Journal of Wuhan University of DOI 10.

1007/s11595-006-3417-3

Technology-Mater. Sci. Ed.

Sept 2007

417

Composition and Morphology of Zn-Co Alloy Coatings Deposited by Means of Pulse Plating Containing Reverse Current
(Department of Applied Chemistry, Science College ,Northwestern Polytechnical University, Xian 710072, China) Abstract: The influence of bath constituents and pulse parameters on cobalt content, surface morphologies and grain size of Zn-Co alloy deposits was studied using a pulse plating technique with a squarewave current containing reverse pulse. It is found that Zn-Co alloy coatings obtained from the bath with the cobalt ion concentration over 60 wt% have a higher cobalt content in deposits. The results of pulse plating show that the average current density and reverse anodic current density amongst the variables investigated have very strong effects on the cobalt content in the Zn-Co alloy deposits. It is possible to electrodeposit Zn-Co alloy coatings with 10-90 wt% cobalt by modulating pulse parameters. The grain size, surface appearance and internal stress in the deposit were improved significantly by introducing the reverse current. Key words: zinc-cobalt alloy; electrodeposition; pulse plating

FEI Jingyin, LIANG Guozheng, XIN Wenli

1 Introduction
The electrodeposited Zn-Co alloy coating with low percentage of alloying element cobalt (<5 wt%) is the most commercially viable option as it is cost effective and exhibits a better corrosion resistance (three or four fold) over the existing zinc coating system[1-6]. Electrodeposited Zn-Co alloys with controlled morphology and composition have also been the subject of many studies as a consequence of their observed catalytic activity, which is very similar to Zn-Ni alloys[7-12]. These two completely different functions of the Zn-Co alloy require very different composition and morphologies. However, the deposits of Zn-Co alloys with cobalt content of more than 6 or 7 wt% have not been widely reported. This may be due to the perceived limitations arising from anomalous co-deposition according to the definition of anomalous co-deposition by Brrenner[13]. The preferential deposition of zinc is observed under a wide range of conditions, while the content of noble element cobalt in the deposits is much less than that in the bath[14,15]. Considerable efforts have been made to determine the cause of the anomalous co-deposition of Zn-Co alloy coatings. The hydroxide suppression mechanism appears to be the most popular model for explaining the reason why anomalous co-deposition of Zn-Co alloy occurs [12,13,16]. In this model, anomalous co-deposition takes place due to
(Received: March 20,2006; Accepted: Apr.14,2007) FEI Jingyin(): Assoc.Prof.;Ph D;E-mail:jyfen@nwpu. edu.cn

the formation and adsorption of a zinc hydroxide film which inhibits cobalt electrodeposition while favors that of zinc[16]. Most results about the electrodeposition of Zn-Co alloy coatings showed that the maximum amount of cobalt was about 6-7 wt%[17,18]. Although an attempt has been made by Bahrololoom et al[19] using a two-compartment glass cell separated by a sintered ceramics membrane to achieve Zn-Co alloy coatings with high percentages (up to 70 wt%) of cobalt in ZnCo alloy deposits, the potential problem with this method is the large electrical resistance of the ceramic membrane, which will convert a large amount of power into heat and limit the plating current. The application of a pulse current (PC) instead of a direct current (DC) may be a possible approach to achieve a very wide range of alloy compositions and properties of deposits by simply varying the applied pulse parameters[20-22]. In the electroprocess using pulsed current (PC), at least three parameters, the peak current density, the on-time and the off-time, can be varied independently. If a pulse with reverse current was used, even more parameters could be used to modulate the composition and morphology of ZnCo alloy deposits. Whereas in the direct current (DC) electrodeposition, only the current density can be varied. In the present work, the PC electrodeposition of Zn-Co alloy from a sulfate bath was studied. The bath was free of additives such as levelers or brighteners. The range of average current density (I av) of pulse plating was chosen in the same range as the current density normally used to produce the DC deposits. The composition and morphology of the deposited alloys were analyzed as a function of the PC parameters.

