Surface & Coatings Technology 205 (2011) 41244134

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Effect of electrodeposition conditions and reinforcement content on microstructure and tribological properties of nickel composite coatings
Tushar Borkar, Sandip P. Harimkar
School of Mechanical and Aerospace Engineering, Oklahoma State University, Stillwater, OK, 74078, United States

a r t i c l e

i n f o

a b s t r a c t
In this work, pure nickel and nickel composite coatings (NiAl2O3, NiSiC, and NiZrO2) were deposited from Watts bath using direct current (DC), pulsed current (PC), and pulsed reverse current (PRC) electrodeposition conditions. Detailed investigations on the effect of deposition conditions on the evolution of surface microstructure, crystallographic micro-texture, microhardness, and sliding wear behavior of pure nickel and nickel composite coatings are presented. For all the coatings, the PC and PRC deposition conditions resulted in more random/weak crystallographic texture compared to DC deposition. The composite coatings deposited using PC and PRC deposition also exhibited signicant improvement in microhardness and wear resistance due to enhanced reinforcement of nanoparticles in the coatings. Also, the effect of nanoparticle content of the electrolyte bath on the surface microstructure, tribological properties, and level of reinforcement in the NiAl2O3 composite coating is investigated. The reinforcement of nanoparticles in the NiAl2O3 composite coatings increased linearly with the amount of nanoparticle loading in the electrolyte bath. The microhardness and wear resistance of the NiAl2O3 composite coatings also improved with increasing Al2O3 content in the coatings. 2011 Elsevier B.V. All rights reserved.

Article history: Received 17 November 2010 Accepted in revised form 23 February 2011 Available online 26 February 2011 Keywords: Electrodeposition Composite coatings Wear resistance X-ray diffraction Microhardness Surface roughness

1. Introduction Electrodeposition or electroplating is one of the most technologically feasible and economically superior techniques for producing metallic coatings. Direct current (DC) electrodeposition methods are commonly used for fabrication of metallic as well as composite coatings. In general, the composite coatings have better microhardness as well as wear resistance [15]. While the DC electrodeposition methods are very simple with a constant applied current throughout the process, the processes are often associated with slower deposition rates and coating defects (surface roughness, porosity, poor adhesion, undesirable microstructure, etc.). Recently, pulse current (PC) and pulse reverse current (PRC) electrodeposition methods have attracted signicant attention to improve deposition rates and microstructure of the coatings for better mechanical and corrosion properties [6,7]. In the PC and PRC electrodeposition methods, the current can be periodically altered between two values (positive and zero for PC, and positive and negative for PRC). The zero current (for PC) or reverse current (for PRC) effectively discharges the electric double layer formed around the cathode and allows better penetration of ions towards cathode (hence higher deposition rates) [8]. Furthermore, the zero current (for PC) or reverse current (for PRC) allows better distribution of ions in the

Corresponding author. Tel.: +1 405 744 5900; fax: +1 405 744 7873. E-mail address: sandip.harimkar@okstate.edu (S.P. Harimkar). 0257-8972/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2011.02.057

electrolyte and improves the quality of deposited coatings. The DC, PC, and PRC electrodeposition methods have been used to fabricate metallic coatings. Qu et al. have reported signicant improvement in hardness of PC electrodeposited nickel coatings compared to DC electrodeposition [9]. Tao et al. have investigated tribological and mechanical properties of nanocrystalline copper coatings deposited using DC and PC electrodeposition [10]. The copper coatings deposited by PC electrodeposition technique exhibited higher hardness and better wear resistance compared to DC electrodeposited coatings. It has been also been reported that the pure nickel coatings deposited by PC and PRC techniques show better corrosion resistance compared to DC electrodeposited coatings [6]. The pulse electrodeposition methods can also be used to deposit metal matrix composite coatings through codeposition process. In the codeposition process, ne (micro- and nano-scale) particles of metallic, non-metallic compounds or polymers from an electrolytic bath are incorporated into the electroplated coating to improve coating properties, such as hardness/strength, toughness, wear/friction resistance, and corrosion resistance [1123]. Several models have been proposed to explain the incorporation of particles from the electrolyte bath into the deposited coatings. According to Guglielmi's model, composite electroplating takes place in two steps: transportation of solid particles surrounded by adsorbed ions to the cathode and adsorption of particles on cathode followed by entrapment in coating [15,24,25]. A widely accepted model that accounts for the particle transport due to agitation in the electrolyte bath was proposed by Kurozaki [18,25]. While complete understanding of the mechanisms of

