Wear 253 (2002) 572–575

Preparation of NiMoO2 S2 nanoparticle and investigation

of its tribological behavior as additive in lubricating oils
Pingping Ye∗ , Xiaoxia Jiang, Shu Li, Shizhuo Li
Institute of Metal Research, Chinese Academy of Science, Shenyang 110015, PR China
Received 19 June 2001; received in revised form 11 February 2002; accepted 12 March 2002

Abstract
Nickel oxythiomolybdate (NiMoO2 S2 ) nanoparticles with an average size of 13 nm were synthesized in the microemulsion system of
sodium dodecyl-sulphate (SDS)/isopentanol/cyclohexanene/water. The tribological performances of the prepared NiMoO2 S2 nanoparticles
as a lubricating additive were evaluated in four-ball wear tester and a pin-on-disc tester at elevated temperature. The results showed that
NiMoO2 S2 nanoparticles as additive exhibit very good EP behavior and possess good anti-frictional performance with a smooth transition
from fluid film lubrication at low temperature to solid film lubrication at elevated temperature, which could fit the needs of lubrication at
large temperature range.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Microemulsion; Oil additive; Solid lubricant

1. Introduction at elevated temperature, but its poor solubility in oils limits

With the challenge of environment protection and energy
crisis, the developing countries are devoting themselves to
the study of advanced heat engine, such as adiabatic or low
heat rejection (LHR) engine. With the use of heat-resisting
materials (ceramic) and the simplicity of cooling system,
engine bearing environmental temperatures are expected
to exceed 65 ◦ C. The severity of thermal environment will
limit the use of conventional and high-performance and
high-temperature liquid lubricants, while most of the solid
lubricants are effective only within a narrow temperature
range. It is difficult to find a solid lubricant with low fric-
tion from room temperature to high temperature (700 ◦ C).
Sutor [1] mentioned that inorganic oxythiomolybdates
(Cs2 MoO2 S2 , ZnMoO2 S2 ) has encouraging tribological re-
sults for ceramic and metal sliding up to 650 ◦ C. Li et al. [2]
and Gao et al. [3] also synthesized nickel oxythiomolybdate
and zinc oxythiomolybdate and investigated their tribologi-
cal behavior, finding that NiMoO2 S2 and ZnMoO2 S2 show
good anti-frictional performance from room temperature to
700 ◦ C and the tribological properties of NiMoO2 S2 are bet-
ter than ZnMoO2 S2 . Nickel oxythiomolybdate (NiMoO2 S2 )
is a good lubricant which can fit the needs of lubrication
∗ Corresponding author. Present address: Department of Chemistry,
Carnegie Mellon University, Pittsburgh, PA 15213, USA.
E-mail address: ppye@andrew.cmu.edu (P. Ye).
its use in lubricating oils. Therefore, it is very interesting
and also urgent to increase oil-solubility of NiMoO2 S2 in
lubricating oils.
This problem could be resolved by suspension of ultra
fine even nanoparticles in fluid. There have been some
reports about modified nanoparticles as lubricant in liquid
paraffin [4–7]. The nanoparticles modified with a layer
of surfactants have good dispersivity in oils. They can be
prepared by microemulsion system [8–10]. In this paper,
NiMoO2 S2 nanoparticles were synthesized in microemul-
sion system and its tribological properties were investigated
both in form of additive at room temperature and solid
lubricant at elevated temperature. An oil–solid lubrication
mixed model also has been explored from room temperature
to high temperature.
2. Experimental procedure
2.1. Chemicals and equipment
Dodecyl-sulphate (SDS), isopentanol, cyclohexanene
and NiSO4 ·7H2 O were AR grade used without further
treatments. The (NH4 )2 MoO2 S2 was synthesized based on
references [3,11,12] with solvents of deionized water and
analytically pure ethanol. The morphology of the nanopar-
ticles were investigated by a JEM-1200 EX/S transmission