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2 Experimental
The substrate for electroplating was mild steel panels (with a plated area of 4 cm4 cm). The pretreatment before plating included an initial soak in an alkaline cleaner (40 g/L sodium carbonate and 5g/L sodium hydroxide) at 60 for 5 min followed by rinsing in tap water, then degreasing by using cathodic cleaning in a solution containing 25 g/L sodium carbonate, 25 g/L sodium hydroxide and 50 g/L trisodium phosphate at ambient temperature. After rinsing in tap water, etching in 50v/v S.G. 1.18 HCl, followed by further rinsing in tap water, the panels were electroplated under the pre-determined conditions. The investigation on the effects of pulse plating parameters on the cobalt content in the Zn-Co alloy deposits was carried out by varying one parameter and keeping other parameters constant. All Zn-Co alloy coatings produced for examination had an overall thickness of 12 m. Electrodeposited Zn-Co alloy coatings were characterized by their surface appearance, composition and surface morphologies. The surface morphologies were evaluated using scanning electron microscopy (SEM), and an attendant energy dispersive X-ray analyzer (EDA) was used to analyze the composition of Zn-Co alloy deposits. Although there are some literatures available on the electrodeposition of Zn-Co alloy, very little attention has been given to the pulse plating of this alloy[20,21]. In the present work a computer-aided pulse plater unit (CAPP, Axel Akermenn A/S) was used for the electrodeposition of Zn-Co alloy deposits. The basic waveform used for the investigation of the effects of pulse parameters is shown in Fig.1. Symbols marked in the schematic diagram, Ip+, Ip- and Iav, stand for positive peak current density (Ip+), reverse peak current density (Ip-) and average current density (Iav), respectively. T is the cycle time. The plating time for every Zn-Co deposit was nT (the value of n depending on the deposit thickness). The range of average current densities (Iav) investigated in this work varied from 5 to 320 mA/cm2, and the value for reverse anodic peak current densities (Ip-) was chosen to be a fraction of the positive peak current density (Ip+), namely Ip-= xIp+ (x=0, 0.2, 0.4, 0.6 or 0.8). For a given average current density (Iav) and the value of fraction (x), the correlations among Iav, Ip+, Ipand x are as follows: Ip+=2Iav/(1-x) (1) Ip-=xIp+ (2) Given the values of Iav, x, and the thickness of deposit, a variety of pulse current patterns were created by inputting Ip+, Ip-, T and number of cycles (n), into a user-friendly program system. Generally, it is easier

to obtain a pulse power supply with a frequency of 50 Hz due to the lower cost of making a big output pulse power plater of this frequency. Therefore, the investigation on the effect of waveform parameters on the cobalt content in the Zn-Co alloy deposits was carried out at the frequency of 50 Hz. Afterwards, the investigation on the effect of frequency on the cobalt content in Zn-Co alloy deposit was undertaken in a frequency range of 1-500 Hz. Fig.1 illustrates a typical pulse current waveform pattern based on the basic condition of Iav=30 mA/cm2, x=0.4, T=20 mS and n=30 000.

3 Results and Discussion

Actually, Zn-Co alloy coatings can be obtained using baths consisting of various compositions and operating conditions. In this work, the bath used for the investigation of Zn-Co alloy pulse electrodeposition was mainly based on the formulation reported by Bahrololoom et al[19] because it is possible to get Zn-Co alloy coatings with a wide range of cobalt content in deposits. Before the electrodeposition of Zn-Co alloy using pulse plating technique, a set of sulfate-based baths was examined to select a suitable bath for further investigation. Referring to the results obtained by Bahrololoom[19], all the baths tested contained the same total main salt concentration of 0.7 M (namely, ZnSO4 7H2O+CoSO47H2O=0.7 M), while the variation range of cobalt sulfate concentration defined as the value of [Co 2+ /(Zn 2+ +Co 2+ )] in percentage was changed from bath to bath in the range of 0.1 M to 0.6 M. The concentrations of other chemicals, such as Na 2SO4 10H2O 80 g/L, (NH4)2SO4 50 g/L, H3BO3 20 g/L were kept constant. The electrodeposition of Zn-Co alloy was carried out at a current density of 50 mA/cm2, pH value of 2 and temperature range of 55-60 .

Table 1 illustrates the preliminary plan and the results of the effect of cobalt ion concentration in the baths on the cobalt content in the deposits. The results are also shown in Fig.2. As can be seen in this figure, the cobalt content in the depositsis is low and increases gradually, and the influence of the cobalt concentration variations in the bath is slight if the cobalt ion

Journal of Wuhan University of

Technology-Mater. Sci. Ed.

Sept 2007

419

concentration is less than 55 wt%. It is evident that the electrodeposition of Zn-Co alloy is an anomalous co-deposition according to Brenners definition [13]. However, the cobalt content in the deposits increases rapidly if cobalt ion concentration in the bath exceeds 60 wt%. Despite that the cobalt content in the deposits increases gradually with increasing the cobalt ion concentration in the bath, using a less concentrated bath is more economical for practical applications. Furthermore, deposits with an uniform and bright surface appearance could be obtained within the widest current density range by using the bath containing Co 2+ =0.5 M and Zn 2+ =0.2 M amongst the baths examined. Fig.3 illustrates the surface morphology of Zn-Co alloy deposit with a cobalt content of about 15 wt%. So further investigations on the effect of pulse plating variables were carried out in the following bath: ZnSO42H2O 60 g/L(0.2 M) CoSO42H2O 140 g/L(0.5 M) Na2SO410H2O 80 g/L (NH4)2SO4 50 g/L H3BO3 20 g/L pH 2 Temperature 55-60 A potential problem associated with using twocompartment cell proposed by Bahrololoom[19] is the large electrical resistance of the ceramic membrane, which will converts a large amount of power into heat and limits the plating current. This investigation on