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co-deposition process is still not reached, several compositions of codeposited composite coatings reinforced with various nanoparticles (such as Al2O3, SiC, CNTs, ZrO2, Si3N4, and WC) into metal matrix have been reported. Wang et al. have investigated mechanical and tribological behavior of codeposited Al2O3Cu(Sn), CaF2Cu(Sn), and talcCu(Sn) composite coatings [26]. Al2O3Cu(Sn) composite coatings exhibited better hardness and wear resistance than other composite coatings due to high hardness of alumina nanoparticles. Arai et al. have reported codeposition of copper matrix composite coatings reinforced with multiwall carbon nanotubes (MWCNT) [27]. The MWCNT reinforcement in the composite coatings signicantly improved hardness, electrical conductivity, and thermal conductivity of the composite coatings. Rajiv et al. have investigated corrosion behavior of CoSi3N4 composite coatings [28]. CoSi3N4 composite coatings exhibited better corrosion resistance compared to pure Co coatings. Hashimoto and Abe also reported better corrosion resistance of codeposited ZnSiO2 composites due to formation of protective corrosion products supported by SiO2 [29]. Pavlatau et al. have reported that pulse electrodeposition method signicantly improves microhardness of NiSiC composite coatings primarily due to grain renement and increasing concentration of SiC in the coatings [30]. Srivastava et al. also investigated electrodeposion of nickel composite coatings using SiC, Si3N4, and Al2O3 nanoparticles and reported that NiSi3N4 composite coatings exhibit better microhardness and wear resistance compared to NiSiC and NiAl2O3 composite coatings [31]. While synthesis of various metal matrix composite coatings using pulse electrodeposition method have been widely reported [11,3234], systematic investigations on the effect of plating conditions (DC, PC, PRC) on the development of microstructure, crystallographic micro-texture, and mechanical properties have not been conducted. In this paper, we are presenting such investigations for nickel matrix composite coatings reinforced with a variety of reinforcements (Al2O3, SiC, ZrO2 nanoparticles). The nickel composite coatings are expected to increase the abrasion resistance of metal surfaces in microdevices. Also, the effect of nanoparticle content of the electrolyte bath on the surface microstructure, tribological properties, and level of reinforcement in the PC electrodeposited NiAl2O3 composite coating is investigated.

Table 1 Overview of the process parameters for electrodeposition of nickel and nickel composite coatings. Electrodeposition Parameters Direct Current (DC) Electrodeposition Current Density Electrolyte Agitation (Magnetic Stirring) Pulse Current (PC) Electrodeposition Peak Current Density Electrolyte agitation (Magnetic stirring) Duty Cycle Frequency Pulse Reverse Current (PRC) Electrodeposition Forward Peak Current Density Electrolyte Agitation (Magnetic Stirring) Forward Duty Cycle Forward Frequency Forward Duration Reverse Peak Current Density Reverse Duty Cycle Forward Frequency Reverse Duration 3 A/dm2 200 rpm 3 A/dm2 200 rpm 20% 10 Hz 3 A/dm2 200 rpm 10% 1000 Hz 200 ms 3 A/dm2 20% 1000 Hz 50 ms

2.2. Characterization of electrodeposited Ni and nickel composite coatings The surface morphology and microstructure of the pure nickel and Ni composite coatings were examined using scanning electron microscope (SEM). The surface roughness of composite coatings was measured using perthometer having measuring range up to 150 m (Mahr). The roughness was measured over a tracing length of 5.6 mm. The surface roughness parameters Ra and Rz were used for analysis. The weight percentage of nanoparticles in the composite coatings was calculated using Energy Dispersive X-ray spectroscopy (EDS). The weight percentages of particles were measured at 5 different locations at same magnication of the images. The mean values are reported along with positive and negative error bars. The phase analysis of the coatings was conducted using Philips Norelco X-ray Diffractometer operating with Cu K ( = 1.54178 ) radiation at 45 kV and 40 mA. The diffraction angle (2) was varied between 30 and 80 with a step increment of 0.02 and count time of 1s. This range covers two strongest peaks of nickel. Most of the reported papers on electrodeposition of nickel indicate development of texture in these primary directions because these are the preferred growth directions for FCC metals [9,35]. The crystallite size for nickel and nickel composite coatings was calculated using Scherrer equation [36]. FWHM = K 180 ; D Cos 1

