Surface and Coatings Technology 167 (2003) 207–211

Development of electroless NiP–PTFE–SiC composite coating
Y.S. Huang, X.T. Zeng*, I. Annergren, F.M. Liu
Singapore Institute of Manufacturing Technology, Singapore 638075, Singapore

Abstract Electroless nickel (EN) and EN composite coatings with polytetrafluoroethylene (PTFE) andyor SiC were deposited by chemical deposition. The microstructure analysis was conducted with scanning electron microscopy and X-ray diffraction. Differential scanning calorimetry was used to study the phase transition of the coating during the heat treatment. The mechanical and tribological properties were measured using hardness indentation, scratch test and pin-on-disc wear test. The surface energy was analysed using water droplet surface contact angle measurement. The synergistic effects of SiC and PTFE on the wear and anti-sticking properties of the coatings are discussed. ᮊ 2002 Elsevier Science B.V. All rights reserved.
Keywords: EN-composite; Wear; Hardness; PTFE; SiC; Anti-sticking

1. Introduction Electroless nickel (EN) coatings are widely used in the chemical, mechanical and electronic industries because of their wear and corrosion resistance properties. The EN deposition process is based on a redox reaction in which the reducing agent is oxidized and Ni2q ions are reduced on the substrate surface. An advance in electroless Ni–P deposition is the co-deposition of solid particles into coatings to further improve certain properties w1x. Electroless Ni–P–PTFE films present excellent self-lubricating and anti-sticking properties w2–4x, however, the coating hardness is correspondingly decreased depending on the volume fraction of polytetrafluoroethylene (PTFE) particles in the coating. On the other hand, electroless Ni–P–SiC coatings are recognized for their hardness and wear resistance and are considered as a replacement for ‘hard chromium’ in the aerospace industry w5,6x. One of the issues with the co-deposited Ni–P–SiC coatings is the higher friction coefficient compared with electroless Ni–P coatings. Nowadays, complex composite coatings containing both hard and lubricating particles are receiving more and more interest. Losiewicz et al. w7x studied the phase composition and surface morphology of an electrolytic
*Corresponding author. Tel.: q65-67938521; fax: q65-67922779. E-mail address: xzeng@simtech.a-star.edu.sg (X.T. Zeng).

Ni–P–TiO2 –PTFE composites for an electrochemical reaction electrode; Deng et al. w8x studied electrodeposited Re–Ni–W–SiC–PTFE composite and their properties; Straffelini et al. w9x studied the dry sliding behavior of a double Ni–P y SiC–PTFE co-deposit composite; Wang et al. w10x reported the tribological behavior of compression molding polyetheretherketone composite filled with nanometer sized SiC and PTFE paticles. Up to now, few studies were reported on electroless plating of complex composite coatings. This work aimed to develop electroless plating of EN–PTFE–SiC composite coatings to achieve high hardness, low friction coefficient and low surface energy. A comparison study of the properties of EN, EN–SiC, EN–PTFE and EN–SiC–PTFE composite coatings was conducted. The effects of SiC and PTFE particles on the coating properties will be discussed. 2. Experiments EN and EN composite coatings containing PTFE and y or SiC particles were deposited on л25=6 mild steel substrate. ENLUBE dispersion of PTFE was used as the PTFE additive. Micro-sized (average size 4.5 mm) bsilicon carbide particles were used for SiC co-deposition. Surfactants were used for particle dispersion and surface charge adjustment. Magnetic stirring was used to keep particles from sediment. The composition of the solution and the plating parameters for electroless EN–PTFE– SiC co-deposition are listed in Table 1.

0257-8972/03/$ - see front matter ᮊ 2002 Elsevier Science B.V. All rights reserved. doi:10.1016/S0257-8972(02)00899-X

