Effect of solution impurities on morphology and composition of copper electrodeposits obtained in membrane based cell

geda1, J. M. Casas1 and T. Vargas2 L. Cifuentes*1, M. Gra

Chemical and physical characterisation of copper electrodeposits obtained on mesh and plate cathodes in a lab scale reactive electrodialysis cell and cells of conventional design have been carried out. The effect of Fe, Mn, Cl and guar in the electrolyte on electrodeposit composition and morphology were determined by means of metallographies, scanning electron microscopy, energy dispersive spectrometer, atomic force microscopy and inductively coupled plasma mass spectrometry. Metallographies revealed that electrolytes with Cl, Fe and FeClMn generated thick columnar deposits. Impurity free and Mn containing solutions produced thin columnar electrodeposits. The presence of all the impurities plus the organic additive resulted in small grained equiaxial electrodeposits. Atomic force microscopy revealed that the latter deposits, and those where Mn was present in solution, exhibited the smoother surfaces (100200 nm mean surface rugosity) whereas other deposits showed higher degrees of roughness (over 400 nm mean surface rugosity). Impurities and additive were present in small concentrations (,1 mg dm23) in the produced electrodeposits.
Keywords: Electrodeposit, Copper, Characterisation, Reactive electrodialysis

List of symbols
A d Ee DEe I m R, Ra1, Ra2, Rc, Rm t Vcell W g, ga, gc surface area, m2 distance travelled by ions, m equilibrium potential, V difference between Ee values of anodic and cathodic reactions, V cell current, A deposited copper mass, g electrical resistance, of anolyte 1, anolyte 2, catholyte and membrane, V time, s cell voltage, V electrical energy, J

overpotential, anodic and cathodic, V k electrical conductivity, V21 m21

Introduction
Copper electrowinning has been reviewed by a number of authors.18 In particular, copper electrodeposits have
1

Departamento de Ingenier a de Minas, Facultad de Ciencias F sicas y Matema ticas, Universidad de Chile, Tupper 2069, Santiago 8370451, Chile 2 Departamento de Ingenier a Qu mica y Biotecnolog a, Facultad de Ciencias F sicas y Matema ticas, Universidad de Chile, Beauchef 861, Santiago 8370456, Chile *Corresponding autor, email luicifue@cec.uchile.cl

been studied by workers who have concluded that impurities in the electrowinning solution strongly inuence cathode quality, because of their effect on the morphology of the produced copper crystals.9 The concentration of impurities at the deposit surface may be drastically different from their concentration in the bulk solution. It has also been pointed out that the properties of the substrate are critical for the nucleation and subsequent growth of copper crystals.10,11 The magnitude of the current that forces the electrodeposition also inuences deposit quality. A high current density causes a low quality deposit, with poor mechanical properties due to its disordered structure. Lowering the cathodic current density allows production of a better deposit. The presence of organic additives in solution has been shown to improve deposit quality, allowing for a higher cathodic current density. Long chain molecules such as guar,12 other polysaccharides13,14 and polyacrylamides15 have been investigated. However, inorganic species with much lower molecular weight (e.g. the chloride ion)16 can also improve the deposit quality. In some cases, it has been shown that inorganic additives cause a decrease in the cathodic current efciency; this effect can be reversed by the use of organic additives.17 This result suggests that organic molecules are responsible not only of producing ordered deposits, but also of hindering unwanted parallel reactions. The electrodeposits studied in the present work were produced in a membrane based three compartment lab

2009 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 18 February 2008; accepted 24 May 2008 DOI 10.1179/174313208X327694

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scale copper electrowinning cell, also known as reactive electrodialysis (RED) cell, which has been fully described elsewhere.18 For the sake of comparison, additional deposits were obtained in lab scale cells of conventional design. The objective of this work is to determine the effect of various impurities and an additive on the quality of copper electrodeposits by means of electrochemical testing and characterisation methods.