2. Experimental procedure 2.1. Electrodeposition of nickel and nickel composite coatings In this investigation, pure nickel and nickel composite coatings were prepared by electrodeposition from Watt baths with pure nickel plate (Surface Area: 100 cm2) as an anode and stainless steel substrate (Surface Area: 8 cm2) as a cathode. The Watts bath consisted of NiSO4.6H2O (265 g/L), NiCl2.6H2O (48 g/L), and H3BO3 (31 g/L). For depositing composite coatings (NiAl2O3, NiSiC, and NiZrO2), the electrolyte bath was suspended with 20 g/L of constituent nanoparticles supplied by Inframat Corporation (Manchester, CT): Al2O3 (150 nm), SiC (3060 nm), or ZrO2 (200 nm). All the coatings were fabricated using DC, PC, and PRC electrodeposition methods with deposition time of 60 mins. The processing parameters corresponding to these electrodeposition conditions are given in Table 1. The parameters selected in the present investigation are based on previous published reports. These are the optimum parameters that give adherent and uniform coatings on the substrates. To investigate the effect of reinforcement content on the microstructure and properties of coatings, NiAl2O3 composite coatings were also prepared from Watt baths suspended with varying amount of Al2O3 nanoparticles: 0, 5, 10, 20, and 40 g/L (PC electrodeposition method with deposition time of 8 hrs). For all the composite electrodeposition experiments, the electrolyte was magnetically stirred for about 24 hrs to suspend the nanoparticles in the electrolyte. After electrodeposition, all the coatings were ultrasonically cleaned using deionized water, and then dried to prepare for further characterization.

where FWHM is full width half maxima in 2 degrees, D is the crystallite size in nm, K is constant (usually evaluated as 0.94), and is the wavelength of Cu K radiation (0.154 nm). To quantify the relative crystallographic textures associated with nickel and nickel composite coatings, texture coefcients (TC) for predominant (h k l) peaks in XRD patterns were calculated. The texture co-efcient (TC) for each (h k l) reection is given by [37]: TC h k l =   I h k l 1 Ih k l 1 ; I0 h k l n I0 h k l 2

where I(h k l) are measured intensities of (h k l) reection, I0(h k l) are powder diffraction intensities of nickel, and n is the number of reections used in the calculations. In this case, (111) and (200) reections were considered for texture coefcient calculation (n = 2). A microhardness tester (Buehler) was used for measuring hardness by performing Vickers indentations at a loading force of 100 g and holding time of 15 s. At least 10 measurements of hardness were made, and the

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average value is reported along with positive and negative error bars. For all the coatings, the hardness was in the range of ~350500 HV; this translates into indentation depth of ~4 m. As the thickness of deposited coatings (~80150 m) was signicantly greater than 10 times the depth of indentation, the reported values of hardness are representative of the deposited coatings without signicant inuence from underlying

substrate. Dry (unlubricated) wear tests were performed on a ball-ondisc tribometer (Nanovea) at room temperature. An alumina ball (diameter 6 mm) was used as a counter body. The wear tests were conducted in dry atmosphere (relative humidity ~ 50%) using load of 20 N, sliding velocity of 200 rpm, and track diameter of 4 mm (total sliding distance = 753.6 m). The optimum wear test parameters, such as

Fig. 1. Surface micrographs from (ac) pure nickel, (df) NiAl2O3, (gi) NiSiC, and (jl) NiZrO2 coatings are deposited by DC, PC, and PRC electrodeposition methods.

