Surface & Coatings Technology 200 (2006) 5836 5842 www.elsevier.

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Electroless NiPSiC 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 nickelphosphorus (NiP) matrix composite (NiPSiC) 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 NiPSiC 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 NiPSiC 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 NiPSiC; Superfine particles; Crystallization and reaction; Microhardness

1. Introduction Since the invention of electroless plating technology in 1946 by A. Brenner and G. Riddell, electroless nickel coatings have been used in many fields due to its unique properties. The structure of electroless NiP as deposited is amorphous with high phosphorus content. However, this amorphous structure is metastable and undergoes a crystalline transition with temperature increase [16]. After adequate heat treatment, the coating turned to crystal and its hardness and anti-wear ability improved greatly. Embedding particles in electroless deposited metals is a convenient method of preparing composite coatings, and the particles increase its mechanical and physical properties [7]. There are wear-resistant composite coatings with SiC, Al2O3 and so on. SiC is a kind of useful electronic material, and has high strength ceramic material with excellent corrosion and erosion resistance. So electroless NiPSiC composite coatings are attractive and have been investigated before [8,9]. The sedimentation velocity of particles in electroless bath is slow with small size, and superfine particles can be dispersed
Corresponding author. Tel.: +86 21 62933585; fax: +86 21 62822012. 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

and suspended in electroless bath for its small-scale-effect and large-specific-area. Up to now, few studies were reported on crystallization and reaction behavior of electroless composite coatings influenced by superfine particles in details [10,11]. In the present work, electroless NiPSiC composite coatings with superfine particles were prepared and the structures as well as the phase transformation of composite coatings were studied later. 2. Experimental An optimized electroless nickel (EN) bath had been developed in our laboratory, and the main solution components and some experimental conditions are summarized in Table 1. All chemicals
Table 1 Main solution components and experimental conditions Component and condition NiSO4 6H2O NaH2PO2 H2O CH3CHOHCOOH 88% (lactic acid) Superfine SiC particles Temperature pH Concentration 1520 g/L 2025 g/L 3033 ml/L 515 g/L 90 1 C 4.34.5

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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 solution, 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 highresolution 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 K 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

5m a2 b2

5m c2

5m

5m (1000nm SiC) (110nm SiC)

1m (50nm SiC)

1m

Fig. 2. (a1, b1, c1) Surface and (a2, b2, c2) cross-section morphology of electroless NiPSiC coatings with three sizes of superfine particles, respectively (the black dots in figures are SiC particles).

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G. Jiaqiang et al. / Surface & Coatings Technology 200 (2006) 58365842 Table 2 Heat of formation and Gibbs free energy of SiC and several nickel compounds [13,14] Phase Hf (kJ/mol) 62.8 148.8 301.4 131.7 223.6 85.3 86.5 67.3 Gf (kJ/mol) 86.0 175.8 68.9 98.0 22.5 39.1 130.1

3. Results and discussion 3.1. Morphology of electroless NiPSiC composite coatings Two kinds of superfine SiC particles are shown in Fig. 1, and they can be suspended in the bath for a long time. With proper surfactant agents, three sizes of SiC particles suspended in electroless bath by air agitation, and three kinds of particles reinforced NiP matrix composite coatings were prepared, respectively. Superfine SiC particles were successfully co-deposited in NiP alloy matrix by electroless plating. With the increase of SiC concentration in the bath, the content of particles in the composite coating increased, but the plating rate decreased. The average deposition rate of composite coatings with 110 nm SiC particles was about 10 m/h at the first metal turnover (5 h). The superfine particles content was about 4.3 wt.%, and the phosphorus content of the composite coating decreased slightly to 10.5 wt.% compared with that of electroless NiP coating (11 wt.% P), and the atomic ratio of Ni with P (4 : 1) did not change. The particles contents were 3.8 and 3.6 wt.% of composite coatings with 1000 nm SiC and 50 nm SiC, respectively, and the atomic ratios of Ni with P in composite coatings were the same as that in electroless NiP alloys. Observed by the naked eye, the composite coatings are smooth and semi-bright as deposited. It is shown in Fig. 2(a1, b1 and c1) that the composite coatings with superfine SiC particles are smooth, and the morphology of coatings was changed slightly. Fig. 2(a2, b2 and c2) shows that superfine SiC particles disperse homogeneously and the content of particles are at high levels. 3.2. Crystallization behavior of electroless NiPSiC composite coatings DSC curves of electroless NiPSiC composite coatings with three sizes of superfine particles and NiP alloy at isochronal heating were shown in Fig. 3. Electroless NiPSiC composite coatings as deposited are amorphous and turn to crystal structure after annealed. There is only one exothermal
2.5 2.0
894C

SiC Ni3Si Ni5Si2 Ni2Si Ni3Si2 NiSi NiSi2 Ni3C

peak of the electroless NiP alloy, and the temperature is considered as the crystallization temperature. It can be seen that, no matter which size of SiC particles are deposited into the composites, the crystallization and melting point hold the same valves, respectively. It implies that the SiC particles did not change the crystallization behavior of composite coatings. There are the other exothermal peaks in three kinds of composite coatings, which respond to the reaction between Ni and SiC. It can be seen that the reaction temperature decreases with the decrease in the size of SiC particles, because nickel atoms diffuse into the finer SiC particles easily and will react with SiC at the lower temperature. SiC particles are embedded into NiP alloy during electroless composite plating, and the nickel atoms deposit as clusters on the particles surface at first [12]. The nickel atom clusters are thermodynamically metastable and nickel atoms will diffuse into SiC particles during heating. The SiC bonds are broken and Ni atoms displace the C, then nickel silicides (simply expressed as NixPy , standing for Ni3Si, Ni2Si, Ni5Si2, etc.) are produced. Neglecting the influence of phosphorus in electroless NiP SiC composite coatings, the change of Gibbs free energy during the reaction can be expressed by: G GNix Siy yGC xGNi yGSiC : 1

