Materials Research Bulletin 41 (2006) 847860 www.elsevier.

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Structure and phase transformation behaviour of electroless NiP composite coatings

J.N. Balaraju a, T.S.N. Sankara Narayanan b,*, S.K. Seshadri c,*
Surface Engineering Division, National Aerospace Laboratory, Bangalore 560017, India National Metallurgical Laboratory, Madras Centre, CSIR Complex Taramani, Chennai 600113, India c Department of Metallurgical Engineering, Indian Institute of Technology Madras, Chennai 600036, India
b a

Received 3 May 2005; received in revised form 21 August 2005; accepted 30 September 2005 Available online 21 October 2005

Abstract This paper addresses the structural characteristics and phase transformation behaviour of plain electroless NiP coating and electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings. The X-ray diffraction patterns of electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings are very similar to that of plain electroless NiP coating, both in as plated and heattreated conditions. Selected area electron diffraction (SAED) patterns obtained on the NiP matrix of NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings exhibit diffuse ring patterns resembling the one obtained for plain electroless NiP coating. Phase transformation behaviour studied by differential scanning calorimetry (DSC) indicates that the variation in crystallization temperature and the energy evolved during crystallization of plain electroless NiP coating and electroless NiPSi3N4, Ni PCeO2 and NiPTiO2 composite coatings is not signicant. The study concludes that incorporation of Si3N4, CeO2 and TiO2 particles in the NiP matrix does not have any inuence on the structure and phase transformation behaviour of electroless NiP coatings. # 2005 Elsevier Ltd. All rights reserved.
Keywords: A. Amorphous materials; B. Chemical synthesis; C. Differential scanning calorimetry (DSC); D. Crystal structure

1. Introduction Electroless plating is a well-established surface engineering process that involves the deposition of a metal metalloid alloy on various substrates. During the past ve decades electroless plating has gained immense popularity due to its ability to produce coatings that possess excellent corrosion, wear and abrasion resistance. Among the various types of electroless plating, hypophosphite reduced electroless nickel plating has received commercial success because of its low cost, ease of control, and ability to offer good corrosion and wear resistance surface [1,2]. The ability to codeposit ne particulate matter with electroless NiP matrix to prepare composite coatings is a key development in this area of research as they extend the potential of electroless nickel coatings for innumerable applications. Numerous studies are available on the development of electroless NiP composite coatings with the incorporation of various hard and soft particles, emphasizing the mechanism of particle incorporation, factors inuencing particle incorporation and the effect of particle incorporation on hardness, friction, wear resistance, abrasion resistance, corrosion resistance, etc.

* Corresponding authors. E-mail addresses: jnbalraj@css.nal.res.in (J.N. Balaraju), tsnsn@rediffmail.com (T.S.N. Sankara Narayanan), sks@iitm.ac.in (S.K. Seshadri). 0025-5408/$ see front matter # 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.materresbull.2005.09.024

