Experimental study of phase equilibria in the PbO-Al2O3-SiO2 system

Equilibrium phase relations in the PbO-Al₂O₃-SiO₂ system have been investigated experimentally by means of high-temperature equilibration, quenching, and electron probe X-ray microanalysis (EPMA). The system has 21 primary phase fields including three monoxides (PbO, Al₂O₃, and SiO₂), seven binary compounds (Al₆Si₂O₁₃, PbAl₂O₄, PbAl₁₂O₁₉, Pb₂Al₂O₅, PbSiO₃, Pb₂SiO₄, and Pb₄SiO₆), and eleven ternary compounds (PbAl₂Si₂O₈, Pb₃Al₁₀SiO₂₀, Pb₄Al₂Si₂O₁₁, Pb₄Al₄SiO₁₂, Pb₄Al₄Si₃O₁₆, Pb₄Al₄Si₅O₂₀, Pb₅Al₂Si₁₀O₂₈, Pb₆Al₂Si₆O₂₁, Pb₈Al₂Si₄O₁₉, Pb₁₂Al₂Si₁₇O₄₉, and Pb₁₂Al₂Si₂₀O₅₅). Three new ternary compounds, Pb₄Al₄SiO₁₂, Pb₄Al₄Si₅O₂₀, and Pb₁₂Al₂Si₁₇O₄₉, were observed and characterized by EPMA. No extensive solid solution in any of the compounds was found in the present study. The liquidus isotherms were experimentally determined in most of the primary phase fields in the temperature range from 923 to 1873 K, and the ternary phase diagram of the PbO-Al₂O₃-SiO₂ system has been constructed.     

Experimental Liquidus Studies of the Pb-Fe-Si-O System in Equilibrium with Metallic Pb

Phase equilibria of the Pb-Fe-Si-O system have been investigated at 943 K to 1773 K (670 °C to 1500 °C) for oxide liquid in equilibrium with liquid Pb metal and solid oxide phases: (a) quartz, tridymite, or cristobalite; (b) (fayalite + tridymite) or (fayalite + spinel); (c) spinel (Fe₃O₄); (d) complex lead-iron silicates (melanotekite PbO·FeO_1.5·SiO₂, barysilite 8PbO·FeO·6SiO₂, 5PbO·FeO_1.5·SiO₂, and 6PbO·FeO_1.5·SiO₂); (e) lead silicates (Pb₂SiO₄, Pb₁₁Si₃O₁₇); (f) lead ferrites (magnetoplumbite Pb_1+x Fe_12?x O_19?x solid solution range); and (g) lead oxide (PbO, massicot). High-temperature equilibration on primary phase or iridium substrates, followed by quenching and direct measurement of Pb, Fe, and Si concentrations in the phases with the electron probe X-ray microanalysis, has been used to accurately characterize the system in equilibrium with Pb metal. All results are projected onto the PbO-“FeO”-SiO₂ plane for presentation purposes. The present study is the first systematic characterization of liquidus over a wide range of compositions in this system in equilibrium with metallic Pb.     

Experimental liquidus in the PbO-ZnO-“Fe2O3”-(CaO + SiO2) System in Air,with CaO/SiO2 = 0.35 and PbO/(CaO + SiO2) = 3.2

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in lead and zinc smelting. The liquidus in the pseudoternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with a CaO/SiO₂ weight ratio of 0.35 and a PbO/(CaO + SiO₂) weight ratio of 3.2 has been constructed to describe liquidus temperatures as a function of composition in the range of commercial operating conditions employed by the Lead Isasmelt smelting process. The section contains the primary phase fields of spinel (zinc ferrite, Zn _x Fe_3−y O_4+z ), zincite (Zn _u Fe_1−u O), melilite (Pb _v Ca_2−v Zn _w Fe_1−w -Si₂O₇), hematite (Fe₂O₃), magnetoplumbite (PbFe₁₀O₁₆), and wollastonite (CaSiO₃).     

