Experimental Techniques for Investigating Calcium Ferrite Slags at Metallic Copper Saturation and Application to the Systems ‘‘Cu2O’’

-‘‘Fe2O3’’ and ‘‘Cu2O’’-CaO at Metallic Copper Saturation
STANKO NIKOLIC, PETER C. HAYES, and EVGUENI JAK Phase equilibrium studies have been carried out on the systems ‘‘Cu2O’’-FeO-Fe2O3 and ‘‘Cu2O’’-CaO at metallic copper saturation. It has been shown that, using synthetic primary phase materials as substrates to support the liquid slag, equilibration at high temperature is possible without contamination of the samples. Rapid quenching of the liquid has been achieved so that it is retained as an amorphous phase on cooling, even in this silica-free system. Through the use of an improved methodology and electron probe X-ray microanalysis (EPMA), accurate, objective, and repeatable phase equilibrium data can be obtained. Experimental data for the pseudo-binary ‘‘Cu2O’’-‘‘Fe2O3’’ and ‘‘Cu2O’’-CaO systems, at metallic copper saturation, are presented. DOI: 10.1007/s11663-009-9259-6 Ó The Minerals, Metals & Materials Society and ASM International 2009

I.

INTRODUCTION

THE predominant industrial practice for the conversion of copper matte to blister copper involves the use of the semibatch Peirce–Smith converter technology and iron-silicate slags.[1] There are a number of technical, environmental, and economic drivers, including difficulties in fugitive gas capture, materials handling, and the need for ease of control, that have facilitated the development of continuous copper converting processes using calcium ferrite slags (such as the Mitsubishi,[1] Outukumpu,[1] and ISACONVERT* processes[2,3]). Cal*ISACONVERT is a trademark of Xstrata Technology Pty Ltd., Brisbane, Australia.

cium ferrite slags have been selected for use in these continuous processes for a number of reasons: the ability of the liquid phase to contain higher ferric iron concentrations at blister copper saturation conditions, lower slag volume, lower copper losses, greater fluidity, and more efficient impurity removal from the molten copper, when compared to iron silicate slags.[1,4–6] The phase chemistry of these calcium ferrite slags is yet to be fully and accurately characterized.
STANKO NIKOLIC, formerly Postdoctoral Graduate, PYROSEARCH—Pyrometallurgical Research Centre, The School of Engineering, The University of Queensland, is Metallurgical Engineer, Xstrata Technology, Brisbane, QLD, 4000, Australia. Contact e-mail: stanko.nikolic@uqconnect.edu.au PETER C. HAYES, Xstrata Chair of Metallurgy, and EVGUENI JAK, Centre Director, are with the PYROSEARCH—Pyrometallurgical Research Centre, The School of Engineering, The University of Queensland, Brisbane, QLD, 4072, Australia. Manuscript submitted May 5, 2008. Article published online July 14, 2009.