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load and sliding velocity that provide measurable weight loss, were obtained after multiple experiments. The position of the specimen on the tribometer was maintained after each weight-loss reading such that wear continues on the same worn track during continued wear testing. 3. Results and discussion 3.1. Effect of Plating Conditions (DC, PC, PRC) on Microstructure and Properties of Pure Nickel and Nickel Composite Coatings (Ni, NiAl2O3, NiSiC, and NiZrO2) 3.1.1. Coating surface morphology SEM micrographs showing surface morphologies of DC, PC, and PRC electrodeposited pure nickel (Ni) and nickel composite (NiAl2O3, NiSiC, and NiZrO2) coatings are presented in Fig. 1. Also, the variation of surface roughness parameters (Ra and Rz) with plating conditions for these coatings is shown in Fig. 2. The Ni coatings fabricated using PC and PRC technique exhibited better uniformity and ner grain structure compared to the coatings obtained by DC deposition techniques. High instantaneous current density during PC and PRC deposition seems to promote the nucleation of the grains on the surface resulting in ner grain structure in the Ni coating. The PRC deposited Ni coatings exhibited lowest surface roughness values (Ra b 50 nm; Rz~ 0.3 m). The surface roughness values for the DC deposited Ni coatings were highest (Ra ~ 75 nm; Rz~ 0.5 m). All the nickel composite coatings (Ni Al2O3, NiSiC, and NiZrO2) exhibited higher surface roughness compared to pure nickel coatings. For the nickel composite coatings, the PC plating condition resulted in uniform and ner microstructure of the coatings. The values of surface roughness parameters for these PC codeposited composite coating were minimum (Ra ~ 120150 nm;

Rz ~ 0.91.1 m). The surface microstructures of the DC codeposited composite coatings show coarser granular features resulting in highest surface roughness values for these coatings. The surface microstructure of the PRC codeposited NiAl2O3 composite coatings show surface inhomogeneities due to agglomeration of the Al2O3 particles on the surface. This also resulted in higher values of surface roughness parameter for PRC codeposited composite coatings. 3.1.2. Coating composition The variation of weight percentage of reinforced nanoparticles in the nickel composite coating as a function of co-deposition conditions (DC, PC, and PRC) is shown in Fig. 3. For all the composite coatings (NiAl2O3, NiSiC, and NiZrO2), the gure clearly indicates signicantly increased reinforcement content in the coating prepared by PC and PRC co-deposition. The reinforcement content is minimum in the coatings deposited using DC co-deposition. As mentioned earlier, the periodic alternation of current (between positive and zero values for PC, and between positive and negative values for PRC) discharges the electric double layer formed around the cathode, and thereby allowing better penetration of nanoparticles (with adsorbed ions on the surface) towards cathode [8]. The adsorbed ions on the surface of the nanoparticles subsequently get reduced at the cathode causing entrapment (reinforcement) of the nanoparticles in the growing coating. Also, for the similar codeposition conditions (DC, PC, or PRC), the reinforcement content of alumina in the NiAl2O3 composite coating is greater than zirconia in the NiZrO2 and silicon carbide in the NiSiC composite coatings. While exact mechanism for this observation is not yet known, this seems to be due to distinctly different size/density of the nanoparticles, surface properties (hydrophobicity/hydrophilicity, zeta potential), and their interactions with the ions in the electrolyte [23]. 3.1.3. Crystallite size and crystallographic texture The X-ray diffraction (XRD) patterns for pure nickel and nickel composite (NiAl2O3, NiSiC, and NiZrO2) coatings deposited by DC, PC, and PRC plating conditions are presented in Fig. 4. All the XRD patterns show typical peaks corresponding to (111) and (200) crystallographic planes of nickel. Note that the peaks corresponding to reinforced nanoparticles (i.e. Al2O3, SiC, and ZrO2) could not be resolved in XRD patterns from composite coatings due to very low reinforcement content. To understand the inuence of electrodeposition condition (DC, PC, and PRC) on the development of coating microstructure and microtexture, detailed analysis of XRD patterns was conducted. Table 2 shows crystallite sizes for all the nickel and nickel composite coatings

Fig. 2. Surface roughness of nickel and nickel composite coatings deposited by DC, PC, and PRC electrodeposition methods: (a) Ra, and (b) Rz.

Fig. 3. Reinforcement contents (wt.% of nanoparticles) in nickel composite coatings deposited by DC, PC, and PRC electrodeposition methods.

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Fig. 4. X-ray diffraction patterns from (a) pure nickel, (b) NiAl2O3, (c) NiSiC, and (d) NiZrO2 composite coatings deposited by DC, PC, and PRC electrodeposition methods.

