Electrochimica Acta 49 (2004) 4313–4319

Corrosion resistance properties of electroless nickel composite coatings
Y.S. Huang a,b , X.T. Zeng a,∗ , X.F. Hu b , F.M. Liu a

Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, Singapore 638075, Singapore b Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China Received 8 October 2003; received in revised form 17 February 2004; accepted 13 April 2004 Available online 24 May 2004

Abstract Electroless nickel (EN) composite coatings incorporated with PTFE and/or SiC particles demonstrated significantly improved mechanical and tribological properties as well as low surface energy which are desired for anti-sticking and wear resistant applications. The corrosion resistance of these composite coatings, however, has not been systematically studied and compared. This work aimed to investigate the corrosion characteristics of EN composite coatings using electrochemical measurements which include open circuit potential (OCP), electrochemical impedance spectroscopy and potentiodynamic test. The effects of the co-deposited particles on corrosion behavior of the coatings in 1.0 N H2 SO4 and 3% NaCl media were investigated. The surface autocatalytic properties and the post-heat-treatment on coating corrosion resistance were also discussed. The results showed that both EN and EN composite coatings demonstrated significant improvement of corrosion resistance in both acidic and salty atmosphere. Ni striking substantially enhanced the corrosion resistance due to the improvement of the surface autocatalytic properties and homogeneity. Proper post-heat-treatment significantly improves the coating density and structure, giving rise to enhanced corrosion resistance. © 2004 Elsevier Ltd. All rights reserved.
Keywords: Electroless composite; Corrosion resistance; Heat-treatment; Electrochemical impedance spectroscopy

1. Introduction Electroless nickel (EN) coatings have been widely used in the chemical, mechanical and electronic industries because of their wear and abrasion resistance and corrosion resistance. Co-deposition of solid particles into coatings can further improve certain properties, thus enhance their performance [1]. EN–PTFE coatings present excellent self-lubricating and anti-sticking properties [2–4]. However, the coating hardness is substantially decreased depending on the volume fraction of PTFE particles in the coating. EN–SiC coatings are recognized for their hardness and wear resistance and are considered as a replacement for “hard chromium” in the aerospace industry [5,6], but the friction coefficient is significantly increased compared with EN coatings, which limits their applications. In our previous study, complex EN–SiC–PTFE composite coatings were firstly developed [7]. The results showed that the com∗

Corresponding author. Tel.: +65-67938521. E-mail address: xzeng@simtech.a-star.edu.sg (X.T. Zeng).

prehensive behaviors of EN–SiC–PTFE coatings such as wear resistance, hardness, and surface energy could be dramatically improved by synergistic effects of co-deposited SiC and PTFE particles. The co-deposition particle effects on coating corrosion resistance, however, are not clear yet. Some conflicting results were reported by different research groups [8–10]. Among the variety of corrosion evaluation techniques, electrochemical measurements are especially suited. Open circuit potential (OCP) is a summation of the half-cell reaction potentials in a specific electrolyte, which can be used as a measure of the spontaneity of the reaction and a rough indication of tendency to corrode. Applying small amplitude sinusoidal potential to the coating and registering the current response to the signal’s amplitude and phase, electrochemical impedance spectroscopy (EIS) has certain advantages thus has been widely used to evaluate the corrosion performance of coating materials [11,12]. Based on EIS, corrosion process can be described by an equivalent electrical circuit model. In this work, the potentiodynamic test is also used to analyze the overall behavior of EN

