Friction 9(4): 774–788 (2021) ISSN 2223-7690

https://doi.org/10.1007/s40544-020-0373-4 CN 10-1237/TH
RESEARCH ARTICLE

Conductive and tribological properties of TiN–Ag composite

coatings under grease lubrication
Feihu LIN, Yanqiu XIA*, Xin FENG
School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China
Received: 26 September 2019 / Revised: 15 November 2019 / Accepted: 16 February 2020
© The author(s) 2020.

Abstract: TiN–Ag composite coatings were prepared by pulsed bias arc ion plating. X-ray diffraction
(XRD) and energy dispersive X-ray spectroscopy (EDS) were applied to analyze the compositions of the
coatings. Tribological properties of the coatings were studied using an MFT-R4000 ball-on-disk friction
tester in the presence of lubricating greases containing multilayer graphene. Scanning electron microscopy
(SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) were used to analyze the worn
surface compositions of the lubricating films. The results show that with the decrease in Ag in the film,
hardness increased but electrical conductivity decreased. The coating with 10 at% Ag content shows the
best friction-reducing and anti-wear properties, which can be attributed to the moderate content of Ag
embedded in the TiN crystal gap that enhanced the grain bonding force to improve the anti-wear and
self-lubricating ability. Graphene can be adsorbed on the coating as a solid lubricant.

Keywords: silver; tribology; contact resistance; lubricating grease

1 Introduction by current-thermal effects and operating conditions.

In terms of tribology, the lubrication and wear
Owing to the rapid development of technology, resistance of electrical contact materials are two
electrical contacts are ubiquitous in various devices [1]. important factors that determine the long-term stable
In a power and signal transmission system, the operation of sliding connections [7, 8]. When current
reliability, stability, accuracy, and service life of the carrying occurs, the heat caused by the combination
system depend on the electrical contact materials of current-thermal effects and friction can significantly
[2, 3]. Most of the electrical contacts are permanent damage the contact pair, resulting in increased friction
connections, however, the relative motion of the coefficient (COF) and wear rate [9].
contacts still occur owing to changing vibrations Ag-based materials exhibit high conductivity, self-
and temperatures because of the different thermal lubricating, anti-oxidation, anti-sulfuration, and anti-
expansion coefficients of the electrical contacts [4–6]. fusion welding properties. However, owing to high
Researchers have focused on the electrical conductivity temperature and its low hardness, the Ag layer
and wear resistance of sliding contact components. suffers from severe wear, plastic deformation, and
However, the wear process between electric contacts surface oxidation during the current-carrying friction
is much more complicated when current-carrying process, resulting in increased contact resistance [10].
occurs because it is not only affected by mechanical Poor performances cannot justify high costs; hence,
factors, such as hardness and roughness, but also Ag-based materials are not widely used as electrical

* Corresponding author: Yanqiu XIA, E-mail: [email protected]