Experimental
The cell operation parameters used here were taken from previous work with a three compartment RED cell,18 where the catholyte compartment was anked by two anolyte compartments. The same cell design was used in the present work. The catholyte was cupric sulphate in sulphuric acid and the anolyte was ferrous sulphate in sulphuric acid. The electrolytes were recirculated to 1000 cm3 ad-hoc thermostatic tanks by means of Watson-Marlow 505S peristaltic pumps. In the cell, catholyte and anolyte were separated by two Ionac MA3475 anion membranes. A copper mesh cathode and platinum sheet anodes were used. The cathodic reaction was Cu2zz2eRCu0 and the anodic reaction was Fe2zRFe3zze. Electrolyte agitation was achieved by oxygen free nitrogen sparging. The chosen conditions were those which produced the best deposit distribution and homogeneity and the lowest cell voltage. They were: current density51650 A m22 (referenced to cathode surface area), electrolyte recirculation owrate5 16 cm3 s21, nitrogen sparging owrate542 cm3 s21, electrolyte temperature550uC. Temperature was kept constant by a Julabo thermostatic bath. The catholyte composition was 40 g dm23 Cu and 190 g dm23 H2SO4; the anolyte contained 56 g dm23 Fe and 190 g dm23 H2SO4. The anion membranes were pretreated by immersion in a 98 g dm23 sulphuric acid solution during 48 h. Agitation was applied during the rst ve hours. Impurities (Fe2z, Fe3z, Cl2, Mn2z) and an additive (guar, a water soluble polysaccharide) were added to the catholyte. Table 1 shows the concentration of impurities/additive used for each experiment. The amount and quality of the electrodeposit, the cathodic current efciency and the specic energy consumption were determined for each run. Deposits obtained in the RED cell were compared with deposits obtained in a conventional, single compartment, single electrolyte lab scale cell, where no membranes are used. The conventional cell was a 200 cm3 double jacket vessel containing the solution and the electrodes. Cathode, anode and temperature were the same as those used in the RED cell. The

composition of the electrolyte in the conventional cell was the same as that of the catholyte in the membrane based (RED) cell. No agitation was applied in the conventional cell given that no agitation is used in industrial copper electrowinning. A cathodic potentiodynamic sweep was carried out in the RED cell using a Solartron 1286 electrochemical interphase. The working electrode was made of copper mesh with a surface area of 0?96 cm2; the counter electrode was made of graphite bars with an apparent surface area of 32 cm2 and the reference electrode was Hg/Hg2SO4. The sweep rate was 1 mV s21 and the electrolyte temperature was 50uC. The following impurities and additive concentrations were present in the catholyte: Fe2z50?2 g dm23; Fe3z50?8 g dm23; Cl25 0?015 g dm23; Mnz250?075 g dm23 and guar50?004 g dm23. Metallographies of copper electrodeposits obtained in the RED cell were carried out. Copper mesh samples were taken from the central part of the mesh cathodes and mounted in Epoxycure resin to produce 161 cm specimens. The latter were polished with 320, 600 and 1500 grit emery paper and then with 1 and 0?5 mm alumina paste. After polishing, the specimens were washed with deionised water, then with methanol and nally, dried in warm air. Etching was carried out with an aqueous solution containing 1 g of analytical grade potassium dichromate, 4 cm3 of sulphuric acid (density51?84 g cm23) and 50 cm3 of distilled water; two drops of hydrochloric acid (density51?19 g cm23) were added to the solution just before etching. A Nikon Labophot optical microscope was used to observe the deposits. Photographic work was carried out with a digital Nikon Coolpix 4500 camera. Atomic force microscopy (AFM), including the measurement of root mean square (RMS) rugosities, was carried out with a Digital Instruments AFM Nanoscope III. Electrodeposit morphologies and composition were established with a JEOL JSM-5410 scanning electron microscope and with its attached energy dispersive spectrometer (EDS), a. k. a. microprobe. Additional chemical analyses were carried out with an inductively coupled plasma mass spectrometry Fisons VG1 Plasma Quad spectrometer.