calculated using FWHM of prominent (111) reection in Scherrer equation. For all the coatings, crystallite size of the nickel matrix is less than 50 nm. The composite coatings deposited by PC method showed slightly lower crystallite sizes of nickel compared to DC and PRC technique. For all the coatings deposited using DC electrodeposition, the intensity of (200) peaks is highest indicating preferred orientation of (200) planes parallel to coating surface. Apparently, [100] is the preferred grain growth direction for face ceneterd cubic crystals. Note that (111) peak at 2 = 44.508 is the strongest peak (relative intensity = 100%) in the standard XRD pattern from randomly oriented polycrystalline nickel (JCPDS: 040850). As indicated in the gure, the intensity of (111) peaks in the XRD patterns of pure nickel and nickel composite coatings increased for PC and PRC deposition indicating more random crystallographic texture in these coatings (approaching that in standard XRD pattern from randomly oriented polycrystalline nickel). The atomic density of (111) plane is higher than that of (200) plane in FCC crystal structure of nickel, so surface energy of (111) plane is lower than that of (200) plane. It seems that nickel atoms migrate from higher energy (100) planes to lower energy (111) planes during zero current time (for PC) and reverse current time (for PRC) resulting in random texture in these coatings [11]. Table 3 summarizes the results of texture coefcient calculations for the observed (111) and (200) reections in pure nickel and nickel composite coatings. The texture coefcients for (111) and (200)

reections of standard randomly oriented polycrystalline sample (JCPDS: 040850) are unity. For all the coatings (except PRC codeposited NiZrO2), the (200) texture coefcient for DC deposition is greater than that for PC and PRC deposition indicating strong (100) crystallographic texture in these coatings. However, the (111) texture coefcients for all the coatings (except PRC deposited NiZrO2) are greater for PC and PRC deposition compared to that for DC deposition. This again indicates relatively random orientation in PC and PRC deposited coatings compared to DC deposition.

3.1.4. Microhardness and wear resistance The variation of microhardness of pure nickel and nickel composite (NiAl2O3, NiSiC, and NiZrO2) coatings with deposition
Table 3 Texture coefcients (TCs) of various (hkl) planes for standard sample, pure nickel, and nickel composite coatings. Coatings Texture Coefcient (TC) (111) Standard Sample Pure Nickel DC PC PRC NiAl2O3 DC PC PRC NiSiC DC PC PRC NiZrO2 DC PC PRC 1 0.24 0.64 0.47 0.06 0.10 0.39 0.06 0.27 0.11 0.14 0.29 0.09 (200) 1 1.76 1.36 1.53 1.93 1.90 1.61 1.94 1.73 1.89 1.86 1.71 1.90

Table 2 Crystallite size for pure nickel and nickel composite coatings. Coatings Crystallite Size (nm) DC Pure Nickel NiAl2O3 NiSiC NiZrO2 46 37 37 35 PC 37 30 32 28 PRC 42 34 35 34

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coatings, the wear weight loss was found to be decreased from DC to PC and PRC deposition conditions due to increasing hardness of the coatings (resulting from increasing reinforced nanoparticle content for composite coatings and texture related effects in pure nickel coatings). Due to complexity of the parameters such as rpm, load, counter-body material/hardness, surface roughness/hardness/microstructure of the coatings, it is extremely difcult to compare the wear testing data from one work with that in the other. Very rarely such comparisons are found in the existing literature. Most of the literature reports present relative wear performance of various coatings testing under similar wear testing conditions.

Fig. 5. Microhardness of pure nickel and nickel composite coatings deposited by DC, PC and PRC electrodeposition methods.

3.2. Effect of reinforcement content on microstructure and properties of NiAl2O3 composite coatings 3.2.1. Coating composition, surface morphology, and thickness To understand the inuence of reinforcement content on the microstructure and properties of composite coatings, several NiAl2O3 coatings were deposited by varying the content of Al2O3 nanoparticles in the electrolytic bath (5, 10, 20, and 40 g/L). The variation of Al2O3 content in the nickel composite coatings as a function of content of Al2O3 nanoparticles in the electrolytic bath is shown in Fig. 7. The wt.% of alumina in the composite coatings (deposited using similar electrodeposition parameters) signicantly increases with increasing alumina content in the electroplating bath. The surface morphologies of the pure nickel coating and NiAl2O3 composite coatings, deposited with varying content of Al2O3 nanoparticles in the electrolytic bath (5, 10, 20, and 40 g/L), are presented in Fig. 8. As the Al2O3 nanoparticles content increases the coating surfaces become increasingly inhomogeneous with appearance of coarser granular features. As such, the surface roughness of composite coatings increases with increasing Al2O3 reinforcement in the coatings (Fig. 9). The NiAl2O3 composite coatings deposited from electrolyte bath with 40 g/L alumina exhibited maximum surface roughness. The cross-sectional images of pure nickel and NiAl2O3 composite coatings deposited using similar pulse electrodeposition parameters are shown in Fig. 10. All the coatings were uniform, crack-free, and homogeneous. Interestingly, the pure nickel coatings were signicantly thicker than NiAl2O3 composite coatings deposited using similar electrodeposition conditions (Fig. 11). Also, the thickness of composite coatings decreased with increasing alumina incorporation in the composite coatings. It seems that the reinforced alumina particles in the composite coatings act as physical barriers to grain growth and slow down the growth rate (hence thinner composite coatings). While hydrogen evolution at the cathode can also result in coating thickness reduction, such effects are not very strong in case

