Corrosion Science 49 (2007) 17771798 www.elsevier.

com/locate/corsci

Protective coating on Mg AZ91D alloy The eect of electroless nickel (EN) bath stabilizers on corrosion behaviour of NiP deposit
Woo-Jae Cheong
a

a,*

, Ben L. Luan

a,b

, David W. Shoesmith

Department of Chemistry, University of Western Ontario, Chemistry Building, 1151 Richmond St. London, Ont., Canada N6A 5B7 b Integrated Manufacturing Technologies Institute, the National Research Council Canada, London, Ont., Canada N6G 4X8 Received 1 November 2005; accepted 21 August 2006 Available online 25 January 2007

Abstract The eects of the electroless nickel (EN) bath stabilizers; thiourea (TU) and maleic acid (MA), on the corrosion of the EN coatings on Cu and Mg substrates were investigated in an aggressive oxygenated chloride environment. Corrosion was limited to the external EN layer, and thus, the intermediate Cu layer as well as Mg AZ91D substrate remained intact. On the EN surface, two dierent types of corrosion morphologies were observed. Specimens prepared with TU showed preferential attack along particle boundaries, while pitting corrosion was observed for specimens prepared either without a stabilizer or with MA. The latter deposits showed higher corrosion resistances due, in part, to the formation of a P-enriched layer on the surface. The poorer corrosion performance of EN specimens prepared with TU was attributed to the presence of the particle boundaries and the trace impurities adsorbed on, or included in, them. The key impurity was sulphur incorporated during formation of deposits in TU-stabilized baths. It was clearly shown that the corrosion behaviour of the EN specimens was predominantly inuenced by the morphological and surface compositional aspects of the deposits. Crown Copyright 2006 Published by Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +1 519 661 2111x86248; fax: +1 519 661 3022. E-mail addresses: wcheong@uwo.ca, cheongw@gmail.com (W.-J. Cheong).

0010-938X/$ - see front matter Crown Copyright 2006 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2006.08.025

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Keywords: A. Magnesium AZ91D alloy; Metal coating; B. EIS; SEM; C. Corrosion electrochemical behaviour

1. Introduction Magnesium (Mg) and its alloys are plated for various reasons, but primarily to improve their corrosion resistance. While Mg is relatively stable under alkaline conditions due to the rapid formation of the hydroxide, Mg(OH)2, it is subject to severe attack in acidic and chloride environments. The metal is also prone to galvanic attack when in contact with another metal [1]. Various methods for applying protective coatings, such as electrochemical plating, chemical conversion coating, hydride coating, anodizing, gas phase deposition, and organic/polymer coatings have been tried [2]. Since it requires a minimum capital investment, chemical conversion coating has been extensively investigated. However, the use of CrO3 or chromate solutions for the conversion process is harmful to the environment. Moreover, a conversion coating can only provide a suitable base for an adherent organic coating [3]. Electroless deposition can also provide a protective coating for common metal surfaces [1,4,5]. In general, an electroless nickel (EN) deposit is less porous and more uniform than an equivalent electrolytically plated deposit, and thus provides better corrosion and wear protection [6]. However, electroless deposition has the inherent problem of sudden bath decomposition, which can be aggravated in the case of reactive substrate plating (i.e. Mg alloys), since the dissolved metal ions enhance decomposition. This results in both an increase in costs and the production of environmentally hazardous pollutants due to large waste generation [5]. To overcome this problem, EN baths commonly contain small amounts of stabilizers to prevent the homogeneous reactions that trigger decomposition [5]. Previously, the stability of EN baths were evaluated with an accelerated stability test in which the bath decomposition time was measured after the addition of the optimum concentration of PdCl2 (40 mg/L) solution [8]. The EN bath stability was increased signicantly with the addition of either thiourea (TU) or maleic acid (MA). The bath life increased from 1.3 0.5 min to >264 min for an increase in TU concentration from 0 mg/L to 2.0 mg/L and from 0.7 0.1 min to 101 9 min for MA concentrations from 0 to 3000 mg/L [8]. While enhancing bath stability, stabilizers may also inuence deposit morphology [7,8], composition [811], and microstructure [8]. These changes would be expected to aect the corrosion behaviour of the EN (NiP) coating. The corrosion behavior of protective NiP coatings has been extensively investigated and is considered to be dependent on many processes and features. These include the following: 1. The process used to apply the NiP coating (i.e. electrolytic, electroless, and melting and quenching processes). 2. The composition of the NiP coating, especially its P content [1214]. 3. The homogeneity of elemental distribution, especially P distribution in the coating surface [12], and throughout the deposit [15]. 4. The surface morphology of the deposit: i.e. whether it is smooth, nodular, or possesses a cauliower-like morphology [16].

