Surface and Coatings Technology 172 (2003) 9094

Electroless nickel plating on silicon carbide nanoparticles

Yujin Chena, Maosheng Caob,*, Qiang Xub, Jing Zhub
a

Department of Materials Science and Engineering, Harbin Engineering University, Harbin 150001, PR China b Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, PR China Received 4 November 2002; accepted in revised form 4 February 2003

Abstract By a simple and controlled method, that is, by electroless plating, nickel has been deposited on the surfaces of silicon carbon nanoparticles. Energy dispersive spectrometry (EDS) spectra show that pre-treatments of the silicon carbide nanoparticles have an important influence on the effect of electroless nickel plating. Transmission electron microscopy images and EDS spectra of silicon carbide nanoparticles before and after electroless nickel plating reveal that nickel has been deposited on the surface of silicon carbide nanoparticles and the deposited nickel and silicon carbide nanoparticles are bound tightly. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Electroless plating; Nickel; SiC; Nanoparticles

1. Introduction Silicon carbide with many excellent properties such as good thermal conductivity, good electrical conductivity, good chemical stability, high mechanical strength and low friction, can serve as both structured materials and functional materials w110x. Silicon carbide particles after deposition of metals are potential candidates for preparing absorbing materials, particle reinforced metal composite and other advanced materials. Because of many advantages of electroless nickel plating such as higher hardness, resistance to wear and corrosion resistance w11,12x, nowadays electroless plating is used in various fields from high-tech industries to traditional industries, especially after improvement of the working life and stability of the plating solution w1316x. Therefore, some researchers are applying electroless plating to low dimensional nanostructured materials. For example, some researchers have attempted to deposit metals or metal compounds on the surface of carbon nanotubes w1719x. As far as depositing metal on the surface of silicon carbide particles by electroless plating is concerned, the studies are focusing on the micron scale w20,21x, and there are very few reports on the electroless
*Corresponding author. E-mail address: caomaosh@mail.tsinghua.edu.cn (M. Cao).

deposits on silicon carbide nanoparticles. In this paper, we present a new route for electroless nickel plating on the surface of silicon carbide nanoparticles. The process of nickel deposition and pre-treatments of silicon carbide nanoparticles are reported in detail. 2. Experimental The silicon carbide nanoparticles used in this work were provided by Institute of Chemical Metallurgy, Chinese Academy of Sciences and prepared by high frequency plasma. The average size of those nanoparticles is 70 nm, of which mainly physical phase is a-SiC. Before electroless plating, the pre-treatments including oxidation, hydrophilic treatment and sensitizing treatment were performed. The oxidation was carried out at 200 8C in atmosphere for an hour. After oxidation, the surface of the nanoparticles became darker. Then the oxidized silicon carbide nanoparticles were put into a plastic bath, in which the hydrophilic treatment was carried out in order to remove metallic impurities that silicon carbide nanoparticles may contain and to improve hydrophilic properties of the nanoparticles. The plastic bath contained a hydrophilic solution of 10%HFy 10%HCl, in which the silicon carbide nanoparticles were ultrasonically dispersed for 20 min and the bath was kept at room temperature. And then the nanoparticles

0257-8972/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0257-8972(03)00320-7

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Fig. 1. Characterization of silicon carbide before electroless nickel plating. (a) TEM image of silicon carbide nanoparticles; (b) distribution of size of silicon carbide nanoparticles; (c) the selected area electron diffraction spectrum of silicon carbide nanoparticles; (d) the energy-dispersive spectrometry of silicon carbide nanoparticles.

rinsed with distilled water, filtered on microfilter and dried at room temperature. Sensitizing treatment was ultrasonically carried out in a 72 h aged solution of 0.1 M SnCl2 y0.1 M HCl at room temperature for 30 min, and then the sensitized silicon carbide nanoparticles were separated from the sensitizing solution with microfilter, rinsed with distilled water and dried at room temperature. After pre-treatments mentioned above, the silicon carbide nanoparticles were then introduced into an electroless plating bath. The electroless plating solution contains 0.25 M nickel chloride, 0.09 M nickel sulfate, 0.084 M sodium hypophosphite, 0.09 M sodium citrate, 1.84 M ammonium chloride and 2.7=10y3 M lead nitrate. During the plating process, the temperature and the pH value of the plating solution were maintained

at 25 and 8.7 8C, respectively, and the electroless plating was carried out for 30 min. The suspension was then filtered, washed with distilled water several times and dried at room temperature. The chemicals used in this experiment are all analyzed reagent products. The pH value of electroless plating solution was measured by PH-4C meter. Samples in the paper were characterized using a transmission electron microscopy (TEM) instrument (JEOL JEM 2010F) equipped with a Gatan GIF 678 (which used to analyze energy dispersive spectrometry (EDS) spectrum). 3. Results and discussion Fig. 1a shows the TEM image of silicon carbide nanoparticles before electroless plating. From the TEM

