Hydrometallurgy 62 2001. 110 www.elsevier.

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Effect of chromium VI/ on electrocrystallisation of cobalt from sulphate solution

N. Pradhan a , U.N. Dash b,) , S.C. Das a
a

Regional Research Laboratory, Council of Scientific and Industrial Research, Bhubaneswar, Orissa 751013, India b Department of Chemistry, Utkal Uniersity, Vaniihar, Bhubaneswar, Orissa 751004, India Received 24 November 2000; accepted 4 April 2001

Abstract The effect of chromiumVI. on current efficiency, deposit quality, polarisation behaviour, crystallographic orientations and surface morphology during the electrocrystallisation of cobalt from sulphate solution has been studied as a function of pH, chromium concentration, temperature and cobalt ion concentration. The behaviour of chromium is found to be very sensitive to the pH of the solution. Addition of CrVI. to cobalt electrolyte results in a decrease in current efficiency and this effect is greater at higher pH. The deposit quality is severely affected at higher pH and cobalt deposition stops when CrVI. concentration exceeds 25 mgrL. At lower pH 1.5., it is possible to achieve cobalt deposits in the presence of CrVI. concentration as high as 100 mgrL. The current efficiency decreases at higher current density and with increasing temperature. The presence of chromium also affects the crystal orientations, surface morphology and polarisation behaviour of the cobalt deposition process. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: ChromiumVI.; Cobalt; Polarisation

1. Introduction The electrocrystallisation of cobalt from acid sulphate electrolytes is very sensitive to the presence of foreign ions in the electrolyte. The cobalt electrolyte generated from different cobalt-containing sources is usually contaminated with a number of cations and anions. The cations are known to affect the current efficiency, deposit morphology and product purity. Cobalt is associated with nickel laterite and secondaries such as super-alloy scrap, cobalt granules, stellites, cobalt sludge, etc. During production of

) Corresponding author. Tel.: q 91-674-581-750; fax: q 91-674581-750. E-mail address: Director@csrrlbhu.ren.nic.in U.N. Dash..

cobalt electrolyte, though chromium is separated along with iron, the purified electrolyte is always contaminated with chromium. It has been reported Sherwood et al., 1979. that chromiumVI. is present as a major interfering impurity in the solution generated by sulphuric acid leaching of nickeliferrous laterite. Accumulation of chromium in the nickel electrolyte decreases the adhesive property of nickel plating on to copper substrate due to passivation Kimburg and Nikulina, 1983.. The presence of chromium is also reported to affect electrowinning of other metals, for example zinc. In the presence of high concentration of chromium wCrVI. ) 1 grL. in the electrolyte, the current efficiency for zinc deposition decreases Lin and Tsai, 1994. Though some information on the effect of chromium during the electrowinning of metals such as Ni and zinc is

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N. Pradhan et al.r Hydrometallurgy 62 (2001) 110

available, data on its effect during cobalt electrowinning are lacking in the literature. The present study, therefore, aims at determining the effect of chromiumVI. on current efficiency, deposit morphology, crystal orientations and polarisation behaviour during cobalt electrocrystallisation.

for determining the crystallographic orientations. The surface morphology of the deposit was examined by SEM. Deposit composition was determined by dissolving it in HNO 3 and analysing the solution by Atomic Absorption Spectophotometry. 2.4. Linear sweep oltammetry

2. Experimental 2.1. Apparatus and materials A 500-mL beaker fitted with a porous refractory diaphragm was used as the electrolytic cell. The electrolysis was carried out using one stainless steel cathode and one PbSb Sb 7%. anode. Both had the same dimensions, i.e. length and width, and kept face to face 2.5 cm apart. The effective cathode area was 15 cm2 and the rest was covered with Araldite glue Ciba Geigy.. All the experiments were carried out without stirring the solution. The electrolyte was prepared from reagent grade cobalt sulphate crystals CoSO4 P 7H 2 O, Merck. and distilled water. The sulphuric acid used for adjusting the pH was also of analytical reagent grade Merck.. In order to study the effect of chromium, H 2 CrO4 was used. 2.2. Electrolysis The volume of the solution taken for each experiment was 200 mL. The electrolyte contained 60 grL cobalt. Its pH was adjusted to the required value by adding sulphuric acid. Addition of chromium was made as aliquots from its stock solution. All the electrowinning experiments unless otherwise stated were conducted for 2 h at a current density of 200 Arm2 and 40 " 0.1 C. After electrolysis, the cathode was removed from the cell, thoroughly washed with water and then acetone and finally dried at room temperature. The cathodic current efficiency was calculated from the cathode weight. 2.3. Deposit examination Photographs of the deposit surface were taken with an optical microscope to examine their quality and appearance. X-ray diffractometry was carried out