conditions (DC, PC, and PRC) is presented in Fig. 5. In general, hardness of the coatings increases with this order of deposition conditions: DC, PC, and PRC. The improvement in the hardness of pure nickel coatings with PC and PRC deposition conditions is very small (b50 HV). This seems to be due to changes in crystallographic texture in pure nickel coatings with the deposition conditions. As discussed earlier, this order of deposition conditions (DC, PC, and PRC) also resulted in increasing content of reinforced nanoparticles in the coatings. Thus, the improvements in the hardness of composite coatings with PC and PRC deposition conditions seem to be due to increased content of reinforced hard particles in the coatings. Also, for all the deposition conditions, the hardness of composite coatings is higher than pure nickel coatings. This seems to be a direct consequence of dispersion strengthening effect where reinforced hard particles in the matrix obstruct the motion of dislocations. Furthermore, the NiAl2O3 composite coatings exhibit highest hardness and the NiSiC coatings exhibit lowest hardness for each deposition condition (DC, PC, or PRC). Note that SiC particles (hardness: ~2243 HV) are harder than Al2O3 (hardness: ~ 1530 HV) and ZrO2 (hardness: ~ 1326 HV) particles. As such, the highest hardness of NiAl2O3 composite coatings seems to be due to relatively larger content of Al2O3 (in NiAl2O3) than SiC (in NiSiC) and ZrO2 (in NiZrO2) in coatings for each deposition condition (Fig. 3). The wear weight loss of pure nickel and nickel composite coatings (NiAl2O3, NiSiC, and NiZrO2) coatings with deposition conditions (DC, PC, and PRC) is presented in Fig. 6. The pure nickel coatings for all the deposition conditions showed maximum weight loss compared to nickel composite coatings. This is a direct consequence of the lower microhardness of the pure nickel coatings compared to nickel composite coatings. Also, the NiAl2O3 composite coatings, which are hardest among all the composite coatings, showed least weight loss. For all the

Fig. 6. The variation of weight loss for pure nickel and nickel composite coatings deposited by DC, PC and PRC electrodeposition methods.

Fig. 7. Reinforcement content (wt.% of Al2O3 nanoparticles) in the NiAl2O3 composite coatings as a function of nanoparticle loading in the electrolyte bath.

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Fig. 8. Surface micrographs from PC electrodeposited (a) pure nickel (0 g/L), (b) NiAl2O3 (5 g/L), (c) NiAl2O3 (10 g/L), (d) NiAl2O3 (20 g/L), and (e) (NiAl2O3 (40 g/L) coatings deposited from electrolyte bath with varying content of suspended nanoparticles.

of electrodeposition from watts bath. Furthermore, boric acid in the electrolyte is known for suppressing the hydrogen evolution during electrodepostion of nickel from watts bath. No change in pH value of the electrolyte after the electrodeposition experiments was observed. 3.2.2. Crystallographic texture The X-ray diffraction (XRD) patterns of pure nickel and NiAl2O3 composite coatings, deposited with varying content of Al2O3 nano-

Fig. 9. Surface roughness of nickel and NiAl2O3 composite coatings as a function of nanoparticle content in the electrolyte bath.

