Applied Surface Science 264 (2013) 516–521

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Applied Surface Science

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Tribological characteristics of electroless Ni–P–MoS2 composite coatings at

elevated temperatures
Zhen Li, Jingbo Wang, Jinjun Lu, Junhu Meng ∗
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Ni–P–MoS2 composite coatings were deposited on AISI-1045 steel plate by electroless plating followed
Received 30 September 2011 by a heat treatment at 300 ◦ C for 2 h. The high-temperature tribological characteristics of the composite
Received in revised form coatings were evaluated under dry sliding conditions in a tribometer with ball-on-disk configuration. The
28 September 2012
effect of the co-deposition of MoS2 on the friction and wear behaviors of composite coatings at elevated
Accepted 10 October 2012
temperature was investigated. Scanning electron microscopy was used to determine the morphology
Available online 17 October 2012
of the worn surface of composite coating. The chemical states of some typical elements on the worn
surfaces were determined by X-ray photoelectron spectroscope. The results indicate that friction coef-
Keywords:
Electroless
ficient of the composite coatings decreases with the increase of test temperature up to 500 ◦ C, and the
Ni–P–MoS2 composite coating best tribological properties of Ni–P–MoS2 composite coatings are achieved at 400 ◦ C. The worn surface of
Tribological characteristic Ni–P–MoS2 composite coatings are characterized by mild scuffing and deformation. The improvement of
Lubricious oxide film tribological properties of the composite coatings was attributed to the formation of the lubricious oxide
High-temperature film composed of oxides of Ni and Mo at high temperatures. With the test temperature increasing to
600 ◦ C, the tribological properties of the composite coating begin to deteriorate due to softening of the
coating.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction coatings [15]. It is found that the excellent mechanical character-

istics and self-lubrication of the hollow nanotubes contribute to
Due to the excellent mechanical and tribological performance, the unique tribological properties. Hu et al. [16] studied the corro-
the tribological behavior of electroless Ni–P coatings (in as- sion and friction behavior of electroless Ni–P coatings containing
deposited and heat-treated states) at room temperature in air has MoS2 nanoparticles. The friction coefficient of Ni–P–MoS2 com-
been extensively investigated [1–4]. It was found that the hard- posite coatings decrease greatly due to the addition of nano-MoS2
ness and wear resistance of electroless Ni–P composite coatings particles.
are improved by the subsequent heat treatment. The incorporation Because Ni has a high melting point (1480 ◦ C) and is resistant
of hard particles (e.g. SiC, WC, ZrO2 , and TiO2 ) [5–8] and solid lubri- to oxidation up to 500 ◦ C, electroless Ni–P coatings and electroless
cants (e.g. PTFE, graphite, MoS2 and carbon nanotube) [9–13] into Ni–P composite coatings are applicable to high temperature. Up to
Ni–P matrix can enhance the mechanical and tribological proper- now, few literatures are available on the tribological behaviors of
ties of Ni–P composite coatings. Alirezaei et al. [14] investigated the the electroless Ni–P composite coatings at elevated temperatures.
sliding wear behavior of Ni–P–Al2 O3 electroless coatings deposited León et al. [17] investigated the high-temperature tribological
on AISI 1045 steel and found that the incorporation of alumina behavior of Ni–P–BN autocatalytic coatings deposited on AISI 316L
particles in Ni–P matrix led to an increase in the hardness and stainless steel and found that the addition of solid lubricant BN
wear resistance of the coatings. Like Ni–P electroless coatings, did not reduce friction and wear. In addition, the friction coeffi-
heat treatment at 400 ◦ C can effectively increase the hardness and cient and wear of the composite coatings increase with increasing
the wear resistance of Ni–P–Al2 O3 electroless coatings. Ni/carbon temperature. The tribological response of the composite coatings
nanotube composite coatings exhibit a higher wear resistance and at high temperatures is related to the mechanical properties of the
lower friction coefficient than those of Ni, Ni/SiC, and Ni/graphite Ni matrix, i.e. its behavior to withstand the applied stresses as the
temperature increases, irrespective to the nature and properties of
the co-deposited particles.
∗ Corresponding author. Tel.: +86 931 4968378; fax: +86 931 4968378. In this work, the high-temperature friction and wear behav-
E-mail address: jhmeng@licp.cas.cn (J. Meng). iors of Ni–P–MoS2 composite coatings against Si3 N4 ball were

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.10.055
 Z. Li et al. / Applied Surface Science 264 (2013) 516–521 517