All the samples studied had a thickness of approximately 15 mm. 3. Fig. To evaluate the tribological properties of the coatings. The coating hardness was measured using microhardness indentation. which linearly increased from 10 to 128 N at a constant rate of 100 N miny1. due to the formation of Ni3P alloy phase (Fig. The SiC particles were much heavier than PTFE. / Surface and Coatings Technology 167 (2003) 207–211 Table 1 Composition of EN and EN-composite bath and plating conditions EN NiSO4 (g l ) NaH2PO2ØH2O (g ly1) CH3COONaØ3H2O (g ly1) Latic acid (85%) (ml ly1) Thiourea (mg ly1) PTFE dispersion (ml ly1) SiC powder (g ly1) Surfactants (mg ly1) pH Plating temperature y1 EN–PTFE 26–30 28–30 35–45 20–25 3–5 6–8 – – 4. The relative intensity of Ni3P to NiP peaks was much weaker in the SiC or PTFE codeposited samples. compared with pure EN samples. It can be seen that the as-plated coatings had an amorphous NiP structure. The hardness of all four type coatings was significantly increased after heat treatment. resulting in the particles being nonuniformly distributed in the coatings. The DSC results confirmed that both SiC and PTFE particles were stable in EN composite coating during the annealing at 400 8C. and the wear track diameter. as measured by a Talysurf profilometer.S.8 88–90 8C EN–PTFE–SiC 26–30 28–30 35–45 20–25 3–5 6–8 8–10 100–200 4. 1 shows the SEM pictures of EN and EN composite coatings. There were two exothermic peaks observed in the DSC curve. However. This affected the co-deposition and distribution of the PTFE particles in the coating. and differential scanning calorimetry (DSC) was used to study the phase transition of the coating during the heat treatment. The introduction of PTFE or SiC particles into the EN resulted in a substantial decrease or increase in hardness. Results and discussion Fig. These particles played a very important role in the wear performance of the composite coating. Fig. A normal load of 10 N was used during the wear tests. No phase transition was observed by XRD for the samples heat-treated at 300 8C.8 88–90 8C The morphology and microstructure of the coatings were analysed using scanning electron microscopy (SEM) and X-ray diffraction (XRD) using Cu Ka Xrays. The surface energy of the coating was analysed using water droplet surface contact angle measurement.5 mm and at a linear speed of 20 cm sy1 for a total sliding distance of 4000 m. The adhesion strength was measured using a Teer 2200 scratch tester at a constant speed of 10 mm miny1 under a normal load. . the DSC samples were prepared by stripping off the coatings from aluminum substrates using 65% NaOH solution. which required strong agitation to keep them from flocculation. Optical microscopy was used to confirm the starting point of the adhesive failure along the scratch track. depending on the corresponding concentration of the PTFE and SiC particles in the coatings. Post-deposition annealing was conducted. wear tests were carried out at an air humidity of 45"10 RH% and a temperature of 24"1 8C using a pin-on-disc tribometer with the sample placed horizontally on a turntable. friction coefficient and the normalized wear rates of the EN and EN composite coatings are listed in Table 2. Huang et al. when SiC and PTFE particles were deposited together. indicating that the embedded particles hindered the Ni3P grain growth. 2 shows a typical DSC thermogram of EN– PTFE–SiC composite coating. The EN–PTFE– SiC composite coating showed a moderate hardness between EN–PTFE and EN–SiC. with the EN–PTFE–SiC the weakest. The small peak at 280 8C may be due to the stress relaxation of the particles–matrix interfaces.8 88–90 8C 26–30 28–30 35–45 20–25 3–5 – – – 4.5 times higher than that of the EN without SiC particles. The heating temperature was controlled at a rate of 10 8C miny1. The hardness. The tests were performed using alumina pins with a radius of 4. A hardness of 1365 HV was measured for the heat-treated EN–SiC. The overlapped sharp peaks at approximately 2us458 were from the high speed steel substrate.8 88–90 8C EN–SiC 26–30 28–30 35–45 20–25 3–5 – 8–10 100–200 4.208 Y. After annealing at 400 8C. 3). the crystallized Ni3P alloy phase was observed. 3a and b show XRD patterns of EN and EN composite coatings before and after annealing. some interference effects occurred. In this experiment. The wear loss and normalized wear rate were calculated from the wear scar cross-sectional area. This was confirmed by XRD analysis. which is approximately 2. EN–PTFE and EN– SiC were deposited with PTFE or SiC particles uniformly distributed in coatings. The peak at approximately 340 8C was associated with the phase transition from the amorphous NiP matrix to a mixed structure of polycrystalline Ni and Ni3P alloy.

Apparently. Fig.Y. (b) EN–PTFE. The results are also shown in Table 2. Huang et al. According to this theory. the contact angle of de-ionised water droplet Fig. This may be explained by Guglielmi’s two step adsorption theory w11x. co-deposition of both PTFE and SiC particles into the EN coating reduced the adhesion. SEM images of (a) EN. (c) EN–SiC and (d) EN–PTFE–SiC composite coatings. Almost no other adhesive force may have existed between the co-deposited particles and the substrate. To estimate the surface energy of the EN composite coatings. then some relative strongly adsorbed (both physical and static electrical) particles were built in to the depositing metal matrix. Thus the adhesion strengths of the EN composite coatings were negatively affected. . / Surface and Coatings Technology 167 (2003) 207–211 209 The adhesion of the coatings to substrates was evaluated by the critical load in scratch test. DSC thermogram of the EN–PTFE–SiC coating obtained at a heating rate of 10 8C miny1. 2. 1. producing a layer of loosely adsorbed particles with a relatively high surface coverage. the dispersed particles were first physically adsorbed on the substrate.S.

