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Advanced Materials Research Vol. 845 (2014) pp 378-381 (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.845.

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Composition Modification of Electroplated Nickel Interlayer on Tungsten Carbide Substrate by Thermal Carburizing H.A. Wahab1,a, M.Y. Noordin1,b, S. Izman1,c, Z. Kamdi2, D. Kurniawan1,d
2 1

Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, Skudai, Malaysia Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, Parit Raja, Malaysia
a

zsgthassan@yahoo.com, noordin@fkm.utm.my, izman@fkm.utm.my, denni@utm.my

Keywords: Nickel layer; Carburizing; WC-Co; Electroplated nickel; Nickel carbides

Abstract. Nickel enables nucleation and growth of well oriented diamond crystals from the small lattice mismatch between nickel and diamond. However, its solubility for carbon causes carbon loss during diamond deposition and, consequently, results in poor nucleation density. In this study, carburizing of Ni/WC-Co specimens in high temperature furnace with inert gas atmosphere was adopted to provide nickel with sufficient carbon prior to diamond deposition. This process was carried out using charcoal powder as source of carbon at different treatment temperatures (750oC and 850oC) and durations (20min and 60min). Effect of the process in altering the nickel layer composition was characterized by microscopy, element analysis, and phase identification techniques. Results show that carburization leads to formation of metallic phases, such as nickel carbide and nickel cobalt, which are considered beneficial for diamond nucleation and growth. Introduction Nickel is categorized as one of few materials that have small lattice mismatch with diamond. The lattice constants for nickel and diamond are 3.52 and 3.56 , respectively [1]. This enables a hetero-epitaxial diamond growth on nickel substrates. With this growth type, interfacial stresses between the two materials upon coaling down from deposition temperature can be relieved which prevents coating cracks and delamination [2]. Although diamond can grow on nickel, but the high solubility of nickel for carbon during diamond deposition could delay diamond growth and results in poor nucleation density [3]. Previous works conducted on nickel attempt to overcome this issue by changing the nickel layer surface in order reduce its solubility for carbon [4,5]. An attempt was done by modifying the nickel surface through formation of a thin Ni-C-H layer which is believed to improve diamond nucleation and growth [3]. This process is called annealing stage and done inside a chemical vapor deposition machine prior to diamond deposition. Another work found that carbon loss which was absorbed by nickel in the process of diamond deposition can be compensated if annealing time and methane concentration can be set at proper values [6]. It was suggested that this annealing stage could improve diamond nucleation and growth on nickel. However, for the case of nickel layer on hard metal, still there is lack of information regarding the effect of this treatment on Ni/WC-Co characteristics. In this paper a different approach was adopted by the authors in order to provide nickel with sufficient carbon before diamond deposition and to study changes on the Ni/WC-Co system. This involves carburizing the Ni/WC-Co in high temperature furnace under inert gas atmosphere using dry charcoal powder as a source for carbon. Experimental Method Electroplated nickel on tungsten carbide (Ni/WC-Co) samples were carburized in a high temperature tube furnace (Elite TSH16/50/180) under atmosphere of Argon gas. The Watts electroplating setup and condition used to coat the nickel on the WC-Co was described previously elsewhere [7]. The samples were placed on a boat-like crucible and were totally covered by dry charcoal powder (at drying temperature of 40oC for 20min) having an average grain size of < 63m.
All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP, www.ttp.net. (ID: 161.139.102.15, Universiti Teknologi Malaysia, Skudai, Malaysia-24/11/13,11:45:42)

