Electrochimica Acta 49 (2004) 43134319

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
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 signicantly 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 signicant 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 signicantly 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]. ENPTFE coatings present excellent self-lubricating and anti-sticking properties [24]. However, the coating hardness is substantially decreased depending on the volume fraction of PTFE particles in the coating. ENSiC 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 coefcient is signicantly increased compared with EN coatings, which limits their applications. In our previous study, complex ENSiCPTFE composite coatings were rstly 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 ENSiCPTFE 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 conicting results were reported by different research groups [810]. 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 specic 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 signals 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

0013-4686/$ see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2004.04.023

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Table 1 Composition of EN and EN-composite bath and plating conditions EN NiSO4 (g/l) NaH2 PO2 H2 O (g/l) CH3 COONa3H2 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) 2630 2830 3545 2025 35 4.8 8890 ENPTFE 2630 2830 3545 2025 35 68 4.8 8890 ENSiC 2630 2830 3545 2025 35 810 100200 4.8 8890 ENSiCPTFE 2630 2830 3545 2025 35 68 810 100200 4.8 8890

and EN composite coatings corrosion protection. Effects of sample surface properties and post-heat treatment on corrosion resistance were discussed.

2. Experimental EN and EN composite coatings were deposited on 25 6 mm mild steel substrates using electroless plating technology. ENLUBE dispersion of PTFE was used as the PTFE adOpen circuit potential vs. SCE / V

ditive. Micro-sized (average size 1.0 m) -silicon carbide particles were used for SiC co-deposition. An ethoxylate type additive (2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate (15EO/OH)) was selected as surfactant for particle dispersion. The chemical compositions of the solutions and the plating process parameters are listed in Table 1. To minimize the inuence of the coating thickness on electrochemical measurement parameters, all the samples were deposited to have a similar thickness of about 15 m. The corrosion tests

-2500
0.0

Z" /!.cm

EN
-0.2

-2000

(a) in 1.0N H2SO4

(a) in 1.0N H2SO4

-60 -50 -40 -30 -20 -10 0 0 102 03 0 40 50 60

mild steel EN-SiC-PTFE

Z" /!.cm2

EN-PTFE

EN-SiC EN-SiC-PTFE

-1500

EN EN-PTFE EN-SiC

-0.4

-1000

Z'/!.cm2

Mild Steel
-0.6

-500

-0.8

0
0 600 1200 1800

500

1000

1500
2

2000

2500

Time / sec

Z'/!.cm
-2500

Open circuit potential vs.SCE / V

-0.1

(b) in 3% NaCl
-0.2 -0.3 -0.4 EN-SiC EN

(b) in 3% NaCl
-2000

EN-PTFE

Z" /!.cm2

-1500

mild steel EN EN-PTFE EN-SiC-PTFE EN-SiC

-1000

EN-SiC-PTFE
-0.5

-500

Mild Steel
-0.6 0 600 1200 1800

500

1000

1500
2

2000

2500

Time / sec
Fig. 1. Open circuit potentials for EN and EN composite coatings in (a) 1.0 N H2 SO4 and (b) 3% NaCl electrolyte.

Z'/!.cm

Fig. 2. Nyquist plot of EN and EN composite coatings in (a) 1.0 N H2 SO4 and (b) 3% NaCl electrolyte.

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were conducted using a Solartron 1287 Electrochemical Interface and Solartron 1260 Impedance/Gain-Phase Analyzer. A standard three-electrode conguration 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. Both acidic (1.0 N H2 SO4 ) and salty (3% NaCl) solutions were used as the corrosion electrolytes. For each sample, the open circuit potential (OCP) was rst measured for a period of 0.5 h. Subsequently, the impedance was measured and plotted by Zplot for Windows Electrochemical Impedance Software (Scribner Associates Inc.) 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 to 1.2 V at a constant scan rate of 0.5 mV s1 .