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5. The microstructure of the deposit: i.e. whether it is crystalline, microcrystalline, amorphous, or composed of mixed phases [17]. 6. The exposure environment, especially the pH [12]. 7. The presence of impurity inclusions and their distribution in the deposit; e.g., Pb or S inclusions [12,18]. 8. The nature of the substrate under the deposit [19]. 9. The presence of surface defects such as microscopic pores or pits [18]. Although the corrosion behaviour of protective NiP deposits have been extensively studied, only limited information is available for NiP deposits prepared in the presence of the common bath stabilizers, TU and MA. In this paper, we have studied the corrosion of such deposits over longer time periods in an aggressive chloride environment. NiP coatings on both copper substrates and on magnesium AZ91D alloy substrates (with an intermediate copper layer produced by a novel Cu immersion process) have been studied. 2. Experimental 2.1. Preparation of NiP deposits NiP binary alloy deposits with P contents ranging from 6% to 9% (wt.%) were prepared on a dumbbell shaped copper (99.9%) substrate in a plating bath containing 30 g/L NiSO4 5H2O, 20 g/L NaH2PO2 xH2O, 20 g/L CH3COONa, and various concentrations of the stabilizers, thiourea (TU) or maleic acid (MA). Six dierent NiP alloy specimens were prepared with dierent TU (0.5 mg/L, 0.9 mg/L, and 2.0 mg/L) and maleic acid (180 mg/L, 1000 mg/L, and 3000 mg/L) concentrations. A reference specimen (RE) was prepared without any stabilizer. These specimens were coded with the name of the stabilizer followed by their concentration. For example, the EN specimen prepared in the solution containing 0.5 mg/L of TU is coded as TU0.5. When prepared on a Mg AZ91D substrate the EN specimen is designated as TU0.5 on Mg. During plating, the EN bath was slowly agitated to minimize local acidity at the substrate surface. The deposition conditions employed were a pH of 4.5, a temperature of 85(1) C, a deposition time of $6.0 h, and a specimen surface area to volume ratio of 7.8 cm2/L. A weight gain analysis was done on a known surface area of specimen to determine the average thickness of the coating. To ensure the Cu substrate or the Cu intermediate layer were not exposed during subsequent corrosion tests, the thickness of the coating was made >50 lm, as suggested by Innes [20]. For the Mg AZ91D alloy substrate, an intermediate Cu layer was required to facilitate deposition of the NiP coating. This intermediate coating was deposited using a novel Cu immersion process in a bath containing 0.67 M CuSO45H2O and 3.3 M HF followed by a surface sealing process. 2.2. Electrochemical measurements The electrolyte used was a 5% NaCl solution prepared with reagent grade NaCl and deionized water (resistivity >18 MX) from Millipore (Milli-Q academic) system. A standard three-compartment cell was used with a saturated calomel electrode (SCE) and a 2 3 cm2 platinum electrode as a reference and counter electrode, respectively. Before introduction of the specimen to the corrosion cell, the solution was purged with Argon

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gas for >30 min. The specimen is only partially immersed in the electrolyte solution to avoid crevices. Before measurement of the open circuit potential, the electrode was cathodically polarized at 0.8 VSCE to remove any air-formed oxide on the surface of the NiP coating. Corrosion potential (Ecorr) and intermittent electrochemical impedance spectroscopy (EIS) measurements were then made, rst in deaerated (argon) (50 1 h), and then in oxygenated (145 1 h) environments. EIS measurements were performed with a Solartron 1255 Frequency Response Analyzer coupled to a 1480 Multistat. The EIS measurements were obtained by applying a sinusoidal perturbation of 5 mV, and measuring the modulus of impedance and the phase shift over the frequency range from 100 kHz to 1 mHz. The electrode potential for each sample was held at its open circuit value during EIS measurements. Curve tting of the EIS data was performed using Zview software, which uses the LevenbergMarquardt non-linear least squares method. This method is based on the complex non-linear least squares (CNLS) program written by Macdonald [21]. 2.3. Surface analysis Surface analysis was performed before and after corrosion experiments. The surface morphology of the NiP deposits was investigated using scanning electron microscopy (Hitachi S3500N electron microscope). Energy dispersive X-ray spectrometry (IncaEnergy 400, Oxford Instrument Ltd.) was used to estimate the Ni and P contents (wt.%). The entire 1.2 1.2 mm2 area was scanned to enhance the reliability of the measurements of average P content. 3. Results and discussion 3.1. Selection of NiP coated specimens The P content of the electroless deposits is shown as a function of stabilizer concentration in Fig. 1. The stabilizer concentrations used to produce specimens for corrosion testing were selected so that the dierence in P content was insignicant ($ 0.5 wt.%) over the range studied. The only exception was the deposit prepared using TU2.0 that contains $1.0 wt.% less P than generally observed. Thus, with this exception, dierences in the corrosion behaviour are unlikely to be attributable to dierences in the P content of the deposits. 3.2. Surface layer composition (XPS) In a previous publication [22], X-ray photoelectron spectroscopy (XPS) was used to examine the composition of lms formed on similar EN deposits after corrosion under the same conditions as those used here. Two distinct corrosion lms were observed. An enrichment of elemental phosphorus compared to nickel was observed on the surface of EN deposits produced with either no stabilizer or maleic acid. By contrast, extensive surface oxidation was observed on EN deposits prepared with TU. Trace impurities of sulfur were blamed for the extensive build-up of corrosion products on EN deposits formed with TU, whereas a P enriched chemical passivation layer was formed on deposits prepared without any stabilizer and with MA.