892—VOLUME 40B, DECEMBER 2009

Research into the phase equilibria of calcium ferrite slags without copper, within the system CaO-FeO-Fe2O3, has been undertaken in air,[7–9] at iron saturation,[10–17] and at intermediate oxygen partial pressures.[6,18] Research into the calcium ferrite system with copper oxide in air was undertaken by Hino et al.[19] To date, however, only two studies of the phase equilibria of calcium ferrite slags at metallic copper saturation have been reported.[20,21] The presence of both slag and copper metal in this system makes it particularly difficult to study because of the aggressive reactions between these phases and conventional ceramic or metallic container materials.[21] Takeda[20] undertook experiments at copper saturation using magnesia crucibles and analyzed the composition of the slag using a wet chemical analysis technique; these results were used to define the liquidus isotherms in the system from 1100 °C to 1400 °C at 50 °C intervals. As a result of the use of magnesia crucibles, magnesia was found to be present within the liquid slag and the solid(s) phases in the samples; the magnesia concentrations were found to be dependent on the temperature and the copper oxide concentration of the slag (average MgO concentration at 1250 °C was reported to be approximately 1.3 wt pct in liquid slag and 10 wt pct in spinel solid). The accuracy of the results reported by Takeda[20] depends on the effectiveness of the physical separation of the quenched liquid slag phase from the metal as well as from the solid crystals—the confirmation of the complete separation may be difficult to ascertain. In the study by Takeda,[20] the oxygen partial pressure of the system was not fixed; however, oxygen potential measurements of the slag phase were undertaken. The method used to undertake these oxygen partial pressure measurements was not stated and the results of individual
METALLURGICAL AND MATERIALS TRANSACTIONS B

5-mm diameter). to remove all air. and concentrations of CaO and MgO in the slag.[20] when it is directly plotted onto the Cu2O-Fe2O3-CaO plane shown in Figure 1. the iron valency at the liquidus. This substrate technique has been previously successfully used by the authors to investigate ferrous calcium silicate slags at copper saturation[27.27] At the lower end of the reaction tube. which does not have a lime-toiron ratio of 0. the VOLUME 40B. the equivalent oxygen partial pressure of the slag was controlled by the condensed phases in the system through the reaction 2CuMetal þ OSlag. Ilyushechkin et al. as reported by Takeda[20] and Ilyushechkin et al. EXPERIMENTAL TECHNIQUE AND PROCEDURE The primary phase substrate. Details of the apparatus are contained in preceding publications. Details of how this methodology has been further improved and modified to enable characterization of calcium ferrite slags are provided in Section II–A–F. temperature. To eliminate the uncertainties associated with crucible contamination. and EPMA analysis techniques selected for the present study were similar to those employed in the previous studies by the authors. although there are differences in the isotherms at high copper oxide concentrations. DECEMBER 2009—893 Fig. therefore. after sealing the furnace with the detachable base.[25–27] This modification eliminates the problem of the seal rupturing due to sections of the substrates breaking off and falling through the seal during equilibration. as reported by Takeda. but rather presented in the form of an empirical equation that related the copper oxide concentration in the slag to the oxygen partial pressure.