Fig. 1. SEM micrographs of (a) as-deposited Ni–P coating, (b) Ni–P–MoS2 composite coating and (c) the cross-section of as-deposited Ni–P–MoS2 composite coating.

investigated using a ball-on-disk high-temperature tribometer. For and a contact radius of 5 mm for the disk. The test temperatures var-
comparison, the tribological behavior of Ni–P coating was also stud- ied between 25, 100, 200, 300, 400, 500 and 600 ◦ C with a certain
ied at high temperatures. sliding distance of 1.8 km. Prior to the tests, all the specimens were
ultrasonically cleaned in acetone and allowed to dry. Friction coef-
2. Experimental details ficient was recorded continuously by computer during the test. The
depth profiles and the area of worn tracks were measured by using
Ni–P–MoS2 composite coatings were prepared by electroless a 2206 profilometry (made in Harbin, China). The wear resistance
plating. The AISI-1045 steel plate (˚ 25 mm × 5 mm) was used was evaluated by calculating wear volume divided by the applied
as the substrate. The plating bath has the following composi- load and the sliding distance.
tion: 25 g L−1 of NiSO4 ·6H2 O, 30 g L−1 of NaH2 PO2 ·H2 O, 20 g L−1 of The phase structures were determined using X-ray diffraction
CH3 COONa, 20 mL L−1 of lactic acid, 10 mL L−1 of propionic acid, analysis (Rigaku D/max-2400) with Cu K␣ radiation. The morpholo-
MoS2 particles (4 ␮m in average size) 2.4 g L−1 , a suitable amount gies and compositions of worn surface were analyzed by a scanning
of stabilizer, the bath temperature was held at 80–85 ◦ C and the pH electron microscopy (JSM-5600LV, JEOL) with energy dispersive
of the bath was maintained at 4.4–4.6 by ammonia. The plating time spectroscopy (EDS). The chemical states of some typical elements
was 3 h. Before depositing, the AISI-1045 steel substrate materials on the worn surfaces were determined using a PHI-5702 X-ray
were ultrasonically cleaned in acetone, subsequently, activated in photoelectron spectroscope (XPS) at a pass energy of 29.4 eV and a
HCl (10%) solution and rinsed in distilled water. MoS2 particles were resolution of ±0.2 eV, using Al K␣ radiation as the excitation source
suspended in bath solution by using surfactant. During the depo- and the binding energy of adventitious carbon (C 1s: 284.8 eV) as
sition, the bath solution was stirred using a magnetic stirrer. After the reference.
electroless plating deposition, heat treatment of the coatings was
carried out in a muffle furnace at 300 ◦ C for 2 h in air. 3. Results and discussion
Friction and wear tests were conducted on a ball-on-disk high-
temperature tribometer (THT07-135, CSEM) under drying sliding 3.1. Morphology and microstructure
condition in air. The disk sample by electroless plating with a diam-
eter of 25 mm was used as a rotating lower specimen. Si3 N4 ball Fig. 1a and b shows the SEM images of as-deposited Ni–P
with a diameter of 3 mm was used as a static upper specimen. Tests and Ni–P–MoS2 composite coating. It can be seen that the MoS2
were carried out at a normal load of 3 N, a sliding speed of 0.5 m/s particles are uniformly embedded in the composite coating in
518 Z. Li et al. / Applied Surface Science 264 (2013) 516–521

Table 1
Average value of the friction coefficient and wear rate of heat-treated Ni–P–MoS2
composite coatings at different temperatures.

Temperature (◦ C) Average friction Wear rate

coefficient (mm3 /N m)

RT 0.78 6.74 × 10−5

100 0.64 1.04 × 10−4
200 0.51 4.21 × 10−4
300 0.41 1.68 × 10−4
400 0.29 8.42 × 10−5
500 0.27 1.42 × 10−4
600 0.33 3.37 × 10−4

