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Industrial Lubrication and Tribology

Tribological properties of metallic nanoparticles as lubricant additives under the applied electric currents
Lina Si, Yan Pan, Xiaoqing Zhang, Jie Wang, Jia Yao, Yanjie Wang, Fengbin Liu, Feng He,
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To cite this document:
Lina Si, Yan Pan, Xiaoqing Zhang, Jie Wang, Jia Yao, Yanjie Wang, Fengbin Liu, Feng He, (2018) "Tribological properties of
metallic nanoparticles as lubricant additives under the applied electric currents", Industrial Lubrication and Tribology, https://
doi.org/10.1108/ILT-12-2017-0373
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Tribological properties of metallic
nanoparticles as lubricant additives under the
applied electric currents
Lina Si
School of Mechanical and Materials Engineering, North China University of Technology, Beijing, China
Yan Pan
Renmin University of China Affiliated High School, Beijing, China
Xiaoqing Zhang
School of Materials Science and Mechanical Engineering, Beijing Technology and Business University, Beijing, China
Jie Wang
Beijing Institute of Astronautical Systems Engineering, Beijing, China
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Jia Yao
High School Affiliated to Renmin University of China, Beijing, China
Yanjie Wang
School of Mechanical Engineering, Beijing Institute of Technology, Beijing, China
Fengbin Liu
School of Mechanical and Materials Engineering, North China University of Technology, Beijing, China, and
Feng He
State Key Laboratory of Tribology, Tsinghua University, Beijing, China

Abstract
Purpose – This paper aims to clarify the effects of metallic nanoparticles (NPs) additives and room temperature ionic liquids (ILs) on the tribological
performance of electric contacts.
Design/methodology/approach – Tribological properties of copper (Cu) and silver (Ag) NPs as lubricant additives in different lubricants of ILs or
polyalphaolefin (PAO) oils under applied electric currents were investigated. After tribological tests, morphologies of worn surfaces were observed;
meanwhile, lubrication and anti-wear properties were analyzed.
Findings – The mixture solution of the IL and Cu NPs showed desirable lubrication and anti-wear properties due to the reduction of electrocorrosion and
the enhancement of rolling effects of particles in the contact region. The anti-wear performance of Cu NPs is better than that of Ag NPs due to the
difference in the particle size. The PAO oil with the Cu NPs additives showed poor lubrication properties due to the low solubility of the particles in the oil.
When the direction of applied current was changed, the friction of the lubricant with better conductivity was more stable in the variation trend.
Originality/value – This paper begins with a study of tribological properties of Cu and Ag NPs as lubricant additives in different lubricants of IL or
PAO oils under applied electric currents. The authors then propose several methods and possible solutions which could be implemented to improve
the tribological performance of electric contacts.
Keywords Ionic liquids, Conductive lubricants, Electric contact, Lubrication property, Nanoparticle additives
Paper type Research paper

1. Introduction friction and wear properties could be influenced greatly by the


applied electric currents by formation of either reversible
The tribological characteristics of sliding interfaces under physical adsorption film or irreversible electrochemical reaction
applied electric currents have been widely studied to improve film (or both) (Xie et al., 2015; Huang et al., 2017; Mahmoud
the tribological performance of electric contacts. The interfacial
et al., 2010; Xie et al., 2014). For instance, it was reported that
current direction played an important role in altering the wear
rates of the cathode and anode surfaces (Goto, 1995; Lavielle,
The current issue and full text archive of this journal is available on
Emerald Insight at: www.emeraldinsight.com/0036-8792.htm
This work was supported by the National Natural Science Foundation of
China (Grant No. 51775044, 51475256, 51575004 and 51605008).

Industrial Lubrication and Tribology Received 16 January 2018


© Emerald Publishing Limited [ISSN 0036-8792] Revised 7 May 2018
[DOI 10.1108/ILT-12-2017-0373] Accepted 11 June 2018
Tribological properties of metallic nanoparticles Industrial Lubrication and Tribology
Lina Si et al.

