Viscosity Measurements of “FeO”-SiO2 Slag in Equilibrium with Metallic Fe

The current study delivered the measurements of viscosities in the system “FeO”-SiO₂ in equilibrium with metallic Fe in the composition range between 15 and 40 wt pct SiO₂. The experiments were carried out in the temperature range of 1473 K to 1773 K (1200 °C to 1500 °C) using a rotational spindle technique. An analysis of the quenched sample by electron probe X-ray microanalysis (EPMA) after the viscosity measurement enables the composition and microstructure of the slag to be directly linked with the viscosity. The current results are compared with available literature data. The significant discrepancies of the viscosity measurements in this system have been clarified. The possible reasons affecting the accuracy of the viscosity measurement have been discussed. The activation energies derived from the experimental data have a sharp increase at about 33 wt pct SiO₂, which corresponds to the composition of fayalite (Fe₂SiO₄). The modified quasi-chemical model was constructed in the system “FeO”-SiO₂ to describe the current viscosity data.     

The rate of reaction of solid iron with oxidized “FeO”-CaO-SiO2-Al2O3 slags at 1360 °C—the chemical diffusivity of iron oxide

Measurements have been made of the rate of reduction of oxidized iron oxide-containing 41CaO-38SiO₂-21Al₂O₃ (wt pct) slags at 1360 °C by a rotating disc of solid iron. For initial total iron concentrations of between 1.8 and 13.4 wt pct and rotation speeds up to 1000 rpm, the rate is shown to be determined by mass transfer in the liquid phase. The chemical diffusivity of iron oxide (in cm² s⁻¹) is found to be given by the empirical expression log D = −6.11 + 0.08 (wt pct Fe). It is concluded that the values of the diffusivity are for melts at close to iron saturation. It is shown that the available measurements of the diffusivity of iron oxide in liquid slags are consistent with increasing diffusivity with increasing state of oxidation, with about a tenfold increase between melts in equilibrium with iron and those in equilibrium with oxygen at 1 atm.     

Viscosity of SiO2-“FeO”-Al2O3 System in Equilibrium with Metallic Fe

The present study delivered the measurements of viscosities in SiO₂-“FeO”-Al₂O₃ system in equilibrium with metallic Fe. The rotational spindle technique was used in the measurements at the temperature range of 1473 K to 1773 K (1200 °C to 1500 °C). Molybdenum crucibles and spindles were employed in all measurements. The Fe saturation condition was maintained by an iron plate placed at the bottom of the crucible. The equilibrium compositions of the slags were measured by EPMA after the viscosity measurements. The effect of up to 20 mol. pct Al₂O₃ on the viscosity of the SiO₂-“FeO” slag was investigated. The “charge compensation effect” of the Al₂O₃ and FeO association has been discussed. The modified quasi-chemical viscosity model has been optimized in the SiO₂-“FeO”-Al₂O₃ system in equilibrium with metallic Fe to describe the viscosity measurements of the present study.     

The Fe−Ho binary system

The Fe?Ho phase diagram was determined on the basis of data obtained by X-ray diffraction, metallographic and differential thermal analysis techniques. Since emphasis was centered in the region where intermetallic compounds predominate, neither the iron nor holmium terminal regions were included in this study. Eutectic reactions were found to occur at 16.5 wt pct Fe and 875° C, 61 wt pct Fe and 1284° C, and 79 wt pct Fe and 1338° C. The congruent melting points of the compounds Ho₆Fe₂₃ and Ho₂Fe₁₇ were found to be 1332° and 1343° C, respectively. Two other intermetallic compounds were found, HoFe₂ and HoFe₃, and had peritectic decomposition temperatures of 1288° and 1293° C, respectively.     