The change of Gibbs energy can be calculated by: G = H TS, where H is the heat of formation, T is the
Ni Ni 3 P SiC NixSiy NiO

Heat flow,mw/mg

1.5 1.0 0.5 0.0 -0.5 -1.0 -1.5 200

340C Ni-P-1000nmSiC, 606C Ni-P Ni-P-110nmSiC, 579C Ni-P-50nmSiC, 551C

Intensity (a.u.)

Ni-P-SiC,600C Ni-P-SiC,400C Ni-P-SiC Ni-P

400

600

800

Temperature,C
Fig. 3. DSC curves of electroless NiP and NiPSiC composite coatings (heating rate: 10 C/min).

2()
Fig. 4. XRD spectra of as-deposited electroless NiP and NiPSiC coatings after heat treatment.

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(2 0 0)

Ni x Si y
(2 2 0)

Ni 3Si

Ni3 Si

SiC

20

40

60

80

2()
Fig. 5. The XRD spectra of the residual of electroless NiPSiC composite coating after heat treatment and dissolved in HNO3 compared with that of superfine SiC particles.

temperature and S is the entropy change. Because S is mostly small in solid-state reaction and can be neglected, G becomes equal to H. To obtain the net gain in energy upon silicide and carbide formation, the enthalpy of SiC should be subtracted. There are many kinds of NiSi 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 G 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 G, while nickel carbide was not observed for positive G. Furthermore, nickel element is rich in the electroless composite coatings, and the final nickel silicide is Ni3Si after complete reaction. 3.3. Structures of electroless NiPSiC composite coatings From the XRD spectra in Fig. 4, it can be found that electroless NiPSiC composite coating is amorphous as

deposited. That is to say, the superfine particles do not change the structure of the NiP alloy during electroless plating. As shown in Fig. 4, the electroless composite coating crystallized into nickel crystal, nickel phosphide and nickel 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 NiPSiC composite coatings with superfine particles, one piece of composite coating with 110 nm SiC was striped from the substrate and heat treated at 600 C for 4 h. Then, the sample was dissolved in diluted nitric 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 NiPSiC composite coatings after completely heat treatment are mainly Ni, Ni3P, Ni3Si and C (free carbon). Electroless NiPSiC 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 NiPSiC composite coatings. We can find that the particles disperse in the NiP 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 SiC bond was broken.

Intensity (a.u.)

(1 1 1)

C A

100nm
Fig. 6. (a) TEM BF image and (b) SAD of A district in electroless NiPSiC composite coating after heat treatment at 400 C for 1 h.

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280nm

50 nm

200nm

Si

Ni

Fig. 7. (a) TEM BF and (b) local element analysis district in electroless NiPSiC 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 NiPSiC 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 5 5 ]. 3.4. Microhardness of electroless NiPSiC composite coatings Not only the reaction process of composite coatings is changed by superfine particles, but also properties of coatings are modified. Microhardness is an important property of electroless coatings, and the results of NiP and NiPSiC coatings as deposited and those after certain heat treatment are shown in Table 3. Microhardness values of electroless NiP SiC composite coatings as deposited increase because of the introduction of hard particles and dispersion strengthening. It can be seen in Table 3 that the microhardness of electroless Ni PSiC composite coating with 1000 nm particles increased 10% as high as that of electroless NiP alloy. With the fine SiC particles, the electroless composite coatings have low microhardness values. After crystallization, microhardness of coatings increases greatly because of the precipitation of hard intermetallic compound Ni3P. It is shown in Table 3 that the microhardness of electroless NiPSiC composite coatings raise to the maximum value (about HV501200) after heat treatment at 400 C for 1 h. After heat treatment at high temperature (e.g. 500 and 600 C), microhardness of composite coatings

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: 3Ni SiCNi3 Si C: 2

The volume variation of the composite coatings after reaction is expressed as: V V ns V c V n V s 3

where Vvolume change during reaction; Vnvolume of nickel matrix needed to react completely with SiC; Vsvolume of a SiC particle; Vnsvolume of reaction product (Ni3Si); Vcvolume of carbon (graphite). According to the data in references [14] and [16], one can obtain that the decrease of

Table 3 Microhardness of electroless NiP and NiPSiC composite coatings after heat treatment (HV50) Coatings As-deposited 300 C 1 h 400 C 1 h 500 C 1 h 600 C 1 h 1000 nm SiC 580 854 1206 967 807 110 nm SiC 537 860 1192 932 826 50 nm SiC 520 781 1186 966 888 NiP 510 776 1012 937 764

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a
SiC

Ni

c
231 112

5 nm

Fig. 8. (a) HREM fringe image of electroless NiPSiC 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 NiPSiC 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 NiPSiC 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 NiPSiC 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 PSiC composite coatings crystallized, and then reacted with SiC at high temperature. The crystallization temperature of NiPSiC 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

final products of the crystallization and reaction of composite coatings were Ni, Ni3P, Ni3Si and free carbon. (3) The microhardness of electroless NiPSiC composite coatings were higher than that of NiP 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. References
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