Experimental study of phase equilibria in the PbO-ZnO-“Fe2O3”-CaO-SiO2 system in air for high lead smelting slags (CaO/SiO2=0.35 and PbO/(CaO + SiO2)=5.0 by weight)

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in commercial lead oxidation smelting. The liquidus in the pseudo-ternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with the CaO/SiO₂ weight ratio of 0.35 and the PbO/(CaO + SiO₂) weight ratio of 5.0 has been constructed using results of over 100 high-temperature equilibration and quenching experiments followed by electron probe X-ray microanalysis. The liquidus in this pseudoternary section contains primary phase fields of spinel (zinc ferrite) Zn _x Fe_3−x O_4+y , zincite Zn _u Fe_1−u O, melilite Pb _v Ca_2−v Zn _w Fe_1−w Si₂O₇, hematite Fe₂O₃, magneto-plumbite PbFe₁₀O₁₆, and dicalcium silicate Ca_2−t Pb _t SiO₄. The laboratory results are compared with the slags obtained from an industrial reactor.     

Phase-diagram study for the Al2O3-CaF2-SiO2 system

Phase relations for the Al₂O₃-CaF₂-SiO₂ system were investigated from 1673 to 1723 K. The hotfilament technique was applied to observe a two-liquid region and liquidus for the ternary system. The liquidus saturated with SiO₂ was investigated at 1673 K by using the hot-filament technique and the chemical equilibrium technique. In this system, the addition of Al₂O₃ to the CaF₂-SiO₂ system reduces the congruent temperature. A small substitution of Al₂O₃ for CaF₂ increases the solubility of SiO₂, namely, if the region of liquid phase could be enlarged. These results suggest that Al₂O₃ would be an effective substitute of CaF₂ in slag for steelmaking.     

Influence of the Al2O3-contents in the ternary-systems (FeO,MnO, CaO,MgO)- Al2O3-SiO2 on the course of the mixture gaps in the ternary space

In accordance with the previous phase equilibria in the ternary systems (FeO, MnO, CaO, MgO)- Al₂O₃-SiO₂ even small Al₂O₃-contents should be sufficient to close the wide mixture gaps in the binary edge systems of FeO-SiO₂, MnO-SiO₂, CaO-SiO₂ and MgO-SiO₂, which are stable in the temperature range from 1700 to 2100-2200°C. Thermodynamically this acceptance is not impossible but rather improb-able. Based on phase-theoretical considerations and the previous results of literature about the course of an unstable mixture gap in the system SiO₂-Al₂O₃ two thermodynamically founded versions were developed as possible, resulting phase equilibria in the SiO₂-rich, but experimentally not exactly examined part of the mentioned ternary-systems, and were added to the experimentally secured sections of these systems unproblematically.     

A reinvestigation of phase equilibria in the system Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-ZnO

The phase equilibria and liquidus temperatures in the binary SiO₂-ZnO system and in the ternary Al₂O₃-SiO₂-ZnO system at low Al₂O₃ concentrations have been experimentally determined using the equilibration and quenching technique followed by electron probe X-ray microanalysis. In the SiO₂-ZnO system, two binary eutectics involving the congruently melting willemite (Zn₂SiO₄) were found at 1448±5 °C and 0.52±0.01 mole fraction ZnO and at 1502±5 °C and 0.71±0.01 mole fraction ZnO, respectively. The two ternary eutectics involving willemite previously reported in the Al₂O₃-SiO₂-ZnO system were found to be at 1315±5 °C and 1425±25 °C, respectively. The compositions of the eutectics are 0.07, 0.52, and 0.41 and 0.05, 0.28, and 0.67 mole fraction Al₂O₃, SiO₂, and ZnO, respectively. The results of the present investigation are significantly different from the results of previous studies.     

