Tribology International 39 (2006) 553559

www.elsevier.com/locate/triboint

The friction and wear of electroless NiP matrix with PTFE

and/or SiC particles composite
Yating Wu*, Hezhou Liu, Bin Shen, Lei Liu, Wenbin Hu
State Key Lab. of Metal Matrix Composites, Shanghai Jiao Tong University, No. 1954 Huashan Road, Shanghai 200030, China
Received 30 December 2004; received in revised form 21 March 2005; accepted 18 April 2005
Available online 27 June 2005

Abstract
In this paper, the friction behaviour and wear mechanism of electroless NiP matrix with PTFE and/or SiC particles composite coating are
investigated by virtue of ring-on-disk wear machine at a high load of 150 N. The worn surface, wear debris and the composition changes after
wear were characterized using scanning electron microscopy (SEM) and energy-dispersive analysis of X-ray (EDAX). By comparison with
NiP and NiPSiC coatings, the results indicated that the combination of a PTFE-rich mechanical mixed layer (PRMML) formed on the
worn surface and hard SiC were responsible for the good tribological properties of the hybrid NiPPTFESiC composites at high load. After
heat treatment at 400 8C for 1 h, the wear rate of NiP matrix composites decreased with corresponding increase in microhardness. During
sliding, an obvious decrease in the temperature rise with PTFE addition was attributed to the good anti-friction of PTFE.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Electroless nickel plating; SiC particles; PTFE particles; Friction and wear

1. Introduction
Electroless nickel has been used as a versatile material to
protect from wear and corrosion. Its wear resistance has
been well-established by suitable heat treatment and as a
composite coating by incorporation of hard particles, i.e.
SiC, Al2O3, etc. or lubricating particles, i.e. PTFE, MoS2,
graphite etc. into the NiP matrix [15]. Composite
coatings, using electroless nickel as the matrix, have been
applied in the surface finishing and engineering communities for many years.
However, the coating hardness of electroless NiP
composites is correspondingly decreased with the volume
fraction of lubricating particles in the coating, and the
friction coefficient becomes worse because of the hard
particles. It has been found that hybrid composites
reinforced with high-strength ceramic particles and soft
PTFE exhibit better tribological properties than

* Corresponding author.
E-mail address: tosunbear@sjtu.edu.cn (Y. Wu).

0301-679X/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2005.04.032

mono-particle-reinforced ones, owing to the cooperative

effect of the respective advantages [6]. Thus, it suggests a
promising approach to producing NiP matrix hybrid
composites with high wear resistance and low friction
coefficient for wide applications. The investigations
involved in hybrid composite coatings have been conducted
by some specialists in recent years. Straffelini [7] studied the
surface durability of double coating NiPSiC/NiPPTFE
composites. Y.S. Huang et al. [8] discussed the microstructure and properties of NiPPTFESiC. Additionally,
Zhongcheng Guo [9] submitted the studies on the wear
resistance and the structure of electrodeposited ReNiP
WSiCPTFE. Deng et al. [10] submitted electrodeposited
ReNiWSiCPTFE composite and their properties. Few
studies, however, were reported in the friction and wear
behaviour of electroless NiPPTFESiC composite,
especially at high load.
This paper described the microhardness changes of Ni
P matrix composites after heat treatment at different
temperature for 1 h. Comparing with NiP, NiPPTFE
and NiPSiC, the friction and wear properties of NiP
PTFESiC were evaluated at high load. Emphases would
have been put on the analyses of the anti-friction and wear
mechanism.

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Y. Wu et al. / Tribology International 39 (2006) 553559

1400

The coating with the thickness of 30 mm for each sample

was deposited on 35!35!1 mm mild carbon steel by
electroless nickel plating and the process parameters and
conditions are shown in Table 1. The average size of SiC
and PTFE are 3.5 and 0.2 mm, respectively. Perfluoro
polyoxypropylene ammonium iodide (FC134) and hexadecyltrimethyl ammonium bromide (HTAB) surfactants were
employed for particles dispersion and surface charge
adjustment. Additionally, mechanical stirring was used to
keep particles from sediment.
The hardness of these coatings was measured using
microhardness tester at 50 gf load and the average value of
three measurements for each sample was taken as the final
result. Dry sliding wear tests were performed using a ringon-disc type wear apparatus at an air humidity of 48G
10 RH% with a temperature of 22G1 8C. A high load of
150 N was used in the wear test and the rotation speed was
50 rpm with a radius of 17.5 mm. The materials of the ring
was 45# carbon steel with the hardness of HRC4045 and its
outer and inner diameter was 30 and 20 mm, respectively
and its height was 10 mm. Prior to wear test, all the contact
surfaces were polished, cleaned in acetone and dried so that
the tests were carried out under nominally dry sliding
conditions. The sample surfaces prepared in this way had an
average roughness RaZ1.2 mm and the surface of the ring
was polished to a roughness of RaZ0.9 mm. The test time
for each specimen was 20 min considering the thinness of
coatings. The wear loss and normalized wear rate were
evaluated by the volume loss converted from the mass loss
which was measured by electric balance with 0.1 mg
accuracy. The temperature of the contact surfaces was
measured by a chromelalumel type thermocouple