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Feldstein [3] has presented a detailed account of electroless nickel composite coatings. Balaraju et al. [4] has recently reviewed the various aspects of electroless nickel composite coatings. Crystallization and phase transformation behaviour of electroless NiP coating during thermal processing has been the subject of various investigations [510]. Keong et al. [1113] studied the crystallization kinetics and phase transformation behaviour of electroless NiP coatings with different phosphorus contents, namely low phosphorus (3 5 wt.% P) [11], medium phosphorus (58 wt.% P [11] and 69 wt.% P [12]) and high phosphorus (1014 wt.% P) [13]. The crystallization of NiP alloys has been investigated by many different methods [1421]; differential scanning calorimetry (DSC), X-ray and electron diffraction, small angle X-ray scattering, transmission electron microscopy, magnetothermal methods and by the change of alloy properties such as microhardness and magnetic properties during crystallization. Though the crystallization process of electroless NiP coatings essentially involves the formation of crystalline nickel, nickel phosphide (Ni3P) and/or other intermediate phases, the phase transformation is not a single stage process and occurs through many stages involving one or more intermediate crystalline phases [1113,2224]. The diffusion of the component elements in the NiP alloy is essential for the simultaneous formation of various crystalline phases (Ni and Ni3P) and any hindrance in diffusion could either control or inhibit the crystallization process of the NiP alloy. Deposition of NiP amorphous alloy on high surface area SiO2 carriers or the introduction of metals such as Pd to the NiP alloy conrms such an occurrence [25]. Chen et al. [26] have shown that codeposition of Cr and W in the NiP alloy lm retards the formation of Ni3P phase and increases the crystallization temperature from 380 to 420 8C. The crystallization temperature of electroless and sputtered ternary NiCuP alloy deposit is approximately 400 8C [10] and 370 8C [27], respectively. Yu et al. [28] have compared the crystallization behaviour of electroless NiP binary and NiCuP ternary alloy deposits and proved that the codeposition of copper in the NiP alloy has a denite inuence on the crystallization behaviour of NiP alloy deposit. Since codeposition of a third element in NiP alloy and deposition of NiP alloy deposit over SiO2 inuence the crystallization behaviour, studies on the inuence of particle incorporation on the structure and phase transformation behaviour of electroless NiP matrix assumes signicance. Hansen and Moller [29] have studied the effect of TiC particle incorporation on the structure of the electroless NiP matrix and showed that the incorporated TiC particles did not affect the structure of the NiP matrix. However, McCormack et al. [30] have shown that addition of yttria particles to a Watts nickel plating bath signicantly change the surface morphology and preferred crystallographic orientation of the Niyttria composite coatings. In this context, the present work aims to study the effect of incorporation of hard ceramic particles, namely Si3N4, CeO2 and TiO2, on the structure and phase transformation behaviour of electroless NiP matrix. 2. Experimental details The electroless NiP coatings of the present study were prepared using an acidic hypophosphite reduced electroless nickel plating bath. Nickel sulphate hexahydrate was the source of nickel while sodium hypophosphite served as the reducing agent and the source of phosphorus. Besides these, the bath also contains suitable amounts of complexing agents and stabilisers. During plating, the temperature of the bath was maintained at 88 1 8C using a constant temperature oil bath and the pH was maintained between 4.8 and 5.0 with frequent addition of small quantities of NaOH. The plating solution was mechanically agitated (600 rpm) using a magnetic stirrer and Teon coated magnetic paddle. The plating rate was in the range of 1012 mm/h. The composition of the plating bath and the operating conditions employed for plating are shown in Table 1. The Si3N4, CeO2 and TiO2, particles were used as received without any further treatment. The particles size of these particles is as follows: among the three, TiO2 particles possess a very narrow range of 2.43 mm, followed by Si3N4 (20% 810 mm; 40% 68 mm; 10% 34 mm; 20% 23 mm; remaining 10% 1628 mm) and CeO2 (40% 810 mm; 30% 68 mm; 20% 46 mm; remaining 10% 1317 mm). In the deposition of electroless NiP composite coatings, a slurry was prepared by thoroughly mixing the required amount of second phase particles (Si3N4/CeO2/TiO2) and a small portion of plating solution in a mortar to ensure prevention of agglomeration and to enable uniform distribution of these particles in the plating bath. Thin foils of electroless NiP composite coatings used for structural and thermal characterization were deposited using stainless steel (AISI 304 grade) substrate and subsequently peeled off. A nickel strike using Woods nickel bath makes the stainless steel substrate catalytically active for electroless plating. The nickel content of the deposits was determined gravimetrically after precipitating the nickel as nickeldimethyl glyoxime complex, whereas the phosphorus content was determined by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The amount of incorporation of second phase particles in their respective deposits was

J.N. Balaraju et al. / Materials Research Bulletin 41 (2006) 847860 Table 1 Chemical composition of the electroless nickel plating bath and its operating conditions Chemical composition Nickel sulphate (NiSO46H2O) Sodium hypophosphite (NaH2PO2H2O) Complexing agents and stabilizers Particles in suspension (Si3N4/CeO2/TiO2) Operating conditions pH Temperature Plating duration Plating rate

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23 g/l 21 g/l Proprietary 025 g/l 4.85.0 88 1 8C 2h 1012 mm/h