Results and discussion

Potentiodynamic sweep and cell voltage versus time curves
Figure 1 shows the cathodic potentiodynamic sweep in the RED cell with all impurities present. From this curve, the limiting current density for copper electrodeposition was estimated at y4150 A m22. This is

Table 1 Concentrations of impurities and additive in catholyte* Exp. 1 2 3 4 5 6 7 Impurity Mn2z Cl2 Mn2z; Cl2 Fe2z; Fe3z Mn2z; Cl2; Fe2z; Fe3z Mn2z;Cl2; Fe2z; Fe3z; guar Impurity concentration, mg dm23 75 15 75; 15 200; 800 75; 15; 200; 800 75; 15; 200; 800; 4

*Basic composition: 40 g dm23 Cu, 190 g dm23 H2SO4; for all experiments, icath51650 A m22 (I52?4 A), T5 50uC.

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1 Cathodic potentiodynamic sweep carried out in RED cell: sweep rate51 mV s21; electrolyte temperature5 50uC; concentrations: Fe2z50?2 g dm23; Fe3z50?8 g dm23; Cl250?015 g dm23; Mnz250?075 g dm23; guar50?004 g dm23

2 Cell voltage versus time curves for various impurities

because at (4150 A m22, 20?08 V) there is an inexion point caused by the superposition of the copper electrodeposition and hydrogen evolution reaction curves. As a result, the plateau corresponding to the copper deposition reaction (controlled by mass transfer), was masked by the hydrogen evolution reaction (controlled by charge transfer). As the cell current density for the electrodeposition was 1650 A m22, it is then possible to state that this process was carried out under mixed control. Figure 2 shows the effect of impurities on the cell voltage as a function of time. There are two distinct groups of curves. The rst one, with the lowest average cell voltage, corresponds to the solutions which contained no impurities or additives and the one which only contained Mn(II). The second group includes all the remaining solutions. The highest cell voltage was obtained for the aggregate of all impurities plus the organic additive (guar). Cell voltage in the three compartment RED cell is given by Vcell ~DEe zga zjgc jzI (Ra1 zRc zRa2 z2Rm ) (1)

In the present case, the addition of Cl (as Cl2), Fe (as Fe2z and Fe3z) and guar caused a cell voltage increase, whereas the addition of Mn (as Mn2z) had the opposite effect. Guar appears to cause the sharpest cell voltage increase, which conrms previous ndings.21 This may be due to an increase in the cathodic overpotential caused by the adsorption of a covering layer of bulky guar molecules on the metal surface. The latter would induce grain rening of copper crystals. Table 2 shows the values of indicators of cell performance for the studied electrolyte compositions. Current efciency decreased as more impurities or additives were added to the solution reaching a minimum of 94% when all the impurities plus guar were present. It is worth noting that the deposited copper mass was clearly lower in those cases where Fe was present in solution. A likely cause for this phenomenon is that when Fe was present, the Fe3zzeRFe2z reaction was possible, which reduced the cathodic current efciency for copper electrodeposition. The specic energy consumption, given by W Vcell It ~ (3) m m increased with cell voltage, as it would be expected. SEC ~

where the electrical resistance of catholyte (Rc) and anolytes (Ra1, Ra2) are given by R~ 1d kA (2)

Metallographies
Figure 3 shows metallographies obtained from copper electrodeposits produced after two hours of RED cell operation (experiments 1, 2, 3, 5, 6 and 7 on Table 1). All deposits showed good adherence to the substrate and absence of discontinuities (porosity, cracks and voids).

and the membrane resistance (Rm) can be measured or calculated.19 It is well known that the electrical conductivity of acidic solutions increases with increasing acid concentration, but shows a more complex behaviour when metals are added.20

Table 2 Cell performance indicators for various solution compositions (RED cell)* Impurities No impurities Mn Cl Mn, Cl Fe Fe, Mn, Cl Fe, Mn, Cl, guar Mass of Cu deposit, g 5.5632 5.6960 5.8125 5.5775 5.4738 5.4279 5.4497 Current efficiency, % 98 99 100 98 96 96 94 Specific energy consumption, kWh kg21 1.27 1.24 1.28 1.35 1.37 1.37 1.40 Average cell voltage, V 1.480 1.475 1.555 1.571 1.557 1.550 1.591

*Conditions are described on Table 1.

