y 201 (2006) 389–395www.elsevier.com/locate/surfcoat

Surface & Coatings Technolog

Electroless NiP micro- and nano-composite coatings

M. Sarret ⁎, C. Müller, A. Amell

ELECTRODEP, Dpt. Química Física, University of Barcelona, Martí i Franquès, 1, 08028-Barcelona, Spain

Received 6 September 2005; accepted in revised form 25 November 2005Available online 28 December 2005

Abstract

Electroless NiP composite coatings were obtained by incorporating two kinds of particles, SiC and Si3N4, to analyze the influence of the typeof particle both on the codeposition process and on the coating properties. Particles with sizes ranging from 30 nm to 2 μm were selected to studythe influence of this parameter on the amount of embedded particles. All composite coatings were characterized by composition, morphology,structure, roughness and some tribological properties. Results indicated that, while there was almost no difference between carbide and nitrideincorporation for micron-sized particles, this variable was very important with the nano-sized ones. Moreover, it was observed that the growthmechanism of the metallic matrix was much more modified by the nano-particles than by the micron-sized ones.© 2005 Elsevier B.V. All rights reserved.

Keywords: Electroless nickel–phosphorous; Micro-composite; Nano-composite

1. Introduction

Composite coatings can be obtained by codeposition of inertparticles onto a metal matrix from an electrolytic or electrolessbath. Nickel–phosphorous (NiP) is widely used as an electro-less coating in different industries because of its corrosion andwear resistances and its uniform coating thickness. Moreover, itis known that the incorporation of particles onto this NiP matrixprovides enhanced surface properties, depending on the particlenature [1].

Hard particle-containing deposits (NiP/X, X=SiC, WC,Al2O3, Si3N4…) have been developed when the main require-ment for the composite coating is wear resistance [2,3]. Amongthese coatings, the combination NiP–SiC has proved to be themost cost-effective and best-performing combination [3]. Thefinal properties of these coatings depend on the phosphorouscontent of the NiP matrix, which determines the structure of thecoatings, and on the characteristics of the embedded particlessuch as type, shape and size. Most studies concerning NiP-hardparticle systems are performed using micron-sized particles andsome commercial processes exist to obtain such composites.However, the development of nanotechnologies has raised the

⁎ Corresponding author.E-mail address: m.sarret@ub.edu (M. Sarret).

0257-8972/$ - see front matter © 2005 Elsevier B.V. All rights reserved.doi:10.1016/j.surfcoat.2005.11.127

interest on the metal matrix nano-composite coatings because oftheir unique mechanical, magnetic and optical properties.

The aim of this study is to obtain electroless NiP compositecoatings using two kinds of ceramic particles, silicon carbideand silicon nitride, so as to investigate the influence of particlenature and size on both the codeposition process and coatingcharacteristics. Various commercial particles, with sizes rangingfrom 30 nm to 2 μm, were selected for both kinds of particles.The effect of the particles content on the deposition rate and onvarious deposit characteristics was analyzed using differentanalysis techniques.

2. Experimental

A commercial electroless nickel bath (NIKLAD 767 fromMacDermid Española SA) with sodium hypophosphite asreducing agent was used to obtain the coatings. The mainsolution components and some experimental conditions aresummarized in Table 1. This bath provides NiP deposits with amedium phosphorous content, 6–8% P. The pH of the bath wasadjusted with a diluted ammoniacal solution.

To obtain NiP composite coatings, SiC and Si3N4 particleswere added to the bath and kept in suspension by magneticstirring and air bubbling. Powders were used as received andultrasonically dispersed in the bath for 30 min before thedeposition. Particle size data were acquired using a Laser

Table 1Main experimental conditions used to obtain the coatings

Chemical composition

Ni2+ 6.0 g L−1

H2PO2− 30 g L−1

Bath particles content 5–30 g L−1

Operating conditions Range Optimum

Temperature 82–93 °C 88 °CpH 4.5–5.2 4.8

Table 2Particle characteristics

Particle type Supplier Designation d10/μm

d50/μm

d90/μm

Size*/μm

SiC Alpha Aesar,Germany

α-SiC 0.357 0.636 1.272 2.0

MarkeTechInternational, USA

SiC nano 0.055 0.084 0.147 0.030

Si3N4 ABCR, Germany B7 0.427 0.695 1.297 1.0ABCR, Germany M11 0.064 0.115 0.447 0.6MarkeTechInternational, USA

Si3N4 nano 0.057 0.086 0.152 0.030

*: Information provided by the supplier.

