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Wear 254 (2003) 12891293

Friction and wear behavior of electroless Ni-based


CNT composite coatings
L.Y. Wang
a
, J.P. Tu
a,
, W.X. Chen
b
, Y.C. Wang
c
, X.K. Liu
c
, Charls Olk
c
,
D.H. Cheng
d
, X.B. Zhang
a
a
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
b
Department of Chemistry, Zhejiang University, Hangzhou 310027, China
c
Surface Engineering and Tribology Center, General Motors Corporation, 515N, Washington Avenue, Washington, DC, USA
d
Department of Environment and Chemical Engineering, Shanghai University, Shanghai 200027, China
Received 5 September 2002; received in revised form 30 December 2002; accepted 6 March 2003
Abstract
Ni-based carbon nanotube (CNT) composite coatings with different volume fraction (from 5 to 12 vol.%) of CNTs were deposited on
medium carbon steel substrates by electroless plating. The friction and wear behavior of the composite coatings were investigated using a
pin-on-disk wear tester under unlubricated condition. Friction and wear tests were conducted at a sliding speed of 0.0623 ms
1
and at an
applied load of 20 N. The experimental results indicated that the friction coefcient of the composite coatings decreased with increasing the
volume fraction of CNTs due to self-lubrication and unique topological structure of CNTs. Within the range of volume fraction of CNTs
from 0 to 11.2%, the wear rate of the composite coatings showed a steadily decreasing trend with increasing volume fraction of CNTs.
Because of the conglomeration of CNTs in the matrix, however, the wear rate of the composite coatings increased with further increasing
the volume fraction of CNTs.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Carbon nanotubes (CNTs); Electroless plating; Composite coating
1. Introduction
Electroless codeposition is one of the most impor-
tant techniques for producing composites of metallic and
non-metallic constituents. Coatings containing solid par-
ticles such as SiC, Al
2
O
3
, WC and diamond, etc. have
been developed for better wear resistance or dispersion
hardening [15]. Recently, carbon nanotubes (CNTs) are
increasingly attracting scientic and technological interest
by virtue of their unique chemical and physical properties
after discovered by Iijima [6]. Many works on the physical
properties, such as bending stiffness [7], Youngs modu-
lus [8], have been done using atomic force microscopy or
electronic transition microscopy. Treacy et al. [9] measured
the Youngs modulus of isolated nanotubules by measuring
the amplitude of their intrinsic thermal vibrations in the
TEM to nd the average value of Youngs modulus to be
1.8 TPa. Wong et al. [7] used the atomic force microscopy
to determine the mechanical properties of the nanotubes to

Corresponding author. Tel.: +86-571-8795-2573;


fax: +86-571-8795-2573.
E-mail address: tujp@cmsce.zju.edu.cn (J.P. Tu).
nd that they are stiff and tensile strength of carbon nan-
otubes reach 150 GPa. CNTs have been used as extremely
strong nano-tubular-reinforcements like bers, for making
nano-composite [1012], which possess extraordinary high
strength. These nano-reinforcements could be used for im-
proving the tensile properties. Some recent researches have
investigated the tribological properties of CNT-reinforced
metallic matrix composites [13,14]. It is found that the wear
resistance of the composites have been improved and the
friction coefcient decreases due to the effect of CNTs.
In the present work, Ni-based composite coatings with
different volume fraction of CNTs were deposited on 45#
steel substrates by electroless plating. The effect of the vol-
ume fraction of CNTs on friction and wear properties of the
Ni-based CNT composite coatings were investigated.
2. Experimental procedure
Multi-walled carbon nanotubes were prepared by chem-
ical catalytic vapor deposition (CCVD). The catalyst was
produced by concentrating cobalt nitrate and magnesium
nitrate solution to gelation and then grinding it to a ne
0043-1648/$ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0043-1648(03)00171-6
1290 L.Y. Wang et al. / Wear 254 (2003) 12891293
powder after being sintered at 650

C. Carbon nanotubes
were obtained on the catalyst at 750

C with a ow rate
of acetylene 100 ml min
1
and nitrogen 300 ml min
1
.
As-prepared CNT products were puried by immersing
them in concentrate nitric acid, then ltered and washed
with de-ionized water and dried at 120