Friction 9(4): 774–788 (2021) 775

contact materials. Meanwhile, Cu-based materials base grease, thereby achieving excellent insulating
are more advantageous compared with Ag-based performances. In addition, the additive (1.5 wt%)
materials in terms of cost [11], however, they oxidize significantly enhances the anti-friction and anti-wear
easily in air under thermal conditions, resulting in abilities.
high contact resistances. Synergistic lubricants offer many advantages,
In recent years, many new materials with superior such as better lubrication efficiency and service life,
mechanical properties have been synthesized and as well as reduced contact resistance and energy.
utilized for tribological applications. These materials Chen et al. [28] investigated the friction and wear
have been effectively incorporated in the fabrication properties of Ag, heat-treated Ag, and Ag–C coatings
of functional coatings to reduce friction and wear [12]. on Cu substrates with and without grease lubrication.
The development of cermet coatings used as an They discovered that the electrical, friction-reducing,
electrical contact material is an attractive research area. and anti-wear properties of Ag coatings were better
André et al. [13] prepared Ti–Ni–C ceramic composite than those of the remaining layers, which was crucial
coatings by unbalanced magnetron sputtering. to satisfy the requirements of stability, safety, and
The results showed that composite coatings with efficient operation of power equipment.
high C content and certain Ni content exhibited The first objective of this study is to investigate
excellent current-carrying tribological properties the mechanical properties of TiN–Ag coatings on a
and the lowest dynamic contact resistance. Wang Cu substrate; the second objective is to prepare a
et al. [14] used magnetron sputtering to deposit highly conductive grease by adding graphene particles;
Ti/MoS2, Pb/MoS2, and MoS2 coatings to obtain a and the third objective is to study the tribological
sliding electrical contact material with high electrical and electrical properties of TiN–Ag coatings in
conductivity and good wear resistance. The results the presence of boundary lubrication and current
showed that the COF of the coating with a current carrying.
of 0.5 A decreased, and the wear rate of the coating Graphene has been widely used as a solid
was higher than that without current. Lewin et al. [15] lubricant or lubricant additive. It is a semi-metal
prepared a nanocrystalline TiC/-C nanocomposite because of the metallic bonding in the in-plane
coating by magnetron sputtering under different direction; hence, its conductivity is high. Therefore,
deposition conditions. They discovered that a coating graphene is added to polyurea grease to improve its
containing a small portion of the -C matrix phase conductive and tribological properties. To investigate
demonstrated good electrical and tribological the relationship between electrical properties and
properties. Compared with Ag-based composites, tribological behaviors, friction and wear tests are
some cermet composites have better mechanical performed, which include the presence of both
properties and similar electrical conductivities [16]. boundary lubrication and current carrying.
Various conductive additives can affect electrical
properties. Ge et al. [17] prepared conductive greases
2 Experimental
with carbon nanotubes, carbon black [18], ionic liquids
[19–23], and Sb-doped SnO2 [24]. They discovered that 2.1 Materials
all these conductive additives improved the conduc-
tivity and tribological performances of conductive Polyurea grease was obtained from Changsha
greases. Jia et al. [25, 26] discovered that graphene Zhongcheng Petrochemical Co., Ltd. (China) and
can significantly enhance the tribological and electrical the base oil was poly alpha-olefins (PAO) (The
properties of electrical contact materials. Cao et al. [27] parameters are shown in Table 1 and 2). Multilayer
used three types of nano-montmorillonite additives graphene (MLG) was obtained from State Key
to afford lubricating greases. The results showed Laboratory of Solid Lubrication, Lanzhou Institute
that the inorganic modification montmorillonite of Chemical Physics, Chinese Academy of Sciences
can increase the number of electron traps in the and was added to the grease. Acetone was purchased

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776 Friction 9(4): 774–788 (2021)

Table 1 Typical data of PAO. acetone for 15 min. In this system, two vertically
Item Typical date Experiment method arranged identical Ag and Ti circular targets were
Clean and used, i.e., 99.9% purity, diameter of 6 cm, and
Appearance Visualization
transparent separated by 10 cm in the chamber. The substrates
American Society of
40 ℃ 396 were clamped to a stainless steel holder in a vacuum
Testing
Viscosity chamber with different angles between the two
Materials ASTM,
100 ℃ 39
D445-2018 targets to control the Ag content of the coatings.
Viscosity index 147 ASTM D2270-2010 The distance between the bases of the bracket and
Pour point 36 ASTM D97-2016 the target was approximately 20 cm (Fig. 1).
Flashpoint (℃) 281 ASTM D2893-2003 When the chamber had been pumped down to a
base pressure less than 6.0 × 10−3 Pa using a mechanical
pump and molecular pump, Ar gas was introduced
Table 2 Typical data of polyurea grease.
into the chamber to 0.3 Pa. Before the deposition,
Typical
Item Experiment method the substrate temperature and duty cycle were
data
Smooth adjusted to 150 ℃ and 20%, respectively, and the
Appearance Visualization
grease substrates were sputtered by Ar ions with a pulsed
Dropping point (℃) > 300 GB/T 3498-2008 bias voltage of 800 V in 5 min. With the preparatory
Non-working cone steps completed, the substrate temperature and duty
278 GB/T 269-1991
penetration/0.1 mm
Corrosion (copper sheet, Up to cycle were adjusted to 300 ℃ and 40%, respectively;
SH/T 0331-1992
aluminum sheet, 100 ℃, 3 h) stand the bias voltage was decreased to 200 V and the Ag
Evaporation (99 ℃, 22 h) (%) 0.65 GB/T 7325-1987 and Ti targets were maintained at 60 and 80 A,
Contact resistance respectively. The Ti–Ag interface layer was deposited
0.57 Enterprise method
stability factor, K
onto two types of substrates to enhance the bonding
pH 7 Enterprise method
property in 5 min. Subsequently, the substrate
Salt spray test A GB/T 2423.17-2008 temperature and duty cycle were increased to
Low-temperature 500 ℃ and 80%; the nitrogen gas flow rate was
No crack GB/T 2423.1-2008
performance (40 ℃, 2 h)
56 sccm after the Ar gas was discontinued, and
the operating pressure was approximately 0.4 Pa.
from Sinopharm Chemical Reagent Co., Ltd., China.
Subsequently, TiN–Ag coatings were deposited onto
Ag and Ti targets were purchased from Oukai
the interface layer, and the coating thickness
Sputtering Target Technology Co., Ltd., China.
was maintained at 10 μm. Finally, annealing was
MLG (0.2 wt%) was added to the ethanol solution
performed in situ to form silver nanoparticles in
as an additive, and the polyurea grease was added
the coating.
and mixed uniformly. Subsequently, ethanol was
evaporated to yield polyurea grease containing MLG.
Finally, the mixture was cooled to room temperature
and homogenized using a three-roll mill to obtain
multilayer graphene grease (MGLG).

