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Nano-MoS2 and Graphene Additives in Oil for Tribological Applications
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DOI: 10.1007/978-3-319-60630-9_6
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Chapter Title Nano-MoS2 and Graphene Additives in Oil for Tribological Applications
Copyright Year 2018
Copyright Holder Springer International Publishing AG
Corresponding Author Family Name Xu
Particle
Given Name Yufu
Suffix
Division Institute of Tribology, School of Mechanical Engineering
Organization Hefei University of Technology
Address Hefei 230009, China
Email xuyufu@hfut.edu.cn
Author Family Name Peng
Particle
Given Name Yubin
Suffix
Author Family Name You
Particle
Given Name Tao
Suffix
Author Family Name Yao
Particle
Given Name Lulu
Suffix
Division School of Chemistry and Chemical Engineering
Author Family Name Geng
Particle
Given Name Jian
Suffix
Author Family Name Dearn
Particle
Given Name Karl D.
Suffix
Division Department of Mechanical Engineering, School of
Engineering
Organization University of Birmingham
Address Edgbaston, Birmingham B152TT, UK
Author Family Name Hu
Particle
Given Name Xianguo
Suffix
Abstract Nano-additives have attracted lots of attentions in recent years due to their
special performances. A traditional lubricating additive MoS2 with nano-
scale and a novel additive graphene were reviewed in this chapter. The
synthesis methods, properties, and tribological applications of these two
kinds of nano-additives dispersed in media have been reported. Nano-MoS2
has three main nanostructures including nano-ball particles, nano-sheets, and
nano-tubes. The wide accepted lubricating mechanisms for the MoS2 nano-
balls, nano-sheets, and nano-tubes are nano-bearing effects, slippery roles,
and combined actions of rolling and sliding, respectively. Exfoliation and
transfer seem to be the main pattern for MoS2 nano-balls. For graphene, the
adsorption and tribo-reaction account for its lubricating properties. A
synergistic lubricating effect for using graphene and MoS2 together
dispersed in oil was found. Graphene was proved to extend the retention of
MoS2 on the surfaces and prevent the oxidation of MoS2. Simultaneously,
MoS2 prevented the graphene from being ground into small and defective
platelets. Both of them help to form a thicker adsorbed and tribo-film which
result in a lower friction and wear. Other properties and applications of nano-
MoS2 and graphene are also reviewed. It shows that these two nano-additives
have diverse functions and great potential for industrial applications.
Keywords Nano-MoS2 - Graphene - Nano-additives - Tribological application
(separated by ‘-’)
Chapter 6 1
Nano-MoS2 and Graphene Additives in Oil 2
for Tribological Applications 3
Yufu Xu, Yubin Peng, Tao You, Lulu Yao, Jian Geng, Karl D. Dearn, 4
and Xianguo Hu 5
Abstract Nano-additives have attracted lots of attentions in recent years due to 6

their special performances. A traditional lubricating additive MoS2 with nano-scale 7
and a novel additive graphene were reviewed in this chapter. The synthesis 8
methods, properties, and tribological applications of these two kinds of nano- 9
additives dispersed in media have been reported. Nano-MoS2 has three main 10
nanostructures including nano-ball particles, nano-sheets, and nano-tubes. The 11
wide accepted lubricating mechanisms for the MoS2 nano-balls, nano-sheets, and 12
nano-tubes are nano-bearing effects, slippery roles, and combined actions of rolling 13
and sliding, respectively. Exfoliation and transfer seem to be the main pattern for 14
MoS2 nano-balls. For graphene, the adsorption and tribo-reaction account for its 15
lubricating properties. A synergistic lubricating effect for using graphene and MoS2 16
together dispersed in oil was found. Graphene was proved to extend the retention of 17
MoS2 on the surfaces and prevent the oxidation of MoS2. Simultaneously, MoS2 18
prevented the graphene from being ground into small and defective platelets. Both 19
of them help to form a thicker adsorbed and tribo-film which result in a lower 20
friction and wear. Other properties and applications of nano-MoS2 and graphene are 21
also reviewed. It shows that these two nano-additives have diverse functions and 22
great potential for industrial applications. 23
Keywords Nano-MoS2 • Graphene • Nano-additives • Tribological application 24
Y. Xu (*) • Y. Peng • T. You • J. Geng • X. Hu

Institute of Tribology, School of Mechanical Engineering, Hefei University of Technology,
Hefei 230009, China
e-mail: xuyufu@hfut.edu.cn
L. Yao
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei
230009, China
K.D. Dearn
Department of Mechanical Engineering, School of Engineering, University of Birmingham,
Edgbaston, Birmingham B152TT, UK
© Springer International Publishing AG 2018

T. Saleh (ed.), Nanotechnology in Oil and Gas Industries, Topics in Mining,
Metallurgy and Materials Engineering, DOI 10.1007/978-3-319-60630-9_6
Y. Xu et al.
25 1 Introduction
26 A general demand from Society for a more sustainable and environmentally

27 friendly development has led to an increasing interest and a growing corpus of
28 work on energy-saving and emission reduction technologies (Price and Levine AU1
29 2011). The internal combustion engine is one such technology that has seen huge
30 improvements in fuel efficiency, reduced overall energy consumption and emis-
31 sions, and a key aspect of this has been improvements to the lubrication system
32 (Abdelaziz and Saidur 2011).
33 With the development of the nanotechnologies, the use of nano-additives added
34 to base oils have been shown to reduce friction and wear due to their excellent
35 lubricating effects. Some common solid particle lubricants such as nano-MoS2 and
36 graphene have made the transition from concept to the application and are showing
37 great potential in the industry. However, there still exists a gap between the
38 scientists and industrial engineers, relating to a general willingness to use the
39 newly formulated additives (Zhmud and Pasalskiy 2013). However, if emissions
40 and fuel consumption targets are to be met, then nano-additives, added to lubricant
41 formulations will be a vital component for industry to deploy to meet these
42 objectives.
43 In this chapter, the progress and particularly the tribological behaviors of some
44 key nano-additives dispersed in base oil are reviewed, and the trends in future
45 developments of nano-additives are discussed in order to accelerate their
46 application.
47 2 An Introduction to and the Tribological Behavior

48 of Nano-MoS2
49 Molybdenum disulfide (MoS2) has a layered two-dimensional structure. Its crystal

50 structure contains 1T-MoS2, 2H-MoS2, and 3R-MoS2. 1T-MoS2, per unit cell, has
51 an octahedral structure with S atoms and one Mo atom; 2H-MoS2 has a Mo atom
52 with a hexagonal structure and two S-Mo-S covalent bonds, and 3R-MoS2 has a Mo
53 atom with a hexagonal structure and three S-Mo-S covalent bonds. Their respective
54 structures are shown in Fig. 6.1. Among these MoS2 crystals, 1T and 3R-MoS2 are
55 metastable and 2H-MoS2 is stable under normal conditions. But no matter which
56 crystal, each S atom is surrounded by 3 Mo atoms, and each Mo atom is surrounded
57 by six S atoms consisting of S-Mo-S covalent bonds (Dickinson and Pauling 1923),
58 such that the atom ratio of Mo and S is 1:2.
59 The layered structure of MoS2 has excellent tribological properties which are
60 attributed to a combination of its low Van der Waals force between the molecule
61 layers and strong covalent bond in the molecule. When MoS2 bears a shear stress,
62 molecular layers slide easily over one another. This is the reason that MoS2 has
63 been widely used as a solid lubricant and used as an additive of lubricating oils. It
6 Nano-MoS2 and Graphene Additives in Oil for Tribological Applications
Fig. 6.1 Hexagonal structure of MoS2 (a), a schematic illustration of the 1T- MoS2 (b), 2H-MoS2,
and 3R-MoS2, and the repeat unit of the MoS2 layers (c) (Ye and Winslow 2015)
has been proved that the size of MoS2 particles has a significant effect on their 64 AU2
performances and so in the following section some typical nanostructures of MoS2 65
are reviewed. 66
2.1 MoS2 Particles: Nano-balls 67
Compared with MoS2 sheets, MoS2 nano-ball particles have some particular char- 68
acteristics, including no dangling bonds that make them more stable. Additionally, 69
the small size of the MoS2 nanoparticles may result in some other enhanced 70
physical properties. 71
2.1.1 Preparation of MoS2 Nano-balls 72
Rosentsveig and Gorodnev (2009) used a four-step method to produce an inorganic 73

fullerene-like (IF) MoS2, which constitutes a typical nano-ball particle. The process 74
includes four consecutive steps: (1) Evaporation of the molybdenum oxide (MoO3) 75
powder at a temperature of between 700 and 750 C; (2) the reduction and 76
condensation of the vapor into MoO3x nanoparticles at 780 C; (3) the 77
sulfurization of the first few layers of the oxide nanoparticles; (4) the complete 78
sulfurization of the nanoparticles with a slow diffusion-controlled reaction at a 79
temperature above 840 C. This method allows the sulfurized degree to be con- 80
trolled (Fig. 6.2); it is however a complex procedure that consumes a large amount 81
of energy. 82
Precipitation is another popular approach used for producing MoS2 nano-balls 83
due to the relatively gentle synthesis conditions. As an example, Huang and Tu 84
(2005) added 28 g Na2S and 5 g (NH4)2MoO4 into 250 mL distilled water, allowing 85
the reaction to occur over an hour. During the reaction, hydrochloric acid was added 86
Y. Xu et al.
Fig. 6.2 TEM images of IF-MoS2 nanoparticles with no oxide (a) and remaining oxide (MoO2) in
the core (b) (Rosentsveig and Gorodnev 2009)
Fig. 6.3 TEM images of the IF-MoS2 nanoparticles from produced using precipitation methods
(Huang and Tu 2005)
87 to the solution in order to control the acidic pH. After this, the as-prepared MoS3
88 precursor was desulfurized in a gas mixture of hydrogen-argon at 1173 K for 8 h.
89 The final nano-balls had diameters varying from 70 to 120 nm (Seen from Fig. 6.3).
90 Hu and Wang (2007) prepared molybdenum sulfide particles with Na2MoO4 and
91 CH3CSNH2 by a quick (c. 5 min) homogenous precipitation technique in an
92 alcohol–water solution at 82 C. The resultant amorphous MoSx nano-ball particles
93 were then desulfurized under H2 flow at an elevated temperature for 50 min. This
94 method seems to be another alternative method that can be used to synthesize nano-
95 ball MoS2.
96 2.1.2 Characterization of MoS2 Nano-balls
97 Transmission electron microscopy (TEM) can be used to observe MoS2