1200

Table 1
Process parameters and conditions of electroless plating
Process
parameters and
conditions

Coatings
NiP

NiP
SiC

NiP
PTFE

NiPPTFE
SiC

NiSO4$6H2O
(g lK1)
NaH2PO2$H2O
(g lK1)
CH3COONa$
3H2O (g lK1)
88% Lactic acid
(ml lK1)
Stabilizer
(mg lK1)
SiC (g)
60 vol% PTFE
(ml)
HTAB (mg lK1)
FC134 (mg lK1)
pH
T (8C)

2025

2025

2025

2025

2530

2530

2530

2530

3040

3040

3040

3040

2030

2030

2030

2030

13

13

13

13

58

610
58

610

200
4.64.9
8991

100300
4.64.9
8991

4.64.9
8991

200
100400
4.64.9
8991

Microhardness HV50

2. Experiments

Ni-P
Ni-P-SiC
Ni-P-PTFE
Ni-P-PTFE-SiC

1000
800
600
400
200
0

100

200
300
Temperature (C)

400

500

Fig. 1. The microhardness of NiP and NiP composites (at as-deposited,

200, 300, 400, 500 8C for 1 h, respectively).

probe,inserted in the specimen through a hole near to the

contact surfaces and was recorded using a digital data
acquisition system. The worn surfaces, subsurface region
and wear debris were analysed using scanning electron
microscope (SEM) and energy-dispersive analysis of X-ray
(EDAX).

3. Results and discussion

3.1. Microhardness of the coatings
The microhardness of NiP and NiP composites as a
function of heat treatment at different temperature were
shown in Fig. 1. It was indicated that the microhardness of
the four coatings significantly increased after heat treatment
and reached the maximum at 400 8C. This was due to the
formation of Ni3P alloy phase which generated the effect of
precipitation hardening [11]. However, the microhardness
of the four coatings had a little decrease after heat treatment
at above 400 8C. This may be the reason that the grains of
coatings became large at higher temperature. As the above
mentioned, the introduction of PTFE or SiC particles into
the NiP matrix resulted in a substantial decrease or
increase in microhardness. Obviously, the microhardness
of NiPPTFESiC coating showed a moderate hardness
between NiPPTFE and NiPSiC, depending on the
corresponding concentration of PTFE and SiC particles in
the coating. The microhardness changes of NiP matrix
composites with different particles could, in part, explain
wear properties of these materials, as described in the later.
3.2. Wear test results
Fig. 2 (a) showed the friction coefficient of the four
coatings (heat treatment at 400 8C for 1 h) as a function of
the revolutions. It was found that NiP and NiPSiC

Y. Wu et al. / Tribology International 39 (2006) 553559

Table 2
The wear rates of the NiP and NiP composites (10K3 mm3 mK1)

1.6
1.4

Coating

NiP

NiP
PTFE

NiPSiC

NiP
PTFESiC

As-deposited
Heat treatment
(400 8C for 1 h)

0.1629
0.0036

0.2003
0.1008

0.0015
K0.2397

0.0877
0.0034

Friction coefficient

1.2
Ni-P-SiC

1.0
0.8
Ni-P

0.6
0.4

Ni-P-PTFE-SiC

0.2

Ni-P-PTFE

0.0
0

200

400
600
Revolutions

800

1000

Fig. 2. The variation of friction coefficient of the as-deposited NiP and

NiP composites.

exhibited high friction coefficient and have a large range of

fluctuation of friction coefficient after transitory mating wear.
By comparison with NiP, the co-deposition of SiC particles
increased the friction coefficient about 10% in comparison to
NiP coating. Additionally, the friction coefficient of NiP
SiC seemed to have the maximum value and then maintain at
a constant level. It was also observed that over 70%
decreased in the friction coefficient with PTFE in NiP
matrix worn against 45# steel in dry sliding conditions and
facilitated the stable state of the whole wear course. The
difference from NiPPTFESiC was that the friction
coefficient of NiPPTFE kept lowest before 300 revolutions, and then increased dramatically because the wear
began between the steel and counterface. Before and after
heat treatment, NiPPTFESiC showed good tribological
behaviour, as displayed in Fig. 3.
The wear rates of the above coatings are listed in Table 2.
Among these coatings, the wear loss of NiPPTFE became
most and NiPSiC coating demonstrated the better loadbearing due to the highest hardness (in Fig. 1) and had
1.6
1
2

1.4

as-deposited
400C for 1h

1.2
Friction coefficient

555

1.0

the lowest wear rate despite the highest friction coefficient.