[21–28] The primary phase material is used to suspend the slag in controlled gas conditions at selected temperatures. Cu2 OSlag There was no experimental measurement or independent control of oxygen partial pressures during this study. 1—Comparison of the liquidus isotherms determined by Ilyushechkin et al. a stainless steel detachable base was constructed for the present study.[22.[25. Particular attention was paid to provide conditions whereby the liquid phase could be retained as an amorphous or glassy phase of uniform composition on cooling. rapid quenching. and objective experimental methodology to enable measurement of the phase equilibria of the ‘‘Cu2O’’-FeO-Fe2O3CaO system at metallic copper saturation using the primary phase substrate support technique proposed by Ilyushechkin et al. Further investigation of the phase equilibria of this system is required to eliminate any possible uncertainties due to the effects of magnesia and to characterize the slag system in the region of direct importance to copper converting. A. METALLURGICAL AND MATERIALS TRANSACTIONS B .28] and considerably extends the range of chemical systems and process conditions that can be accurately characterized. before the sample was raised into the hot zone of the furnace. The liquidus isotherms for the system ‘‘Cu2O’’-FeOFe2O3-CaO at metallic copper saturation at 1200 °C and 1250 °C.. The isotherms presented by Ilyushechkin et al. II. Takeda[20] represented iron oxide as FeOx but only defined the Fe2+/Fe3+ ratio for the slag with a lime-to-iron ratio of 0. The purposes of the present study are as follows: (1) to establish an accurate.[21] are projections onto the Cu2O-Fe2O3-CaO plane and do not give information on the Fe2+/Fe3+ ratios. After equilibration. Takeda[20] stated that the Fe2+/Fe3+ ratio changed with concentration of lime in the slag.23] These experiments were undertaken in a neutral gas atmosphere. Gas . The results of both authors are in general agreement.[21] and (2) to experimentally determine the phase equilibria of this system at metallic copper saturation. This introduces uncertainty in the position of the liquidus. All substrates were suspended in the reaction tube by platinum support wire (0. At the start of the experiments. and therefore.25. The liquid slag and copper are held by surface tension to the outer surface of the substrate.[21] are plotted together for comparison in Figure 1. was not strictly defined.experiments were not given. in a flowing gas stream. argon gas was flushed through the furnace tube for a period of 30 minutes. Experimental Apparatus and Procedure The present studies were undertaken in vertical tube furnaces using recrystallized alumina reaction tubes.25. this replaced the polyethylene-wrap seal previously used. The use of relatively small masses of liquid slag and direct contact of the slag with the quenching media enabled rapid cooling rates to be achieved and the phase assemblages present during equilibration to be retained unchanged on cooling to room temperature. The stainless steel base supports a borosilicate watch glass that also enables the samples to be viewed during equilibration.[21] conducted phase equilibrium experiments on small masses of calcium ferrite slags using both copper droplets levitated in an electromagnetic field and substrates made from the primary phases being investigated. the end of the furnace tube was immersed in a NaClaq-saturated water solution. The slag samples were rapidly quenched into water after equilibration.[21] and Takeda[20] at 1200 °C and 1250 °C in the ‘‘Cu2O’’-‘‘Fe2O3’’-CaO system at metallic copper saturation.. and the compositions of each of the phases present within the samples were measured with electron probe X-ray microanalysis (EPMA) using the techniques previously established by Jak et al. repeatable.

