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Int. J. Miner. Process. 77 (2005) 208 216 www.elsevier.

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Oxidation of chalcopyrite by extended milling


C.J. Agnew, N.J. Welham *
Extractive Metallurgy, Murdoch University, Perth, WA 6150, Australia Received 4 February 2004; accepted 19 May 2005 Available online 2 August 2005

Abstract Chalcopyrite has been milled for up to 50 h in oxygen, air and argon atmospheres using a laboratory ball mill. No phase changes were evident in argon but the XRD peaks were weaker and broader indicating crystalline refinement. In oxygen, even after 1 h milling peaks for CuSO4d 5H2O were present and these became predominant after 20 h milling where the chalcopyrite peaks were absent. In air, partial oxidation to CuSO4d 5H2O was evident after 50 h. Leaching of the resultant powders with water showed 80% dissolution after 50 h milling in oxygen, significantly greater than the 20% and 6% dissolution after milling for 50 h in air and argon respectively. Solution analyses showed the Cu/Fe ratio increased with milling time in oxygen suggesting selectivity may be possible. The insoluble residue was found to consist of haematite, elemental sulphur and unreacted chalcopyrite. D 2005 Elsevier B.V. All rights reserved.

1. Introduction Chalcopyrite is the most important global source of copper and is almost invariably smelted producing 2 tonnes of SO2 for every tonne of copper produced. The SO2 produced has to be sequestrated for environmental reasons, typically as sulphuric acid. If smelting could be avoided there are potential benefits in avoiding the production of SO2. Unfortunately, chalcopyrite is probably the most difficult sulphide to process hydrometallurgically as it forms a protective layer on the surface during oxidation (Burkin, 2001; Hackl et al. 1995) and references therein. Once this layer forms,
* Corresponding author. Tel.: +61 8 9360 2831; fax: +61 8 9360 6343. E-mail address: nicholas.welham@murdoch.edu.au (N.J. Welham). 0301-7516/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.minpro.2005.05.001

access to unreacted surface is greatly hindered and oxidation slows considerably. It is well known that a solution Eh of N 1 V is needed to oxidise the chalcopyrite with minimal sulphur formation, however, there are few metallurgical oxidants capable of this. Pressure leaching of b 45 mm chalcopyrite under 7 atm oxygen gave poor recovery after 3 h, unless operated at N 180 8C (Hackl et al., 1995). Bacterial oxidation seems to offer some prospect with high recoveries being obtained by thermophilic bacteria (Rubio and Frutos, 2002). However, high recoveries typically necessitate residence times in the order of days or weeks. This residence time is only likely to be commercially economic in heap or dump leaches where maintenance of temperature is very difficult. It has been shown that ultrafine grinding of sulphide minerals leads to enhanced reactivity (Balaz, 2000;

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Tkacova, 1989) and references therein. In these volumes, the authors attribute most of the increased reactivity to structural changes within the mineral. A number of previous investigations on the reactivity of chalcopyrite after extended milling have shown that reactivity is enhanced and high recoveries of copper can be achieved (Balaz et al., 1996, 1998; Gerlach et al., 1973; Maurice and Hawk, 1998, 1999; Tkacova and Balaz, 1996). However, these authors used oxidative leaching processes, either pressure leaching (Gerlach et al., 1973), bacterial oxidation (Balaz et al., 1996) or ferric leaching (Balaz et al., 1998; Maurice and Hawk, 1998; Tkacova and Balaz, 1996) after activation confirming the importance of oxidation in chalcopyrite hydrometallurgy. After 2 h of activation, pressure leaching was significantly more effective with N90% Cu leached in 2 h at 110 8C under 20 atm oxygen (Gerlach et al., 1973), this can be compared with a similar recovery achieved from unactivated chalcopyrite after 3 h leaching at 190 8C under 7 atm oxygen (Hackl et al., 1995). The improvement due to activation is even greater when it is considered that the latter experiments also used a higher acid concentration and started with ferric ions in solution. Interestingly, Maurice and Hawk (1999) attempted to leach within the mill by using ferric chloride as the grinding solution, to minimise the oxidative corrosion of the mill and balls the grinding was carried out autogenously by using the chalcopyrite ore as media. In this case, the high solution concentrations used were sufficient to produce solid copper chlorides. High concentrations were used to minimise the solution volume thereby maximising the milling action. No recovery data was presented but the XRD peaks for chalcopyrite were absent after milling suggesting it had been oxidised. However, in most of the above instances the minerals were ground in air which would be expected to lead to some oxidation. For example, enargite, Cu5AsS4 was milled in air and XRD of the product showed the presence of enargite, CuS and an unidentified phase (Balaz et al., 2000). The five unidentified peaks can all be attributed to CuSO4d 5H2O implying that part of the activation process was the oxidation reaction reported elsewhere for enargite milled in oxygen (Welham, 2001a,b). The greatest increases in solubility have been observed after milling in oxygen (Welham, 1997, 2001a,b,c) rather than in air. In these cases the