3. Results and discussion Fig. 1 shows the open circuit potentials of EN and EN composite coatings. All coating samples had a higher sur1.0 0.8 0.6

face potential than that of the substrate, indicating an improved anodic protection for mild steel in both acid and salty atmosphere. Samples co-deposited with particles showed a slightly decreased OCP in 1.0 N H2 SO4 . ENPTFE samples, however demonstrated the highest OCP in 3% NaCl. All coating surface potentials are relatively stable, indicating that coatings were homogenous and pore free. Fig. 2 shows the Nyquist plots of EN and their composite coatings. It can be seen that EN, ENSiC and ENPTFE almost showed the same corrosion resistance when tested in 1.0 N H2 SO4 . However, a relatively lower corrosion resistance was observed for complex ENSiCPTFE composite, which might be resulted from the lower density of the coating structure. In this case, the PTFE and SiC particles, which are intrinsically different in their electrochemical properties, and the surfactants used to activate the particles made the plating bath chemistry and the sample surface autocatalytic plating reaction more complicated, resulting in the coating microscopically inhomogeneous and porous. In corrosion test, pitting corrosion can be initiated from these defects, resulting in poorer corrosion resistance. Similarly, in 3% NaCl, EN and EN composite coatings also demonstrated high corrosion resistance with a

Evs. SCE / V

0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 1E-7

mild steel (a) in 1.0N H 2SO4 EN EN-SiC EN-PTFE EN-SiC-PTFE

Open circuit potential vs.SCE /V

0.0 -0.1 -0.2 -0.3 EN-SiC-PTFE -0.4 -0.5 -0.6 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

0.01

0.1

I / A.cm
0.8 0.6

Time / sec
-120
2

E v s. SCE / V

0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 1E-7

Z" /!.cm2

mild steel (b) in 3% NaCl EN EN-SiC EN-PTFE EN-SiC-PTFE

-1200 -1000 -800 -600 -400 -200

Z" /!.cm

-80 -40 0 0

mild steel mild steel with Ni plating EN-SiC-PTFE

40 80 2 Z'/!.cm

120

EN-SiC-PTFE with Ni plating

1E-6

1E-5

1E-4

1E-3
-2

0.01

0.1

200

400

600

800
2

1000

1200

I /A .cm

Z'/!.cm

Fig. 3. The polarization curves of EN and EN composite coatings (a) 1.0 N H2 SO4 and (b) 3% NaCl electrolyte.

Fig. 4. Ni strike effects on corrosion resistance of ENSiCPTFE composite coating.

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-20 -15 -10 -5

as-plated o 400 C, 1hr treated

-40 -30 -20 -10

as-plated 400oC,1hr treated

EN in 1.0N H2SO4

EN in 3% NaCl

Z'' / !.cm2 (102)

Z'' / ! .cm2(103)

10

15

10

20

30

-15 -10 -5 0 5 10 15

-30 -20 -10 0 10 20 30

EN-PTFE in 1.0N H2SO4

EN-PTFE in 3% NaCl

-15 -10 -5 0

EN-SiC-PTFE in 1.0N H2SO4

-30

EN-SiC-PTFE in 3% NaCl
-20 -10

10
2

15
2

20

10

20

30
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40
3

Z' / !.cm (10 )

tted resistance of coatings several times higher than that of the mild steel substrate. While the coatings containing PTFE particles showed lower corrosion resistance than those without PTFE particles. 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]. Fig. 3 shows the comparison of polarization curves of the three types of coatings. Similar polarization mechanism was observed for EN and EN composite coatings in both 1.0 N H2 SO4 and 3% NaCl corrosion media. It is obvious

Z' / !.cm (10 )

Fig. 5. Heat-treatment effects on corrosion properties of EN and EN composite coatings.

that all the coatings exhibit more positive corrosion potentials (Ecorr ) and dramatically lower corrosion currents (Icorr ) than the substrate. These results further conrmed that these coatings can be used for corrosion protection application in both acidic and salty environments. No passivation tendency was observed in the measurement range, which is consistent with the report of Mimani and Mayanna [14]. Electroless deposition is an autocatalytic chemical deposition process. In complex composition system such as ENSiCPTFE, 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: 1.0 N H2 SO4 CPEc-T CPEc-P 3% NaCl CPEc-T CPEc-P 7.809 656.1 5.063E4 0.88189 34.56 1526 4.275E4 0.80442 Heated 7.791 907.7 3.724E4 0.86314 33.81 16596 0.578E4 0.83166 ENPTFE As-plated 7.541 1447 12.45E4 0.77067 30.61 1227 5.433E4 0.63401 Heated 7.551 1964 2.182E4 0.84452 34.46 15061 0.187E4 0.92549 ENSiCPTFE As-plated 7.603 450 26.23E4 0.75152 35.11 13996 0.61E4 0.81134 Heated 7.831 990 5.294E4 0.84281 36.13 46619 0.33E4 0.87654

cm2 ; CPEc-T: F cm2 .