Linear sweep voltammetry was carried out at 25 C to determine the polarisation characteristics of cobalt deposition in the presence of chromium. A platinum foil was used as the anode and a saturated calomel electrode as the reference electrode. A freshly cobalt-coated platinum disc of area 0.1257 cm2 was used as cathode. The platinum rotating disk electrode was plated with cobalt from a sulphate bath containing 60 grL cobalt by passing 2.5 mA current for 5 min. After removal from the cell, the electrode was washed thoroughly with distilled water and acetone. The freshly prepared electrode was then transferred into the cell containing desired cobalt electrolyte. A PAR Princeton Applied Research. 175 Universal programmer was used to drive a PAR 173 potentiostat. The cathodic potentials were swept from y0.6 to y1.4 V vs. SCE at a sweep rate of 50 mVrs and at 4000 rotation miny1 . The potentiodynamic curves were recorded using an XY recorder. The reproducibility of the results was confirmed by duplicate experiments. 3. Results and discussion 3.1. Effect of chromium(VI) concentration The effect of chromiumVI. concentration on cobalt deposition at three different pHs in the concentration range 0200 mgrL was investigated. The current efficiency is found to decrease in the presence of chromium at all the pH studied. The effect of chromium in reducing the current efficiency is much more pronounced at higher pH ; 2.5.. At this pH, it is observed that the current efficiency decreases sharply by 25% when chromium concentration in the solution is increased to 25 mgrL. An increase in chromiumVI. concentration beyond this concentration results in drastic fall in the current efficiency 15% at 50 mgrL CrVI. and further reduces with increase in CrVI. concentration. and no cobalt sheet

N. Pradhan et al.r Hydrometallurgy 62 (2001) 110

Fig. 1. Effect of chromiumVI. concentration on current efficiency of cobalt deposition at different pH.

deposition is observed formation of a few cobalt granules at the edges.. When the bath pH is decreased, the plot of current efficiency vs. chromiumVI. concentration shows different behaviour Fig. 1.. The rate of fall in current efficiency on addition of chromium to the bath pH 2.0. up to 25 mgrL is relatively less than that at pH 2.5. With addition of 25 mgrL of chromium, the fall in the current efficiency is 17% compared to 25% at pH 2.5. In addition, cobalt deposits up to a chromium concentration of 100 mgrL, although fall in current efficiency is relatively higher beyond 25 mgrL of CrVI.. However, above CrVI. concentration of 100 mgrL, there was no deposition of cobalt as sheet but blackened cobalt granule formation at the edges of the cathode was observed. When the bath pH is further decreased to 1.5, it is possible to deposit cobalt up to 200 mgrL of CrVI.. In this case, the rate of fall in current efficiency is much slower than at higher pHs studied. The chromium content of the deposit is found to be very small. It varies between 0.02% and 0.04% in the pH range studied.

The cathode contamination and fall in the current efficiency due to presence of chromiumVI. may be explained as follows. Chromium in a dilute chromic 2y acid solution may be present as a monomer CrO4 or as a dimer Cotton and Wilkinson, 1972.. ChromiumVI. reduction is a pH-dependent process and it is reduced to CrIII. Abda et al., 1991; Bennouna et al., 1986.. In concentrated acidic solution chromiumVI., which is a strong oxidising agent, is reduced to CrIII. Mandich, 1997. by the following reaction:
2y Cr2 O 7 q 14Hqq 6eys 2Cr 3qq 7H 2 O

E0 s 1.33 V

1.

The chromate ion in basic solution, however, is a much weaker oxidiser. The electroreduction reaction takes place according to:
2y CrO4 q 4H 2 O q 3eys Cr OH . 3 q 5OHy

E0 s y0.13 V

2.

