Contributed papers Deposition of high wear resistance of Nicomposite coatings

Saher Shawki and Z. Abdel Hamid

The authors Saher Shawki and Z. Abdel Hamid are at the Central Metallurgical R&D Institute, Helwan, Cairo, Egypt. Abstract Electrodeposited Ni-P composite coatings incorporating a variety of inorganic particles were obtained from Watts nickel bath containing sodium hypophosphite. The mechanism of co-deposition of various particles (SiC, Al2O3, quartz and sand) was studied in view of the electro-kinetic charge characterizing the solid particles. Means to improve the mobility of the particles in the plating solution were investigated using sodium oleate as surface active agent. The purpose was to increase particle content in the coating to attain high hardness values. Special attention was given to the deposition process using SiC particles. The surface morphology, hardness and wear resistance of the composite coatings were determined. Hardness values were maximized by simple heat treatment in air atmosphere which led to the precipitation of the hard Ni3P phase. Sound, coherent and high wear resistance coatings could be produced.

As new materials, composite coatings offer many attractive properties that can be very useful for various engineering applications such as machine construction and aeroengines. Composite coatings are produced by direct entrapment of solid particles during the build-up of the metal matrix by electro- or electroless deposition[1]. In order to reinforce the mechanical or antifrictional properties of the coating, the foreign particles can be of refractory[2-4] or dry-lubricant nature[5,6]. The properties of the coatings are governed by the type and size of the particle, its content in the coating and the mode of distribution. The addition of other alloying elements such as phosphorus to the metal matrix (Ni) adds to the improvement of properties. Electroless Ni-P coatings are characterized by their superior hardness and corrosion resistance. Generally, the electroless plating process is hampered by its slow rate of deposition, complicated operation and high cost. Instead, electrodeposition of Ni-P composite coatings is faster, the solution is more stable and has fewer replenishment problems. The present work was undertaken to elucidate the mechanism and principal factors affecting the incorporation of the solid particles into a growing deposit. The aim was to improve the plating process technology and to modify the coating properties such as wear resistance. Most of the work was carried out on Ni-P-SiC composite coatings.

Experimental procedure
Plating solution (Watts bath) (1) Composition NiSO4.6H2O 300 g/l NiCl2.6H2O 60 g/l H3BO3 40 g/l NaH2PO2 5 g/l Dispersed particles: Material SiC, Al2O3, sand, quartz Content in solution 20-100 g/l Particle size < 7 m (2) Operating conditions:Temperature 60C pH 4 Current density 2.5-10 A/dm2 Mechanical stirring 150 rpm Wear measurements For measurement of wear resistance, the coated samples (20 50 1 mm) were rotated

Anti-Corrosion Methods and Materials Volume 44 Number 3 1997 pp. 178185 MCB University Press ISSN 0003-5599

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Deposition of high wear resistance of Ni-composite coatings

Anti-Corrosion Methods and Materials Volume 44 Number 3 1997 178185

Saher Shawki and Z. Abdel Hamid

tangentially in a sand/water (ratio 4:2)[7]. The rotation speed was kept constant at 150 rpm and the wear effect was measured in terms of loss in weight expressed as /hr.The wear measurements were performed to be within the thickness of the coating without reaching to the base metal. Zeta-potential The zeta meter was used to determine the direction and speed of the solid particles moving in a dilute plating solution between two electrodes under an applied electric potential difference. The sign and magnitude of the potential ( ) of the solid particles are related to the mobility of the particles in solution.

Figure 1 Effect of current density on SiC content of the composite (particle content in plating solution, 80g/l)