2.2 Coating deposition

TiN–Ag composite coatings were deposited on Cu

bases (25 mm × 25 mm × 5 mm) by a DG-2-Z Y arc
ion plating system. The Cu bases were polished
using sandpapers and a diamond polishing agent
to the required roughness of approximately 0.02 μm.
Polished Cu sheets were ultrasonically cleaned in Fig. 1 Sketch of the vacuum chamber.

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2.3 Characterization

The surface morphology and Ag content of the

TiN–Ag coatings were analyzed through scanning
electron microscope (SEM; EVO-18, Zeiss) and energy
dispersive spectroscopy (EDS; Bruker), respectively.
The Vickers hardness of these coatings was measured
using a microhardness meter (AE TTX, Anton Paar).
The bonding strength of the samples was qualitatively
tested using a bending tester (RST3, Anton Paar). The
phase structure was analyzed by X-ray diffraction
(XRD; D/Max-2400, Rigaku). The binding energies
of the chemical composition and the carbon allotrope on
Fig. 2 Schematic diagram of electrical conductivity.
wear scars were analyzed through X-ray photoelectron
spectroscopy (XPS; PHI-5702, American Institute of applied load, H is the grinding crack length, and A
Physics Electronics Company) and Raman microscopy is the cross-sectional area of the wear scar.
(inVia, Renishaw), respectively.

2.4 Tribological and electrical conductivity tests

3 Results and analysis

The tribological properties and contact resistance 3.1 Surface morphology of coatings
of the samples were investigated using a current- Figures 3(a), 3(e), and 3(i) show that many droplets
carrying friction and wear tester (MFT-R4000) with and pits appeared on the coating surfaces, which
a ball-on-disk configuration (Fig. 2). The upper were likely caused by bias arc-ion plating [29].
tribological pair was a Cu ball ( 5 mm). Grease was Many Ag nanoparticles embedded in TiN crystal
coated onto the contact area of the sliding pair. The can be observed [30, 31]. Figure 3(i) shows that
upper pair was driven to yield a reciprocating motion when the Ag content increased to a sufficiently
against the lower coatings under grease lubrication. high amount, the surface became coarser with
The surrounding humidity and temperature were plenty of sputtered grains on the surface.
maintained at approximately 40% and 20 °C for As shown in Fig. 3, all related elements were
all tests, respectively. Constant static loads were distributed uniformly in the TiN–Ag coatings,
applied to the upper pair (5, 10, and 15 N). Constant implying that the coatings were prepared successfully.
voltages were applied (0.5 and 1.5 V) under the A small amount of Ag can be observed in Fig. 3(d),
whereas a large amount in Fig. 3(l). These are
sliding pair during every 30 min. The length of the
consistent with the EDS analysis.
sliding track was 4 mm, and the sliding frequency
was 2 Hz. The COF and instantaneous current was 3.2 Phase structure and chemical composition
recorded by a computer attached to this instrument.
The electrical contact resistance (ECR) can be Figure 4 shows the XRD patterns of the coatings
calculated using Ohm’s law, and its stability is with 2 at%, 10 at%, and 30 at% Ag contents. The
expressed by the standard deviation (SD). The mean phase compositions were determined based on the
value of the COF was calculated, and the wear rate Bragg angle and the intensity of diffraction peaks.
was calculated using Eq. (1): The face-centered cubic (fcc) TiN and fcc-Ag phase
were generated through the deposition of the
V HA
W  (1) coatings. With the increase in Ag content, the Ag
S L S L phase position exhibited stronger diffraction peaks.
where W is the substrate wear rate, V is the wear The TiN diffraction peaks were weaker than the
scar volume, S is the total sliding distance, L is the Ag peaks with increased Ag content, because the