The solubility and solution behavior of antimony and tin in α-lron and the effects of nickel and chromium additions

The solid solubilities of Sn and Sb in α-Fe have been determined by means of lattice parameter measurements. The Sb solubility ranges from a maximum of 11 wt pct (5.4 at. pct) at 1000°C down to 5.3 wt pct (2.5 at. pet) at 600°C; the Sn solubility ranges from a maximum of 17.7 wt pct (9.2 at. pet) at 900°C to 6.5 wt pct (3.2 at. pet) at 600°C. These solubilities are remarkably large in view of the large sizes of the Sb and Sn atoms in relation to the Fe atom. It was not possible to rationalize the variation of the α-phase lattice parameter with Sb or Sn content from the point of view of atomic diameter or atomic volume. The addition of 1 wt pct Ni lowers the Sb solubility at 600°C from 5.3 to 3.5 wt pct (2.5 to 1.6 at. pet); the effect of Cr on the Sb solubility appears to be small. The addition of 1 wt pct Ni or 1 wt pct Cr lowers the Sn solubility from 6.5 to 5.2 wt pct (3.2 to 2.5 at. pet). It was found that a substantial amount of Ni substitutes for Fe in both the FeSb phase and the Fe₅Sn₃ phase. Formerly Research Fellow, Department of Metallurgy and Materials Science and LRSM, University of Pennsylvania     

On the interfacial rate of reaction of CO2 with a calcium ferrite melt

Measurements of the rate of dissociation of CO₂ have been made by the¹⁴CO₂-CO isotope exchange technique on calcium ferrite melts with Ca/Fe = 0.30 at 1300 °C. Studies have also been made of the interfacial rates of oxidation of calcium ferrite melts with an average CaO content of 19.45 wt pct (CaJFe ≃0.33) in CO₂-CO atmospheres at 1362 °C. It is shown that the rates of oxidation are consistent with the rates of isotope exchange, indicating a common rate determining step. Measurements of the equilibrium Fe³⁺/Fe²⁺ ratio as a function of the CO₂/CO ratio for 19.3 wt pct CaO melts at 1360 °C and for 28.7 and 18.6 wt pct CaO melts at 1300 °C are found to be in close agreement with the deductions of Takeda, Nakazawa, and Yazawa. Combination of the equilibrium data with the results of the isotope exchange studies indicate that the apparent first order rate constant for the dissociation of CO₂ is inversely proportional to the square of the Fe³⁺JFe²⁺ ratio of the melt, as has been previously found for liquid iron oxide, lime-saturated calcium ferrites, silicasaturated iron silicates, and an equimolar “FeO”-CaO-SiO₂ melt.     

Viscosity Measurements of SiO2-“FeO”-MgO System in Equilibrium with Metallic Fe

The present study delivers the measurements of viscosities in the SiO₂-“FeO”-MgO system in equilibrium with metallic Fe. The rotational spindle technique was used for the measurements at the temperature range of 1523 K to 1773 K (1250 °C to 1500 °C). Molybdenum crucibles and spindles were employed in all measurements. The viscosity measurements were carried out at 31 to 47 mol pct SiO₂ and up to 18.8 mol pct MgO. Analysis of the quenched sample by Electron probe X-ray microanalysis after the viscosity measurement enables the composition and microstructure of the slag to be directly linked with the viscosity. The replacement of “FeO” by MgO was found to increase viscosity and activation energy of the SiO₂-“FeO”-MgO slags. The modified Quasi-chemical Viscosity Model was further optimized in this system based on the current viscosity measurements.     

Liquidus temperatures in calcium ferrite slags in equilibrium with molten copper

Experimental laboratory methods have been developed that enable phase-equilibria studies to be carried out on slags in the system Ca-Cu-Fe-O in equilibrium with metallic copper. These techniques involve equilibration at temperature, rapid quenching, and chemical analysis of the phases using electron-probe X-ray microanalysis (EPMA). Equilibration experiments have been carried out in the temperature range of 1150 °C to 1250 °C (1423 to 1523 K) and in the composition range of 4 to 80 wt pct “Cu₂O,” 0 to 25 wt pct CaO, and 20 to 75 wt pct “Fe₂O₃” in equilibrium with metallic copper. Liquidus and solidus data are reported for the primary-phase fields of spinel (magnetite) and dicalcium ferrite. The resulting data have been used to construct liquidus isotherms of the CaO-“Cu₂O”-“Fe₂O₃” system at metallic copper saturation.     

