Investigation of Liquidus Temperatures and Phase Equilibria of Copper Smelting Slags in the FeO-Fe2O3-SiO2-CaOMgO-Al2O3 System at PO2 108 atm

HECTOR M. HENAO, COLIN NEXHIP, DAVID P. GEORGE-KENNEDY, P.C. HAYES, and E. JAK Copper concentrates and uxes can contain variable levels of SiO2, CaO, and MgO in addition to main components Cu, Fe, and S. Metal recovery, slag tapping, and furnace wall integrity all are dependent on phase equilibria and other properties of the phases and are functions of slag composition and operational temperature. Optimal control of the slag chemistry in the copper smelting, therefore, is essential for high recovery and productivity; this, in turn, requires detailed knowledge of the slag phase equilibria. The present work provides new phase equilibrium experimental data in the FeO-Fe2O3-SiO2-CaO-MgO-Al2O3 system at oxygen partial pressure of 108 atm within the range of temperatures and compositions directly relevant to copper smelting. For the range of conditions relevant to the Kennecott Utah Copper (South Magna, UT) smelting furnace, it was conrmed experimentally that increasing concentrations of MgO or CaO resulted in signicant decreases of the tridymite liquidus temperature and in changes in the position of the tridymite liquidus in the direction of higher silica concentration; in contrast, the spinel liquidus temperatures increase signicantly with the increase of MgO or CaO. Olivine and clinopyroxene precipitates appeared at high MgO concentrations in the liquid slag. The liquidus temperature in the spinel primary phase eld was expressed as a linear function of 1/(wt pctFe/wt pctSiO2), wt pctCaO, wt pctMgO, and wt pctAl2O3. The positions of each of the liquidus points (wt pctFe)/(wt pctSiO2) at a xed temperatures in the tridymite primary phase eld were expressed as linear functions of wt pctCaO, wt pctMgO, and wt pctAl2O3. DOI: 10.1007/s11663-010-9369-1 The Minerals, Metals & Materials Society and ASM International 2010

I.

INTRODUCTION

OPTIMAL control of the slag chemistry in copper smelting is one of the important issues inuencing ecient and stable operation of the process. Detailed knowledge of the slag phase equilibria, therefore, is essential to optimize the overall smelter performance. The eects of CaO, MgO, and Al2O3 impurities, introduced in the slag with the concentrates and uxes on the tridymite (SiO2) and spinel primary phase elds of silica and spinel are of particular interest. The average slag composition in the copper ash smelting furnace (FSF) at Rio TintoKennecott Utah Copper LLC (South Magna, UT) is given in Table I. The operational temperature is approximately 1588 K (1315 C). The composition was recalculated with the elements as oxides and then normalized to 100 wt pct.
HECTOR M. HENAO, Senior Research Fellow, is with the Pyrometallurgy Research Centre (PYROSEARCH), School of Engineering, The University of Queensland, Brisbane 4072, Australia. Contact e-mail: h.henaozapata@uq.edu.au COLIN NEXHIP, Manager - Technical Services (Smelter), and DAVID P. GEORGEKENNEDY, Manager - Operations (Smelter) are with the Rio TintoKennecott Copper LLC, Magna, UT 84044. P. C. HAYES and E. JAK, Professors, are with the Pyrometallurgy Research Centre (PYROSEARCH), School of Engineering, The University of Queensland, Brisbane 4072, Australia. Manuscript submitted December 2, 2009. Article published online April 14, 2010.
METALLURGICAL AND MATERIALS TRANSACTIONS B

The direct measurement of oxygen partial pressure (PO2) with an oxygen probe in a slag under industrial process conditions indicated an average PO2 of 108 atm at 1588 K (1315 C). This oxygen partial pressure, therefore, was selected for the present experimental work. The system was simplied to six components (Fe-Si-O-Ca-Mg-Al), assuming that a smallconcentration Cu oxide chemically dissolved in the slag at this low PO2 has a small eect on the liquidus. Table II indicates the range of target slag compositions selected to investigate the eect of MgO on liquidus at a given CaO (3.3 wt pct) and Al2O3 (3.3 wt pct) concentrations in slag as well as the eect of CaO on liquidus at a given MgO (2.2 wt pct) and Al2O3 (3.3 wt pct) concentrations in slag. The eect of MgO was investigated at three levels of 2.2, 6.0, and 9.0 wt pct and the eect of CaO was investigated at four levels of 0, 3.3, 4.5, and 6.0 wt pct. In each case, the change in a concentration of the minor component was oset by the change in sum of the FeO and SiO2 concentrations. Information in the literature related to the FeOSiO2-CaO-MgO-Al2O3 multicomponent system at intermediate oxygen partial pressures and temperatures relevant to the copper smelting operation is limited. Henao et al.[1,2] reported experimental results for the FeO-SiO2-CaO-(MgO-Al2O3) system at 108 atm and at 1573 K (1300 C) in the spinel primary phase eld. Zhao et al.[3,4] studied the eect of Al2O3 and MgO on
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Table I. PO2 Average 10

8

Average Compositions of KUC Flash Smelter Slags (Wt Pct) 1588 K (1315 C) Cu 0.7 Cu2O 0.8 0.9 Fe 40.0 FeO 51.5 57.0 SiO2 30.0 SiO2 30.0 33.3 CaO 3.0 CaO 3.0 3.3 MgO 2.0 MgO 2.0 2.2 Al2O3 3.0 Al2O3 3.0 3.3 Total 90.3 100.0 Total Fe/SiO2 1.33 Fe/SiO2 1.33 1.33

PO2 Average (as oxides) Normalized (as oxides) 10

8

108

Table II.