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10

P Content, wt. %

Ref MA TU

0 0 1 2 500 1000 1500 2000 2500 3000

Concentration, mg/L
Fig. 1. Phosphorus content in a NiP binary alloy produced by EN deposition with dierent types and amounts of the stabilizer.

3.3. Surface morphology and composition (SEM/EDS) As deposited surfaces of the EN specimens are shown in Fig. 2(A1)(G1). The surfaces can be categorized into two types; (a) surfaces with particle boundaries and (b) smooth surfaces. Deposits formed in an unstabilized bath or in a bath containing larger than 1 g/L MA exhibited smooth surfaces with a number of small defects (Fig. 2(A1), (F1) and (G1)). For surfaces with particle boundaries, slightly dierent structures were observed depending on the type of stabilizer and its concentration. The MA180 specimen had regular small nodular features $100 nm in diameter (Fig. 2(E1)). The TU0.5 specimen showed non-uniformly ordered particle boundaries (Fig. 2(B1)) while very clear uniformly ordered boundaries were produced with TU0.9 (Fig. 2(C1)). A cauliower like surface with many boundaries was observed on the TU2.0 specimen (Fig. 2(D1)). After immersion in 5% NaCl solution for 195 h (Ar-purged (50 h) and O2-purged (145 h)), two distinctly dierent corrosion morphologies were observed (Fig. 2(A2) (G2)). For specimens with particle boundaries, preferential attack occurred along the boundaries (Fig. 2(B2)(E2)), and the severity of attack increased with an increase in the concentration of TU. The blurred SEM micrograph (Fig. 2(D2)) observed for the TU2.0 specimen may indicate the presence of a thick corrosion/oxide layer on this surface. By contrast, evenly distributed small pits with a high number density were formed on the surfaces of smooth deposits (Fig. 2(A2), (F2), and (G2)). These dierences in morphology of corrosion attack were correlated with the two distinctly dierent surface layer compositions determined by XPS [22]. EDS analysis conrmed the higher O content and lower P content (compared to the bulk P content of $6 wt.%) obtained on the corroded TU2.0 specimen prepared on Mg AZ91D substrate (Fig. 3). For the corroded RE and MA3k specimens prepared on a Mg AZ91D substrate, the P and Ni contents were comparable to the bulk values (Fig. 3). In addition, an SEM

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Fig. 2. The SEM micrograms of NiP deposits surface prepared with various concentrations of TU and MA: (A) no stabilizer; (B) 0.5 mg/L TU; (C) 0.9 mg/L TU; (D) 2.0 mg/L TU; (E) 180 mg/L MA; (F)1.0 g/L MA; (G) 3.0 g/L MA. The SEM micrograms of each specimen were obtained (1) before and (2) after corrosion experiments in 5% NaCl purged with Ar (48 h) and O2 (145 h).

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Fig. 2 (continued)

investigation of the specimens (Fig. 4(A)(E)) after the 50 h Ar purged period indicated that the pitting and intergranular attack initiated during the Ar-purged period. 3.4. Corrosion potential (Ecorr) measurements and electrochemical impedance spectroscopy (EIS) 3.4.1. General corrosion behaviour and equivalent circuit models The corrosion potentials (Ecorr) of dierent specimens were monitored in deaerated (Ar) (50 1 h) and then oxygenated (145 1 h) 5% NaCl solution (Fig. 5). In addition, EIS measurements were acquired periodically for every specimen (Fig. 6). For all specimens, the absolute impedances at low frequencies (103102 Hz) were much higher for

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Ni Ni
Intensity

RE on Mg TU2.0 on Mg MA3k on Mg

P O

Ni

10

keV

Specimens RE on Mg TU2.0 on Mg MA3k on Mg

O (wt. %) 0.61 8.05 0.51

P (wt. %) 6.77 3.54 6.30

Ni (wt. %) 92.62 88.41 93.19

Fig. 3. EDS spectrum of EN deposits prepared with dierent stabilizers (RE no stabilizer, TU thiourea, and MA maleic acid) on an Mg AZ91D alloy substrate (with a Cu intermediate later) after immersion in Ar-purged (50 h) and O2-purged (145 h) 5% NaCl solution. The table shows the elemental content of each specimen.

Ar-purged conditions than for O2-purged conditions (Fig. 6(A2)(G2)). The increase in the Ecorr (Fig. 5) observed on switching from Ar to O2-purged conditions, can be attributed to the increased polarization of the corrosion process by oxygen reduction leading to an increase in corrosion rate. In addition, the introduction of oxygen leads to less noise in the Ecorr. The noise amplitude was 5 mV for Ar-purged conditions, but only 0.1 mV for the O2-purged condition. The Ecorr of the uncoated Mg AZ91D alloy substrate was extremely negative (1.5 VSCE, Fig. 5), consistent with its instability in water. In addition, the introduction of oxygen did not change Ecorr, indicating that the oxygen reduction reaction does not inuence the already rapid corrosion of the Mg AZ91D alloy (Fig. 5) in 5% NaCl solution. Inspection of the EIS spectra suggests three dierent equivalent circuit models are required to t the results (Fig. 7). A one time constant (s) model (Fig. 7(a)) is appropriate for smooth deposits (RE, MA1k or MA3k) corroding under Ar-purged conditions (Fig. 6(A), (F), and (G); plots in black). Such a circuit suggests a uniform corrosion process on smooth deposits. The development of small pits in the latter stages of the Ar-purged period required the tting of the spectra with a 2 s-circuit (Fig. 7(b)), consistent with a corrosion process occurring predominantly at the base of pits. A 2 s-circuit model was also required to t the spectra measured on specimens with particle boundaries when preferential corrosion along particle boundaries occurred (Fig. 6(B)(E)). Lastly, a 2 s circuit with an added Warburg circuit element (Fig. 7(c)) was required to t the spectra generated from specimens prepared with >0.9 mg/L TU after prolonged exposure to oxygenated solution (Fig. 6(C) and (D); plot in olive). Such a model is consistent with a