The slag-metal equilibrium in tin smelting

An equilibrium study was undertaken to investigate the effect of the CaO/SiO₂ and Fe/SiO₂ ratios and the SnO and Al₂O₃ contents of slags on the distribution of Fe and Sn between slag and metal in tin smelting. The experiments were performed at 1200 °C by equilibrating Sn-Fe alloys with silicate slags under reducing conditions in closed crucibles. The slag and metal analyses were used to calculate the γ_SnO/γ_FeO ratio in the slags and a multiple-linear regression on these values indicated that, in the range of slag compositions investigated, γ_SnO/γ_FeO is a function only of the CaO/SiO₂ ratio. At 1200 °C, γ_SnO/γ_FeO varies from about 1.1 for CaO-free slags to 3.6 for slags in which the CaO/SiO₂ ratio is 1.0. In practical applications, the slag-metal equilibrium in tin smelting is usually discussed in terms of the variation of the distribution coefficient,k, with the Fe content of the metal, wherek is defined ask = [pct Sn]/[pct Fe] · (pct Fe)/(pct Sn). An equation fork was derived in terms of the atom fraction of iron in the metal, the γ_SnO/γ_FeO in the slag, and the temperature. This equation was used to construct graphs ofk as a function of the iron content over the slag compositions and at temperatures which cover the range of tin smelting practice.     

Experimental study of phase equilibria in the “FeO”-ZnO-(CaO + SiO2) system with the CaO/SiO2 weight ratio of 0.71 at metallic iron saturation

The pseudoternary section “FeO”-ZnO-(CaO + SiO₂) with a CaO/SiO₂ weight ratio of 0.71 in equilibrium with metallic iron has been experimentally investigated in the temperature range from 1000 °C to 1300 °C (1273 to 1573 K). The liquidus surface in this pseudoternary section has been determined in the composition range of 0 to 33 wt pct ZnO and 30 to 70 wt pct (CaO + SiO₂). The system contains primary-phase fields of wustite (Fe _x Zn_1−x O_1−y ), zincite (Zn _z Fe_1−z O), fayalite (Fe _w Zn_2−w SiO₄), melilite (Ca₂Zn _u Fe_1−u Si₂O₇), and pseudowollastonite (CaSiO₃). The phase equilibria involving the liquid phase and the solid solutions have also been measured.     

Phase equilibria and thermodynamic properties of the Cu<Subscript>2</Subscript>O-CaO-Na<Subscript>2</Subscript>O system in equilibrium with copper

The liquidus surfaces of the Cu₂O-CaO, Cu₂O-Na₂O, and Cu₂O-CaO-Na₂O phase diagrams in equilibrium with metallic Cu were measured by thermal analysis at compositions varying from approximately 0 to 35 wt pct Na₂O and 0 to 15 wt pct CaO. Solubilities in the solid binary terminal solutions were also measured by wavelength dispersive X-ray spectrometer analysis. Copper oxide activities in binary liquid slags were determined from the measured oxygen content of the metallic copper equilibrated with the slags. The ternary system is a simple eutectic system. No ternary compounds were observed. The Cu₂O-CaO binary eutectic was measured at 1140 °C±10 °C at 10±1 wt pct CaO and the Cu₂O-Na₂O binary eutectic was measured at 803 °C±15 °C at 28±2 wt pct Na₂O. The liquid slag was thermodynamically modeled with the modified quasi-chemical model, while the solid Cu₂O-rich solution was treated as Henrian ideal. All data from the present work and from the literature (phase diagrams and activities) for the binary systems were evaluated simultaneously by least-squares optimization in order to obtain the best model parameters. With only these binary parameters, the calculated ternary liquidus surface is in very good agreement with the measurements. Finally, using the model, the liquidus projection of the Cu₂O-CaO-Na₂O system in equilibrium with Cu was calculated as well as the oxygen content of the equilibrated Cu as a function of slag composition.     