0043-1648/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 3 - 1 6 4 8 ( 0 2 ) 0 0 0 4 2 - X
 P. Ye et al. / Wear 253 (2002) 572–575
electron microscope. The XRD results of NiMoO2 S2 at
different temperature were taken from D/max-rA X-ray
diffraction (Cu K␣ radiation source). A four-ball tester and
pin-on-disc tester were used to characterize the tribological
performances of the NiMoO2 S2 as an additive in oil at
room temperature and elevated temperature, respectively.
2.2. Preparation of NiMoO2 S2 nanoparticles
A microemulsion system of sodium SDS/isopentanol/
cyclohexanene/water was selected for the synthesis of
the NiMoO2 S2 nanoparticles. The certain weight ratio of
SDS:isopentanol:cyclohexanene:water is fixed. Both of the
concentrations of NiSO4 solution and (NH4 )2 MoO2 S2 so-
lution were 0.02 mol/l. SDS, isopentanol, cyclohexanene
and NiSO4 solution were blended to form microemulsions
using ultrasonic vibration. Then the (NH4 )2 MoO2 S2 solu-
tion with the same volume of the NiSO4 solution were also
gradually dropped into the microemulsion system during the
ultrasonic vibration. The reaction should be prompted with
ultrasonic excitation for an hour further and the tempera-
ture maintained at 30 ◦ C. The final product was obtained
by centrifugation, rinsing in ethanol and keeping in a de-
gassed desiccator for 24 h. Consequently, a dark powder of
NiMoO2 S2 nanoparticle was obtained.
The above nickel oxythiomolybdate is produced accord-
ing to the following chemical reaction [2]:
NiSO4 + (NH4 )2 MoO2 S2
→ Ni MoO2 S2 ↓ +(NH4 )2 SO4
2.3. Tribological performances of the synthesized
NiMoO2 S2 nanoparticles as additive in synthetic oils
NiMoO2 S2 nanoparticles were dispersed well in syn-
thetic oil of Pentaerythritoltetraester (PETE) with dispersant
Fig. 1. (a) TEM of NiMoO2 S2 nanoparticles. (b) The ED pattern of NiMoO2 S2 nanoparticles.
573
alkenyl polyamine succinimide (T154). The maximum non-
seizure loads (PB) were evaluated on a modified four-ball
tester at 1973 rpm and room temperature, according to
ASTM D2783. The balls (12.7 mm in diameter) in the
test are made of GCr 15 bearing steel with a hardness of
HRc 59–61.The experiments of the effect of NiMoO2 S2
on transition of lubrication from oil film lubrication at low
temperature to solid film lubrication at elevated temperature
were evaluated on pin-on-disc tester. An Al2 O3 ceramic ball
in diameter of 12.7 mm against a stainless steel plate forms
the rubbing pair. The roughness of the steel plate is 4.2 ␮m.
The loading is 30 N, while the sliding speed is 0.2 m/s.
3. Results and discussion
3.1. NiMoO2 S2 nanoparticles size
Fig. 1 shows the TEM image and the electron diffraction
pattern of the NiMoO2 S2 nanoparticles. Fig. 2 shows the par-
ticle size distribution of NiMoO2 S2 . It is found that the par-
ticles have an average size of about 13 nm, and the even and
wide electron diffraction circle in ED pattern also showed
that the size of the prepared particles is in nanosize. This in-
dicated that the microemulsion method is a powerful method
to obtain ultrafine particles because the small size and the
cage-like nature of the microemulsion water cores limit the
growth and aggregation of particles. What’s more, the highly
dispersed surfactants can prevent NiMoO2 S2 nanoparticles
from agglomerating effectively.
(1)
3.2. Load carrying capacity
The maximum nonseizure loads (PB) of NiMoO2 S2 as ad-
ditive in PETE are shown in Fig. 3. It can be seen that when
the dosage of NiMoO2 S2 nanoparticles is 0.2%, the PB in-
creased by nearly two times, while the PB of NiMoO2 S2
574 P. Ye et al. / Wear 253 (2002) 572–575

Fig. 2. Size histograms of NiMoO2 S2 .