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3 Optical micrographs showing microstructure of copper deposits: zones 1 and 2 (see text) are shown

All metalographies exhibited similarities regarding crystal growth due to their common circular crosssection substrate. Two growth zones were in evidence: zone 1, relatively narrow, was in contact with the substrate and zone 2 was on the periphery. In what follows, the structure types present in the deposits are classied according to Fischer.22 The morphologies observed in this work are: (i) unoriented dispersion (UD) fine grained deposit with small equiaxial crystals, low surface rugosity (ii) basis reproduction (BR) thick columnar deposit with large crystals which reproduces the features of the basis (substrate). Surface rugosity grows with deposition time (iii) field oriented texture (FT) thin columnar deposit which also tends to reproduce the features of the basis. Surface rugosity tends to remain constant with deposition time.

In most cases, zone 1 presented a UD type ne grained structure, the only exception being the case where Fe was present in solution; in this case the structure was BR type. In contrast, zone 2 presented a variety of structures. The non-impurity case showed an FT structure with some UD characteristics, with a rugged surface morphology. The presence of Mn in solution produced an FT type structure, whereas the presence of Cl produced a BR structure with large crystals, which caused a more rugged surface. The presence of Fe in solution resulted in a Z type structure, which is an intermediate between BR and FT structures. The crystals, in this case, were smaller than those caused by Cl, giving raise to a surface of similar rugosity to the non-impurity case. The presence of Fe, Cl and Mn produced a Z type structure with elongated grains and uniformly distributed large sized grains, which resulted in a surface with varying degrees of rugosity. On the other hand, the guar

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In the metallography corresponding to experiment 6 (Mn, Fe and Cl) a mixture of BR and FT morphologies was observed. This was in agreement with previous considerations on the effect of each individual metal.

SEM and AFM analyses

Scanning electron microscopy and atomic force microscopy were used to characterise the surface structure of the electrodeposits. Figure 5 shows SEM images which allow a comparison of the effects of the studied metals and additive on the surface structure of the copper electrodeposits. The non-impurity case and the case which included guar exhibited a more even distribution of the deposit, giving a smoother surface. As expected, the presence of guar produced the smoothest surface. Each added impurity and their combinations produced very distinct morphologies. The ones caused by the presence of Cl, ClMn or FeClMn in solution, appeared to have a more uneven surface than the one with Fe. A quantitative comparative study of surface rugosity was carried out via AFM. The effects of cathode type, cell type, impurities in solution and their concentrations on surface roughness were studied. Results are presented in Table 3. Minimum rugosity (103 nm) was achieved with a guar containing electrolyte on a mesh cathode (Fig. 6). However, with the same electrolyte, the surface roughness more than doubled when the deposition was carried out on a plate cathode. This result could be explained by the fact that the mesh geometry promotes turbulence, causing much higher values of the electrolytes Reynolds number on a mesh than on a plate cathode. This enhancement of the mass transfer process could lead to more even deposits. The electrodeposits obtained in the conventional cell (experiments 5 and 6) exhibited much greater rugosities (up to 4?5 times greater) than the ones obtained in the RED cell. This was likely to be caused by the different hydrodynamic conditions in the said cells. In terms of crystal size and roughness, the deposits range from (i) BR type (large crystals, rough surface) for solutions containing Cl, Fe or FezClzMn, through (ii) FT type (medium sized crystals, medium roughness) for solutions without impurities or with Mn as sole impurity, to (iii) UD type (small crystals, smooth surface) for solutions containing FezClzMnzguar.