particles in the electrolytic bath are shown in Fig. 12. The XRD patterns show typical peaks corresponding to (111) and (200) crystallographic planes of pure nickel at 2 positions 44.508 and 51.847, respectively. Note that the peaks corresponding to reinforced Al2O3 nanoparticles could not be resolved in XRD patterns from composite coatings due to very small size of the nanoparticles and low reinforcement content. Detailed analysis of XRD patterns is necessary to understand effect of alumina reinforcement on the development of coating microstructure and microtexture. The crystallite sizes for pure nickel and NiAl2O3 composite coatings, calculated from FWHM using Scherrer's equation, are presented in Table 4. For all the coatings, crystallite size of the nickel matrix is less than 40 nm. While the data shows slight decrease in crystallite size with incorporation of Al2O3 nanoparticles in the coating, this calculated data should be used only as general information. For more accurate analysis of the crystallite and grain size in nano-scale range, high resolution transmission electron microscopy (TEM) needs to be done. A careful analysis of XRD patterns also revealed distinct difference in the relative intensities of primary (hkl) peaks from nickel and NiAl2O3 composite coatings. As mentioned earlier, the standard randomly oriented polycrystalline nickel exhibits strongest peak corresponding to (111) crystallographic plane at 2 = 44.508 (JCPDS 040850). All the pure nickel and Ni Al2O3 coatings exhibit strongest peak corresponding to (200) plane at 2 = 51.847 indicating development of crystallographic texture.

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Fig. 10. Cross-sectional images PC electrodeposited (a) pure nickel (0 g/L), (b) NiAl2O3 (5 g/L), (c) NiAl2O3 (10 g/L), (d) NiAl2O3 (20 g/L), and (e) NiAl2O3 (40 g/L) composite coatings deposited from electrolyte bath with varying content of suspended nanoparticles.

However, as the Al2O3 nanoparticle content in the electrolyte increases up to 20 g/L, the intensity of (111) peak increases. This also corresponds to increasing values of (111) texture coefcient and decreasing values of (200) texture coefcients (Table 4). Since (111) peak is the strongest peak in the standard pattern of randomly oriented polycrystalline sample, the increasing intensity of this peak in the NiAl2O3 composite coatings indicates decreasing preferential orientation (or increasing randomness) with reinforcement content

in the coating. It seems that reinforcement of alumina particles in nickel matrix inhibit grain growth of primary columnar grains (oriented in fastest growing [100] direction) and also provide nucleation sites for the growth of new randomly oriented grains. This also supports the observations of smaller thickness of NiAl2O3 composite coatings compared to pure nickel coatings deposited using similar pulse electrodeposition parameters. The texture in primary

Fig. 11. Variation of thickness of NiAl2O3 composite coatings with nanoparticle content in the electrolyte bath.

Fig. 12. X-ray diffraction patterns from PC electrodeposited pure nickel and NiAl2O3 composite coatings deposited from electrolyte bath with varying content of suspended nanoparticles.

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Table 4 Crystallite size and texture coefcients (TCs) of various (hkl) planes for standard sample, pure nickel, and NiAl2O3 composite coatings. Coatings Crystallite Size (nm) Texture Coefcient (TC) (111) 1 0.03 0.03 0.24 0.24 0.09 (200) 1 1.97 1.97 1.76 1.76 1.91

Standard Sample Pure Nickel NiAl2O3 (5 g/L) NiAl2O3 (10 g/L) NiAl2O3 (20 g/L) NiAl2O3 (40 g/L)

38 33 31 30 27

[100] crystallographic direction (fastest growing directions) is often associated with higher thickness [38]. The NiAl2O3 composite coatings deposited from electrolyte bath with 40 g/L did not follow above trend, and exhibited the intensities of various planes and values of texture coefcients similar to that for pure nickel coatings (oriented through [100] direction). This is probably due to agglomeration of nanoparticles during deposition at such high level of Al2O3 content in the electrolyte. Note that this composite coating exhibited highest surface roughness (Fig. 9) and smallest crystallite size. 3.2.3. Microhardness and wear resistance The variation of microhardness NiAl2O3 composite coatings as a function of Al2O3 nanoparticle content in the electrolytic bath is presented in Fig. 13. The microhardness of NiAl2O3 composite coatings is about 50150 HV higher than pure nickel coatings, and the hardness increases with increasing alumina content in the electrolyte bath. The hardness of composite coatings is mainly determined by the microstructure of matrix and properties of reinforced particles in the coatings. Since all the coatings have nanocrystalline nickel matrix (crystallite size: 2738 nm), the increasing hardness of the NiAl2O3 composite coatings with increasing alumina content in the electrolyte bath seems to be primarily due to enhanced dispersion strengthening effects [39]. The variation of cumulative weight loss as a function of wear time for nickel and NiAl2O3 composite coatings (deposited with varying content of Al2O3 nanoparticles in the electrolytic bath) is presented in Fig. 14. The relative wear behavior of all the coatings is in agreement with the general understanding that the harder coatings are more wear resistant. The pure nickel coatings showed severe weight loss compared to all the NiAl2O3 coatings. Furthermore, the wear resistance of the composite coatings improved with increasing content of Al2O3 nanoparticles in the electrolytic bath. Note that the microhardness of the NiAl2O3 composite coatings has increased with increasing content of Al2O3 nanoparticles in the electrolytic bath. These reinforced Al2O3 particles in nickel matrix restrain the plastic deformation of matrix under loading due to dispersion strengthening