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Then the samples were positioned inside a 48mm diameter ceramic tube of the high temperature furnace. At each run, a 99.9% purity Argon gas was allowed to flow inside the tube at a rate of 55ml/min. The gas flow starts 2h before each run and continues at the same flow rate till the sample cools down inside the furnace to the room temperature. A systemized heating/coaling rate of 5oC/min was used for all runs. In this treatment process, two temperatures (750oC and 850oC) were used as carburizing temperatures for 20min and 60min durations. Each high and low temperature formed two combinations with shorter and longer time. After completion of the carburizing process, the samples were examined by scanning electron microscope, energy dispersive x-ray spectroscope (EDS), and x-ray diffraction. X-ray diffraction was performed using Ni-filtered CuK radiations at diffraction angle of 2 (10o-90o) with a step of 0.05o. Results and Discussions Morphology. The nickel coating on WC-Co substrates were obtained by electro-deposition. Fig. 1 shows examples of the cross-section of the nickel coatings after carburizing at low and high temperatures for 60 min duration. It can be seen that at both temperatures a continuous, gap free joint at the coating/substrate interface was formed. This suggests that not only carbon has diffused into the nickel layer but also other elements could have been moved from the substrate to the nickel layer by diffusion. The trend was the same for all carburizing conditions of this experiment. However, at low temperature or short treatment duration, the amount of elements migrating towards the nickel layer was less.

a b Fig.1 Cross-section of Ni/WC-Co carburized for 60min at (a) 850oC and (b) 750oC Elements Analysis. Table 1 shows the detected elements within the nickel layer for the samples carburized at high and low temperature (i.e., 850oC and 750oC) for 60 min. The measurements were performed at two different positions on each sample, near the nickel surface and near the Ni/WC-Co interface. Under different conditions, it seems that carbon moved from the charcoal powder towards the nickel layer by thermal diffusion. The amount of carbon traveled into nickel was affected by the treatment temperature and duration. The highest surface carbon was measured on the sample treated at 850oC for 60min. This diffusion did not only occur for carbon but also some elements such as W, V, and Co that moved from the substrate into the nickel layer. Table 1. Weight of elements detected near the surface of carburized nickel layer. Carburizing Condition 850oC, 60min 750oC, 60min Ni (%) 2.50 53.56 C (%) 81.14 21.68 Co (%) 23.05 W (%) O (%) 16.36 1.71

When the carburizing duration was reduced to 20min for the above mentioned temperatures, the same phenomenon occured, although the weight of diffused elements into the nickel layer was reduced (Table 2).

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Table 2. Weight of elements detected near the surface of carburized nickel layer for different setting. Carburizing Condition 850oC, 20min 750oC, 20min Ni (%) 12.46 52.09 C (%) 35 13.8 Co (%) 13.86 25.52 W (%) 19.95 5.44 V (%) 9.20 O (%)

Interestingly, at 850oC and 20min treatment, a new element (vanaduim) was found within the nickel layer. Murarka et. al [8] studied the diffusion of vanadium in nickel at temperature range of 800oC to 1300oC. They found that vanadium could diffuse in nickel at temperature of 800oC but at very low diffusion coffiecient. Accordingly, it was expected to trace vanadium with the nickel layer at 850oC for both durations of 20min and 60 min, however, this element was found only in nickel layer treated at the former setting. This could be due to the less amount of other elements (W and Co) diffused from the substrate into nickel, and thus allowed the simultanous diffusion of vanadium. It could be observed that high diffusion of carbon in nickel layer limits the amount of cobalt coming towards the nickel coating. This could be due to each elements diffusion mode in nickel. Carbon atoms are smaller in size compared to W and Co and therefore diffuse through the nickel lattice by interstitial mechanism [9]. Interstital difussion is more rapid and can occur in shorter time than the vacancy mode which is the diffusion mode of both cobalt and tungsten. The high flux of carbon atoms arriving at the nickel layer could play a role in limiting cobalt atoms movement within the nickel lattice, and thus reduced this elements diffused amount. This is considered beneficial for diamond deposition on the carburized nickel layer since no cobalt can diffuse during diamond deposition which could lower the diamond films quality. In addition, diffused carbon into the nickel layer can compensate for carbon loss during diamond deposition and enhances diamond nucleation on this material. Phases Identification. From Fig. 5, it is evident that the diffused carbon reacted with nickel and formed different nickel carbides, i.e. face centered cubic NiC and hexagonal NiCx. The result is consistent for all conditions. However, the intensity of NiCx phase was higher in the case of low carburizing condition (750oC, 20min) and no peak was found for NiC phase (Fig. 5b). This could be due to high energy required to undergo formation of rich carbon NiC phase [10,11]. Therefore, the sharp peak at 2 of 44.618o in Fig.5b corresponds to face centered cubic (FCC) nickel with (111) crystal orientation and 3.554 lattice constant. While the strong reflection at 2 of 44.39o of Fig. 5a corresponds to FCC nickel carbide NiC having (111) crystal orientation and 3.539 lattice constant. No diffraction peak was identified for nickel tungsten. However, some traces of Co3Ni7 were found to overlap with NiC peaks for the sample carburized at 850oC for 60min. This suggests that nickel cobalt phase could be formed in small amount as the x-ray diffraction usually comes from the richest phase within the sample. Although W diffused into nickel, formation of nickel tungsten compound was not expected within the range of carburizing conditions. This is because although Ni has very low solubility in W, the latter can move freely through nickel atoms [12].