Phase equilibria in the system Fe-Zn-O at intermediate conditions between metallic-iron saturation and air

The phase equilibria in the FeO-Fe₂O₃-ZnO system have been experimentally investigated at oxygen partial pressures between metallic iron saturation and air using a specially developed quenching technique, followed by electron probe X-ray microanalysis (EPMA) and then wet chemistry for determination of ferrous and ferric iron concentrations. Gas mixtures of H₂, N₂, and CO₂ or CO and CO₂ controlled the atmosphere in the furnace. The determined metal cation ratios in phases at equilibrium were used for the construction of the 1200 °C isothermal section of the Fe-Zn-O system. The univariant equilibria between the gas phase, spinel, wustite, and zincite was found to be close to pO₂=1 · 10⁻⁸ atm at 1200 °C. The ferric and ferrous iron concentrations in zincite and spinel at equilibrium were also determined at temperatures from 1200 °C to 1400 °C at pO₂ = 1·10⁻⁶ atm and at 1200 °C at pO₂ values ranging from 1 · 10⁻⁴ to 1 · 10⁻⁸ atm. Implications of the phase equilibria in the Fe-Zn-O system for the formation of the platelike zincite, especially important for the Imperial Smelting Process (ISP), are discussed.     

The Nd-Zn phase diagram

Metallographie, thermal, and X-ray techniques were used to determine the phase relations in the Nd-Zn system. Eight compounds, three eutectics and a eutectoid were found. The compounds NdZn, NdZn₂, and Nd₂Znn melt congruently at 923°, 925°, and 981°C respectively. The compounds Nd₃Zn₁₁, NdZn_4.46, and Nd₃Zn₂₂ undergo peritectic decomposition at 870°, 902°, and 950°C respectively, while NdZn₃ undergoes peritectoid decomposition at 849°C. The eutectics occur at 12 wt pct Zn and 630°C, 38 wt pct Zn and 868°C, and 56 wt pct Zn and 854°C. The eutectoid occurs at 4 wt pct Zn and 622°C. The existence of a NdZn₁₂ phase of the SmZn₁₂ type structure has been confirmed. An allotropie transformation between the tetragonal NdZn₁₁ structure and the hexagonal NdZn₁₂ defect structure is proposed.     

Reduction of Sn-Bearing Iron Concentrate with Mixed H<Subscript>2</Subscript>/CO Gas for Preparation of Sn-Enriched Direct Reduced Iron

The development of manufacturing technology of Sn-bearing stainless steel inspires a novel concept for using Sn-bearing complex iron ore via reduction with mixed H₂/CO gas to prepare Sn-enriched direct reduced iron (DRI). The thermodynamic analysis of the reduction process confirms the easy reduction of stannic oxide to metallic tin and the rigorous conditions for volatilizing SnO. Although the removal of tin is feasible by reduction of the pellet at 1223 K (950 °C) with mixed gas of 5 vol pct H₂, 28.5 vol pct CO, and 66.5 vol pct CO₂ (CO/(CO + CO₂) = 30 pct), it is necessary that the pellet be further reduced for preparing DRI. In contrast, maintaining Sn in the metallic pellet is demonstrated to be a promising way to effectively use the ore. It is indicated that only 5.5 pct of Sn is volatilized when the pellet is reduced at 1223 K (950 °C) for 30 minutes with the mixed gas of 50 vol pct H₂, 50 vol pct CO (CO/(CO + CO₂) = 100 pct). A metallic pellet (Sn-bearing DRI) with Sn content of 0.293 pct, Fe metallization of 93.5 pct, and total iron content of 88.2 pct is prepared as a raw material for producing Sn-bearing stainless steel. The reduced tin in the Sn-bearing DRI either combines with metallic iron to form Sn-Fe alloy or it remains intact.     