1994; Csapo et al., 1996). One explanation for such a dissolved into 50 ml [BMIm]PF6 or PAO oil. Because the
phenomenon is that for two surfaces with dissimilar metals, dispersibility of NPs and the stability of the mixed solution play
static electric charges could be generated on each surface under an important role in its tribological performance, the mixed
the effect of external current; the interaction force between the solution was ultrasonically treated for 15 min to improve the
two charged surfaces could increase or offset the normal load. dispersibility of the NPs. The stability of the mixed solution was
Moreover, the relations between the wear of cathode surface judged by observing its transparency, and no obvious
and newly formed surface film have been discussed (Senouci precipitation can be seen in the stationary solution after 30 min
et al., 1999; Yasar et al., 2007; Tu et al., 2009). It is notable that storage, which was sufficient for tribological tests. Finally, the
the impact of electricity varied under boundary lubrication mixed solutions were diluted to different concentrations for
(Karuppiah et al., 1999; de Wijn et al., 2014; Guriyanova et al., further experiments. The pictures of various mixed solutions of
2011), thin film lubrication (Xie et al., 2010a; Xie et al., 2011; NPs with [BMIm]PF6 or PAO oil keeping for 30 min are
Xie et al., 2010b; Xie et al., 2010c) and elastohydrodynamic shown in Figure 1(a). It can be seen that there is no
lubrication regimes (Wong et al., 2003). precipitation in the mixed solutions, indicating that NPs has
Room temperature ionic liquids (ILs), highly marked by been dispersed well in the [BMIm]PF6 and PAO oil.
their non-volatility, inflammability, thermal stability, distinct The schematic diagram of a ball-plate tribometers used in
solubility and high conductivity, are not only novel materials this work is shown in Figure 1(b). Cu sheets were used as the
applied as solar collector working fluids (Liu et al., 2015) or tested samples, and Cu balls (U 5 mm, roughness: 5 m m) were
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battery electrolytes (Armand et al., 2009), but they also exhibit used as the counterpart. The electric current provided by a
satisfying load-carrying, friction-reducing and anti-wear constant-current power supply (DH1716A DC, Beijing
properties in diverse tribo-pairs (Xie et al., 2009). Another Dahua) was connected to the copper sheet and the Cu ball. To
intriguing material called nanoparticles (NPs), such as copper avoid the interference of electric wires to the friction force
(Cu), silver (Ag), Ag-MoS2 and polytetrafluoroethylene, measurement, one end of the thin copper wire was connected
adding into motor oils, can improve the tribological properties to the holder of the ball, and the other end connected to the
dramatically. For example, Yu et al. found that with Cu NPs in fixture of the friction force sensor. During the experiments,
lubricant an enhanced lubrication performance could be different electric currents of 0, 0.1, 0.2, 0.5 and 1.0 A were
achieved due to the fact that a copper-based film was formed applied. The effect of the applied current direction on the
under high temperature and pressure in the rubbing area (Yu friction behavior was also investigated. Positive electric current
et al., 2008). More interestingly, a series of researches in which was defined as the case that the larger potential was applied to
ILs additives and NPs additives were co-dispersed thoroughly the sample, and vice versa. A micro-pipette was used to control
in polymer matrices indicated that the additions of ILs and NPs the amount of the injected lubricant into the ball and sheet
led to an obvious decrease in friction coefficient, wear rate and interface, and a liquid meniscus was then formed at the
the residual depth of the scratch groove, improving the interface after being equilibrium, as schematically shown in
tribological performance obviously (Sanes et al., 2010; Carri on
et al., 2011; Wang et al., 2018). The potential cooperation Figure 1 (a) Pictures of various mixed solutions: 1. ILs, 2. ILs 1 0.05
between ILs lubricants and metallic NPs begins to attract Wt.% Cu NPs, 3. ILs 1 0.1 Wt.% Cu NPs, 4. ILs 1 0.05 Wt.% Ag NPs,
increasing attention in recent years. For instance, Dewan et al. 5. ILs 1 0.1 Wt.% Ag NPs, 6. PAO, 7. PAO 1 0.1 Wt.% Cu NPs; (b)
managed to synthesize stably dispersed nanocopper in 1-butyl- schematic diagrams of the tribometers and the capillary bridge at the
3-methylimidazolium hexafluorophosphate ([BMIm]PF6, a lubricated interface
typical room temperature ILs)-ethylene glycol system, showing
a possible extension of stability of NPs in ILs (Dewan et al.,
2012).
In the present work, the tribological characteristics of the
combination of ILs and NPs additives under applied electric
current have been discussed using conventional lubricant oil –
polyalphaolefin (PAO) oil with similar viscosity as a contrast.
The objective of this study is to clarify the effects of ILs and
NPs additives on the tribological performance of electric
contacts.