Target Liquidus Sections FeO-Fe2O3-SiO2-CaOMgO-Al2O3 (Wt Pct) Wt pct Minor Components

Set of Experiments Base case Eect of MgO on tridymite liquidus and spinel liquidus Eect of CaO on tridymite liquidus and spinel liquidus

CaO 3.3 3.3 3.3 0 4.5 6.0

MgO 2.2 6.0 9.0 2.2 2.2 2.2

Al2O3 3.3 3.3 3.3 3.3 3.3 3.3

the liquidus temperatures of a fayalite slag at iron metal saturation. Imlach et al.[5,6] reported the liquidus surfaces in the Al2O3-CaO-FeOX system at PO2 of 108 atm. Muan et al.[7] reported the phase equilibrium and the liquidus temperatures in the system MgO-FeOFe2O3-SiO2 at various ratios of CO2/H2 xed from 132 to 24. Nikolic et al.[8,9] constructed the phase diagrams for the system FeO-Fe2O3-SiO2-CaO at oxygen partial pressures and temperatures relevant to copper converting. Wu et al.,[10,11] Eriksson et al.,[12] Degterov et al.,[13] Jak et al.,[14,15] and Selleby et al.[16,17] reported predicted binary and ternary phase diagrams related to the Fe-SiCa-O-Mg-Al multicomponent system. It seems, however, that there are no systematic experimental studies on the combined eects of MgO, CaO, and Al2O3 in the FeO-Fe2O3-SiO2 system at the intermediate oxygen partial pressures relevant to the copper smelting processes reported.

Fig. 1Experimental approach to phase equilibrium determination using subliquidus equilibration, quenching, and EPMA.

II.

EXPERIMENTAL TECHNIQUE AND PROCEDURE

There are several diculties in obtaining accurate chemical equilibrium data for complex slag systems at controlled laboratory conditions. Experimental procedures have been developed by the Pyrometallurgy Research Centre at the University of Queensland[1820] that have resolved several experimental diculties and have been applied successfully to several complex industrial slags. The technique for phase equilibrium measurements is based on the high-temperature equilibration of the synthetic slag sample in a controlled gas atmosphere and temperature followed by rapid quenching and analysis of the composition of the phases present.
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The experimental technique can be explained with reference to Figure 1. The liquid slag phase is converted on quenching into glass, and crystalline solids present at the high temperature remain unaltered. The quenched samples then are mounted and polished, and compositions of the liquid and solid phases are measured by electron probe X-ray microanalysis (EPMA) with wavelength dispersive detectors (WDD). All equilibration experiments were conducted in a vertical reaction tube (impervious recrystalized alumina, 30-mm internal diameter (i.d.)) in electrical resistance silicon carbide (SiC) heated furnaces. The furnace temperature was controlled by an alumina shielded Pt/Pt-13 wt pctRh thermocouple placed immediately adjacent to the sample. The thermocouple was calibrated periodically against the standard thermocouple (supplied by the National Measurement Institute of Australia, West Lindeld, New South Wales, Australia). The overall temperature accuracy was estimated to be within 5 K (5 C). The atmosphere within the reaction tube was maintained at a xed oxygen partial pressure using CO/CO2 (CO-99.5 wt pct pure, CO2-99.99 wt pct pure) mixtures. The ow rates of gases to the furnace were controlled using glass capillary ow meters with the gas owing from the bottom to the top of the furnace. The volumetric ratio of the gases used to achieve the selected thermodynamic oxygen partial pressure at a set temperature was calculated using the FactSage thermodynamic package (Thermfact/CRCT, Montreal, Canada).[12] The oxygen partial pressures
METALLURGICAL AND MATERIALS TRANSACTIONS B

were checked periodically with a partially stabilized zirconium oxygen probe (SIRO2, DS-type oxygen probe; Australian Oxygen Fabricators (AOF), Melbourne, Australia). It was conrmed that the results of the measurements in the present study are within the accuracy of the DS-type oxygen probe (i.e., close to log PO2 of 0.1 units [PO2 in atm]). The starting mixtures were made from CaO, SiO2, Fe2O3, MgO, and Al2O3 powders (99.9 wt pct purity). The powders for each sample were weighed and mixed with an agate mortar and pestle and then pelletized. The pellets (0.3 g) were placed inside open platinum crucibles. All crucibles were suspended by platinum wire within the reaction tube in the furnace. Particular attention was paid to assure equilibrium. First, to approach the equilibrium from two dierent directions, metallic Fe powder was used to make the starting mixture. Achievement of equilibria also was ensured by checking the homogeneity of phases using EPMA. Equilibrium was conrmed by carrying out an experiment for dierent equilibration times. One experiment was carried out at the standard equilibration time of 12 hours, whereas another experiument was carried out at a prolonged time. The result indicated that even 12-hours holding time of slag is sucient to achieve equilibrium between phases. A holding time of 24 hours was used for experiments. Premelt at a higher temperature for a shorter time (5 to 30 minutes) always was used before the temperature was lowered to the nal equilibration temperature. This ensured the homogenization of the liquid phase, the precipitation of new crystals from the liquid phase, and avoids uncertainty of some solids remaining undissolved. After the holding time, the base of the reaction tube was immersed in water and ice, and the lower rubber stopper sealing the tube was removed. Then, the sample was allowed to fall directly into the iced water. The samples then were dried and mounted in an epoxy resin and polished for metallographic observation and microanalysis. Measurement of the compositions of the various phases within the sample was undertaken using a JEOL JXA 8200L (Japan Electron Optics Ltd., Tokyo, Japan) EPMA with WDD. An acceleration voltage of 15 kV and a probe current of 15 nA were used. The Duncumb Philibert atomic number absorption X-R uorescence correction model (ZAF) correction procedure supplied with the JEOL JXA 8200 L 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, hematite, (Fe2O3) for Fe, MgO for Mg, and Al2O3 for Al. The compositions were measured to an accuracy within 1 wt pct. Iron oxide is present in both 2+ and 3+ states; only the Fe cation concentration was measured with EPMA. All iron was recalculated to the ferrous state 2+ (FeO) for presentation purposes to ensure that the projected points are dened unambiguously. In addition, the experiments were planned and conducted with the aim of representing the information in the form of ternary phase diagrams. Thus, all compositions are projected onto the FeOSiO2-MgO or the FeO-SiO2-CaO sections.
METALLURGICAL AND MATERIALS TRANSACTIONS B

III.