4 Winand diagram23 showing effect of various solution components on structure of copper electrodeposits (FI5eld oriented isolated; BR5basis reproduction; FT5eld oriented texture; UD5unoriented dispersion)

containing solution produced a mixture of UD and FT structures. Crystals were smaller than in previous cases and the surface was less rough. This was to be expected, as guar is used as an additive in copper electrowinning to produce ne grained deposits which provide better mechanical properties to the cathode. Figure 4 shows a Winand diagram,23 which relates deposition rate, inhibition intensity and electrodeposit structure. The presence of impurities inuenced the inhibition intensity (vertical axis), going from a BR structure for Cl and Fe, through an FT structure for Mn, to a UD structure for guar. The non-impurity case produced a similar degree of inhibition as the Mn containing solution. The effect of Cl on the microstructure of copper electrodeposits was studied by Lakshmanan et al.24 These authors showed that, above a chloride concentration of 10 mg dm23, the deposits grain size increased. In experiment 3, Table 1, the concentration of Cl2 was 15 mg dm23 (i.e. above 10 mg dm23), which explains the enlarged grain size. Vargas and Parra25 have shown that the ferrous ion caused a decrease in the size of copper grains. When both ferrous and ferric ions were present in solution, the effect of ferrous ion was diminished. In experiment 5, Table 1, the ferric ion concentration was four times greater than the concentration of ferrous ion, which gave raise to a Z type microstructure. The manganous ion acts as a grain rener at concentrations below 500 mg dm23 and tends to decrease the cathodic overpotential.10 In experiment 2, Table 1, manganous concentration was 75 mg dm23 and, according to the observed microstructures, it acted as a grain rener, with smaller crystals than those obtained in experiments 3, 5 and 6. Their size was similar to that obtained in the experiment without impurities in the electrolyte, giving raise to an FT structure.
Table 3 Square mean rugosity of electrodeposited surfaces Exp. 1 2 3 4 5 6 Cathodetype Mesh Mesh Mesh Plate Plate Plate Cell type RED RED RED RED Conventional Conventional Impurities Mn, Cl Mn, Fe, Cl Guar Guar no Mn, Fe, Cl

Chemical analyses
Chemical analysis by EDS did not detect any Fe or Mn in the electrodeposits when these metals were present in the electrolyte. On the other hand, it detected small amounts of Cl when this element was added to the solution and of C when guar was added (,1 mg dm23

Impurity concentration, mg dm23 75; 15 75; 1000; 15 40 40 No 75; 1000; 15

Root mean square rugosity, nm 126 296 103 239 460 453

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5 Images (SEM) of copper electrodeposits: impurities in solution are shown 6500

in both cases). Traces of S were also detected in some specimens, which points to electrolyte entrapment. Chemical analysis by inductively coupled plasma mass

spectrometry detected less than 1 mg dm23 of Mn in deposits obtained with this element in solution; Fe was not detected by this method. These results show that

6 Images (AFM) of Cu electrodeposit obtained from guar containing electrolyte

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impurities and additive were not present in signicant amounts in the electrodeposits.

Significance of present results and further work

This work may contribute to a better understanding of the quality of copper electrodeposits produced in electrowinning cells of unconventional design (membrane based). These cells have shown a potential for industrial use due to their lower specic energy consumption (up to 75% reductions have been achieved at lab scale compared to conventional industrial cells) and the fact that the spent anolyte might be used for the production of ferric compounds. The latter are between 6 and 10 times more expensive than the ferrous salts that these cells use as raw material. No deleterious effects of nitrogen sparging on the structure of deposits (cathode quality) were observed at lab scale when the guar additive was present in solution. Pilot plant scale experiments would help to determine potential problems in an industrial operation. No micropores or microcracks were observed in the deposits by optical or electron microscopy during the present work. As pointed out in the previous paragraph, further observations will have to be made at pilot plant scale to gain new insights regarding the physical quality of the electrodeposits in a potential industrial production.

5. Impurities and the additive inuenced deposit morphologies, but they did not deposit in signicant amounts. 6. Further work at pilot plant scale is required to establish the likelihood of cathode quality problems in a full scale industrial operation due, for instance, to nitrogen sparging.

Acknowledgements
This work was funded by the National Committee for Science and Technology (CONICYT, Chile) via FONDECYT projects nos. 101 0138 and 103 0530. Atomic force microscopy analysis was carried out at INIFTA, La Plata, Argentina, under the guidance of Dr Patricia Schilardi; thanks are also due to Dr Roberto Salvarezza (INIFTA Director). One of the authors (M. Gra geda) would like to thank MECESUP for financial support (grant no. UCH0205).

