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 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 PeirceSmith converter technology and iron-silicate slags.[1] There are a number of technical, environmental, and economic drivers, including diculties 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 uidity, and more ecient impurity removal from the molten copper, when compared to iron silicate slags.[1,46] The phase chemistry of these calcium ferrite slags is yet to be fully and accurately characterized.
STANKO NIKOLIC, formerly Postdoctoral Graduate, PYROSEARCHPyrometallurgical 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 PYROSEARCHPyrometallurgical 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.
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Research into the phase equilibria of calcium ferrite slags without copper, within the system CaO-FeO-Fe2O3, has been undertaken in air,[79] at iron saturation,[1017] 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 dicult 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 dene 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 eectiveness of the physical separation of the quenched liquid slag phase from the metal as well as from the solid crystalsthe conrmation of the complete separation may be dicult to ascertain. In the study by Takeda,[20] the oxygen partial pressure of the system was not xed; 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
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experiments were not given, but rather presented in the form of an empirical equation that related the copper oxide concentration in the slag to the oxygen partial pressure, temperature, and concentrations of CaO and MgO in the slag. To eliminate the uncertainties associated with crucible contamination, Ilyushechkin et al.[21] conducted phase equilibrium experiments on small masses of calcium ferrite slags using both copper droplets levitated in an electromagnetic eld and substrates made from the primary phases being investigated. The slag samples were rapidly quenched into water after equilibration, 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.[22,23] These experiments were undertaken in a neutral gas atmosphere, and therefore, the equivalent oxygen partial pressure of the slag was controlled by the condensed phases in the system through the reaction 2CuMetal OSlag; Gas , Cu2 OSlag There was no experimental measurement or independent control of oxygen partial pressures during this study. The liquidus isotherms for the system Cu2O-FeOFe2O3-CaO at metallic copper saturation at 1200 C and 1250 C, as reported by Takeda[20] and Ilyushechkin et al.,[21] are plotted together for comparison in Figure 1. The isotherms presented by Ilyushechkin et al.[21] are projections onto the Cu2O-Fe2O3-CaO plane and do not give information on the Fe2+/Fe3+ ratios. Takeda[20] represented iron oxide as FeOx but only dened the Fe2+/Fe3+ ratio for the slag with a lime-to-iron ratio of 0.25. Takeda[20] stated that the Fe2+/Fe3+ ratio changed with concentration of lime in the slag; therefore, the iron valency at the liquidus, which does not have a lime-toiron ratio of 0.25, was not strictly dened. This introduces uncertainty in the position of the liquidus, as reported by Takeda,[20] when it is directly plotted onto the Cu2O-Fe2O3-CaO plane shown in Figure 1. The results of both authors are in general agreement, although there are dierences in the isotherms at high copper oxide concentrations. Further investigation of the phase equilibria of this system is required to eliminate any possible uncertainties due to the eects of magnesia and to characterize the slag system in the region of direct importance to copper converting.

The purposes of the present study are as follows: (1) to establish an accurate, repeatable, 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.;[21] and (2) to experimentally determine the phase equilibria of this system at metallic copper saturation.

II.

EXPERIMENTAL TECHNIQUE AND PROCEDURE

The primary phase substrate, rapid quenching, and EPMA analysis techniques selected for the present study were similar to those employed in the previous studies by the authors.[2128] The primary phase material is used to suspend the slag in controlled gas conditions at selected temperatures. The liquid slag and copper are held by surface tension to the outer surface of the substrate. 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. 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. This substrate technique has been previously successfully used by the authors to investigate ferrous calcium silicate slags at copper saturation[27,28] and considerably extends the range of chemical systems and process conditions that can be accurately characterized. Details of how this methodology has been further improved and modied to enable characterization of calcium ferrite slags are provided in Section IIAF. A. Experimental Apparatus and Procedure The present studies were undertaken in vertical tube furnaces using recrystallized alumina reaction tubes, in a owing gas stream. Details of the apparatus are contained in preceding publications.[25,27] At the lower end of the reaction tube, a stainless steel detachable base was constructed for the present study; this replaced the polyethylene-wrap seal previously used.[2527] This modication eliminates the problem of the seal rupturing due to sections of the substrates breaking o and falling through the seal during equilibration. The stainless steel base supports a borosilicate watch glass that also enables the samples to be viewed during equilibration. All substrates were suspended in the reaction tube by platinum support wire (0.5-mm diameter). At the start of the experiments, after sealing the furnace with the detachable base, argon gas was ushed through the furnace tube for a period of 30 minutes, to remove all air, before the sample was raised into the hot zone of the furnace. After equilibration, the end of the furnace tube was immersed in a NaClaq-saturated water solution, the
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Fig. 1Comparison of the liquidus isotherms determined by Ilyushechkin et al.[21] and Takeda[20] at 1200 C and 1250 C in the Cu2O-Fe2O3-CaO system at metallic copper saturation.
METALLURGICAL AND MATERIALS TRANSACTIONS B