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Fig. 3 Surface morphologies of the coatings: (a) TiN–Ag coating with 2 at% Ag content, (e) TiN–Ag coating with 10 at%
Ag content, (i) TiN–Ag coating with 30 at% Ag content, and (b–d, f–h, j–l) the surface elements distribution in green frames
by EDS corresponding to (a, e, and i).

Table 3 Critical load (LC1), Vickers hardness (HV), and

module of elasticity (EIT) of TiN–Ag coatings with different
Ag contents.
Ag content (at%) LC1 (N) HV (GPa) EIT (GPa)
2 13.2 25.7 392.5
10 12 20.7 379.7
30 No crack 13.7 227.9

will decrease as well [31]. Furthermore, the elastic

modulus increases rapidly with the decrease in Ag
content. As the Ag content decreases to a certain
extent, the elastic modulus of the coating increases,
Fig. 4 XRD pattern of coatings with 2 at%, 10 at%, and which indicates that the coating has a higher
30 at% Ag contents. resistance to plastic deformation.
increase in Ag content resulted in difficult fcc-TiN
3.4 Conductive and tribological properties
crystallization.
In general, the high temperature generated in the
3.3 Physical property of the coatings
electrical contact zone can be changed by different
Table 3 shows that the bonding strength of the current densities, which may significantly affect
coatings did not change significantly with Ag the tribological and electrical performances. To
content, whereas the Vickers hardness of the samples analyze the conductive and tribological properties
increased rapidly with the decrease in Ag content. of the TiN–Ag coatings under current-carrying,
When the Ag content decreased to 2 at%, the current densities were adjusted in the experiment
hardness reached the highest value of 25.7 GPa. If by changing the loop voltage.
the Ag content continues to decrease, the hardness Figures 5(a) and 5(c) compare the coatings with

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2 at%, 10 at%, and 30 at% Ag contents and a Cu than those of others. As shown in Fig. 5(d), the
base under 0.5 V. When the Ag content was 30 at%, wear rate of the coating with 10 at% Ag was minimal
the COF was the lowest compared with those of compared with that of the coatings with other Ag
others. With the decrease in Ag content, the COFs contents, and its wear rate was slightly less than
of the coatings increased, and the COF of the that of the Cu base. However, although the reduction
2 at% Ag content was much higher than that of the in Ag content increased the hardness of the coating,
Cu base, indicating that the self-lubricating ability the wear rate of the coating with 2 at% Ag content
weakened with decreasing Ag content. The COF increased significantly.
of the coating with 2 at% Ag content increased As the load voltage increased to 1.5 V, compared
significantly to approximately 0.4. This implies that with Figs. 5(a), 5(c) and Figs. 6(a), 6(c), the COF of
the lower the Ag content, the lower is the loading the coatings decreased slightly. As shown in Fig. 6(b),
capacity. Figure 5(b) shows the ECR versus time, as the load voltage increased to 1.5 V, the contact
which can be used to characterize the electro- resistance of different materials increased significantly,
tribological properties. As shown in Figs. 5(b) and which might be attributed to the higher temperature
5(c), the Ag content did not significantly affect the at the surrounding of the friction pair contact area.
ECR at a certain range, e.g., the electrical conductivity However, as shown in Fig. 6(d), as the voltage
increased only slightly as the Ag content reached increased from 0.5 to 1.5 V, the coatings with 10 at%
30 at%, whereas the current stabilities of the Cu Ag content exhibited better anti-wear properties,
base and 10 at% Ag coating were relatively higher especially at high currents. This might because the

Fig. 5 Evolution of (a) COF, (b) ECR for Cu base and TiN–Ag coating samples, (c) average of COF and SD of ECR, and (d)
wear rate under grease (voltage: 0.5 V; load:15 N).