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Diffraction Particle Size Analyzer (LS 13 320, BeckmanCoulter, Inc., USA).

Coatings were obtained on iron substrates of 40×40×2.0 mm vertically positioned in a 250 mL bath (surface area/bath volume ratio of 2 dm2 L−1). Deposition was performedafter a suitable pre-treatment sequence including electrolyticdegreasing using an aqueous alkaline solution, immersion in20% v/v HCl for 1 min and activation in 1% v/v NH3. Aftercoating, the deposits were rinsed, ultrasonically cleaned inwater for 5 min and dried.

In some cases, the electroless plated samples were heattreated for 4 h at 400 °C to determine the change in morphology,structure, wear and hardness properties. In order to modelcommon industrial practice no special atmosphere was main-tained during heat treatment.

The specimens were analyzed in both as-deposited and post-heat treated conditions. The morphology of NiP and NiPcomposite coatings (surface and cross-section) was examinedusing a Hitachi S 2300 scanning electron microscopy (SEM).The same equipment was used to determine the shape of themicroparticles and a Hitachi H 800 TEM was used for nano-particles. When higher resolution was needed, an FEI StrataDB235 focussed ion beam equipment was used. Phosphoruscontent and particle concentration in the NiP matrix surface andacross the coating thickness was determined by energy-dispersive X-ray spectroscopy (EDS) using an X-ray analyserincorporated in a Leica Cambridge Stereoscan S-360 SEM.Surface roughness (rms) was evaluated using a Zygo Corpora-tion NewWiew 100 3D surface profiler based on scanningwhite-light interferometry. X-ray fluorescence (XRF) was usedto analyze coating thickness (Fischerscope XDL). X-raydiffraction (XRD) phase analysis was performed on a SiemensD-500 diffractometer, using CuKα radiation. Vickers hardnesstests were performed using a Matsuzawa Seiki DMH-1 testerequipped with television screen to measure the diagonals of theimprint. The indentation load was 100 g and the indentationtime was 15 s. Eight readings were taken from each deposit andthe values were then averaged. Friction tests were conductedusing a pin-on-disc tribometer. Samples were cut into 10×10 mm squares and mounted on a stationary holder. Thespecimen was pressed onto a disc with a load of 3 N and 220-grit SiC abrasive paper was stuck onto the disc. A fresh sheet ofabrasive paper was used for each test. The disc was rotated at aconstant velocity of 5 rpm and the specimens slid with a speedof 15.7 mm s−1 for 15 min [4]. Wear curves were obtained byrecording the weight loss of the specimens using an analytical

balance with a precision of 10−5 g. Before and after weartesting, the specimens were ultrasonically cleaned for 1 min inacetone and dried in warm air to ensure accuracy ofmeasurements. Each experimental point was the average ofthree tests.

3. Results and discussion

3.1. Particles characterization

Previous to the codeposition process, all particles werecharacterized with respect to size, morphology and structure.Table 2 shows the sizes obtained for all particles using lightscattering. In most cases they were slightly different from thesizes indicated by the supplier, but the values obtained for thetwo kinds of nano-particles were almost the same. However,TEM micrographs of the powders (Fig. 1) indicate that theyare very different: Si3N4 particles are spherical, with a ratherhomogeneous size of about 50 nm, while SiC powder isheterogeneous, with particles ranging from 50 nm, almostspherical, to 500 nm, with a clear hexagonal shape. These dataindicate that most of the nano-particles form agglomerateswhen they are dispersed in the bath. The morphologicalcharacterization of micrometric particles was performed usingSEM. The SEM images indicate that the shape of the biggestparticles is polyhedrical, becoming more rounded as particlesize decreases.

X-ray diffraction was used to analyze the structure of thevarious powders. The diffractogram of micrometric SiCindicates the presence of the hexagonal α-phase (JCPDSnumber 49-1428) while the nanometric powder correspondsto the cubic structure (JCPDS 29-1129). With regards to thenitride, the structure is the same for all sizes and suppliers andcorresponds to the hexagonal α-Si3N4 phase (JPCDS 41-0360).

