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Journal of Alloys and Compounds

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Inuence of SiC nanoparticles and saccharin on the structure and properties of electrodeposited NiFe/SiC nanocomposite coatings
Hamed Ataee-Esfahani a,b , M.R. Vaezi a, , Leila Nikzad a , Bahare Yazdani a , S.K. Sadrnezhaad a,b
a b

Materials and Energy Research Center, P.O. Box 14155-4777, Tehran, Iran Department of Materials Science and Engineering, Sharif University of Technology, P.O. Box 11365-9466, Tehran, Iran

a r t i c l e

i n f o

a b s t r a c t
In this study, NiFe/SiC nanocomposite coatings with smooth and crack-free surface were successfully prepared by means of the conventional electrodeposition in the presence of saccharin in electrolyte. The goal of this work was to investigate the effect of SiC nanoparticles and saccharin on the structure and properties of permalloy nanocomposite coatings. The nanocomposite coatings were characterized using optical and scanning electron microscopy, energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD) technique. The signicant variation in the crystallographic texture of the coatings was observed due to the addition of SiC nanoparticles and saccharin in the electrodeposition bath. Increasing the amount of saccharin in the electrolyte led to a change in the texture from a (2 0 0) ber texture to mixed (3 1 1) and (2 0 0) textures. Our results indicated that inclusion of SiC nanoparticles suppressed the preferred growth direction of the NiFe matrix, resulting in a decrease in the sharpness of the (2 0 0) ber texture and formation of a more random texture. The presence of SiC nanoparticles in the metallic matrix also led to the production of composite lms with better corrosion resistance and higher microhardness than the NiFe coating. 2009 Elsevier B.V. All rights reserved.

Article history: Received 15 December 2008 Received in revised form 28 April 2009 Accepted 29 April 2009

Keywords: Electrodeposition NiFe/SiC nanocomposite coating X-ray diffraction Microhardness Corrosion resistance Saccharin

1. Introduction In the last decade, a great deal of attention has been paid to the study of permalloy (80% Ni20% Fe), because of the widespread use of this material in applications involving micro-electromechanical-systems (MEMS) and mesoscopic systems [14]. NiFe coatings are easily produced using electrodeposition techniques. The deposited lms have been shown to have low residual stress, low energy requirement, rapid deposition rate, low cost, capability to handle complex geometry and to control the lm thickness, and simple scale-up with easily maintained equipment. Permalloy is introduced as a structural material for the LIGA (Lithographie, Galvanformung, Abformung, equivalent to lithography, electroplating and molding) method which is used to fabricate discrete, freestanding metallic parts and high-aspect ratio microstructures [2]. Saccharin is a strong leveling and grain renement agent, capable of decreasing internal stress in the permalloy coating [2,4]. Saccharin, as a sulfur-bearing additive, increases the sulfur content in the electrodeposited coating which is insoluble in permalloy. Sulfur segregation to grain boundaries after the coating is exposured to high temperatures, promotes grain boundary embrittlement and intergranular fracture [2].

Corresponding author. Tel.: +98 261 6204131; fax: +98 261 6201888. E-mail address: vaezi9016@yahoo.com (M.R. Vaezi). 0925-8388/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2009.04.146

The codeposition of inert particles in metallic coatings improves physical and mechanical properties of these coatings and forms a nanocrystalline metallic deposit due to the modied growth [511]. Since the electrodeposited composite coatings combine the advantages of both the electrodeposited coatings and codeposition of hard particles, NiFe nanocomposite coatings have properties superior to the NiFe alloy coatings [12,13]. Two articles related to the reinforcement of NiFe alloys with ceramic particles have been published in the past ve years. Li and Li [12] have studied the effect of Si3 N4 nanoparticles content and annealing on the microhardness of electrodeposited NiFe/Si3 N4 nanocomposites. More recently, Starosta and Zielinski [13] investigated the inuence of coating composition on corrosion and wear behavior of the NiFe/Al2 O3 composite coatings. However, to our knowledge, the electrodeposition of NiFe/SiC nanocomposite coatings has not been studied up to now. Due to the effect of microstructure on the physical and mechanical properties of nanocomposite coatings, it seems to be necessary to examine the inuence of some parameters such as embedded nanoparticles and organic additives, on the microstructure of the resulting nanocomposite coating. In this research, we reported the effect of saccharin and SiC nanoparticles on the microstructure of the permalloy nanocomposites, special attention was paid to the distribution of crystallographic orientations because texture can have a great inuence on physical and mechanical properties of coating due to the anisotropic properties. The relationship between

