J. Mater. Sci. Technol., 2010, 26(1), 82-86.

Eect of Electroplating Parameters on Microstructure of Nanocrystalline Nickel Coatings

A.M. Rashidi1,2) and A. Amadeh2)
1) Faculty of Engineering, Razi University, P.O. Box 67149-67346, Kermanshah, Iran 2) School of Metallurgy & Materials Engineering, University College of Engineering, University of Tehran, Tehran, Iran
[Manuscript received October 16, 2008, in revised form August 6, 2009]

In order to achieve the optimum conditions for electroplating nanocrystalline nickel coating from Watts-type bath, the eect of some process parameters namely, bath temperature, current density, and saccharin addition on grain size and texture coecient (TC= I(200) /I(111) ) of the deposits were investigated by X-ray diraction (XRD). The results showed that in a bath containing 5 g/L saccharin, by increasing the bath temperature from 45 C to 55 C, the grain size decreased, whereas further increase of bath temperature resulted in a contrary eect. By increasing the current density from 10 to 75 mA/cm2 , both the grain size and TC decreased, while further increase in current density had no signicant eect on the grain size. At a given current density, the grain size and TC decreased rapidly by increasing the saccharin content before leveling o at 3 g/L of saccharin. Finally, based on the grain rening the optimum conditions for producing nanocrystalline nickel coating from Watts-type bath have been proposed. KEY WORDS: Electroplating; Grain size; Nanocrystalline; Coating

1. Introduction Recently, the development, production and characterization of nanocrystalline (NC) materials, with the grain size typically smaller than 100 nm, have been the subject of intensive researches both in scientic and industrial communities[1] . Among the various manufacturing methods, electroplating has received considerable attention as a feasible, inexpensive and economically viable processing technique which has been used in the synthesis of bulk NC metals for over twelve years[2] . However, it has been demonstrated[3,4] that under certain conditions, only electrodeposition can produce NC nickel coatings. Although there are numerous studies focused on synthesis of NC nickel deposits[311] , but determination of optimum conditions for production NC nickel coating from the reported results is dicult because they
Corresponding author. Prof.; Tel.:+98 831 4274535, Fax: +98 831 4274542; E-mail address: rashidi673@yahoo.com (A.M. Rashidi).

are, in some cases, inconsistent or dierent. For instance, Dai et al.[8] found that the grain size of nickel deposits decreased from 50 nm to about 20 nm by increasing the current density from 50 mA/cm2 to 100 mA/cm2 while the eect of current density higher than 100 mA/cm2 was negligible. Unlike these results, a continuous increasing in grain size vs current density has also been recognized in direct current electrodeposition of nickel coating[47] . On the other hand, Aruna et al.[10] reported that the current density had no signicant eect on grain size of nickel electrodeposits. The eect of saccharin concentration in the electroplating bath on grain size of Ni deposits is another example. The overall behavior observed by dierent researchers[8,9,11] is similar but the saccharin contents corresponding to leveling o in grain size reduction are dierent. Moreover, little information deals with the eect of bath temperature on grain size of nickel deposits, whereas in some cases, a deviation more than 5 C from optimum temperature is sucient to harm the coating quality, deposition rate,

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Table 1 Electroplating conditions of Ni coatings Parameter Series I Series II Series III i/(mA/cm2 ) 10-20-30-50-75-100-150-200 100 100 Cs /(g/l) 5 1-2-3-5-7.5-10 5 T em/( C) 55 55 45-50-55-60-65 i: Current density, Cs : Saccharin content, T em: Bath temperature

and other properties[12] . Therefore, more studies in this eld can be useful to manufacturing of components and devices coated with NC nickel. The aim of our present work is to provide a consistent set of experimental data within a large range of process parameters for synthesis of NC nickel coatings. Results on the optimization and synthesis conditions of NC nickel deposits from Watts-type bath are presented. 2. Experimental Nickel coating was prepared by using a Watts-type bath containing 300 g/L nickel sulfate (Ni2 SO4 6H2 O), 30 g/L nickel chloride (NiCl2 6H2 O), and 30 g/L boric acid (H3 BO3 ). A nickel sheet of 99.99% purity with dimensions of 100 mm50 mm5 mm was used as anode and pure annealed copper plate with dimensions of 20 mm15 mm2 mm as cathode (substrate) materials. Prior to deposition, the copper substrates were mechanically polished with silicon carbide papers of 400, 600, 800, 1200 grits and alumina suspensions of 8, 1 and 0.25 m, then rinsed with distilled water and activated in 10% H2 SO4 solution at room temperature for 30 s. The deposition time was adjusted to achieve an average thickness of 100 m based on the Faraday s law. During the electroplating process, it was found that the pH of the solution play an important role on quality of the deposits and the pH range of 3.5 to 4.5 resulted in the deposits with bright appearances and free of voids and cracks. Hence, the pH of the bath was kept to 4.00.2. Other electroplating conditions have been summarized in Table 1. The structure of the deposits was studied by X-ray diraction (XRD), and scanning electron microscopy (SEM). The grain size of NC nickel coatings was calculated from full width at half maximum (FWHM) intensity of XRD prole using modied WilliamsonHall relation[13,14] . An annealed nickel sample with an average grain size of 30 m was also used for correction of instrumental peak broadening. The preferred orientations were investigated by calculating the texture coecient (TC) using the following relation: I(200) (1) TC = I111) where I(200) and I(111) are the peak intensities of scattered X-ray radiation from (200) and (111) crystallographic planes of the deposits, respectively.

