Surface & Coatings Technology 207 (2012) 503507

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Surface & Coatings Technology

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Preparation of passive CuNiFe coating on low-carbon steel for improving corrosion resistance
Qiongyu Zhou, Yi Wang, Hongyan Wu, Qingdong Zhong , Jibo Jiang
Shanghai Key Laboratory of Modern Metallurgy and Material Processing, Shanghai University, Shanghai, 200072, PR China

a r t i c l e

i n f o

a b s t r a c t
CuNiFe alloy coating was prepared on low-carbon steel by surface alloying. The surface heat treatment of coated low-carbon steel was performed at 700 C, 800 C, 900 C and 1000 C for 3 h under hydrogen atmosphere. The structure and microstructure of coatings were separately analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). A series of electrochemical analysis was carried out to examine the corrosion resistance of CuNiFe alloy coatings in borate buffer solution. Results indicated that a uniform and homogeneity CuNiFe alloy coating constituted of -phases was prepared on the surface of low-carbon steel at 1000 C, which promoted the formation of compact passive lm. The passive lm signicantly improved the substrate's corrosion resistance in alkaline solution. 2012 Published by Elsevier B.V.

Article history: Received 5 January 2012 Accepted in revised form 20 July 2012 Available online 27 July 2012 Keywords: CuNiFe alloy coating Low-carbon steel Passive lms Corrosion resistance

1. Introduction Surface alloying technique is a simple and cost-effective fabrication process to improve the corrosion resistance of the steel substrate [1,2]. The use of surface coatings opens up the possibilities for material design to meet the demands for specic properties where they are most needed. Recently, there has been an extensive research on CuNi alloy coatings and FeNi alloy coatings because of their exciting mechanical properties, corrosion resistance and reasonable price [3,4]. The passive lms formed on metals or alloys can be considered as a barrier layer to lessen the metals' corrosion rate, therefore the passivity of metals and formation of passive lms on metals have been a subject of intense interest all the time [5]. Lots of researches have showed that CuNi alloy surface will form oxidation products lm in acid, alkaline, chloride and inhibiters solutions [611]. Besides, much attention has already been drawn to CuNiFe alloys. Iron can provide added resistance to corrosion in CuNi based alloys. And the corrosion resistance can be improved with increasing iron or nickel content so long as it remains in solid solution [12]. CuNiFe alloys are currently being considered as possible candidates for anodes for the electrolysis of Al in industry, since the oxide lms are formed in Al electrolysis as the oxygenevolving-anodes, which contain Cu2O, NiO, FeOx to provide corrosion protection [4,1315]. However, the iron (Fe)copper (Cu) system does not form intermetallic compounds and has negligible mutual solid solubility, and conventional surface alloying processes such as electrodeposition technique or salt bath treatment are unsuitable for the preparation of CuNiFe alloy coatings. The studies of alloy coatings

within the CuNiFe system to improve the corrosion resistance are less common than that of CuNi alloy coatings. In this study, an attempt is made to develop a more economical and simple process for surface modication of low-carbon steel. In order to improve the corrosion resistance, we adopted high-energy ball milling to produce the nano-hybrid particles (nano-sized CuONiO) and applied the surface treatment for low-carbon steel to develop the CuNiFe alloy coatings. Because of the strong effect of passive lm on corrosion kinetics, electrochemical behaviors of the passive lm formed on CuNiFe alloy coatings were also investigated by using the potentiodynamic polarization curve, potentiostatic polarization measurement and electrochemical impedance spectroscopy (EIS).

2. Experimental 2.1. Preparation of nano-sized particles and samples For the preparation of the coating, nano CuO was used as the copper source and nano NiO as the nickel source. CuO and NiO were placed in an agate jar with absolute ethanol used as the dispersing agent and then ball-milled for 24 h. Molar ratio of CuO:NiO was 1:2 and liquid:solid ratio was 80:15. The compositions of CuONiO particles in this study are given in Table 1. The low-carbon steel (10101.2 mm) was used as substrate, which was mechanically polished by using 240 to 1200 grit papers in sequence. Then the samples were rinsed in acetone, ethanol and water for 5 min respectively by an ultrasonic cleaner in order to degrease and clean the surfaces to improve the adhesion of the coating. After cleaning, the low-carbon steel was placed horizontally. The coating solution was vertically sprayed onto the substrates from a distance of approximately 15 cm using a detail spray gun (IT-powered Manufacturing, HD-470).