detachable base was removed, and the sample was quenched into the solution. The samples were then thoroughly washed in water before being dried, mounted in epoxy resin, and polished for metallographic examination and microanalysis. B. Mixture Preparation In these types of experiments, careful planning of the compositions of the mixtures equilibrated in the substrates is essential to maximize the success rate of the experiments. It is particularly important to maintain an adequate liquid slag layer on the substrate surface, facilitating rapid quenching of the melt while avoiding breakage of the substrate. For a given reaction temperature, starting mixture compositions were selected to minimize the possibility of primary phase substrate dissolution or precipitation, as indicated in Figure 2. The problem of substrate precipitation, indicated in Figure 2, exists if a mixture is prepared at a composition that is well inside the two-phase region. The precipitation of the primary phase results in a reduction in the thickness of the liquid slag layer that is suspended from the substrate; this drastically reduces the probability of the formation of a well-quenched, microcrystal-free glass phase upon quenching. If a mixture is prepared that is not saturated with the primary phase, the liquid slag phase will dissolve the substrate as equilibration proceeds; this dissolution commonly results in breakage of the substrate and failure of the experiment. To maximize the success rate of experiments conducted in the present study, mixtures were made, close to the liquidus dened by the work of Ilyushechkin et al.[21] These mixtures were made from CaO powder (calcined from 99.9+ wt pct pure CaCO3 powder), Fe2O3 powder (99+ wt pct pure), Cu2O powder (made from 0.1-mm-thick 99.9 pct pure Cu foil that had been oxidized in air at 1075 C for 30 minutes, then at 1125 C for 30 minutes, and then ground in an agate mortar and pestle), and metallic copper powder (99.7 pct pure), which was 30 wt pct in excess of the mass of the oxide components of the mixture. Appropriate proportions of these powders were rst 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 pellet.

These pellets were cut to the required shape to t into the designed substrates and bound into place with approximately 0.003 g of 0.065-mm-diameter Fe wire (99.5 pct pure) and approximately 0.03 g of 0.125-mmdiameter Cu wire (99.9 pct pure). The lower portions of the substrates were, in each case, lightly dusted with metallic copper powder, to assist in the reaction between the oxide pellets and the substrate surface, before the mixtures were bound into place. C. Substrate Preparation The following major primary phase elds have been identied[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 (FeOFe2O3 or Fe3O4), dicalcium ferrite (2CaOFe2O3 or Ca2Fe2O5), delafossite (Cu2OFe2O3 or Cu2Fe2O4), monocalcium ferrite (CaOFe2O3 or CaFe2O4), cuprite (Cu2O), lime (CaO), and 4CaOFeO4Fe2O3 phase (Ca4Fe9O17).

