Surface & Coatings Technology 198 (2005) 173 177 www.elsevier.

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Heat treatment effects on EN-PTFE-SiC composite coatings

Y.S. Huanga,b, X.T. Zenga,*, X.F. Hub, F.M. Liua
a

Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, Singapore, 638075, Singapore b Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China Available online 2 December 2004

Abstract Electroless nickel (EN) composite coatings embedded with SiC and PTFE particles were deposited on mild steel substrates. Postdeposition heat treatment effects on coating properties were studied in a N2 atmosphere. Differential scanning calorimetry (DSC), X-ray diffractometry (XRD), scanning electron microscopy (SEM), EDX and EIS were used to analyse the temperature dependence of the microstructure, composition, mechanical and corrosion properties of the coatings. It was found that the as-deposited EN-PTFE-SiC coatings had a homogeneous structure with microsized SiC and PTFE particles embedded in an amorphous NiP matrix. Phase transition from an amorphous NiP matrix to a mixture of polycrystalline Ni and Ni3P alloy occurred at around 340 8C. The highest microhardness and best adhesion properties were observed for the samples annealed at 400450 8C for 1 h. It is interesting to note that the embedded PTFE particles were still stable even when heat treated at 450 8C, probably owing to the NiP metal matrix package effect. EIS results showed that proper heat treatments also enhanced the corrosion resistance in both acidic (1.0 N H2SO4) and salty (3% NaCl) media, attributing to the coating density and structure improvement. D 2004 Elsevier B.V. All rights reserved.
Keywords: Heat treatment; Electroless composite; Corrosion resistance; Electrochemical impedance spectroscopy

1. Introduction Electroless nickel (EN) coatings are well known for their wear and corrosion resistance. Codeposition of hard or lubricant particles into the EN to form a composite coating can further improve the tribological properties of the coating and also add on additional functions. Hard silicon carbide has been widely used as codepositing particles for wearresistant composites [13]. On the other hand, PTFE was used for lubricant particles to improve wear resistance and antisticking performance in many areas [47]. We have developed a multicomponent EN-PTFE-SiC composite coating which demonstrated a promising combination of mechanical and tribological properties as well as low surface energy [8]. This work studied the postdeposition heat treatment effects on the mechanical and corrosion-resistant properties of EN-PTFE-SiC composite coatings. The temperature
* Corresponding author. Tel.: +65 67938521. E-mail address: xzeng@SIMTech.a-star.edu.sg (X.T. Zeng). 0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2004.10.045

dependence of the coating structures and compositions were also evaluated and discussed.

2. Experiments Multicomponent EN-PTFE-SiC composite coatings were deposited on / 256 mm mild steel substrates. ENLUBE dispersion of PTFE (Ethone-OMI) was used as the PTFE
Table 1 Composition of EN-PTFE -SiC bath solution and plating conditions NiSO4 NaH2PO2SH2O CH3COONa.3H2O Lactic acid (85%) Thiourea PTFE dispersion SiC powder Surfactants pH Plating temperature 2630 g l1 2830 g l1 3545 g l1 2025 ml l1 35 mg l1 68 ml l1 810 g l1 100200 mg l1 4.8 8890 8C

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Fig. 1. Typical DSC thermogram of EN-PTFE-SiC complex composite coating.

Fig. 2. XRD spectra of EN-PTFE-SiC coating measured after heat treated at different temperatures.

