Corrosion Science 47 (2005) 28072815 www.elsevier.

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Comparisons of corrosion rates of NiP based composite coatings in HCl and NaCl solutions
Q. Zhao *, Y. Liu
Department of Mechanical Engineering, University of Dundee, Nethergate, Dundee, DD1 4HN, UK Received 23 June 2004 Available online 16 December 2004

Abstract The composite coatings of electroless NiP, NiPPTFE, NiCuP and NiCuPPTFE were prepared and their corrosion rates in HCl and NaCl solutions have been measured. The thickness and the compositions of the coatings were measured using a digital micrometer and an energy dispersive X-ray microanalysis (EDX), respectively. Surface morphology of the coatings was analysed by a scanning electron microscope (SEM). The incorporation of PTFE particles into NiP or NiCuP matrixes by gradually increasing the PTFE content from the substrate to the top surface improved the corrosion-resistant properties of the coatings significantly. The incorporation of copper into NiP or NiPPTFE matrixes also improved the corrosion-resistant properties of the coatings. 2004 Elsevier Ltd. All rights reserved.
Keywords: Electroless deposition; NiP based coatings; Corrosion; HCl solution; NaCl solution

1. Introduction The composite coatings of electroless plating NiP, NiPPTFE, NiCuP and NiCuPPTFE have been applied successfully in chemical, mechanical and
*

Corresponding author. Tel.: +44 1382 345651; fax: +44 1382 345508. E-mail address: q.zhao@dundee.ac.uk (Q. Zhao).

0010-938X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2004.11.001

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electronic industries due to their desirable physical and mechanical properties. NiP coatings have several unique properties, such as the anticorrosive property, wear resistance, paramagnetic characteristics, hardness and the electrocatalytic activity of hydrogen evolution [1]. The incorporation of PTFE particles into the NiP matrix can improve the properties of the coatings, such as non-stick, non-fouling, dry lubricity, low friction and good wear/corrosion resistance [24]. It was reported that the corrosion resistance of NiP coating was improved by the incorporation of PTFE as the PTFE particles blocked the pores in the NiP coating [5]. However a sudden increase in PTFE content in the coating is usually accompanied by a decrease in the adherence of the coating to the substrate, which has an adverse eect on corrosion resistance. To improve the adhesion of NiPPTFE coating containing high PTFE content, a gradient composite coating method is developed by gradually increasing the PTFE content from the substrate to the top surface. Since there is no obvious interface between coatings, the coating adhesion is improved signicantly [3]. The addition of copper into electroless NiP matrix also improved the corrosion resistance of the NiCuP coatings [68]. Wang et al. [9] found that the corrosion resistance of electroless 90%Ni7%Cu3%P in 50% NaOH solution was better than that of as-plated NiP or 1Cr18Ni9Ti stainless steel. It was also found that NiCu PPTFE composite coatings improved the wear resistance, compared with NiP PTFE composite coatings in the oiled condition [10]. The anti-corrosion performance of electroless plating NiP coatings has been investigated extensively [11]. A concise review of electroless NiP composite coatings and their industrial applications were given by Balaraju et al. [12]. However, few corrosion data for the NiP based composite coatings are available. In this paper, the corrosion rates of electroless plating NiP, NiPPTFE, NiCuP and NiCuP PTFE coatings in HCl and NaCl solutions were investigated, and compared with those of copper plates and carbon steel plates.

2. Experimental NiP, NiCuP, NiPPTFE and NiCuPPTFE were coated on copper sheets (purity 99.99%) of 15 mm 10 mm 0.35 mm. The sheets were rst cleaned with alkaline solution at 6080 C for 1020 min and then rinsed with water. The composition of the alkaline solution includes NaOH 25 g/l; Na2CO3 25 g/l; Na3PO4 30 g/l and Na2SiO3 8 g/l. They were then dipped into a dilute HCl solution (1 M) for 30 s and then were rinsed with cold water and deionized water, respectively. A 60% PTFE emulsion from Aldrich (UK) with a particle size in the range 0.050.5 lm and a FC-4 (C20H20F23N2O4I) cationic surfactant were diluted with demineralised water and stirred for 1 h. Then the solution was ltered with a lter of pore size 0.2 lm before use. PTFE particles in the baths were dispersed uniformly by the surfactant without using any mechanical agitation or ultrasonic homogeniser. In this investigation the concentrations of CuSO4 5H2O, PTFE and FC-4 were in the range 01.4 g/l, 020 ml/l and 01.0 g/l, respectively, and the pH and temperature were in the range 49.5 and 70 95 C, respectively. The PTFE contents in the coatings mainly depend on the concen-