solubility is achieved without oxidative leaching using water and/or relatively weak acid. This paper examines the effect of extended milling in an oxygen atmosphere on the dissolution of chalcopyrite in non-oxidising media.

2. Experimental technique The chalcopyrite used was from the 510 mm fraction screened from a bulk sample from Mount Lyall, Tasmania. Pieces were hand picked to minimise quartz which was the major mineral impurity. The selected pieces were ground in a ring mill and the 106212 Am fraction used in the experiments. XRD of the resultant powder showed the major phase present was chalcopyrite, a small peak for quartz was also present at 318 2h, relative peak areas indicted that quartz was b2%. A 7.0 g sample of chalcopyrite was loaded into a laboratory scale ball mill (Calka and Radlinski, 1991) along with five 25.4 mm stainless steel balls giving a ball to powder mass ratio of 45:1. After sealing, the mills were evacuated to ~ 10 2 Pa and backfilled with the required atmosphere (argon, air or oxygen). The argon and oxygen mills were run under positive pressure to prevent ingress of air, the valve on the mill with the air atmosphere was simply left open to allow free exchange with atmosphere. No pressure change was registered in the argon mill confirming the mills were sealed. Those mills which ran with an oxygen atmosphere were periodically replenished as it was consumed by the chalcopyrite. The unmilled concentrate and the milled powders were subjected to 24 h agitated leaching in both water and 0.1 M HCl at room temperature to determine whether solubilisation had occurred during milling. Solutions were analysed for copper and iron by atomic absorption spectroscopy. All powders were analysed by XRD using mono chromatic Cok a radiation (k = 1.78896 A) to give a profile of the phases present before and after milling and leaching.

3. Thermodynamic assessment Fig. 1 shows the equilibrium composition for chalcopyrite oxidation with varying amounts of oxygen at

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1 0.9 0. 0.8 0. 0.7 0. 0.6 0.


CuFeS2 FeSO4 CuS CuS CuSO4 FeSO4

fraction

O2

0.5 0. 0.4 0. 0.3 0. 0.2 0. 0.1 0. 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Fe2O3 Fe2(SO4)3

mol O2/ mol CuFeS2


Fig. 1. Thermodynamic equilibrium composition of 1 mol of chalcopyrite in increasing oxygen contents.

25 8C. The diagram represents the composition which has the free energy minimum of the system calculated independently for each starting mixture (Roine, 1994). At 25 8C there are three major stages of reaction, an initial oxidation to iron(II) sulphate and CuS, oxidation of the CuS to CuSO4 and the oxidation of the iron(II) sulphate to haematite and ferric sulphate. CuFeS2+2O2=CuS+FeSO4 CuS+2O2=CuSO4 12FeSO4+3O2=4Fe2(SO4)3+2Fe2O3 (1) (2) (3)

Despite their presence in the thermodynamic model, neither sulphur dioxide nor elemental sulphur was predicted to occur under the conditions examined. Elemental sulphur is a well known product of chalcopyrite oxidation (Burkin, 2001; Hackl et al., 1995) and is clearly a thermodynamically metastable phase in this system. However, attempts to oxidise elemental sulphur by milling it in oxygen proved unsuccessful, confirming that were it a primary product of chalcopyrite oxidation it would be expected to remain. This reaction scheme suggests that it may be possible to separate the copper and iron by controlling the

oxygen content of the system to form a soluble iron product, FeSO4 whilst leaving the copper behind in an insoluble form, CuS. The high affinity of these anhydrous sulphates for water is likely to lead to hydration of the milled products on exposure to atmospheric moisture or during wet milling. If the solubilities of FeSO4 and CuSO4 are ignored then little effect is noted, other than the formation of the hydrated forms of these sulphates, most likely the copper pentahydrate and iron hexahydrate at 25 8C. The extent of hydration of these sulphates is complex and dependent upon the temperature with dehydration reportedly starting at ~26 8C and ~38 8C for iron and copper sulphates respectively (Duval, 1963).