2. Experimental part
The base oils used in this study were [BMIm]PF6 and PAO,
and the additives were Cu NPs (Nanjing Xianfeng; diameter:
20 nm; purity 99.9 Wt.%) and Ag NPs (Nanjing Xianfeng;
diameter: 80-90 nm; purity 99.9 Wt.%). The viscosity of
[BMIm]PF6 is 210 mPa·s (25°C), and the electric conductivity
1.4 mS/cm (Xie et al., 2011). PAO oil is a conventional base oil
which has a close viscosity (189.7 mPa·s) with [BMIm]PF6,
and its electric conductivity is approximately 10 12 mS/cm
(Rosenkranz et al., 2014). First, Cu or Ag NPs of 0.5 g were
Tribological properties of metallic nanoparticles Industrial Lubrication and Tribology
Lina Si et al.

Figure 1(b). Reciprocating motion of the sample was used 0.1 Wt.% Cu NPs suggests that the concentration of the
during the friction experiments and the ball was kept stationary. NPs plays an important role in the lubrication performance.
The average linear sliding speed was 3 mm/s, and the sliding When the NPs concentration is small, the lubricity does not
length was 10 mm. The applied load during the test was 5 N, improve apparently; when the concentration is relatively
corresponding to a maximum contact pressure of 880 MPa. larger, obvious reductions in the friction coefficients can be
Prior to the friction experiments, Cu sheets and balls were observed under different electric currents in magnitude. It is
ultrasonically cleaned in acetone and deionized water speculated that the reduction of the friction coefficients is
successively, and finally dried with pressurized nitrogen gas. caused by the rolling effects of the particles in lubricant due
The experiments were conducted under ambient temperature to the addition of NPs (Guo et al., 2013). It can be also
(25-30°C). confirmed from the morphologies of the worn surfaces
In this article, friction coefficient curves could be lubricated with two kinds of mixed solutions of ILs and Cu
obtained using the ball-plate tribometer. An optical NPs, as shown in Figure 4, that grinding tracks can be
microscope was used to observe the surface morphologies observed due to the rolling effects of Cu NPs. The lubricant
of the worn areas of the tested samples. The surface solution with 0.05 Wt.% Cu NPs shows a few furrows, while
roughness of Cu sheets before and after tests along and no clear furrow is present on the surface lubricated with the
perpendicular to sliding direction was tested using 3D solution containing 0.1 Wt.% Cu NPs, and merely some
surface topography. The wear was evaluated by measuring slight scratches can be seen. It can be also seen from Figure 4
that the roughness value of Cu sheet at sliding direction
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the cross-sectional area and height of the sliding track with


a 3D surface topography at different points. The wear lubricated with mixed solution containing 0.05 Wt.% Cu
volume was calculated by multiplying the average track NPs is larger than that lubricated with solution containing
area by the circumference of the sliding circle. To ensure 0.1 Wt.% Cu NPs. These phenomena indicate that the
that the results are reliable, all experiments were increased concentration of NPs can improve the lubrication
determined statistically using three test samples per property.
condition. Figure 5 shows the wear volume of the Cu sheets under
dry and lubricated conditions with different positive
3. Results and discussions currents in magnitude. It can be seen that the wear volume
under dry friction increases slightly as the increase of
3.1 Influences of magnitude of the applied current current, which is coincident with the results of friction
Figure 2 shows typical friction coefficient curves obtained with coefficient. The wear after the addition of ILs is the smallest.
the ball-plate tribometer under various positive electric The wear volume with the mixed solution of ILs and Cu NPs
currents. During the friction experiments, reciprocating motion increases obviously compared with that under dry friction
of the sample was used and the sample was move forth and back and lubricated with ILs. However, the wear volume with a
ten times. In this article, we define the forward direction as smaller NPs concentration is larger than that with a larger
Trace and the backward direction as Retrace, as shown in NPs concentration.
Figure 2(a). From Figure 2, it can be seen that compared to dry
friction, the friction coefficients lubricated by ILs and mixed 3.2 Influences of different nanoparticles
solutions are more sensitive to the magnitude of electric Figure 6 shows the average friction coefficients of the
currents. As the friction time increases, the friction coefficients lubricant solutions with different NPs as additives under
of dry friction and that lubricated with mixed solutions of ILs varied positive electric currents in magnitude. Figure 7
and NPs keep almost unchanged, while that lubricated with ILs shows the wear volume of the Cu sheets under various
increases gradually. lubricated conditions with different electric currents in
Figure 3 shows the average friction coefficients with magnitude. From Figures 6 and 7, it can be seen that in the
different lubricants under different applied positive currents case of ILs, the addition of Cu NPs has a better effect on
in magnitude obtained from Figure 2. It can be seen that the friction reduction than that of Ag NPs, and the wear
friction coefficient under dry friction grows slightly as volume lubricated with mixed solution of ILs 1 0.1 Wt.%
the increase of current. It can be explained by the fact that Ag NPs is much higher than that lubricated with mixed
as the current grows, metal oxide layers are formed at the solution of ILs 1 0.1 Wt.% Cu NPs. As mentioned
interface, causing the increase of friction. The friction previously, the diameter of Cu NPs is around 20 nm, while
coefficient after adding ILs is slightly larger than that under that of the Ag NPs is 80-90 nm. Hence, the size difference
dry friction when the current is relatively small, due to the has been considered as an important cause of the inferior
capillary force of the formed liquid meniscus. In contrast, lubrication property of Ag NPs as additives because the
when the current is increased gradually, influences of the large size of the Ag NPs would hinder the rolling effect of
capillary force become less significant because of the NPs which have been proved helpful for the reduction of
electrospreading effect of the liquid bridge (Xie et al., 2017). the friction coefficients.
Therefore, the addition of ILs as the lubricant may improve From Figures 6 and 7, it can be also seen that generally the
the lubrication properties to some extent, due to the usage of friction coefficient of the mixed solution with PAO oil and
lubricant droplet rather than full immersion of the 0.1 Wt.% Cu NPs is the largest, while that of the mixed
tribopairs. solution with ILs and 0.1 Wt.% Cu NPs is the smallest. This
The comparison of friction coefficients between the mixed is because the solubility of Cu NP in the PAO oil is relatively
solution of ILs and 0.05 Wt.% Cu NPs and that of ILs and low due to the slightly high viscosity of the base oil, and
Tribological properties of metallic nanoparticles Industrial Lubrication and Tribology
Lina Si et al.