C. CNT samples
were characterized by transmission electronic microscope
(TEM, Philips 200UT). In order to improve the dispersion
of CNTs, the puried CNTs were mechanically ball milled
for 8 h with a planetary ball mill in an aether liquid at a
rotating speed of 430 rev min
1
. The weight ratio of steel
balls to puried CNTs is 50:1. The CNTs have been rela-
tively shortened after ball milling. Then ultrasonic agitation
was used to disperse the shortened CNTs in the plating bath.
Ni-based composite coatings were deposited on test disk
specimens, which were fabricated by a low carbon steel with
a hardness of HB86, with a diameter of 15 mm by electro-
less plating. The electroless bath has the following compo-
sition: 20 g l
1
NiSO
4
6H
2
O, 26 g l
1
NaH
2
PO
4
, 15 g l
1
CH
3
COONa, 5 ml l
1
HCOOH and 300 mg l
1
surfactant
(cetyl-trimethylamine bromide). The bath temperature was
held at about 85

C and the pH value of the bath was main-


tained 4.6. The thickness of the Ni-based CNT composite
coatings were about 25 m after depositing for 2 h. In or-
der to avoid the hydrogen brittleness, the composite coatings
were treated at 673 K for 2 h in vacuum before wear test.
Microstructure analysis of the composite coatings was iden-
tied by X-ray diffraction (XRD) (Cu K
1
, Philips X Pert
MPD). The surface morphology of the composite coatings
was evaluated using scanning electron microscopy (JEOL
JSM-5600LV) and atomic force microscopy. Microhardness
of the coatings was determined with a Vickers hardness in-
denter (MT-3), using a load of 50 g.
Friction and wear properties of the coatings were investi-
gated using a pin-on-disk wear tester (MMW-1) under un-
lubricated condition. Fig. 1 shows the schematic diagram of
the test machine. The spherical pins with a radius of 5 mm
were fabricated by a quenched-and-tempered medium car-
bon steel with a hardness of HB220. And the surface rough-
ness of the pins was about 4 m center-line average (CLA).
Tests were conducted at a sliding speed of 0.0623 ms
1
and
at load of 20 N in air (relative humidity 60%). Mass loss was
Fig. 1. Schematic diagram of pin-on-disk wear tester.
measured with an analytical balance at an interval of 15 min
throughout the tests. The coefcients of friction were cal-
culated by dividing the friction force which was recorded
on line via torque as measured by the strain gauge. In order
to take the repeatability into account, the test results for the
friction and wear under steady state sliding were obtained
from the average of three readings. The worn surfaces of the
electroless composite coatings on the disk specimens were
examined using scanning electron microscopy.
3. Results and discussion
3.1. Microstructure of composite coatings
Fig. 2a shows a TEM image of the puried carbon nan-
otubes. It can be found that the CNTs have central hollow
tubes, which are of typical multi-walled carbon nanotube
structure. The outer diameters of the most of CNTs range
from 20 to 40 nm. As shown in Fig. 2a, the CNTs are much
longer in length than in their diameter, and most of CNTs en-
wind with each other, which has a negative effect on dispers-
ing of CNTs in the bath. In order to improve the dispersity
of CNTs in electroless bath, the CNTs were mechanically
milled. The TEM image of carbon nanotubes after being
Fig. 2. TEM images of: (a) puried CNTs; (b) ball milled CNTs.
L.Y. Wang et al. / Wear 254 (2003) 12891293 1291
Table 1
Volume fraction of CNTs and microhardness of electroless composite
coatings
CNT content in
bath (g l
1
)
Volume fraction of
CNTs in coatings (%)
Microhardness of
coatings (Hv 50)
0 0 1095
1.0 5.1 1130
2.0 10.0 1330
3.0 11.2 1524
4.0 12.5 1197
mechanical milled for 8 h is shown in Fig. 2b. It is evident
from this gure that carbon nanotubes become shorter.
Compared with the density of NiP coating, the volume
fractions of CNTs in the composite coatings were calculated.
As shown in Table 1, the volume fraction of CNTs increased
sharply in the beginning and then slowly with the content
of CNTs in the plating bath. Fig. 3 shows the XRD patterns
Fig. 3. XRD patterns of Ni-based CNT composite coatings before and
after treatment at 673 K for 2 h.
Fig. 4. AFM image of electroless Ni-based CNT composite coating after
treatment at 673 K for 2 h.
of the composite coatings with 5.1 vol.% CNTs before and
after treatment at 673 K for 2 h. It is found that their crystal
structures change from amorphous to typical crystalline
state, and Ni
3
P phase precipitates in the Ni matrix. Fig. 4
shows an AFM image of the surface of the as-prepared
Ni-based CNT composite coating with 10.0 vol.% CNTs,
revealing a relatively smooth surface morphology. Sur-
