Surface & Coatings Technology 200 (2006) 5836 – 5842

www.elsevier.com/locate/surfcoat

Electroless Ni–P–SiC composite coatings with superfine particles

Gao Jiaqiang ⁎, Liu Lei, Wu Yating, Shen Bin, Hu Wenbin
State Key Lab of MMCs, Shanghai Jiao Tong University, Shanghai, 200030, P.R. China
Received 17 May 2005; accepted in revised form 27 August 2005
Available online 19 October 2005

Abstract

Superfine silicon carbide (SiC) particles reinforced nickel–phosphorus (Ni–P) matrix composite (Ni–P–SiC) coatings were prepared by
electroless plating. The morphology and structure as well as the phase transformation of the composite coatings with three sizes of SiC particles
were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and transmission electron
microscopy (TEM), respectively. It was shown that SiC particles co-deposited homogeneously, and the structure of Ni–P–SiC composite coatings
as deposited was amorphous. After certain heat treatment, the matrix of composite coatings crystallized into nickel crystal and nickel phosphide
(Ni3P). At the higher temperature nickel reacted with SiC, and nickel silicides with free carbon were produced. The reaction temperature in
electroless composites coatings decreased with the decrease in the size of SiC particles. Microhardness of electroless Ni–P–SiC composite
coatings increased due to the existence of particles, and reached to the maximum value after heat treatment at 400 °C for 1 h.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Electroless Ni–P–SiC; Superfine particles; Crystallization and reaction; Microhardness

1. Introduction and suspended in electroless bath for its small-scale-effect and

large-specific-area. Up to now, few studies were reported on
Since the invention of electroless plating technology in 1946 crystallization and reaction behavior of electroless composite
by A. Brenner and G. Riddell, electroless nickel coatings have coatings influenced by superfine particles in details [10,11]. In
been used in many fields due to its unique properties. The the present work, electroless Ni–P–SiC composite coatings with
structure of electroless Ni–P as deposited is amorphous with superfine particles were prepared and the structures as well as
high phosphorus content. However, this amorphous structure is the phase transformation of composite coatings were studied
metastable and undergoes a crystalline transition with tempe- later.
rature increase [1–6]. After adequate heat treatment, the coating
turned to crystal and its hardness and anti-wear ability improved 2. Experimental
greatly.
Embedding particles in electroless deposited metals is a An optimized electroless nickel (EN) bath had been developed
convenient method of preparing composite coatings, and the in our laboratory, and the main solution components and some
particles increase its mechanical and physical properties [7]. experimental conditions are summarized in Table 1. All chemicals
There are wear-resistant composite coatings with SiC, Al2O3 and
so on. SiC is a kind of useful electronic material, and has high Table 1
strength ceramic material with excellent corrosion and erosion Main solution components and experimental conditions
resistance. So electroless Ni–P–SiC composite coatings are Component and condition Concentration
attractive and have been investigated before [8,9].
NiSO4 • 6H2O 15∼20 g/L
The sedimentation velocity of particles in electroless bath is NaH2PO2 • H2O 20∼25 g/L
slow with small size, and superfine particles can be dispersed CH3CHOHCOOH 88% (lactic acid) 30∼33 ml/L
Superfine SiC particles 5∼15 g/L
⁎ Corresponding author. Tel.: +86 21 62933585; fax: +86 21 62822012. Temperature 90 ± 1 °C
pH 4.3∼4.5
E-mail address: jdgjq@yahoo.com.cn (G. Jiaqiang).

