
[6] J.K. Lancaster, in: E.R. Booser (Ed.), CRC Handbook of Lubrication, Vol. 2, Theory of
Lubrication, CRC Press, New York, 1984, p. 269.
[7] T. Spalvins, ASLE Trans. 14 (1971) 267.
[8] P.D. Ehni, I.L. Singer, in: L. Pope, L. Fehrenbacher, W. Winer (Eds.), New Materials
Approaches to Tribology: Theory and Applications, Materials Research Society
Symposium Proceeding, 140, 1989, p. 245.
[9] D.G. Teer, J. Hampshire, V. Fox, V. Bellido- Gonzalez, Surf. Coat. Technol. 94/95
(1997) 572.
[10] D.G. Teer, J.H. Hampshire, V. Bellido, EU Patent EU 96924987.9, 1996.
[11] J. Rechberger, R. Dubach, Surf. Coat. Technol. 60 (1993) 584.
[12] V. Fox, V. Bellido-Gonzalez, A.H.S. Jones, J. Hampshire, T.J. Allen, J. Witts, D.G. Teer,
K.J. Ma, D. Upton, Surf. Coat. Technol. 97 (1997) 687.
[13] N.M. Renevier, V.C. Fox, D.G. Teer, J. Hampshire, Surf. Coat. Technol. 127 (2000) 24.
[14] N.M. Renevier, J. Hamphire, V.C. Fox, J. Witts, T. Allen, D.G. Teer, Surf. Coat.
Technol. 142/144 (2001) 67.
[15] E. Arslan, F. Bulbul, A. Alsaran, A. Celik, I. Efeoglu, Wear 259 (2005) 814.
[16] D.G. Teer, N.M. Renevier, D. Boscarino, A. Patelli, G. Maggioni, V. Rigato, Surf. Coat.
Technol. 131 (2000) 206.
[17] J. Lince, M. Hilton, A.S. Bommannavar, J. Mater. Res. 10 (1995) 2091.
[18] M.C. Simmonds, A. Savan, H. Van Swygenhoven, E. Puger, S. Mikhailov, Surf. Coat.
Technol. 108/109 (1998) 340.
[19] M.R. Hilton, G. Jayaram, L.D. Marks, J. Mater. Res. 13 (1998) 1022.
[20] J.D. Holbery, E. Pueger, A. Savan, Y. Gerbig, Q. Luo, D.B. Lewis, W.-D. Munz, Surf.
Coat. Technol. 169 /170 (2003) 716.
[21] S. Mikhailov, A. Savan, E. Puger, L. Knoblauch, R. Hauert, M. Simmonds, H. Van
Swygenhoven, Surf. Coat. Technol. 105 (1998) 175.
[22] J. Lince, H.I. Kim, P.M. Adams, D.J. Dickrell, M.T. Dugger, Thin Solid Films 517
(2009) 5516.
Fig. 4. (a) Cross-sectional and (b) surface SEMimages of MoS
2
/Au coatings after pin-on-
disc wear test (3000 cycles) at a load 40 N, using a 5 mm dia. WC/Co ball as the pin,
and the sliding speed was 150 rpm.
7534 H.-H. Chien et al. / Thin Solid Films 518 (2010) 75327534