It could be concluded that the NiPPTFE had bad wear
resistance at testing high load of 150 N. The NiPPTFE
SiC coating showed a combination of the advantages of Ni
PSiC in high load-bearing and NiPPTFE in a low
friction coefficient. The wear resistance abilities of each
coating were improved effectively after heat treatment at
400 8C for 1 h because of the formation of hard nickel
phosphide precipitates, as described in section 3.1.
Specially, the minus wear loss of NiPSiC indicated the
severe wear of the counterpart.
3.3. Analyses of worn surfaces
The SEM micrographs of the worn surfaces of the NiP
matrix composites with SiC and/or PTFE particles were
shown in Fig. 4. The worn surface of NiP coating was
mainly composed of longitudinal grooves and partial
irregular pits along the sliding direction. The presence of
grooves indicated that the micro-cutting and microploughing effect of the counterface, while pits were the
proof of ductile fracture. In the case of NiPPTFE, there
were wider and deeper grooves on the worn surface than that
of NiP. Apparently, large part of NiPPTFE coating was
detached from the substrate, implying its bad wear
resistance at high load. As for the NiPSiC, the worn
surface had wide grooves and was hard adhered by some
wear products which was rich in O and Fe elements from
Fig. 5(a), implying the oxidation of the surface and severe
wear of the counterpart by the composite. For the NiP
PTFESiC, however, the worn surface was relatively
smooth with fine grooves and scratch marks, and covered
by a thin and compact film, despite partial discontinuousness at high load. As seen in Fig. 5(b), the O and Fe content
of the surface was much lower, while the F was high,
indicating the presence of a PTFE-rich film on the worn
surface of the NiPPTFESiC.

0.8

3.4. The role of PTFE and SiC in tribological behaviour

0.6
0.4

0.2

0.0
0

200

400
600
Revolutions

800

1000

Fig. 3. The friction coefficient of NiPPTFESiC during sliding.

From the above results, it was evident that the introduction

of PTFE and SiC particles reduced the friction coefficient and
imparts the NiP matrix composites with good wear
resistance. In the course of wear, a PTFE-rich film (PRF)
formed on the worn surface of the NiP matrix with PTFE
which seemed to be responsible for good tribological
behaviour. The subsurface feature of the NiPPTFE

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Y. Wu et al. / Tribology International 39 (2006) 553559

Fig. 4. SEM micrographs of the worn surface of the composites tested at 150 N: (a) NiP; (b) NiPPTFE; (c) NiPSiC; (d) NiPPTFESiC.

and NiPPTFESiC tested was shown in Fig. 6. A tribolayer

was found to cover the worn surface. Since, it consists of
materials from the composite and the counterface as well as
environment, it was denoted as a mechanically mixed layer
(MML) [12], PTFE-rich mechanically mixed layer
(PRMML) here. Because of the softness and catenarian

structure of PTFE, the subsurface cavities containing PTFE

particles tend to deform with the subsurface matrix,
squeezing out PTFE to the wearing surface during the sliding
process under the high pressure. In addition, the PTFE
molecule has 13 or 15 chemical repeat units and the molecule
has no branches and is not bulky, which results in a smooth

Fig. 5. EDAX spectra of the worn surface of the as-deposited composites: (a) NiPSiC; (b) NiPPTFESiC.

Y. Wu et al. / Tribology International 39 (2006) 553559

557

Fig. 6. Subsurface feature of the as-deposited composites: (a) NiPPTFE; and (b) NiPPTFESiC.

molecular profile. It has been pointed out that the smooth

molecular profile leads to low friction coefficient and easy
formation of a thin film transferred on the counterface during
sliding [13]. Simultaneously, non-sticking and good chemical inert of PTFE improved the seizure resistance and avoid
oxidation wear of NiP matrix with PTFE. The worn surface
of the corresponding counterparts of NiPPTFE and NiP
PTFESiC composite coating are analysed by EDAX. As
shown in Fig. 7, the results indicate that the rich F and C
elements exist on the surface of the counterpart of NiP
PTFE and F, C and SiC elements are on the surface of the
counterpart of NiPPTFESiC. In the wear course, the
PTFE-rich film transferred into the surface of the counterpart
and lead to the decrease of the friction coefficient of NiP
matrix with PTFE tribo-system.
Hard SiC particles which were co-deposited with the NiP
matrix played a load-bearing role. During the wear of NiP
PTFESiC, SiC particles which were projected in the NiP
matrix were mixed with PTFE and improved the bearing
capability of PRMML, protecting PRMML from shearing.
The hybrid composites NiPPTFESiC, therefore, demonstrated good wear resistance and low friction coefficient, even
under high load.