98 nanoparticles, operating levels of resolution that are much higher than light
Fig. 6.4 SEM image of MoS3 precursor (Huang and Tu 2005)
Fig. 6.5 XRD (a), TEM (b), and HRTEM (c) of the MoS2 nano-ball particles (Hu and Wang
2009)
microscopes, due in part to the small de Broglie wavelength of electrons. It can also 99
be used to show structure, morphology, and to check the aggregation of nanoparticles. 100
Scanning electron microscopy (SEM) is another effective tool to observe the 101
form of nanoparticles. As an example, Fig. 6.4 (Huang and Tu 2005) shows a MoS3 102
precursor produced by Huang, with a clear spherical shape, with a diameter of 103
~150 nm. However, the aggregation of the nanoparticles is severe as no dispersing 104
media can be used with this method. 105
X-ray powder diffraction (XRD) can be used to assess the crystal structure of 106
MoS2 nanoparticles. The work of the Institute of Tribology at Hefei University of 107
Technology has proved that the MoS2 nanoparticles have the similar XRD spectra 108
in Fig. 6.5 with the standard curve of MoS2 in PDF number 37-1492. Its holly 109
structures are also shown in TEM in Fig. 6.5 110
The crystallinity and shape of MoS2 nano-balls are the main characteristics that 111
affect frictional properties. These two properties are governed by the parameters 112
and conditions selected during synthesis. Crystallinity governs the order degree of a 113
MoS2 layer which is composed of closed shells nano-balls. Perfectly crystalline 114
MoS2 nano-balls have a well-crystalline order with few defects present in closed 115
shells, whereas poor crystallinity shows some extent of disorder with many point 116
defects (Fig. 6.6). Moreover, perfectly crystalline MoS2 nano-balls will have good 117
physical properties. The shape of a MoS2 nano-ball is not a perfect sphere most of 118
the time. There are corners of the structure which are likely to induce stress 119
Y. Xu et al.
Fig. 6.6 HRTEM images of perfect (a, a1) and incomplete crystalline MoS2 nano-balls (b, b1)
(Lahouij and Vacher 2014)
120 concentrations. With this in mind, therefore the more perfectly crystalline and
121 spherically shaped that the MoS2 nano-ball is the higher the ability resisting
122 deformation (Lahouij and Vacher 2014).
123 2.1.3 Dispersion of MoS2 Nano-balls in Base Oil
124 MoS2 nanoparticles have lots of functions including lubrication, catalysis (Li and
125 Magnuson 2011; Li and Wang 2011), functional materials, and so on (Radisavljevic
126 and Radenovic 2011). Among them, one of the most important functions for MoS2
127 seems to be lubrication. Usually, it is used as an additive in base oil or grease. Thus,
128 the choice of the base oil is very important for improving the lubricating properties
129 of MoS2 nanoparticles. For example, an industrial oil composed of many fractions
of hydrocarbons has been used for dispersing MoS2 nanoparticles (Aralihalli and 130
Biswas 2013). The industrial oil will have contained has many other additives with 131 AU3
a variety of roles. To reduce the effects of the other additives, paraffin oil is often 132
chosen as a base oil for use with MoS2 nanoparticles (Huang and Tu 2005) because 133
of the similar components with traditional mechanical oils. Poly alpha olefin (PAO) 134
has attracted lots of attention, with excellent thermal stability and anti-oxidation 135
properties, as a base oil with MoS2 nanoparticles in recent years (Rosentsveig and 136
Gorodnev 2009). Moreover, Xu et al. have tried some renewable bioenergies, such 137
as bio-oil, as the base oil for MoS2 micro-sheets, which have also shown good 138
lubricating effects. 139
It has been reported that the addition of the nanoparticles on their own in base oil 140
has little effect on the tribological properties of a tribo-systems. But takes effect 141
after using a dispersing agent (Aralihalli and Biswas 2013; Desai and Banat 1997; 142
Moshkovith and Perfiliev 2006). This suggests that the selection of the dispersive 143
agent and method of mixing are very important. Zhou and Shi (2008) used an 144
extractant Cyanex 301 (di-(2,4,4-trimethylpentyl) dithiophosphinic acid) to modify 145
the surface of MoS2 nano-hollow spheres in liquid paraffin. Results showed that the 146
modified MoS2 had better extreme pressure, antiwear, and antifriction properties 147
than commercial MoS2. Sorbitol monooleate was selected by Huang and Tu (2005) 148 AU4
as the dispersing agent for IF-MoS2 in paraffin oil. The mixture was stirred with a 149
high-speed dispersion machine before ultrasonic treatment. 150
Dispersant agents can be grafted or adsorbed on nanoparticles with 151
ultrasonication or stirring. The chemical affinity between dispersants and 152
nanoparticles is the main factor that affects the dispersion. When chemical affinity 153
is low, the particles can be easily separated from the base oil and the nanoparticles 154
will agglomerate again under the effect of friction (Aralihalli and Biswas 2013). 155
It is important not to increase the concentration of dispersants to levels that are 156
too high in the lubricant. Under such conditions, though the nanoparticles will be 157
well dispersed, a large amount of dispersant agent, will reduce the life of the 158
lubricant and increase friction. As shown in Fig. 6.7, the tribological benefits of 159
MoS2 were eliminated when 5% dispersant was used. However, when the disper- 160
sant concentration was adjusted to 0.05%, the friction coefficient decreased. The 161
reason for this is that with high concentrations of dispersants, MoS2 nanoparticles, 162
MoS2 cannot be adsorbed on the rubbing surface and reduced the friction coeffi- 163
cient (Rabaso and Dassenoy 2014). 164
2.1.4 Comparison with Micro-MoS2 165
MoS2 nanoparticles have better lubricating properties than MoS2 micro-particles 166
(Hu and Hu 2010). According to the Risdon’s investigation (Risdon and Gresty 167
1975), the energy consumed on transportation in the USA during the period 168
1963–1974 can be reduced by 4.4% with a proper dispersion of 1% weight 169
commercial molybdenum disulfide in the engine oil. Thus, it can be inferred 170
that more fuel can be saved by the introduction of nano-MoS2. Hu’s results 171
Fig. 6.7 Friction coefficient of PAO +1% IF-MoS2+5% dispersant (left), and PAO +1% IF-MoS2+0.05% dispersant (right) (Rabaso and Dassenoy 2014)
Y. Xu et al.
0.62
micro-MoS2 + LP
liquid paraffin(LP)
Average wear scar dimeter (mm) 0.60 MoS2 nano-balls + LP
MoS2 nano-slices + LP
0.58
0.56
0.54
0.52
0.50
0 0.5% 1.0% 1.5% 2.0%
Content of MoS2 (wt.%)
Fig. 6.8 Effects of the concentration of MoS2 on the average wear scar check fig. for diameter
spelling (Hu and Hu 2010)
(Hu and Hu 2010) showed that the addition of MoS2 nano-balls in liquid paraffin at 172
a concentration of 1.5 wt% resulted in a better antifriction and antiwear properties 173
than micro-MoS2. Figure 6.8 shows a friction coefficient reduction of 21% and 174
10%, respectively, when compared to those of 1.5% micro-MoS2 and 1.0% nano- 175
slices. 176
2.1.5 Effect of ZDDP on Tribological Properties 177
ZDDP (Zinc Dialkyl Dithiophosphates) is an important oxidation and corrosion 178

inhibitor often found in fully formulated lubricating oil which extends the oxidation 179
resistance of lubricating oil. It also has excellent antiwear properties but has no 180
effect on friction. Lamellar MoS2 nanoparticles derived from nano-sheets or the 181
exfoliation of nano-balls are easily oxidized to MoO3 which degrade the friction- 182
reducing properties of MoS2. When ZDDP and MoS2 nanoparticles exist together, 183
both friction coefficient and wear are reduced significantly. It is believed that there 184
is a synergistic effect between ZDDP and MoS2: the MoS2 is believed to be 185
embedded into ZDDP chemical reaction film and therefore reinforces its antiwear 186
effect, at the same time, the ZDDP film provides protection for the MoS2 from 187
being oxidized resulting in the improvement of the antifriction behaviors (Tomala 188
and Vengudusamy 2015; Aldana and Vacher 2014). 189
Y. Xu et al.
Fig. 6.9 Friction coefficient of perfect (SC) and poorly crystalline (SpC) on HFRR (Rabaso and
Ville 2014)
190 2.1.6 Effect of Crystallinity on Tribological Properties
191 The tribological properties of MoS2 nano-balls to some extent are dependent on its
192 structural characteristics and particularly its crystallinity. MoS2 nano-balls that are
193 perfectly crystalline have a better ability to resist deformation, whereas MoS2 with
194 incomplete crystallinity are easily deformed and exfoliated under the similar sliding
195 conditions (Lahouij and Vacher 2014). Rabaso and Ville (2014) compared the
196 frictional properties of MoS2 with poorly crystalline structures with similar average
197 diameters (150 nm). They found that perfect MoS2 nano-balls played a significant
198 role in friction-reduction during running in, however, the friction coefficient
199 increased after this due to the lack of perfect MoS2 nano-balls. On the contrary,
200 poorly crystalline MoS2 maintained a stable low friction coefficient as shown in
201 Fig. 6.9. The difference is because poorly crystalline can be easily exfoliated and
202 transferred onto the rubbing surfaces forming an adsorbed layer. Perfect crystalline
203 nanoparticles were much harder to exfoliate before being squeezed out from the
204 rubbing interfaces, thanks to the better physical properties. In addition to the
205 frictional process, the MoS2 adsorbed film formed during the early stages of
206 rubbing was gradually worn off. Due to the two reasons above, there were few
207 MoS2 particles remaining between the frictional interfaces resulting in the increase
208 of the friction coefficient.
Fig. 6.10 A MoS2 nano-