Critical assessment of activity coefficients of oxides in molten binary and ternary silicates,aluminates and aluminosilicates

Critical assessment is made of the activity coefficients of CaO, MgO, MnO, FeO, Al₂O₃ and SiO₂ in molten silicates, aluminates and aluminosilicates. In this assessment due consideration is given to the consistency of the free energies of formation of the interoxide compounds derived from the oxide activity data, compared with those derived from the compiled thermochemical data. For most oxides, it is found that by using an empirical formulation of the melt composition in ternary systems, the composition dependence of the oxide activity coefficient, γOX, can be represented by a single curve. For example, over a wide composition range in the FeO‐CaO‐SiO₂ system, the log(γCaO) is a single function of the melt composition in mol fraction as (?SiO₂ + 0.3xFeO); this relation being similar to that in the binary CaO‐SiO₂ melts. Therefore, with respect to γCaO, this ternary system is reduced to a pseudo binary system as xCaO ‐ (?SiO₂ + 0.3xFeO). With respect to γCaO, the ternary system CaO‐Al₂O₃‐SiO₂ is reduced to a pseudo binary system as xCaO ‐ (?SiO₂ + 0.4 xAl₂O₃). With γSiO₂, this ternary system is reduced to a pseudo binary system as (?CaO + xAl₂O₃) ‐ xSiO₂.     

Phase Diagram of the Al2O3—ZrO2—Nd2O3 System. Part 1. Isothermal Sections of the Phase Diagram at 1250 and 1650°C

Isothermal sections at 1250 and 1650°C have been constructed for the Al₂O₃—ZrO₂—Nd₂O₃ phase diagram, and the phase equilibria at those temperatures have been identified. No ternary compounds are found, and nor are there appreciable solid-solution ranges based on the components or binary compounds. Partially quasibinary sections have been observed: NdAlO₃—(66.7 mole% ZrO₂—33.3 mole% Nd₂O₃), AL—F, and β—F, which triangulate the ternary system, and the mechanism for the penetration of the phase Nd₂Zr₂O₇ into the ternary system has been established.     

Nitrogen Ceramics: Liquid Phase Sintering

Abstract

The role of a minor silicate eutectic liquid phase as a transport medium in sintering hot–pressed silicon nitride (β Si₃N₄) ceramics was identified in the 1970s. A similar mechanism is applicable to hot–pressed Si–Al–O–N ceramic alloys which offer an advantage in control of the final liquid volume and hence in superior high temperature mechanical properties. By increasing the liquid volume it is possible to densify ceramic alloys without application of pressure at the sintering temperature and hence to fabricate components of complex shape. The Lucas Syalon ceramics typify the new range of pressureless–sintered ceramics based on the β Si₃N₄ structure. They are fabricated from the ultrafine compound powders α Si₃N₄, SiO₂, Al₂O₃, Y₂O₃, and a polytypoid phase (a substitute for A1N). The ceramics consist of submicrometre solid solution crystals of general composition Si_3?xAl_xO_xN_4?x(x < 1) within a minor matrix phase which may be either a glassy Y–Si–Al oxynitride or be crystallized to form yttrogarnet. Analysis of matrix glass compositions shows them to be residues of liquids near to a ternary eutectic in the Y₂O₃–SiO₂–Al₂O₃ system which is well below the sintering temperature of ～ 1800°C. Sintering models, based on particle rearrangement due to dissolution of the major α Si₃N₄ component in the eutectic liquid and its reprecipitation as a β Si₃N₄ solid solution, are discussed. Properties and current applications of Syalon ceramics are surveyed briefly. PM/0266     

Use of phase diagrams for the prediction of the ferrite-and silicate-binder compositions of fluxed sinters

The compositions of the calcium aluminosilicatoferrite phases in commercial iron-ore sinters, which are solid solutions based on CaFe₄O₇, CaFe₂O₄, and Ca₂Fe₂O₅ ferrites of the CaO-Fe₂O₃ system, are studied. The sequence of the formation of the calcium aluminosilicatoferrites and their compositions with Ca₂SiO₄ and Ca₃SiO₅ silicates in sinters is found to be analogous to the crystallization of the ferrite and silicate phases in the ternary CaO-SiO₂-Fe₂O₃ system. This allows the phase diagram of this system to be used for the explanation of the formation of the mineral binder compositions for ore grains during sintering of commercial superfluxed sinters.     