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SiC incorporation and nal performance such as the corrosion resistance and microhardness for deposited NiFe/SiC nanocomposite was also studied. Besides, in order to better understand the nature of the procedure of electrode reactions, the role of SiC nanoparticles in the electrodeposition of NiFe/SiC nanocomposite was analyzed.
2. Experimental In this study, the plating bath was composed of 112 g/l NiSiO4 6H2 O and 5 g/l FeSO4 as metal sources, 2 g/l boric acid as a buffer, 0.5 g/l sodium dodecylsulfate (SDS) as a surfactant and saccharin as a brightener and stress-reducer. Also, 1 g/l L-ascorbic acid was added to minimize Fe2+ oxidation. The concentration of saccharin was varied from 0 to 6 g/l to investigate the effect of saccharin addition on microstructure of the nanocomposite. Analytical reagents and distilled water were used to prepare the plating solution. With the aim to synthesis of NiFe/SiC nanocomposite, the SiC nanoparticles of a mean diameter 50 nm (Kaier, Hefei, China) with different concentrations (i.e. 0, 5, 10, 15, 20, 25 g/l) were dispersed in the electrolyte prior to plating. During the experiments, the electrolyte was agitated by a mechanical stirrer, as shown in Fig. 1. The pH of the electrolyte was 4, and temperature was kept constant at 50 C. NiFe/SiC nanocomposite was deposited onto polished copper substrate using a current density of 30 mA/cm2 . A platinum plate of 40 mm 40 mm was used as the anode. The distance between anode and cathode was 4 cm. Before each experiment, cathode was ultrasonically cleaned in ethanol, acetone and distilled water for 10 min, activated in 10% H2 SO4 for 30 s, washed in distilled water, before immediately immersed in the plating bath, to allow the electrodeposition of the target nanocomposite coatings. Deposits were ultrasonically cleaned in de-ionized water for 15 min in order to remove loosely adsorbed nanoparticles. The average thickness of deposited layers was about 50 m. All electrochemical experiments were performed in a three-electrode cell using an AUTOLAB PGSTAT 30 potentiostat/galvanostat device and an Ag/AgCl electrode (Argenthal, 3MKCl, 0.207 V vs. SHE at 25 C) was used as the reference electrode. The polarization curves of the electrolyte were recorded at a sweep rate of 1 mV/s. The Tafel curves were measured at a sweep rate of 1 mV/s in 0.5 M NaCl at room temperature. Surface morphologies of nanocomposite coatings were examined by a Philips MV2300 scanning electron microscope (SEM) operating at 25 kV. The chemical composition of the deposits was determined using the Kevex model energy dispersive X-ray spectroscopy (EDAX) system attached to the SEM. All chemical composition values are expressed in weight percent and represent the average of at least ve measurements. X-ray diffraction (XRD) was used to determine the present phases and the preferred orientation of the deposits. A Philips Xpert-Pro X-ray diffractometer with a Cu K radiation ( = 1.5418 ) was employed to obtain XRD spectra using standard 2 geometry. A computer-based search and match was used for phase identication. The hardness of the nanocomposite coatings was measured on a Vickers microhardness instrument at an applied load of 50 g for 5 s. Five measurements were conducted on each sample and the results were averaged.

Fig. 2. Cathodic potentiodynamic diagrams for co-deposited SiC nanoparticles with NiFe (20 g/l SiC in the electrolyte) and electrodeposited NiFe at a sweep rate 1 mV/s.

3. Results and discussion 3.1. Effect of SiC nanoparticles on permalloy electrodeposition Fig. 2 shows the potentiodynamic diagram plotted at various cathodic potentials with and without dispersed nanoparticles in the permalloy plating bath. The addition of silicon carbide nanoparticles affected the reduction curve by increasing the current densities. This behavior can be associated with two facts; on one hand, when introduced to the electrolyte, the SiC nanoparticles are surrounded by an adsorbed thin layer of metallic ions, resulting in a possible increase in ionic transport by nanoparticles. On the other hand, incorporation of nanoparticles increases the available nucleation sites for the metallic ions [1417]. 3.2. Effect of sachharin on the structure of NiFe/SiC nanocomposite The surface of electrodeposited nanocomposite coating in the solution with 20 g/l SiC nanoparticles (without saccharin in electrolyte) is shown in Fig. 3a. It is easily seen that the surface of coating has a network of cracks. It is attributed to very high-generated internal stress during NiFe/SiC electrodeposition, exceeding the fracture strength of the deposit [1820]. In contrast, as seen in Fig. 3b, the nanocomposite coating electrodeposited in the presence of saccharin has a smooth, shiny and crack-free surface, which can be explained by a decrease in internal stress due to the presence of saccharin [21,22]. NiFe/SiC composite coatings were electrodeposited with different saccharin concentrations in electrolyte containing 20 g/l SiC nanoparticles. Each electrodeposited lm was investigated by XRD technique to determine the crystalline structure and phase formation. The XRD patterns of the electrodeposited NiFe/SiC composite coatings for various saccharin concentrations are shown in Fig. 4. It can be seen that all the coatings exhibit single phase of NiFe matrix with FCC crystal structure. In order to describe the structure and preferred orientation of the deposit in detail, the TC is used, as dened in Eq. (1): TC(hkl) = I(hkl) 1 I0 (hkl) n I(hkl) I0 (hkl)
1