ball bearing two different
forms of pressure: isotropic
(a), normal stress (b) (Joly-
Pottuz and Martin 2006)
2.1.7 Effect of Different of Pressure on Exfoliation Behavior 209
MoS2 nano-balls can be ruptured under a high normal stress on the frictional 210
interfaces. However, this will not happen in oil though oil pressure might be 211
much higher than critical ruptured normal stress. That is because oil pressure is 212
isotropic and the shape of the nano-ball is quasi-spherical which makes bearing 213
force of MoS2 uniform (Fig. 6.10) (Joly-Pottuz and Martin 2006). 214
2.1.8 Tribological Mechanisms 215
MoS2 nano-balls have excellent lubricating properties as lubricating oil additives. 216
There are three main frictional mechanisms that can explain this property: rolling, 217
sliding, and exfoliation-transfer (third body) as shown in Fig. 6.11 (Tevet and 218
Von-Huth 2011). 219
1. Rolling: MoS2 nano-balls roll as a ball bearing across frictional interfaces under 220
relatively low normal stress. The roller is dependent on the shape of nano-balls 221
which should be quasi-spherical structures. 222
2. Sliding: Similar to nano-sheets, friction happens between external surfaces of 223
the nano-balls under higher normal stress. The behavior of sliding is due to the 224
shape of nano-MoS2 particles, which is not perfectly spherical but of a faceted 225
polyhedron structure. The corner of the faceted polyhedron structure can be 226
easily distorted by asperities on the rough mating surfaces. 227
3. Exfoliation and transfer (third body): Exfoliation is the main action of behavior 228
under high normal stress resulting in deformation and even rupture of the nano- 229
balls. Under the combined effects of the normal stress and shear stress, the 230
external surface of the nano-ball particles can be exfoliated producing MoS2 231
Y. Xu et al.
Fig. 6.11 Schematic of the three main tribological mechanisms of MoS2 nano-balls: rolling (a),
sliding (b), and exfoliation and transfer (third body) (c) (Tevet and Von-Huth 2011)
232 nano-sheets which can be adsorbed on the rubbing surfaces providing a protec-
233 tive layer and reduced the friction coefficient.
234
235 Among these three behaviors, rolling is generally accepted as the most prevalent
236 mechanisms of friction reduction, motion because they cannot be detected directly
237 only by micro-frictional tests on the single MoS2 nano-balls.
238 Particle size and crystalline perfection of the MoS2 nano-balls are the most
239 important factors that affect tribological behavior (Rosentsveig and Gorodnev
240 2009). Generally, due to a nano-bearing effect, the small MoS2 nanoparticles
241 have better antiwear and friction reducing properties than larger nanoparticles.
242 However, with the decrease of particle size, the aggregation effects of the MoS2
243 can increase and chemical stability reduces, which might result in reduced lubricity.
244 Hence, the particle size is very important in the efficacy of the additives. It is
245 believed that exfoliation, rolling friction, and third body transfer of MoS2 sheets
246 into surface asperities are the prevalent mechanisms that can explain the excellent
247 tribological properties of MoS2 nanoparticles (Rosentsveig and Gorodnev 2009).
248 There are no active dangling bonds in the closed-structure MoS2; consequently,

249 the oxidation temperature of MoS2 nano-ball particles is ~100 C higher than that of
250 2H-MoS2. Moreover, under some testing conditions, the MoS2 nano-ball particles
251 had better lubricating properties than MoS2 nano-sheets. This was ascribed to the
252 chemical stability of the layer-closed spherical structure of nano-balls. The detailed
253 mechanisms for this are shown in Fig. 6.12. In air or when used in liquid paraffin
254 nano-sheets, due to the rim-edge site of the nano-sheets, they are easier to oxidized
255 into MoO3, there was a poor lubrication. MoS2 nano-ball particles are relatively
256 stable and can bear the shearing via rolling and elastic deformation.
a
Basal surface with
chemical inertness Shearing
Air and LP
Active Easily
rim-edge Rubbing
surface Difficultly MoO3
Air and LP
5nm
Shearing Shearing
b Air and LP
Basal surface with Difficultly

chemical inertness
MoO3
Rolling Elastic deformation
Rubbing
Air and LP
MoO3 Easily
Shearing
150nm
Exfoliation
Fig. 6.12 TEM images and schematics of the lubrication mechanisms of MoS2 nano-slices (a)
and MoS2 nano-balls (b) (Hu and Hu 2010)
2.2 MoS2 Nano-sheets 257
In recent years, the study of graphene-like two-dimensional layered materials has 258
attracted great interest due to the successful exploration of graphene (Zhang and Lai 259
2016; Zhang and Liu 2016; Huang and Qi 2012; Xu and Liang 2013). Among them, 260
MoS2 nano-sheets are the popular research molecular as a result of their distinct 261
structure and superior properties. Functionalization, hybridization, and modifica- 262
tion of MoS2-based nano-sheets have seen them used widely in various applica- 263
tions. Here, the preparation, characterization, and properties of nano-sheets are 264
reviewed. 265
2.2.1 Preparation of MoS2 Nano-sheets 266
It has been demonstrated that most of the methods for preparing 2-D nano-material 267
such as graphene are effective for MoS2 nano-sheets. The classic and straightfor- 268
ward way to prepare the nano-sheets is micro-mechanical cleavage (Radisavljevic 269
and Radenovic 2011). Using this top-down approach, a high-quality 2-D nano- 270
material can be obtained (Lopez-Sanchez and Lembke 2013). However, the short- 271
comings of this method are also obvious. The productive efficiency is low and it is 272
Y. Xu et al.
Fig. 6.13 Schematic illustration of electrochemical lithiation and exfoliation process for the
fabrication of 2D nano-sheets from layered bulk crystals (Zeng and Yin 2011)
273 difficult to synthesize the 2D nano-sheets in large quantities. Moreover, the geom-
274 etry can be very difficult to control precisely.
275 Ion-intercalation exfoliation is another popular method that can be used for the
276 preparation of MoS2 nano-sheets. As shown in Fig. 6.13, there are three steps in this
277 method: (1) introduction of Li+ ions into the interlayer of bulk MoS2; (2) immersion
278 of LixMoS2 nano-sheets into water; and (3) ultrasonic processing of the solution.
279 Bottom-up methods have been used to fabricate MoS2 nano-sheets with desired
280 size and thickness. Choudhary and Park (2014) adopted a sputter–chemical vapor
281 deposition (CVD) technology to synthesize large-area, high-quality, and layer-
282 controlled MoS2 nano-sheets on Si-based substrates. They also demonstrated that
283 the single-layer MoS2 over an area of 2 inches with the domain size of 10–15 μm2,
284 showing good potential in future flexible, high-temperature, and radiation hard
285 electronics/optoelectronics. Although CVD is an effective method for producing
286 high-quality MoS2 nano-sheets, there are some obvious disadvantages with the
287 synthesis conditions, such as high temperatures, the requirement for a vacuum,
288 and specific substrates, which restrict the practical applications of MoS2 nano-
289 sheets (Zhang and Lai 2016; Zhang and Liu 2016).
290 Owing to specific merits such as cheap raw materials, size and thickness
291 controllable, high productive efficiency and no requirements on the substrates,
292 solution-based methods have become prevalent in recent years. Smith and King
293 (2011) prepared MoS2 nano-sheets through 1.5 mg mL1 sodium cholate as a
294 surfactant to exfoliate bulk MoS2 in aqueous solutions. In a typical run, ultrasonic
295 treatment can be used for the solution lasting 30 min, followed by centrifugation at
296 1500 rpm for 90 min.
2.2.2 Application of MoS2 Nano-sheets 297
One of the most important applications for MoS2 nano-sheets is a substitute of 298
noble metal catalysts such as Pt/C. It has been proved that the active edges of MoS2 299
can be used as the active center for electro-catalysis (Zhang and Lai 2016; Zhang 300
and Liu 2016). Electro-catalytic performance can be improved by reducing the 301
dimension and by exposing the edges of the 2-D MoS2. 302
Efficient energy storage is an important challenge for sustainable development. 303
MoS2 nano-sheets can be used in energy storage devices. One such application is in 304
Li-ion batteries, which have been shown to be a highly efficient energy storage 305
system. Although the charge capacity of the bulk MoS2 is easy to reduce after use, 306
after intercalating Li-ion into the interlayer of MoS2, fewer layers of nano-sheets, 307
the composites exhibited a high energy density capacity of 750 mA h g1 even after 308
50 cycles (Du and Guo 2010). Na ion intercalation in MoS2 sheets has also shown 309
promising results. Bang and his coworkers (2014) reported a simplest method for 310
enhancing the productive efficiency of MoS2 nano-sheets in 1-methyl-2- 311
pyrrolidinone with the assistant of sodium hydroxide. They also proved that at 312
the high current densities, the exfoliated MoS2 electrode exhibited better capacities 313
than the pristine particle electrode (Fig. 6.14), indicating improved properties of the 314
exfoliated MoS2 nano-sheets with the reduced diffusion lengths of Na ions. 315
Wu and Zeng (2012) used electrochemically reduced single-layer MoS2 nano- 316
sheets for sensor applications. It was found that the prepared MoS2 nano-sheets had 317
good conductivity and high electrochemical sensitivity to detect glucose and 318
Fig. 6.14 Charge–discharge curves (a) and the cycling properties and their coulombic efficiencies
of the MoS2 nano-sheets (b); the rate capability of pristine MoS2 powder and the prepared MoS2
nano-sheets at various current densities (c) (Bang and Nam 2014)
Y. Xu et al.
Fig. 6.15 Friction coefficient of the base oil with different additives: Without additives (a), MoS2
micro-particles (b), and MoS2 nano-sheets (c) (Wu and Wang 2010)
319 biomolecules. Thus, reduced MoS2 nano-sheets can be used in the development of
320 novel electrode materials and can supply a novel platform for the sensing applica-
321 tions. Li and Yin (2012) used MoS2 film-based field-effect transistors to detect NO
322 at room temperature. The results showed that a single-layer MoS2 nano-sheet had a
323 rapid response to NO, but the current was unstable. A few-layer (less than 5) MoS2
324 nano-sheet assembly presented both stable and sensitive responses to NO up to
325 0.8 ppm.
326 Another important application for MoS2 nano-sheets is as lubricating additives.
327 According to Wu and Zeng (2012), with the addition of MoS2 nano-sheets in liquid
328 particles with concentration of 1.5 wt%, the friction coefficients decreased signif-
329 icantly and are shown in Fig. 6.15. In addition, MoS2 nano-sheets have a lower and
330 more stable friction coefficient than commercial MoS2 micro-particles with the size
331 of 3–5 mm, owing to the surface effect just as can be seen graphene (Huang and Tu
332 2006). This can be explained by the fact that MoS2 nano-sheets have a larger
333 surface area and higher chemical activity, which makes them easier to adsorb on
334 to rubbing surfaces in the form of a stable tribo-film, reducing the friction and wear.
335 Hu and Liu (2009) prepared MoS2 nano-sheets with a thickness of 30–70 nm via
336 a monolayer-restacking process and studied tribological behaviors on a four-ball
337 tribometer. Experimental results indicated that MoS2 nano-sheets had better
338 antifriction, antiwear, and extreme pressure properties than micro-MoS2
339 (Fig. 6.16). The excellent tribological properties of MoS2 nano-sheets were attrib-
340 uted to a surface effect, dimension effect of the nanoparticles, and a complex tribo-
341 film composed of MoO3 and FeSO4 on the worn surfaces.
Fig. 6.16 PB values (a), average friction coefficient (b), and wear scar diameter (c) of liquid
paraffin (a) with MoS2 nano-sheets (b) and MoS2 micro-sheets (Hu and Liu 2009)
2.2.3 Tribological Mechanisms of MoS2 Nano-sheets 342
As shown in Fig. 6.17, there are some S dangling bonds on the rim of MoS2 nano- 343
sheets. When they enter into frictional interfaces, MoS2 nano-sheets could be 344
adsorbed onto the frictional interfaces forming an adsorbed film depending on the 345
formation of S-O or S-Fe bonds. The O and Fe came from the oxide layer on the 346
surfaces of the substrate. The adsorbed film prevented frictional interfaces from 347
direct contact and improved the tribological properties. 348
Due to the chemical activity of dangling bonds, MoS2 nano-sheets could be 349
oxidized to MoO3 and progressively sulfated, where oxygen might come from air or 350
water during the sliding process. Fleischauer and Lince (1999) compared tribolog- 351
ical properties of a typical MoS2 film in which the sulfur was substituted for 352
different contents of oxygen. They found that friction coefficient increased with 353
increases in oxygen content at first, up to a saturation point of 3% followed by a 354
decrease. It is still higher than pure MoS2 when oxygen content exceeded the 355
critical value (Fig. 6.18). 356
Y. Xu et al.
Fig. 6.17 Schematic a b S S S S