3.2. Coating characterization

3.2.1. Coatings compositionThe incorporation of particles does not modify the

composition of the coatings and the phosphorous content ismaintained at the medium level, between 6–8% P. However,some changes are observed in the deposition rate, whichremains almost the same when the micron-sized particles areincorporated, but is slightly reduced with the nano-sized ones,

Fig. 1. TEM micrographs of (A) SiC and (B) Si3N4 nanopowders.

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from 20 to about 18 μm h− 1. Fig. 2A shows particleincorporation to the NiP composites as a function of theirconcentration in the plating bath. For the same operatingconditions, the amount of codeposited particles increases withparticle size. For the biggest particles of both SiC and Si3N4, theamount of embedded particles reaches a plateau between 10 to20 g/L and then decreases. At these concentrations, interparticledistance is reduced to a point where they tend to agglomerateand to settle down; since the real concentration is thenunknown, for these particles the point at 30 g/L has beenomitted. In any case, it is observed that to obtain a particularlevel of incorporation, electrocodeposition requires a greateramount of particles in the bath than electroless codeposition[1,5]. With the smallest particles (M11 and SiC nano), theincorporation level is lower but uniform for all concentrations,while Si3N4 nano-particles are hardly codeposited. However, it

0 10 20 300

5

10

15

20

25

wt

% o

f co

dep

osi

ted

par

ticl

es

concentration of particles / g L-1

A

Nu

mb

er d

ensi

ty o

f co

dep

osi

ted

par

ticl

es /

m-3

Fig. 2. (A) Dependence of the percentage of incorporated particles on the particle conumber density of particles in the bath.

has been pointed out that this “classical” representation can leadto a misapprehension of codeposition because it does not takeinto account the size of particles [6] and it is suggested thealternative representation of the number density of particles inthe coating vs. the number density in the bath (Fig. 2B). Thesenumber densities were calculated using the values of d90 ofTable 2 and assuming mono-disperse systems of sphericalparticles. This representation leads to rather different conclu-sions, since it is observed that the number density ofcodeposited particles is always larger than the number densityin the solution, even for nitride nano-particles. For the SiCparticles, the codeposition efficiency (ratio between the numberdensity of particles in the coating and in the bath) increasessubstantially with decreasing particle size, as observed in Ref.[6]. The behaviour is the same for micron and submicronnitride particles, but the nano-sized ones have much lower

1016 1017 1018 10191021

1022

1023

1024

SiC-α

SiC nano

B7

M11

Si3N4 nano

B

Number density of particles in the bath / m-3

ncentrations in the bath; (B) Number density of particles in the coatings vs. the

392 M. Sarret et al. / Surface & Coatings Technology 201 (2006) 389–395

codeposition efficiency. On the other hand, when the numberdensities of codeposited SiC-α and B7 nitride are compared, itis observed that for these micron-sized particles the codeposi-tion is size-dependent, but this does not occur with thenanoparticles, which having almost the same medium size,have a very different number density of particles in thecoating. Thus, in the present case the incorporation of the SiCand Si3N4 nano-sized particles is more related to the particlenature than to the particle size.

Since SiC particles have been codeposited with many metals,they have been extensively studied to explain their behaviour,mainly in electrodeposition [7,8] but also in electrolessprocesses [9]. These studies show that the surface of untreatedSiC is always oxidized to some extent and covered with a layerof silicon oxide. Taking into account that SiC deposits well withmost metals while the codeposition of SiO2 is rather limited, ithas been suggested that it is the ratio between the hydrophobic(SiC)/hydrophilic (SiO2) parts of the particle who determines itsbehaviour in a codeposition process [10,11]. Using a Wattselectrolyte, Kaisheva and Fransaer also concluded that thepresence of a thin oxide layer on the SiC surface leads to asolvation force, which reduces or inhibits the codeposition ofSiC particles with Ni [7]. On the other hand, XPS investigationsrevealed that the surface of Si3N4 powders is also partiallyoxidized [12] and thus, the surface of the particles contains two

Fig. 3. SEM images of the cross-section deposits: (A) NiP

different kinds of groups: silanol groups (Si–OH) andsilylamine (secondary and/or primary) groups (Si–NH2, Si2–NH) [13]. The ratio between these acidic/basic groupsdetermines the charge behaviour of the powder in aqueousmedia [14,15]. Then, to try to explain the differences observedbetween the nano-particles used in this study a detailed analysisof their characteristics must be performed. This study mustinclude an analysis of their surface state, to know their oxidationdegree and which are the main oxidation compounds, and canbe completed with an electrokinetic analysis to know theircharge in the deposition bath.