Figure 2 Typical friction coefficient curves under dry and lubricated conditions with various positive currents in magnitude
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hence the particles could aggregate locally, which would Figure 3 The average friction coefficient under dry and lubricated
then give rise to the inefficient reduction of the friction conditions with different positive currents in magnitude
coefficient and wear with the mixed solution of PAO oil and
0.30
Cu NPs. Figure 8 shows the optical images of the worn
Dry friction
surfaces lubricated by pure PAO oil and the mixed solution 0.25 ILs
with PAO oil and 0.1 Wt.% Cu NPs. Although both surfaces ILs+0.05 wt% Cu NPs
ILs+0.1 wt% Cu NPs
Friction coefficient

have clear scratches, the one lubricated with pure PAO oil 0.20
has shallower scratches as compared with that lubricated
0.15
with the mixed solution. The deeper and extremely uneven
scratches in the latter case confirm that the formation of 0.10
aggregated NPs gives rise to severe damages on the worn
surface. Furthermore, little changes in the friction 0.05
coefficients of the mixed solution with ILs and 0.1 Wt.% Cu
0.00
NPs or the mixed solution with ILs and 0.1 Wt.% Ag NPs 0A 0.1A 0.2A 1.0A
can be noted as the electric current changes, suggesting the Electric current
Tribological properties of metallic nanoparticles Industrial Lubrication and Tribology
Lina Si et al.

Figure 4 The worn surfaces lubricated by mixed solutions with Figure 5 The wear volume of the Cu sheets under dry and lubricated
different concentration of Cu NPs obtained by optical microscope [(a) conditions with different positive currents in magnitude
and (b)] and 3D surface topography [(c) and (d)]: (a), (c) ILs 1 0.05 Wt.
% Cu NPs; (b), (d) ILs 1 0.1 Wt.% Cu NPs 500,000 Dry friction
450,000 ILs
ILs+0.05 wt% Cu NPs
400,000
ILs+0.1 wt% Cu NPs

3
Wear volume/µm
350,000
300,000
250,000
200,000
150,000
100,000
50,000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Electric current/A

Figure 6 The average friction coefficients under the lubrication of


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various mixed solutions


0.5
Dry friction
ILs
0.4 ILs+0.1 wt% Cu NPs
ILs+0.1 wt% Ag NPs

Friction Coefficient
PAO
0.3
PAO+0.1 wt% Cu NPs

0.2

0.1

0.0
0A 0.1A 0.5A
Electric current

Figure 7 The wear volume of the Cu sheets under various lubricated


conditions with different electric currents in magnitude
800,000
ILs+0.1 wt% Cu NPs
700,000 ILs+0.1 wt% Ag NPs
PAO+0.1 wt% Cu NPs
600,000
PAO
3
Wear volume/ m