N. Pradhan et al.r Hydrometallurgy 62 (2001) 110

The reduction rate of CrVI. to CrIII. increases when the pH decreases Abda et al., 1991.. In the basic solution, the CrIII. generated in the equation Sherwood et al., 1979. may undergo precipitation reaction Abda et al., 1991. as follows: Cr 3qq 3OHys Cr OH . 3

3.

During electrodeposition of cobalt from aqueous solutions, the hydrogen evolution reaction takes place more readily because of its position in the emf series. This may lead to formation of OHy ions causing local pH increase in the diffusion layer Landolt, 1994; Lantelme et al., 1998.. Since Co and Ni belong to the same group and their standard electrode potentials do not differ much, it is expected that they will have similar deposition mechanism Heusler, 1967.. It has been reported that Cooper, 1990; Matulis and Slizys, 1964. electrodeposition of Ni proceeds through NiOHq ion. Heusler 1967. and Scoyer and Winand 1977. proposed a similar mechanism for cobalt deposition where deposition proceeds through formation of CoOHq Heusler. or CoOHq and CoOH. 2 Scoyer and Winand.. The pH change at the cathode site and cobalt deposition through hydroxide mechanism proceeds through the following steps. The hydrogen evolution reaction during electrodeposition of cobalt is given by: 2H 3 Oqq 2eys H 2 q 2H 2 O 2H 2 O q 2eys H 2 q 2OHy

4. 5.

At more acidic pH, the surface is covered by hydrogen and the reaction proceeds Scoyer and Winand, 1977. as follows: Co 2qq OHys CoOHq Hqq eys H ads CoOH q H ads q 2e s Co q OH q H ads
q y y

6. 7. 8.

Co 2q ions are hydrolysed as Eq. 6. Bennouna et al., 1986.. At higher pH 4 and 4.5., the reaction proceeds through: Co 2qq 2OHys Co OH . 2 Co OH . 2 q e s Co OH . ads q OH Co OH . ads q eys Co q OHy
y y

9. 10 . 11 .

It is observed from the above equations that cobalt deposits through discharge of cobalt hydroxides. In addition, the reactions given in Eqs. 4. 11. show formation of OHy ions at different steps which is likely to be responsible for the rise in the surface pH. The present study deals with the electrodeposition of cobalt in the presence of CrVI. as an impurity which is added to cobalt electrolyte at mgrL levels. It has been discussed earlier that by the addition of chromic acid to cobalt electrolyte CrVI. may be 2y 2y at present as Cr2 O 7 at acidic pH and CrO4 2y alkaline pH. If there is any Cr2 O 7 , it is likely to undergo reduction at lower pH. But since the surface pH increases during cobalt deposition, the possibility 2y of Cr2 O 7 reduction is remote. Moreover, its reduction takes place at higher potential Eq. 1... In addition, the presence of dimer in the freshly prepared chromic acid is also unlikely. Thus, the only CrVI. species which is available for reaction is 2y CrO4 . Because the surface pH increases, the reduc2y tion of CrO4 to CrOH. 3 is likely to occur as Eq. 2.. However, according to Eq. 1., if there is any formation of CrIII., then it is likely also to precipitate as hydroxide according to Eq. 3.. Addition of CrVI. to cobalt electrolyte results in a decrease in current efficiency and this effect is greater at higher pH Fig. 1.. This may be due to formation of CrOH. 3 and its adsorption on the cathode, thus, blocking the active sites for cobalt reduction which proceeds under mixed control. In addition, reduction of chromiumVI. is associated with hydrogen evolution Lin and Tsai, 1994. This may further add to the fall in the current efficiency during cobalt deposition. At higher pH, the formation rate of CrOH. 3 is likely to be higher as the reaction given in Eq. 2. is pH dependent. which relatively blocks more cathodic sites for discharge of cobalt ion. Decrease in current efficiency during electrodeposition of zinc in the presence of CrVI. was also observed by Lin and Tsai 1994.. Under present experimental conditions, though the cathodic cobalt is contaminated with chromium, the impurity content is negligible in the range of 0.020.04%.. This contamination may be due to adsorption of CrOH. 3 on to the cathode surface and occlusion during electrocrystallisation of cobalt and not due to reduction of CrVI. to metal. The deposition of chromium metal from CrVI. solutions is