illustration of possible
formation mechanisms of
Mo Mo Mo Mo O
MoS2 adsorbed film on the Fe Fe
iron oxide layer (a) and the
S S S S
metal atom (b) (Tannous O S O S
and Dassenoy 2011) Fe
S S S S
O Mo Mo O
Mo Mo Mo Mo O
Fe
S S
O O S S S S
Fe Fe
Fe Fe Fe Fe
Fig. 6.18 Variation of

friction coefficient with the
oxygen concentration in the
film (Fleischauer and Lince
1999)
357 Onodera and Morita (2009) drew similar conclusions by simulating single sheet
358 MoS2 lubrication with computational chemistry methods. They proposed that the
359 excellent tribological properties of MoS2 sheets were attributed to the increase of
360 coulombic repulsion energies between the two sulfur layers reacting with the iron
361 surfaces as shown in the Fig. 6.19. With oxygen introduced into MoS2, coulombic
362 interaction energy reduced and roughness of MoS2 layer increased. These resulted
363 in the rising of the friction coefficient. MoS2 layers became flat again and decreased
364 the friction coefficient with further increases in oxygen contents.
365 2.3 MoS2 Nano-tubes
366 The MoS2 nano-tubes, an analog of carbon nano-tubes, are considered to derive from
367 lamellar compounds (Chen and Kuriyama 2001; Dresselhaus and Dresselhaus 1996).
Fig. 6.19 Average frictional force (a), Ra of top MoS2 layer on sliding surface (b); total interlayer
coulombic interaction energy (c); coulombic attractive and repulsive energies (d) along with
oxygen concentration in MoS2 structures; schematic illustration (e) for lubricating properties of
MoS2 single sheet (Onodera and Morita 2009)
The discovery of the carbon nano-tube has aroused great interest for the 368
one-dimensional nano-tubes such as MoS2 due to their small dimensions, high 369
anisotropy, and special tube-like structures (Remskar and Mrzel 2001). In this 370
section, the preparation, characterization, and application of MoS2 nano-tube will 371
be described and discussed. 372
Y. Xu et al.
373 2.3.1 Preparation and Characterization of MoS2 Nano-tube AU5
374 Remskar and Mrzel (2001) used 5 wt% C60 as a catalyst during the production
375 process. In a typical run, the reaction conditions were controlled as follows:
376 reaction time: 22 days; temperature: 1010 K; reactor: silica ampoule; pressure: 10
3
377 Pa. The SEM and TEM images of the nano-tubes are shown in Fig. 6.20. The
378 conversation rate was about 15% for MoS2 nano-tubes.
379 Template synthesis is another path to obtain MoS2 nano-tubes. Zelenski and
380 Dorhout (1998) used aluminum oxide templates to prepare near-mono-dispersed
381 MoS2 nano-tubules. As shown in Fig. 6.21, the fibers in the picture were synthe-
382 sized in 0.1 M (NH4)2MoS4 DMF solutions. They were separated from the template
383 by the dissolution of the template using 1.0 M NaOH solutions. Figure 6.21b
384 presents an end-on view of the nano-tubes and confirms their hollow nature.
385 Nath and Govindaraj (2001) developed a simple synthesis method of MoS2 and
386 WS2 nano-tube. The first step was to prepare MoS3 precursors via decomposition of

387 (NH4)2 MoS4 at 400 C in an argon atmosphere. Then, the precursors were heated at

388 1200–1300 C under H2 atmosphere. MoS2 nano-tubes were formed, and the TEM
389 images are shown in Fig. 6.22. It can be seen that the external diameter of the nano-
390 tube is about 20–30 nm, and the wall thickness is about 10–15 nm. There are also
391 some onion-like clusters in the Figure, suggesting the existence of an intermediate
392 stage between MoS3 precursors and MoS2 nano-tubes (Margulis and Salitra 1993).
393 Feldman and Wasserman (1995) used the gas-phase reaction between MoO3 and
394 H2S in a reducing atmosphere at high temperature and also got high-rate growth of
395 MoS2 nano-tubes.
Fig. 6.20 SEM and TEM images on different length scales. (a) Bundles appear to self-assemble
into various different microscopic structures. (b) The bundles end in sharp points. (c) A split tip of
a bundle terminating in strands 4 nm wide. (d) Expanded electron transmission view of a strand
composed of an only few individual nano-tubes (Remskar and Mrzel 2001)
Fig. 6.21 A TEM image of the MoS2 tubes after the dissolution of the aluminum oxide template
(a). A TEM image of a bend in a tubule of MoS2 emphasizing the hollow nature of the tubules (b)
(Zelenski and Dorhout 1998)
Fig. 6.22 TEM images of MoS2 nano-tubes: (a) Images of several nano-tubes; (b) and (c) high-
resolution images of the nano-tubes; and (d) nested-shell and onion-like clusters with a hollow
core (Nath and Govindaraj 2001)
2.3.2 Applications of MoS2 Nano-tubes 396
Besides the synthesis and characterization of MoS2 nano-tubes, studies have been 397
focused on a great number of particular properties and applications (Deepak and 398
Y. Xu et al.
Fig. 6.23 Catalytic

abilities of MoS2 nano-
tubes (Chen and Li 2002)
399 Jose-Yacaman 2010), for instance, mechanical properties (Hassanien and

400 Tokumoto 2005), field emission properties (Nemanič and Žumer 2003), in hydro-
401 gen storage applications (Chen and Li 2003), and as catalysts (Chen and Li 2002).
402 Chen and Li (2002) synthesized an open-ended MoS2 nano-tube and used it as
403 the catalyst of methanation of CO and H2 at relatively low temperatures (Fig. 6.23).
404 Techniques such as this contribute to new ways of reducing the environmental load
405 resulting from CO emissions. By analyzing the shear and Young’s moduli of the
406 MoS2 nano-tubes, Kis and Mihailovic (2003) used an atomic force microscope to
407 study the interaction between the MoS2 nano-tubes, finding the MoS2 nano-tube
408 ropes were highly anisotropic and very weak.
409 Chen and Kuriyama (2001) prepared MoS2 nano-tubes by heating (NH4)2MoS4
410 in hydrogen/thiophene. They studied the electrochemical properties. It was found
411 that the highest capacity was 260 mAh g1 because of a highly nano-porous
412 structure, suggesting a potential application in electrochemical catalysis and high-
413 energy batteries.
414 Analogously to MoS2 nano-tube, WS2 nano-tubes, can be used for tips in
415 scanning-probe microscopy (Rothschild and Cohen 1999). They have been suc-
416 cessfully applied in the inspection of microelectronics circuitry. With improve-
417 ments in productivity for producing these, the application of MoS2 nano-tubes will
418 widen to include nanolithography, photocatalysis, sensors, and others (Tenne
419 2006).
420 MoS2 nano-tubes also have excellent lubricating properties whether as lubricat-
421 ing oil additives or prepared as self-lubricating composite materials (Mertens and
422 Senthilvelan 2016; Zhou and Zhang 2007). However, due to their thin and long
423 structure and chemical inertness, MoS2 nano-tubes are hard to disperse in lubricat-
424 ing oil which limits their tribological application. Modification, treatment, or the
425 addition of a dispersion agent is an effective method to improve dispersion in oil of
426 nano-tube (Khalil and Mohamed 2016; Chen and Chen 2005). Kalin and Kogovšek
427 (2012) investigated the frictional properties of MoS2 nano-tubes as oil additives.
428 They found that the lubrication mechanism was mainly exfoliation and deformation
which was similar to that of MoS2 nano-balls. Exfoliated nano-sheets were 429
adsorbed onto the rubbing surfaces, and compacted and deformed to form a 430
boundary film. With these two combined effects, MoS2 nano-tubes reduce friction 431
and wear significantly. 432
3 Graphene and Its Tribological Applications 433
Graphene, just like the structured MoS2, is a 2-D layered material with sp2-bonded 434
carbon, that has received substantial attention (Novoselov and Geim 2004; Li and 435
Cai 2009; Bonaccorso and Colombo 2015) due to its good conductivity, excellent 436
mechanical properties, potential applications in electrochemical energy storage 437
(Raccichini and Varzi 2015), microelectronics, and lubricating additives (Wu and 438
Cheng 2015; Yao and Shi 2014). In this section, the preparation, characterization, 439
and applications of graphene are reviewed to give a view on the increasingly wide 440
scope of applications. 441
3.1 Preparation and Characterization of Graphene 442
Graphene was firstly prepared by Geim et al. at the University of Manchester in 443
2004 by using tape (Novoselov and Geim 2004). This was the work for which they 444
were awarded the Nobel Prize in Physics in 2010. From this point, graphene has 445
attracted substantial research attention such that its synthesis, characterization, its 446
unique structures, and superior properties are well studied 447
3.1.1 Exfoliation in Liquid or Gas 448
Exfoliation of graphite in liquid or gas is a physical method to obtain graphene. 449