Results and discussion

Ni-P- particle composites Preliminary experiments showed that Ni-P composites containing 4.5 wt. per cent phosphorus could be deposited from Watts nickel bath with the addition of 5 g/l sodium hypophosphite. The solid particle inclusion in the coating (2-4.5 wt per cent for SiC) was found to depend on the amount of the particles in the electrolyte (20-80 g/l). The effect of current density on the amount of particle inclusion is illustrated in Figure 1, which depicts that the particle content in the coating increases with the increase of applied current. While deposition is very slow at current density (c.d) less than 2 A/dm2, deposits with c.d. higher than 7.5 A/dm2 are brittle and can be spalled off at the edges of the substrate because of the built-in high internal stress in the coating. The results indicated that the mobility of solid particles in the electrolyte is increased by the applied electric current. The growth of the Ni-P-SiC coating is almost regular during the deposition process, as shown in Figure 2. The deposition rate at a certain current density is not affected by the amount of solid particles in plating solution as indicated by the results given in Figure 3 for SiC and Al2O3. The deposition rate is known to be controlled by the composition and operating conditions of the plating electrolyte such as c.d, pH value and temperature. Mechanism of deposition The precise nature of the process of codeposition and the arrival to the cathode of

the solid particle was subject to controversy. Three main mechanisms were previously suggested[1] to explain the difference in the ability to deposit various types of solid particles: electrophoresis, mechanical entrapment and physical adsorption In this research it was initially thought that the inclusion of solid particles depends largely on their mobility and electrokinetic nature in the plating solution. The work described below has been designed to elucidate the aspect of the deposition process on the basis of the electrokinetic mechanism. Solid particles in solutions are electrolytically charged by adsorbing ions on their surfaces. The sign and magnitude of the electrolytic charge is known as zeta potential ( ). The values of zeta potential for different particles were determined in dilute solution of pH 4 containing all the plating species. The results indicated that the various particles are negatively charged with a magnitude ranging from 35 to 60 mV. Figure 4 demonstrates the dependence of the amount of incorporated particles on the magnitude of potential. The mechanism of solid particle electrodeposition could be suggested as follows: positively charged Ni ions in solution are adsorbed on negatively charged solid particles. The particle with adsorbed ions migrates to the cathode where metal ions are reduced to Ni atoms forming the coating with the entrapped solid particle occupying a place in the metal (or alloy) matrix. A schematic diagram illustrating the mechanism is shown in Figure 5. The results shown in Figure 4 indicated that the higher the magnitude of the charge on the particle ( potential), the lower the amount

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Deposition of high wear resistance of Ni-composite coatings

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Saher Shawki and Z. Abdel Hamid

Figure 2 Effect of plating time on the coating thickness of composite coatings

Figure 3 The effect of particle content in the electrolyte on the deposition rate of composite coatings

deposited in the coating. This can be explained on the basis of the following assumptions: Particle/ion mobility: with high potential a greater number of Ni ions are adsorbed on the surface of the solid particle. The aggregates of Ni ions surrounding a particle behave as one large charged body suspended in the electrolyte. The mobility of the later formation is, therefore, expected to decrease under the heavy weight of the coupled formation. The result will be a smaller number of solid particles reaching the cathode. Relative amount occluded: since Ni ions surrounding each particle are immediately reduced to Ni atoms at the cathode surface, the relative amount of particles of high potential (quartz, sand) incorporated in the

Figure 4 Effect of Zeta potential on the percentage of particle in the composite

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Saher Shawki and Z. Abdel Hamid

Figure 5 Schematic diagram of the mechanism of solid particle mobility in the plating electrolyte

coating will be less than the amount of particles of lower potential (SiC, Al2O3). In solution, the later type of particles are surrounded by fewer Ni ions; the result is high content of particles in the coating. Although both assumptions may be valid together, the authors are in favour of the particle/ion mobility. For conrmation of that view a number of experiments were carried out using additives of anionic surfactant (sodium oleate) in variable concentrations. The aim was to overcome the gravitational effect of the assumed heavy aggregates of ions entrapping the solid particle. The results of surfactant addition showed an increase in the amount of particles deposited in the coating by the increase of the concentration of sodium oleate up to an optimum value of 5 10-3 mole/l (Figure 6). Higher concentrations of oleate did not yield a corresponding increase in the SiC in the coating.
Figure 6 The effect of surfactant concentration on the content of SiC in the deposit