3.2.2. Coatings morphologyFig. 3 shows cross-sections of some of the coatings. Particles

are successfully codeposited in the NiP matrix and a uniformdistribution across the layer thickness is observed. Fig. 3Ashows the cross-section of a NiP /6% SiC nano. The micro-graphs are similar to those obtained in other cases with SiCnanoparticles [16], although at this magnification individualnano-sized particles cannot be distinguished. When thesecoatings are analyzed using FIB (Fig. 4A) it can be observedthat very few of the smallest particles (50 nm) have beenincorporated, and that most of the particles correspond toaggregates with a minimum size of about 140 nm or to thehexagonal big single particles observed by TEM. When the

/ 6% SiC nano, (B) NiP /11% B7, (C) NiP /8% M11.

Fig. 4. FIB micrographs of (A) NiP/SiC and (B) NiP/Si3N4 nanocomposite coatings. Cross-sections were created by ion sputtering.

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same FIB magnification was used to analyze the NiP/Si3N4

nano, only a few groupings of the Si3N4 particles are observed inthe cross-section of the coatings (Fig. 4B). It has been suggestedthat particle shape plays an important role in determiningincorporation level [17]. It is believed that angular-shapedparticles will have a greater tendency to hold on to the surfaceupon impingement than round particles. Taking into account themorphologies of the various particles used in this study, thiscould explain the good incorporation of the micron-sizedparticles and some differences favouring the SiC versus theSi3N4 nano-particles. However, as mentioned above, it seemsthat some factors other than shape must be considered to explainthe low incorporation of the nano-sized nitride particles.

Fig. 5 shows the surface morphology of NiP and NiPcomposite coatings. A uniform distribution of particles oncoating surfaces is observed and the appearance of depositsbearing microparticles (0.6–2 μm) is very similar. However, thesurface morphology of the coatings with SiC nano is verydifferent (Fig. 5B), with a NiP matrix growing in a nodularstructure. The appearance of these spheroids on the surface hasbeen observed in other cases where micro-sized particles areincorporated to a NiP matrix [17], but also in NiP deposition

Fig. 5. Surface morphology of as deposited coa

without particles [3]. In those cases, this morphology wasattributed to an increase of the bath pH: as the pH increases, thephosphorous content of the deposit decreases and the number ofnodules on the surface increases. However, in the present case,the pH of the solutions was carefully maintained in all conditionsand, as mentioned above, the phosphorous content was notaffected by the presence of particles. In a parallel studyperformed to try to understand the incorporation mechanismfor nano-particles, the iron substrate was polished to mirrorfinish and deposits were obtained from 30 s to 10 min andanalyzed using AFM. Fig. 6 shows the coating obtained after10 min with SiC nano-particles. This deposit is 4 μm thick,contains 8.5% SiC and no nodules are observed on the surface,although the P content is even slightly lower than that of Fig. 5B(6% P). It has been seen that, with non-polished surfaces, theappearance of surface aggregates does not depend on the depositthickness, since they are observed after very short depositiontimes. Thus, it is clear that the incorporation of nano-sizedparticles modifies the growth of the NiP matrix to a larger extentthan that of micro-sized ones, as surface nodules do not appearwith the larger particles. However, with the experimentalconditions used in the present study, the formation of these

tings: (A) NiP/α−SiC, (B) NiP/SiC nano.

Table 3Vickers microhardness and weight loss of some composite coatings

HV0.1 Δ weight/mg

As-obtained Annealed As-obtained Annealed

NiP 511±22 850±31 8.36±2.14 4.10±1.58NiP /13% α-SiC 600±30 1020±38 5.21±1.84 2.02±0.77NiP /5% M11 622±35 975±35 6.53±1.32 4.01±1.12NiP /6% SiC nano 590±46 1075±46 6.32±2.67 3.22±0.54

Fig. 6. Surface profile of NiP /8.5% SiC nano obtained on a mirror polishedsurface.