additive. Microsized h-silicon carbide particles (CERAC, average size 1.0 Am) were used for SiC codeposition. Selected surfactants were used for particle dispersion and surface charge adjustment [8]. Magnetic stirring was used to keep particles from sedimentation. After pretreatment (grinding, degreasing, etching and washing), the substrates were dipped into an EN composite plating bath and the coating thickness (~15 Am) was controlled by plating time. The compositions of the plating bath solution and the operation parameters for EN-PTFE-SiC codeposition are listed in Table 1. The morphology and microstructure of the coatings were analysed using scanning electron microscopy (SEM, Cambridge S360) and X-ray diffractometry (XRD, Philips XPert Multi-Purpose Diffractometer) using Cu-Ka X-rays. Differential scanning calorimetry (DSC, TA Instruments) was used to study the phase transition of the coating during the heat treatment. The DSC samples were prepared by stripping off the coatings from aluminum substrates using 10% NaOH solution. The coating hardness was measured using a microhardness tester (Akishi) under 50 g indentation load. The adhesion strength was measured using a Teer 2200 scratch tester at a constant speed of 10 mm min1 under a normal load, which linearly increased from 10 to 128 N at a constant rate of 100 N min1. Optical microscopy was used to confirm the starting point of the adhesive failure along the scratch track. The corrosion tests were conducted using a Solartron 1287 Electrochemical Interface and Solartron 1260 Impedance/Gain-Phase Analyzer [9]. A standard three-electrode configuration consisting of the sample as the working electrode, a conventional saturated calomel electrode (SCE) and a carbon counter electrode was used to estimate the polarization behaviors.

Fig. 3. SEM morphology images of EN-PTFE-SiC coating after heat treated at (a) 300 8C, (b) 400 8C, (c) 450 8C and (d) 500 8C for 1 h in N2 atmosphere.

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Impedance Software (Scribner Associates) at their respective corrosion potentials. A 30-mV AC voltage (sine wave) was used as imposing signal, and the measurement frequency range was set from 10,000 to 0.01 Hz. Finally, the polarization curve was measured in the range of 0.2 1.2 V at a constant scan rate of 0.5 mV s1.

3. Results and discussions Fig. 1 shows a typical DSC thermogram of EN-PTFESiC composite coating. The heating temperature was controlled at a rate of 10 8C min1. There were two exothermic peaks observed in the DSC curve. The peak at about 340 8C was associated with the phase transition from the amorphous NiP matrix to a mixed structure of polycrystalline Ni and Ni3P alloy. This was confirmed by XRD analysis. The small peak at 280 8C may be due to the stress relaxation of the particlesmatrix interfaces [10]. Fig. 2 shows the XRD patterns of EN-PTFE-SiC coatings after heat treatment under different temperatures

Fig. 4. Microhardness and critical load in scratch test of EN-PTFE-SiC composite coating heat treated at different temperatures for 1 h.

Both acidic (1.0 N H2SO4) and salty (3% NaCl) solutions were used as the corrosion electrolytes. For each sample, the open circuit potential was first measured for a period of a half hour. Subsequently, the impedance was measured and plotted by Zplot for Windows Electrochemical

Fig. 5. Heat treatment effects on corrosion properties of EN-PTFE-SiC composite coating.

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in N2 atmosphere for 1 h. The spectrum of the as-deposited sample shows peaks corresponding to crystalline SiC, PTFE and amorphous NiP matrix, respectively. There was no significant change in XRD pattern observed for the samples treated at 300 8C, indicating that no phase transition took place at this temperature. When the heat treatment temperature was increased to 350 8C, new XRD peaks corresponding to crystalline Ni and Ni3P appeared, indicating that the NiP matrix crystallization was initiated. The Ni and Ni3P peak intensities increased with the heat treatment temperature. At 500 8C, the PTFE XRD peak at 2h ~18.08 disappeared, indicating that the decomposition of PTFE occurred at or before this temperature. Fig. 3 shows the surface morphologies of EN-PTFE-SiC coating after heat treatment at different temperatures in N2 atmosphere for 1 h. It can be seen that all SiC and PTFE particles were homogenously distributed in the NiP matrix. The heat treatment did not change the coating morphologies before 400 8C. When the temperature was increased to 500 8C, dramatic change in coating morphology was clearly observed with small pores appearing on the whole surface due to the decomposition of PTFE particles, as confirmed by the XRD analysis. It is interesting to note that the PTFE decomposition temperature observed in this work is surprisingly higher than the reported value which was at around 350 8C. Both the XRD and SEM analysis showed that the PTFE particles were kept stable in EN-PTFE-SiC composite coating for annealing at temperatures up to 450 8C for 1 h. We attribute this to the NiP matrix package effect which increased the temperature tolerance of PTFE particles. Fig. 4 shows the microhardness of EN-PTFE-SiC composite coating heat treated at different temperatures for 1 h. The hardness increased from 310 to 770 Vickers hardness with the treatment temperature below 400 8C. This is consistent with the phase transition from the amorphous NiP to Ni3P and Ni crystalline phase. The highest hardness appeared at the temperature somewhere between 400 and 450 8C. Further increasing treatment temperature led to overgrowth of the crystalline Ni3P and Ni grains, resulting in the decreased hardness. The other possible reason for the hardness decrease is the PTFE decomposition at high temperatures, resulting in a loose