Fig. 1 SEM micrographs of surface morphology of nickel coatings deposited from: (a) a saccharin-free bath at i=100 mA/cm2 , (b) a bath containing 5 g/L saccharin at i=100 mA/cm2 , (c) a bath containing 5 g/L saccharin at i=300 mA/cm2

3. Results and Discussion The typical SEM micrographs of surface morphology of electrodeposited nickel have been presented in Fig. 1. It can be seen that at the current densities higher than 75 mA/cm2 , in the absence of saccharin the nickel layer exhibits a pyramidal-like morphology (Fig. 1(a)) while it changes to a colony-like morphology in presence of saccharin. An increase in current

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Fig. 2 Variation of grain size of nickel deposits with: (a) bath temperature, (b) current density, (c) saccharin content

density results in larger colonies and brighter appearance. Panek et al.[15,16] , Weil and Cook[17] , El-Sherik and Erb[3] reported the formation of colony-like morphology similar to that observed in Figs. 1(b) and 1(c). El-Sherik and Erb[3] and Nakamura et al.[18] also observed similar morphological transition in nickel electrodeposited from a Watts bath in presence of saccharin. This may be ascribed to the inhibition eect of organic additives on nickel ion reduction[1820] . The variations of the grain size of nickel coatings as a function of bath temperature (T ), current density (i), and saccharin concentration (Cs ) have been presented in Fig. 2. The grain size of deposits decreases as the plating temperature increased up to 55 C and then increases by further increasing bath temperature. As seen in Fig. 2(a), nanostructured nickel deposits with a mean grain size from 24 nm to 32 nm is obtained at all the investigated temperatures. It is also evident that the bath temperature has a minor eect on the grain size of the coatings compared with current density (Fig. 2(b)) and saccharin addition (Fig. 2(c)).

According to the pattern presented by Dini[21,22] , it is generally expected that the grain size of the deposits increases by increasing the bath temperature. Such behavior has been experimentally observed for other nanocrystalline deposits[2,23] . The present results (Fig. 2(a)) for plating temperatures above 55 C are consistent with above-mentioned idea but at the temperatures lower than 55 C an unexpected behavior is observed, that is an increase in bath temperature leading to grain rening of nickel deposits. It is well known that the energy of grain nucleus formation depends on the cathodic overpotential[24,25] . A large cathodic overpotential reduces the energy of nucleus formation, and therefore increases the nucleus densities (the number of nucleus per surface area) and renes the grains of the coating. Consequently, since the cathodic overpotential decreases with increasing the bath temperature[2,21] , it is expected that the grain size of the deposits increases. Nevertheless, it should be noted that increasing the bath temperature has two contradictory eects; (i) an increase in critical size of nucleus due to a decrease in thermodynamic driving force of crystallization process which leads to lower nucleus densities, and (ii) an increase in kinetic driving force that can lead to higher nucleation rate[26,27] . At the bath temperatures in which the size of critical clusters is in atomic dimension, every active site can act as a critical nucleus. So, the thermodynamic barriers for nucleus formation are negligible and the grain size of deposit is controlled by kinetics variables. In such conditions, according to Arrhenius equation, the nucleation rate increases by increasing the bath temperature[27] leading to ner grain in our present work. According to Fig. 2(b), the grain size decreases by increasing the current density up to 75 mA/cm2 , whereas further increase in current density has no signicant eect on grain rening. This behavior is consistent with the data presented by Dai, et al.[8] . In general, according to the pattern presented by Dini[21,22] , it is expected that the grain size of the deposits decreases by increasing the current density, because an increase in the current density results in a higher overpotential that increases the nucleation rate. However, several researchers[47,28] have reported an increase of grain size of nickel deposits with increasing the current density and attributed it to a decrease in the concentration of Ni ions[38] and/or the co-deposition of hydrogen[6] at cathode-electrolyte interface. As it has been mentioned above, the grain size of nickel deposits does not change at the current density beyond 75 mA/cm2 , which can be attributed to co-deposition of hydrogen at cathode surface. The codeposition of hydrogen changes the surface energy[29] and the growth mechanism[6] and also the distribution of applied currents between the reduction of Ni2+ and H+ ions[30] . In the latter case, despite an increase