394 M. Sarret et al. / Surface & Coatings Technology 201 (2006) 389–395

nodules is not due to a decrease of the phosphorous content, butrather seems related to a change in the growth mechanismpromoted by the incorporation of the nano-particles.

The incorporation of particles to the NiP matrix alwaysmodifies the surface finish, both in terms of brightness andsurface roughness. During particle codeposition via theautocatalytic process, the NiP matrix grows around the particlesand, when the deposition process is stopped at a certain time,many particle edges remain uncovered. Thus, it is usuallyconsidered that polyhedral particles lead to more rough depositsthan spherical ones [18]. The NiP coatings obtained with ourelectrolyte are very bright and smooth with a rms of about10 nm. After particle incorporation, the surface becomes eithermore or less foggy and rough, depending on the incorporationpercentage and particle characteristics. The highest rms isobtained with the smallest particles, which are SiC nano,because of the nodules that cover the surface (270 nm for a6% SiC incorporated). With the micro-sized particles, and withsimilar incorporation contents, the rms values increase asexpected, depending on the particle characteristics: for coat-ings containing about 8% particles, the lowest values (85 nm)are obtained with the smallest and more rounded particles ofM11 and the highest (170 nm) with α-SiC.

30 40 50 60 70 80 90abc

d

Fe Fe

NiNi3PSiC(n)M11

2 θ / …

Fig. 7. X-ray diffractograms corresponding to: a, NiP; b, NiP /8% M11; c, NiP /6.5% SiC nano and d, NiP /6% SiC nano after heat treatment.

3.2.3. StructureFig. 7 shows diffractograms of some coatings, as-obtained

and after heat treatment. Particle incorporation does not affectthe structure of the electroless NiP matrix that consists of asupersaturated solid solution of phosphorous in nickel. Theaverage grain size calculated with the Scherrer equation isapproximately 3 nm. After heating to 400 °C for 4 h, the nickelphosphide (Ni3P) phase precipitates in the matrix anddiffractograms show well-defined peaks corresponding tocrystalline Ni, Ni3P and embedded particles [19,20]. Theannealing process causes deposit grains to undergo remarkablegrowth, reaching an average size of approximately 25–30 nm.

3.2.4. Wear resistance and hardnessFinally, Table 3 summarizes weight loss as measured by

wear tests, and Vickers microhardness of NiP and some NiPcomposite coatings as-deposited and after heat treatment. Thehardness values of NiP coatings as plated and heat-treated aresimilar to those obtained in other cases for deposits with asimilar phosphorous content [21,22]. The values for thecomposite coatings are more difficult to compare due tovariations in type and particle content but, as expected, theyincrease with the incorporation of all ceramic particles.However, it is interesting to note that, after the annealingprocess, a low percentage of SiC nanoparticles results in thesame (or even slightly higher) hardness that a coating contain-ing a higher amount of SiC micro-sized particles. Weight losspatterns are also as expected, since the presence of hard particlesdecreases mass loss. In this case, the best results are obtainedwith the biggest particles (α-SiC) but it must be considered thatthey have the highest incorporation content. Although there isno comparison between micro- and nano-sized Si3N4 particles,Table 3 also includes the results obtained with M11 nitride. Asobserved, the microhardness increases with the particlesincorporation but the weight loss of the composites is similarto that obtained without particles, in accordance with otherexperiments where it is suggested that these coatings must beused only under lubricating conditions [23].

4. Conclusions

With the commercial NiP electrolyte and the ceramicparticles used in this study, two different patterns have beenobserved when trying to obtain composite coatings. In the rangebetween 0.6 and 2 μm, no significant differences have beenobserved between the silicon carbide and nitride particles. Inboth cases, the amount of embedded particles increases with

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particle size and their incorporation modifies neither thephosphorous content nor the deposition rate of the process.The analysis of the incorporation results in terms of the numberdensity of particles shows that for micron and submicronparticles the codeposition depends on the particle size and noton the particle nature. The composite coatings obtained in thisrange of sizes show uniformly distributed particles and thehardness and wear resistance are improved, particularly with theSiC particles and after annealing.