N. Pradhan et al.r Hydrometallurgy 62 (2001) 110

2y possible only within certain limits of CrO 3rSO4 ratio which ranges from 18.2 to 127.5 Isserlis, 1971.. The impossibility of depositing chromium from strongly acidic solutions below pH 1.8 has been demonstrated by other workers Radwan et al., 1992; Hoare et al., 1980; Hoare, 1983; Lioyed et al., 1946; Lee and Sekine, 1976.. Similar opinion is also given by Lin and Tsai 1994. for absence of Cr in zinc deposits. The presence of a small amount of chromiumVI. in the cobalt electrolyte ; 5 mgrL. severely affects the deposit at a pH above 2.0. But when the solution pH is decreased to 2.0, smooth sheet is obtained until the chromium concentration reaches 25 mgrL. At higher chromium concentration, i.e. ) 25 mgrL, pitting of the deposit starts Fig. 2a. and it cracks

when its concentration exceeds 50 mgrL. But at pH ; 1.5, a perfect smooth deposit is obtained even at higher chromium concentration 100 mgrL. although the surface is covered with a number of small pits Fig. 2b.. This indicates that the presence of chromiumVI. in the electrolyte is highly detrimental to the electrodeposition of cobalt when the electrolyte pH is high. 3.2. Effect of current density The effect of chromiumVI. with increasing current density on current efficiency for cobalt deposition was studied in the range 200600 Arm2 and the results are shown in Fig. 3. The current efficiency increases in the range 300500 Arm2 and

Fig. 2. Macrophotograph of cobalt deposits at different pH. a. pH 2.0, CrVI. 50 mgrL, =10; b. pH 1.5, CrVI. 50 mgrL, =10.

N. Pradhan et al.r Hydrometallurgy 62 (2001) 110

Fig. 3. Effect of current density on current efficiency at pH 2.0, CrVI. 50 mgrL.

decreases slowly when the current density increases beyond 250 Arm2 . Increase in current density is associated with increase in the rate of hydrogen evolution reaction Dubrovsky and Evan, 1982.. The latter tends to raise the pH and enhances the formation of CrOH. 3 which blocks the active sites of the cathode for electrocrystallisation of cobalt. Both increase in hydrogen evolution and blocking of cathodic sites due to adsorption of CrOH. 3 may be responsible for the decrease in cathode current efficiency. Inhibition of cobalt deposition due to adsorption of ZnOH. 2 has been reported by Akiyama and Fukushima 1992., Hall 1983. and Fisher 1960.. The chromium content of deposit is relatively high 0.03%. at lower current density and low 0.01%. at higher current density. Low cathode contamination at higher current density may be explained as follows. During electrodeposition of cobalt increase in current density results in the precipitation of CrOH. 3 and its adsorption on to the cathode. When the current density exceeds the critical value in the present case the critical value is observed to be 350 Arm2 . CrOH. 3 precipitation is inhibited probably due to non-availability of Cr 3q ion in the diffusion layer, thus reducing cathode contamination. The deposits obtained at lower current density, i.e. - 300 Arm2 , are characterised by cracking and peeling. This is likely to be due to the internal stress caused by inclusion of CrOH. 3 in the cobalt deposit. At higher current densities the deposits obtained are smooth.

3.3. Effect of temperature The effect of temperature on current efficiency and cathode contamination during electrocrystallisation of cobalt was studied in a temperature range of 30 to 60 C in the presence of 50 mgrL of chromiumVI.. The results on the current efficiency are given in Table 1. As in the case of cadmium Pradhan et al., submitted for publication., the presence of chromium in the cobalt electrolyte causes a fall in the cathode current efficiency. Though the cathode contamination due to chromium is insignificant in the range of 0.020.04%., fall in chromium content is observed with increase in temperature. The fall in the current efficiency and chromium contamination of cathode may be explained as follows. An increase in temperature increases the rate of cobalt deposition as well as hydrogen evolution

Table 1 Effect of temperature on current efficiency during cobalt deposition in presence of chromium Cobalt 60 grL, pH 2.0, CrVI. 50 mgrL, current density 230Arm2 . Temperature C. 30 40 50 60 Current efficiency %. 83 82 81 79