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moderate Ag content yielded good effects on the microprotrusions, and slight polishing appeared
lubricating coatings at high temperatures. However, on the worn surface, as shown in Figs. 8(c) and
this contributed negatively to the Cu base and the 8(d). The particles might be mounts of Ag grains
coatings with 2 at% and 30 at% Ag contents because precipitated at a relatively high temperature [30],
the wear rate was more severe as the voltage increased. and arc erosion was produced in pairs. Figures 7(f)
In summary, it was discovered that when the Ag and 8(f) show that not only many severe furrows
content was 10 at%, the coating exhibited excellent and pits, but also some microcutting and microfraction
anti-wear and electrical properties. appeared on the surface; this could be attributed
to the embedded Ag nanocrystals in TiN crystal,
3.5 Wear scars of TiN–Ag coating surface which resulted in constitutional defects and hence
Figures 7 and 8 show the surface morphologies yielded an unstable coating structure, thereby reducing
of worn scars. As shown in Figs. 7(b) and 8(b), at the anti-wear property of the coating. If the current
the Ag content of 2 at% and loading of 15 N, the is sufficiently large and the conductive medium
adhesive wear damaged the surface and further has high conductivity, then arc erosion can be
deteriorated the surface when the voltage increased generated at a low voltage.
to 1.5 V. Widespread pulling-out, avulsion, and some 3.6 Raman spectra and XPS analyses of worn
furrows were observed on the worn surfaces. The surfaces
phenomenon was attributed to the failure of the
boundary lubricating film. Figures 7(c) and 7(d) Table 3 shows the Raman shift list. To investigate
show slight sliding cracks on the surface under 0.5 the absorption films and the partial carbonization
V. As the voltage increased to 1.5 V, many particles, of the grease on the wear scar under current-carrying

Fig. 6 Evolution of (a) COF, (b) ECR for the Cu base and TiN–Ag coating samples, (c) average of COF and SD of ECR values;
(d) wear rate under grease (voltage: 1.5 V; load:15 N).

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Fig. 7 SEM morphologies of (a) worn surfaces and (b) TiN–Ag coatings with 2 at% Ag content; (c, d) TiN–Ag coatings with 10 at%
Ag content; (e, f) TiN–Ag coatings with 30 at% Ag content under MGLG (voltage: 0.5 V; load: 15 N; frequency: 2 Hz; stroke: 4 mm).

Fig. 8 SEM morphologies of (a) worn surfaces and (b) TiN–Ag coatings with 2 at% Ag content; (c, d) TiN–Ag coatings with
10 at% Ag content; (e, f) TiN–Ag coatings with 30 at% Ag content under MGLG (voltage:1.5 V; load:15 N; frequency: 2 Hz;
stroke: 4 mm).