4. Results and discussion The XRD traces for samples milled in oxygen, air and argon for up to 50 h are shown in Fig. 2. As is clear from the traces of the samples milled for 50 h in air and argon, the peaks for chalcopyrite weakened and broadened, as is typical of crystallite size refinement (Balaz, 2000; Cullity, 1978). However, no new peaks were evident implying that no phase transformations occurred during milling.

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CuFeS2 CuSO4.5H2O S Fe2O3


as received

1hr O2

intensity

2h O2

10h O2 20h O2 50h O2 50h air

50h Ar

10

15

20

25

30

35

40

45

50

55

60

2 / o
Fig. 2. XRD traces of chalcopyrite milled for up to 50 h in oxygen and for 50 h in air and argon.

The sample milled in oxygen showed significant changes in the phases present with new peaks evident after 1 h of milling. The most obvious new peak is at 41.68 which can be ascribed to Fe2O3, peaks were also evident at 21.88, 358 and 518. The first of these peaks is most probably due to the presence of CuSO4d 5H2O, confirmatory peaks for this phase became stronger in samples milled for longer than 1 h and were somewhat more obvious after 10 h when peaks for elemental sulphur also appeared. The peaks at 358 and 518 could not be positively identified due to the lack of sufficient confirmatory peaks. It is possible that these peaks are both from pyrrhotite, FeS but the lack of further peaks makes this attribution doubtful. After 20 h milling, the peaks for chalcopyrite were absent. The only phases which could be confirmed as present were Fe2O3, CuSO4d 5H2O and S. Further milling to 50 h resulted in crystallite refinement of these phases with the concomitant weakening and broadening of the peaks making positive identification difficult.

The mass losses of the as-milled powders after 24 h agitated leaching in water and 0.1 M HCl ar shown in Fig. 3. Clearly, the mass loss in acid is greater than in water, as would be expected, although at longer milling times the difference between the different leachants diminished. This suggests that there are at least two phases present, one acid soluble and another water soluble. The proportion of water soluble material increases with time at the expense of the acid soluble phase(s). The solubility of the starting material was extremely small with only 1.6% mass loss after 24 h in 0.1 M HCl. However, after 1 h milling the acid solubility had increased to ~ 38% whilst the water solubility increased to ~ 15%. It could be argued that these increases are due to particle size reduction and therefore, an increase in the specific surface area. Examination of the solubility of the sample milled for 50 h in argon demonstrate that the surface area can only have had a minor effect since this sample had the same solubility in acid as the powder milled 1 h in

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100 90 80 70
water 0.1M HCl

% mass loss

60 50 40 30 20 10 0 0 10 20 30 40 50
100 80

% mass loss

60 40 20 0 0 1 2 3 4 5 6 7 8

air argon

leaching time / h

milling time / h
Fig. 3. Mass loss of milled powders after 24 h leaching in water and 0.1 M HCl. Inset is the mass loss as a function of milling time for the sample milled for 50 h in oxygen.

oxygen had in water. The beneficial effect of oxygen in the system can be gained from the solubility of the powder milled for 50 h in air which was between that of the powder milled in argon and that of the sample milled 1 h in oxygen. Milling for more than 20 h resulted in a 4% increase in acid solubility but 13% increase in water solubility, clearly the longer milling time resulted in conversion of acid soluble to water soluble. Inset in Fig. 3 is the effect of leaching time on the solubility in acid of the sample milled for 50 h in oxygen. Clearly, the 24 h leach time used is substantially greater than needed with dissolution of all soluble material evident within 15 min. The rapid solubility of the products is of importance in any process, the leaching tanks could be extremely small since the required residence time for leaching is very short compared with most chalcopyrite leaching processes where residence times of hours or days are more typical. Fig. 4 shows the molar ratio of copper to iron as a function of milling time in oxygen. From the initial composition of the chalcopyrite a unity ratio of copper and iron would be expected if it dissolved congruently. However, it is clear that milling results in a differential solubility of the two metals indicating that