pulse plating was carried out in a single cell using a platinised titanium mesh as an anode. However, no phenomenon as reported by Bahrololoom was observed during plating. Fig.4 shows the variation of the cobalt content in Zn-Co alloy deposits with the average current density (Iav). It is evident that all the curves illustrate a similar profile. The cobalt content in the deposits is more than 90 wt% if the average current density (Iav) is less than 10 mA/cm2. It decreases rapidly to 10-20 wt% at the average current density of 20 mA/cm2, then increases gradually with the further increase in average current density (Iav). The surface appearance of the deposits obtained at a low current density was uniform but dull, whilst the deposits electrodeposited at average current densities of higher than 20 mA/cm2 were uniform and bright. Fig.5 illustrates the surface morphologies of ZnCo alloy deposits with very different cobalt contents obtained by varying the average current density and reverse pulse component. Obviously, the Zn-Co alloy deposits were micro-crack free over this wide range of cobalt contents. It is obvious that the variation of the cobalt content in the deposits can also be obtained by modulating the reverse fraction (x) besides adjusting the average current density (Iav). The reverse current, amongst the operating parameters investigated, has the greatest effect on the cobalt content in Zn-Co alloy deposits. Fig.6 shows the variation of cobalt content

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with reverse fraction (x) at different current densities. Except for low current density (less than 10 mA/cm2), as shown by curves 1 and 2 in Fig.6, the reverse current density has a great effect on the cobalt content when the average current density is more than 20 mA/cm2. A significant variation of the cobalt content in the ZnCo alloy deposits was obtained by changing the reverse current (Ip-). For a given average current density (Iav), it is evident that higher cobalt contents correspond to higher reverse fraction (x) values. It is likely that the zinc component in the Zn-Co alloy deposit obtained during the cathodic part of the cycle dissolves selectively as the reverse current flows, resulting in an increase in the cobalt content of the deposit[23]. Fig.7 shows the images of Zn-Co alloy deposits obtained with the same average current density (Iav), but with and without the reverse current, respectively. The

deposits prepared without the reverse current present a big grain size and micro-cracks, as shown in Fig.7(a), whereas the deposits obtained using the reverse current show a relatively smooth surface and possess refined grains (Fig.7(b)). This suggests that the internal stress could perhaps be reduced and the grain refinement occured if the reverse current was used. The effect of the peak current density (Ip+ and I p- ) on the microstructural characteristics of the deposits was tested by adjusting the fraction (x) and keeping other parameters constant. As can be seen from Equation (1) and (2), an increase in the value of x results in increases both in Ip+ and Ip-. Images in Fig.8 show the effect of the peak current density on the deposit surface morphology. An increase in the peak current resulted in a considerable grain refinement. The reduction in the grain size may be due to two

Journal of Wuhan University of

Technology-Mater. Sci. Ed.

Sept 2007

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factors. Firstly, the higher over-potential resulting from a higher peak current density (Ip+) accompanied with an increase in nucleation rate. Secondly, the big grains dissolve more quickly when the reverse current flows through[23]. The effect of frequency on the cobalt content and the microstructural characteristics of Zn-Co alloy deposits was examined in the frequency range of 1500 Hz. Fig.9 shows the variation of the cobalt content in Zn-Co deposits with frequency. The cobalt content decreased very slowly with increasing frequency and then remained relatively constant at about 12 wt%-16 wt% in the frequency range tested. However, the images of Zn-Co alloy deposits were affected significantly by frequency. As shown in Fig.10, microcracks occurred at frequencies of lower than 5 Hz and no micro-cracks could be found at frequency of higher than 10 Hz, which means that the Zn-Co alloy deposits with a low internal stress were formed under these conditions.

[3] [4] [5]

[6] [7]

[8]

[9] [10]

4 Conclusions
a) The reverse current density plays an important role in modulating the cobalt content in the Zn-Co alloy deposits. The internal stress of Zn-Co alloy deposits could also be reduced to some extent by introducing a reverse current. b) Compared with the deposits prepared by Dc plating, crack-free Zn-Co alloy coatings with fine grain, compact crystal structures could be obtained by adjusting pulse plating parameters. c) Given an average current density (I av), the reverse fraction (x) has a considerable effect on the cobalt content, grain size and internal stress. Such phenomena may be attributed to the high nucleation rate accompanying with high over-potentials resulting from the high peak current densities and the dissolution of large grains during the reverse current cycle (since the values of peak current density both Ip+, and Ip- are proportional to the values of x). d) The frequency has a little effect on the cobalt content in Zn-Co alloy deposits, but changes the microstructure of the deposits. The fact that deposits with micro-cracks could be obtained at a low frequency (less than 5 Hz) suggests that a higher frequency should be employed (such as 50 Hz) in order to get deposits with a low internal stress.

[11] [12] [13] [14]

[15] [16] [17] [18]

[19]

[20] [21]

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