Hernandez and Nicolosi (2008) demonstrated that dispersion and exfoliation of 450
graphite in N-methyl-pyrrolidone to obtain graphene-blended solutions with a 451
concentration of 0.01 mg ml1. However, the yield of single-layer graphene was 452
low at about 1%. 453
3.1.2 Modified Mechanical Exfoliation 454
Recently, in order to improve the yield of production of single-layer graphene, Xu 455

and Geng (2016) used a friction-induced exfoliation from graphite to graphene in 456
esterified bio-oil. They dispersed flake graphite into the esterified bio-oil and then 457
measured the tribological response of the dispersed graphene after ultrasonication 458
for 20 min. Testing was performed on a ring-on-plate tribometer. It was found that 459
Y. Xu et al.
460 both load and sliding speed had an important effect on the quality of the graphene.
461 Higher loads and lower sliding speed were helpful to form the single-layer
462 graphene. In addition, higher loads also contributed to friction and wear reduction
463 in the tribosystem due to the formation of a thicker tribofilm.
464 3.1.3 Epitaxial Growth
465 Due to the low efficiency of the mechanical exfoliation method, epitaxial growth
466 has become one of the most important methods to produce the graphene film on
467 certain substrates such as SiC and transition metals (Oshima and Nagashima 1997).
468 Yang and Chen (2013) used a plasma-assisted deposition epitaxial growth method
469 to obtain the single-domain graphene on hexagonal boron nitride. The graphene
470 was produced at ~500 C. A schematic illustration of this process is shown in
471 Fig. 6.24, suggesting a typical edge growth of carbon atoms. The sp2 carbon
472 structure of the graphene was confirmed by Raman spectra in Fig. 6.24b. The
473 AFM images also showed the existence of single-layer graphene.
474 Fumihiko and Hiroki (2011) grew graphene on a SiC (0001) substrate under the
475 temperatures varying from 600 to 915 C by thermal decomposition of a cracked-
476 ethanol source. This is an example of one kind of gas-source molecular beam
477 epitaxy (MBE) methods. The experimental results showed that higher temperatures
478 were helpful to prepare high-quality single-layer graphene. Unfortunately, the
479 growth rate decreased with the increase in temperatures. Moreover, there was a
480 network of fin-like ridge shapes of graphene (Fig. 6.25).
481 However, the epitaxial growth method for producing graphene has some disad-
482 vantages. For instance, it requires some harsh conditions, including high tempera-
483 ture, high vacuum, special atmosphere, and substrates. The synthesized graphene is
484 also hard to separate from the substrate. It is also hard to produce graphene on a
485 large scale in the industry.
486 3.1.4 Chemical Vapor Deposition
487 Chemical vapor deposition (CVD) has been used to produce high-quality thin films
488 on substrates in the semiconductor industry. In recent years, this technique has also
489 been applied to synthesize graphene. The principle is to deposit volatile precursors
490 onto the substrate.
491 A single- and few-layer (less than 10) graphene film with a large area (~cm2) was
492 prepared by Reina et al. over a Ni surface using CVD technology (Reina and Jia
493 2008). But the lateral size was limited to 20 μm. The domain boundaries have
494 proved adverse to the transport properties. Thus, graphene with a larger area is still
495 the pursuit of the scientists. Li and Magnuson (2011) and Li and Wang (2011)
496 prepared single crystal graphene with a domain size of up to 0.5 mm (Fig. 6.26),
497 which were grown at low-pressure and high-temperature chemical vapor deposition
498 (8 mTorr at 1035 C) on copper-foil enclosures using methane as a precursor. The
Fig. 6.24 Schematic illustration of the growth mechanism (a); Raman spectra for hexagonal MLG (h-MLG) grains (red), BLG film (blue), and bare h-BN
surface (black) (b). (c–e) AFM images of as-grown graphene on h-BN at different stages including small grains nucleation (c), coalescence of grains (d), and
continuous monolayer graphene with some second-layer nuclei on top. A height profile was extracted along the dashed white line cut in d, with white and cyan
arrows indicating the first and second layer, respectively. The scale bars in c–e are 500 nm. f, g, Zoom-in AFM image of as-grown graphene showing aligned
hexagonal grains (f) or pits after plasma etching (g). The scale bars in f, g are 200 nm (Yang and Chen 2013)
Y. Xu et al.
Fig. 6.25 Topographic

AFM image of graphene (a)
and the height of the line in
the AFM image (b)
(Fumihiko and Hiroki 2011)
Fig. 6.26 SEM images of

graphene on copper grown
by CVD: Graphene domain
grown at 1035 C on Cu at
an average growth rate of
6 μm/min (a). Graphene
nuclei formed during the
initial stage of growth (b).
High-surface-energy
graphene growth front (c)
(Li and Magnuson 2011; Li
and Wang 2011)
Fig. 6.27 The preparation process of reduced graphene oxide (Tkachev and Buslaeva 2012)
flow rates and partial pressures of the methane were less than 1 sccm and 50 mTorr, 499
respectively. The transport properties of the graphene film were measured, and the 500
mobility of the films was found to be a little bit higher than 4000 cm2 V1 s1, 501
indicating further improvements for this graphene film should be possible. 502
CVD methods can produce high-quality graphene with a large area, with the 503
products easily separated or transferred from substrates. In addition, CVD-derived 504
graphene can be processed at relatively low temperatures and ambient pressure. 505
However, the thickness of the graphene is hard to control and the yield remains low. 506
3.1.5 Reduced Graphene Oxide 507
A reduced graphene oxide method for the production of graphene in aqueous 508
solution has attracted great interests due to its low cost, easy processability, and 509
high efficiency. The process includes three steps: (1) preparation of oxide graphite 510
from graphite using strong oxidants such as concentrated sulfuric acid, concentrated 511
nitric acid, and potassium permanganate; (2) ultrasonic process for separating the 512
lattices of oxide graphite; (3) reduction of the graphene oxide with reducers such as 513
hydrazine hydrate and sodium borohydride. 514
Tkachev and Buslaeva (2012) used a modified Hummers method to prepare 515
graphite oxide and then synthesized the graphene oxide by ultrasonic processing. 516
The final reduced graphene oxide was obtained after the appropriate amount of 517
graphene oxide and ethanol was mixed and reacted at 200–380 С for 10–90 h. A 518
typically detailed process for preparing reduced graphite oxide is shown in 519
Fig. 6.27. 520
3.2 Properties and Applications of Graphene 521
Graphene has become a star molecule over the last c.10 years because of the ability 522
to its particular structure and properties such as electrochemical, mechanical, and 523
other properties. The progress of the main properties of graphene is reviewed in this 524
section. 525
3.2.1 Electrochemical Properties 526
Electrons in graphene have a character that can be described by a linear dispersion 527
relationship. It has been confirmed that at room temperature the electron mobility of 528
Y. Xu et al.
529 single-layer graphene amounts to 15, 000 m2 V1 s1. Therefore, graphene has
530 many potential applications in microelectronic devices (Geim and Macdonald
531 2007). Geim and Macdonald (2007) noted that the conductivity of graphene was
532 much higher than that of single-walled carbon nano-tubes by about 60 times. In
533 addition, they found that graphene had higher surface negative charge, better
534 stability, and signal-to-noise ratio than single-walled carbon nano-tubes, indicating
535 the potential of graphene in the detection of some small molecules such as dopa-
536 mine and serotonin by graphene electrodes.
537 Shan and Xin (2016) used graphene to increase the conductivity and electro-
538 chemical stability of MoS2 since MoS2 has a high theoretical specific capacity
539 (about 670 mA h g1) but low cycle charging performance. A unique film–foam–
540 film structure was designed to solve this problem. The experimental results showed
541 that the appropriate structures resulted in a high, reversible Li storage capacity of
542 1200 mA h g1 and a longer lifetime, suggesting its potential application in high-
543 energy-density batteries.
544 3.2.2 Mechanical Properties
545 With the potential application of graphene in nanoelectromechanical systems, the

546 mechanical properties of monolayer or few-layer graphene (less than 5) have
547 aroused great interest. Frank and Tanenbaum (2007) used an atomic force micro-
548 scope to measure the effective spring constants of the graphene sheets with a
549 thickness between 2 and 8 nm ranging from 1 to 5 N m1 and Young’s modulus
550 of graphene sheets is 0.5 TPa, which is a half of bulk graphite.
551 Young’s modulus was studied by molecular dynamics and was predicted higher
552 than 1 TPa (Van Lier and Van Alsenoy 2000). According to Lee et al. (Zhu and
553 Murali 2010; Lee and Wei 2008), Young’s modulus and fracture strength of a
554 defect-free graphene were 1.0 TPa and 130 GPa, respectively, being measured by
555 an AFM indentation approach (Fig. 6.28).
556 3.2.3 Optical Properties
557 Of main interest for graphene is the comparison of the permittivity features.
558 Falkovsky (2008) investigated the transmittance of graphene in the optical region
559 and found that optical properties were affected by the interband electron transitions.
560 Moreover, the transmittance of graphene in the visible spectrum range was not
561 affected by the frequency and had a constant value depending on its fine structure.
562 3.2.4 Extreme Pressure Properties
563 The extreme pressure value (PB) of oil is an important parameter when evaluating
564 the load carrying capacity of lubricating oil. Nano-scale lubricating particles being
Fig. 6.28 Images of graphene membranes: SEM images of a large graphene flake spanning an
array of circular holes 1 μm and 1.5 μm in diameter. Scale bar, 3 μm (a). Non-contact mode AFM
image of one membrane (b). Schematic of nanoindentation on suspended graphene membrane (c).
AFM image of a fractured membrane (d) (Lee and Wei 2008)
Fig. 6.29 Effect of concentration of MoS2 nano-sheets (left) (Hu and Liu 2009) and graphene
(right) on the PB value (Lin and Wang 2010)
mixed with oil can penetrate into rubbing surface during sliding and protect rubbing 565
surfaces from contacting directly and can form an adsorbed layer. Because of the 566
excellent antiwear properties, nanoparticles with a low concentration can improve 567
PB values significantly. As shown in Fig. 6.29, comparing with the base oil or base 568
oil with flake graphite, MoS2 nano-sheets and graphene can increase PB value to 569
approximately 2 and 1.6 times, respectively, at optimum concentrations (Hu and 570
Liu 2009; Lin and Wang 2010). 571
Y. Xu et al.
572 3.2.5 Dispersion Properties
573 The advantage of nanoparticles is that they can penetrate into mating surfaces
574 during the frictional process even in severe boundary lubrication. However,
575 nanoparticles tend to agglomerate due to nanometric size effects. The size of the
576 agglomeration might amount to a few microns which make the particles much less
577 likely to penetrate into frictional interfaces, and so they cannot reduce the friction
578 and wear of the tribosystem. Therefore, the dispersive properties of the nano-
579 lubricating additives are very important. Modification treatments are a chemical
580 reaction method to graft a modifier on the nanoparticles to improve the dispersive
581 properties. The modifiers commonly have an oleophylic functional group of long
582 chain alkane. Although graphene has excellent tribological properties, the disper-
583 sion of graphene in oil is poor which leads to coagulation and precipitation of
584 graphene quickly because of chemical inertness.
585 The modification is an effective approach to forming stable dispersions and
586 preventing aggregation of graphene. Lin and Wang (2010) modified graphene by
587 using stearic and oleic acids. The modifiers, cyclohexane and dried graphene, were
588 heated and stirred at 80 С for 5 h. There were some residual oxygen-containing
589 functional groups, as a result of the incomplete diminution of reduced graphene
590 oxide, that could react with carboxyl groups of stearic and oleic acids. Therefore as
591 a result of the long chain molecular structures of stearic and oleic acids, modified
592 graphene has better dispersive properties than the pristine graphene as shown in
593 Fig. 6.30.
Fig. 6.30 Dispersive stability of graphene in lubricating oil (Lin and Wang 2010)
3.2.6 Tribological Properties and Applications of Graphene 594
Graphene has excellent tribological properties as lubricating oil additive in part due 595
to its layered structure similar in many respects to MoS2, Eswaraiah and 596
Sankaranarayanan (2011) synthesized ultrathin graphene with a thickness of 597
~2 nm via reducing graphene oxide with focused solar radiation. The tribological 598
properties were investigated by using a four-ball tribometer. They found that the 599
ultrathin graphene dramatically reduced average coefficient friction and wear loss 600
at a relative low concentration in a formulated engine oil as shown in Fig. 6.31. 601
Also, graphene can significantly improve the load capacity of a lubricant owing to 602
its excellent antiwear performances especially at a concentration of 0.025 mg mL1 603
. In addition, graphene in the base oil could be adsorbed on the frictional interfaces 604
and by forming a physically adsorbed film. The adsorbed film protected the rubbing 605
surfaces and reduced wear and the coefficient of friction. 606
According to the results in Fig. 6.31, graphene has an optimal concentration. The 607
antifriction and antiwear behaviors deteriorated when the concentration of 608
graphene exceeded the optimal concentration. This can be explained by the fact 609
that graphene can form an adsorbed film protecting frictional interfaces at an 610
Fig. 6.31 Tribological properties of graphene dispersed in engine oil: Coefficient of friction (a),
wear scar diameter (b), and load capacity (c) (Eswaraiah and Sankaranarayanan 2011)
Y. Xu et al.
Fig. 6.32 Schematic of the lubrication mechanisms of graphene as oil additives at different
lubricating states (Zhang and Zhou 2011)
611 optimal concentration. However, when the concentration exceeded the critical
612 value, the lubricating oil in the friction region is reduced by the aggregation of
613 graphene, which makes the oil film discontinuous and reduces the lubricating
614 effects. The corresponding lubrication mechanisms of graphene as an oil additive
615 in the different lubricating state are shown in Fig. 6.32 (Zhang and Zhou 2011).
616 4 Synergistic Lubricating Behaviors of Graphene