Phase Equilibria of “Cu2O”-“FeO”-CaO-MgO-Al2O3 Slags at PO2 of 10-8.5 atm in Equilibrium with Metallic Copper for a Copper Slag Cleaning Production

Limited data are available on phase equilibria of the multicomponent slag system at the oxygen partial pressures used in the copper smelting, converting, and slag-cleaning processes. Recently, experimental procedures have been developed and have been applied successfully to characterize several complex industrial slags. The experimental procedures involve high-temperature equilibration on a substrate and quenching followed by electron probe X-ray microanalysis. This technique has been used to construct the liquidus for the “Cu₂O”-“FeO”-SiO₂-based slags with 2 wt pct of CaO, 0.5 wt pct of MgO, and 4.0 wt pct of Al₂O₃ at controlled oxygen partial pressures in equilibrium with metallic copper. The selected ranges of compositions and temperatures are directly relevant to the copper slag-cleaning processes. The new experimental equilibrium results are presented in the form of ternary sections and as a liquidus temperature vs Fe/SiO₂ weight ratio diagram. The experimental results are compared with the FactSage thermodynamic model calculations.     

Phase diagram and thermodynamic properties of the yttrium-zinc system

The phase relations of the yttrium zinc system have been reexamined. A total of eight compounds have been identified by differential thermal analysis, metallographic and X-ray diffraction techniques. The three compounds YZn, YZn₂ and YZn_8.5 melt congruently at 1105, 1080 and 890°C, respectively. The compounds YZn₃, YZn_3.67, YZn_4.46, YZn₆ and YZn₁₂ all decompose peritectically at 905, 896, 882, 872 and 685°C, respectively. Three eutectics were found at 875°C and 23.2 wt pct Zn (29.12 at. pct), 1015°C and 51 wt pet Zn (59 at. pct) and at 863°C and 82 wt pct Zn (86 at. pct). A polymorphic transformation was observed in the YZn₂ compound that proceeds at 750°C in the yttrium rich region but drops to approximately 630°C in the zinc rich region. The thermodynamic properties of the intermetallic compounds have been determined using the dewpoint method to measure the vapor pressure of zinc. The standard free energy relations vary from δG° (YZn) = −24,020 + 8.76T to δG° (YZn₁₂) = -85,940 + 48.61T cal/mole.     

Experimental study of phase equilibria in the “FeO”-ZnO-(CaO + SiO2) system with CaO/SiO2 weight ratios of 0.33, 0.93, and 1.2 in equilibrium with metallic iron

The pseudoternary sections “FeO”-ZnO-(CaO + SiO₂) with CaO/SiO₂ weight ratios of 0.33, 0.93, and 1.2 in equilibrium with metallic iron have been experimentally investigated in the temperature range from 1000 °C to 1300 °C (1273 to 1573 K). The liquidus surfaces in these pseudoternary sections have been experimentally determined in the composition range from 0 to 33 wt pct ZnO and 30 to 70 wt pct (CaO + SiO₂). The sections contain primary-phase fields of wustite (Fe _x Zn_1−x O_1+y ), zincite (Zn _z Fe_1−z O), fayalite (Fe _w Zn_2−w SiO₄), melilite (Ca₂Zn _u Fe_1−u Si₂O₇), willemite (Zn _v Fe_2−v SiO₄), dicalcium silicate (Ca₂SiO₄), pseudowollastonite and wollastonite (CaSiO₃), and tridymite (SiO₂). The phase equilibria involving the liquid phase and the solid solutions have also been measured.     