RESULTS OF PHASE EQUILIBRIA EXPERIMENTS

Two sets of experiments were carried out to evaluate the eect of MgO and CaO addition on liquidus in the FeO-Fe2O3-SiO2-CaO-MgO-Al2O3 system at compositions relevant to copper smelting slags as indicated in Table II. One set was completed to determine the eect of MgO at xed concentrations of 3.3 wt pctCaO and 3.3 wt pctAl2O3 in the liquid phase, and another set was completed to evaluate the eect of CaO at xed concentrations of 3.3 wt pctAl2O3 and 2.2 wt pctMgO in liquid. All results of EPMA measurements are reported in Tables III through V. The liquid composition changes as the solid phases precipitate from the melt so that the exact targeted MgO, CaO, and Al2O3 concentrations usually are not achieved in the rst experiment. Several experiments were necessary for each point at xed CaO, MgO, and Al2O3 concentrations, and linear interpolation was used to calculate positions of liquidus on the sections with exact target MgO, CaO, and Al2O3 concentrations. Two sets of equations were obtained to correlate the following experimental points: (a) The position of a liquidus point (wt pctFe)/(wt pctSiO2) at a given temperature in the tridymite primary phase eld was expressed as is indicated in Eq. [1] as follows: wt pctFe=wt pctSiO2 C1 wt pctAl2 O3 C2 wt pctMgO C3 wt pctCaO C4 1

where C1, C2, C3, and C4 are empirically determined parameters for each temperature. The numerical values of the parameters are shown in Tables VIA and VIB. (b) The liquidus temperature in the spinel primary phase eld was expressed as indicated in Eq. [2] as follows: T Cliquidus B1 1=Fe=SiO2 wt pct B2 wt pctAl2 O3 B3 wt pctMgO B4 wt pctCaO B5 2

where B1, B2, B3, B4, and B5 are empirically determined parameters. The numerical values of the parameters are shown in Tables VIC. The parameters were obtained for each tridymite and spinel primary phase eld by minimizing the sum of squared dierences between the calculated and the experimental values to obtain the best t. The optimized parameters then were used to calculate the tridymite and spinel liquidus at exact target MgO, CaO, and Al2O3 compositions. The equations also were used to interpolate (or extrapolate over a short range) the liquidus and to construct the corresponding phase diagrams. The use of these simplied mathematical expressions is justied by the relatively small range of compositions investigated. The two right-hand columns in Tables III and V
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Table III.

Experimental Measurements of Phase Equilibria for Liquid-Tridymite in the FeO-Fe2O3-SiO2-MgO(3.3 wt pctCaO-3.3 wt pctAl2O3) System at PO2 1028 atm Slag Composition (wt pct) Wt pctFe/Wt pctSiO2 Al2O3 3.3 0.0 3.3 0.0 3.5 0.0 3.3 0.0 5.8 0.0 3.4 0.0 3.5 0.0 3.1 0.0 3.1 0.0 3.2 0.0 3.3 0.0 2.8 0.0 3.5 0.0 3.8 0.0 3.2 0.0 6.1 0.0 3.5 0.0 3.6 0.0 3.2 0.0 3.4 0.0 3.4 0.0 2.8 0.0 3.2 0.0 3.1 0.0 3.5 0.0 5.8 0.0 3.5 0.0 3.1 0.0 3.0 0.0 Experimental 0.66 0.71 0.75 0.77 0.66 0.75 0.74 0.65 0.71 0.66 0.66 0.66 0.60 0.56 0.78 0.68 0.78 0.78 0.66 0.69 0.66 0.67 0.62 0.82 0.83 0.72 0.79 0.69 0.74 *Calculated 0.67 0.71 0.75 0.76 0.68 0.73 0.75 0.68 0.68 0.67 0.67 0.64 0.58 0.56 0.80 0.69 0.78 0.75 0.67 0.69 0.68 0.68 0.62 0.83 0.82 0.72 0.78 0.70 0.76

Exp. No. 1 68 92 R68 70 39 126 69 57 127 93 58 94 128 59 76 28 95 75 96 129 61 R130 62 98 79 38 78 63

Temperature 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C)

Phases liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid Tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite

FeO 40.2 0.9 45.5 0.6 44.8 0.7 45.5 0.6 40.8 1.0 44.6 0.8 44.2 0.6 40.3 0.8 42.2 1.0 40.2 0.7 40.2 0.9 39.9 0.7 36.7 0.3 35.1 0.6 45.8 1.0 41.5 0.7 45.5 0.8 45.3 0.9 40.6 0.8 41.2 0.8 40.2 0.7 40.1 0.8 37.7 0.6 47.1 0.7 47.0 0.9 42.7 0.7 45.6 0.8 41.6 0.9 43.4 0.5

SiO2 47.6 99.1 45.9 99.4 46.2 99.3 45.9 99.3 48.3 99.0 46.0 99.2 46.8 99.3 48.1 99.0 46.1 98.9 47.7 99.2 47.6 99.1 46.6 99.2 47.8 99.6 48.7 99.3 45.8 98.9 47.3 99.3 45.5 99.1 45.1 99.1 47.6 99.2 46.5 99.2 47.2 99.2 46.5 99.1 47.1 99.3 44.4 99.2 44.2 99.1 46.2 99.2 44.9 99.1 46.6 99.1 45.4 99.4

CaO 3.1 0.0 3.2 0.0 3.2 0.0 3.2 0.0 3.0 0.0 3.7 0.0 3.2 0.0 4.1 0.2 3.1 0.1 3.1 0.0 3.1 0.0 3.0 0.0 3.1 0.0 3.2 0.0 3.2 0.0 3.0 0.0 3.1 0.0 3.5 0.0 4.2 0.0 3.2 0.0 3.2 0.0 2.9 0.0 3.2 0.0 3.3 0.0 3.2 0.0 3.0 0.0 3.7 0.0 4.1 0.0 3.0 0.0

MgO 5.8 0.0 2.1 0.0 2.2 0.0 2.1 0.0 2.2 0.0 2.3 0.0 2.3 0.0 4.4 0.0 5.5 0.0 5.7 0.0 5.8 0.0 7.7 0.0 8.8 0.0 9.1 0.0 2.0 0.0 2.2 0.0 2.4 0.0 2.5 0.0 4.5 0.0 5.7 0.0 6.0 0.0 7.7 0.0 8.7 0.0 2.2 0.0 2.2 0.0 2.3 0.0 2.3 0.0 4.5 0.0 5.2 0.0

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Table III.