Fig. 6. Equivalent circuit of electrochemical impedance spectroscopy test of EN-PTFE-SiC complex composite coating.

coating structure. The scratch test results (shown in Fig. 4) demonstrated a similar trend to hardness, and the highest scratch adhesion was observed at the temperatures between 400 and 450 8C. From these results, we can conclude that the optimized heat treatment temperature is in the range of 400 to 450 8C. Fig. 5 shows the corrosion test results of EN-PTFE-SiC composite coatings in 1.0 N H2SO4 and 3% NaCl media before and after 400 8C heat treatment. It can be seen that heat treatment reduced the value of coating open circuit potentials (from 0.32 to 0.25 V in 1.0 N H2SO4, and from 0.33 to 0.24 V in 3% NaCl electrolytes, respectively), resulting in a better corrosion resistance. The electrochemical impedance analysis results confirmed this conclusion. The fitted results of Nyquist plots are tabulated in Table 2 based on the widely used equivalent circuit as shown in Fig. 6, where the Constant Phase Element (CPEc) resembles a capacitor, whose phase angle is independent of the frequency and has a value of (90CPEc-P) degree. Firstly, the fitted capacitance (CPEc-T) decreased and CPEc-P were closer to 1.0, indicating that the coating became denser and more homogenous. Furthermore, the fitted corrosion resistance was doubled in 1.0 N H2SO4 and tripled in 3% NaCl, respectively. From the polarization EI curves measured during the corrosion test experiments (the shape of EI curves are almost the same), we can conclude that the heat treatment did not change the coating polarization mechanism. All these results show that the corrosion resistance of the EN-PTFE-SiC coating was significantly improved after heat treatment.

Table 2 Heat treatment effects on EN-PTFE-SiC corrosion resistant properties Electrolyte Coating states Open circuit potentials mV vs. SCE 1.0 N H2SO4 3% NaCl As plated Heat treated As plated Heat treated 331 251 328 239 Coating corrosion resistance Rs V cm2 7.603 7.831 35.11 36.13 450 990 13996 46619 Rc CPEc CPEc-T F cm
2

CPEc-P 0.75152 0.84281 0.81134 0.87654

26.23e4 5.294e4 0.61e4 0.33e4

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Fig. 7. Morphology images of EN-PTFE-SiC coating before (a,c) and after (b,d) corrosion tests in 1.0 H2SO4 (a) and (b) as plated; (c) and (d) heat treated at 400 8C for 1 h.

Fig. 7 shows the heat treatment effects on corrosion morphologies of EN-SiC-PTFE composite coatings evaluated in 1.0 N H2SO4. Many corrosion cracks and holes were observed in the as-plated samples after the corrosion test, and the EDX spectra confirmed a relatively stronger iron peak intensity contributed from the substrate (mild steel) after the corrosion test. In contrast, the morphology of heat-treated coating was less affected and iron peaks in the EDX spectra were almost the same before and after corrosion test. This supports the above results.

(2) The optimal heat treatment temperature for ENPTFE-SiC was found to be at 400450 8C, at which, the highest hardness and adhesion strength were measured. (3) Proper heat treatment can significantly improve the corrosion resistance of EN-PTFE-SiC coating both in acidic and salty environments.

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4. Conclusions EN-PTFE-SiC composite coating was deposited on mild steel substrates. The heat treatment effects on coating properties were systematically studied. The results show that: (1) As-deposited EN-PTFE-SiC composite coating has a homogeneous structure with crystalline PTFE and SiC particles uniformly distributed in an amorphous NiP matrix. The phase transition from amorphous NiP matrix to polycrystalline Ni and Ni3P alloy occurred at around 340 8C. The PTFE particles were kept stable at temperatures up to 450 8C, which might result from the NiP matrix package effects.