617 and MoS2
618 Previous studies (Kalin and Kogovšek 2012; Wang and Li 2014; Rabaso and
619 Dassenoy 2014; Rabaso and Ville 2014; Marquart and Wahl 2013; Kogovšek and
620 Remškar 2013; Zhang and Demydov 2012; Xu and Peng 2015; Xu and Xu 2015)
621 have shown that the tribological mechanisms of MoS2 are interlayer slippage,
622 rolling deformation, and a slippery exfoliation. But the MoS2 particles are easily
623 removed during the frictional process, which affects their long-term effects. Con-
624 sidering good adhesive and lubricating properties of graphene (Lin and Kim 2011;
625 Kandanur and Rafiee 2012; Berman and Erdemir 2013; Zhang and Pu 2014; Fan
626 and Wang 2014), the joint use of graphene and MoS2 seems to be a good choice.
627 Currently, graphene/MoS2 composites have been selected as a photoresponsive
628 coating (Huang and Han 2014), electrochemical sensors (Feng and Duan 2014),
629 catalyst supports (Zhai and Zhu 2015), and for lithium storage (Ma and Ye 2014).
630 Xu and Peng (2015) and Xu and Xu (2015) have systematically studied the
(a) 1.0
0.9 (b)
Average Friction coefficient
0.060 WSD of Stationary ball
WSD and WSW (mm)

0.8
WSW of Rotational Ball
0.048 0.7
0.6
0.036
0.5
0.024 0.4
0.3
0.012 0.2
0.1
0.000
0:0 0:1 1:4 2:3 1:1 3:2 4:1 1:0 0.0
0:0 0:1 1:4 2:3 1:1 3:2 4:1 1:0
Graphene/MoS2 Graphene/MoS2
Fig. 6.33 Average friction coefficient (a) and WSD and WSW (b) of graphene and MoS2
dispersed in base oil with different mass ratio (Xu and Peng 2015; Xu and Xu 2015)
lubricating properties of graphene/MoS2 composites; the results and tribological 631

mechanisms are reviewed in detail in the following sections. 632
4.1 Tribological Behaviors 633
Tribological tests were performed on a four-ball tribometer. The dispersive media 634
was bio-oil and detailed frictional conditions were as follows: concentration of the 635
additives: 0.5 wt%; Load:300 N; Rotating speed: 1000 rpm; Sliding time: 30 min. 636
As shown in Fig. 6.33, the MoS2/graphene composite had a lower friction coeffi- 637
cient and wear loss including wear scar diameter (WSD) and wear scar width 638
(WSW) than MoS2 or graphene. This suggested a clear synergistic lubricating 639
role of graphene/MoS2 composites. 640
The effect of the loads on the tribological behavior of the graphene/MoS2 641
composite is shown in Fig. 6.34. The friction coefficient, WSD and WSW of pure 642
base oil and esterified bio-oil (EBO), increased with load, due to the smaller micro- 643
intervals between the friction pairs under higher loads (Xu and Zheng 2014b). 644
There was a great decrease in the friction coefficient and wear loss of the EBO with 645
graphene/MoS2 composite additives, up to 300 N. Exceeding this load, the friction 646
coefficient and wear loss remained stable or increasing. At the same time, for the 647
same load, the EBO with graphene/MoS2 composite additives showed the best 648
lubricity in all the four lubricants. This confirms the synergistic lubricating effects 649
between graphene and MoS2. 650
4.2 Friction and Wear Mechanisms 651
In order to explore the friction and wear mechanisms of the graphene/MoS2 652
composites, XPS spectra of the typical elements on the rubbed surfaces are 653
Y. Xu et al.
0.08
1.0
(a)
Average friction coefftcient
0.07 (b)
0.06 0.8
WSD (mm)
0.05
0.6
0.04
0.03 0.4
0.02
0.2
0.01
0.00 0.0
100 200 300 400 500 100 200 300 400 500
Load (N) Load (N)
1.0
(c)
0.8
WSW (mm)
0.6
0.4
0.2
0.0
100 200 300 400 500
Load (N)
Fig. 6.34 Average friction coefficient (a), WSD (b), and WSW (c) of steel specimens under
different loads (Xu and Peng 2015; Xu and Xu 2015). Notes: Filled star EBO; Filled circle EBO
+0.5 wt% graphene; Filled square EBO+0.5 wt% MoS2; Filled triangle EBO+0.3 wt% graphene
+0.2 wt% MoS2 AU6
654 shown in Fig. 6.35 The position of the two C1s peaks suggested the existence of
655 carbon or sp3 C (C–C/C–H) and sp2 C (C¼C/C¼O) (Xu and Zheng 2014a),
656 respectively. This indicated that the adsorbed film was made from carbon or
657 organics, coming from the graphene or base oil. The largest areas of C1s peaks of
658 graphene/MoS2 blends suggested the formation of the thickest adsorbed film
659 containing graphene and organics. The O1s peak can be ascribed to hydroxides or
660 sulfates, confirming the existence of an adsorbed film with organics or a tribo-film
661 with sulfates. The O1s peak at 530.3 eV was attributed to Fe2O3, suggesting the
662 tribo-oxidation of the substrate during sliding. The Fe2p peaks belonged to Fe2O3,
663 and no simple Fe0 peak was found, confirming the existence of a complete tribo-
664 oxide film on the rubbing surfaces. The Cr2p peaks belonged to Cr2O3 and CrN,
665 respectively. This confirmed a tribo-oxidation and tribo-reaction during the sliding
666 process.
667 For graphene/MoS2 lubrication, the two main Mo3d peaks at 232.6 and 235.8 eV
668 were ascribed to MoO3 (Hu and Wang 2009). Another peak at 229.7 eV was
669 ascribed to Mo3d of MoS2, but this peak was not detected for MoS2 lubrication.
670 Moreover, the two S2p peaks at 169 eV and 161.6 eV were indexed to SO42 and
671 MoS2, respectively (Moulder and Stickle 1995). When MoS2 was used
(b) 532 530.3