Corresponding author. Tel.: +86 13391312191; fax: +86 21 56338244. E-mail address: qdzhong@shu.edu.cn (Q. Zhong). 0257-8972/$ see front matter 2012 Published by Elsevier B.V. doi:10.1016/j.surfcoat.2012.07.060

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Table 1 The composition of CuONiO particles with size in this study. Composite particles size CuO 100 nmmax 34.74 wt.% NiO 65.25 wt.% Impurities C Si S P Ca b 0.1 wt.%

2.2. Characterization of the CuNiFe alloy coatings After the heat treatment, the surface morphology and microstructure of CuNiFe alloy coatings were evaluated by Scanning Electron Microscopy (SEM) using the JEOL JSM-6700F microscope. At the same time, the chemical composition of the coatings was determined by an X-ray energy dispersive spectrometer (EDS). The structural character of the coatings was investigated by X-ray diffraction (XRD) with a diffractometer D/max-2200 V and Cu K radiation. All electrochemical measurements were performed in a conventional three-electrode cell. The potentials were referred to a saturated calomel electrode (SCE). The electrochemical measurements were carried out by Electrochemistry Station (CHI660C). The potentiodynamic polarization measurements were carried out in borate buffer solution (0.15 mol/L B(OH)3 +0.075 mol/L Na2BO410H2O, pH=8.4) at a potential sweep rate of 1 mV/s. The potentiostatic polarization experiments were carried out at potential of 0.2 V. The variation of current with time at setting potential was measured directly after cathodic reduction. The samples were passivated for 15 min in borate buffer solution at designated

The spray cycle consisted of spraying for 15 s and then allowing the substrate to air-dry for 45 s. The spray-dry cycle was repeated up to 20 times to achieve the desired coatings' uniformity and thickness. The nanohybrid particle layers were dried completely at room temperature for 5 h and the weight of nano-hybrid particle layer was controlled at 620.10 g/dm2. Then the heat treatment was carried out at temperatures of 700 C, 800 C, 900 C and 1000 C for 3 h under hydrogen atmosphere with the heating rate of 10 C/min. At the last step, a mass of hydrogen was continually used to accelerate cooling.

Fig. 1. SEM micrograph of the CuNiFe coatings at various temperatures: (a,700 C; b,800 C; c,900 C; d,1000 C; e, cross-section morphology at 1000 C).

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Fig. 2. The element composition of the CuNiFe coatings at various temperatures.

Fig. 4. Potentiodynamic polarization plots of the samples in borate buffer solution.

potential in order to form stable passive lms on the electrode surface, and then followed by electrochemical impedance spectroscopy (EIS) tests carried out in the frequency ranging from 100 kHz to 0.01 Hz. 3. Results and discussions 3.1. CuNiFe alloy coatings The topography of CuNiFe coating at 700 C is shown in Fig. 1a. In this gure, the coating which cannot adhere to substrate well is rough, and microcracks are obviously observed. With further increase in temperature, the structure of the coating becomes smoother and more uniform (see Fig. 1b, c and d). This phenomenon was probably caused by the improved gradual fusion of the surface particles and the enhanced diffusion of new metal atoms, which generated by hydrogen reduction of oxide particles. When heating temperature reaches 1000 C, a compact, non-porous coating covering the entire surface formed. The cross-section morphology of the coating at 1000 C is displayed in Fig. 1e. As shown, a compact alloy layer is formed on the surface. The average thickness of the coating was about 30 m and no crack was observed. In addition, a transition zone which contained two phase, was clearly observed between the alloy coating and the substrate. Fig. 2 shows that the element composition of the CuNiFe coatings varies with heating temperature. As shown, the coatings are composed of Cu, Ni and Fe. The Ni content decreases and Fe content increases on

the surface coating, while the change of Cu content was much less obvious. This phenomenon probably is caused by the high speed of diffusion of the atoms of Ni deposited on the surface of Fe on having increased the heating temperature, however the Cu diffusivity is very slow due to the low solid solubility between Cu and Fe. Specially, Fe was reduced at 800 C, which is because the microcracks disappeared and the uncovered low-carbon steel substrate fade away at higher temperature. Fig. 3 shows the XRD patterns of all alloy coatings. All coatings show diffraction peaks of both -phases and -phases. From the obtained patterns, there is an obvious increase in the intensity of reections for -phases and a sharp decrease in that for -phases, which nearly disappeared at 1000 C. In the present study, the -phases are bcc -[Fe,Ni] phases, while the -phases cannot be totally excluded on the basis of the XRD data of the consolidated samples because the formation of -[Cu]-rich fcc phases and -[Fe, Ni]-rich fcc phases is hardly differentiable by XRD analysis due to the small difference that exists between the lattice constants of these two phases [16,17]. However, a compact coating and nearly no structure characteristic of a spinodal decomposition were detected from SEM analyses for the surface of alloy coating prepared at 1000 C (as illustrated in Fig. 1d and e). This means, homogeneity -phases would be formed at a higher temperature, which is expected to be benecial for the material corrosion resistance properties [4]. The corrosion resistance of CuNiFe coating was

Fig. 3. X-ray diffraction patterns of CuNiFe coatings at various temperatures.