determined by dissolving a known weight of the deposits in nitric acid and then ltering the particles through a weighed 0.1 mm membrane. From the weight of the second phase particle and weight of the electroless NiP composite coatings taken for analysis, the percentage weight of second phase particles incorporated in the deposit was calculated. X-ray diffraction (XRD) measurements were made with a Shimadzu (Model: XD-D1) diffractometer using Cu Ka (l = 1.54 A) radiation. A Philips scanning transmission electron microscope (Model CM 12) attached with an EDAX to facilitate elemental distribution analysis was used for the analysis of deposits. The foils were electrolytically thinned using a twinjet polishing using perchloric acid-methanol mixture at very low temperatures (about 5 8C) and carefully placed inside a copper grid for analysis. The bright eld/dark eld TEM micrographs and selected area electron diffraction (SAED) patterns were obtained to gain a better insight into the structure of the electroless NiP coatings. The EDAX analysis were performed both on electroless NiP matrix region as well as in the region of incorporated second phase particles to analyse the constituents present. The phase transformation behaviour of electroless NiP and NiP composite coatings were studied using differential scanning calorimetry (DSC) (NETZSCH-Geratebau GmbH) at non-isothermal (linear heating) conditions, which involves the measurement of heat ow corresponding to the nucleation and growth processes. The activation energy of the crystallization process was calculated using the method proposed by Duswalt [31], based on the major exothermal DSC peaks obtained at different heating rates. 3. Results and discussion The optical micrograph of the cross section of plain electroless NiP coating and electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings is depicted in Fig. 1ad, respectively. It is evident from the micrographs that the Si3N4, CeO2 and TiO2 particles are uniformly distributed throughout the thickness of the coating. The X-ray diffraction pattern of plain electroless NiP coating in its as deposited condition exhibits only a single broad peak around 458 2u (Fig. 2). Theoretically, a disorder in arrangement of atoms manifests itself as a broad peak in X-ray diffractograms [32]. The mechanism of formation of electroless NiP coatings suggests that during electroless nickel deposition, random capturing of phosphorus on nickel atoms occurs and the variation in the rate of segregation of nickel and phosphorus atoms determines the crystallinity of the resultant coating. Between these two atoms, the rate of diffusion of phosphorus is relatively small compared to that of nickel [33]. Hence, electroless NiP coating having a higher amount of phosphorus involves the movement of a larger number of phosphorus atoms from a given area per unit time during deposition to achieve segregation of nickel and phosphorus [34]. Chemical analysis of the plain electroless NiP coating shows that it contains 89 wt.% Ni and 11 wt.% P. Since the required phosphorus segregation is very large, it prevents the nucleation of face centered cubic nickel phase and this results in an amorphous structure in as deposited condition. Other investigators [13,28] also conrm the amorphous nature of electroless NiP coatings with high phosphorus content (>7 wt.% P) in its as deposited condition. Fig. 3 shows the X-ray diffraction pattern of the electroless NiP coating heat-treated at 400 8C for 1 h. During heat treatment, transformation of electroless NiP coating from a disordered structure to an ordered arrangement of face centered cubic Ni and body centered tetragonal Ni3P occurs and, this results in the formation of several sharp peaks. No metastable phases are observed in the X-ray diffraction pattern as the composition of the NiP alloy (89 wt.% Ni

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Fig. 1. Optical micrograph of the cross section of the plain electroless NiP coating and electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings (a) NiP; (b) NiPSi3N4; (c) NiPCeO2; (d) NiPTiO2 [R, resin; C, Cu over layer; EN, electroless NiP coating; ENSN, electroless NiPSi3N4 coating; ENCE, electroless NiPCeO2 coating; ENTI, electroless NiPTiO2 coating].

and 11 wt.% P) is very close to eutectic. The X-ray diffraction patterns obtained for electroless NiPSi3N4, NiP CeO2 and NiPTiO2 composite coatings, both in as-plated and heat-treated conditions, are very similar to those obtained for plain electroless NiP coating both in as plated and heat-treated conditions. This suggests that the incorporated second phase particles have no inuence on the structure of electroless NiP matrix. However, X-ray diffraction measurements alone are not sufcient to reach such a conclusion and hence warrant further characterization using transmission electron microscopy (TEM). Fig. 4 shows the TEM micrograph (bright eld image) of plain electroless NiP coating in as plated condition. The micrograph exhibits a dark network due to the inhomogeneous distribution of phosphorus in the electroless NiP matrix. In general, inhomogeneity in phosphorus content is prevalent in electroless NiP coatings having high phosphorus content. The energy dispersive X-ray analysis (EDAX) (Fig. 5) performed on the NiP matrix indicates a phosphorus content of about 11 wt.%. The selected area diffraction (SAED) pattern of the plain electroless NiP coating (Fig. 6) exhibits a diffuse ring pattern, which is typical of an amorphous structure [15,3537].

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Fig. 2. X-ray diffraction pattern of electroless NiP deposit in its as deposited condition.