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conditions, a Raman spectrum is shown (Fig. 9). absorption peak between 1,230 and 1,580 cm1, and
Figure 9(a) shows the Raman spectrum of the wear the obvious peaks indicate the formation of physical
scar with 2 at% Ag coating. The Raman spectrum adsorption films of amorphous carbon or graphene.
peaks only at approximately 230 and 530 cm1, and The amorphous carbon was likely owing to the partial
almost no adsorption films were detected on the coking of PAO and carbonaceous additives at high
wear scar. Figure 9(b) shows the Raman spectrum temperatures and current-carrying conditions. The
of the surface with 10 at% Ag coating, where a weak D peak generated at approximately 1,350 cm1 was
absorption peak appeared near 1,111 cm1, which derived from the breathing pattern of the disordered
can form adsorption films through additives in sp2 carbon atom, and the G peak at approximately
grease. Several other absorption peaks appeared in 1,580 cm1 from the in-plane bond extension of all
dark and bright spots. The broad asymmetric sp 2 atom pairs [32, 33]. The absorption peak at
2,874–2,903 cm1 was owing to the amount of PAO
adsorbed on the surface of the wear scar during
the tribological process [34]. It is apparent from
Fig. 9(c) that a broad asymmetric peak appeared in
the range of 1,100–1,700 cm 1, and strong D and
G peaks were identified by fitting Raman
spectroscopy. Stronger adsorption film layers, which
can be produced by amorphous carbon and graphene,
were formed.
The composition of the adsorbed films on the
worn surface was further analyzed through XPS-
peak-differentiating analysis. As shown in Figs.
10(a), 10(b), and 10 (c), the wear scar on sample B
exhibited better absorbing films compared with
the others. Furthermore, Fig. 10(d) shows that Cu
barely appeared in sample B, which was attributed
to the excellent synergistic lubrication, indicating
complex chemicals with different-level reactions
during the current-carrying friction. The strong Cu
peak in sample C was owing to the rupture of the
TiN–Ag coating to expose the substrate, and the
weak peak of sample A was attributed to the
physical adsorption of abrasive Cu chips on the
surface of the coating. Figure 11(a) shows the XPS
spectra of C 1s on the wear scars of the samples to
clarify the composition of absorbing films containing
C. The strong peak at 284.9 eV of C 1s can be

Table 3 Raman shift list.

Index Raman shift (cm1)
Olefin 1,655–1,677; 2,920–2,937
Titanium nitride 210–320; 500–680
Fig. 9 Raman spectrum of wear scar of (a) TiN–Ag of 2 at% Poly-α-olefin 2,800–3,000
Ag, (b) TiN–Ag of 10 at% Ag, and (c) TiN–Ag of 30 at% Ag Graphite 1,580–2,700
(voltage: 1.5 V; load: 15 N).

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Fig. 10 XPS spectra of several elements on the worn surface of (A) TiN–Ag of 30 at% Ag content, (B) TiN–Ag of 10 at% Ag
content, and (C) TiN–Ag of 2 at% Ag content lubricated with MGLG (voltage: 1.5 V; load: 15 N).

Fig. 11 XPS spectra of the worn surface of TiN–Ag (10 at%) with fitting peaks (voltage: 1.5 V; load: 15 N).

assigned to the C–H chemical bond of organic C organic nitrogen compounds [35–38]. This was
on the surface scar, and the peak at binding energy owing to the high-temperature chemical reaction
285.5 eV was associated with the C–C hydrocarbon. during the friction process on the coating surface.
The two peaks were derived from the physically The peaks of O 1s located at 530 and 531.8 eV, as
adsorbed films of PAO or other organic chemical shown in Figs. 10(c) and 11(c), were those of the
absorbing films [35]. In addition, the weak peak at C=O organic compound [36] and TiO2 [38], respectively.
288.5 eV belonged to the C–O chemical bond [36]. This illustrates that the surface of the coatings
As shown in Fig. 10(b), the peak of N 1s centered with moderate Ag content under grease lubrication
at 399.9 eV, corresponding to the C–N bond in forms ideal adsorption or reaction films.

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4 Discussion produced a large amount of worn debris serving as