However, when nano-sized particles are used, the behaviourof the two ceramics diverges: SiC is incorporated to a relativelyhigh amount, while Si3N4 is not. At this size level, the nature ofthe particle seems to be the most important factor in determiningits incorporation into the metallic matrix. With regards todeposition, the presence of SiC nano-particles reduces the rateand modifies the coating morphology, with the appearance ofnodules that cover the entire surface. This indicates that nano-particles alter NiP growth to a much greater extent than domicro-sized ones. From the literature, it is known that thesurfaces of SiC and Si3N4 powders can be oxidized to someextent and this fact can reduce or even inhibit their codeposi-tion. More work is needed to establish the differences betweenthe SiC and Si3N4 nano-particles and to understand the growthmechanisms when these particles are incorporated into the NiPmatrix. Finally, it must be mentioned that, for SiC particles, adecrease in the particle size affects the microhardness in apositive way, as lower amounts of embedded nano-particles areneeded to obtain the same response.

Acknowledgements

The authors are grateful to the MEC (project number MAT2003-09483). They also thank the Serveis Cientificotècnics ofthe University of Barcelona for surface analysis measurements.

References

[1] J.N. Balaraju, T.S.N. Sankara Narayanan, S.K. Seshadri, J. Appl.Electrochem. 33 (2003) 807.

[2] A. Grosjean, M. Rezrazi, J. Takadoum, P. Bercot, Surf. Coat. Technol. 137(2001) 92.

[3] M.R. Kalantary, K.A. Holbrook, P.B. Wells, Trans. Inst. Met. Finish 71(1993) 55.

[4] P. Wu, et al., Wear 257 (2004) 142.[5] C. Müller, M. Sarret, M. Benballa, Surf. Coat. Technol. 162 (2003) 49.[6] I. García, J. Fransaer, J.P. Celis, Surf. Coat. Technol. 148 (2001) 171.[7] M. Kaisheva, J. Fransaer, J. Electrochem. Soc. 151 (2004) C89.[8] S.C. Wang, W.C.J. Wei, Mater. Chem. Phys. 78 (2003) 574.[9] A. Grosjean, M. Rezrazi, P. Berçot, M. Tachez, Met. Finish. 96 (1998) 14.[10] R.P. Socha, K. Laajalehto, P. Nowak, Colloids Surf., A Physicochem. Eng.

Asp. 208 (2002) 267.[11] V. Médout-Marère, A. El Ghzaoui, C. Charnay, J.M. Douillard, G.

Chauveteau, S. Partyka, J. Colloid Interface Sci. 223 (2000) 205.[12] I. Bertóti, G. Varsányi, G. Mink, T. Székely, J. Vaivads, T. Millers, J.

Grabis, Surf. Interface Anal. 12 (1988) 527.[13] L. Bergström, R.J. Pugh, J. Am. Cream. Soc. 72 (1989) 103.[14] Y. Fukada, P.S. Nicholson, J. Eur. Ceram. Soc. 24 (2004) 17.[15] J. Zhang, F. Ye, D. Jiang, M. Iwasa, Colloids Surf., A Physicochem. Eng.

Asp. 259 (2005) 117.[16] G. Jiaqiang, L. Lei, W. Yating, S. Bin, H. Wenbin. Surf. Coat. Technol.

(in press).[17] A. Grosjean, M. Rezrazi, P. Berçot, Surf. Coat. Technol. 130 (2000) 252.[18] A. Grosjean, M. Rezrazi, P. Berçot, M. Tachez, Met. Finish. 96 (1998) 14.[19] I. Apachitei, F.D. Tichelaar, J. Duszczyk, L. Katgerman, Surf. Coat.

Technol. 149 (2002) 263.[20] I. Apachitei, F.D. Tichelaar, J. Duszczyk, L. Katgerman, Surf. Coat.

Technol. 148 (2001) 284.[21] K.G. Keong, W. Sha, S. Malinov, Surf. Coat. Technol. 168 (2003) 263.[22] M.H. Staia, E.S. Puchi, G. Castro, F.O. Ramirez, D.B. Lewis, Thin Solid

Films 355-356 (1999) 472.[23] J.N. Balaraju. PhD thesis, I.I.T. Madras, Chennai (2000).