Fig. 1b. Compared with Ni–P coating, the co-deposited MoS2 par-
ticles lead to the increasing of the surface roughness with the
appearance of many nodules. The surface roughness of Ni–P–MoS2
coating is 2.53 ␮m, which is about 10 times larger than that of N–P Fig. 4. Variations of wear rate of Ni–P–MoS2 composite coatings with the temper-
coating (0.21). The SEM image of the cross-section of Ni–P–MoS2 ature.
composite coating (see Fig. 1c) shows the MoS2 particles are uni-
formly distributed in the nickel–phosphorous matrix. Meanwhile, The peaks corresponding to the MoS2 phase approve that the MoS2
a coating thickness of about 40 ␮m is obtained from the SEM image particles have been co-deposited in the Ni–P matrix in Fig. 2. Addi-
of cross-section. tionally, no other reaction products derived from MoS2 are found
Fig. 2 shows the XRD patterns of as-deposited and heat-treated from the XRD pattern in the heat-treated state, which indicates
Ni–P–MoS2 composite coatings. In the as-deposited state, the coat- that the co-deposition of MoS2 in the Ni–P matrix did not affect the
ing consists of amorphous nickel–phosphorous matrix and MoS2 formation of phases during heat treatment.
phase. Heat treatment can result in crystallization of the coating,
which has been confirmed by other researchers [18–20]. Peaks of
3.2. Tribological properties
NiP, Ni3 P, Ni2 P, and Ni are identified in the heat-treated coating.

3.2.1. Friction coefficient and wear rate

Table 1 shows the values of the average friction coefficients
and wear rates for Ni–P–MoS2 composite coatings at elevated tem-
peratures. It can been seen that the average friction coefficient of
Ni–P–MoS2 composite coating decreases from 0.78 at room tem-
perature to 0.27 at 500 ◦ C, and then slightly increases to 0.33 at
600 ◦ C. The MoS2 particles distributed in Ni–P matrix has no appar-
ent effect on the friction reduction at room temperature. This can
been explained that MoS2 lubrication effect are counteracted by
increasing the surface roughness due to the addition of the MoS2
particles, a similar view explained by Ramalho and Miranda [18].
Compared with room temperature, the average friction coefficient
of Ni–P–MoS2 composite coating at 100 ◦ C slightly decreases. The
decrease in the friction coefficient of the composite coating is very
significant between 400 and 500 ◦ C as shown in Table 1. The fric-
tion coefficient of the composite coating at 400 ◦ C was 2.7 times
lower than that of at room temperature. Hence, it can be con-
cluded that the co-deposition of MoS2 plays a little role in the
Fig. 2. XRD patterns of (a) as-deposited and (b) heat-treated Ni–P–MoS2 composite friction reduction at room temperature, but plays a crucial role in
coatings. the friction reduction at higher temperatures. The wear rates of

Fig. 3. (a) Variations of friction coefficient of Ni–P–MoS2 composite coatings with the sliding distance at different temperatures and (b) comparison of friction coefficient
between Ni–P and Ni–P–MoS2 at 400 and 500 ◦ C.
 Z. Li et al. / Applied Surface Science 264 (2013) 516–521 519

Fig. 5. SEM micrographs of worn surface of Ni–P–MoS2 composite coatings at (a) 100 ◦ C, (b) 200 ◦ C, (c) 300 ◦ C, (d) 400 ◦ C, (e) 500 ◦ C, and (f) 600 ◦ C.

Ni–P–MoS2 composite coatings vary little between 10−5 and 10−4 coefficients become very stable throughout the friction test with
(see Table 1). The wear rate of the composite coating at 400 ◦ C is increasing of the sliding distance (Fig. 3a). At 600 ◦ C, friction coef-
lower. Fig. 3a shows the evolution of the friction coefficient with the ficient is low and stable at the first half stage and increases slowly
sliding distance at different temperatures. It can be found that the at the later half stage. The evolution of friction coefficient of Ni–P
friction coefficients at room temperature keep stable at 0.78 after a coating at room temperature is similar to that of Ni–P–MoS2 (the
running-in stage. At the mediate temperatures (100, 200, 300 ◦ C), graph was omitted). At high temperatures, however, the friction
friction coefficients are unstable with large fluctuations. However, coefficients of Ni–P coating are greatly different from Ni–P–MoS2
when the temperature increases to 400 and 500 ◦ C, the friction composite coating, as shown in Fig. 3b. The friction coefficients of
520 Z. Li et al. / Applied Surface Science 264 (2013) 516–521

Fig. 6. XPS spectra of (a) Mo3d5/2 and (b) Ni2p3/2 of worn surface of Ni–P–MoS2 composite coatings at different temperatures.