The presence of the PRMML decreased the direct contact

area between the testing sample and the counterpart,
therefore improving the wear resistance of the hybrid
composite. A quantity of PTFE in the MML dramatically
decreased the shear strength of the near-surface region, so
reducing the friction coefficient. A direct reflection of the
anti-friction property of the NiP matrix with PTFE was the
contact surface temperature in the wear test. The results
displayed in Fig. 8 indicated that the surface temperature of
NiP without PTFE increased slowly and linearly from
room temperature, while the temperature of NiPPTFE
SiC nearly unchanged during the whole wear course and of
NiPPTFE increased abruptly because of the wear
happening between substrate and counterface after 400
revolutions. It was observed that the friction coefficient of
each coating coincides well with its temperature change,
namely the higher the firction coefficient, the quicker the
temperature raised.
3.5. Wear mechanism at high load
From the worn surface (Fig. 4) and wear debris shown in
Fig. 9(a) and Fig. 10(a), it could be concluded that three-body

Fig. 7. EDAX spectra of the worn surface of the corresponding counterpart of (a) NiPPTFE; (b) NiPPTFESiC.

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Y. Wu et al. / Tribology International 39 (2006) 553559

35
Ni-P
Ni-P-SiC
Ni-P-PTFE
Ni-P-PTFE-SiC

Temperature (C)

30

25

20

15
0

200

400

600
800
Revolutions

1000

1200

Fig. 8. The variation of surface temperature of NiP matrix composites

during sliding.

wear mechanism and abrasive wear was primary mechanism

in the wear of NiP coating. For NiPSiC, three-body wear
and oxidation wear control the wear process.
According to analyses in section 3.4, the worn surfaces of
the NiP matrix with PTFE were covered by a PTFE-rich

mechanically mixed layer (PRMML) because of the low

shearing force of PTFE. Therefore, the first step for the wear
of substrate materials was the removal of the PRMML. In
Fig. 3(b) and (d), a low magnification view of the worn
surface showed partial detachment of the PRMML for the
NiP matrix with PTFE. Under the repeating friction of
the counterface, cracks may propagate in the PRMML or the
PRMML-substrate interface and result in the detachment of
the PRMML, as shown in Fig. 6. The fresh materials
exposed on the worn surface may participate in the
following friction process and formed a new PRMML. It
was this process of formation and partial detachment of the
PRMML that controlled the wear process of the composites.
However, at high load, the PRMML of NiPPTFE was
detached quickly and largely because of cutting severely,
while a new fresh PRMML could not be formed timely.
Consequently, NiPPTFE presented high wear rate under
the control of the detachment of the PRMML until the
exposure of the steel substrate which is proved by the sheet
wear debris in Fig. 9(b) and element analyses of EDAX in
Fig. 10(b).
In the case of NiPPTFESiC, SiC particles of the worn
surface were contained in the PRMML during the formation

Fig. 9. SEM micrographs illustrating the wear debris of (a) NiP; (b) NiPPTFE; (c) NiPSiC; (d) NiPPTFESiC.

Y. Wu et al. / Tribology International 39 (2006) 553559

559

Fig. 10. EDAX spectra of the wear debris of (a) NiP; (b) NiPPTFE.

of PRMML. Under the bearing of hard SiC, the PRMML

was not easily deformed so that it was enough time to form
new fresh PRMML. A high magnification view of fine wear
debris (15 mm) in Fig. 9(d) of NiPPTFESiC provided
the proof for the above wear mechanism. When a balance
between the two process was attained, the NiPPTFESiC
would be worn at a steady state rate and formed the final
worn surface in Fig. 4(d).

4. Conclusions
The dry friction and wear behaviour of NiP matrix
composite with PTFE and/or SiC particles were investigated at
high load. The wear resistance of the NiP matrix composites
coincides well with the microhardness of each coating. NiP
PTFE exhibits the lowest friction coefficient and NiPSiC
has the lowest wear rate. At high testing load, NiPPTFE
SiC presents the better anti-friction and wear resistance than
other three NiP matrix composites. The PRMML formed on
the worn surface is responsible for the good anti-friction
properties and SiC particles mixed with PRMML plays a loadbearing role in protecting PRMML from shearing easily. A
continuous supply of PTFE to the tribo-surface is an important
precondition for the formation of PRMML and the exertion of
its anti-friction properties. The low friction coefficient of NiP
matrix with PTFE particles causes a little change of the
temperature and further ensures the stable state of the whole
sliding. Non-sticking and good chemical inert of PTFE make
the surface of PRMML clean, and then avoid the severe
adhesive wear and oxidation wear.

Acknowledgements
The work is financially supported by Science and
Technology Commission of Shanghai Municipality

(No.035211037) and Science and Technology Commission

Nano Special Fund of Shanghai Municipality
(No.0352nm025).

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