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Rs

Rc

CPEc

Rs - Resistance of Solution Rc - Resistance Coating CPEc -Constant Phase Element

Fig. 6. Equivalent circuit of EIS test of EN and EN composite coatings.

system (such as EN) due to the interaction and mass transportation. Among the many factors, which affect the coating structure and corrosion properties, substrate surface composition and property plays an important role [15]. By Ni striking, a thin layer of Ni on the sample surface provides more homogenous initiate catalytic effect, leading to a more uniform, denser coating structure and improved corrosion resistance. Corrosion experiment results conrmed this supposition. In Fig. 4, the tted corrosion resistance of ENSiCPTFE complex coating in 1.0 N H2 SO4 was increased from 40 to 1500 cm2 by Ni striking. Given the fact that the struck Ni layer is very thin (less than 200 nm), this corrosion resistance enhancement should be mainly

resulted from the improvement of the higher density of the ENSiCPTFE induced by the thin Ni layer. The heat treatment after deposition is the other critical factor determining the electro-chemical corrosion properties. For comparison, all three group samples (EN, ENPTFE and ENSiCPTFE) studied in this work were annealed at the same temperature (400 C) for 1 h. The corrosion characterization curves were measured and compared with those of as-deposited samples in 1.0 N H2 SO4 and 3% NaCl media, respectively. Fig. 5 is the Nyquist plots of EN and their composite coatings with and without heat-treatment. The equivalent circuit shown in Fig. 6 was used as to t the coating corrosion property parameters, where the constant phase element (CPE) resembles a capacitor, but the phase angle is not 90 , which is mainly used to explain the system inhomogeneous and some distribution (dispersion) of the value of physical property of the system. The tted results were listed in Table 2. It can be seen that all tted corrosion parameters of heated coating varied with the same tendency, the coating corrosion resistances Rc increased and the constant phase elements (CPEc-T) decreased in different range, which means the coating structures changed to denser and more homogenous after heat-treatment. The coating corrosion resistance improved with heat-treatment, which can be further conrmed by SEM and EDX later.

Fig. 7. Morphologies (25) and EDX spectra of ENPTFE after 1.0 N H2 SO4 corrosion test.

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Fig. 8. Morphologies (3000) and EDX spectra of ENSiCPTFE after 1.0 N H2 SO4 corrosion test.

Fig. 7 shows the SEM images and EDX spectra of as-deposited and post-heat-treated ENPTFE samples, taken after the corrosion tests. When 1.0 N H2 SO4 electrolyte was used, the as-plated coatings were almost completely removed, leaving naked substrate surfaces. In contrast, the heat-treated coatings were only partially etched away. EDX spectra could hardly see the substrate elements (Fe), indicating a good protection from corrosion. Fig. 8 shows the SEM images and EDX spectra of as plated and post-heat-treated ENSiCPTFE samples. Many cracks/defects were observed in as-plated ENSiCPTFE coating after corrosion, resulting in accelerated electrochemical cells corrosion once they penetrated to the substrate surface. For heat-treated samples, the coating surface was slightly etched away; no cracks and pitting defects were observed. 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, and also release the internal stress.

and 3% NaCl electrolyte solutions. The effects of Ni striking to improve the sample surface autocatalytic properties and post-heat-treatment on corrosion performance were investigated. The results show that: (1) both EN and EN composite coatings demonstrated signicant improvement of corrosion resistance in both acidic and salty atmosphere; (2) co-deposition of either SiC or PTFE particles slightly decreased corrosion resistance of the coatings in 3% NaCl aqueous solution but had insignicant effects on their corrosion resistance in 1.0 N H2 SO4 ; (3) for ENSiCPTFE complex composite coating, Ni striking substantially enhanced the corrosion resistance due to the improvement of the surface autocatalytic properties and homogeneity; (4) proper post-heat-treatment (400 C and 1 h) signicantly improve the coating density and structure, giving rise to enhanced corrosion resistance.

4. Conclusions Corrosion resistance of EN and EN composite coatings on mild steel substrates were evaluated by EIS in 1.0 N H2 SO4

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