References
1. T. N. Andersen: Proc. Int. Symp. on Hydrometallurgy, (ed. D. J. I. Evans and R. S. Shoemaker); 1973, New York, AIME. 2. W. C. Cooper: J. Appl. Electrochem., 1985, 15, 789805. 3. K. P. Gopala: Hydrometallurgy, 1992, 31, 243255. 4. F. J. Alguacil: Revista de Metalurgia (Madrid), 1998, 34, (6), 499 506. 5. S. K. Young: Proc. COPPER 99 Int. Conf., Vol. IV, (ed. S. K. Young), 611620; 1999, Phoenix, TMS. 6. G. M. Zagorovskii: Russian J. Appl. Chem., 2001, 74, (3), 424426. 7. A. Vicenzo and P. L. Cavallotti: J. Appl. Electrochem., 2002, 32, (7), 743753. 8. M. Moats and M. Free: JOM, 2007, 59, (10), 3436. 9. T. Subbaiah and S. Das: Hydrometallurgy, 1994, 36, 271283. 10. T. B. Vaughan and H. J. Pick: Electrochimica Acta, 1960, 2, 179 194. 11. U. Bertocci, C. Bertocci and B. C. Larson: J. Crystal Growth, 1972, 13/14, 427432. 12. J. Wang, P. Somasundaran and D. R. Nagaraj: Miner. Eng., 2005, 8, 7781. 13. Q. Liu, Y. Zhang and J. S. Laskowski: Int. J. Miner Process., 2000, 60, 229245. 14. P. G. Shortridge, P. J. Harris, D. J. Bradshaw and L. K. Koopal: Int. J. Miner. Process., 2000, 59, 215224. 15. J. Vereecken and R. Winand: Surface Technol., 1976, 4, 227 235. 16. M. A. Loshkarev, A. A. Kriukova, Y. M. Loshkarev and T. F. Diachenko: Electrochim. Acta, 1964, 9, 1191127. 17. I. Ivanov: Hydrometallurgy, 2004, 72, 7378. 18. L. Cifuentes, M. Gra geda and G. Crisostomo: Chem. Eng. Sci., 2006, 59, 36233631. 19. L. Cifuentes, J. M. Castro, J. M. Casas and J. Simpson: Appl. Mathemat. Modell., 2007, 31, 13081320. 20. D. C. Price and W. G. Davenport: Metall. Trans. B, 1981, 12B, 639643. 21. L. Cifuentes and D. Pino: Unpublished results, 2008. 22. H. Fischer: Elektrolytische Abscheidung und Elektrokristallisation von Metallen; 1954, Berlin, Springer Verlag. 23. R. Winand: Hydrometallurgy, 1992, 29, 567598. 24. V. I. Lakshmanan, D. J. Mackinnon and J. M. Brannen: J. Appl. Electrochem., 1977, 7, 8190. 25. T. Vargas and P. L. Parra: Private communication, 2008.

Conclusions
1. The lowest RED cell voltages for copper electrodeposition were obtained with an electrolyte free of impurities and additives and also with an electrolyte which contained only Mn as impurity, whereas the highest cell voltage was obtained with an electrolyte with the full set of impurities plus guar. 2. Metallographies revealed that electrolytes with Cl, Fe and FeClMn generated BR type (thick columnar) deposits; impurity free and Mn containing electrolytes generated FT type (thin columnar) deposits and an electrolyte with all the impurities plus the organic additive resulted in UD type (small equiaxial) deposits. 3. Atomic force microscopy revealed that equiaxial deposits, and those where Mn was present in solution, exhibited the smoothest surfaces, whereas other deposits showed various degrees of roughness. It also showed that electrodeposits obtained on mesh cathodes exhibited lower root mean square rugosities than those obtained on plate cathodes, due to the different hydrodynamic conditions caused by these geometries. 4. On the other hand, electrodeposits obtained in the RED cell, irrespective of cathode geometry, exhibited lower RMS rugosities than those obtained in a conventional design lab scale cell. This was likely to be caused by the higher degree of electrolyte agitation in the RED cell.

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