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Table 1 Bath compositions and operating conditions for electroless NiP, NiPPTFE, NiCuP and NiCuP PTFE NiP NiSO4 6H2O (g/l) CuSO4 5H2O (g/l) Na3C6H5O7 2H2O (g/l) NaH2PO2 H2O (g/l) CH3 COONa (g/l) (CH2)CS (ppm) NH4CH3COO (g/l) PTFE (60 wt.%) (ml/l) C20H20F23N2O4I (FC-4) (g/l) pH Temperature (C) 25 18 30 18 1 NiPPTFE 25 18 30 18 1 10 0.4 4.8 88 NiCuP 50 1.25 60 25 NiCuPPTFE 50 0.5 60 25

40

4.8 85

7 80

40 10 0.4 7 85

trations of PTFE and the surfactant in the plating solutions. In this study several plating baths with various concentrations of PTFE and the surfactant were used. The baths were used to produce NiPPTFE coatings with the various PTFE contents (e.g. 5%, 10%, 20%, 25%). The coating thickness was measured using a digital micrometer and the coating surface morphology was analysed with a scanning electron microscope (SEM). The coating composition was analysed with an energy dispersive X-ray microanalysis (EDX) in a scanning electron microscope model JEOL T-300 at a beam energy of 20 keV. EDX was calibrated using samples with known composition. To obtain a graded NiPPTFE coating, a copper sheet was rst plated in a NiP bath, then plated in the NiPPTFE baths with various concentrations of PTFE and the surfactant, respectively. The PTFE content in the NiPPTFE coating increased gradually from the bottom to the top layer. Since there is no obvious interface between the multi-layer coatings, the coating adhesion is improved signicantly. It was found that both the plating solution compositions and the plating conditions had a signicant inuence on the corrosion behaviour of these coatings. The coating quality (e.g. uniformity and adhesion strength) of the top layer is crucial on the anticorrosion performance of the NiP based coatings. Table 1 lists the optimal plating solution compositions and the plating conditions for preparing these coatings. The corrosion rates of these coatings in various concentrations of HCl and NaCl solutions were measured at room temperature with an immersion weight loss technique and were compared with those of copper (Cu: 99.99%) and AISI 1020 low carbon steel (C: 0.180.23; Mn: 0.300.60; P: 0.04, S: 0.05).

3. Results and discussion 3.1. Coating thickness, morphology and compositions The thickness of the electroless NiP, NiCuP, NiPPTFE or NiCuPPTFE coatings in this investigation was around 16 lm. Figs. 1 and 2 show typical surface

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Fig. 1. Uniform distribution of PTFE particles in NiPPTFE coatings (PTFE: 10 ml/l, FC-4: 0.4 g/l, pH: 4.8, T: 88 C).

Fig. 2. Uniform distribution of PTFE particles in NiCuPPTFE (CuSO4 5H2O: 0.5 g/l, PTFE: 10 ml/l, FC-4: 0.4 g/l, pH: 7, T: 85 C).

morphologies of NiPPTFE and NiCuPPTFE, respectively. The SEM photos show that the black PTFE particles were uniformly distributed throughout the NiP or NiCuP matrix. Table 2 shows typical element compositions of electroless NiCuP coating (CuSO4 5H2O: 1.25 g/l, pH: 7, T: 80 C) and NiCuPPTFE coating (CuSO4 5H2O: 0.5 g/l, PTFE: 10 ml/l, FC-4: 0.4 g/l, pH: 7, T: 85 C) measured using EDX. The PTFE content was calculated based on F element content in the coating. For example, the PTFE content in Fig. 2 was 8.0 wt.%.
Table 2 Element compositions (wt.%) for NiCuP and NiCuPPTFE coatings Element Cu Ni P C F NiCuP 17.2 76.2 6.6 NiCuPPTFE 6.5 76.4 7.9 3.1 6.1

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3.2. Corrosion rate measurement The corrosion behaviour of the copper sheet, carbon steel and the coatings was measured at room temperature with an immersion weight loss technique in various HCl concentrations (01 M) for various immersion period (0356 h) and in various NaCl concentrations (020 wt.%) for various immersion period (0652 h). Fig. 3 shows a typical corrosion behaviour of NiP based composite coatings in 1 M HCl solutions. The anti-corrosion properties of the graded NiPPTFE or Ni CuPPTFE coatings were much better than those of general NiPPTFE or Ni CuPPTFE coatings. In this study the weight loss WLoss (mg/cm2) of NiP based coatings increased approximate linearly with immersion time t (hours) (see Fig. 3): W Loss at b 1 where a and b are constants for a given coating in a given HCl (or NaCl) concentration. They can be determined by least square technique. The average corrosion rate  c (mg/cm2 h) can be calculated using the following equation:  c dW Loss a dt 2