Phase diagram of the Al2O3-ZrO2-Sm2O3 system. I. Triangulation and isothermal sections at 1250 and 1650°C

Isothermal sections at 1250 and 1650 °C have been constructed for the Al₂O₃-ZrO₂-Sm₂O₃ phase diagram, and phase equilibria at those temperatures have been demonstrated. No ternary compounds are found and nor are areas of solid solutions based on components and binary compounds in the system. Partially quasibinary sections Al₂O₃-F, SmAlO₃-(66.7% ZrO₂ · 33.3% Sm₂O₃), and Sm₄Al₂O₉-F have been detected, which triangulate the ternary system, and a demonstration is given of the mechanism for penetration of a phase Sm₂Zr₂O₇ with the structure of the pyrochlore into the middle of the Al₂O₃-ZrO₂-Sm₂O₃ system.     

Phase diagram of Er-Sn-Te system for diluted magnetic semiconductor developments

Phase diagrams of the RE (rare earth)-IV-VI systems are very important for the design of rare earth doped diluted magnetic semiconductors (DMSs), but related information is very limited. In this work, ...     

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.     

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.     

Analysis of the Fe–Ce–O–C–<Emphasis Type="Italic">M</Emphasis> phase diagrams (<Emphasis Type="Italic">M</Emphasis> = Ca,Mg, Al,Si) by constructing a component-solubility surface

Analysis of the ternary phase diagrams of Ce₂O₃- and CeO₂-containing oxide systems allowed us to find the oxide compounds that form during steel deoxidizing with cerium and with cerium together with aluminum, calcium, magnesium, or silicon. The temperature dependences of the equilibrium constants of formation of Ce₂O₃ oxides and Ce₂O₃ · Al₂O₃, Ce₂O₃ · 11Al₂O₃, Ce₂O₃ · 2SiO₂, 7Ce₂O₃ · 9SiO₂ and Ce₂O₃ · SiO₂ compounds are found. Surfaces for the component solubility in metallic melts Fe–Al–Ce–O–C, Fe- Ca–Ce–O–C, Fe–Mg–Ce–O–C, and Fe–Si–Ce–O–C are constructed. Nonmetallic inclusions that form in the course of experimental melts of St20 steel after its deoxidizing with silicocalcium and rare-earth metal (REM)-containing master alloys in a ladle furnace after degassing are studied. Phase inhomogeneity of the inclusions is found. As a rule, they consist of phases classified into the following three groups: oxide–sulfide, sulfide–oxide, and multiphase oxide–sulfide melt. Calcium aluminates are found to be components of complex sulfide-oxide noncorrosive inclusions.     

Phase equilibria in the system HfO2-Y2O3-La2O3 AT 1900°C

We have used x-ray phase analysis, electron-probe microanalysis, petrography, and electron microscopy on annealed specimens to study phase equilibria in the ternary system HfO₂-Y₂O₃-La₂O₃ at 1900 °C over the entire concentration range. We have plotted the isothermal cross section of the phase diagram for this system at the indicated temperature. We found 23 phase regions. A typical feature of the system is formation of solid solutions based on different crystal modifications of the starting components (A-and H-La₂O₃, C-Y₂O₃, T-and F-HfO₂) and also the compounds La₂Hf₂O₇, LaYO₃. We did not observe new phases in the system. The nature of the phase equilibria in the system is consistent with the high relative thermodynamic stability of lanthanum hafnate (ΔH °La₂Hf₂O₇ ≈ 100 kJ/mole) compared with LaYO₃. We established that adding a third component extends the thermal stability region for the ordered phase of LaYO₃ toward higher temperatures. __________ Translated from Poroshkovaya Metallurgiya, Nos. 1–2(447), pp. 73–87, January–February, 2006.     