0257-8972/$ - see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.08.134
 G. Jiaqiang et al. / Surface & Coatings Technology 200 (2006) 5836–5842 5837

a b

50nm

Fig. 1. (a) SEM of 110 nm SiC and (b) TEM of 50 nm SiC particles, respectively.

used were of analytic grade. In addition, a small count of stabilizer
agents and complex non-ionic surfactant agents containing
polyethylene glycol were introduced into the bath.
Electroless composite bath contained particles pretreated by
hydrofluoric acid. Three kinds of SiC particles were used and the
mean sizes are 1000, 110 and 50 nm, respectively. The bath was
air-agitated and the agitation magnitude was adjusted for different
SiC particles during plating. Copper coupons (40 × 40 × 0.1 mm3)
were used as substrate and pre-treated before immersed in the
bath. And the pretreatment procedure of substrates can be shown
as below (rinsing samples with de-ionized water):
Polish → rinsing → oil removing (sodium hydroxide solu-
tion, 30 min) → rinsing → activation (diluted hydrochloric acid,
60 s) → rinsing.
The chemical composition of coatings was determined by
energy dispersive spectrum (EDS) and chemical titration, and
the average values were adopted. Specimens of heat treatment
were heated and cooled in air atmosphere. Philips Sirion 200
field emission scanning electron microscope (SEM), Hitachi
S-520 SEM, Philips CM-12 transmission electron microscope
(TEM, 100 kV) and JEOL JEM-2010 F field emission high-
resolution electronic microscope (HREM, 200 kV) were used
to show the structure of particles and coatings. Crystallization
and reaction processes were examined by NETZSCH 404
differential scanning calorimetry (DSC) and Rigaku X-ray
diffractometer (XRD) with Cu Kα radiation. The microhardness
of coatings was measured by HX-100 Vickers hardness tester at
the load of 50 g for 15 s.

a1 b1 c1

5μm 5μm 5μm

a2 b2 c2

5μm 1μm 1μm

(1000nm SiC) (110nm SiC) (50nm SiC)

Fig. 2. (a1, b1, c1) Surface and (a2, b2, c2) cross-section morphology of electroless Ni–P–SiC coatings with three sizes of superfine particles, respectively (the black
dots in figures are SiC particles).
5838 G. Jiaqiang et al. / Surface & Coatings Technology 200 (2006) 5836–5842

3. Results and discussion Table 2

Heat of formation and Gibbs free energy of SiC and several nickel compounds
[13,14]
3.1. Morphology of electroless Ni–P–SiC composite coatings
Phase ΔHf (kJ/mol) ΔGf (kJ/mol)
Two kinds of superfine SiC particles are shown in Fig. 1, and SiC − 62.8 –
they can be suspended in the bath for a long time. With proper Ni3Si − 148.8 −86.0
Ni5Si2 − 301.4 −175.8
surfactant agents, three sizes of SiC particles suspended in
Ni2Si − 131.7 −68.9
electroless bath by air agitation, and three kinds of particles Ni3Si2 − 223.6 −98.0
reinforced Ni–P matrix composite coatings were prepared, NiSi − 85.3 −22.5
respectively. NiSi2 − 86.5 39.1
Superfine SiC particles were successfully co-deposited in Ni3C 67.3 130.1
Ni–P alloy matrix by electroless plating. With the increase of
SiC concentration in the bath, the content of particles in the peak of the electroless Ni–P alloy, and the temperature is
composite coating increased, but the plating rate decreased. The considered as the crystallization temperature. It can be seen that,
average deposition rate of composite coatings with 110 nm SiC no matter which size of SiC particles are deposited into the
particles was about 10 μm/h at the first metal turnover (5 h). The composites, the crystallization and melting point hold the same
superfine particles content was about 4.3 wt.%, and the valves, respectively. It implies that the SiC particles did not
phosphorus content of the composite coating decreased slightly change the crystallization behavior of composite coatings.
to 10.5 wt.% compared with that of electroless Ni–P coating (11 There are the other exothermal peaks in three kinds of
wt.% P), and the atomic ratio of Ni with P (4 : 1) did not change. composite coatings, which respond to the reaction between Ni
The particles contents were 3.8 and 3.6 wt.% of composite and SiC. It can be seen that the reaction temperature decreases
coatings with 1000 nm SiC and 50 nm SiC, respectively, and the with the decrease in the size of SiC particles, because nickel
atomic ratios of Ni with P in composite coatings were the same atoms diffuse into the finer SiC particles easily and will react
as that in electroless Ni–P alloys. with SiC at the lower temperature.
Observed by the naked eye, the composite coatings are SiC particles are embedded into Ni–P alloy during electroless
smooth and semi-bright as deposited. It is shown in Fig. 2(a1, composite plating, and the nickel atoms deposit as clusters on the
b1 and c1) that the composite coatings with superfine SiC particles surface at first [12]. The nickel atom clusters are
particles are smooth, and the morphology of coatings was thermodynamically metastable and nickel atoms will diffuse into
changed slightly. Fig. 2(a2, b2 and c2) shows that superfine SiC SiC particles during heating. The Si–C bonds are broken and Ni
particles disperse homogeneously and the content of particles atoms displace the C, then nickel silicides (simply expressed as
are at high levels. NixPy , standing for Ni3Si, Ni2Si, Ni5Si2, etc.) are produced.
Neglecting the influence of phosphorus in electroless Ni–P–
3.2. Crystallization behavior of electroless Ni–P–SiC composite SiC composite coatings, the change of Gibbs free energy during
coatings the reaction can be expressed by:

DSC curves of electroless Ni–P–SiC composite coatings ΔG ¼ ΔGNix Siy þ yΔGC −xΔGNi −yΔGSiC : ð1Þ
with three sizes of superfine particles and Ni–P alloy at
isochronal heating were shown in Fig. 3. Electroless Ni–P–SiC The change of Gibbs energy can be calculated by:
composite coatings as deposited are amorphous and turn to ΔG = ΔH − TΔS, where ΔH is the heat of formation, T is the
crystal structure after annealed. There is only one exothermal
Ni
2.5 894ºC
Ni 3 P
2.0 SiC
NixSiy
Heat flow,mw/mg

1.5 NiO
Intensity (a.u.)

Ni-P
1.0
Ni-P-110nmSiC, 579ºC
Ni-P-50nmSiC, 551ºC Ni-P-SiC,600ºC
0.5

0.0 Ni-P-SiC,400ºC

-0.5 Ni-P-1000nmSiC, 606ºC

Ni-P-SiC
-1.0 Ni-P
340ºC
-1.5
200 400 600 800
Temperature,ºC 2θ(º)

Fig. 3. DSC curves of electroless Ni–P and Ni–P–SiC composite coatings Fig. 4. XRD spectra of as-deposited electroless Ni–P and Ni–P–SiC coatings
(heating rate: 10 °C/min). after heat treatment.
 G. Jiaqiang et al. / Surface & Coatings Technology 200 (2006) 5836–5842
(1 1 1)
(2 0 0)
(2 2 0)
Intensity (a.u.)
20 40 60
2θ(º)
Fig. 5. The XRD spectra of the residual of electroless Ni–P–SiC composite
coating after heat treatment and dissolved in HNO3 compared with that of
superfine SiC particles.
temperature and ΔS is the entropy change. Because ΔS is
mostly small in solid-state reaction and can be neglected, ΔG
becomes equal to ΔH. To obtain the net gain in energy upon
silicide and carbide formation, the enthalpy of SiC should be
subtracted. There are many kinds of Ni–Si compounds, such
as NiSi, Ni2Si, Ni3Si, and Ni5Si2. Several nickel silicides can
be obtained after the reaction of nickel with SiC, which is
influenced by the local nickel concentration. The heat of
formation and ΔG of several nickel compounds are shown in
Table 2 calculated according to the references [13] and [14],
which have some differences with that of reference [9]. Some
nickel silicides can be obtained because of negative ΔG, while
nickel carbide was not observed for positive ΔG. Further-
more, nickel element is rich in the electroless composite
coatings, and the final nickel silicide is Ni3Si after complete
reaction.
3.3. Structures of electroless Ni–P–SiC composite coatings
From the XRD spectra in Fig. 4, it can be found that
electroless Ni–P–SiC composite coating is amorphous as
a B
Fig. 6. (a) TEM BF image and (b) SAD of A district in electroless Ni–P–SiC composite coating after heat treatment at 400 °C for 1 h.
5839
deposited. That is to say, the superfine particles do not change
Ni x Si y
the structure of the Ni–P alloy during electroless plating.
Ni 3Si
As shown in Fig. 4, the electroless composite coating
crystallized into nickel crystal, nickel phosphide and nickel
Ni3 Si silicides (NixPy) after heat treated at 400 °C for 1 h. After heat
treated at 600 °C, there is no special diffraction peak of nickel
silicides except for Ni3Si, whose grain lattice approaches to that
of nickel [8].
To make sure the final products of the crystallization and
reaction in electroless Ni–P–SiC composite coatings with