The annual corrosion rate c (mm/year) can be calculated using the following equation: ca 365 24 100q 3

where q is the density of the sample (g/cm3). Fig. 4 shows the comparison of annual corrosion rate of NiP based coatings in various HCl solutions. It shows that the annual corrosion rates of NiP or NiP based composite coatings were much lower than those of copper or carbon steel in the HCl solutions. The corrosion rate of pure copper was much higher than those of NiP based coatings. The corrosion mechanism of pure copper was explained in details by Shams El Din et al. [13].

4 Weight loss [mg/cm] 3.5 3 2.5 2 1.5 1 0.5 0 0

Copper Ni-P-PTFE Ni-Cu-P-PTFE Ni-P Graded Ni-P-PTFE Graded Ni-Cu-P-PTFE

50

100

150

200

250

Time [hour]

Fig. 3. Comparison of corrosion behaviour of NiP based composite coatings in 1 M HCl solutions.

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Corrosion rate [mm/year]

Q. Zhao, Y. Liu / Corrosion Science 47 (2005) 28072815

1 0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1 1.2 HCl concentration [M]
Carbon steel Copper Ni-P -P TFE Ni-Cu-P- PT FE Ni-P Ni-Cu-P

Fig. 4. Comparison of corrosion rate of NiP based composite coatings in HCl solutions.

The eect of PTFE content in the coating on the corrosion rate is complex. It was reported that the corrosion resistance of NiP coating was improved by the incorporation of PTFE as the PTFE particles blocked the pores in the NiP coating [5]. However in this study the incorporation of PTFE particles into NiP or NiCuP matrixes did not improve the corrosion-resistant properties of the coatings prepared by general electroless NiPPTFE or NiCuPPTFE technique, since the PTFE particles were generally found to peel-o during corrosion tests, leading to the increased porosity. To reduce porosity and to improve coating adhesion, a graded NiPPTFE or NiCuPPTFE composite coating method was developed by gradually increasing the PTFE content from the substrate to the top surface. In this study the maximum PTFE contents in graded NiPPTFE coating and NiCuPPTFE coating with improved corrosion resistance were 11.5 wt.% and 10.1 wt.%, respectively. Figs. 3 and 4 also show that the incorporation of copper into NiP or Ni PPTFE matrixes improved the corrosion-resistant properties of the coatings. Normally 1 ppm thiourea as stabilizer is added to NiPPTFE plating solutions. The trace amounts of thiourea in the coatings could have adverse eects for the corrosion resistance of the coatings [68]. It was found by large amounts of experiments that copper ions could act as stabilizer without the addition of thiourea [6,7]. In this investigation copper ions act as stabilizer without the addition of thiourea. Perhaps this is one of the main reasons for the improvement of the corrosion resistance of the NiCuP and NiCuPPTFE coatings. When the Cu contents in the NiCuP and NiCuPPTFE coatings were 17.2 wt.% and 6.5 wt.% respectively, the anti-corrosion performance of the coatings was best. In general the corrosion resistance of NiP coatings increases with increasing P content [14]. The eect of P content in the NiP based coatings on the corrosion resistance will be further investigated. Figs. 5 and 6 show the comparison of corrosion rates of NiP based composite coatings in NaCl solutions. Fig. 5 shows that the incorporation of PTFE particles into NiP or NiCuP matrixes did not improve the corrosion-resistant properties of the coatings as some PTFE particles peeled o during the 652-h corrosion tests. The incorporation of copper into NiP or NiPPTFE matrixes improved the corrosion-resistant properties of the coatings. The corrosion rates of copper, NiP or

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0.1 Corrosion rate [mm/year]
Carbon steel

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0.01

Copper Ni-P-PTFE Ni-Cu-P-PTFE N-Pi

0.001

Ni-Cu-P

0.0001 0 5 10 15 20 25 30 NaCl concentration [wt%]

Fig. 5. Comparison of corrosion rate of NiP based composite coatings in NaCl solutions.