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5 -500 Mild Steel -0.6 0 600 1200 1800 0 0 500 1000 1500 2 2000 2500 Time / sec Fig.9-tetramethyl-5-decyne-4.7-diol ethoxylate (15EO/OH)) was selected as surfactant for particle dispersion.8 0 0 600 1200 1800 0 500 1000 1500 2 2000 2500 Time / sec Z'/!. SCE / V ditive. 2.cm -2500 Open circuit potential vs. / Electrochimica Acta 49 (2004) 4313–4319 Table 1 Composition of EN and EN-composite bath and plating conditions EN NiSO4 (g/l) NaH2 PO2 ·H2 O (g/l) CH3 COONa·3H2 O (g/l) Latic acid (85%) (ml/l) Thiourea (mg/l) PTFE dispersion (ml/l) SiC powder (g/l) Surfactants (mg/l) pH Plating temperature (◦ C) 26–30 28–30 35–45 20–25 3–5 – – – 4.4. The corrosion tests -2500 0.0 N H2 SO4 and (b) 3% NaCl electrolyte.8 88–90 EN–PTFE 26–30 28–30 35–45 20–25 3–5 6–8 – – 4. all the samples were deposited to have a similar thickness of about 15 ␮m.2 -0. The chemical compositions of the solutions and the plating process parameters are listed in Table 1. Huang et al.2 -2000 2 (a) in 1.0 N H2 SO4 and (b) 3% NaCl electrolyte.4314 Y.8 88–90 and EN composite coatings’ corrosion protection. Nyquist plot of EN and EN composite coatings in (a) 1.cm2 Mild Steel -0. Experimental EN and EN composite coatings were deposited on ∅ 25 × 6 mm mild steel substrates using electroless plating technology.S. Z'/!.0N H2SO4 -60 -50 -40 -30 -20 -10 0 0 102 03 0 40 50 60 mild steel EN-SiC-PTFE Z" /!.0 ␮m) ␤-silicon carbide particles were used for SiC co-deposition. 2. An ethoxylate type additive (2.3 -0.7. To minimize the influence of the coating thickness on electrochemical measurement parameters.cm Fig.1 (b) in 3% NaCl -0.6 -500 -0.cm2 -1500 mild steel EN EN-PTFE EN-SiC-PTFE EN-SiC -1000 EN-SiC-PTFE -0. Open circuit potentials for EN and EN composite coatings in (a) 1. Effects of sample surface properties and post-heat treatment on corrosion resistance were discussed.8 88–90 EN–SiC 26–30 28–30 35–45 20–25 3–5 – 8–10 100–200 4.8 88–90 EN–SiC–PTFE 26–30 28–30 35–45 20–25 3–5 6–8 8–10 100–200 4. ENLUBE dispersion of PTFE was used as the PTFE adOpen circuit potential vs.cm2 EN-PTFE EN-SiC EN-SiC-PTFE -1500 EN EN-PTFE EN-SiC -0.cm EN -0.4 -1000 Z'/!. . 1.4 EN-SiC EN (b) in 3% NaCl -2000 EN-PTFE Z" /!.0N H2SO4 (a) in 1.SCE / V -0.0 Z" /!. Micro-sized (average size 1.

A standard three-electrode configuration consisting of the sample as the working electrode. EN–SiC and EN–PTFE almost showed the same corrosion resistance when tested in 1. and the measurement frequency range was set from 10.0 -0. in 3% NaCl.Y. 4. which are intrinsically different in their electrochemical properties.01 0.cm2 mild steel (b) in 3% NaCl EN EN-SiC EN-PTFE EN-SiC-PTFE -1200 -1000 -800 -600 -400 -200 Z" /!. EN and EN composite coatings also demonstrated high corrosion resistance with a Evs.000 to 0. and the surfactants used to activate the particles made the plating bath chemistry and the sample surface autocatalytic plating reaction more complicated.0 N H2 SO4 and (b) 3% NaCl electrolyte.0 -0.1 -0.cm Z'/!.S. .0 0.8 1E-7 Z" /!.2 -0.4 0.2 -0.4 -0.cm -80 -40 0 0 mild steel mild steel with Ni plating EN-SiC-PTFE 40 80 2 Z'/!.3 EN-SiC-PTFE -0. indicating an improved anodic protection for mild steel in both acid and salty atmosphere. indicating that coatings were homogenous and pore free.1 I / A.4 0. SCE / V 0. However. 2 shows the Nyquist plots of EN and their composite coatings.cm 120 EN-SiC-PTFE with Ni plating 1E-6 1E-5 1E-4 1E-3 -2 0. Huang et al. Results and discussion Fig. Similarly.1 0 0 200 400 600 800 2 1000 1200 I /A . the polarization curve was measured in the range of −0.2 0. In this case.2 -0. which might be resulted from the lower density of the coating structure.01 0.0 N H2 SO4 .2 V at a constant scan rate of 0.6 -0. Fig. A 30 mV ac voltage (sine wave) was used as imposing signal. Subsequently. For each sample. All coating samples had a higher sur1.6 mild steel with Ni plating mils steel 0 600 1200 1800 EN-SiC-PTFE with Ni plating 1E-6 1E-5 1E-4 1E-3 -2 0. / Electrochimica Acta 49 (2004) 4313–4319 4315 were conducted using a Solartron 1287 Electrochemical Interface and Solartron 1260 Impedance/Gain-Phase Analyzer. the PTFE and SiC particles. Both acidic (1.2 to 1.4 -0.8 1E-7 mild steel (a) in 1. however demonstrated the highest OCP in 3% NaCl.cm 0. In corrosion test.0 N H2 SO4 .5 -0. The polarization curves of EN and EN composite coatings (a) 1.6 face potential than that of the substrate. EN–PTFE samples. SCE / V 0.01 Hz.8 0.5 mV s−1 . resulting in poorer corrosion resistance.4 -0. It can be seen that EN. All coating surface potentials are relatively stable. the open circuit potential (OCP) was first measured for a period of 0.8 0. resulting in the coating microscopically inhomogeneous and porous.0 N H2 SO4 ) and salty (3% NaCl) solutions were used as the corrosion electrolytes. Ni strike effects on corrosion resistance of EN–SiC–PTFE composite coating. a conventional saturated calomel electrode (SCE) and a carbon counter electrode was used to estimate the polarization behaviors.SCE /V 0.) at their respective corrosion potentials. Finally.6 -0. 3.5 h. a relatively lower corrosion resistance was observed for complex EN–SiC–PTFE composite. the impedance was measured and plotted by Zplot for Windows Electrochemical Impedance Software (Scribner Associates Inc.0N H 2SO4 EN EN-SiC EN-PTFE EN-SiC-PTFE Open circuit potential vs. 1 shows the open circuit potentials of EN and EN composite coatings.2 0. Samples co-deposited with particles showed a slightly decreased OCP in 1. pitting corrosion can be initiated from these defects.6 Time / sec -120 2 E v s.cm Fig. Fig. 3.0 -0.