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in applied current density, the pure current density available for nickel deposition does not increase considerably. Figure 2(c) shows that at a given current density, initially the grain size decreased rapidly by increasing the saccharin content before leveling o at 3 g/L of saccharin. By addition of 3 g/L or more of saccharin additive a reduction of the crystallite size by a factor more than 16 is observed. Similar eect has been reported by El-Sherik and Erb[3] , Dai et al.[8] and Xuetao, et al.[11] . This phenomenon can be related to the combined eects of retarding the surface diusion, blocking the crystalline growth[3133] , hydrogen evolution and/or absorption[34,35] , and the change in overpotential[18,35] . Figure 2(c) also indicates that the saccharin concentration corresponding to the initiation of curve plateau is about 3 g/L. This value conrms the values reported by Dai et al.[8] and Xuetao et al.[11] . As seen in Fig. 2(c), beyond 3 g/L of saccharin, the grain size of the coating is approximately independent of saccharin concentration. This phenomenon can be attributed to the leveling o in the overpotential[36] and/or saturation of adsorption sites on the cathode surface[37] with increasing the saccharin amount in the bath. Based on the grain size, the optimum conditions for producing nanocrystalline nickel coating by direct current electroplating from Watts-type bath at pH4, could be proposed as: current density 75 100 mA/cm2 , saccharin concentration 3 g/L and plating temperature 55 C. The XRD pattern of nickel coating produced under optimum conditions has been presented in Fig. 3. For comparison, the XRD pattern of reference sample (annealed nickel) has also been shown in Fig. 3. It can be observed that the crystal structure of the coating is pure fcc nickel and no characteristic peaks of other phases have been recorded. The peak broadening of electrodeposited coatings with respect to reference sample is also evident in this gure indicating the grain rening into nano-scale size. The eects of plating parameters on the preferred orientation of the coatings have been presented in Fig. 4. The preferred texture of the coating deposited at the current density of 10 mA/cm2 is (200) texture, while at other current densities, the random texture is observed. Also by increasing the saccharin content in the electrolyte, the texture of the coating changes from a (200) preferred orientation to random texture. Similar observations have been reported by other researchers[3,8,11,18] . Figure 4(a) shows that increasing the bath temperature from 45 C to 55 C, results in an increase in TC (I(200) /I(111) ), whereas further increase in bath temperature has an opposite eect. Comparing Figs. 2 with 4 reveals that when initially increasing current density and saccharin content, both the grain size and TC decrease, whilst fur-

Fig. 3 XRD patterns of nickel (a) electrodeposited under optimum conditions, (b) annealed at 700 C for 24 h

Fig. 4 Variation of crystallographic texture of nickel deposits with: (a) bath temperature, (b) current density, (c) saccharin content

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ther enhancement of bath temperature is accompanied by grain growth and an increase of TC. This indicates that the mechanism of grain size control in latter case is dierent from the former ones. These results imply that perhaps the mechanism of electrocrystallization of nickel changes when the bath temperature decreases down to 55 C. However, more electrochemical experiments are still needed to reveal the exact dependence of grain size of the deposits on bath temperature and details of the mechanisms which leads to unusual results. 4. Conclusions (1) The grain size of the coatings decreased as the plating temperature increased up to 55 C and then increased by further increasing bath temperature. (2) An increase in current density up to 75 mA/cm2 as well as addition of saccharin up to 3 g/L resulted in a decrease in the average grain size and TC of nickel coatings. (3) Based on the rening of grain size, the optimum conditions for producing nanocrystalline nickel coating could be proposed as: current density 75 100 mA/cm2 , saccharin concentration 3 g/L and plating temperature 55 C.

Acknowledgements This work was supported by University of Tehran and Razi University. The authors thank them for nancial support of this work. We would also thank Dr. S.F. KashaniBozorg for his fruitful helps. REFERENCES [1 ] S.C. Tjong and H. Chen: Mater. Sci. Eng, 2004, R45, 1. [2 ] H. Natter and R. Hempelmann: Z. Phys. Chem., 2008, 222, 319. [3 ] A. M.El-Sherik and U. Erb: J. Mater. Sci., 1995, 30, 5743. [4 ] I. Bakonyi, E. Tth-Kdr, L. Pogny, A. Czirki, o a a a a I.Gercs, K. Varga-Josepovits, B. Arnold and K. o Wetig: Surf. Coat. Technol., 1996, 78, 124. [5 ] I. Bakonyi, E. Tth-Kdr, T. Tarnczi, L.K. Varga, o a a o A. Czirki, I. Gercs and B. Fogarassy: Nanostruct. a o Mater., 1993, 3, 155. [6 ] F. Ebrahimi and Z. Ahmed: J. Appl. Electrochem., 2003, 33, 733. [7 ] K.L. Morgan, Z. Ahmed and F. Ebrahimi: MRS Proc., 2001, 634, B3.11.1. [8 ] P.Q. Dai, Hui Yu and Q. Li: Trans. Mater. Heat Treatment, 2004, 25, 1283. (in Chinese)

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