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Fig. 4. The SEM micrograms of NiP deposits prepared with various concentrations of TU and A: (A) no stabilizer; (B) 0.5 mg/L TU; (C) 2.0 mg/L TU; (D) 1.0 g/L MA; (E) 3.0 g/L MA. The SEM micrograms were obtained after immersion in 5% NaCl purged with Ar (48 h).

corrosion process occurring preferentially at the base of deep particle boundary channels in which O2 transport is partially rate controlling. 3.4.2. Ar-purged condition For the deposit prepared in an unstabilized bath, Ecorr rapidly established a value of 400 mV to 425 mV followed by a slow rise (Fig. 5). A deposit grown in the presence of a low TU concentration (TU0.5) exhibited similar behaviour, but as the TU concentration was increased, an Ecorr value in the range 450 mV to 500 mV was established more slowly and no subsequent gradual increase was observed (Fig. 5). The MA180 specimen behaved similarly to these last specimens. Inspection of Fig. 2 shows this latter behaviour

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Fig. 5. Corrosion potential of deposits formed in dierently stabilized baths exposed to 5% NaCl solution.

is consistently observed with deposits comprising ne and nodular features (Fig. 2(C1), (D1), and (E1)). The Ecorr behaviour in the MA1k specimen was similar to that observed for the RE specimen. For the MA3k specimen, Ecorr was initially very low but eventually the Ecorr rose as if undergoing a transition (Fig. 5). A comparison of values after the Ar-purging period shows Ecorr shifted to less noble values with an increase in TU concentration from 0 mg/L to 2.0 mg/L, Fig. 8. By contrast, Ecorr values for the MA1k and MA3k specimens (Fig. 8) were closer to the Ecorr for the RE specimen. The onset of pitting during the Ar-purging period forced the use of a 2 s-circuit to t the impedance results. Fig. 8 also shows the total surface resistances determined from the low frequency limit of the impedance spectra. The resistances (Rt) clearly correlate with the Ecorr values, with specimens with Ecorr < 0.45 V possessing lower resistance than those with Ecorr P 0.40 V. This indicates that the positive shift in Ecorr under Ar-purged conditions leads to an enhanced corrosion resistance, suggesting the formation of a corrosion resistant surface lm/layer. The increases in Ecorr and total resistance for the RE and the MA3k specimens can be attributed to the gradual inhibition of the anodic reaction due to the build-up of a P-enriched layer containing PO3 , H2 PO , and P0, as indicated by 4 2 XPS [22]. It is likely this build-up is due to the selective dissolution of Ni at the beginning of the immersion period [17]. The formation of a hypophosphite lm has also been reported on both electroless NiP (12.8% and 8.0%) alloys under natural corrosion conditions in 3.5% NaCl at pH of 10 [4] and on electroless NiP (13.2%) deposits in a 0.2 N HCl solution [23]. The oxidation of phosphorus to P1+ was considered to occur as follows [24]: P 2H2 O H2 PO 2H e 2 The P1+ species can then be further oxidized to a P5+ species [24] H2 PO 2H2 O H2 PO 4H 3e 2 4 and stabilized on the metal surface by an Ni
2+

1 2 cation.

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By comparison, XPS analysis showed a low P/Ni ratio on the TU2.0 specimen [22], and the low total resistance indicated that the anodic reaction (i.e. Ni ! Ni2+ + 2e) was not inhibited in this case. The TU0.5 specimen exhibits a similar high resistance to the unstabilized system, Fig. 8, but in this case XPS showed the inhibiting surface possessed a high O/Ni ratio and only a small P/Ni ratio. The high resolution Ni 2p3/2 peak indicated most of nickel species on the surface were bound to hydroxide [22]. The MA1k specimen exhibited a particularly high Rt value suggesting the presence of an air-formed oxide, incompletely removed by the cathodic cleaning step.

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Fig. 6. Bode plots recorded after various periods of corrosion in 5% NaCl solution with Ar (50 h) or O2 (145 h) purging for deposits produced from dierently stabilized EN baths: (A) RE; (B) TU0.5; (C) TU0.9; (D) TU2.0; (E) MA180; (F) MA1k; (G) MA3k.

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Fig. 7. Equivalent circuit models for electroless NiP deposits exposed in 5% NaCl solution. (a) Uniform corrosion lm on the NiP surface, (b) corrosion lm with pores of low aspect ratio and (c) corrosion lm with pores of high aspect ratio.