they were in separate phases resulting from the oxidation of the chalcopyrite. It is clear that the ratio increased with milling time from ~ 0.7 after 1 h to ~ 1.7 after 50 h. The data for unmilled powder is subject to the greatest error due to the relatively small extent of dissolution shown in Fig. 3. It is also noticeable that the ratio is greater for water
2.0 1.8

solution Cu/Fe molar ratio

1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 10 20 30 40 50 water 0.1M HCl

time / h
Fig. 4. Molar ratio of copper to iron after 24 h leaching in water and 0.1 M HCl of powders milled for up to 50 h in oxygen.

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than acid, clearly either the copper phase was more soluble in water, or the iron phase was less soluble in water. The latter is more likely given that XRD showed the presence of water and acid soluble CuSO4d H2O and acid soluble Fe2O3. Thus, in the early stages of milling it seems that iron is preferentially solubilised in both water and acid, but as the system became more oxidised either the copper became more soluble or the iron less soluble. Fig. 5 shows the actual copper and iron concentrations in the solutions derived from the leaching experiments in water and acid. In both solutions, the iron is preferentially solubilised for the shorter milling times, however, its solubility is less than the copper for milling times of more than 10 h. Indeed, the iron solubility actually decreased beyond 20 h. This decrease could be explained by the occurrence of the third stage of oxidation to soluble ferric sulphate and insoluble ferric oxide. The constant increase in copper solubility with milling time suggests that oxidation of the water insoluble, copper-containing phase present was occurring up to 50 h. Thus, the greater ratio of copper to iron in the longest milling times is due to increased copper dissolution and a decrease in iron solubility, presumably due to Fe2O3 formation. XRD traces of some acid leach products are shown in Fig. 6. The removal of the soluble products has resulted in the enhancement of the peaks for insoluble phases. This is most obvious for the emergence of
30

chalcopyrite in the residue of the sample milled for 20 h in oxygen when it was apparently absent in the asmilled powder. Peaks for CuS also emerge in the residue of the samples milled for 1, 20 and 50 h in oxygen. Previous work on enargite (Balaz et al., 1999, 2000; Welham, 2001b) has shown the formation of CuS as an intermediate during mechanochemical oxidation. This phase was shown to be insoluble in acid and water, but could be oxidised to soluble CuSO4d 5H2O. The same would appear to be true in this system. The presence of CuS is also evident in the sample milled in air, but not that milled in argon where chalcopyrite was the only phase present. Clearly, the formation of CuS can only be due to an oxidative reaction, such as that outlined by reaction (1). Several other peaks are evident which were previously weak, or absent from, in the unleached powder, the peaks are clearly for insoluble intermediate phases. In the 20 h residue, the peak at ~ 518 is more intense than in the unleached powder and in the 50 h powder was somewhat weaker. No other peaks could be conclusively associated with this peak, the attribution to FeS for this peak and the peak at 358 remains doubtful. Fig. 7 shows a micrograph of the leach residue of the sample milled for 50 h in oxygen. Analysis of the powder showed the presence of elemental sulphur and haematite along with unreacted chalcopyrite. This is in reasonable agreement with the XRD trace in Fig. 6 which showed S and Fe2O3 as major phases, however chalcopyrite could not be found suggesting it was a

Cu

mmol Cu or Fe in solution

25 20

Cu Fe Fe

15 10 5 0 0 10 20 30 40 50 0 10 20 30 40 50

water

0.1M HCl

milling time / h
Fig. 5. Solution concentrations of copper and iron after 24 h leaching of powders milled for up to 50 h in oxygen.