125-mmdiameter Cu wire (99. this dissolution commonly results in breakage of the substrate and failure of the experiment. These pellets were cut to the required shape to fit into the designed substrates and bound into place with approximately 0. B. The cuprite (Cu2O) substrate was made from 99. 2—Example of solid dissolution and precipitation problems associated with starting mixtures not exactly on the liquidus surface in the ‘‘Cu2O’’-‘‘Fe2O3’’-CaO system at copper saturation. starting mixture compositions were selected to minimize the possibility of primary phase substrate dissolution or precipitation. The lower portions of the substrates were. lime (CaO). which was 30 wt pct in excess of the mass of the oxide components of the mixture. mounted in epoxy resin.9 wt pct pure copper foil (0. 2-mm-thick pellet.9 pct pure).detachable base was removed. The two successful designs applied for the spinel substrate were prepared from 99. was formed. and 4CaOÆFeOÆ4Fe2O3 phase (Ca4Fe9O17).9+ wt pct pure CaCO3 powder). The dicalcium ferrite substrate was prepared from a stoichiometric mixture of Fe2O3 powder and precalcined CaO powder that had been pelletized. was identified due to the formation of a Cu-Pt alloy at the contact point between the platinum suspension wire and the Cu2O substrate. microcrystal-free glass phase upon quenching.03 g of 0. and the sample was quenched into the solution. 1-mm-thick pellet. careful planning of the compositions of the mixtures equilibrated in the substrates is essential to maximize the success rate of the experiments. delafossite (Cu2OÆFe2O3 or Cu2Fe2O4). mixtures were made.1-mm thick) that had been folded to specific shapes (schematics of the two substrate designs. to a 15-mm-diameter. Mixture Preparation In these types of experiments. at a pressure of 30 MPa. (2) remain intact for the duration of the equilibration. Fe2O3 powder (99+ wt pct pure). lightly dusted with metallic copper powder. to assist in the reaction between the oxide pellets and the substrate surface.7 pct pure).[21] These mixtures were made from CaO powder (calcined from 99. DECEMBER 2009 . The other substrate supports were made from the sintering of oxide powders.5 wt pct pure iron foil (0. and (3) be easy to handle and manufacture. 894—VOLUME 40B. The problem of substrate precipitation. The cut Cu-foil substrates were oxidized to Cu2O in a stream of air at 1075 °C for 30 minutes followed by another 30 minutes at 1125 °C. and metallic copper powder (99. These pellets were cut into tear-drop shapes (refer to Figure 3(b)) to METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. for these substrate experiments. cuprite (Cu2O). The iron foil was equilibrated for 1 hour at 1250 °C (1523 K) at a fixed oxygen partial pressure of 10À6 atm to ensure magnetite. before the mixtures were bound into place. and polished for metallographic examination and microanalysis. Appropriate proportions of these powders were first mixed in an agate mortar and pestle for 30 minutes and then pelletized using a pressure of 40 MPa to produce a 15-mm-diameter.1-mm thick) that had been cut to the flat substrate design (refer to Figure 3(c)). It is particularly important to maintain an adequate liquid slag layer on the substrate surface. Cu2O powder (made from 0. The samples were then thoroughly washed in water before being dried. the delafossite (Cu2Fe2O4) primary phase fields. are shown in Figures 3(a) and (c). monocalcium ferrite (CaOÆFe2O3 or CaFe2O4). in each case. the liquid slag phase will dissolve the substrate as equilibration proceeds.5 pct pure) and approximately 0. dicalcium ferrite (2CaOÆFe2O3 or Ca2Fe2O5). close to the stoichiometric composition of Fe3O4. facilitating rapid quenching of the melt while avoiding breakage of the substrate. Considerable efforts were put into the development of the substrate designs for the successful experimental investigation of this system that would: (1) retain a layer of liquid slag on its surface to allow for rapid quenching. This was sufficient time to completely oxidize the entire sample to Cu2O. and then ground in an agate mortar and pestle). Substrate Preparation The following major primary phase fields have been identified[20.21] in the calcium ferrite system at copper saturation in the regions relevant to copper converting: (1) (2) (3) (4) (5) (6) (7) spinel solid solution (FeOÆFe2O3 or Fe3O4). If a mixture is prepared that is not saturated with the primary phase.9 pct pure Cu foil that had been oxidized in air at 1075 °C for 30 minutes. C. For a given reaction temperature. close to the liquidus defined by the work of Ilyushechkin et al. through precipitation. indicated in Figure 2. To maximize the success rate of experiments conducted in the present study. An upper experimental temperature limit of 1160 °C. as indicated in Figure 2.003 g of 0. named finger and flat.1-mm-thick 99.065-mm-diameter Fe wire (99. exists if a mixture is prepared at a composition that is well inside the two-phase region. then at 1125 °C for 30 minutes. respectively). this drastically reduces the probability of the formation of a well-quenched. The precipitation of the primary phase results in a reduction in the thickness of the liquid slag layer that is suspended from the substrate. These spinel substrates were used for the investigation of both the spinel and.