Considerable eorts 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, (2) remain intact for the duration of the equilibration, and (3) be easy to handle and manufacture. The two successful designs applied for the spinel substrate were prepared from 99.5 wt pct pure iron foil (0.1-mm thick) that had been folded to specic shapes (schematics of the two substrate designs, named nger and at, are shown in Figures 3(a) and (c), respectively). The iron foil was equilibrated for 1 hour at 1250 C (1523 K) at a xed oxygen partial pressure of 106 atm to ensure magnetite, close to the stoichiometric composition of Fe3O4, was formed. These spinel substrates were used for the investigation of both the spinel and, through precipitation, the delafossite (Cu2Fe2O4) primary phase elds. The cuprite (Cu2O) substrate was made from 99.9 wt pct pure copper foil (0.1-mm thick) that had been cut to the at substrate design (refer to Figure 3(c)). 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. This was sucient time to completely oxidize the entire sample to Cu2O. An upper experimental temperature limit of 1160 C, for these substrate experiments, was identied due to the formation of a Cu-Pt alloy at the contact point between the platinum suspension wire and the Cu2O substrate. The other substrate supports were made from the sintering of oxide powders. The dicalcium ferrite substrate was prepared from a stoichiometric mixture of Fe2O3 powder and precalcined CaO powder that had been pelletized, at a pressure of 30 MPa, to a 15-mm-diameter, 2-mm-thick pellet. These pellets were cut into tear-drop shapes (refer to Figure 3(b)) to
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Fig. 2Example 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.
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Fig. 3Substrate experimental designs: (a) schematic of nger design, (b) schematic of tear-drop design, and (c) schematic of at design.

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. The tear-drop cut pellets were then sintered at 1250 C in air for 6 to 24 hours to obtain the desired strength. 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-magnication 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), for the cuprite substrate sample, has been adjusted to enable the metallic copper and copper oxide phases to be clearly distinguished. D. 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., Tokyo.

80 wt pct and with CaO concentrations within 5 to 25 wt pct, with the remaining balance being Fe2O3, were measured using both the sulde chalcopyrite standard and a specially purchased Cu2O standard (Structure Probe Inc. (SPI) Supplies, West Chester, PA). The dierence between the EPMA measurements using the two dierent copper standards was less than 0.5 wt pct for all the measured elements for all of the measured compositions. The measurement of phases by EPMA provides information only on the total concentration of a particular element; this technique does not provide information on the proportion of cations of the same element having dierent valencies. In the slags, iron is always present as both Fe2+ and Fe3+, while copper is present as both Cu2+ and Cu+. Since the concentrations of the various cations were not measured in the present study, for representation purposes, all of the copper was recalculated to the cuprous state Cu+ and all of the iron was recalculated to the ferric state Fe3+. In eect, the composition is represented as a projection onto the Cu2O-Fe2O3-CaO plane. Figure 5 illustrates how the individual actual slag compositions, marked in gray, are projected onto the Cu2O-Fe2O3-CaO plane, by maintaining constant Cu/Fe/Ca ratios. E. Equilibration of Calcium Ferrite Slags in a Neutral Atmosphere of Argon Premelting and equilibration of experiments during the present study were conducted in a 0.5 L/min stream of ultra-high-purity argon gas (99.999 pct pure). This eectively created a closed system for the equilibration experiments, and therefore, the equivalent oxygen partial pressure of the slag was controlled by the condensed phases in the system through the reaction 2CuMetal OSlag; Gas , Cu2 OSlag The samples were premelted at 10 C above the equilibration temperature for 30 minutes; the samples
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wavelength dispersive detectors. An accelerating voltage of 15 kV and a probe current of 15 nA were used. The DuncumbPhilibert ZAF correction procedure supplied with the JEOL 8200L probe was applied. The standards (Charles M. Taylor, Stanford, CA) that were used in the EPMA measurements were as follows: wollastonite (CaSiO3) for Si and Ca, chalcopyrite (CuFeS2) for Cu, and hematite (Fe2O3) for Fe. The compositions were measured to an accuracy of 1 wt pct.[22] A special targeted study was conducted to investigate whether the use of a sulde standard, as opposed to an oxide standard to measure copper oxide in slag, inuenced the accuracy of the EPMA measurements. Slag samples with a range of Cu2O concentrations within 8 to
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Fig. 4SEM micrographs of samples showing well-quenched slag in equilibrium with metallic copper and the primary phase(s): (a) spinel-nger substrate, (b) spinel-at substrate, (c) dicalcium ferritetear drop substrate, 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 nal equilibration temperature. Equilibration times of 30 minutes and 2 hours were tested for the spinel substrate at 1150 C, as listed in Table I. 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 nal composition of the solid and liquid phases within 0.5 wt pct of the 2-hour equilibrated sample. F. 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. The intention of the rapid quenching technique is to retain the liquid as a glassy or amorphous phase of uniform composition. However, this is exceedingly dicult to attain in the silica-free calcium ferrite slag system due to the very low viscosity of the slag, which allows it to crystallize readily on cooling. It was therefore necessary to establish an objective and
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Fig. 5Projection of slag compositions in the system Cu-Fe-Ca-O onto the Cu2O-Fe2O3-CaO plane.
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Table I. Number 1 2