Continued Wt pctFe/Wt pctSiO2 Al2O3 3.3 0.0 3.0 0.0 3.2 0.0 3.2 0.0 2.9 0.0 3.5 0.0 3.3 0.0 3.2 0.0 5.7 0.0 3.3 0.0 3.1 0.0 2.9 0.0 3.3 0.0 3.2 0.0 2.7 0.0 3.3 0.0 3.3 0.0 0.3 Experimental 0.69 0.69 0.62 0.89 1.0 0.90 0.88 0.88 0.78 0.87 0.75 0.79 0.76 0.73 0.70 0.70 0.66 *Calculated 0.71 0.69 0.62 0.90 0.93 0.89 0.88 0.88 0.79 0.87 0.76 0.82 0.74 0.74 0.75 0.66 0.65

Slag Composition (wt pct) Exp. No. 99 64 100 R45 54 31 65 101 73 131 72 66 102 132 67 103 133 Temperature 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) Phases liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite Orthopyroxene FeO 41.3 1.0 41.2 0.8 37.6 0.8 49.1 0.8 51.7 0.7 48.9 1.1 48.4 1.0 48.4 1.0 44.7 1.0 48.0 0.9 43.3 1.0 44.9 1.0 43.1 0.6 42.4 0.7 41.3 0.6 40.3 1.0 38.8 0.6 23.1 SiO2 46.4 99.0 45.2 99.1 47.0 99.1 42.7 99.1 40.6 99.2 42.4 98.8 42.9 98.9 42.9 98.9 44.4 98.8 43.1 99.1 45.0 98.9 44.1 98.9 44.2 99.3 45.0 99.2 45.6 99.3 44.5 98.9 45.9 99.4 53.0 CaO 3.2 0.0 2.9 0.0 3.2 0.0 3.1 0.0 2.8 0.0 2.9 0.0 3.2 0.0 3.3 0.1 2.9 0.2 3.4 0.0 4.1 0.0 2.8 0.0 3.3 0.0 3.3 0.0 2.7 0.0 3.2 0.1 3.3 0.0 23.2 MgO 5.9 0.0 7.6 0.0 8.9 0.0 1.9 0.0 1.9 0.0 2.2 0.0 2.2 0.0 2.2 0.0 2.2 0.0 2.3 0.0 4.5 0.0 5.3 0.0 6.1 0.0 6.1 0.0 7.7 0.0 8.7 0.0 8.7 0.0 0.4

*Fe/SiO2 was calculated using interpolation parameters from Table VIA.

give the calculated values of Fe/SiO2 wt pct ratios, and the right column in Table IV gives the calculated liquidus temperatures for each experimental point. Comparison of experimental and calculated values indicates a good agreement between the experimental and the calculated data as well as consistency within the experimental dataset. A. Effect of MgO Addition in Slag at Fixed CaO and Al2O3 Concentrations in the FeO-Fe2O3-SiO2-CaOMgO-Al2O3 System at PO2 of 108 atm The experiments were carried out to target the gas liquidtridymite or gasliquidspinel equilibria. Experimental results at temperatures lower than 1250 C were obtained for the gasliquidtridymitespinel equilibria. At high concentrations of MgO, the gasliquid tridymiteclinopyroxene or gasliquidspinelolivine phase assemblages were observed. Examples of typical microstructures of equilibrated slags are given in Figure 2. The crystal structure of solid phases in the samples were not analyzed by XRD. Thus, the tridymite, spinel,
METALLURGICAL AND MATERIALS TRANSACTIONS B