Effects of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CaO/SiO<Subscript>2</Subscript> Ratio on Phase Equilbria in the ZnO-“FeO”-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-SiO<Subscript>2</Subscript> System in Equilibrium with Metallic Iron

The phase equilibria and liquidus temperatures in the ZnO-“FeO”-Al₂O₃-CaO-SiO₂ system in equilibrium with metallic iron have been determined experimentally in the temperature range 1383 K to 1573 K (1150 °C to 1300 °C). The experimental conditions were selected to characterize lead blast furnace and imperial smelting furnace slags. The results are presented in a form of pseudoternary sections ZnO-“FeO”-(Al₂O₃ + CaO + SiO₂) with fixed CaO/SiO₂ and (CaO + SiO₂)/Al₂O₃ ratios. It was found that wustite and spinel are the major primary phases in the composition range investigated. Effects of Al₂O₃ concentration as well as the CaO/SiO₂ ratio on the primary phase field, the liquidus temperature, and the partitioning of ZnO between liquid and solid phases have been discussed for zinc-containing slags.     

A Reaction Between High Mn-High Al Steel and CaO-SiO2-Type Molten Mold Flux: Part I. Composition Evolution in Molten Mold Flux

In order to elucidate the reaction mechanism between high Mn-high Al steel such as twin-induced plasticity steel and molten mold flux composed mainly of CaO-SiO₂ during continuous casting process, a series of laboratory-scale experiments were carried out in the present study. Molten steel and molten flux were brought to react in a refractory crucible in a temperature range between 1713 K to 1823 K (1440 °C to 1550 °C) and composition evolution in the steel and the flux was analyzed using inductively coupled plasma atomic emission spectroscopy, X-ray fluorescence, and electron probe microanalysis. The amount of SiO₂ in the flux was significantly reduced by Al in the steel; thus, Al₂O₃ was accumulated in the flux as a result of a chemical reaction, 4[Al] + 3(SiO₂) = 3[Si] + 2(Al₂O₃). In order to find a major factor which governs the reaction, a number of factors ((pct CaO/pct SiO₂), (pct Al₂O₃), [pct Al], [pct Si], and temperature) were varied in the experiments. It was found that the above chemical reaction was mostly governed by [pct Al] in the molten steel. Temperature had a mild effect on the reaction. On the other hand, (pct CaO/pct SiO₂), (pct Al₂O₃), and [pct Si] did not show any noticeable effect on the reaction. Apart from the above reaction, the following reactions are also thought to happen simultaneously: 2[Mn] + (SiO₂) = [Si] + 2(MnO) and 2[Fe] + (SiO₂) = [Si] + 2(FeO). These oxide components were subsequently reduced by Al in the molten steel. Na₂O in the molten flux was gradually decreased and the decrease was accelerated by increasing [pct Al] and temperature. Possible reactions affecting the Al₂O₃ accumulation are summarized.     

Triangulation and Liquidus Surface in the Al2O3 ― ZrO2 ― La2O3 Phase Diagram

A projection has been constructed for the liquidus surface in the phase diagram for the Al₂O₃ ― ZrO₂ ― La₂O₃ system on to the plane of the concentration triangle. There are found to be two partially quasibinary sections LaAlO₃ ― (98.5 mole% ZrO₂ ― 1.5 mole% La₂O₃) and La₂O₃·11Al₂O₃ ― (98.5 mole% ZrO₂ ― 1.5 mole% La₂O₃) together with one quasibinary LaAlO₃ ― La₂Zr₂O₇ section, which triangulate the ternary system, and the phase diagrams have been constructed for them. There are nine fields of primary crystallization for phases based on the T and F forms of ZrO₂, the X, H, and A forms of La₂O₃, and also the phases La₂Zr₂O₇, LaAlO₃, La₂O₃·11Al₂O₃, and Al₂O₃, together with two quasibinary eutectics and three ternary ones. It is not found that there are any ternary phases and solid-solution regions based on the components and the binary compounds. The minimum temperature in the system is 1665°C. The interactions are basically of eutectic type.