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Fig. 8. Corrosion potential and total resistance (from EIS measurements) for deposits produced with dierent amounts of stabilizer: MA maleic acid; TU thiourea; Ref no stabilizer; 50 h immersion in Ar-purged 5% NaCl.

3.4.3. O2-purged condition The onset of O2 purging resulted in a shift of Ecorr to more positive values for all the specimens (Fig. 5), as expected. After the initial increase, Ecorr varied for individual specimens. Ecorr for the MA3.0, MA1.0 and RE specimens rapidly stabilized (Fig. 5), while the

Total Resistance, cm2

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TU specimens relaxed to lower values (Fig. 5). This relaxation was most marked for the TU0.9, TU2.0 and MA180 specimens, and suggests an accelerated corrosion reaction, which is consistent with the signicantly lower Rt values obtained for these specimens, Fig. 9. The behaviour of the three specimens prepared in TU makes an instructive series. The relaxation in Ecorr is much less marked for TU0.5 compared to TU0.9 and TU2.0 (Fig. 5), and so is the decrease of Rt with time (Fig. 9). Inspection of Fig. 2(B)(D) shows that the extent of intergranular attack is also lower for the TU0.5 specimen. However, the decrease

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1000
Rt - RE Rt - MA180 Rt - MA1K Rt - MA3k Rt - RE on Mg Rt - 3kMA on Mg

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Fig. 9. Total resistances from EIS measurements of the deposits produced from dierently stabilized baths after various periods of corrosion in 5% NaCl; 050 1 h Ar-purged; >50 h oxygenated: (a) RE and TU specimens; (b) RE and MA specimens.

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of Rt with time was much greater for the TU0.9 specimen than that for the TU2.0 specimen. This may be attributed to the fact that the well dened particle boundaries present on the TU0.9 specimen (Fig. 2(C)) are prone to the intergranular attack. Also, the decrease in Rt for TU2.0 on Mg in the oxygenated solution was much less than that prepared on the copper substrate (Fig. 9(a)). This dierence might be attributed to the high roughness of the Mg alloy surface and the electrochemically produced Cu intermediate layer, leading to the production of a deposit with less well dened particle boundaries. By comparison, noticeable dierences were not observed for RE and MA specimens (Fig. 9(b)). The EIS spectra for the TU specimens evolve considerably as Ecorr relaxes during the O2-purging period. This is best appreciated from the phase angle plots in Fig. 6(B1) (D1). A second time constant evolves with time at low frequencies and for the TU0.9 and TU2.0 specimens, a Warburg impedance is required to accurately t the spectra. This suggests partial control of the corrosion by O2 transport within the deepening intergranular sites (Fig. 6(C1) and (D1)). By contrast, the RE, MA1k, and MA3k specimens do not obviously develop a second time constant during the O2-purging period, although MA180 shows a slight tendency to do so. This is consistent with the SEM micrograms obtained at the end of the Ar-purged (Fig. 4) and the O2-purged (Fig. 2) periods which both show a generally uniform distribution of numerous pits. The slight dierences might be due to the presence of the patches of surface lm on the surface as indicated at the end of the Arpurged period. XPS analyses showed these dierences coincided with the formation of two distinctly dierent corrosion lms/layers after the oxygenated period [22]. Higher P/Ni ratios (12) were observed on smooth specimens (RE, MA1k, and MA3k) than on the nodular TU specimens (<0.5). The P/Ni ratios after O2-purging were much higher than those measured on sputter-cleaned surfaces for the RE, MA1k, and MA3k specimens. By contrast the TU0.5 and TU2.0 specimens had similar P/Ni ratio as those of the sputter-cleaned surface [22]. In general, corrosion of smooth deposits lead to an increase in P/Ni ratio while those specimens exhibiting intergranular corrosion experienced little change in this ratio [22]. The composition of corroded smooth surfaces was mainly P0 along with PO3 , H2 PO 4 2 and only a minor amount of nickel oxide or hydroxide. By comparison, the intergranularly attacked TU specimens had a high O content mostly in the form of nickel hydroxide. The nature of these surface layers inuenced the corrosion rates of the specimens. The P enriched surface layers of the RE and MA specimens lead to the higher Rt values observed, relative to those for the intergranularly attacked TU2.0 specimens (Fig. 9). However, a thick generally uniform hydroxide layer also provides some corrosion resistance as in the case of the TU0.5 specimen and the TU2.0 specimen prepared on the Mg AZ91D substrate when the particle boundaries are not as well dened or subsequently corroded (Fig. 2(B1) and Fig. 9(a)). The use of the two time constant circuit shown in Fig. 7(b) allows the determination of the resistance associated with pits and intergranularly corroded sites. The evenly distributed preformed defects resulted in pit formation on the surface of the RE deposit, Fig. 4(A), and the high pore resistance (Rpo > 10,000 X cm2) (Fig. 10(a)) suggests a large aspect ratio. The pore resistance increased slightly during the Ar-purged period as the P-rich surface layer started to form on the surface. However, for more aggressive O2-purging conditions, Rpo initially decreased by an order of a magnitude, suggesting opening up of the pits. As the pits propagated, the aspect ratio became larger resulting in the observed