Silico-ferrite of Calcium and Aluminum (SFCA) Iron Ore Sinter Bonding Phases: New Insights into Their Formation During Heating and Cooling

The formation of silico-ferrite of calcium and aluminum (SFCA) and SFCA-I iron ore sinter phases during heating and cooling of synthetic iron ore sinter mixtures in the range 298?K to 1623?K (25?°C to 1350?°C) and at oxygen partial pressure of 5?×?10^?3 atm has been characterized using in situ synchrotron X-ray diffraction. SFCA and SFCA-I are the key bonding phases in iron ore sinter, and an improved understanding of their formation mechanisms may lead to improved efficiency of industrial sintering processes.?During heating, SFCA-I formation at 1327?K to 1392?K (1054?°C to 1119?°C) (depending on composition) was associated with the reaction of Fe₂O₃, 2CaO·Fe₂O₃, and SiO₂. SFCA formation (1380?K to 1437?K [1107?°C to 1164?°C]) was associated with?the reaction of CaO·Fe₂O₃, SiO₂, and a phase with average composition 49.60, 9.09, 0.14, 7.93, and 32.15?wt pct Fe, Ca, Si, Al, and O, respectively. Increasing Al₂O₃ concentration in the starting sinter mixture increased the temperature range over which SFCA-I was stable before the formation of SFCA, and it stabilized SFCA to a higher temperature before it melted to form a Fe₃O₄?+?melt phase assemblage (1486?K to 1581?K [1213?°C to 1308?°C]). During cooling, the first phase to crystallize from the melt (1452?K to 1561?K [1179?°C to 1288?°C]) was an Fe-rich phase, similar in composition to SFCA-I, and it had an average composition 58.88, 6.89, 0.82, 3.00, and 31.68?wt pct Fe, Ca, Si, Al, and O, respectively. At lower temperatures (1418?K to 1543?K [1145?°C to 1270?°C]), this phase reacted with melt to form SFCA. Increasing Al₂O₃ increased the temperature at which crystallization of the Fe-rich phase occurred, increased the temperature at which crystallization of SFCA occurred, and suppressed the formation of Fe₂O₃ (1358?K to 1418?K [1085?°C to 1145?°C]) to lower temperatures.     

Electroslag remelting with all-fluoride low conductivity slags

The electrical conductivity of liquids in the composition ranges CaF₂ + 0 to 12 wt pct AIF₃; CaF₂ + 0 to 20 wt pct LaF₃; and CaF₂ + 0 to 30 wt pct YF₃ has been determined at 1500° and 1600°C. It is deduced from the conductivities and the form of the phase diagrams of these systems that CaF₂ + 20 wt pct YF₃ is the optimum all-fluoride composition for electroslag melting or welding high melting point materials. It is demonstrated that pure iron, AISI 4340, AISI 321, and Hastelloy-X may all be electroslag melted without arcing through this slag using 60 Hz power. However, the initial postulate is confirmed in that only those materials with liquidus temperatures below that of the phase precipitated on freezing the slag can be made into ingots with good surface quality. The use of this slag in electroslag welding pure iron is investigated. It is inferred from the results that the slag composition chosen could probably be used to electroslag weld thick sections of titanium. Formerly Student in the Department of Metallurgy, University of British Columbia.     

Activity Coefficient of SiO2 in SiO2-Al2O3-CaO Slags with Low SiO2-Content at 1873 K (1600 °C)

The activity coefficient of SiO₂ in SiO₂-Al₂O₃-CaO slags with limited Al₂O₃ content was measured by equilibrating Fe-C-Si melt and slags at 1873 K (1600 °C). When the Al₂O₃ content was between 48 and 54 wt pct, the results show that $ \gamma_{{{\text{SiO}}_{ 2} }} $ rapidly decreases as the amount of SiO₂ in the slag decreases. The equilibrium amounts of Si and Al in a Fe melt in equilibrium with SiO₂-Al₂O₃-CaO slags were calculated based on the result of this study.