Ni–P coating are very high with large fluctuation initially and then fluctuates initially. With prolonging of sliding distance, the friction
decrease dramatically to about 0.35. Compared with Ni–P coating, coefficient of Ni–P coating decreases gradually and becomes sta-
the co-deposition of MoS2 particles in the composite coating is ble due to the formation and thickening of the oxide film of Ni.
favorable to the reduction of friction and could maintain friction Compared with Ni–P coating, the friction coefficient of Ni–P–MoS2
coefficient stable during the whole sliding distance in higher tem- composite coating is low and keeps stable throughout the whole
perature. Fig. 4 shows the variations of wear rates of Ni–P–MoS2 sliding process, which is attributed to formation of mixture of
composite coatings with temperature. It can be found that the wear nickel oxide and molybdenum oxide. It reveals that the surface
rate increases with temperature increasing from room tempera- of Ni–P–MoS2 composite coatings takes place tribochemical reac-
ture to 200 ◦ C, and then decreases with temperature increasing tions and a dense lubricious oxide film is formed during sliding at
up to 400 ◦ C. The lower wear rate is obtained at 400 ◦ C. Above higher temperature. The formation of continued and glazed oxide
400 ◦ C, the wear rate starts to increase. MoS2 particles embedded film leads to the reduction of friction coefficient and wear at 400
in coating lead to a lower friction coefficient and wear rate at high and 500 ◦ C without significant adhesive and abrasive wear. The
temperature. The tribological properties of the composite coatings similar wear mechanism has been proposed in previous publica-
are best at 400 ◦ C. The results of friction and wear we obtained tions [23–25]. At 600 ◦ C, the worn surface of composite coating
are significantly different from those of literature [17]. León et al. presents severe adhesive wear and the composite coatings spall off
[17] reported that the friction coefficient and wear of the com- (Fig. 5f) resulting from softening of the coating at higher tempera-
posite coatings increase with the increase of temperature, which ture. An increase in the contact area for the worn surface at 600 ◦ C
is ascribed to the degradation of the mechanical properties of the is obviously observed (Fig. 5f). The adhesive wear is the dominant
Ni–P matrix. wear mechanism at 600 ◦ C, which is responsible for the increase of
the friction coefficient and the worn rate. Thus, Ni–P–MoS2 com-
posite coating exhibits excellent lubricating performance and wear
3.2.2. Friction and wear mechanisms resistance. Ni–P–MoS2 composite coating could be a good candi-
Fig. 5 shows the SEM morphologies of worn surfaces for date under dry sliding conditions between 400 and 500 ◦ C.
Ni–P–MoS2 composite coatings against Si3 N4 ball at elevated tem-
peratures. At 100 ◦ C, the worn surface of Ni–P–MoS2 composite
4. Conclusions
coating is characterized by ploughing and slight scuffing due to
the asperities of the harder couple, with the temperature increas-
a. Ni–P–MoS2 composite coatings were deposited on AISI-1045
ing to 200 and 300 ◦ C, mild ploughing and some pits as result of
steel by electroless deposition and subsequently with heat treat-
shearing fracture take place at the worn surface (Fig. 5b). Fig. 6
ment at 300 ◦ C for 2 h. The co-deposition of MoS2 in the Ni–P
shows XPS spectra of worn surface for the Ni–P–MoS2 compos-
matrix did not affect the formation of phases during heat treat-
ite coatings at different temperatures. At 200 and 300 ◦ C (Fig. 6a),
ment.
local oxidization of MoS2 particles occurs as a consequence of
b. Friction coefficient of Ni–P–MoS2 composite coating decreases
the high flash temperature during rubbing. Local and discontin-
with increasing temperature up to 400 and 500 ◦ C. The best tribo-
uous oxides contribute to formation of the cracks and fracture
logical properties are obtained at 400 ◦ C and the worn surface is
at the worn surface. This explains why the friction coefficients
characterized by mild scuffing. The improvement of tribological
of Ni–P–MoS2 composite coatings at 200 and 300 ◦ C are unstable
properties of the composite coatings is attributed to the forma-
with large fluctuation (Fig. 3a), and Ni–P–MoS2 composite coat-
tion of the lubricious oxide film composed of NiO and MoO3 at
ing at 200 ◦ C presents the higher worn rate (Fig. 4). However, the
high temperature.
worn surfaces of Ni–P–MoS2 composite coatings at 400 and 500 ◦ C
c. With the test temperature increasing to 600 ◦ C, the tribological
are relatively smooth and are characterized by mild scuffing. The
properties of the composite coating begin to deteriorate due to
worn surface of composite coating is covered by a dense and con-
softening of the coating.
tinuous oxide film. The XPS spectra of the worn surfaces at 400
and 500 ◦ C (Fig. 6a and b) indicates that the oxide film is mainly
composed of nickel oxide and molybdenum oxide. The peaks of Acknowledgments
molybdenum oxide in Fig. 6a is quite weak due to its volatilization
[21,22] at high temperature. The signal of molybdenum is not dis- The authors would like to acknowledge the financial support
tinctly detected by XPS. However, what one can ensure is oxide of from “Hundred Talents Program” of Chinese Academy of Sciences
Mo still works for reducing friction. As shown in Fig. 3b, at 400 and (Junhu Meng) and State Key Laboratory of Solid Lubrication (No:
500 ◦ C, the friction coefficient of Ni–P coating is high and acutely 0704).
 Z. Li et al. / Applied Surface Science 264 (2013) 516–521 521