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1000

100
Rpo - RE Rpo - MA180 Rpo - MA1k Rpo - MA3k Rpo - RE on Mg Rpo - MA3k on Mg

10 0 20 40 60 80 100 120 140 160 180 200

Time, h
Fig. 10. Pore resistances of the deposits produced from dierently stabilized baths after various periods of corrosion in 5% NaCl; 050 1 h Ar-purged; >50 h oxygenated: (a) RE and TU specimens; (b) RE and MA specimens.

recovery in Rpo (Fig. 10(a)). The Rpo value for the RE on Mg specimen did not show the decrease and subsequent increase, but the Rpo was similar to that of the RE specimen after long immersion in the oxygenated solution. For the TU specimens (including the TU2.0 on Mg specimen), a similar drop in Rpo occurred on switching from Ar to O2, except for the TU0.5 specimen. This can be attributed to the enlarged corrosion surface area with the introduction of O2. For the TU0.5 specimen, the particle boundaries are not clearly dened (Fig. 2(B2)). Also, the high surface oxide content prevented the corrosion from penetrating to the particle boundaries.

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Thus, the Rpo was much smaller compared to the others (Fig. 10(a)). After the introduction of oxygen, the corrosion reaction started to occur along the particle boundaries as in the case of the other TU specimens, and the Rpo values comparable to those of the other TU specimens were observed through the long oxygen purged period (Fig. 10(a)). For the MA specimens, two dierent behaviours were observed. A drop in Rpo was observed for the MA180 and MA3k specimens but not for the MA1k and the MA3k on Mg specimens on switching from Ar to O2 (Fig. 10(b)). This drop can be attributed to the increase in the number densities and/or opening up of pits, in the more aggressive corrosion environments, Fig. 2(E) and (G). For the MA1k specimen, the high Rpo value ($20,000 X cm2) under Ar-purging did not change on switching to O2. This is consistent with the presence of very few pits on this specimen, Fig. 2(F2). XPS results indicated this specimen is protected by a thick oxide layer under Ar-purged conditions and a strong surface enrichment of P after O2-purging. Steady and high lm resistances (Rlm $ 10,000 X cm2) were observed on all MA specimens (Fig. 11(b)) while signicantly lower lm resistances were observed on most TU specimens (Fig. 11(a)). The high values of Rlm can be attributed to passivation by P-enriched surface layers as indicated by XPS [22]. The lm resistances for the TU samples decreased as intergranular corrosion became severe with oxygen purging. The noticeably lower Rlmobserved for the TU0.9 specimen (compared to the TU2.0 specimen) can be attributed to the much larger particle boundaries for TU0.9 compared to TU2.0. This results in the accumulation of a thinner layer of corrosion products on the particles. 3.5. Signicant factors governing the corrosion characteristics of the protective NiP coating 3.5.1. Microstructure vs. microscopic defects The microstructure of the deposit as characterized previously [8] indicated that the EN deposits are polycrystalline with mixed amorphous and nanocrystalline phases. The deposits with a higher degree of amorphicity or smaller grain sizes (i.e. the MA3k specimen) exhibited slightly poorer corrosion characteristics than those with ordered nanocrystals (i.e. the RE specimen). This result is not consistent with the literature; amorphous NiP coatings passivate in acidic and neutral solution, but the presence of crystalline structures increased corrosion rates dramatically [12,25]. This conclusion was drawn knowing that the deposit only diers in microstructure [12] by applying heat treatment, or microstructure and P content [25] by adjusting electroplating bath composition. In the present corrosion study, for a deposit with smooth morphology, the dominant factor for the corrosion performance appeared to be the pre-formed microscopic defects/preferentially attacked sites since the morphologies observed after etching and corrosion were similar; i.e. both exhibited evenly distributed small pit formation (Fig. 2(A2) and Fig. 12). 3.5.2. Morphology Specimens with a smooth morphology (i.e. the RE, MA1k and MA3k specimens) were much more corrosion resistant than those with a nodular morphology, except for the MA180 specimen. The variation in P content between specimens was insignicant and, therefore, not a factor in determining the dierences in corrosion behaviour. However, the corrosion resistance decreased at the high TU concentration, consistent with published observations [18]. Our study of deposit microstructure [8] showed TU0.9 to be more amorphous than the RE specimen. Clearly amorphicity is not critically important in determin-

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100000
Rfilm - RE Rfilm - TU0.5 Rfilm - TU0.9 Rfilm - TU2.0 Rfilm - RE on Mg Rfilm - TU2.0 on Mg

10000

Rfilm, cm
1000 100 0 20 40 60 80 100 120 140 160 180 200

Time, h
100000

10000

Rfilm, cm
1000
Rfilm - RE Rfilm - MA180 Rfilm - MA1k Rfilm - MA3k Rfilm - RE on Mg Rfilm - MA3k on Mg

100 0 20 40 60 80 100 120 140 160 180 200

Time, h
Fig. 11. Film resistances of the deposits produced from dierently stabilized baths after various periods of corrosion in 5% NaCl; 050 1 h Ar-purged; >50 h oxygenated: (a) RE and TU specimens; (b) RE and MA specimens.

ing corrosion behaviour since the corrosion rate for TU0.9 is greater than that of the RE specimen. It appears that the presence and density of particle boundaries are more important. As the particle boundaries become more clearly dened (Fig. 2(A2), (B2), and (C2)), the corrosion resistance decreases, due to intergranular corrosion along these boundaries. However, the MA180 specimen dose not t this pattern, since despite the presence of ne particle boundaries, the total resistance value was high and compatible with that of the MA3k specimen.