for the cuprite substrate sample. Gas . marked in gray. The Duncumb–Philibert ZAF correction procedure supplied with the JEOL 8200L probe was applied..999 pct pure). (SPI) Supplies. maximize the available surface area at the base of the sample used for suspending slag while minimizing the mass of the substrate and thereby maximizing the cooling rate of the slag on quenching.[22] A special targeted study was conducted to investigate whether the use of a sulfide standard. CA) that were used in the EPMA measurements were as follows: wollastonite (CaSiO3) for Si and Ca. influenced the accuracy of the EPMA measurements. Tokyo. Slag samples with a range of Cu2O concentrations within 8 to METALLURGICAL AND MATERIALS TRANSACTIONS B . were measured using both the sulfide chalcopyrite standard and a specially purchased Cu2O standard (Structure Probe Inc. Cu2 OSlag The samples were premelted at 10 °C above the equilibration temperature for 30 minutes. the samples VOLUME 40B. Sample Examination Analysis of the compositions of the various phases within the quenched samples was undertaken using a JEOL** 8200L electron microprobe analyzer with **JEOL is a trademark of Japan Electron Optics Ltd.Fig. The standards (Charles M. PA). West Chester. the composition is represented as a projection onto the Cu2O-Fe2O3-CaO plane. the equivalent oxygen partial pressure of the slag was controlled by the condensed phases in the system through the reaction 2CuMetal þ OSlag. chalcopyrite (CuFeS2) for Cu. An accelerating voltage of 15 kV and a probe current of 15 nA were used. and hematite (Fe2O3) for Fe. by maintaining constant Cu/Fe/Ca ratios. Stanford. In effect.5 L/min stream of ultra-high-purity argon gas (99.5 wt pct for all the measured elements for all of the measured compositions. and (c) schematic of flat design. as opposed to an oxide standard to measure copper oxide in slag. 80 wt pct and with CaO concentrations within 5 to 25 wt pct. Taylor. and therefore. all of the copper was recalculated to the cuprous state Cu+ and all of the iron was recalculated to the ferric state Fe3+. this technique does not provide information on the proportion of cations of the same element having different valencies. has been adjusted to enable the metallic copper and copper oxide phases to be clearly distinguished. for representation purposes. (b) schematic of tear-drop design. The measurement of phases by EPMA provides information only on the total concentration of a particular element. The scanning electron microscopy (SEM) backscattered electron image micrographs of the cross sections of typical well-quenched samples of all substrate designs are given in Figure 4 (refer to high-magnification inserts) demonstrating that a well-quenched slag could be obtained using the preceding techniques. Note that the image contrast in Figure 4(d) and (e). In the slags. DECEMBER 2009—895 wavelength dispersive detectors. This effectively created a closed system for the equilibration experiments. with the remaining balance being Fe2O3. while copper is present as both Cu2+ and Cu+. Equilibration of Calcium Ferrite Slags in a Neutral Atmosphere of Argon Premelting and equilibration of experiments during the present study were conducted in a 0. The compositions were measured to an accuracy of ±1 wt pct. Figure 5 illustrates how the individual actual slag compositions. The difference between the EPMA measurements using the two different copper standards was less than 0. E. The tear-drop cut pellets were then sintered at 1250 °C in air for 6 to 24 hours to obtain the desired strength. Since the concentrations of the various cations were not measured in the present study. iron is always present as both Fe2+ and Fe3+. 3—Substrate experimental designs: (a) schematic of finger design. are projected onto the Cu2O-Fe2O3-CaO plane. D.

It was therefore necessary to establish an objective and METALLURGICAL AND MATERIALS TRANSACTIONS B Fig. Equilibration times of 30 minutes and 2 hours were tested for the spinel substrate at 1150 °C. DECEMBER 2009 .Fig. However. 5—Projection of slag compositions in the system Cu-Fe-Ca-O onto the Cu2O-Fe2O3-CaO plane. (c) dicalcium ferrite–tear drop substrate. (b) spinel-flat substrate. this is exceedingly difficult to attain in the silica-free calcium ferrite slag system due to the very low viscosity of the slag. 4—SEM micrographs of samples showing well-quenched slag in equilibrium with metallic copper and the primary phase(s): (a) spinel-finger substrate. as listed in Table I. 896—VOLUME 40B. The intention of the rapid quenching technique is to retain the liquid as a glassy or amorphous phase of uniform composition. which allows it to crystallize readily on cooling. It was determined that 30 minutes was an adequate experimental time for these pseudo-binary ‘‘Cu2O’’-‘‘Fe2O3’’ and ‘‘Cu2O’’-CaO systems at copper saturation to reach equilibrium with the final composition of the solid and liquid phases within 0. Analysis of the Quenched Slags in the Calcium Ferrite System at Copper Saturation A critical factor in all phase equilibrium studies is the accurate measurement of the composition of the liquid phase. and (d) and (e) cuprite substrate with dual solid phase saturation with dicalcium ferrite. were then cooled at a rate of 2 °C/min to a final equilibration temperature.5 wt pct of the 2-hour equilibrated sample. F.