superfine particles, one piece of composite coating with 110
SiC
nm SiC was striped from the substrate and heat treated at 600
°C for 4 h. Then, the sample was dissolved in diluted nitric
80
acid (HNO3) solution for several hours. The residual product
was filtered, rinsed and dried, then was studied by XRD. The
result of XRD spectrum of the residual is shown in Fig. 5
compared with that of SiC added into the bath. It
demonstrated that there was Ni3Si mainly without SiC in the
residual product. So it is concluded that the final products of
electroless Ni–P–SiC composite coatings after completely
heat treatment are mainly Ni, Ni3P, Ni3Si and C (free
carbon).
Electroless Ni–P–SiC composite coatings containing
superfine particles (selecting the coating with 110 nm SiC as an
example) after heat treatment at 400 °C for 1 h were
investigated, and Fig. 6(a) shows the TEM bright field (BF)
image of electroless Ni–P–SiC composite coatings. We can find
that the particles disperse in the Ni–P matrix. The selected area
diffraction of C district in Fig. 6(a) is shown in Fig. 6(b), which
corresponds to polycrystalline nickel. From the results of EDS,
the object of A district in Fig. 6(a) is SiC and B district in Fig. 6
(a) is Ni3P, respectively.
JEM 2010 F TEM BF images and local element distribution
analysis in electroless composite coatings with 110 nm SiC
particles after heat treatment are shown in Fig. 7. It can be seen
that the edge of SiC particles is ambiguous due to the reaction.
The element distribution in Fig. 7(b) of C, Si, Ni and P are shown
in Fig. 7(c), (d), (e) and (f), respectively. It can be seen that C
element diffused everywhere, which implies that nickel diffused
into SiC particle and the Si–C bond was broken.
100nm
5840 G. Jiaqiang et al. / Surface & Coatings Technology 200 (2006) 5836–5842

a b

280nm

50 nm
200nm

c d e f

C Si Ni P

Fig. 7. (a) TEM BF and (b) local element analysis district in electroless Ni–P–SiC composite coating after heat treatment, as well as the distribution of (c) C, (d) Si,
(e) Ni and (f) P, respectively.

Fig. 8 shows the JEM 2010F HREM image of Ni–P–SiC
containing 110 nm SiC particles after heat treatment at 400
°C for 1 h. The interfacial reaction of Ni and SiC was studied
in details in Fig. 8(a), and the arrows point to the reacted
interface. Fig. 8(b) shows modified image by fast Fourier
transform at the same position. From SAD of A district
shown in Fig. 8(c), it can be concluded that the main phase of
the district is body-centered tetragonal Ni3P with the direction
of [7 5̄ 5̄].
decreases, because the grains grow and become coarse leading
to strength decrease after heat treatment at high temperature
more than 400 °C [15].
From Table 3, we can find that the composite coatings with
finer particles have higher microhardness values after heated at
600 °C. The existence of free carbon and the volume shrinkage
after reaction lead to the strength decrease of composite
coatings. When nickel is abundant, the following reaction takes
place:

3.4. Microhardness of electroless Ni–P–SiC composite coatings 3Ni þ SiC→Ni3 Si þ C: ð2Þ

The volume variation of the composite coatings after

Not only the reaction process of composite coatings is
reaction is expressed as:
changed by superfine particles, but also properties of coatings
are modified. Microhardness is an important property of ΔV ¼ ðV ns þ V c Þ−ðV n þ V s Þ ð3Þ
electroless coatings, and the results of Ni–P and Ni–P–SiC
coatings as deposited and those after certain heat treatment are where ΔV—volume change during reaction; Vn—volume of
shown in Table 3. Microhardness values of electroless Ni–P– nickel matrix needed to react completely with SiC; Vs—volume
SiC composite coatings as deposited increase because of the of a SiC particle; Vns—volume of reaction product (Ni3Si);
introduction of hard particles and dispersion strengthening. It Vc—volume of carbon (graphite). According to the data in
can be seen in Table 3 that the microhardness of electroless Ni– references [14] and [16], one can obtain that the decrease of
P–SiC composite coating with 1000 nm particles increased 10%
as high as that of electroless Ni–P alloy. With the fine SiC
particles, the electroless composite coatings have low micro- Table 3
hardness values. Microhardness of electroless Ni–P and Ni–P–SiC composite coatings after heat
After crystallization, microhardness of coatings increases treatment (HV50)
greatly because of the precipitation of hard intermetallic Coatings 1000 nm SiC 110 nm SiC 50 nm SiC Ni–P
compound Ni3P. It is shown in Table 3 that the microhardness As-deposited 580 537 520 510
of electroless Ni–P–SiC composite coatings raise to the 300 °C × 1 h 854 860 781 776
maximum value (about HV501200) after heat treatment at 400 °C × 1 h 1206 1192 1186 1012
400 °C for 1 h. After heat treatment at high temperature 500 °C × 1 h 967 932 966 937
600 °C × 1 h 807 826 888 764
(e.g. 500 and 600 °C), microhardness of composite coatings
 G. Jiaqiang et al. / Surface & Coatings Technology 200 (2006) 5836–5842
SiC
c b
231
112
Fig. 8. (a) HREM fringe image of electroless Ni–P–SiC composite coating containing 110 nm SiC particles, (b) modified image and (c) SAD of A district. Indexing is
for Ni3P.
volume of the system is 1.244 cm3/mol. It indicates that
shrinkage, even porosity, will occur in electroless composite
coatings after reaction of Ni with SiC. The mechanical
properties of Ni–P–SiC composites deteriorated and the
microhardness decreased after heat treatment at high
temperature. The composite coatings containing the finer
particles, there is the smaller porosity produced after complete
reaction. So electroless Ni–P–SiC composite coatings
containing 50 nm SiC particles have higher strength after high
temperature treatment than that of composite coatings with
larger particles.
4. Conclusions
(1) Electroless Ni–P–SiC composite coatings with superfine
SiC particles were prepared by electroless plating.
Superfine SiC particles dispersed homogeneously and the
content of particles was at high level in composite
coatings. The structure of the composite coatings as
deposited was amorphous.
(2) During heating, the amorphous alloy in electroless Ni–
P–SiC composite coatings crystallized, and then reacted
with SiC at high temperature. The crystallization
temperature of Ni–P–SiC composite coatings was not
influenced by superfine particles obviously, but the
reaction temperature of electroless composites coatings
decreased with the decrease in the size of particles. The
5841
Ni
A
5 nm
final products of the crystallization and reaction of
composite coatings were Ni, Ni3P, Ni3Si and free
carbon.
(3) The microhardness of electroless Ni–P–SiC composite
coatings were higher than that of Ni–P alloy coating
due to the existence of superfine particles, and the
microhardness were increased to the maximum value
(about HV501200) after heat treatment at 400 °C for
1 h.
Acknowledgements
This work has been funded by the Science and Technology
Commission of Shanghai Municipal Government (0352 nm025
and 035211037), for which the authors are grateful. Thanks are
also due to Dr. Gu Jiajun, Dr. Zhang Hongxiang and Prof. Luo
Shoufu for their help and advice.
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