olivine, and clinopyroxene solid phases identications were derived from the chemical composition measured by EPMA and the reported temperatures of stability.[21,22] For the investigated range of conditions, clinopyroxene is the stable phase, according to the FactSage[21,22] predictions. 1. Phase Diagram FeO-Fe2O3-SiO2-MgO(3.3 wt pctCaO-3.3 wt pctAl2O3) at PO2 of 108 atm The projection of the multicomponent slag onto the FeO-SiO2-MgO plane is illustrated schematically in Figure 3(a). Each of the recalculated liquid compositions was determined by normalizing the compositions considering only relative FeO, SiO2, and MgO concentrations. The constructed pseudoternary section showing primary phase elds, liquidus isotherms, and the experimental points close to the target composition is given in Figure 4. The tridymite, spinel, olivine, and clinopyroxene primary phase elds were identied in the range of bulk compositions and conditions studied. The liquidus isotherms in the tridymite and spinel primary phase elds at exact Al2O3 and CaO concentrations of
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Table IV. Experimental Measurements of Phase Equilibria for Liquid Spinel and Liquid Olivine in the FeO-Fe2O3-SiO2-MgO-CaO-(3.3 wt pct Al2O3) System at PO2 1028 Atm Slag Composition (wt pct) Exp. No. 51 40 138 52 139 140 48 107 113 176 108 109 153 154 111 112 177 148 178 150 185 151 152 181 156 Temperature 1498 K (1225 C) 1503 K (1230 C) 1503 K (1230 C) 1503 K (1230 C) 1503 K (1230 C) 1503 K (1230 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1528 K (1255 C) 1528 K (1255 C) 1528 K (1255 C) 1528 K (1255 C) 1533 K (1260 C) 1533 K (1260 C) 1533 K (1260 C) 1533 K (1260 C) 1543 K (1270 C) 1543 K (1270 C) 1543 K (1270 C) 1543 K (1270 C) 1553 K (1280 C) Phases liquid spinel tridymite liquid spinel tridymite liquid spinel tridymite liquid spinel tridymite liquid spinel tridymite liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel olivine liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel liquid spinel olivine liquid spinel olivine liquid spinel olivine liquid spinel olivine FeO 48.5 96.8 0.9 43.2 96.4 1.1 50.0 97.1 0.9 48.6 97.0 1.0 43.5 96.5 1.4 43.9 95.9 57.3 97.2 56.1 94.6 56.3 96.9 52.2 94.7 39.8 44.2 95.6 41.4 95.2 59.8 96.3 48.1 95.8 52.5 95.1 46.2 94.8 65.2 94.4 55.9 96.4 59.1 92.8 46.2 93.8 67.1 94.2 57.4 91.2 40.3 56.7 89.7 33.8 63.0 92.0 39.0 56.6 87.0 36.7 SiO2 41.5 0.5 99.1 43.3 0.3 98.8 40.8 0.4 99.0 41.1 0.4 98.9 43.5 0.4 98.4 42.6 0.4 34.6 0.4 32.4 0.6 34.9 0.4 34.6 0.6 35.0 41.5 0.4 42.7 0.4 31.7 0.4 38.5 0.4 34.7 0.5 38.9 0.4 26.9 0.5 33.1 0.3 28.6 0.5 36.7 0.4 24.0 0.0 27.5 0.5 33.0 26.6 0.4 34.1 25.6 0.6 34.8 26.3 0.4 34.1 CaO 3.7 0.0 0.0 5.6 0.0 0.0 3.8 0.0 0.0 4.0 0.0 0.0 4.0 0.0 0.1 3.3 0.0 3.2 0.0 3.0 0.6 3.2 0.6 3.4 0.0 0.1 3.8 2.0 3.4 2.6 3.2 0.0 3.9 0.0 3.2 1.8 3.2 2.4 2.7 0.0 4.5 0.0 3.1 0.0 3.9 0.0 3.4 0.5 4.3 0.0 0.3 5.9 0.0 0.6 2.9 0.0 0.3 5.5 0.0 0.5 MgO 2.6 0.7 0.0 3.4 1.0 0.0 2.0 0.6 0.0 2.8 0.7 0.0 5.5 1.4 0.1 7.1 2.0 2.0 0.5 2.0 0.1 2.2 0.0 6.4 1.9 25.2 7.0 0.0 9.2 0.0 1.9 0.6 5.7 1.6 6.3 0.0 8.4 0.0 2.2 0.8 2.6 0.7 5.8 2.2 9.3 2.9 1.1 0.5 6.7 2.7 26.3 6.6 3.0 31.4 5.4 2.3 25.8 6.6 3.3 28.7 Al2O3 3.7 2.1 0.0 4.6 2.3 0.1 3.5 1.9 0.0 3.6 1.9 0.1 3.6 1.7 0.1 3.1 1.7 2.9 1.9 6.5 4.0 3.5 2.1 3.5 2.9 0.0 3.5 2.0 3.3 1.9 3.4 2.7 3.8 2.2 3.3 2.6 3.3 2.4 3.0 4.2 4.0 2.6 3.4 4.5 3.9 3.0 4.4 4.8 4.1 5.7 0.1 4.3 6.9 0.1 3.2 5.2 0.1 5.1 9.3 0.1 (*)Temperature Calculated 1506 K (1233 C) 1502 K (1229 C) 1507 K (1234 C) 1506 K (1233 C) 1506 K (1233 C) 1511 K (1238 C) 1520 K (1247 C) 1525 K (1252 C) 1520 K (1247 C) 1530 K (1257 C) 1514 K (1241 C) 1514 K (1241 C) 1525 K (1252 C) 1520 K (1247 C) 1530 K (1257 C) 1524 K (1251 C) 1533 K (1260 C) 1525 K (1252 C) 1540 K (1267 C) 1532 K (1259 C) 1537 K (1264 C) 1546 K (1273 C) 1549 K (1276 C) 1544 K (1271 C) 1550 K (1277 C)

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Table IV.

Continued Slag Composition (wt pct) (*)Temperature Calculated

Exp. No. 163 149 179 165

Temperature 1523 K (1250 C) 1533 K (1260 C) 1533 K (1260 C) 1533 K (1260 C)

Phases liquid olivine liquid olivine liquid olivine liquid olivine

FeO 43.13 42.24 55.4 42.5 53.2 40.1 46.44 38.8

SiO2 41.94 34.43 30.3 32.5 33.8 34.8 38.74 34.6

CaO 3.7 0.1 4.1 0.3 3.0 0.1 3.4 0.1

MgO 7.5 23.2 6.3 24.7 6.8 25.0 7.9 26.5

Al2O3 3.7 0 3.9 0.1 3.2 0.1 3.5 0

*Lquidus temperature: calculated using interpolation parameters from Table VIC.