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1hr O2 20h O2

CuFeS2 CuS S Fe2O3

intensity
20

50h O2

50h air

50h Ar

25

30

35

40

45

50

55

60

2 /
Fig. 6. XRD traces after 24 h leaching in 0.1 M HCl of chalcopyrite milled for up to 50 h in oxygen, air and argon.

very minor phase. The haematite particles are around 0.5 Am, similar to the size of particles present after milling for size reduction (Welham and Llewellyn, 1998) suggesting that they were formed directly during milling and not by a dissolutionprecipitation process. The chalcopyrite particle has sharp edges and clear fracture surfaces suggesting it had not undergone the same extent of milling as the majority of the ore, possibly due to dead volume in the mill. On initial examination, the elemental sulphur particle was

rhombohedral with facets and edges clearly visible. However, lengthy exposure to the electron beam has resulted in partial volatilisation and loss of these features. The presence of elemental sulphur was unexpected from the thermodynamic prediction in Fig. 1. It is possible that it was formed as an intermediate in chalcopyrite oxidation since it has been suggested as the reaction hindering surface layer (Burkin, 2001). It was noted on opening the mills that there was the odour of SO2, this too was not predicted from thermodynamics. The odour for the short milling times was greater than for longer milling times indicating SO2 was being consumed. Modelling of the system using SO2 as an oxidant showed that the same product profile was obtained as for oxygen, Fig. 1, with the addition of elemental sulphur. Thus, it is reasonable that the elemental sulphur was the result of the reduction of SO2 by the sulphide minerals in the system, e.g. by reaction (4) which is directly analogous to reaction (1). CuFeS2+2SO2=CuS+FeSO4+2S (4)

Fig. 7. Micrograph of the residue of 24 h leaching in 0.1 M HCl of chalcopyrite milled for 50 h in oxygen.

From these results, it seems that the initial stage of oxidation is to form a soluble iron compound and an insoluble copper compound. The copper to iron ratio

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is less than unity confirming the enhanced solubility of iron over copper. This scenario can be explained by the occurrence of reaction (1) which forms FeSO4 and CuS. The former phase could not be determined by XRD but the latter is clearly present in the leached residues. The solubilisation of some copper in the early stages indicates that reaction (2) was occurring concomitantly with reaction (1), but at a slower rate. The presence after 1 h of Fe2O3 shows that the oxidation of iron was comparatively facile and that reaction (3) also occurred to some extent within 1 h. Thus, it seems that a separation of the reaction stages is not feasible. As milling time increased, the conversion of CuS to CuSO4 continued as the FeSO4 was oxidised to Fe2O3 (and presumably Fe2(SO4)3, although this was not identified as a product by XRD). Thus, copper solubility increased as iron solubility decreased, leading to the apparently preferential solubility of copper as demonstrated by the copper to iron ratio greater than unity. It should be noted that the tumbling type of ball mill used in this investigation is extremely inefficient at energy transfer and other types of mill (e.g. planetary, vibratory, stirred ball) could be expected to produce the same results in a shorter milling time. A model based on number of ball impacts per gram of powder has indicated a vibratory mill would be around 300 times faster than the mill used here (Welham, 2000). A more exacting model, accounting for differing ball masses and velocities, has indicated that vibratory mills may be ~ 1000 times faster than ball mills (Maurice and Courtney, 1996), a further improvement has been reported for stirred mills (Warris and McCormick, 1997).

the chalcopyrite remaining unreacted. The solubility of the resultant powder increased with milling time until around 80% dissolved. The leaching stage was rapid with dissolution completed within 15 min. The solution ratio of copper to iron increased with milling time, this was due to preferential dissolution of iron at short milling times and by increased copper solubility and formation of insoluble Fe2O3 at longer milling times. The use of a substantially more efficient mill could lead to a commercially viable process by minimising the energy input.