Fig. 5. Double log plots of current-time for the samples in borate buffer solution.

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Table 2 Straight equation parameters for the double log plots of current-time. Samples Low-carbon steel Low-carbon steel 700 800 900 1000 Straight line a-1 a-2 b c d e Slope( k) 0.952 0.063 0.745 0.802 0.875 1.094 Intercept( A) 2.88 4.76 5.15 4.73 4.23 3.53

Fig. 7. Equivalent circuit employed for tting the electrochemical impedance spectra (Rssolution resistance; Qpfconstant phase element of passive lm; Rpfresistance of passive lm; RWthe diffusion resistance; Qdlconstant phase element of double electric layer capacitor; Rctthe charge transfer resistance of electrode reaction.).

evaluated by various electrochemical analysis and all samples are denoted by their heating temperatures in this paper. 3.2. Potentiodynamic polarization results The potentiodynamic polarization plots of the CuNiFe alloy coatings and substrate in borate buffer solution are shown in Fig. 4. It can be observed that the CuNiFe alloy coating is passivated over a potential range of 0.60.5 V. The passive current density appears to be independent of passive potential range, indicating that stable and favorable passive lms are formed on nickel and CuNiFe alloy coatings. Four anodic peaks are evident at 0.86 V, 0.69 V together with a shoulder at 0.36 and 0.14 V. In line with previous literature, these peaks may be attributed to the oxidation Nickel(II) oxide, Fe(III) such as Fe3O4 and -FeOOH, and Cu(II), respectively [1820]. Indeed, the breakdown potentials of four coatings are more positive than low-carbon steel because the passive current density of low-carbon steel slightly increases with potential above 0.35 V. The minimum passive current density (ipass) decreases in the order 1000 C b 900 C b 800 C b 700 C b low-carbon steel. The results indicate that the corrosion resistance increases in the order 1000 C >900 C>800 C> 700 C >low-carbon steel. 3.3. Potentiostatic polarization results The variations of current with time for different samples were tested at a potential of 0.2 V after cathodic reduction. Under potentiostatic conditions, the current I, of many time-dependent processes is well described by the universal law [21,22]. If the contribution of the double layer charge is neglected, the initial fall of current density should be related to a lm growth on the electrode surface. The current decreased with time, conforming to the following relationship [23]: I 10
Ak lgt

by the increasing lm thickness. The oxide lm is dielectric media. The metal oxide lm behaves like ideal dielectric materials and shows dielectric relaxation effects. According to the literatures [24,25], k = 1 points to the formation of a compact, highly eld-controlled and protective passive lm, while k = 0.5 shows the presence of a porous and diffusion-controlled lm. The double-log plots (lg(i)lg(t)) are shown in Fig. 5 and the equation parameters for tting straight are listed in Table 2. It can be observed that the value of k for low-carbon steel in borate buffer solution changed from 0.95 to 0.06, which indicates that a compact passive lm formed at the beginning and then a porous passive lm was present on its surface. The straight lines of the coatings are comparatively stable and the slope of double-log plots for the coating prepared at 1000 C is 1.09. Thus, the passive lm formed on the surface of the specimen is close to compact. However, the values of k for the other coatings change from approximately 0.74 to 0.87, which indicates that the passivatability of coating prepared at lower temperature is not so remarkable as the coating prepared at 1000 C.

3.4. The electrochemical impedance measurements Fig. 6 shows the impedance spectra for passive lms of the CuNiFe alloy coatings and substrate. As shown in Bode plots, the impedance of the alloy coating is bigger than that of substrate, indicating the passive lm formed on alloy coating is more protective. Comparing with substrate, the phase angle curve for all alloy coating specimens originates the presence of a new time constant at higher frequencies associated with the CuNiFe alloy coating, because the high frequency region in impedance spectroscopy describes the behavior of the coating formed on the outer surface of the substrates [26]. What's more, the alloy coating specimens except those prepared at 700 C exhibit a horizontal line in the intermediate and low frequency regions, indicating that the system presented a predominant capacitive behavior. Therefore, the lms formed on the coating surface can be considered as a barrier layer blocking electron/ionic transfer, which will signicantly lessen the metals' corrosion rate [5].