3.3 wt pct were interpolated using Eqs. [1] and [2] to calculate Fe/SiO2 wt pct ratios. For practical convenience, an additional-scale wt pctFe/wt pctSiO2 ratio at MgO = 0 wt pct is included in Figures 4, 5, 7, and 8. However, it is necessary to clarify that the indicated Fe/SiO2 ratio is valid only for MgO = 0 and is not constant at constant SiO2/(FeO + SiO2 + MgO) ratio. The gasliquidspinelolivine, gasliquidtridymite spinel and gasliquidtridymiteclinopyroxene boundary lines were constructed directly from corresponding experimental points, and the position of the gasliquid olivineclinopyroxene boundary line then was derived from the aforementioned boundary lines. The spinel phase formed at high iron oxide concentrations at PO2 of 108 atm. The spinel liquidus temperature decreases with increasing silica and increases with an increasing CaO concentration. The tridymite primary phase is encountered at high silica concentrations; there is a eutectic between the spinel and tridymite phase eld. The boundary line between spinel and olivine primary phase elds run almost parallel to the FeOSiO2 binary join. 2. Compositions of Solid Phases The observed solid phases in this system, investigated up to 9 wt pctMgO in the liquid phase, included tridymite, spinel, olivine, and clinopyroxene. The concentration of FeO in tridymite is less than 1 wt pct, and the concentrations of CaO, MgO, and Al2O3 in tridymite are below the limit of detection by EPMA. The compositions of spinel and olivine are plotted in Figure 4. As a general tendency, the concentrations of Al2O3 and MgO in the spinel phase are approximately 1/2 and 1/4 of the corresponding concentrations in the liquid slag, respectively. The concentrations of SiO2 in spinel are less than 1 wt pct, and it is apparent that the concentration of CaO decreases with an increased concentration of MgO. The concentrations of CaO and Al2O3 in the olivine phase are also less than 1 wt pct. 3. Comparison with FactSage Prediction Figure 5 shows the proposed phase diagram based on the experimental data and that predicted by
METALLURGICAL AND MATERIALS TRANSACTIONS B

FactSage[21,22] version 5.3.1. There are important dierences between the present experimental results and FactSage predictions as follows: (a) The point gasliquidspinel at 0 wt pctMgO, 3.3 wt pctAl2O3, and 3.3 wt pctCaO is close in composition in both the present experimental work and in the FactSage prediction. However, the experimental temperature of 1228 C was determined approximately from the present experimental data by extrapolation using coecients of Table VI and was 53 K (53 C) greater than that calculated with FactSage 1448 K (1175 C). This is equivalent to only a 2 wt pct dierence in SiO2 concentration in the steep tridymite liquidus. (b) The experimentally determined positions of the boundary line gasliquidspinelolivine and the points gasliquidspinelolivineclinopyroxene, and gasliquidtridymiteolivineclinopyroxene occur at higher MgO concentrations than predicted using FactSage. Note that the FactSage thermodynamic database used for comparison[22] was developed using experimental data existing at that time when these present results were not available. This outcome highlights the need for further fundamental experimental studies. 4. Temperature vs Fe/SiO2 Diagram The representation of the experimental temperature data vs the Fe/SiO2 diagram is useful to visualize the eects of MgO addition on the tridymite and spinel liquidus. The tridymite and spinel liquidus calculated for interpolated values of Al2O3 3.3 wt pct, CaO of 3.3 wt pct, and MgO of 2.2, 6.0, and 9.0 is shown in Figure 6. The results were extrapolated to 0 wt pctMgO using Eqs. [1] and [2]. The experimental points obtained close to the target composition of 3.3 wt pct of CaO and 3.3 wt pct of Al2O3 also are plotted in this gure. The experiments at temperatures below 1523 K (1250 C) and at concentrations of MgO above 6 wt pct resulted in the precipitation of olivine and clinopyroxene. A tentative line for the olivine and clinopyroxene liquidus also is plotted in Figure 6. This form of representation clearly shows very dierent behavior of the system in the tridymite and spinel
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Table V. Experimental Measurements of Phase Equilibria for Liquid Tridymite in the FeO-Fe2O3-SiO2-CaO-(2.2 wt pctMgO3.3 wt pctAl2O3) System at PO2 1028 atm Slag Composition (wt pct) Exp. No. 80 82 92 126 39 68 R68 116 83 85 28 59 95 74 117 86 R77 88 98 77 62 38 118 31 65 101 131 71 119 Temperature 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1623 K (1350 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1588 K (1315 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1573 K (1300 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) Phases liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite liquid tridymite FeO 39.0 0.7 50.1 0.9 44.8 0.7 44.2 0.6 44.6 0.8 42.9 0.6 45.5 0.7 40.8 0.8 35.6 0.4 50.4 0.8 45.5 0.7 45.8 1.0 45.3 0.9 42.2 0.9 42.7 0.7 41.9 0.5 46.72 0.7 51.6 0.9 47.0 0.9 46.7 0.9 47.1 0.7 45.6 0.8 41.8 0.8 48.9 1.1 48.4 1.0 48.4 1.0 48.0 0.9 44.4 0.8 44.2 0.8 SiO2 47.9 99.3 43.6 99.1 46.2 99.3 46.8 99.3 46.0 99.1 46.7 99.3 45.9 99.3 47.9 99.1 49.6 99.5 42.9 99.2 45.5 99.2 45.8 98.9 45.1 99.1 46.3 99.1 46.9 99.2 45.1 99.4 44.82 99.2 42.0 99.1 44.2 99.1 44.8 99.0 44.4 99.2 44.9 99.1 46.9 99.1 42.4 98.8 42.9 98.9 42.9 98.9 43.1 99.1 44.5 99.1 45.0 99.2 CaO 8.0 0.0 0.0 0.0 3.2 0.0 3.2 0.0 3.7 0.0 5.1 0.0 3.2 0.0 6.1 0.0 9.0 0.0 0.0 0.0 3.1 0.0 3.2 0.0 3.5 0.0 5.3 0.0 6.0 0.0 8.0 0.1 3.2 0.1 0.0 0.0 3.2 0.0 3.2 0.1 3.3 0.0 3.7 0.0 6.1 0.0 2.9 0.0 3.2 0.0 3.3 0.1 3.4 0.0 5.5 0.0 5.8 0.0 MgO 2.1 0.0 2.6 0.0 2.2 0.0 2.3 0.0 2.3 0.0 2.1 0.0 2.1 0.0 1.9 0.0 2.3 0.0 2.8 0.0 2.4 0.0 2.0 0.0 2.5 0.0 2.2 0.0 1.9 0.0 2.0 0.0 2.0 0.0 2.6 0.0 2.2 0.0 2.0 0.0 2.2 0.0 2.3 0.0 1.9 0.1 2.2 0.0 2.2 0.0 2.2 0.0 2.3 0.0 2.3 0.0 1.8 0.0 Al2O3 3.0 0.0 3.7 0.0 3.5 0.0 3.5 0.0 3.4 0.0 3.1 0.0 3.3 0.0 3.2 0.1 3.5 0.1 4.0 0.0 3.5 0.0 3.2 0.0 3.6 0.0 4.0 0.0 2.5 0.0 3.0 0.1 3.3 0.1 3.8 0.0 3.5 0.0 3.3 0.0 3.1 0.0 3.5 0.0 3.3 0.0 3.5 0.0 3.3 0.0 3.2 0.0 3.3 0.0 3.3 0.0 3.1 0.0 Wt pctFe/Wt pctSiO2 Experimental 0.63 0.89 0.75 0.74 0.75 0.71 0.77 0.66 0.56 0.91 0.78 0.78 0.78 0.71 0.71 0.72 0.81 0.95 0.83 0.71 0.82 0.79 0.69 0.90 0.88 0.88 0.87 0.77 0.76 *Calculated 0.62 0.88 0.76 0.76 0.75 0.73 0.76 0.66 0.57 0.91 0.79 0.79 0.78 0.70 0.70 0.68 0.81 0.94 0.81 0.76 0.83 0.80 0.70 0.90 0.88 0.87 0.86 0.79 0.79