References
Balaz, P., 2000. Extractive Metallurgy of Activated Minerals. Elsevier, Amsterdam. 290 pp. Balaz, P., Kupka, D., Bastl, Z., Achimovicova, M., 1996. Combined chemical and bacterial leaching of ultrafine ground chalcopyrite. Hydrometallurgy 42 (2), 237 244. Balaz, P., Havlik, T., Kammel, R., 1998. Leachability of mechanochemically pretreated chalcopyrite. Transactions of the Indian Institute of Metals 51 (1), 1 6. Balaz, P., Achimovicova, M., Sanchez, M., Kammel, R., 1999. Attrition grinding and leaching of enargite concentrate. Metall 53 (12), 53 66. Balaz, P., Achimovicova, M., Bastl, Z., Ohtani, T., Sanchez, M., 2000. Influence of mechanical activation on the alkaline leaching of enargite concentrate. Hydrometallurgy 54 (23), 205 216. Burkin, A.R., 2001. Chemical Hydrometallurgy, Theory and Principles. Imperial College Press, London. 414 pp. Calka, A., Radlinski, A.P., 1991. Universal high performance ball milling device and its application for mechanical alloying. Materials Science & Engineering. A, Structural Materials: Properties, Microstructure and Processing 134, 1350 1353. Cullity, B.D., 1978. Elements of X-ray Diffraction. Addison-Wesley, Reading, MA. 555 pp. Duval, C., 1963. Inorganic Thermogravimetric Analysis. Elsevier, Amsterdam. 327 pp. Gerlach, J.K., Gock, E.D., Ghosh, S.K., 1973. Activation and leaching of chalcopyrite concentrates by dilute solutions of sulphuric acid. In: Evans, D.J., Shoemaker, R. (Eds.), Proceedings of the International Symposium on Hydrometallurgy. AIME, New York, pp. 87 94. Hackl, R.P., Dreisinger, D.B., Peters, E., King, J.A., 1995. Passivation of chalcopyrite during oxidative leaching in sulfate media. Hydrometallurgy 39 (13), 25 48. Maurice, D., Courtney, T.H., 1996. Milling dynamics: 2. Dynamics of a Spex mill and a one-dimensional mill. Metallurgical and Materials Transactions. A, Physical Metallurgy and Materials Science 27 (7), 1973 1979. Maurice, D., Hawk, J.A., 1998. Ferric chloride leaching of mechanically activated chalcopyrite. Hydrometallurgy 49 (12), 103 123.

5. Conclusions Chalcopyrite can be oxidised to soluble phases by milling for extended periods in oxygen. A thermodynamic assessment indicated oxidation could occur in three stages, oxidation to a soluble iron phase and CuS, oxidation of the CuS to CuSO4 and partial oxidation of the soluble iron phase to Fe2O3. The experimental results demonstrated that the three stages overlapped with all three stages occurring within the first hour of milling despite a significant fraction of

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C.J. Agnew, N.J. Welham / Int. J. Miner. Process. 77 (2005) 208216 Welham, N.J., 1997. The effect of extended milling on minerals. CIM Bulletin 90 (1007), 64 68. Welham, N.J., 2000. A novel route to micronised tungsten carbide. Journal of the American Institute of Chemical Engineers 46 (1), 68 71. Welham, N.J., 2001a. Ambient temperature oxidation of enargite (Cu3AsS4). Proceedings of the Australasian Institute of Mining & Metallurgy 306 (1), 79 81. Welham, N.J., 2001b. Mechanochemical processing of enargite (Cu3AsS4). Hydrometallurgy 62 (3), 165 173. Welham, N.J., 2001c. Mechanochemical processing of gold-bearing sulphides. Minerals Engineering 14 (3), 341 347. Welham, N.J., Llewellyn, D.J., 1998. Mechanical enhancement of the dissolution of ilmenite. Minerals Engineering 11 (9), 827 841.

Maurice, D., Hawk, J.A., 1999. Simultaneous autogenous milling and ferric chloride leaching of chalcopyrite. Hydrometallurgy 51 (3), 371 377. Roine, A., 1994. HSC Chemistry for Windows. Outokumpu Research Oy, Pori. Rubio, A., Frutos, F.J.G., 2002. Bioleaching capacity of an extremely thermophilic culture for chalcopyritic materials. Minerals Engineering 15 (9), 689 694 (Sep.). Tkacova, K., 1989. Mechanical Activation of Minerals. Elsevier, Amsterdam. 179 pp. Tkacova, K., Balaz, P., 1996. Reactivity of mechanically activated chalcopyrite. International Journal of Mineral Processing 4445, 197 208. Warris, C.J., McCormick, P.G., 1997. Mechanochemical processing of refractory pyrite. Minerals Engineering 10 (10), 1119 1125.