Eect of Equilibration Time in the Cu2O-Fe2O3 System at Metallic Cu Saturation Equilibration 0.5 h 2h Phase liquid spinel liquid spinel CaO (Wt Pct) 0.0 0.0 0.0 0.0 Cu2O (Wt Pct) 75.4 6.2 75.9 6.0 Fe2O3 (Wt Pct) 24.6 93.8 24.1 94.0

Temperature 1150 C 1150 C

Table II. Eect 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 CaO 10.9 11.2 11.1 11.2 11.6 11.9 St. Dev. Wt Pct CaO 0.2 0.3 0.4 0.9 1.4 1.7 Avg. Wt Pct Cu2O 41.0 40.8 41.6 40.5 39.2 39.1 St. Dev. Wt Pct Cu2O 0.6 0.6 1.2 2.1 3.0 3.6 Avg. Wt Pct Fe2O3 47.9 47.9 47.2 48.3 49.2 49.0 St. Dev. Wt Pct Fe2O3 0.5 0.4 1.1 1.5 1.8 2.3

Fig. 6Eect of distance from the well-quenched surface of the slag inuences the standard deviation of a data set of 20 analysis points in Cu-Ca-Fe-O slags.

accurate method for analysis of these slags with EPMA. First, 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, the rate of extraction of heat from the liquid phase decreases with increasing distance from the quench surface. At best, there will be a transition from an amorphous slag to a fully crystalline material at some distance from the free surface. For accurate EPMA measurement of slag compositions, the take-o area of the electron beam should be contained within one phase. The results of EPMA measurements, given in Table II, of a typical Cu-Ca-Fe-O slag sample, shown in Figure 6(a), show that as the measurement distance from the quenched surface is increased, the uncertainties, reected in the standard deviations, increase. The average and standard deviation values in Table II were
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obtained by considering 20 analyzed points along each line in Figure 6(a). It can be seen that the standard deviations increase for all components with increasing distance above 15 lm from the surface; the standard deviation in the near surface region is within 1 wt pct. Therefore, all of the results that are reported, within this present series of articles investigating calcium ferrite slags at copper saturation, have been subjected to the following criteria to ensure accurate, repeatable, and objective measurements. (1) Analysis was only undertaken if copper metal droplets were observed in close proximity to the measured area. (2) Analysis was only undertaken on the slag that was well quenched, within the rst 15 lm from the quenched surface at the liquid/quenching medium interface.
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(3) The data set must contain 20 or more analyzed points measured equidistance from the quenched surface. (4) The data set must have a standard deviation less than 1 wt pct.

The experimental results of the present study are in general agreement with the previous results of Ilyushechkin et al.[21] for the spinel liquidus in Figure 7. 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.

RESULTS AND DISCUSSION

A. Phase Equilibria in the Cu2O-Fe2O3 and Cu2O-CaO Systems at Metallic Copper Saturation Experiments in the Cu2O-Fe2O3 and Cu2OCaO systems at metallic copper saturation were conducted at 1140 C, 1150 C, 1160 C, 1200 C, and 1250 C. The compositions of the phases present in the equilibrated samples, as measured by EPMA, are presented in Table I and Table III. 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, respectively. The experimental liquid compositions measured in the present study are shown as lled squares in Figure 7 and Figure 8, while the full lines dene the experimental liquidus and solidus of the spinel primary phase eld in Figure 7. Tie-lines, which connect the solid compositions to the respective liquid compositions, are represented as dashed lines on both gures. The previous experimental results of Ilyushechkin et al.[21] are included as open squares in Figure 7, and the liquidus, as dened by Takeda,[20] is shown as dotdot-dashed lines in both Figure 7 and Figure 8. Due to the high copper oxide concentrations in the slag phase, quenching of all of these experiments was exceedingly dicult even with direct contact of the liquid slags with the quenching medium (use of at substrates). Experiments targeting the liquidus composition at 1250 C on the spinel liquidus of the Cu2OFe2O3 pseudo-binary at copper saturation were unsuccessful. Therefore, only the solidus measurement for 1250 C is reported in Table III, and the previous liquidus measurement conducted by Ilyushechkin et al.,[21] using the same technique as the present study, is used for the construction of the spinel liquidus in Figure 7.