56 1526 4. .0N H2SO4 -30 EN-SiC-PTFE in 3% NaCl -20 -10 0 5 10 2 15 2 20 0 0 10 20 30 2 40 3 Z' / !.cm (10 ) Fig.81 16596 0.063E−4 0.182E−4 0.80442 Heated 7.294E−4 0.551 1964 2.45E−4 0.791 907.433E−4 0. Electroless deposition is an autocatalytic chemical deposition process.13 46619 0.7 3.541 1447 12. The SEM studies suggested that the lower corrosion resistance was resulted from the non-uniformity and lower density caused by co-deposition of PTFE particles [13]. that all the coatings exhibit more positive corrosion potentials (Ecorr ) and dramatically lower corrosion currents (Icorr ) than the substrate.23E−4 0. It is obvious Z' / !.92549 EN–SiC–PTFE As-plated 7.0 N H2 SO4 CPEc-T CPEc-P 3% NaCl CPEc-T CPEc-P 7. Fig. Heat-treatment effects on corrosion properties of EN and EN composite coatings.724E−4 0.4316 Y. Huang et al. These results further confirmed that these coatings can be used for corrosion protection application in both acidic and salty environments.86314 33. CPEc-T: F cm−2 . both the solution chemistry and sample surface properties become more complicated than simple Table 2 Heat-treatment effects on corrosion resistance of EN and EN composite coatings Electrolyte EN As-plated Rs Rc CPEc Rs Rc CPEc R: 1.81134 Heated 7.1hr treated EN in 1.84452 34. No passivation tendency was observed in the measurement range. While the coatings containing PTFE particles showed lower corrosion resistance than those without PTFE particles.61E−4 0. 5.77067 30. 1hr treated -40 -30 -20 -10 as-plated 400oC.61 1227 5.0N H2SO4 EN-PTFE in 3% NaCl -15 -10 -5 0 EN-SiC-PTFE in 1.63401 Heated 7.cm2 (102) Z'' / ! . In complex composition system such as EN–SiC–PTFE.87654 cm2 .1 5.cm2(103) 0 5 10 15 0 10 20 30 -15 -10 -5 0 5 10 15 -30 -20 -10 0 10 20 30 EN-PTFE in 1.46 15061 0.cm (10 ) fitted resistance of coatings several times higher than that of the mild steel substrate.83166 EN–PTFE As-plated 7.S.809 656. Similar polarization mechanism was observed for EN and EN composite coatings in both 1.603 450 26. which is consistent with the report of Mimani and Mayanna [14].0N H2SO4 EN in 3% NaCl Z'' / !.11 13996 0.831 990 5.187E−4 0.75152 35.33E−4 0. 3 shows the comparison of polarization curves of the three types of coatings.88189 34.275E−4 0. / Electrochimica Acta 49 (2004) 4313–4319 -20 -15 -10 -5 as-plated o 400 C.578E−4 0.0 N H2 SO4 and 3% NaCl corrosion media.84281 36.