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Table V. Continued Slag Composition (wt pct) Exp. No. R45 89 115 Temperature 1523 K (1250 C) 1523 K (1250 C) 1523 K (1250 C) Phases liquid tridymite liquid tridymite liquid tridymite FeO 49.1 0.8 41.5 0.7 45.4 1.0 SiO2 42.7 99.1 45.2 99.2 43.2 98.9 CaO 3.1 0.0 8.2 0.1 6.1 0.0 MgO 1.9 0.0 2.1 0.0 1.9 0.1 Al2O3 3.2 0.0 3.0 0.0 3.4 0.1 Wt pctFe/Wt pctSiO2 Experimental 0.89 0.71 0.8 *Calculated 0.88 0.70 0.81

*Fe/SiO2 was calculated using interpolation parameters from Table VIB.

Table VI. Temperature C1 C2

Coecients Parameters for Eqs. [1] and [2] C3 0.031 0.054 0.067 0.059 0.04 0.04 0.03 0.03 C4 1.02 1.15 1.26 1.30 1.04 0.95 0.90 0.76 R2 0.91 0.93 0.97 0.93 0.97 0.99 0.89 0.95 Range of Application in Terms of Liquid Slag wt pctMgO: 1.9 to 9.1 wt pctCaO: 2.7 to 4.2 wt pctAl2O3: 2.7 to 6.1 wt pctMgO: 1.8 to 2.8 wt pctCaO: 0 to 6.1 wt pctAl2O3: 1.8 to 2.8

(A) Tridymite Saturation (MgO Eect) 1623 K (1350 C) 0.034 1588 K (1315 C) 0.039 1573 K (1300 C) 0.046 1523 K (1250 C) 0.045 (B) Tridymite Saturation (CaO Eect) 1623 K (1350 C) 0.10 1588 K (1315 C) 0.02 1573 K (1300 C) 0.07 1523 K (1250 C) 0.09

0.025 0.027 0.031 0.035 0.08 0.01 0.11 0.04

(wt pctFe)/(wt pctSiO2) = C1 9 (wt pctAl2O3) + C2 9 (wt pctMgO) + C3 9 (wt pctCaO) + C4 (1).

B1

B2

B3

B4 1.31

B5 1273.8

R2 0.88

Range of Application in Terms of Liquid Slag wt pctMgO: 1.9 to 9.3 wt pctCaO: 2.7 to 5.9 wt pctAl2O3: 2.9 to 6.5

(C) Spinel Saturation (MgO and CaO Eect) 53.13 1.15 3.22

T[C]liquidus = B1 9 1/(Fe/SiO2(wt pct)) + B2 9 (wt pctAl2O3) + B3 9 (wt pctMgO) + B4 9 (wt pctCaO) + B5 (2).

primary phase elds. The tridymite temperatures liquidus decrease rapidly with an increasing Fe/SiO2 wt pct ratio. The results presented in Figure 6 indicate that increasing MgO from 2.2 to 9 wt pct results in a signicant decrease of the tridymite liquidus temperatures; alternatively, this can be described as a movement of the gasliquidtridymitespinel eutectic from values of Fe/SiO2 wt pct ratios of 0.8 to 0.9 when MgO = 2.2 to 0.6 to 0.65 when MgO = 6.0 wt pct. The spinel liquidus temperatures, by contrast, increase by approximately 20 K (20 C) as MgO increases from 0 to 6 wt pct at any given Fe/SiO2 wt pct ratio. B. Effect of CaO Addition in Slag at Fixed Concentration of MgO and Al2O3 in the FeO-Fe2O3SiO2-CaO-(2.2 wt pctMgO-3.3 wt pctAl2O3) system 1. Ternary Phase diagram FeO-Fe2O3-SiO2-CaO(2.2 wt pctMgO-3.3 wt pctAl2O3) The construction of the corresponding pseudoternary section by projection of the multicomponent slag compositions onto the FeO-SiO2-CaO plane is
METALLURGICAL AND MATERIALS TRANSACTIONS B

illustrated in Figure 3(b). The recalculated liquid compositions were determined by normalizing the original EPMA-measured compositions considering only the relative FeO, CaO, and SiO2 concentrations. The Al2O3 and MgO concentrations were interpolated to 3.3 wt pct and 2.2 wt pct, respectively, using Eqs. [1] and [2] with parameters given in Table VI. The constructed pseudoternary phase diagram is shown in Figure 7. Experimental points close to the target composition also are plotted in Figure 7. 2. Comparison with FactSage Predictions There are important dierences between the present experimental data and those predicted by FactSage,[21,22] as is shown in Figure 8. The slopes of the experimental liquidus lines as a function of CaO concentration in the tridymite and spinel primary phase elds are less steep than those predicted by FactSage. 3. Temperature vs Fe/SiO2 Diagram The tridymite and spinel liquidus are shown in Figure 9 on a temperature-vs-Fe/SiO2 diagram. The
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Fig. 2Examples of slag microstructures from phase equilibria experiments in the system FeO-Fe2O3-SiO2-MgO-CaO-Al2O3 at PO2 = 108 atm.

