View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Tamkang University Institutional Repository Electrochimico Acta, Vol. 43, Nos 3-4, pp. 315-324, 1998 0 1997 Elsevier Science Ltd. All rights reserved. Pergamon Printed in &eat Britain PII: SOO13-4686(97)00072-8 0013-4686/98 519.00 + 0.00 Process aspects of the electrolytic codeposition of molybdenum disulfide with nickel Yu-Chi Chang,“” Ying-Yin Changb and Chun-I Linb BDepartment of Chemical Engineering, Tamkang University, Tamsui, Taipei Hsien, Taiwan 25137, R.O.C. bDepartment of Chemical Engineering, National Taiwan Institute of Technology, Taipei, Taiwan 106, R.O.C. (Received 7 October 1996; in revised form 2 January 1997) Abstract-Process characteristics of the electrolytic codeposition of molybdenum disulfide particles with nickel from a Watts bath have been analysed in this study using statistical experimental design. The results show that temperature and concentration of suspended particles significantly affect the weight percentage of molybdenum disulfide in the deposit. Particle concentration has a positive effect, while temperature exerts an adverse effect. Moreover, pH and temperature have been observed to be significant factors affecting the nickel deposition efficiency. Both factors exert positive effects. A second order model, relating the current efficiency to pH and temperature, has been developed. This model adequately approximates the performance measures. The physical model proposed by Guglielmi has been shown to be valid from the present system at low current densities. The results at high current densities, however, show different features. It has also been observed that the presence of particles affects the nickel reduction reaction in an unknown way. 0 1997 Elsevier Science Ltd Kept words: composite electrodeposition, Ni--MO&, Guglielmi’s model, response contours. INTRODUCTION electrolytic codeposition is not sufficient to predict the effects of variations in electrolysis conditions on Composite electrodeposition, consisting of inert solid the resulting codeposition. Further studies are particles embedded in metallic matrix, has been necessary to determine the influence of plating developed in recent years for various applications. variables on the resulting codepositions, so that the However, the insights into the mechanisms behind mechanisms behind codeposition may be understood the codeposition process have grown at a much more completely. slower pace than the applications of the composite Molybdenum disulfide is often dispersed in metal coatings. Theories pertaining to the mechanisms of matrices like copper and nickel to achieve enhanced capture and encapsulation of particles during metal strength of the final composite material for good deposition have only begun to be developed in the wear resistance [7]. Recently, it has been pointed last few years [l]. The models developed by Guglielmi out that molybdenum disulfide-coatings can be used [2], Celis et al. [3], and Fransaer et a/. [4] provide a as appropriate hydrogen evolution catalysts, pro- better theoretical insight into the codeposition vided there exists an easy way to prepare and process. Several excellent review papers concerning apply them [8]. Towards this end, Chang has re- electrolytic codeposition have been published in cently prepared the nickel-molybdenum disulfide recent years [S, 61. In-depth understanding of the composite by composite electrodeposition and has codeposition mechanism is very important, since it examined its electrocatalytic properties in alkaline can help to control the plating structure, and electrolytes [9]. consequently the plating properties. Unfortunately, The plating variables which are likely to be the present understanding of the mechanism of important towards controlling the degree of particle incorporation in the deposit include the metal to be *Author to whom correspondence should be addressed. plated, composition of the plating bath, pH of the 315 316 Yu-Chi Chang et al. bath, composition of the non-metallic phase, size and deserves mention that in all cases, bath pH decreased shape of the non-metallic particles, current density, (values ranged from 0.1 to 0.3) with the introduction current form and stirring efficiency [lo]. Ghouse et al. of MO& particles. Solution pH was adjusted with [l I] have studied the effects of pH (1.5 and 5.5) H2S04 prior to each deposition. The size of MoS2 current density (255100 mA/cm’) and particle con- particles was less than 2 microns. The electrolyte was centration (I-50 g/dm3) on the extent of incorpor- prepared from reagent grade chemicals and deionized ation of MO& in the Ni-MoS2 composites, prepared water. 