(a)
C1s 284.8 O1s
288.7
Isp /Isp =9.95/1
3 2
Intensity (a.u.)
(d)
Intensity (a.u.)
(d)
2
sp C(C=C/O) Isp /Isp =7.68/1
3 2
(c)
Ia/Ib/Ic/Id=1/1.77/1.34/3.51 (c)
3
sp C(C-C/H) Isp /Isp =7.32/1
3 2
(b) (b)
Ia/Ib/Ic/Id=1/1.55/1.12/2.55
Isp /Isp =6.39/1
3 2
(a) (a)
300 297 294 291 288 285 282 279 276 542 540 538 536 534 532 530 528 526 524 522
Binding energy (eV) Binding energy (eV)
(c)
Fe2p (d)
Cr2p 585.9 576.1
724.5 710.9 586.7 576.9
584.2
574.4
719.7
Intensity (a.u.)
Intensity (a.u.)
(d)
707 (c)
(d)
(c) (b)
(b)
(a)
(a)
744 736 728 720 712 704 696 595 590 585 580 575 570 565
(e)
Mo3d (f)
S2p 169
232.6
235.8
Intensity (a.u.)
Intensity (a.u.)
161.6
(d)
229.7
(d)
(c)
(c)
240 236 232 228 224 220 177 174 171 168 165 162 159 156 153
Fig. 6.35 XPS spectra of the worn surfaces of the rotating specimen lubricated by base oil (a),
base oil with graphene additives (b), base oil with MoS2 additives (c), base oil with graphene/
MoS2 composite additives (d) (Xu and Peng 2015; Xu and Xu 2015)
independently (c), the peak at 161.6 eV in the curve was very weak, suggesting that 672
MoS2 was easily oxidized during sliding. That is, the introduction of graphene was 673
helpful to the adhesion of the MoS2 on the frictional surface and further prevents the 674
oxidation of MoS2. 675
The friction and wear mechanisms were summarized as follows. For graphene, 676
the main antifriction and antiwear components were the small graphene particles, 677
and ploughing was the dominant form of wear. For MoS2, the MoS2 with the 678
Y. Xu et al.
679 smaller surface area was the main lubricant but it is easy to be removed from the
680 frictional surface or oxidized. For graphene/MoS2 composites, a thicker tribo-film
681 was formed to play an antifriction and antiwear role. The synergistic lubricating
682 effect of graphene and MoS2 allows complete graphene and unoxidized MoS2 to
683 remain on the sliding surfaces.
684 5 Conclusions
685 In summary, in this chapter, two kinds of nano-additives MoS2 and graphene have
686 been reviewed. The preparation methods, properties, and applications have also
687 been discussed. Both MoS2 and graphene have various functions and applications
688 and their tribological properties have been explored this chapter. For MoS2, differ-
689 ent structures have different physical properties. Nano-MoS2 showed obvious
690 advantages over the more conventional micro-MoS2. In a widely accepted opinion,
691 rolling is the main antifriction and antiwear mechanism for nano-MoS2 particles.
692 The slippery role is the friction-reducing mechanism of MoS2 nano-sheets and the
693 combined actions of rolling and sliding account for the excellent lubricating effect
694 of MoS2 nano-tubes. However, exfoliation and transfer cannot be ignored when
695 explaining the tribological behaviors of nano-MoS2. More combined applications
696 of nano-MoS2 with different structures require further study.
697 As for graphene, good adsorption onto the frictional surfaces is helpful to the
698 lubricating behaviors of graphene. However, the effects of the layer, area, and
699 defects in the graphene on the tribological behaviors still remain unknown and need
700 further clarification in the future. The graphene/MoS2 composites showed excellent
701 synergistic lubricating effect. The mechanisms were attributed to the protective
702 roles of the graphene preventing the oxidation of MoS2 and also MoS2 preventing
703 graphene being destroyed and reduced into small, defective additives. The MoS2
704 used in the composites was micro-MoS2, nano-MoS2 composites needed to be
705 studied further. To conclude, both graphene and MoS2 as lubricating additives
706 have a bright future and more specialized applications will be researched and found.
707 Acknowledgements This work was supported by the National Natural Science Foundation of
708 China (Grant No. 51405124), the China Postdoctoral Science Foundation (Grant Nos.
709 2015T80648 and 2014M560505), the Anhui Provincial Natural Science Foundation (Grant
710 No. 1408085ME82), and the Tribology Science Fund of State Key Laboratory of Tribology,
711 Tsinghua University (Grant No. SKLTKF15A05). In the UK, the research was supported by the
712 Engineering and Physical Sciences Research Council, grant number EP/L017725/1.
713 References
714 Abdelaziz EA, Saidur R (2011) A review on energy saving strategies in industrial sector. Renew
715 Sust Energ Rev 15:150–168
Aldana PU, Vacher B (2014) Action mechanism of WS2 nanoparticles with ZDDP additive in 716
boundary lubrication regime. Tribol Lett 56:249–258 717
Aralihalli S, Biswas SK (2013) Grafting of dispersants on MoS2 nanoparticles in base oil 718
lubrication of steel. Tribol Lett 49:61–76 719
Bang GS, Nam KW (2014) Effective liquid-phase exfoliation and sodium ion battery application 720
of MoS2 nanosheets. ACS Appl Mater Interfaces 6:7084–7089 721
Berman D, Erdemir A (2013) Few layer graphene to reduce wear and friction on sliding steel 722
surfaces. Carbon 54:454–459 723
Bonaccorso F, Colombo L (2015) Graphene, related two-dimensional crystals, and hybrid systems 724
for energy conversion and storage. Science 347:1246501 725
Chen CS, Chen XH (2005) Modification of multi-walled carbon nanotubes with fatty acid and their 726
tribological properties as lubricant additive. Carbon 43:1660–1666 727
Chen J, Kuriyama N (2001) Electrochemical hydrogen storage in MoS2 nanotubes. J Am Chem 728
Soc 123:11813–11814 729
Chen J, Li SL (2002) Synthesis of open-ended MoS2 nanotubes and the application as the catalyst 730
of methanation. Chem Commun:1722–1723 731
Chen J, Li SL (2003) Novel hydrogen storage properties of MoS2 nanotubes. J Alloys Compd 732
356:413–417 733
Choudhary N, Park J (2014) Growth of large-scale and thickness-modulated MoS2 nanosheets. 734
ACS Appl Mater Interfaces 6:21215–21222 735
Deepak FL, Jose-Yacaman M (2010) Recent highlights in the synthesis, structure, properties, and 736
applications of MoS2 nanotubes. Isr J Chem 50:426–438 737
Desai JD, Banat IM (1997) Microbial production of surfactants and their commercial potential. 738
Microbiol Mol Biol Rev 61:47–64 739
Dickinson RG, Pauling L (1923) The crystal structure of molybdenite. J Am Chem Soc 740
45:1466–1471 741
Dresselhaus MS, Dresselhaus G (1996) Science of fullerenes and carbon nanotubes: their proper- 742
ties and applications. Academic Press, New York 743
Du GD, Guo ZP (2010) Superior stability and high capacity of restacked molybdenum disulfide as 744
anode material for lithium ion batteries. Chem Commun 46:1106–1108 745
Eswaraiah V, Sankaranarayanan V (2011) Graphene-based engine oil nanofluids for tribological 746
applications. ACS Appl Mater Interfaces 3:4221–4227 747
Falkovsky LA (2008) Optical properties of graphene. J Phys Conf Ser 129:012004 748
Fan XQ, Wang LP (2014) Highly conductive ionic liquids toward high-performance space- 749
lubricating greases. ACS Appl Mater Interfaces 6:14660–14671 750
Feldman Y, Wasserman E (1995) High-rate, gas-phase growth of MoS2 nested inorganic fuller- 751
enes and nanotubes. Science 267:222 752
Feng QL, Duan KY (2014) A novel way for detection of eugenol via poly 753
(diallyldimethylammonium chloride) functionalized graphene-MoS2 nano-flower fabricated 754
electrochemical sensor. Sens Actuat B-Chem 192:1–8 755
Fleischauer PD, Lince JR (1999) A comparison of oxidation and oxygen substitution in MoS2 solid 756
film lubricants. Tribol Int 32:627–636 757
Frank IW, Tanenbaum DM (2007) Mechanical properties of suspended graphene sheets. J Vac Sci 758
Technol B 25:2558–2561 759
Fumihiko M, Hiroki H (2011) Molecular beam epitaxial growth of graphene and ridge-structure 760
networks of graphene. J Phys D-Appl Phys 44:435305 761
Geim AK, Macdonald AH (2007) Graphene: exploring carbon flatland. Phys Today 60:35 762
Hassanien A, Tokumoto M (2005) Structural and mechanical properties of MoS2-Ix nanotubes and 763
Mo6SxIy nanowires. Phys E 29:684–688 764
Hernandez Y, Nicolosi V (2008) High-yield production of graphene by liquid-phase exfoliation of 765
graphite. Nat Nanotechnol 3:563–568 766
Hu KH, Hu XG (2010) The effect of morphology on the tribological properties of MoS2 in liquid 767
paraffin. Tribol Lett 40:155–165 768
Y. Xu et al.
769 Hu KH, Liu M (2009) Tribological properties of molybdenum disulfide nanosheets by monolayer
770 restacking process as additive in liquid paraffin. Tribol Int 42:33–39
771 Hu KH, Wang YR (2007) Preparation and characterisation of ball-like MoS2 nanoparticles. Mater
772 Sci Technol 23:242–246
773 Hu KH, Wang J (2009) Tribological properties of MoS2 nano-balls as filler in polyoxymethylene-
774 based composite layer of three-layer self-lubrication bearing materials. Wear 266:1198–1207
775 Huang ZY, Han WJ (2014) Graphene/MoS2 hybrid structure and its photoresponse property.
776 Ceram Int 40:11971–11974
777 Huang X, Qi XY (2012) Graphene-based composites. Chem Soc Rev 41:666–686
778 Huang HD, Tu JP (2005) Friction and wear properties of IF–MoS2 as additive in paraffin oil.
779 Tribol Lett 20:247–250
780 Huang HD, Tu JP (2006) An investigation on tribological properties of graphite nanosheets as oil
781 additive. Wear 261:140–144
782 Joly-Pottuz L, Martin JM (2006) Pressure-induced exfoliation of inorganic fullerene-like WS2
783 particles in a Hertzian contact. J Appl Phys 99:023524
784 Kalin M, Kogovšek J (2012) Mechanisms and improvements in the friction and wear behavior
785 using MoS2 nanotubes as potential oil additives. Wear 280-281:36–45
786 Kandanur SS, Rafiee MA (2012) Suppression of wear in graphene polymer composites. Carbon
787 50:3178–3183
788 Khalil W, Mohamed A (2016) Tribological properties of dispersed carbon nanotubes in lubricant.
789 Fuller Nanotub Carbon Nanostruct 24:479–485
790 Kis A, Mihailovic D (2003) Shear and Young’s moduli of MoS2 nanotube ropes. Adv Mater
791 15:733–736
792 Kogovšek J, Remškar M (2013) Influence of surface roughness and running-in on the lubrication
793 of steel surfaces with oil containing MoS2 nanotubes in all lubrication regimes. Tribol Int
794 61:40–47
795 Lahouij I, Vacher B (2014) Direct observation by in situ transmission electron microscopy of the
796 behaviour of IF-MoS2 nanoparticles during sliding tests: influence of the crystal structure. Lubr
797 Sci 26:163–173
798 Lee CG, Wei XD (2008) Measurement of the elastic properties and intrinsic strength of monolayer
799 graphene. Science 321:385–388
800 Li XS, Cai WW (2009) Large-area synthesis of high-quality and uniform graphene films on copper
801 foils. Science 324:1312–1314
802 Li XS, Magnuson CW (2011) Large-area graphene single crystals grown by low-pressure chem-
803 ical vapor deposition of methane on copper. J Am Chem Soc 133:2816–2819
804 Li YG, Wang HL (2011) MoS2 nanoparticles grown on graphene: an advanced catalyst for the
805 hydrogen evolution reaction. J Am Chem Soc 133:7296–7299
806 Li H, Yin ZY (2012) Fabrication of single- and multilayer MoS2 film-based field-effect transistors
807 for sensing NO at room temperature. Small 8:63–67
808 Lin LY, Kim DE (2011) Friction and wear characteristics of multi-layer graphene films investi-
809 gated by atomic force microscopy. Surf Coat Technol 205:4864–4869
810 Lin JS, Wang LW (2010) Modification of graphene platelets and their tribological properties as a
811 lubricant additive. Tribol Lett 41:209–215
812 Lopez-Sanchez O, Lembke D (2013) Ultrasensitive photodetectors based on monolayer MoS2. Nat
813 Nanotechnol 8:497–501
814 Ma L, Ye JB (2014) Gemini surfactant assisted hydrothermal synthesis of nanotile-like MoS2/
815 graphene hybrid with enhanced lithium storage performance. Nano Energy 10:144–152
816 Margulis L, Salitra G (1993) Nested fullerene-like structures. Nature 365:113–114
817 Marquart M, Wahl M (2013) Enhancing the lifetime of MoS2-lubricated ball bearings. Wear
818 303:169–177
819 Mertens AJ, Senthilvelan S (2016) Mechanical and tribological properties of carbon nanotube
820 reinforced polypropylene composites. Proc Inst Mech Eng Part L-J Mat Des Appl 0:1–12
Moshkovith A, Perfiliev V (2006) Friction of fullerene-like WS2 nanoparticles: effect of agglom- 821
eration. Tribol Lett 24:225–228 822
Moulder JF, Stickle WF (1995) Handbook of X-ray photoelectron spectroscopy. Physical Elec- 823
tronics Inc., Eden Prairie, MA 824
Nath M, Govindaraj A (2001) Simple synthesis of MoS2 and WS2 nanotubes. Adv Mater 825
13:283–286 826
Nemanič V, Žumer M (2003) Field-emission properties of molybdenum disulfide nanotubes. Appl 827
Phys Lett 82:4573–4575 828
Novoselov KS, Geim AK (2004) Electric field effect in atomically thin carbon films. Science 829
306:666–669 830
Onodera T, Morita Y (2009) A computational chemistry study on friction of h-MoS2. Part 831
I. Mechanism of single sheet lubrication. J Phys Chem B 113:16526–16536 832
Oshima C, Nagashima A (1997) Ultra-thin epitaxial films of graphite and hexagonal boron nitride 833
on solid surfaces. J Phys Condens Matter 9:1–20 834
Price L, Levine MD (2011) Assessment of China’s energy-saving and emission-reduction accom- 835
plishments and opportunities during the 11th Five Year Plan. Energy Policy 39:2165–2178 836
Rabaso P, Dassenoy F (2014) An investigation on the reduced ability of IF-MoS2 nanoparticles to 837
reduce friction and wear in the presence of dispersants. Tribol Lett 55:503–516 838
Rabaso P, Ville F (2014) Boundary lubrication: influence of the size and structure of inorganic 839
fullerene-like MoS2 nanoparticles on friction and wear reduction. Wear 320:161–178 840
Raccichini R, Varzi A (2015) The role of graphene for electrochemical energy storage. Nat Mater 841
14:271–279 842
Radisavljevic B, Radenovic A (2011) Single-layer MoS2 transistors. Nat Nanotechnol 6:147–150 843
Reina A, Jia XT (2008) Large area, few-layer graphene films on arbitrary substrates by chemical 844
vapor deposition. Nano Lett 9:30–35 845
Remskar M, Mrzel A (2001) Self-assembly of subnanometer-diameter single-wall MoS2 846
nanotubes. Science 292:479–481 847
Risdon TJ, Gresty DA (1975) An historical review of reductions in fuel consumption of United 848
States and European engines with MoS2. SAE Technical Paper 849
Rosentsveig R, Gorodnev A (2009) Fullerene-like MoS2 nanoparticles and their tribological 850
behavior. Tribol Lett 36:175–182 851
Rothschild A, Cohen SR (1999) WS2 nanotubes as tips in scanning probe microscopy. Appl Phys 852
Lett 75:4025–4027 853
Shan TT, Xin S (2016) Combining nitrogen-doped graphene sheets and MoS2: a unique film– 854
foam–film structure for enhanced lithium storage. Angew Chem 128:12975–12980 855
Smith RJ, King PJ (2011) Large-scale exfoliation of inorganic layered compounds in aqueous 856
surfactant solutions. Adv Mater 23:3944–3948 857
Tannous J, Dassenoy F (2011) Understanding the tribochemical mechanisms of IF-MoS2 858
nanoparticles under boundary lubrication. Tribol Lett 41:55–64 859
Tenne R (2006) Inorganic nanotubes and fullerene-like nanoparticles. J Mater Res 21:2726–2743 860
Tevet O, Von-Huth P (2011) Friction mechanism of individual multilayered nanoparticles. Proc 861
Natl Acad Sci U S A 108:19901–19906 862
Tkachev SV, Buslaeva EY (2012) Reduced graphene oxide. Inorg Mater 48:796–802 863
Tomala A, Vengudusamy B (2015) Interaction between selected MoS2 nanoparticles and ZDDP 864
tribofilms. Tribol Lett 59:1–18 865
Van Lier G, Van Alsenoy C (2000) Ab initio study of the elastic properties of single-walled carbon 866
nanotubes and graphene. Chem Phys Lett 326:181–185 867
Wang CQ, Li HS (2014) Effect of strain on atomic-scale friction in layered MoS2. Tribol Int 868
77:211–217 869
Wu KH, Cheng HH (2015) Electron-beam writing of deoxygenated micro-patterns on graphene 870
oxide film. Carbon 95:738–745 871
Wu ZZ, Wang DZ (2010) Preparation and tribological properties of MoS2 nanosheets. Adv Eng 872
Mater 12:534–538 873
Y. Xu et al.
874 Wu SX, Zeng ZY (2012) Electrochemically reduced single-layer MoS2 nanosheets: characteriza-
875 tion, properties, and sensing applications. Small 8:2264–2270
876 Xu YF, Geng J (2016) Friction-induced transformation from graphite dispersed in esterified bio-oil
877 to graphene. Tribol Lett 63:1–11
878 Xu MS, Liang T (2013) Graphene-like two-dimensional materials. Chem Rev 113:3766–3798
879 Xu YF, Peng YB (2015) Synergistic lubricating behaviors of graphene and MoS2 dispersed in
880 esterified bio-oil for steel/steel contact. Wear 342:297–309
881 Xu ZY, Xu Y (2015) Formation and tribological properties of hollow sphere-like nano-MoS2
882 precipitated in TiO2 particles. Tribol Int 81:139–148
883 Xu YF, Zheng XJ (2014a) Effect of catalytic esterification on the friction and wear performance of
884 bio-oil. Wear 311:93–100
885 Xu YF, Zheng XJ (2014b) Comparison and analysis of the influence of test conditions on the
886 tribological properties of emulsified bio-oil. Tribol Lett 55:543–552
887 Yang W, Chen GR (2013) Epitaxial growth of single-domain graphene on hexagonal boron
888 nitride. Nat Mater 12:792–797
889 Yao J, Shi XL (2014) The enhanced tribological properties of NiAl intermetallics: combined
890 lubrication of multilayer graphene and WS2. Tribol Lett 56:573–582
891 Ye M, Winslow D (2015) Recent advancement on the optical properties of two-dimensional
892 molybdenum disulfide (MoS2) thin films. Photonics 2:288–307
893 Zelenski CM, Dorhout PK (1998) Template synthesis of near-monodisperse1 microscale
894 nanofibers and nanotubules of MoS2. J Am Chem Soc 120:734–742
895 Zeng ZY, Yin ZY (2011) Single-layer semiconducting nanosheets: high-yield preparation and
896 device fabrication. Angew Chem Int Ed 50:11093–11097
897 Zhai CY, Zhu MS (2015) Two dimensional MoS2/graphene composites as promising supports for
898 Pt electrocatalysts towards methanol oxidation. J Power Sources 275:483–488
899 Zhang WY, Demydov D (2012) Fundamental understanding of the tribological and thermal
900 behavior of Ag-MoS2 nanoparticle-based multi-component lubricating system. Wear 288:9–16
901 Zhang X, Lai ZC (2016) Solution-processed two-dimensional MoS2 nanosheets: preparation,
902 hybridization, and applications. Angew Chem Int Ed 55:8816–8838
903 Zhang G, Liu HJ (2016) Two-dimensional layered MoS2: rational design, properties and electro-
904 chemical applications. Energy Environ Sci 9:1190–1209
905 Zhang LL, Pu JB (2014) Frictional dependence of graphene and carbon nanotube in diamond-like
906 carbon/ionic liquids hybrid films in vacuum. Carbon 80:734–745
907 Zhang W, Zhou M (2011) Tribological properties of oleic acid-modified graphene as lubricant oil
908 additives. J Phys D-Appl Phys 44:205303
909 Zhmud B, Pasalskiy B (2013) Nanomaterials in lubricants: an industrial perspective on current
910 research. Lubricants 1:95–101
911 Zhou XD, Shi HQ (2008) Tribological properties of Cyanex 301-modified MoS2 nano-sized
912 hollow spheres in liquid paraffin. Ind Lubr Tribol 60:147–152
913 Zhou SM, Zhang XB (2007) Fabrication and tribological properties of carbon nanotubes
914 reinforced Al composites prepared by pressureless infiltration technique. Compos Part
915 A-Appl Sci Manuf 38:301–306
916 Zhu YW, Murali S (2010) Graphene and graphene oxide: synthesis, properties, and applications.
917 Adv Mater 22:3906–3924
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Nano-MoS2 and Graphene Additives in Oil for Tribological Applications