results were extrapolated to 0 wt pctCaO using Eqs. [1] and [2]. The experimental points obtained close to the target composition in the spinel and tridymite primary phase elds also are plotted in this gure. Increasing CaO from 0 to 6 wt pct results in the signicant decrease of the tridymite liquidus temperatures; the gasliquid tridymitespinel eutectic moves from values of Fe/SiO2 wt pct ratios of 0.900.95 at CaO = 0.0 to Fe/SiO2 wt pct ratios of 0.670.70 at CaO = 6.0 wt pct. The spinel liquidus temperatures increase by approximately 10 C as CaO increases from 0 to 6 wt pct at any given Fe/SiO2 wt pct ratio.

IV.

INDUSTRIAL CONSIDERATIONS

At Kennecott Utah Copper LLC, the compositions of industrial copper smelting slags usually are selected to minimize dissolved copper losses to slag. Preventing the formation of solid silica is necessary to avoid diculties in skimming/tapping the slags. The present study has shown that at a given temperature, the formation of tridymite can be controlled by adjusting the MgO
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and/or CaO concentrations in the melt. However, in the spinel primary phase, increasing the concentration of SiO2 will result in dissolution of spinel. If this spinel is used to protect the refractories, then there is the potential to compromise the side-wall integrity. Excessive dissolution of spinel can be controlled by MgO and, to a lesser extent, by CaO. The precipitation of olivine and/or clinopyroxene at high MgO concentrations is possible. The present study brings accurate quantitative information regarding the windows of operation in terms of slag composition. However, the operation at a given slag composition correspond to a trade o between several factors, including the concentrate composition, vessel heat balance, slag volumes, and concentration of copper in slag. This evaluation is beyond the scope of the present study.

V.

CONCLUSIONS

The experimental data from this study have made it possible to evaluate the phase equilibria of synthetic
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 4Projected liquidus of the FeO-Fe2O3-SiO2-MgO-(3.3 wt pctCaO-3.3 wt pctAl2O3) system at PO2 = 108 atm, including the experimental liquidus points close to the target composition.

Fig. 3Compositional space in the system FeO-SiO2-MgO-Al2O3CaO and projection on the (a) FeO-SiO2-MgO section and the (b) FeO-SiO2-CaO section.

slags in the FeO-SiO2-CaO-MgO-Al2O3 system at conditions directly relevant to the Kennecott Utah Corporation Flash Smelting Furnace operation. Targeted experiments have been undertaken to determine liquidus in the temperature range ~1523 K to 1623 K (~1250 C to 1350 C) at oxygen partial pressure PO2 of 108 atm as well as the concentration ranges close to 3.3 wt pctAl2O3, from 0 to 8 wt pctCaO and from 2.2 to 9.0 wt pctMgO. Tridymite, spinel, olivine, and clinopyroxene primary phase elds have been identied in the range of conditions investigated. Phase diagrams for the FeO-Fe2O3-SiO2-MgO-(3.3 wt pctCaO-3.3 wt pctAl2O3) and FeO-Fe2O3-SiO2-CaO (2.2 wt pctMgO3.3 wt pctAl2O3) systems have been constructed.
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 5Comparison of the proposed liquidus of the FeO-Fe2O3-SiO2MgO-(3.3 wt pctCaO-3.3 wt pctAl2O3) system at PO2 = 108 atm with that obtained by the calculations with FactSage (projected section).

An increase of MgO or CaO results in a signicant decrease of the tridymite liquidus and in movement of the tridymite liquidus toward higher silica; however, the spinel liquidus increases with an increase of MgO or
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Fig. 6Experimental measurements demonstrating the eects of MgO addition on the tridymite and spinel liquidus at PO2 = 108 atm in the FeO-Fe2O3-SiO2-MgO-(3.3 wt%CaO-3.3 wt%Al2O3) system. The gure includes the experimental point close to the target compositions.

Fig. 8Comparison of the proposed liquidus in the FeO-Fe2O3-SiO2CaO-(2.2 wt pctMgO-3.3 wt pctAl2O3) system at PO2 = 108 atm with that obtained by the calculations with FactSage.

Fig. 7Proposed liquidus of the FeO-Fe2O3-SiO2-CaO (2.2 wt pct MgO-3.3 wt pctAl2O3) system at PO2 = 108 atm, including the experimental liquidus points close to the target composition.

Fig. 9Experimental measurements demonstrating the eects of CaO addition on the tridymite and spinel liquidus at PO2 = 108 atm in the FeO-Fe2O3-SiO2-CaO-(2.2 wt pctMgO-3.3 wt pctAl2O3) system. The gure includes experimental points close to the target compositions.

CaO concentration in the liquid. Olivine and clinopyroxene precipitated at MgO in the liquid greater than approximately 6.5 wt pct. The experimental results were compared with those calculated by FactSage. Signicant dierences were identied between the experimental and some of the calculated liquidus compositions and the positions of boundary lines.

ACKNOWLEDGMENTS The research has been founded by Rio Tinto Kennecott Utah Copper LLC. The authors would like to thank the following individuals for their assistance in this project: Ms. Jie Yu and Dr. Baojun Zhao from the Pyrometallurgy Research Centre (PYROSEARCH) within the University of Queensland; Mr. Ron Rasch and Mr. Ying Yu from the Centre of Microscopy and

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Microanalysis Queensland.

(CMM)

within

the

University

of

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METALLURGICAL AND MATERIALS TRANSACTIONS B

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