Fig. 7Pseudo-binary phase diagram of the Cu2O-Fe2O3 system at metallic copper saturation.

Fig. 8Pseudo-binary phase diagram of the Cu2O-CaO system at metallic copper saturation.

Table III. Number 3 4 5 6 7 8

Phase Compositions in Cu2O-Fe2O3 and Cu2O-CaO Systems at Metallic Cu Saturation Equilibration 1h 0.5 h 2h 2h 1.5 h 0.5 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

0.0 77.6 22.4 0.0 46.6 53.3 0.0 83.5 16.5 0.0 99.3 0.7 0.0 72.2 27.8 0.0 5.1 94.9 liquidus not measured due to poor quenching 0.0 4.0 96.0 97.5 2.5 0.0 0.3 99.7 0.0 6.8 93.2 0.0 0.3 99.7 0.0

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Spinel Liquid Cu metal<>Delafossite Liquid Cu metal It was not possible, in the present study, to identify the exact temperature of this reaction, but it was shown to occur in between 1140 C and 1150 C. There are dierences 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. At 1150 C, Takeda[20] reports a 3.5 wt pct higher and at 1200 C a 6 wt pct higher concentration of Cu2O within the liquid phase, compared to the present study. The apparently higher spinel liquidus temperature dened by Takeda[20] may be the result of the presence of MgO in the samples, as that study was undertaken using MgO crucibles. The MgO would not have a large solubility in the liquid slag at these temperatures, but it would have larger solubility in the spinel phase, thus increasing its stability. As compositional data were not reported in the study of Takeda,[20] the eect of the MgO on the spinel liquidus cannot be quantied. Figure 8 shows the results of the present study on the pseudo-binary Cu2O-CaO system at metallic copper saturation with the diagram previously proposed by Takeda.[20] The results are in agreement for the position of the cuprite isotherm at 1160 C. There are dierences between the results of the present study and that of Takeda[20] regarding the eutectic temperature of the system. Takeda[20] reported the eutectic temperature as 1145 C, but experiments conducted by the present study at 1150 C identied the presence of only lime and cuprite solid crystals in equilibrium with metallic copper. The results of the present study indicate that the eutectic temperature for this system is between 1150 C and 1160 C. No new data are available on the liquidus in the CaO primary phase eld. IV. CONCLUSIONS

(PYROSEARCH) within the University of Queensland; Alistair Burrows, Gerardo Alvear, Bill Errington, James Edwards, Martin Bakker, and Philip Arthur (Xstrata Technology) for useful discussions on this topic; Mr. Ron Rasch, Mr. Kim Sewell, and Ms. Ying Yu, Centre for Microscopy and Microanalysis (CMM), the University of Queensland. Xstrata Technology and the Australian Research Council provided nancial support for this project under the ARC Linkage Program.

REFERENCES
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VOLUME 40B, DECEMBER 2009899

The rapid quenching primary phase substrate support technique, with EPMA analysis, has been rened and applied in the present study to experimentally dene the phase equilibria of the Cu2O-Fe2O3-CaO system at copper saturation. The details of the production and application of four dierent primary phase substrate support materials were dened. The experimental analysis methodology was developed dening the strict measures required to ensure accurate, repeatable, and objective phase equilibrium measurements of this system. Experimental results have been presented for the pseudo-binary systems Cu2O-Fe2O3 and Cu2OCaO at metallic copper saturation.

ACKNOWLEDGMENTS The authors thank the following for their assistance in this project: Mr. Graeme Goodall, Mr. Adrian Riding, and Dr. Baojun Zhao, for their assistance and work at the Pyrometallurgy Research Centre
METALLURGICAL AND MATERIALS TRANSACTIONS B