References [14] S. Alirezaei, S.M. Monirvaghefi, M. Salehi, A. Saatchi, Wear 262 (2007)
978.
[1] R. Taheri, I.N.A. Oguocha, S. Yannacopoulos, Wear 249 (2001) 389. [15] X.H. Chen, C.S. Chen, H.N. Xiao, H.B. Liu, L.P. Zhou, S.L. Li, G. Zhang, Tribol. Int.
[2] L.G. Yu, X.S. Zhang, Thin Solid Films 229 (1993) 76. 39 (2006) 22.
[3] J. Sudagar, K. Venkateswarlu, J. Lian, J. Mater. Eng. Perform. 19 (2010) 810. [16] X.G. Hu, P. Jiang, J.C. Wan, Y.F. Xu, X.J. Sun, J. Coat. Technol. Res. 6 (2009) 275.
[4] Q.J. Zhou, J.X. Li, W.Y. Chu, Int. J. Miner. Metall. Mater. 17 (2010) 241. [17] O.A. León, M.H. Staia, H.E. Hintermann, Surf. Coat. Technol. 163–164 (2003)
[5] A. Grosjean, M. Rezrazi, J. Takadoum, P. Berçot, Surf. Coat. Technol. 137 (2001) 578.
92. [18] A. Ramalho, J.C. Miranda, Wear 259 (2005) 828.
[6] Y.Y. Liu, J. Yu, H. Huang, B.H. Xu, X.L. Liu, Y. Gao, X.L. Dong, Surf. Coat. Technol. [19] M. Ebrahimian-Hosseinabadi, K. Azari-Dorcheh, S.M. Moonir Vaghefi, Wear 260
201 (2007) 7246. (2006) 123.
[7] P.-A. Gay, J.M. Limat, P.-A. Steinmann, J. Pagetti, Surf. Coat. Technol. 202 (2007) [20] D. Dong, X.H. Chen, W.T. Xiao, G.B. Yang, P.Y. Zhang, Appl. Surf. Sci. 255 (2009)
1167. 7051.
[8] W.W. Chen, W. Gao, Y.D. He, Surf. Coat. Technol. 204 (2010) 2493. [21] N. Solak, F. Ustel, M. Urgen, S. Aydin, A.F. Cakir, Surf. Coat. Technol. 174–175
[9] Y.T. Wu, H.Z. Liu, B. Shen, L. Liu, W.B. Hu, Tribol. Int. 39 (2006) 553. (2003) 713.
[10] Y.T. Wu, H.Z. Liu, B. Shen, L. Liu, W.B. Hu, Surf. Coat. Technol. 201 (2006) 441. [22] T. Iizuka, H. Kita, Mater. Sci. Eng. A 366 (2004) 10.
[11] T.Z. Zou, J.P. Tu, S.C. Zhang, L.M. Chen, Q. Wang, L.L. Zhang, D.N. He, Mater. Sci. [23] J.S. Han, J.H. Jia, J.J. Lu, J.B. Wang, Tribol. Lett. 34 (2009) 193.
Eng. A 426 (2006) 162. [24] T. Aizawa, A. Mitsuo, S. Yamamoto, T. Sumitomo, S. Muraishi, Wear 259 (2005)
[12] L.Y. Wang, J.P. Tu, W.X. Chen, Y.C. Wang, X.K. Liu, C. Olk, D.H. Cheng, X.B. Zhang, 708.
Wear 254 (2003) 1289. [25] C.H. Hager Jr., J. Hu, C. Muratore, A.A. Voevodin, R. Grandhi, Wear 268 (2010)
[13] Z. Yang, H. Xu, M.K. Li, Y.L. Shi, Y. Huang, H.L. Li, Thin Solid Films 466 (2004) 86. 1195.