Fig. 14. The variation of weight loss with time for pure nickel and nickel composite coatings deposited from electrolyte bath with varying content of suspended nanoparticles.

effects. These effects become stronger with increasing alumina content in the composite coatings. These reinforced nanoparticles also lowers the adhesive wear between nickel matrix and alumina ball by reducing the direct contact between these counter bodies during the sliding. The SEM micrographs from wear tracks of pure nickel and NiAl2O3 composite coatings are presented in Fig. 15. The worn surface from pure nickel shows many continuous and wide grooves. The severe plastic deformation of the nickel under loading causes abrasive grooves parallel to sliding direction. The formation of wide grooves and plastic deformation are indicative of poor wear resistance of pure nickel coatings. As the nanoparticle content in the NiAl2O3 composite coatings increases, the wear grooves on the wear surfaces become progressively discontinuous indicative of increased resistance to plastic deformation. For coatings with higher nanoparticle content, for example the coating deposited from electrolyte bath with 20 g/L Al2O3 nanoparticles), the micro-cracking on the wear surface of the coatings is clearly visible. Furthermore, the width of the wear tracks progressively decreases with increasing Al2O3 reinforcement content in the composite coatings which is indicative of better wear resistance of these coatings. Fig. 16 shows the variation of coefcient of friction with time for pure nickel and NiAl2O3 coatings. For all the coatings, the coefcient of friction increases with time (b50 min) and quickly stabilizes to steady state value. While the average coefcient of friction decreases with increasing reinforcement content in the NiAl2O3 composite coatings, the variation is not signicant and the coefcient of friction for all the coatings ranges between ~0.20.25.

4. Conclusions For all the composite coatings (NiAl2O3, NiSiC, and NiZrO2), the amount of reinforcement in the coating was increased with PC and PRC deposition as compared to DC deposition. All the pure nickel and nickel composite coatings prepared using PC and PRC deposition exhibited more random or weak [100] crystallographic textures compared to those deposited using DC deposition. For all the electrodeposition conditions (DC, PC, and PRC), the composite coatings (NiAl2O3, NiSiC, and NiZrO2) had signicantly improved microhardness and wear resistance compared to pure nickel coatings. For each electrodeposition condition (DC, PC, or PRC), NiAl2O3 composite coatings exhibited better microhardness and wear resistance compared to NiSiC and NiZrO2 composite coatings due to relatively higher content of Al2O3 reinforcement in the coatings.

Fig. 13. Variation of microhardness of NiAl2O3 composite coatings with nanoparticle content in the electrolyte bath.

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Fig. 15. Morphology of worn surfaces of PC electrodeposited (a) pure nickel (0 g/L), (b) NiAl2O3 (5 g/L), (c) NiAl2O3 (10 g/L), (d) NiAl2O3 (20 g/L), and (e) NiAl2O3 (40 g/L) composite coatings deposited from electrolyte bath with varying content of suspended nanoparticles.

The reinforcement content of Al2O3 in the composite coatings increased with increasing content of nanoparticle loading in the electrolyte bath (up to 40 g/L). Except with the coatings deposited from electrolyte bath with 40 g/L nanoparticle content, the NiAl2O3 composite coatings showed

relatively random/weak crystallographic texture compared to pure nickel coatings. For similar electrodeposition condition (PC), the NiAl2O3 composite coatings were thinner compared to pure nickel coatings due to more random or weak [100] crystallographic texture in composite coatings as well as due to increasing reinforcement content in the composite coatings. The microhardness and wear resistance of the NiAl2O3 composite coatings increased with increasing content of reinforced nanoparticles in the coatings (and also the content of nanoparticle loading in the electrolyte bath) due to enhanced dispersion strengthening effects.

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Fig. 16. Variation of coefcient of friction with sliding time for pure nickel and nickel alumina composite coatings.

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