Na oleate is known to be present in acidic solutions of pH 3-7 in a polarized form[8]. In a plating solution of pH 4 Na oleate is adsorbed on the surface of SiC particles. The following mechanism can be suggested as an interpretation for the results shown in Figure 6. There exists in solution a competition between Ni and Na ions (both positively charged) to cover the negatively charged SiC particle. Meanwhile, the oleate group, with its -COO- part, are attached to the adsorbed Ni ions. The surface of the solid particle is then partly covered with the oleate while the tail (-R) hangs in the solution bulk (Figure 7). With increased amounts of Na oleate a larger area of the particles surface is covered with Na+ at the expense of the area covered with Ni++. On reaching the cathode surface, nickel (and phosphorus) will be deposited with a higher content of SiC. The mechanism can thus justify the ascending part of the relation shown in Figure 6. However, the optimum values of SiC content are explained as being due to adsorption of only one monolayer of the oleate, which hardly competes with Ni ions. To conrm the later idea, SiC particles were treated separately with the surfactant (without Ni ions) prior to addition to the
Figure 7 Schematic diagram of the mechanism of adsorption of surfactant (Na-oleate) on a solid particle

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Saher Shawki and Z. Abdel Hamid

plating solution (conditioning). The result (shown in Figure 6) was the deposition of SiC in a smaller amount than that obtained with optimum value of the surfactant.

Plate 1 Surface morphology of composite coatings, Ni-P-SiC

Properties of composite coating

Morphology and structure The deposited Ni-P-SiC coatings were dark grey in colour, rough to the touch and rmly adherent to the base metal. The roughness was affected by the amount and size of SiC particles. Plates 1-3 gives scanning electron microscopic views of the surface of Ni-P composites with SiC, sand and Al2O3 inclusions. The ne particles were dispersed homogeneously in the matrix. Plate 4 is a photomicrograph of unetched cross section of the as-plated Ni-P-SiC coating (4.3 wt per cent SiC) which shows that the SiC particles (less than seven microns) are evenly distributed in the deposit. Hardness and wear The properties of the coatings are generally related to and controlled by the amount of solid particles in the coating. The microhardness tests on the coatings are affected by the solid particles inclusion. The resulting indentation is not a measure of the plastic deformation of the alloy material but the indenter force is diverged by the embedded rigid and uncompressible particles. For this reason the examination of hardness of various coatings was restricted to the assessment of surface hardness and not to the coating prole structure (cross-section). The effect of SiC content in the electrolyte (20-100 g/l) on the hardness of two types of deposits (Ni-SiC and Ni-PSiC) is shown in Figure 8, curves (a) and (b) respectively. The hardness values of the composites increase with the increase of SiC in the coating. In the as-deposited Ni-P coating, P exists as super-saturated solid solution in the nickel matrix. On heat treatment at 400C for one hour the coating hardness was increased from 400 to 500 VHN as a result of the precipitation of Ni3P phase[9]. The values, however, depend on the P content in the alloy. The incorporation of SiC into Ni-P deposits led to further increases in the hardness values when subjected to the same heat treatment cycle (Figure 8 curve (c)). A value up to 1,200 VHN could be reached with SiC 182

Plate 2 Surface morphology of composite coatings, Ni-P-Sand

Plate 3 Surface morphology of composite coatings, Ni-P-Al2O3

Plate 4 The photomicrograph of cross section of the Ni-P-SiC coating

Steel substrate

Composite coating

Sample holding resin

Deposition of high wear resistance of Ni-composite coatings

Anti-Corrosion Methods and Materials Volume 44 Number 3 1997 178185

Saher Shawki and Z. Abdel Hamid

content in the coating of 4.3 wt per cent. The drastic increase is due to formation of Ni3P phase as identied by X-ray diffraction analysis. Figure 9 shows a comparison between the X-ray pattern for the as-plated and heat treated Ni-P-SiC coatings.