These observations conrm that the plain electroless NiP coating is amorphous in as deposited condition and strongly support the observations made from X-ray diffraction measurements. Fig. 7ac show the TEM micrographs (bright eld images) of electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings, respectively. The contrast from the matrix is uniform. The TEM micrographs (Fig. 7ac) clearly reveal the presence of individual second phase particles having an angular/sub-angular shape as well as agglomerated particles in some regions. Fig. 8 shows the EDAX pattern obtained in the matrix region of electroless NiPSi3N4 composite coating. Besides nickel and phosphorus, the presence of silicon is also apparent from the EDAX pattern,

Fig. 3. X-ray diffraction pattern of the electroless NiP deposit heat-treated at 400 8C for 1 h.

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Fig. 4. Transmission electron micrograph (bright eld image) of electroless NiP deposit in its as plated condition.

making evident of the incorporation of Si3N4 particles in the electroless NiP matrix. Similarly, electroless NiP CeO2 and NiPTiO2 composite coatings shows the presence of cerium and titanium, conrming the incorporation of CeO2 and TiO2 particles in the NiP matrix of the respective coatings. SAED patterns obtained on the NiP matrix of electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings exhibit diffuse ring patterns resembling the one obtained for plain electroless NiP coatings. However, the EDAX pattern taken on the particle region of the matrix reveals the presence of the silicon, cerium and titanium in the electroless NiPSi3N4, NiPCeO2 and NiP TiO2 composite coatings, respectively. Fig. 9ac, respectively, show the SAED patterns taken on the region of the Si3N4, CeO2 and TiO2 particles and conrm the crystalline nature of these particles. Hansen and Moller [29] also made similar observations for incorporation of TiO2 particles in electroless NiP matrix. The observations of the present study and that of Hansen and Moller [29] postulate that the incorporated second phase particles did not alter the structure of the electroless NiP matrix. The DSC trace of plain electroless NiP coating (at a heating rate of 10 K/min) exhibit a well-dened exothermic peak at 337.4 8C and a shoulder around 344 8C in the temperature range of 310370 8C (Fig. 10). The crystallization occurs over a narrow temperature range of 320360 8C and the energy evolved during the exothermic transition, calculated from the area of the peak is 68.14 J/g. The peak temperature and the energy evolved during the phase transition calculated for electroless NiP coating, 337.4 8C and 68.14 J/g, respectively, is comparable to the values obtained for similar coatings reported earlier [38]. Figs. 1113, respectively, depict the DSC traces of electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings obtained under similar conditions. Similar to plain electroless NiP coating, the electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings also exhibit a well-dened exothermic peak in the temperature range

Fig. 5. EDAX pattern of electroless NiP deposit in its as plated condition.

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Fig. 6. SAED pattern of electroless NiP deposit in its as plated condition (aperture size: 155 mm).

of 320360 8C. However, the DSC traces obtained for the composite coatings differ from one another and from that obtained for plain electroless NiP coating. Electroless NiPSi3N4 coating exhibit only a single sharp peak at 339.3 8C. Electroless NiPCeO2 coating, besides the sharp exothermic peak at 339.1 8C, also exhibit a shoulder around 345 8C. Electroless NiPTiO2 coating, besides the sharp peak at 338.7 8C, exhibit an additional peak at 347.5 8C. The energy evolved during the exothermic transition, calculated from the area of the peaks of NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings are 70.37, 70.45 and 80.22 J/g, respectively. Table 2 shows the peak temperatures and DH values calculated for all the coatings studied. The peak temperature and the energy evolved during phase transformation in electroless NiP coatings are very sensitive to the phosphorus content and the rate of heating of the coatings [15,33,3740]. Since a constant heating rate (10 K/min) is adopted in the DSC studies of all these coatings, this variable will not have any inuence on the peak temperature and the energy evolved during phase transformation. However, it is interesting to recall the results of chemical analysis of these coatings. The electroless NiP coating is found to have 11 wt.% phosphorus and 89 wt.% nickel, whereas with the incorporation of Si3N4, CeO2 and TiO2 particles in the NiP coating, the nickel and phosphorus content vary slightly. The nickel and phosphorus contents of the composite coatings are as follows: 10.1 wt.% phosphorus and 81.79 wt.% nickel for electroless NiPSi3N4 coating; 10.18 wt.% phosphorus and 82.38 wt.% nickel for electroless NiPCeO2 coating; 10.40 wt.% phosphorus and 84.18 wt.% nickel for NiPTiO2 coating. Many process variables could cause variation in phosphorus content of the electroless NiP coating and among them; the pH of the electroless nickel bath is the most inuencing parameter. One possible reason for variation of the pH of electroless nickel plating bath could be the adsorption of H+ ions over the second phase particles added to the bath. However, Yeh and Wan [41] and Szczygiel [4244] suggest that such a presumption is not valid in plating baths that contain very high concentration of Ni2+ ions (1 mol/dm3), where the adsorption of Ni2+ ions will be preferred over the H+ ions. This appears to be true as very little change in phosphorus content of the NiP coatings of the present study. Hence, it is evident that some other mechanism is responsible for the decrease in the phosphorus content of the electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings. During deposition of electroless NiP composite coatings, adsorption of the second phase particles on the electrode surface is a prime factor that decides their incorporation in the coating. This adsorption process continues during the