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due to decrease in activation overpotential. This should result in an increase in the rate of both cobalt deposition and hydrogen evolution reactions. The present result fall in cathode current efficiency under the present experimental conditions. shows that probably the rate of hydrogen evolution only increases with increase in bath temperature. Due to hydrogen evolution, the surface pH increases. The condition favours the reduction of CrVI. to CrIII. and the precipitation of CrOH. 3 and its adsorption. This may block the cathode sites for Co 2q discharge thereby decreasing the cathode current efficiency. With rise in electrolyte temperature, as more hydrogen evolution takes place, the surface pH further increases. This leads to precipitation of both chromium and cobalt as hydroxides. Precipitation of cobalt hydroxide probably inhibits chromium transportation to the cathode Diaz and Schermer, 1985. for its reduction and precipitation of CrOH. 3 . This results in the fall in cathode contamination at higher temperature. 3.4. Effect of cobalt concentration The change in current efficiency with increasing cobalt concentration in the presence of 50 mgrL chromiumVI. was studied in the range 1560 grL of cobalt. The results Table 2. show that the current efficiency increases significantly with increasing cobalt concentration from 1545 mgrL beyond which it is marginal. At lower cobalt concentration the rate of hydrogen evolution predominates over cobalt deposition due to decrease in effective metal ion concentration at the cathode. In addition, higher hydrogen evolution reaction leads to precipitation of

Table 3 Effect of chromiumVI. on crystallographic orientations of cobalt deposits at different experimental conditions pH CrVI. concentration mgrL. 0 50 1.5 2.0 50 50) 50) ) 50) ) ) Crystallographic orientations

2.0

110. ) 112.201. ) 100.002.101. 110. ) 100. ) 112. ) 200.101. ) 103. 110. ) 100. ) 101. ) 002.102. ) 103. 110. ) 112. ) 101. ) 002. ) 100. ) 201. 110. ) 100. ) 101. ) 002. 110. ) 100. ) 112. ) 002.101.102.

Current density 400 Arm2 . Current density 450 Arm2 . ))) Temperature 60 C.
) ))

CrOH. 3 and its adsorption on to the cathode thereby blocking sites for Co 2q discharge. These two factors may cause a fall in the current efficiency for cobalt deposition at lower cobalt concentration. But at higher cobalt concentration, cobalt deposition reaction predominates over the hydrogen evolution reaction thus inhibiting reduction of CrVI. to CrIII. and its precipitation. As a result the cathodic current efficiency increases Table 2.. The cathodic contamination due to chromium is also negligible 0.03 0.05%. in this case. 3.5. Crystallographic orientations The cathode cobalt deposits obtained in the presence of chromiumVI. were subjected to X-ray diffraction to determine the crystallographic orientations. The results are given in Table 3. In the absence of chromium at pH of 2.0 the deposit shows 110. as the most preferred plane and the order of orientations is 110. ) 112.201. ) 100.002.101.. On addition of 50 mgrL chromium, though the 110. plane remains as the most preferred one, crystallite growth in the direction of 100 . is promoted and at the same time growth of the 112. plane is suppressed. The order of crystallographic orientations is thus changed to 110. ) 100. ) 112. )

Table 2 Effect of cobalt concentration on current efficiency during cobalt deposition in presence of 50 mgrL chromiumVI. pH 2.0, CrVI. 50 mgrL, temperature 40 C, current density 230 Arm2 . Cobalt concentration grL. 15 30 45 60 Current efficiency %. 60 72 81 82

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200.101. ) 103.. When the solution pH is lowered to 1.5 keeping chromium concentration same, the orientations of different planes remain almost the same where 110. is the most preferred one. But in

this case the growth of 101. is promoted along with 100.. Increase in bath temperature from 40 C to 60 C does not show any significant change in the orientations and the order observed is 110. ) 100.

Fig. 4. SEM photomicrograph of cobalt deposit in presence of chromiumVI. at different experimental conditions. a. pH 1.5, CrVI. 50 mgrL, =100; b. pH 2.0, CrVI. 50 mgrL, =100; c. pH 1.5, CrVI. 50 mgrL, =1200; d. pH 2.0, CrVI. 50 mgrL, =1200; e. pH 2.0, CrVI. 50 mgrL, current density 450 Arm2 , =1200; f. pH 2.0, CrVI. 50 mgrL, temperature 60 C, =1200.