Figure 8 The effect of SiC (wt. per cent) in the coating on the hardness of deposits

The wear reistance and hardness of electrodeposited composite coatings were found to be related to each other as well as to the particle content in the coating. Coatings with maximum hardness exhibited highest wear resistance. A tangential motion wear test in sand/water mixture was used to assess the resistance to sliding and abrasive wear. The weight loss of the coated sample was determined and the relation between the test time and loss in coating thickness (/hr) was drawn. Figure 10 shows a group of the straight line relationships obtained with various coatings. The abrasion resistance was estimated by calculating the reciprocal of the slope of the straight line. The results are shown in the collective diagram, Figure 11, which indicates the following general features: Phosphorus deposition: slightly increased the wear resistance of Ni electrodeposits (coating B compared to A); SiC inclusion; considerably increased the wear resistance of the as-plated Ni-P coatings (coatings D and E); and Heat treatment: further improved the wear resistance of the composite coatings (coatings C and F).

Figure 9 The X-ray diffraction pattern for Ni-P-SiC composite: without heat treatment and with heat treatment

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Saher Shawki and Z. Abdel Hamid

Figure 10 The relationship between the test time and loss in coating thickness

Figure 11 Hardness and wear resistance of the composite coatings compared to others electrodeposited

Ni Ni-P as plated Ni-P heat treated Ni-SiC Ni-P-SiC as plated Ni-P-SiC heat treated 0 0 50 250

Key
B

Wear resistance VHN

C

100 500

150 750

200 1,000

250

Wear resistance X102 ( m/hr)1

1,250 VHN

The highest values of wear resistance could be achieved by heat-treated Ni-P-SiC coatings.

Conclusions
Ni-P composite coatings can be electrodeposited from Watts Ni solution containing Na hypophosphite and ultrane particles of SiC, Al2O3, sand or quartz. The particle content in the plating solution and the applied c.d. were found to be important factors in controlling the inclusion of the solid particles into the deposit. The amount was, however, limited by the volume content of the particles that can be

accommodated in the metallic matrix of the coating. The co-deposition of solid particles with Ni-P coatings was explained on the basis of the mobility and electrokinetic nature of the particles in the electrolyte. Under the same operating conditions, the amount of particles deposited in the coating could be increased from 4 to 9 wt per cent by the addition of surface active agents of anionic type to the plating solution. It has been shown that the coating properties such as hardness and wear resistance were related and controlled by the amounts and distribution of the solid particles in the coating matrix. The hardness of Ni-P-SiC

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Saher Shawki and Z. Abdel Hamid

coating could be increased by heat treatment to values over 1,200 VHN. These coatings are coherent and characterized by high wear resistance which can be of benet in several industrial applications. Attention should be given to the internal stresses and the means of releasing these stresses, which may hamper the coating performance if they are subjected to postmechanical working operations.

phosphorus electrodeposits, Plating & Surface Finishing, Vol. 81 No. 10, 1994. 4 Roos, J.R., Celis, J.P., Fransaer, J. and Buelens, C., The development of composite plating for advanced materials, Jouirnal of Metals, No. 11, 1990, p. 60. 5 Cowieson, D.R., Sadowska-Mazur, J. and Warwick, M.E., Codeposition of non-metallic particles with tin and tin-nickel alloy, Proceedings of 3rd International Congress for Surface Technology, Berlin, 1985. 6 Lipp, L.C.Solid lubricants their advantages and limitations, Lubrication Engineering, Vol. 32 No. 11, 1976, p. 574. 7 Soror, T.Y., Electroless deposition of nickel as related to the structure, morphology and properties of the coatings, PhD Thesis, Cairo University, 1995. 8 Arbiter, N. and Williams, E.K.C., Conditioning in oleic acid otation, in Fine Particle Processing, SME-AIME, USA, Vol. 1, 1980, pp. 802-31. 9 Changgeng, X., Zonggeng, D. and Lijun, Z., The properties of electrodeposited Ni-P-SiC composite coating, Pating & Surface Finishing, Vol. 75 No. 10, 1988.

References
1 Celis, J.P., Roos, J.R., Buelens, C. and Fransaer, J., Mechanism of electrolytic composite plating: survey and trends, Transactions of the Institute of Metal Finishers, Vol. 69 No. 4, 1991, p. 133. 2 Poeton, A.R., Composite coatings for advanced performance, Metals & Materials, No. 702, 1988. 3 Periene, N., Cesuniene, A. and Matulionis, E., Codeposition of mixtures of dispersed particles with nickel-

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