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Y. Chen et al. / Surface and Coatings Technology 172 (2003) 9094

Fig. 2. EDS spectra of silicon carbide nanoparticles after electroless nickel plating. (a) An EDS spectrum of silicon carbide nanoparticles after pre-treatments; (b) an EDS spectrum of silicon carbide nanoparticles without pre-treatments.

image, we can see that those particles are in triangle or hexagon. The size of them ranges from 20 to 300 nm, the average size is approximately 70 nm, and distribution of sizes of silicon carbide is shown in Fig. 1b. Obviously, aggregation of the particles occurred, resulting from high chemical activity of nanoparticles. The corresponding selected area electron diffraction spectrum in Fig. 1c indicates that silicon carbide particles used in this work are a-SiC. In addition, few diffraction points appeared in the spectra, of which reason is that the most crystal faces of the particles are {1 1 1}. The result of an EDS spectrum in Fig. 1d further reveals that the nanoparticles are composed of silicon and carbon. Fig. 2 is EDS spectra of silicon carbide nanoparticles after electroless nickel plating. Fig. 2a is an EDS spectrum of silicon carbide nanoparticles that performed the pre-treatments and Fig. 2b is an EDS spectrum of silicon carbide nanoparticles without the pre-treatments. The nickel peaks in the Fig. 2a are much higher than those in Fig. 2b. It has been proved that the pretreatments have a very important influence on the effect of electroless nickel plating. The reasons consist in the following facts. Oxidation can form some SiO2 points at the surface of silicon carbide nanoparticles. SiO2 will easily react with HF in the hydrophilic solution, of which formulation is represented as Eq. (1), and the product SiF4 on the surface of those nanoparticles can remarkably modify wettability of those nanoparticles and further increase the absorption velocity of tin-ion in

the sensitizing solution to the surface of those nanoparticles. In addition, those tin ions will react with nickel ion in the plating solution, of which formulation is represented as Eq. (2). These produced nickel particles are distributed on the surface of the nanoparticles and played as nucleation of nickel that subsequently deposited on the surface of the nanoparticles in the process of electroless plating. In sum, these factors led to increase in plating rate on the surface of silicon carbide nanoparticles. SiO2q4HFSiF4q2H2O Sn
2q

(1) (2)

qNi

2q

Sn

4q

qNi

Fig. 3a shows the low-magnification TEM image of silicon carbide nanoparticles after electroless nickel plating. From the figure, we can see that the color of silicon carbide nanoparticles turns darker, indicating that nickel has been deposited on their surface. The longitudinal high-magnification TEM image in Fig. 3b shows that some darker spots are found on the surface of the nanoparticles. The corresponding EDS spectrum in Fig. 3c and atomic image of silicon carbon (upper left set) at point a (in Fig. 3b) prove that these dark spots are nickels, which confirms that nickel has been deposited on the surface of silicon nanoparticles. Fig. 4 displays lateral high-magnification TEM image of silicon carbide particles, in which atomic image of nickel (upper left set) and that of silicon carbide (upper right set), respectively come from the point a and the

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Fig. 3. Characterization of silicon carbide nanoparticles after electroless nickel plating. (a) TEM image of silicon carbide nanoparticles; (b) the longitudinal high-magnification TEM image of silicon carbide nanoparticles; (c) the EDS spectrum of silicon carbide nanoparticles at point a.

point b in the Fig. 4. Those atomic images indicate that the main constituent of point a is nickel and that of point b is silicon carbide. In Fig. 4, we also find that the deposited nickel particles are embedded into silicon carbide nanoparticles. Those above results further prove that nickel is deposited on the surface of silicon carbide nanoparticles, and also reveal that the deposited nickel and the substrate silicon carbide are bound tightly.

4. Conclusions In summary, a method based on deposition of silicon carbide nanoparticles with nickel by electroless plating was proposed and demonstrated. This method is simple and inexpensive. Furthermore, it may be used to prepare a wide variety of nanoparticles. According to this work, pre-treatments of the silicon carbide nanoparticles are necessary before the electroless nickel plating of nickel. After pre-treatments the wettability and structure of surface of silicon carbide nanoparticles have been remarkably improved, which led to increase in electroless nickel plating rate on the surface of silicon carbide nanoparticles. The results of EDS spectra, atomic images and high-magnification TEM images reveal that nickel has been deposited on the surface of silicon carbide nanoparticles and the deposited nickel and silicon carbide are bound tightly. Acknowledgments This work was supported by the National Nature Science Foundation, National 973 Project of the Republic of China, the Nation Advanced Materials Committee of China, and 985 Project of Tsinghua University.

Fig. 4. The lateral high-magnification TEM image silicon carbide nanoparticles after electroless plating.

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