face roughness of the coatings ranged from 0.1 to 0.3 m
center-line average (CLA). A SEM surface morphology of
the Ni-based composite coating with 10.0 vol.% CNT after
treatment at 673 K for 2 h is shown in Fig. 5. It can be found
that CNTs appear well dispersed and are embedded in the
nickel matrix. The microhardness of the composite coatings
with different volume fractions of CNTs are also listed in
Fig. 5. SEM surface morphology of Ni-based composite coating with
10.0 vol.% CNTs.
1292 L.Y. Wang et al. / Wear 254 (2003) 12891293
Fig. 6. Variation of friction coefcient and wear rate of composite coatings
with volume fraction of CNTs.
Table 1. It is evident that the Ni-based CNT composite coat-
ings reveal higher hardness than NiP coating. The hardness
of the composite coatings increases with increasing the
volume fraction of CNTs, but then decreases with further
increasing the volume fraction. As shown in Table 1, the
hardness of the composite coating with 11.2 vol.% CNTs is
the highest.
3.2. Friction and wear
Fig. 6 shows variation of steady-state wear rate and fric-
tion coefcient for composite coatings with volume fraction
of CNTs at a sliding speed of 0.0623 ms
1
and at load of
20 N. The friction coefcient decreases with increasing the
volume fraction of CNTs in composite coatings. It is sug-
gested that an increase in surface fraction of CNTs reduces
the direct contact between the nickel matrix and steel pin.
Due to self-lubrication of CNTs, the short and tube shape
of the CNTs would more easily slide or roll between the
mating metal surface, thus resulting in the decrease in the
friction coefcient of the composite coatings.
The effect of volume fraction of CNTs on the wear rate
of the Ni-based composite coating is also shown in Fig. 6.
Within the range of volume fraction of CNTs from 0 to
11.2%, the wear rate of the composite coatings showed a
steadily decreasing trend with increasing volume fraction of
CNTs. When the volume fractions of CNTs were lower, the
favorable effects of CNTs on wear resistance are attribute
to their excellent mechanical properties and well dispersed
in the composite coating. However, increasing of volume
fraction of CNTs higher than 11.2% resulted in an increase
in wear rate. The fact is likely to be attributed to that the
conglomeration of CNTs in the matrix for the composite
coating with high volume fraction of CNTs decreases the
efciency of the reinforcement of CNTs.
Fig. 7 shows worn surface morphology of the Ni-based
composite coatings with different volume fractions of CNTs
under unlubricated condition. Plastic deformation with
Fig. 7. Worn surface morphology of the Ni-based CNT composite coatings:
(a) 5.1 vol.% of CNTs in coating; (b) 12 vol.% of CNTs in coating.
grooves can be observed on the worn surface of the compos-
ite coating with lower volume fraction of CNTs (Fig. 7a).
With increasing the volume fraction of CNTs, the reunited
CNTs on the coating surface would ake away during the
wear process. Cracking and spalling may also be seen on
the worn surface of the composite coating with higher vol-
ume fraction of CNTs (Fig. 7b), indicating that the peeling
of reunited CNTs lead to an increase in wear loss.
4. Conclusions
Ni-based CNT composite coatings were deposited on a
medium carbon steel substrate by electroless plating. After
treatment at 673 K for 2 h, their crystal structures changed
from amorphous to typical crystalline state, and Ni
3
P phase
precipitated in the Ni matrix. The results demonstrated that
Ni-based CNT composite coatings exhibited higher wear re-
sistance and lower friction coefcient than NiP electroless
coating under unlubricated condition. Due to self-lubrication
and unique topological structure of CNTs, the friction coef-
cient of the composite coatings decreased with increasing
the volume fraction of CNTs. The wear rate of the compos-
ite coatings increased with increasing the volume fraction of
CNTs within the range from 0 to 11.2%, but then decreased
with further increasing the volume fraction. Because of con-
glomeration of CNTs in the matrix, cracking and spalling
occurred on the worn surface of the composite coatings with
higher volume fraction of CNTs during wear process.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 20003009), the Special Founda-
tion of the Education Ministry of China for Young Teacher
(2002-350), Hi-Tech research and development program of
China (2002AA334020), the Special Fund of General Mo-
tors Corporation and the Open Fund of State Key Lab of
Solid Lubrication, to whom we are very grateful.
L.Y. Wang et al. / Wear 254 (2003) 12891293 1293
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