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Fig. 12. SEM microgram of a polished NiP deposit surface after etching with dilute HNO3 (5%) for 5 s.

3.5.3. Surface composition and impurity The higher corrosion resistance observed for the RE specimen and the MA specimen can be attributed to the formation of a P-enriched layer shown to be present by XPS and mostly in the P0 valence state. Such a layer has been claimed to be a chemical passivation layer against corrosion [12,17,26], the accumulation of elemental P on the alloy surface acting as a barrier against dissolution. On the contrary, the more rapidly corroding TU specimens possessed a low P/Ni ratio but a high O/Ni ratio (>2.0). In addition, trace amounts of the sulfur were detected by the XPS on TU specimen before and after corrosion [911,22] and its presence was conrmed by high resolution TOF-SIMS [22]. The S peaks were detected at a binding energy of $167168 eV corresponding to an oxidized form of sulfur, most likely SO2 [27]. This form of sulfur was pro4 posed by Eklund as the dominant dissolved sulfur species originating from the corrosion of sulde inclusions in stainless steel (SS) [28]. The acidity formed via this corrosion process MnS 4H2 O ! Mn2 SO2 8H 8e 4 3

was considered to activate the surface. The stability domain of adsorbed sulfur extends beyond the usually predicted range of stability of metal suldes; i.e., adsorbed sulfur can exist under conditions in which no bulk sulde is stable [29]. The presence of the adsorbed sulfur has been shown to increase the dissolution rate of nickel based alloys, a weakening the metalmetal bond induced by adsorbed sulfur. This lowers the activation energy barrier for the passage of metal atoms from the surface to the solution [29]. Furthermore, this inuence can be localized if the sulfur is adsorbed on specic sites, where it can be more tightly bonded [29]. For TU specimens, sulfur adsorption may be concentrated on the particle boundaries (Fig. 2(A2) (D2)), where the higher adsorption density of TU during the EN deposition is expected

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due to the higher diusive ux. Adsorbed sulfur is also thought to retard the growth of passive lms by blocking the sites utilized in oxide growth by OH adsorption. Anodic segregation of sulfur caused by the selective dissolution of nickel could lead to large surface concentrations of adsorbed sulphur on the surface [29]. These sites could be continuously exposed to further corrosion. Such processes could explain the large dierences in total resistance between surfaces with particle boundaries (TU0.9, TU2.0 and MA180). The signicantly lower resistance values for TU0.9 and TU2.0 compared to MA180 could be attributed to the presence of S on particle boundaries. In addition to the inuence of S impurities, local acidity could be enhanced at particle boundaries by Ni2+ hydrolysis to NiOH+, Ni(OH)2, and Ni2OH3+ [30]

O2
OH-

Ni

Ni2+ 2SO4 Sulfide oxidation S2- + 4H2O 8H+ H+ Sads Ni2++ H2O Ni(OH)2

Ni dissolution enhanced by Sads Ni(OH)+ Ni2+ hydrolysis O2

Ni

Ni

Sads 8H+ P + 4H2O PO43Ni2+

OH P oxidation

O2

Ni-P 5 % NaCl Solution

O2 OH Ni2+
-

Ni dissolution is blocked

5% P-rich

P Ni Ni-P

Ni-P

Fig. 13. Schematic models for (a) intergranular corrosion of NiP deposits prepared with TU and (b) chemical passivation of NiP deposits prepared with no stabilizer or with MA during corrosion in oxygenated neutral 5% NaCl.