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Nano-MoS2 and Graphene Additives in Oil 2

for Tribological Applications 3

Abstract Nano-additives have attracted lots of attentions in recent years due to 6

Keywords Nano-MoS2 • Graphene • Nano-additives • Tribological application 24

Y. Xu (*) • Y. Peng • T. You • J. Geng • X. Hu

© Springer International Publishing AG 2018

26 A general demand from Society for a more sustainable and environmentally

47 2 An Introduction to and the Tribological Behavior

49 Molybdenum disulfide (MoS2) has a layered two-dimensional structure. Its crystal

2.1 MoS2 Particles: Nano-balls 67

2.1.1 Preparation of MoS2 Nano-balls 72

Rosentsveig and Gorodnev (2009) used a four-step method to produce an inorganic 73

96 2.1.2 Characterization of MoS2 Nano-balls

97 Transmission electron microscopy (TEM) can be used to observe MoS2

Fig. 6.4 SEM image of MoS3 precursor (Huang and Tu 2005)

123 2.1.3 Dispersion of MoS2 Nano-balls in Base Oil

2.1.4 Comparison with Micro-MoS2 165

2.1.5 Effect of ZDDP on Tribological Properties 177

ZDDP (Zinc Dialkyl Dithiophosphates) is an important oxidation and corrosion 178

190 2.1.6 Effect of Crystallinity on Tribological Properties

Fig. 6.10 A MoS2 nano-

2.1.7 Effect of Different of Pressure on Exfoliation Behavior 209

2.1.8 Tribological Mechanisms 215

Basal surface with Difficultly

2.2 MoS2 Nano-sheets 257

2.2.1 Preparation of MoS2 Nano-sheets 266

2.2.2 Application of MoS2 Nano-sheets 297

2.2.3 Tribological Mechanisms of MoS2 Nano-sheets 342

Fig. 6.17 Schematic a b S S S S

Fig. 6.18 Variation of

365 2.3 MoS2 Nano-tubes

373 2.3.1 Preparation and Characterization of MoS2 Nano-tube AU5

2.3.2 Applications of MoS2 Nano-tubes 396

Fig. 6.23 Catalytic

399 Jose-Yacaman 2010), for instance, mechanical properties (Hassanien and

3 Graphene and Its Tribological Applications 433

3.1 Preparation and Characterization of Graphene 442

3.1.1 Exfoliation in Liquid or Gas 448

Exfoliation of graphite in liquid or gas is a physical method to obtain graphene. 449

3.1.2 Modified Mechanical Exfoliation 454

Recently, in order to improve the yield of production of single-layer graphene, Xu 455

464 3.1.3 Epitaxial Growth

486 3.1.4 Chemical Vapor Deposition

Fig. 6.25 Topographic

Fig. 6.26 SEM images of

3.1.5 Reduced Graphene Oxide 507

3.2 Properties and Applications of Graphene 521

3.2.1 Electrochemical Properties 526

544 3.2.2 Mechanical Properties

545 With the potential application of graphene in nanoelectromechanical systems, the

556 3.2.3 Optical Properties

562 3.2.4 Extreme Pressure Properties

572 3.2.5 Dispersion Properties