(1)

Fig. 1. Schematic diagram of the electrodeposition system.

where I (hkl) is the measured intensity of the (hkl) reection, I0 (hkl) is standard intensity of the standard powder pattern diffraction data (JCPDS 47-1417), n is the number of reections used in the

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Fig. 5. TCs of the electrodeposited NiFe/SiC composite coating as a function of saccharin concentration.

calculation. It is noteworthy that if TC is greater than 1, it indicates the existence of a preferred orientation [22,23]. Fig. 5 illustrates the relationship between the saccharin concentration in electrolyte and the TCs of composite coating. When the saccharin concentration was less than 2 g/l, the preferred orientation of the electrodeposited nanocomposite was the (2 0 0) ber texture. However, by further increasing saccharin, the (2 0 0) ber texture diminished and (3 1 1) ber texture strongly developed. In addition, (2 2 0) ber texture, which was negligible at low concentration of saccharin starts to develop with increasing saccharin concentration. So, it was observed that as the amount of saccharin increased, the crystal orientation progressively changed from a (2 0 0) ber texture to mixed (3 1 1) and (2 0 0) textures. The calculated TC of each diffraction line and total TCs of diffraction lines of each coating in Fig. 4 are listed in Table 1. The results suggesting that microstructure of the NiFe matrix is signicantly changed due to the addition of saccharin to the plating bath are in agreement with earlier observations in other electrodeposition systems [22,24,25]. 3.3. Effect of SiC incorporation on the structure of NiFe/SiC nanocomposite The SEM images (Fig. 6) show the nodular surface structure of the NiFe/SiC nanocomposite coating. It is observed that the SiC nanoparticles are covered by a NiFe layer. It can be due to the reduction of the adsorbed layer of metallic ions on SiC nanoparticles [14,26]. Embedded particles are uniformly distributed in the NiFe matrix which is conrmed by EDX analysis. Agglomeration of the co-deposited SiC nanoparticles is also seen on the magnied image of nanocomposite coating surface (See Fig. 6b). It is attributed to the fact that nanoparticles strongly tend to agglomerate due to their activity. [27]. Fig. 7 shows the XRD patterns of NiFe/SiC composite coatings with different SiC contents. It is observed that incorporation of SiC nanoparticles has affected the XRD patterns and crystallographic texture. X-ray diffraction line broadening analysis was employed for the determination of crystallite size. Pure NiFe deposit exhibTable 1 The calculated TC of each diffraction line and the total TCs of diffraction lines of each coating in Fig. 4. Saccharin concentration (g/l) 0 2 4 6 TC2 0 0 1.57 1.44 1.41 1.30 TC1 1 1 0.92 0.94 0.94 0.96 TC3 1 1 0.51 0.62 1.47 1.53 TC2 2 0 0 0 0.18 0.21 Total TCs of diffraction lines 3 3 4 4

Fig. 3. Electrodeposited NiFe/SiC nanocomposite without sachharin (a) and with 2 g/l saccharin (b) in electrolyte containing 20 g/l SiC.

Fig. 4. XRD patterns of NiFe/SiC composite coatings with saccharin concentrations of (a) 0, (b) 2, (c) 4, and (d) 6 g/L.

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Fig. 8. TCs of the electrodeposited NiFe/SiC composite coating as a function of SiC content in coatings.