a b Fig. 5. X-ray diffraction for the carburized nickel at (a) 850oC, 60min and (b) 750oC, 20min.

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Conclusions The carburizing process carried out in this work enabled carbon diffusion into the nickel layer. It appeared that carbon reacted with nickel and formed different nickel carbides for all treatment conditions. The cross-section images showed a rigid and crack free carburized nickel layer with improved interface. When high carburizing condition (850oC, 60min) was set, the amount of nickel carbide and tungsten was higher. Although the weight of cobalt diffused into the nickel was limited by the rich carbon in nickel, this condition could promote formation of cobalt nickel alloy. Finally, the metallurgical changes made by this process are expected to enhance nickels tribological characteristics, to reduce its solubility for carbon, and to improve diamond nucleation. Acknowledgements Financial supports from the Ministry of Higher Education, Malaysia and Universiti Teknologi Malaysia through Fundamental Research Grant Scheme (No. 78572) and University Research Grant (No. 05H27) are gratefully acknowledged. HAW acknowledges scholarship from the Ministry of Higher Education, and Scientific Research, Sudan. References [1] Z. Sitar, W. Liu, P.C. Yang, C.A. Wolden, R. Schlesser, J.T. Prater, Hetero-epitaxial nucleation of diamond on nickel, Diamond and Related Materials. 7 (1998) 276-282 [2] P. C. Yang, R. Schlesser, C. A. Wolden, W. Liu, R. F. Davis, and Z. Sita, Control of diamond hetero-epitaxy on nickel by optical reflectance, Appl. Phys. Lett. 70 (1997) (22). [3] P.C. Yang, W. Liu, R. Schlesser, C.A. Wolden, R.F. Davis, J.T. Prater, Z. Sitar, Surface melting in the hetero-epitaxial nucleation of diamond on Ni, Journal of Crystal Growth .187 (1998) 81-88. [4] S. Rey, J. Hommet, G. Schmerber, F. Le Normand, Diamond growth on polycrystalline nickel silicides, Journal of Crystal Growth. 216 (2000) 225-234 [5] Y. HayashiU, N. Shiraokawa, S. Nishino, Effect of bias-enhancement in diamond nucleation and growth on nickel, Thin Solid Films .374 (2000) 268-273 [6]Y.J. Fei, Xuejin wang, Xue wang, Yanyun Xiong, Kean Feng, effect of additional methane during the annealing process on diamond nucleation on polished polycrystalline nickel substrate, Applied surface science 183(2001) 173-181. [7] Hassan A. Wahab, M.Y. Noordin, S. Izman, and Denni Kurniawan, Quantitative analysis of electroplated nickel coating on hard metal, The Scientific World Journal. 631936 (2013). [8] S.P. Murarka , M.S. Anand , R.P. Agarwala, Diffusion of vanadium in aluminium and nickel, Acta Metallurgica. 16 (1968) 6972 [9] William D. Callister, Jr., Material Science and Engineering an introduction. Sixth ed., John Wiley and sons, Inc, 2003. [10] Josh S Gibson, Jamal Uddin, Thomas R Cundari, Nelli K Bodiford and Angela K Wilson, First-principle study of structure and stability of nickel carbides, J. Phys.: Condens. Matter. 22 (2010) 445503 (7pp). [11] Hartsell M L, Piano L S. Growth of diamond films on copper, Journal of Materials Research. 9 (1994) 921926. [12] G. H. Gessinger, H. F. Fischmeister, A modified model for the sintering of tungsten with nickel additions, Journul ofthe Less-Common Metuls. 27 (1972).