with a average size of 3 ␮m as additive in PETE increased
by 20%. It is suggested that the NiMoO2 S2 as additive can
improve the PB of lubricating oils, and with the size of par-
ticles decreasing to nanosize, the PB increased remarkably.
3.3. Friction-reducing property from room temperature
20 ◦ C to high temperature 700 ◦ C
The results of the friction coefficient of NiMoO2 S2 as
additive in lubricating oils at room temperature 20 ◦ C and
solid lubricant at elevated temperature are shown in Fig. 4.
The friction coefficients of NiMoO2 S2 as additive with the
average size of 3 ␮m are higher than the synthetic oil below
around 300 ◦ C. It is suggested that in this condition, the fluid
lubrication and moderate boundary lubrication play the ma-
jor role. Under that temperature, the synthetic oil possesses
good lubricating properties itself, while the big size additive
increased the friction coefficient. At 300 ◦ C, the oil begins to
volatile or decompose, NiMoO2 S2 could form a protection
layer on the friction surface, therefore, the friction coeffi-
cient with NiMoO2 S2 additive lower than the corresponding
synthetic oil without additive. When the temperature kept
increasing, the friction coefficients change due to the differ-
ent decomposing products of NiMoO2 S2 at different tem-
perature, which can be roughly explained by the XRD of
NiMoO2 S2 at different temperature shown in Table 1. Fur-
ther experiments will be done to explore the mechanism of
this friction behavior.
The friction coefficient of NiMoO2 S2 nanoparticles as ad-
ditive is as same as synthetic oil under 200 ◦ C, and lower
than synthetic oil above 200 ◦ C, and it is indicated that the
friction coefficient from room temperature 20 ◦ C to high
temperature 700 ◦ C was below 0.25 ␮m, lower than that of
the big size NiMoO2 S2 , which may be due to the special

Fig. 3. Four-ball test results for NiMoO2 S2 additive.

 P. Ye et al. / Wear 253 (2002) 572–575 575

Fig. 4. Effect of load on friction coefficient for NiMoO2 S2 additive.

Table 1 4. Nanosize NiMoO2 S2 has better tribological properties

The XRD of the products of NiMoO2 S2 at different temperature than big size NiMoO2 S2 .
Temperature (◦ C) NiMoO2 S2 MoO3 NiMoO4 NiO NiS MoS2 5. An oil–solid lubrication mixed model has been explored
20 Major
successfully.
300 Major Micro
400 Major Trace Trace
500 Major Trace Minor Trace Acknowledgements
600 Major Major Major Minor Micro
700 Major Minor Micro
The project was supported by the National Nature Science
Foundation of China, no. 59775040.
properties of nanoparticles compared with the big size parti-
cles. The low friction coefficients which change gently from
References
room temperature to high temperature imply that a smooth
transition of frictional state could exist from oil film lubri- [1] P. Sutor, MRS Bull. 16 (5) (1991) 24.
cation to solid film lubrication. [2] S. Li, H. Gao, et al., in: Proceedings of ASIATRIB’98, Beijing,
1998, pp. 722–725.
[3] H. Gao, S. Li, X. Jiang, J. Mater. Sci. Technol. 5 (1994) 313–320.
4. Conclusion [4] J. Zhou, J. Yang, Z. Zhang, W. Liu, Q. Xue, Mater. Res. Bull. 34 (9)
(1999) 1361–1367.
[5] S. Chen, W. Liu, L. Yu, Wear 218 (1998) 153–158.
1. NiMoO2 S2 nanoparticles with about 13 nm were pre- [6] W. Liu, S. Chen, Wear 238 (2000) 120–124.
[7] Z. Zhang, W. Liu, Q. Xue, Wear 248 (2001) 48–54.
pared by the microemulsion of SDS/isopentanol/ [8] P. Lianos, J.K. Thomas, Mater. Sci. Forum 25/26 (1988) 369.
cyclohexanene/water. [9] T. Dannhausser, T.F. Towey, S. Zourab, A.J. Visser, A.V. Hoek,
2. NiMoO2 S2 nanoparticle as additive in PETE has high Colloids Surf. 61 (1991) 175.
load carrying capacity. [10] M.L. Steigerwald, A.P. Alivisators, J.M. Gibson, T.D. Harns, R.
3. NiMoO2 S2 nanoparticle possesses very good anti-fric- Kortan, A.J. Muller, A.M. Tyayer, T.M. Duncan, D.S. Doughlas, L.E.
Brus, J. Am. Chem. Soc. 110 (1988) 3046.
tional performances both in form of additive in lubri- [11] W.M. John, et al., Inorg. Chim. Acta 72 (1983) 205–210.
cating oils at room temperature and solid lubricant at [12] Von.A. Muller, E. Diemann, U. Heidbon, Zeitschrift fur anorganische
elevated temperature. und allgemeine Chemie B 371 (1969) 136–146.