50 cm3 solution was used for each experiment. by the conventional electrodeposition and sediment A copper disc of 0.9cm in diameter formed the codeposition techniques using the Watts type bath as working electrode, whereas platinum gauze formed electrolyte. The influence of current density (25- the anode. The disc electrode was embedded into a 100 mA/cm2) and particle concentration (l-50 g/ cylindrical Teflon base of 1.5 cm diameter. A hot dm3) on the percentage of the MO& particles plate with magnetic stirring facility was used for incorporated in the Cu-MO& system using copper heating and stirring the bath. sulfate bath as electrolyte have also been studied [7]. In order to prevent agglomeration of particles and The effects of pH, current density, particle concen- to obtain uniform dispersion of molybdenum tration and temperature on the effectiveness of disulfide in the bath, the required amount of MO& molybdenum disulfide incorporation in the nickel- powder was first thoroughly blended with a small molybdenum disulfide composite prepared by sedi- quantity of wetting agent sodium lauryl sulfate (in ment codeposition technique by using the fluoborate I M concentration, 0.4 cm3 SLS/g MO&) in the bath as the electrolyte have also been reported [12]. reactor, a small amount of electrolyte (8 cm3) was The extent to which the inert solid particles can be then added to make a slurry, and the remaining incorporated, however, depends on the nature of the electrolyte was finally added to the resulting slurry. system. For instance, increasing the current density The particles were kept suspended in the solution by has an adverse effect on the percentage of the a magnetic stirrer and electrocodeposition was molybdenum disulfide particles incorporated in the performed galvanostatically for the required period Ni-MoSl system [ Ii], whereas incorporation of the of time. The product of the current times the same particles increases up to a critical current electrolysis time gives the number of coulombs, which density in the Cu-MoS2 system [7]. Sautter [13] has was 56.55 C for each experiment. The theoretical reported that there is no effect of temperature on the thickness of the coating was 31 microns for the codeposition of Al203 with nickel from a Watts type corresponding reaction of nickel deposition with bath, whereas Bapu [12] has reported that tempera- 100% current efficiency. The actual thickness of the ture severely affects the incorporation of MO& in the electrodeposited composites varied with electrolytic Ni-MoS2 system. Therefore, it is important properly conditions. to characterize the basic plating parameters that A survey of relevant literature reveals that process affect the incorporation of solid particles into the variables (factors) that are likely to be important in deposit, for specific systems. affecting the composition of the deposit and current The process characteristics of electrocodeposition efficiency are: particle concentration, current density, of molybdenum disulfide particles and nickel metal pH, temperature and hydrodynamic conditions. An are far from being well understood. The present approach for studying the effects of these parameters investigation therefore aims systematically to study by one-factor-at-a-time experimentation is certainly the effects of various plating bath variables on the ineffective. Since the number of parameters involved amount of molybdenum disulfide codeposited with is large, a fractional factorial design is an effective nickel from the Watts bath and the current efficiency way to identify the influential factors in a systematic of the electrolytic process. Further, the relative fashion [14]. Moreover, in some chemically reacting importance of these variables has been judged from systems the difference in response (the performance the present experimental findings by carrying out the measure) between particular levels of one factor is not statistical analysis. The applicability of Guglielmi’s the same at all levels of the other factors, indicating model to the nickel-molybdenum disulfide composite a significant interaction between various factors. electrodeposition system has also been studied. Such significant interaction might even sometimes mask the significance of main effects. A factorial EXPERIMENTAL design, in this regard, is necessary when such interactions are present, in order to avoid misleading The nickel-molybdenum disulfide composite coat- conclusions. ings were prepared on copper substrate by the Table 1 shows the 27-run 3” design used in the rotating disc electrode technique with external present investigation, the columns indicating the auxiliary stirring, using a Watts type bath as the actual effects that they estimate. The last two columns electrolyte. The basic bath composition was: show the experimentally