0 0. Wt Pct Cu2O 0. Number 1 2 Effect of Equilibration Time in the ‘‘Cu2O’’-‘‘Fe2O3’’ System at Metallic Cu Saturation Equilibration 0.1 St. The results of EPMA measurements.6 0.3 Fig.9 47. within the first 15 lm from the quenched surface at the liquid/quenching medium interface.Table I. Wt Pct CaO 10.9 1.9 11.0 3. the rate of extraction of heat from the liquid phase decreases with increasing distance from the quench surface. all of the results that are reported.2 49.0 0.9 47.0 40. of a typical Cu-Ca-Fe-O slag sample.8 41. Wt Pct Fe2O3 47. The average and standard deviation values in Table II were METALLURGICAL AND MATERIALS TRANSACTIONS B obtained by considering 20 analyzed points along each line in Figure 6(a). reflected in the standard deviations.4 1.0 St.2 2. 6—Effect of distance from the well-quenched surface of the slag influences the standard deviation of a data set of 20 analysis points in Cu-Ca-Fe-O slags. DECEMBER 2009—897 .1 94.0 0.1 11. have been subjected to the following criteria to ensure accurate.2 11.2 48.2 75.3 49. Dev.8 2. (1) Analysis was only undertaken if copper metal droplets were observed in close proximity to the measured area. accurate method for analysis of these slags with EPMA.5 0. analysis of a selected slag region was only undertaken if the quenched liquid was in equilibrium with a metallic copper droplet and the primary phase(s) as viewed under SEM. On cooling. increase. show that as the measurement distance from the quenched surface is increased.9 St.2 11. and objective measurements. Effect of Distance from Well-Quenched Surface on the Average Values and Standard Deviations in Composition for the Sample Shown in Figure 6 Distance (lm) 5 10 15 20 25 30 Avg. Wt Pct Cu2O 41. For accurate EPMA measurement of slag compositions. Dev. First. It can be seen that the standard deviations increase for all components with increasing distance above 15 lm from the surface.6 11.5 39.6 93.4 6.6 Avg. Wt Pct CaO 0.5 1.0 Cu2O (Wt Pct) 75.0 Fe2O3 (Wt Pct) 24. given in Table II.3 0. At best.6 40.0 Temperature 1150 °C 1150 °C Table II. (2) Analysis was only undertaken on the slag that was well quenched. the uncertainties. the standard deviation in the near surface region is within ±1 wt pct.2 0. the take-off area of the electron beam should be contained within one phase.4 0.8 24. repeatable. within this present series of articles investigating calcium ferrite slags at copper saturation.2 39.9 6. Therefore.1 3.6 1. VOLUME 40B.7 Avg. shown in Figure 6(a). Wt Pct Fe2O3 0.1 1.4 1. there will be a transition from an amorphous slag to a fully crystalline material at some distance from the free surface. Dev.5 h 2h Phase liquid spinel liquid spinel CaO (Wt Pct) 0.

5 h 0.0 96. Fig.5 h Phase liquid delafossite liquid cuprite liquid spinel liquid spinel lime cuprite liquid cuprite CaO (Wt Pct) Cu2O (Wt Pct) Fe2O3 (Wt Pct) Temperature 1140 °C 1150 °C 1200 °C 1250 °C 1150 °C 1160 °C 0. only the solidus measurement for 1250 °C is reported in Table III.5 2. as defined by Takeda.7 0.2 0.3 0.(3) The data set must contain 20 or more analyzed points measured equidistance from the quenched surface.0 97. DECEMBER 2009 METALLURGICAL AND MATERIALS TRANSACTIONS B . (4) The data set must have a standard deviation less than 1 wt pct.0 898—VOLUME 40B. Table III. Experiments targeting the liquidus composition at 1250 °C on the spinel liquidus of the ‘‘Cu2O’’’’Fe2O3’’ pseudo-binary at copper saturation were unsuccessful.0 46. is used for the construction of the spinel liquidus in Figure 7.0 4.1 94. Fig. are represented as dashed lines on both figures.8 0. Number 3 4 5 6 7 8 Phase Compositions in ‘‘Cu2O’’-‘‘Fe2O3’’ and ‘‘Cu2O’’-CaO Systems at Metallic Cu Saturation Equilibration 1h 0.9 liquidus not measured due to poor quenching 0.0 83. and 1250 °C.0 99. 