three-body wear under boundary lubrication. This
Most electrical contact materials are Cu or Cu-based was because the small contact area between the wear
Ag-plated sheets, which offer better conductivities debris and the coatings tended to produce great stress.
and current stability compared with other materials; Even if the soft material is plastically deformed, the
however, their anti-wear property is poor owing to stress applied to the hard material will far exceed
their low hardness. Therefore, they cannot satisfy the yield limit, resulting in serious wear. In addition,
cases that require high wear resistance, system stability, the residual particles generated between the two
and long life circles. Ceramic metal composites are friction pairs can cause further wear. Therefore, the
expected to solve this problem. However, it is difficult to worse synergistic lubrication effect results in severe
lubricate ceramic composites, and their self-lubricating adhesive wear in the contact area.
ability and conductivity are not sufficient to satisfy As the Ag content increased to an appropriate
the requirements of reciprocating friction situations range, the tribological property of the coating was
in the presence of current-carrying [39]. improved significantly, especially at high voltages.
In this study, when the Ag content was 2 at%, This occurred because when the applied voltage
the COF of the TiN–Ag composite coating was 0.4– increased, the temperature around the contact point
0.5 and the fluctuation was significant. The main of the friction pairs increased, and the high specific
wear form was severe adhesive wear, indicating that
surface area of the Ag nanoparticles rendered them
a stable boundary lubrication was difficult to form,
highly chemically active. Under the action of cyclic
and its tribological property was much lower than
stress and high temperature, it is easy to form a
that of coatings under the same conditions. When
Ag-rich layer on the friction interface [29, 39–41].
the Ag content of the coating was 10 at% and 30 at%,
In addition, the high temperature of the contact area
repectively, the COF was maintained in the range
softened the coatings; furthermore, with a certain
of 0.05–0.15. The main wear forms were slight adhesive
polishing effect, the direct contact area of the friction
wear and abrasive wear, and distinct adsorption
pair increased, and thereby reducing the peak pressure.
films were detected on the surface of the wear scars.
These factors facilitated the formation of stable
These are the general case in boundary lubrication.
lubricating and absorption films on the surface.
When the Ag content (2 at%) was low, the contact
The moderate Ag content-enabled most of the Ag
area of the coating exhibited severe wear. One of the
grains to be intercalated between the TiN crystal
reasons was that the surface of the coating could not
gap and increased the bonding force between the
easily produce an Ag-rich layer under current-carrying
friction, and microbumps and pits could not easily grains, which reduced the generation of internal
deform plastically to form a smooth surface, resulting stress, ensuring a more stable structure in the coatings
in poor solid lubrication performance. Because the to reduce avulsion [40]. In addition, when the hardness
true contact area of the friction pairs was reduced of the coating approached that of the upper Cu ball,
and the contact resistance of the coating was relatively the wear debris decreased, and thereby reducing
high, a large amount of heat was generated to cause the three-body wear.
a significant increase in the temperature of the As the Ag content continued to increase, a thick
contact region, which might cause the grease to fail. Ag-rich film was formed on the coating surface
Furthermore, an extremely low Ag content resulted during friction in the presence of current-carrying.
in failed absorption films. The polar group in the The tribological properties of the TiN–Ag coatings
grease and the long-chain structure of the hydrocarbon improved owing to the use of grease. However, the
could not be adsorbed on the surface by weak van materials existed primarily in the form of grains
der Waals force, and extreme pressure additives inside the coatings, which decreased the stability
could not react with the surface coating and form of the crystal structure and weakened the anti-wear
chemical adsorption films. In addition, the significantly property.
different hardness between the two friction pairs The contact resistance of the coatings changed