substrate surface composition and property plays an important role [15]. but the phase angle is not 90◦ . which means the coating structures changed to denser and more homogenous after heat-treatment.S. The equivalent circuit shown in Fig. a thin layer of Ni on the sample surface provides more homogenous initiate catalytic effect. which is mainly used to explain the system inhomogeneous and some distribution (dispersion) of the value of physical property of the system. The coating corrosion resistance improved with heat-treatment. Fig. 4. which affect the coating structure and corrosion properties. By Ni striking. Morphologies (25×) and EDX spectra of EN–PTFE after 1. this corrosion resistance enhancement should be mainly resulted from the improvement of the higher density of the EN–SiC–PTFE induced by the thin Ni layer. 7.Resistance of Solution Rc . all three group samples (EN. system (such as EN) due to the interaction and mass transportation. the fitted corrosion resistance of EN–SiC–PTFE complex coating in 1. Corrosion experiment results confirmed this supposition. Among the many factors. EN–PTFE and EN–SiC–PTFE) studied in this work were annealed at the same temperature (400 ◦ C) for 1 h. where the constant phase element (CPE) resembles a capacitor. It can be seen that all fitted corrosion parameters of heated coating varied with the same tendency.0 N H2 SO4 and 3% NaCl media. denser coating structure and improved corrosion resistance. Given the fact that the struck Ni layer is very thin (less than 200 nm). 6. the coating corrosion resistances Rc increased and the constant phase elements (CPEc-T) decreased in different range. The fitted results were listed in Table 2. For comparison.0 N H2 SO4 corrosion test. . 6 was used as to fit the coating corrosion property parameters.0 N H2 SO4 was increased from 40 to 1500 cm2 by Ni striking. In Fig. The corrosion characterization curves were measured and compared with those of as-deposited samples in 1. respectively. Fig.Y. which can be further confirmed by SEM and EDX later. leading to a more uniform. 5 is the Nyquist plots of EN and their composite coatings with and without heat-treatment.Resistance Coating CPEc -Constant Phase Element Fig. The heat treatment after deposition is the other critical factor determining the electro-chemical corrosion properties. / Electrochimica Acta 49 (2004) 4313–4319 4317 Rs Rc CPEc Rs . Huang et al. Equivalent circuit of EIS test of EN and EN composite coatings.

J. . Ni striking substantially enhanced the corrosion resistance due to the improvement of the surface autocatalytic properties and homogeneity. and also release the internal stress. the as-plated coatings were almost completely removed. 8. (3) for EN–SiC–PTFE complex composite coating. Many cracks/defects were observed in as-plated EN–SiC–PTFE coating after corrosion.0 N H2 SO4 corrosion test. 38 (1998) 1383. Thin Solid Films 245 (1994) 98. leaving naked substrate surfaces. 7 shows the SEM images and EDX spectra of as-deposited and post-heat-treated EN–PTFE samples.-S. Zhang. the heat-treated coatings were only partially etched away. Huang et al. L. (4) proper post-heat-treatment (400 ◦ C and 1 h) significantly improve the coating density and structure.J. and 3% NaCl electrolyte solutions. For heat-treated samples. [2] L. resulting in accelerated electrochemical cells corrosion once they penetrated to the substrate surface. Apachitei. the coating surface was slightly etched away. 4.-G. Fig. When 1. P.B.4318 Y. Fig. The effects of Ni striking to improve the sample surface autocatalytic properties and post-heat-treatment on corrosion performance were investigated. taken after the corrosion tests. These substantial differences were resulted from the effects that proper post-heat-treatment converted the coating from an amorphous and porous structure to a crystalline alloy and dense structure.0 N H2 SO4 electrolyte was used. Conclusions Corrosion resistance of EN and EN composite coatings on mild steel substrates were evaluated by EIS in 1. Overkamp. Duszczyk. no cracks and pitting defects were observed. EDX spectra could hardly see the substrate elements (Fe). Yu.S. indicating a good protection from corrosion. 8 shows the SEM images and EDX spectra of as plated and post-heat-treated EN–SiC–PTFE samples. The results show that: (1) both EN and EN composite coatings demonstrated significant improvement of corrosion resistance in both acidic and salty atmosphere.0 N H2 SO4 References [1] I.0 N H2 SO4 . Katgerman. X. Scripta Mater. In contrast. Morphologies (3000×) and EDX spectra of EN–SiC–PTFE after 1. / Electrochimica Acta 49 (2004) 4313–4319 Fig. giving rise to enhanced corrosion resistance. (2) co-deposition of either SiC or PTFE particles slightly decreased corrosion resistance of the coatings in 3% NaCl aqueous solution but had insignificant effects on their corrosion resistance in 1.

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