Fig. 6. SEM image of surface morphology of NiFe/2.5% SiC nanocomposite coating (a) and the magnied image (b).

ited a crystallite size of 22 nm (reference to (2 0 0) reection). The codeposition of SiC nanoparticles (2.5 wt%) decreased the crystallite size of the deposit to 10 nm. During the electrodeposition process a competition occurred between the nucleation sites and crystalline growth. When introduced to the electrolyte, the SiC nanoparticles provided more nucleation sites for the metallic ions and perturbed the crystalline growth of NiFe deposit. Subsequently, a nanocrystalline structure was facilitated by incorporation of SiC nanoparticles. In order to study the effect of SiC content on microstructure of NiFe/SiC coatings, the TC was calculated according to Eq. (1). It

is evident from Fig. 8 that all of the electrodeposited coatings have (2 0 0) preferred orientation. But, it should be mentioned that (2 0 0) ber texture of the NiFe/SiC decreases with increasing SiC content from 0 to 2.5 wt%, in spite of the fact that (1 1 1) and (3 1 1) ber textures are slowly developed. The increasing of (1 1 1) and (3 1 1) ber textures can be linked with the reinforcement of [2 1 1] crystalline orientation [28]. From the TC values, it can be concluded that the embedding of silicon carbide nanoparticles results in more random distribution of crystallographic orientation and textural modication from [1 0 0] to the mixed [2 1 1] orientation. It can be attributed to the suppression of the preferred growth direction, due to the codeposition of SiC nanoparticles during the electrodeposition process [2830]. The amounts of TC of each diffraction line and total the TCs of diffraction lines of each coating in Fig. 7 are listed in Table 2. 3.4. Effect of SiC incorporation on the corrosion and microhardness of NiFe/SiC nanocomposite According to the literature, a uniform distribution of SiC nanoparticles yields in improved mechanical and corrosion resistance properties [5]. The effect of the SiC content in the coating on the microhardnesss of the NiFe/SiC composite coating layer was investigated. It is evident from Fig. 9 that the microhardness of the NiFe/SiC increased with increasing SiC content in the coating, similar to what was reported on NiFe/Si3 N4 nanocomposite coatings [12]. The hardening effect can be associated with uniform dispersion of SiC nanoparticles in the NiFe matrix that yields in ne grain size and dispersion strengthening [8,3134]. The corrosion rate of NiFe coatings containing SiC nanoparticles was also investigated. Fig. 10 shows the anodic polarization curves for NiFe alloy and NiFe/SiC nanocomposite coating in 0.5 M/l NaCl solutions. The values of corrosion potential and current density were estimated using Tafel slope method. The corrosion potential and corrosion current density of the nanocomposite were found to be 254 mV and 5.1 105 A/cm2 , respectively, and those for the NiFe alloy coating were determined to be 314 mV and 9 104 A/cm2 . The obtained results reveal that the presence of
Table 2 The calculated TC of each diffraction line and the total TCs of diffraction lines of each coating in Fig. 7. SiC content (wt%) 0 0.85 1.44 2.5 TC1 1 1 0.39 0.83 0.88 0.99 TC2 0 0 1.61 1.58 1.5 1.28 TC3 1 1 0 0.59 0.62 0.73 Total of the TCs of diffraction lines 2 3 3 3

Fig. 7. XRD patterns of NiFe/SiC composite coatings (in the presence of 2 g/L saccharin) with different SiC contents: (a) 0, (b) 0.8, (c) 1.4, and (d) 2.5 wt%.

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was proved to be necessary for obtaining smooth and crack-free deposits. Saccharin addition also affected the crystallographic texture of the NiFe matrix. It was indicated that as the concentration of saccharin increased, ber texture changed from a (2 0 0) ber texture to mixed (3 1 1) and (2 0 0) textures. In this study, it was established that incorporation of SiC nanoparticles suppressed the preferred growth direction of the NiFe deposit, and a more random texture was produced as a result. The texture studies determined (2 0 0) ber texture of the NiFe/SiC decreased with increasing SiC content, in spite of the fact that (1 1 1) and (3 1 1) ber textures developed. According to the experimental ndings, the microhardness and corrosion resistance of the nanocomposite coatings were enhanced with the increasing of SiC nanoparticles content. Enhanced microhardness was attributed to the smaller grain size and dispersion strengthening effect of the embedded hard SiC nanoparticles.
Fig. 9. Effect of SiC content in coatings on the microhardness of NiFe/SiC composite coatings.

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Fig. 10. Potentiodynamic polarization behavior of NiFe and NiFe/2.5% SiC composites in 0.5 M NaCl solution using a scan rate of 1 mV/s.

nanosized SiC particles in the deposit gives better corrosion resistance than a pure layer which is in agreement with our previous study for the electrodeposited NiSiC nanocomposite [5]. It is considered that when SiC nanosized particles are embedded in the alloy matrix, the defect size of nanocomposite coating can be reduced. These SiC nanoparticles also act as inert physical barriers to the initiation and development of defect corrosion, hence improve the corrosion resistance of the coating [5,32]. 4. Conclusion NiFe/SiC nanocomposite coatings were successfully electrodeposited in the presence of saccharin. The presence of saccharin

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