Where k represents the lm growth rate and is given by the slope of the double-log plot of potentiostatic polarization. The increase of the lm thickness depends on time t. The oxide lm grew and the thickness of the lm increased with time. As a result, the eld strength is reduced

Fig. 6. BodePhase plots for passive lms of the samples in borate buffer solution.

Q. Zhou et al. / Surface & Coatings Technology 207 (2012) 503507 Table 3 Impedance parameters for the substrate and CuNiFe coatings in borate buffer solution. Samples Low-carbon steel 700 800 900 1000 RS () 3.78 147.1 10.74 0.01 0.12 QpfY0 (Fcm 2) 60.53 87.71 59.35 28.5 22.42 npf 0.74 0.78 0.84 0.85 0.91 Rpf (k) 0.22 1.51 116.9 799.6 2062 W (s1/2) 4.02 4.91 0.24 0.04 0.01 QdlY0 (Fcm 2) 580 32.97 0.01 0.03 0.11 ndl 0.55 0.58 0.90 0.80 0.71

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Rct () 189.3 12.67 0.12 0.16 0.14

In order to account for the presence of a diffusion process in the passive lm, and for the particular chemical reaction that occurred in the metal/solution interface, the impedance data was analyzed using software provided by the impedance system where the dispersion formula was used [27,28]. When the complete passive lm formed, it can prevent or delay aqueous solution from penetrating to the surface of metal, and consequently enhance the corrosion resistance. But in actual situation, micropores and crevices more or less exist in the passive lm. Consequently, the diffusion permeability of water and ion through them in the passive lm should be taken into consideration during electrode process in solution of passive lm. These water and ion would react with the metal right under the lm. So the equivalent circuit model is displayed in Fig. 7. Where Rs is solution resistance, Qpf stands for the possibility of a non-ideal capacitance of passive lm (CPE, constant phase element) with varying n. The CPE is a special element. For n =1, the CPE represents an ideal capacitor; for n =0, the CPE is an ideal resistor; for n =0.5, the CPE describes a Warburg impedance with diffusion character; for 0.5 b n b 1, the CPE represents a frequency dispersion of time constants because of local inhomogeneity or roughness or porosity of the surface. Qdl represents constant phase element of double electric layer capacitor. Rct is the charge transfer resistance of electrode reaction. W is the diffusion resistance. And Zw is the resistance of constant phase element (ZQ) when the value of n is equal to 0.5. The total electrode impedance (Z) corresponds to modied circuit (Fig. 7) that is represented by the following mathematical formulation: n   o   Z Rs 1= 1= Rpf Z w 1=Z Q c 1= 1=Rct 1=Z Q dl : 2

4. Conclusions 1. It is feasible to develop a compact CuNiFe coating on the surfaces of low-carbon steel using nano-particles that are composed of CuO and NiO. A compact and uniform CuNiFe alloy coating constituting of homogeneous -phases was prepared at 1000 C. 2. Electrochemical test results showed that the corrosion resistance of the low-carbon steel was improved after surface alloying. Stable and favorable passive lms formed on the prepared CuNiFe coatings, provided corrosion protection and barrier properties.

Acknowledgment This paper is nancially supported by the Natural Science Foundation of China 50571059 and 50615024, program for New Century Excellent Talents in University NCET-07-0536, and Innovative Research Team in University IRT073.

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The above equation considers deviation from ideal RC-behavior due to the surface inhomogeneity, roughness and formation of porous layers. n can be used as a measure of the formation of porous layers here. Fitted data using the equivalent electrical circuits are presented in Table 3. It can be seen in this table that the coating formed at 1000 C has the highest Rpf value and lowest Qpf and Qdl values, which imply the best anti-corrosion ability due to the homogeneity -phases. It is signicative to remark that larger Rpf values indicate extremely slow electrochemical dissolution process, on account of the presence of a stable thin passive lm between the electrolyte and the coating. Accordingly, npf value approximated to 1, which means that the passive coating actually behaves almost like an approximate ideal capacitor. By contrast, Rpf value of the low-carbon steel is thousands times less and npf value deviates from the ideal capacitor, which indicated that the low-carbon steel is not perfectly passivated. From the above EIS results, it was concluded that the corrosion resistance of the low-carbon steel was improved after surface alloying. This meant that preparation of passive CuNiFe alloy coatings is an effective process to improve the corrosion resistance ability.