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Fig. 7. Bright eld images of electroless NiP composite coatings in their as deposited condition (a) NiPSi3N4; (b) NiPCeO2; (c) NiPTiO2.

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Fig. 8. EDAX pattern of electroless NiPSi3N4 composite coating in its as plated condition.

Fig. 9. SAED patterns obtained from the particle region (a) NiPSi3N4 (aperture size: 110 mm); (b) NiPCeO2 (aperture size: 530 mm); (c) Ni PTiO2 (aperture size: 530 mm).

entire duration of the deposition. Such a process is most likely to cause a decrease in the active surface area available for reduction of nickel and phosphorus. Electroless deposition of nickel, being an autocatalytic process, continuously makes available surface sites that are catalytically active for further reduction of nickel and phosphorus. The adsorption of second phase particles over this catalytically active area affects the possibility of reduction of nickel and

Fig. 10. DSC trace of electroless NiP coating.

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Fig. 11. DSC trace of electroless NiPSi3N4 coating.

Fig. 12. DSC trace of electroless NiPCeO2 coating.

Fig. 13. DSC trace of electroless NiPTiO2 coating.

phosphorus at those sites and this result in coatings with decreased nickel and phosphorus content. Dennis et al. [45] also observed a similar phenomenon with the incorporation of Cr2C3 particles in the NiP coating. The other interesting feature of the composite coatings of the present study is that in spite of the decrease in the nickel and phosphorus content with the incorporation of the second phase particles, the ratio of nickel to phosphorus remains the
Table 2 Peak temperatures and DH values obtained for electroless NiP and NiP composite coatings Type of coating Peak temperature (8C) I NiP NiP8.10 wt.% Si3N4 NiP7.44 wt.% CeO2 NiP5.42 wt.% TiO2 337.4 339.3 339.1 338.7 II 347.5 68.14 70.37 70.45 80.22 DH (J/g)

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Fig. 14. DSC traces of electroless NiP coating at varying heating rates, viz., 3, 7, 12 and 15 K/min.

Fig. 15. DSC traces of electroless NiPSi3N4 coating at varying heating rates, viz., 3, 7, 12 and 15 K/min.

same as that of the plain NiP coating. As a result, the peak temperature for all the coatings remains around 338 1 8C. Similarly, the DH value of all the coatings of the present study is also of the same order. The higher DH value obtained for electroless NiPTiO2 coating is due to the contribution from the additional higher temperature peak at 347.5 8C. DSC traces were recorded at different heating rates to get a better insight on the effect of these second phase particles on the phase transformation behaviour of electroless NiP coatings. Figs. 14 and 15, respectively, show the DSC traces obtained for electroless NiP and NiPSi3N4 coatings at varying heating rates, viz., 3, 7, 12 and 15 K/ min. Using the onset temperatures obtained at different heating rates (Table 3) it is possible to calculate the activation energy (Qc) for crystallization of the electroless nickel coatings using the relationship developed by Duswalt [31]: dln v d1=T

Qc R

Table 3 Variation of peak temperature for electroless NiP and NiPSi3N4 coatings with heating rate Type of coating NiP Heating rate (K/min) 3 7 12 15 3 7 12 15 Onset temperature (K) 591.4 602.0 609.1 612.2 592.7 603.3 610.5 613.2 1/T (103 K) 1.690 1.661 1.641 1.633 1.687 1.657 1.638 1.631 ln v (K/min) 1.098 1.945 2.484 2.708 1.098 1.945 2.484 2.708

NiP8.10 wt.% Si3N4

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Fig. 16. Plot of ln v vs. 1/T made using the variation in peak temperatures with heating rate.