500,000

400,000

300,000

200,000

100,000
–0.5 –0.4 –0.3 –0.2 –0.1 0.0 0.1 0.2 0.3 0.4 0.5
Electric current/A

In the case of mixed solutions with ILs and NPs as well as


the PAO oil and 0.1 Wt.% Cu NPs, the application of
desirable stability in the friction under the passage of applied negative electric current in general merely results in a slight
currents. In contrast, the friction coefficient of the mixed change of the friction coefficient as compared with the
solution with PAO oil and 0.1 Wt.% Cu NPs increases with application of positive current. The influence of electric
the applied current. current direction on friction properties can be mainly
ascribed to the different electrocorrosion behaviors of
the tribopairs. Specifically, when the positive electric
3.3 Influences of the electric current direction current (i.e. Cu sheets sample with higher potential) is
Figure 9 shows the average friction coefficients of the applied, the Cu sheets would be more easily corroded, while
lubricants under applied currents with different directions. when the negative electric current is applied, corrosion
Tribological properties of metallic nanoparticles Industrial Lubrication and Tribology
Lina Si et al.

Figure 8 Optical graphs of the worn surfaces lubricated by PAO oils whole sliding track, as the upper ball is fixed, and the sample
without and with Cu NPs sheet is in motion. In contrast, the anodic dissolution on the
upper ball surface is more concentrated, giving rise to a
rapid corrosion on the ball surface into a planar wear scar.
In the case of the pure PAO oil of low conductivity, the
application of the reverse electric current would increase the
friction significantly as compared with the case with positive
electric currents. The mechanism could be explained as:
The corrosion mechanisms on the tribopairs could be
slightly different depending on the lubricant conductivity.
For the lubricant with a relatively good conductivity, the
corrosive effect on the friction property was dominated by
anodic dissolution. In contrast, for the low conductivity
lubricant, e.g. pure PAO oil, the anodic dissolution and its
Figure 9 The average friction coefficients under applied currents with effect on the friction and wear behaviors becomes less
different directions significant, as verified by the optical images of the worn
tracks lubricated by the PAO oil under the positive and
0.5 negative currents in Figure 10. Alternatively, the application
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ILs+0.1 wt% Cu NPs of the electric current would cause the buildup of electric
ILs+0.1 wt% Ag NPs
0.4 charges on the tribopair surfaces, which would result in the
PAO+0.1 wt% Cu NPs
PAO discharge across the oil film. The electrons from the cathode
Friction coefficient

0.3 surface could move rapidly toward the anode surface, and
the resulting impacting force would contribute to the
0.2
friction force when the negative current was applied, as
schematically shown in Figure 11.
0.1

0.0 4. Conclusions
0A 0.1A 0.5A –0.1A –0.5A
Electric current 1 The mixed solution of ILs and Cu NPs has desirable
lubrication and anti-wear performances due to the
enhancement of the particles’ rolling effect at the
Figure 10 Optical graphs of the worn surfaces lubricated by PAO oils lubricated interface.
with different current directions 2 The Cu NPs as the lubricant additive shows better
lubrication performance than Ag NPs due to the size
difference of the particles. The relatively low solubility of
NPs in the PAO oil could deteriorate the lubrication
properties.
3 The friction coefficient of the lubrication under the
negative current is slightly higher than that under the
positive current due to the difference in the anodic
dissolution on the tribopair surfaces. When the direction
of the applied current was changed, the lubricant of
relatively good conductivity shows a better stability in
friction due to the absence of capacitive discharge.
Figure 11 The schematic diagram of the friction pairs under the
applied currents with different directions

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Further reading
electrical sliding wear behaviors of the polyimide modified
polymer-matrix pantograph contact strip”, Tribology Karuppiah, K.S.K., Zhou, Y.B., Woo, L.K. and Sundararajan,
International, Vol. 42 No. 6, pp. 995-1003. S. (2009), “Nanoscale friction switches: friction modulation
Wang, W., Xie, G.X. and Luo, J.B. (2018), “Black phosphorus of monomolecular assemblies using external electric fields”,
as a new lubricant”, Friction, Vol. 6 No. 1, pp. 116-142. Langmuir, Vol. 25 No. 20, pp. 12114-12119.
Wong, P.L., Huang, P. and Meng, Y. (2003), “The effect of
the electric double layer on a very thin water lubricating Corresponding author
film”, Tribology Letters, Vol. 14 No. 3, pp. 197-203. Lina Si can be contacted at: silina_thu@163.com

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