1200 °C.[21] using the same technique as the present study.3 99. This information was used to construct the pseudo-binary phase diagrams for the ‘‘Cu2O’’-‘‘Fe2O3’’ and ‘‘Cu2O’’-CaO systems at copper metal saturation presented in Figure 7 and Figure 8.3 0. 1150 °C. RESULTS AND DISCUSSION A. The experimental liquid compositions measured in the present study are shown as filled squares in Figure 7 and Figure 8.8 93.5 0. as measured by EPMA.0 6.6 53. and the liquidus. quenching of all of these experiments was exceedingly difficult even with direct contact of the liquid slags with the quenching medium (use of flat substrates).. Tie-lines.0 77. The results of the present study are in agreement with the cuprite liquidus reported by Takeda[20] and for the 1144 °C temperature reported for the peritectic reaction: III. Due to the high copper oxide concentrations in the slag phase. 1160 °C. The compositions of the phases present in the equilibrated samples. which connect the solid compositions to the respective liquid compositions.3 99. 8—Pseudo-binary phase diagram of the ‘‘Cu2O’’-CaO system at metallic copper saturation. Therefore. and the previous liquidus measurement conducted by Ilyushechkin et al.5 h 2h 2h 1.0 5.0 72. Phase Equilibria in the ‘‘Cu2O’’-‘‘Fe2O3’’ and ‘‘Cu2O’’-CaO Systems at Metallic Copper Saturation Experiments in the ‘‘Cu2O’’-‘‘Fe2O3’’ and ‘‘Cu2O’’CaO systems at metallic copper saturation were conducted at 1140 °C.[20] is shown as dotdot-dashed lines in both Figure 7 and Figure 8.7 0. are presented in Table I and Table III.[21] for the spinel liquidus in Figure 7.4 0. respectively.0 0. The previous experimental results of Ilyushechkin et al.5 0.[21] are included as open squares in Figure 7.6 22.7 0. 7—Pseudo-binary phase diagram of the ‘‘Cu2O’’-‘‘Fe2O3’’ system at metallic copper saturation.5 16. while the full lines define the experimental liquidus and solidus of the spinel primary phase field in Figure 7.2 27. The experimental results of the present study are in general agreement with the previous results of Ilyushechkin et al.0 0.

as that study was undertaken using MgO crucibles. and Philip Arthur (Xstrata Technology) for useful discussions on this topic. M. 12 (4).S. pp. 1970. Mater. 9. 203–15. Hayes. C. Hayes. Jak: Metall. Jak: Metall. San Diego. Jak: Metall. 85–104. United Kingdom. TMS.K. Symp. 35B. IMM J. Nikolic. compared to the present study. Am. 1976. Trans. Hayes: VII Int. vol. pp. 19. Schuermann and G. in the present study. 327–31. pp. Takeda[20] reports a 3. F. 22.J. Kongoli and R. Yazawa. B. Scheel: Arch. Kim Sewell. Chipman: Trans. 3. IV. No new data are available on the liquidus in the CaO primary phase field. Mr. Edwards and G. S. Eisenhuettenwes. Johannesburg.. vol. A. A. Biswas: Extractive Metallurgy of Copper. 1974. PA. E. vol.J. 1989. vol. TMS-CIM. Ron Rasch. A. 791–804.C. 12. 28. Fleischer: Arch.. ACKNOWLEDGMENTS The authors thank the following for their assistance in this project: Mr. Yazawa: Shigen to Sozai.. 337–42. vol. and E. Vahed. K. and Dr. vol. 20. Molten Slags Fluxes and Salts.B. Abbattista.E. P. Jahanshahi: Australian Patents C22B 015/06 and C22B 009/05.Spinel þ Liquid þ Cu metal<¼>Delafossite þ Liquid þ Cu metal It was not possible. W. 328–33. Conf. CA.J. S. 1982. 200–09. Jpn. F. Nikolic. There are differences between the results of the present study and those of Takeda[20] with respect to the position of the spinel liquidus in this pseudo-binary system. Takeda[20] reported the eutectic temperature as 1145 °C. 27. Trans. Thermo and Physiochemical Principles. pp. 615–17.. Montreal. Ceram. Martin Bakker. pp. 2. 267–69. San Diego.C. Snow: J. 1961. 