where R is the gas constant (8.314 J/(K mol)), v the heating rate (K/min) and T is the onset of crystallization temperature (in K). A plot of ln v versus 1/T is made using the variation in peak temperatures with heating rate (Fig. 16a and b). The activation energy calculated using the slope values of the above plot are 234.39 and 237.75 kJ/ mol, respectively, for electroless NiP and NiPSi3N4 coatings. Mahoney and Dynes [38] also performed a similar analysis for electroless NiP coatings. According to them, the activation energy for crystallization of electroless NiP (11 wt.% P) coating is 227.6 kJ/mol. For pure nickel, the activation energy for self-diffusion is approximately 289 kJ/ mol. The above observations suggest that the incorporation of the Si3N4, CeO2 and TiO2 particles do not seem to have any inuence on the phase transformation behaviour of electroless NiP coating. This is not surprising as the temperature range involved in the phase transformation of these coatings is of the order of 300350 8C, the second phase particles will not undergo any modication to cause a major change in the phase transformation behaviour of the coating. It seems possible that even the observed variations in the DSC traces of the electroless NiP composite coatings, such as, the formation of the second peak in the case of electroless NiPTiO2 coating, is not due to inuence of the incorporated second phase particles but due to the NiP matrix itself.

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Literature reports on electroless NiP coatings present different mechanisms based on which the phase transformation occurs [15,16,19,24,3440,46]. These studies classify the electroless NiP coatings in three categories with respect to their phosphorus content. Accordingly, hypoeutectic alloys (<20 at.% P) exhibit at least two peaks; one corresponds to the primary crystallization of Ni which occurs at lower temperature, whereas the other peak due to the phase transformation with Ni and Ni3P as nal products occurs at higher temperatures. Eutectic NiP alloys (20 at.% P), in general, shows only a single sharp peak in their DSC traces. Hypereutectic NiP alloys (>20 at.% P) also exhibit at least two peaks. Ni, Ni3P and Ni5P2 phases form at low temperature, whereas at higher temperature, the metastable Ni5P2 phase transforms into stable Ni3P. All these reactions exhibit distinct peaks in the DSC thermograms. The phosphorus content of plain electroless NiP and electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings lies close to 20 at.% P and hence their DSC traces are expected to be similar to that of an eutectic NiP alloy coating. However, Figs. 1013, besides the sharp exothermic peak, also exhibit other features such as the appearance of a shoulder (Figs. 10 and 12) and a second peak (Fig. 13). The appearance of the shoulder (Figs. 10 and 12) may be due to the relaxation of lattice strain energy during the phase separation. Park and Lee [36] also observed a similar shoulder pattern for electroless NiP (10.07 wt.% P) coating. Keong et al. [13] suggest that the formation of shoulder is due to the rst stage of transformation involving short-range atomic movements and incipient crystallization of metastable crystallization structures [8,36]. The additional high temperature peak observed for electroless NiPTiO2 coating cannot be accounted for the recrystallization and growth of Ni3P phase, as its occurrence is expected only around 400 8C [34,35]. The small difference in the peak temperature between the rst (338.7 8C) and second peak (347.5 8C) suggest a possible splitting. Hypoeutectic NiP alloys also exhibit a split in the higher temperature peak [40] due to the differences in activation energy for crystallization from partially crystallized matrix and amorphous matrix. Though such occurrence is not prevalent in eutectic NiP alloys, Rajam et al. [40] suggest that these peaks too may show splitting. 4. Conclusion The structural characteristics and phase transformation behaviour of plain electroless NiP coating and electroless NiPSi3N4, NiPCeO2 and NiPTiO2 composite coatings are studied. X-ray diffraction pattern, transmission electron micrograph, selected area electron diffraction pattern and energy dispersive X-ray analysis reveal that the structure of electroless NiP matrix is not changed with the incorporation of Si3N4, CeO2 and TiO2 particles. Phase transformation behaviour studied by differential scanning calorimetry indicates that the variation in crystallization temperature and the energy evolved during crystallization of plain electroless NiP coating and electroless NiP Si3N4, NiPCeO2 and NiPTiO2 composite coatings, is not signicant. Hence, the study concludes that incorporation of Si3N4, CeO2 and TiO2 particles in the NiP matrix does not have any inuence on the structure and phase transformation behaviour of electroless NiP coatings. Acknowledgement The authors wish to express their sincere thanks to Prof. T.S. Sampath Kumar, Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai, for his help and suggestions in DSC studies. References
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