The EN–FTFE–SiC coating demonstrated a combination of the advantages of the EN–SiC in high loadbearing capacity and EN–PTFE in low surface energy and high wear resistance. The results are also shown in Table 2.0. 4.0. which reduced the friction coefficient and wear w12x. Huang et al. The three EN–composite coatings showed significantly improved wear resistance.0 120. Conclusions EN and EN composite coatings with PTFE and y or SiC particles were deposited by chemical deposition. 4 shows the friction coefficients of the four tested coatings as a function of sliding distance.52 0. Fig. indicating a decrease in surface energy.59) resulted in a relatively higher wear rate. The results showed that: (1) The as-deposited coatings had an amorphous NiP structure incorporated with uniformly distributed PTFE or SiC particles. the highest friction coefficient (. the EN–PTFE coating showed the lowest friction coefficient (.2 101. to the coating surface was measured using a goniometer. Phase transition from the amorphous NiP to a mixed structure of crystalline Ni and Ni3P alloy was observed at 340 8C.48) and. Friction coefficient vs. 4. representing the lowest surface energy among the four tested coatings. 3.36 0. correspondingly the lowest wear rate despite the lowest hardness. / Surface and Coatings Technology 167 (2003) 207–211 Fig. A comparison of the properties of EN. The uneven curve with the EN coating was caused by the coating spalling along the wear track. The EN– PTFE coating showed the highest surface contact angle (upto 1208).2 79.59 0. EN–SiC. The EN–SiC coating demonstrated better load-support due to the higher hardness.S. Table 2 Main properties of EN and EN-composites Microhardness (HV50) As-plated EN EN–PTFE EN–SiC EN–PTFE–SiC 453 340 530 450 Heat-treated 956 421 1365 701 Friction coefficient (average) – 0.52 Wear rate (10#6 mm3 N#1 m#1) Critical load (N) Contact angle 2. XRD patterns of (a) as-plated and (b) heat-treated at 400 8C for 1 h of EN and EN composite coatings. EN– PTFE and EN–SiC–PTFE composite coatings was conducted. Among them.210 Y.45 0.36 70 62 60 60 95.7 .48 0. The inclusion of PTFE particles effectively increased the surface contact angle. However. sliding distance for EN and EN composite coatings. This could be explained by the formation of a PTFE transfer film between coating and pin ball during the wear sliding. This is desired in many applications for anti-sticking performance. Fig.

/ Surface and Coatings Technology 167 (2003) 207–211 211 (2) Annealing at 400 8C resulted in a substantial increase in coating hardness. A.J. Xu-Shou Zhang. Gierlotka. Apachitei. Stepien. Rezrazi. Morvan. w9x G. Scripta Mater. w8x Lun-Hao Deng. which was about a seventh of that recorded for the EN coating. 9 (1988) 65–68. Huang et al. The EN–SiC coating showed the highest hardness (. Wear 236 (1999) 179–188. A. D. w4x Z. w5x I. Surf. Finish. Thin Solid Films 349 (1999) 43–50.S. Thin Solid Films 245 (1994) 98–103. P. Overkamp. J. Under the experimental conditions. P.J. 18 (1999) 9–11. 38 (1998) 1383–1389.1365 HV) while the EN–PTFE showed the lowest friction coefficient (. Losiewicz.R. Plat. Bercot. Zhong-Cheng Guo.48). Wei-Min Liu. Xian-Wan Yang. (3) The EN–PTFE–SiC composite coating demonstrated a combination of the advantages of the EN–SiC in high hardness and load-bearing capacity and of the EN–PTFE coating in low friction coefficient. References w1x I. J. . w10x Qi-Hua Wang. w7x B. Rezrazi. automobile parts and general wear components. Electrochem. Overkamp. w6x A. depending on the percentage of the particles included in the coating. Duszczyk.0. Straffelini. low surface energy and high wear resistance. 38 (1998) 1347–1353.Y. w2x Lai-Gui Yu. Thin Solid Films 245 (1994) 98–103. P. Colombo. Pagetti. A. Coat. M. Berc. J. Jian-Min Chen. a sliding wear rate against an alumina pin of approximately 3. w12x Lai-Gui Yu. Apachitei. Surf. Serhal. The EN–PTFE–SiC showed a moderate hardness and friction coefficient in between. Soc. Electroplat. M. Surf. Finish. Katgerman. Guglielmi. The significantly improved wear resistance plus low surface energy of the EN–PTFE–SiC coatings will find applications for moulds. Budnik. D. J. L. Qun-Ji Xue.B. 145 (2001) 233–241. Scripta Mater.B. Molinari. Technol. Coat. J. Duszczyk. Ebdon. 137 (2001) 92–96. Grosjean.6=10y7 3 y1 y1 mm N m was measured for EN–PTFE and EN– PTFE–SiC. w3x P. Wear 243 (2000) 140–146. L. P. 119 (1972) 1009–1015. Technol. Xu-Shou Zhang. w11x N. Takadoum. Katgerman. J.