2008. pp. and objective phase equilibrium measurements of this system. 5. 2006.C. pp. Experimental results have been presented for the pseudo-binary systems ‘‘Cu2O’’-’’Fe2O3’’ and ‘‘Cu2O’’CaO at metallic copper saturation. vol. J.. A. pp. 751–56. 2003. Graeme Goodall. 105. Schlesinger. pp. 1975. Stradtmann: Arch. pp. vol. James Edwards. Capetown. Jak and P. The results of the present study indicate that the eutectic temperature for this system is between 1150 °C and 1160 °C. Yazawa and Y. and E. and R. Ilyushechkin. As compositional data were not reported in the study of Takeda. Soc. Nikolic. Nikolic. Book 2: The Carlos Diaz Symp. pp. 13. 37. but it was shown to occur in between 1140 °C and 1150 °C. P. but it would have larger solubility in the spinel phase. Jak: Sohn Int. and J. Met.Y.. Bill Errington. the University of Queensland..F. Eisenhuettenwes. Adrian Riding. and M. S. R. W.. vol. Phillips and A. 23. 2004. and E. B. and H. 25. 4. 47. Eisenforsch. Kongoli. Metall. and A. Kaiser-Wilhelm Inst. Hayes. H.S. Q. 1995. At 1150 °C. has been refined and applied in the present study to experimentally define the phase equilibria of the ‘‘Cu2O’’-‘‘Fe2O3’’-CaO system at copper saturation. pp. 1. 4th ed. pp. 195–245. Refract. Symp. 189–99. 23. and A. 155–71. Obst and J. Y. pp. P. vol. B. 1966. Morris: Metall. 2008. and Ms. 1958. and A.. vol. pp. 23.. Takeda: Trans. 2006. 24. Newman. repeatable. P. DECEMBER 2009—899 The rapid quenching primary phase substrate support technique. eds. E. F. 2004. Allen and R. Q. pp. 39B. vol. pp. vol. SAIMM. K. 2007. Centre for Microscopy and Microanalysis (CMM). Schuermann and G. vol. Goerl. for their assistance and work at the Pyrometallurgy Research Centre METALLURGICAL AND MATERIALS TRANSACTIONS B . 2004. E. S. VOLUME 40B. on Pyrometallurgy. vol. pp. 10. Hayes. vol. Mr. Mater. vol. vol. P.. Takeda. pp. The MgO would not have a large solubility in the liquid slag at these temperatures. D. B. Fischer and H.G. Soc. 1976. 40. W. 7. Oxford. but experiments conducted by the present study at 1150 °C identified the presence of only lime and cuprite solid crystals in equilibrium with metallic copper. 315–20. 47. I. There are differences between the results of the present study and that of Takeda[20] regarding the eutectic temperature of the system. 2003. Metall. Edwards and S. CONCLUSIONS (PYROSEARCH) within the University of Queensland. pp. Jak: Metall.R. Trans. 3193–201. The apparently higher spinel liquidus temperature defined by Takeda[20] may be the result of the presence of MgO in the samples. Kraume: Arch. 212. Yazawa: Can.C. TMS-AIME.5 wt pct higher and at 1200 °C a 6 wt pct higher concentration of Cu2O within the liquid phase.[20] the effect of the MgO on the spinel liquidus cannot be quantified. vol. and Y. Hayes. pp. 21. 39B. Toronto. F. Baojun Zhao. The experimental analysis methodology was developed defining the strict measures required to ensure accurate. Inst. Y. Materials Processing Fundamentals and New Technologies. Eisenhuettenwes.. Takeda. and E. 15.. vol. M. Mackey.H. 1969. Mater. vol. 210–17. B. Davenport.. with EPMA analysis. vol. 129–34. Eisenhuettenwes.C. Bishop. vol. 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Hayes. King. Timucin and A. pp. Henao. TMS. 297–305. Jak.[20] The results are in agreement for the position of the cuprite isotherm at 1160 °C. I. 8. 39B. 441–51. Scheel: Arch. Yamauchi. W. Hautes Temp. 6.L. 16. 41. 11.. 2002. J.J. Hino. and A. 39B. P.C.G.M. 185–92. J. pp. 45. 1. Oelsen and H. Warner. pp. Warrendale. Muan: J. and E. Mater. Reddy. 1941. 179–88.. 1. Trans. Burdese. A. 1958. 305–13.. to identify the exact temperature of this reaction. 19. eds. N. Warczok. Nakazawa. 1–8.

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