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slightly according to the Ag content, and a moderate morphology [43], indicating that the local high
Ag content improved the electrical property. The temperature caused by the current–thermal effect
conductive mechanism under boundary lubrication was one of the main influencing factors of wear,
can be attributed to the quantum tunnel effect. and that the grease exerted a good lubrication effect.
When the Ag content was 2 at%, the conductivity In our previous studies, excellent current-carrying
of the coating was relativity poor, because the tribological properties were obtained by preparing
discontinuous Ag-rich layer and low Ag content Ag coatings and PAN grease [28]. Subsequently,
increased the electrical resistance, and significant using TiN–Ag coatings and MGLG, wear resistance
adhesive wear occurred on the contact surface, causing was further improved while ensuring electrical
the surface Ag-rich layer to fail and the current performance.
stability to decline. This caused the contact face of
the friction pairs to be unstable and the contact 5 Conclusions
resistance to fluctuate significantly. When the Ag
content was approximately 10 at%, the sample indicated In this study, a synergetic strategy based on conductive
a lower ECR and SD of the ECR compared with those grease and TiN–Ag coatings of different Ag contents
with 2 at% Ag content. This occurred because of was developed to enhance tribological and electrical
the relatively thick Ag-rich layer and the low resistance properties for sliding electrical contact applications.
of the coatings, as well as the more stable coating The conclusions are as follows:
conductivity by the Ag-rich layer. In addition, the 1) Both fcc-TiN and fcc-Ag phases were generated
SD of the ECR caused the moderate content of Ag in the coatings, as shown by XRD. With increasing
embedded in the TiN crystal gap to enhance the Ag content, the main diffraction peaks of the Ag
grain bonding force to reduce wear. As the Ag phase became stronger, but the main diffraction
content increased to a high percentage (30 at%), the peaks of the TiN phase became weaker. This
coatings showed a comparative higher ECR. This deteriorated the stable coating structure, resulting
in lower hardness and elastic modulus.
was because the coating surface was smoothed by
2) At 10 at% Ag content, the coating demonstrated
deformation and microshear effect, and thereby
excellent anti-wear performance, and its electrical
thickening the lubricating film layer and causing a
and tribological properties were excellent under
high electrical resistance. In addition, the high
high voltages. This was because a large amount of
contact resistance produced a significant amount
Ag precipitated during the current-carrying friction
of heat and enabled an oxidation layer, which had
experiment, which improved the self-lubricating
a high resistivity, to form on the wear surface, and
performance. In addition, the addition of Ag improved
thereby increasing the contact resistance.
the electrical properties of the coating.
As reported in previous studies, TiN coatings
possess excellent anti-wear properties and lower 3) MGLG and TiN–Ag (10 at%) coating demonstrated
resistance values, however, the wear volume can a good synergistic lubrication effect. This was because
reach 1.401×104 mm3 under non-current-carrying the graphene and adsorption films formed on the
conditions, which is much higher than the wear friction surface demonstrated anti-wear and conductive
rate obtained in this experiment [42]. Adding Ag to properties. Furthermore, MLG formed conductive paths
TiN can yield better tribological properties, and in the grease to enhance the electrical performance.
the lowest wear rate was 1×107 mm3/(N·mm) with
0.8 at% Ag content under room temperature and Acknowledgements
non-current-carrying conditions, which was close to
the optimal value obtained in this experiment [31]. The This study is supported by the Natural Science
experimental rule of TiN–Ag at high temperatures Foundation of Beijing Municipality (2172053) and
was reflected in the results of this experiment, but the National Natural Science Foundation of China
the wear was more severe compared with the wear (51575181). We thank Li MA for assistantance in

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786 Friction 9(4): 774–788 (2021)

format modification. We thank Qianqian CHEN for W. Empirical model of effects of pressure and temperature
analysis using XRD and Xia LI for analysis using on electrical contact resistance of metals. Sci Technol
Weld Join 6(3): 126–132 (2001)
XPS.
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Commons Attribution 4.0 International License, which [11] Hasegawa M, Imai K, Makimoto J, Sawa K. An
permits use, sharing, adaptation, distribution and experimental study on operating characteristics of Ag,
reproduction in any medium or format, as long as Pd and Cu contacts in argon atmosphere. In Proceedings
you give appropriate credit to the original author(s) of the Forty-ninth IEEE Holm Conference on Electrical
and the source, provide a link to the Creative Commons Contacts, Washington, DC, USA, 2003: 190–197.
[12] Khadem M, Penkov O V, Yang H, Kim D. Tribology of
licence, and indicate if changes were made.
multilayer coatings for wear reduction: A review. Friction
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licence, unless indicated otherwise in a credit line contact resistance of nanocomposite TiNiC coatings.
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[15] Lewin E, Olsson E, André B, Joelsson T, Öberg Å,
To view a copy of this licence, visit
Wiklund U, Ljungcrantz H, Jansson U. Industrialisation
http://creativecommons.org/licenses/by/4.0/. study of nanocomposite Nc-TiC/a-C coatings for electrical
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Feihu LIN. He received his bachelor Electric Power University. His research interests
degree from Shaanxi University of focus on preparation and tribological property
Science & Technology University investigation of coatings and lubricating greases.
in 2015, China. He is currently a
master student at North China

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788 Friction 9(4): 774–788 (2021)

Yanqiu XIA. He received his Ph.D. Science) in 2007. He joined the School of Energy
degree in mechanical engineering Power and Mechanical Engineer, North China
from Northeastern University, Electric Power University in 2010. His current
China, in 1999, and was selected position is as a professor. His research areas cover
as a professor (Hundreds Talent the tribology of mechanical and electrical equipment,
Program of Chinese Academy of oil monitoring, and artificial intelligence.

Xin FENG. She received her Ph.D. Engineer, North China Electric Power University
degree in systems engineering from in 2010. Her current position is as an associate
Northeastern University, in 2007, professor. Her research areas cover tribology and
China. She joined the School of artificial intelligence.
Energy Power and Mechanical

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