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Ni2 H2 O NiOH H 2Ni

2

H2 O Ni2 OH

The schematic in Fig. 13(a) attempts to summarize the reactions described as occurring on an EN surface prepared with TU present. Ni2+ hydrolysis, combined with S and P oxidation, lowers the pH at the particle boundaries and increases the solubility of various Ni2+ hydrolysis products such as NiOH+ and Ni2OH3+ [30]. Thus, these Ni2+ hydrolysis products readily diuse out of particle boundaries and precipitate to form a thick oxide layer on the outer surfaces as shown by XPS analyses. Due to the acidity within the corroding particle boundaries, oxide/hydroxide formation is prevented and corrosion continues. On the contrary, in the absence of the particle boundaries and sulfur impurities, the general preferential dissolution of nickel produces a P-rich chemically passive layer which hinders further dissolution of nickel as illustrated schematically in Fig. 13(b). 4. Conclusions The eects of the EN bath stabilizers, TU and MA, on the corrosion of the EN coatings on copper and magnesium substrates (with an intermediate copper layer produced by a novel Cu immersion process) were investigated in an aggressive oxygenated chloride environment. The dissolution or the corrosion attack of the AZ91D Mg alloy and Cu substrates were not observed throughout the corrosion experiments, with corrosion limited to the external EN layer. Two dierent types of corrosion morphology were observed. Specimens prepared with TU, and the MA180 specimen, showed preferential attack along particle boundaries while those prepared with no stabilizer and MA showed a pitting-type corrosion on the smooth surfaces. Higher corrosion resistances were observed for smooth deposits, which is attributed to the formation of a P-enriched layer on the surface. The poorer corrosion performance of EN specimens prepared with TU is attributed to the presence of the particle boundaries and the trace impurities adsorbed on, or included in, them. It was clearly shown that the corrosion behaviour of the EN specimens studied was not governed by the microstructural aspects of the EN deposit but was predominantly inuenced by morphological and surface compositional aspects (i.e. surface impurities). Acknowledgements This research is funded by the Natural Science and Engineering Research Council of Canada (NSERC). The authors gratefully acknowledge the general technical help of John Nagata (IMTI-NRC) and help of Mike Meinert (IMTI-NRC) and Brad Kobe (SSW) in the acquisition of SEM micrographs. The authors would like to thank Dr. Zack Qin (UWO) for the design of the corrosion cell and Dr. Jamie Noel (UWO) for the help in showing problems related to electrochemical instrumentation. References
[1] R. Ellmers, D. Maguire, Global View Magnesium: Yesterday, Today, Tomorrow, 1993, p. 28. [2] J.E. Gray, B.L. Luan, Journal of Alloys and Compounds 336 (2002) 88.

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[3] H. Huo, Y. Li, F. Wang, Corrosion Science 46 (2004) 1467. [4] P.-H. Lo, W.-T. Tsai, J.-T. Lee, M.-P. Hung, Surface and Coating Technology 67 (1994) 27. [5] G.O. Mallory, J.B. Hajdu, Electroless Plating, Noyes Publications/William Andrew Publishing, LLC, New York, 1996, pp. 3555. [6] R. George, S. Venkatachalam, K.N. Ninan, British Corrosion Journal 37 (2002) 37. [7] E. Lanzoni, C. Martini, R. Ruggeri, R. Bertoncello, A. Glisenti, in: EUROCORR 96, 1997, p. 232. [8] W.J. Cheong, B.L. Luan, D.W. Shoesmith, Applied Surface Science 229 (2004) 282. [9] L. Das, D.T. Chin, Plating and Surface Finishing 83 (1996) 55. [10] I.V. Petukhov, M.G. Shcherban, Protection of Metals 35 (1999) 566. [11] J.K. Sallo, J.S. Sallo, Journal of the Electrochemical Society 112 (1965) 1201. [12] Z. Longfei, L. Shoufu, L. Pengxing, Surface and Coating Technology 36 (1988) 455. [13] R.N. Duncan, T.L. Arney, Plating and Surface Finishing 76 (1989) 60. [14] J. Flis, D.J. Duquette, Corrosion 41 (1985) 700. [15] G. Salvago, G. Fumagalli, Metal Finishing 85 (1987) 31. [16] G. Salvago, D. Sinigaglia, G. Fumagalli, D. Continenza, G. Taccani, in: Proceedings of INTERFINISH 80, 1980. [17] A. Krolikowski, European Federation of Corrosion Publication 2 (1993) 119. [18] I.V. Petukhov, M.G. Shcherban, N.E. Skryabina, L.N. Malinina, Protection of Metals 38 (2002) 370. [19] G. Salvago, G. Fumagalli, in: 10th International Congress on Metallic Corrosion, 1987. [20] W.P. Innes, Electroplating and Electroless Plating on Magnesium and Magnesium Alloys, WileyInterscience, New York, 1974, p. 601. [21] J.R. Macdonald, in: J.R. Macdonald (Ed.), Impedance Spectroscopy Emphasizing Solid Materials and Systems, John Wiley & Sons, New York, 1987, pp. 179180. [22] W.J. Cheong, B.L. Luan, N.S. McIntyre, D.W. Shoesmith, Surface and Interface Analysis, submitted for publication. [23] R.B. Diegle, N.R. Sorensen, C.R. Clayton, M.A. Helfand, Y.C. Yu, Journal of Electrochemical Society 135 (1988) 1085. [24] M. Pourbaix, in: J.V. Muylder, M. Pourvaix (Eds.), Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamon Press Ltd., Oxford, 1966, pp. 504515. [25] A. Krolikowski, B. Pokrywa, Metalurgia i Odlewnictwo 16 (1990) 111. [26] H. Habazaki, S.-Q. Ding, A. Kawashima, K. Asami, K. Hashimoto, Corrosion Science 29 (1989) 1319. [27] K.-P. Han, J.-L. Fang, International Journal of Chemical Kinetics 28 (1996) 259. [28] G.S. Eklund, Journal of Electrochemical Society 121 (1974) 467. [29] P. Marcus, Sulfur-assisted corrosion mechanisms and the role of alloyed elements, in: P. Marcus, J. Oudar (Eds.), Corrosion Mechanisms in Theory and Practice, Marcel Dekker, Inc., New York, 1995, pp. 239263. [30] C.F. Baes, R.E. Mesmer, The Hydrolysis of Cations, John Wiley & Son, New York, 1976, pp. 241247.