0.25 Weight loss [mg/cm] 0.2 0.15 0.1 0.05 0 0 100 200 Time [hour] 300 400
Copper Ni-P-PTFE Ni-Cu-P-PTFE Ni-P Graded Ni-P-PTFE

Fig. 6. Comparison of corrosion behaviour of NiP based composite coatings in 20% NaCl solutions.

NiP based composite coatings increased with increasing NaCl concentration; while the corrosion rate of carbon steel decreased with increasing NaCl concentration. Steel corrodes in water according to the following reaction if oxygen exists: Fe Fe2 2e 1 O2 H2 O 2e 2OH 2 Overall reaction: 1 Fe O2 H2 O FeOH2 2 The ferrous hydroxide is further oxidized to form rust by the reaction 1 1 2FeOH2 H2 O O2 FeOH3 2 4 6 4 5

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One may expect that the corrosion rate should increase with chloride content. This does indeed occur up to about 3 wt.% NaCl (seawater concentration), but at high concentrations the rate decreases to values considerably less than for chloride-free water containing oxygen [15]. The decrease results from a signicant decrease in oxygen solubility with increasing chloride content [15]. Fig. 6 shows that the incorporation of PTFE particles into NiP matrix with the graded electroless NiPPTFE technique improved the corrosion-resistant property of the coating signicantly in 20% NaCl solutions. The corrosion rate of the graded NiPPTFE composite coating was much lower than those of general NiPPTFE or NiP coatings. The further experiments will be performed in order to understand the corrosion mechanisms of the NiP based coatings, such as the eects of each component in the coatings and PTFE particle size distribution and uniformity on the corrosion rates. The change in the corrosion rate with chloride concentration will be predicted/modelled. In addition, electrochemical measurements and solution analysis results will be performed to back up the weight loss measurements. 4. Conclusions The corrosion rates of NiP or NiP based composite coatings were much lower than those of copper or carbon steel in HCl or NaCl solutions. The incorporation of PTFE particles into NiP or NiCuP matrixes did not improve the corrosion-resistant properties of the coatings prepared by general electroless plating NiPPTFE or NiCuPPTFE technique due to the peeling-o of PTFE particles during corrosion tests. The incorporation of PTFE particles into NiP or NiCuP matrixes improves the corrosion-resistant properties of the coatings prepared by gradually increasing the PTFE content from the substrate to the top surface. The incorporation of copper into NiP or NiPPTFE matrixes also improved the corrosion-resistant properties of the coatings. Acknowledgment This work was supported by the Engineering and Physical Sciences Research Council, UK. References
[1] [2] [3] [4] [5] [6] [7] A. Bai, P.Y. Chuang, C.C. Hu, Mater. Chem. Phys. 82 (2003) 93. J.S. Hadley, L.E. Harland, Metal Finish. 85 (12) (1987) 51. Q. Zhao, Y. Liu, H. Muller-Steinhagen, G. Liu, Surf. & Coat Tech. 155 (2002) 279. Y. Liu, Q. Zhao, Trans. Inst. Met. Finish. 81 (5) (2003) 168. S. Takashi, Y. Shuji, K. Yuichi, Corrosion preventing structure, EP0737759, 1996. M. Gulla, US Patent 3,764,352, 1973. S. Armyanov, J. Georgieva, D. Tachev, E. Valova, N. Nyagolova, S. Mehta, D. Leibman, A. Runi, Electrochem. Solid State Lett. 2 (7) (1999) 323.

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[8] G.O. Mallory, J.B. Hajdu, Electroless Plating Fundamentals and Applications, Noyes/William Andrew Publishing, AESF, FL, 1990, p. 263. [9] Y.W. Wang, C.G. Xiao, Z.G. Deng, Plat. Surf. Finish. 79 (3) (1992) 57. [10] J.N. Tang, Y.B. Xie, Trans. Inst. Met. Finish. 74 (1996) 99. [11] M.C. GarciaAlonso, M.L. Escudero, V. Lopex, A. Macias, Corros. Sci. 38 (3) (1996) 515. [12] J.N. Balaraju, T.S.N.S. Narayanan, S.K. Seshadri, J. Appl. Electrochem. 33 (2003) 807. [13] A.M. Shams El Din, M.E. El Dahshan, A.M. Taj El Din, Desalination 130 (2000) 89. [14] G. Lu, G. Zangari, Electrochem. Acta 47 (2002) 2969. [15] H.H. Uhlig, Corrosion & Corrosion Control, second ed., Wiley & Sons, New York, 1971, p. 113.