Subsolidus Phase Relationships in the System Fe2O3–Al2O3–TiO2 between 1000° and 1300°C

Subsolidus phase equilibria in the system Fe₂O₃–Al₂O₃–TiO₂ were investigated between 1000° and 1300°C. Quenched samples were examined using powder X-ray diffraction and electron probe microanalytical methods. The main features of the phase relations were: (a) the presence of an M₃O₅ solid solution series between end members Fe₂TiO₅ and Al₂TiO₅, (b) a miscibility gap along the Fe₂O₃–Al₂O₃ binary, (c) an α-M₂O₃( ss ) ternary solid-solution region based on mutual solubility between Fe₂O₃, Al₂O₃, and TiO₂, and (d) an extensive three-phase region characterized by the assemblage M₃O₅+α-M₂O₃( ss ) + Cor( ss ). A comparison of results with previously established phase relations for the Fe₂O₃–Al₂O₃–TiO₂ system shows considerable discrepancy.     

Influence of SO3 on the Phase Relationship in the System CaO–SiO2–Al2O3–Fe2O3

The influence of the additive SO₃ on the phase relationships in the quaternary system CaO-SiO₂-Al₂O₃-Fe₂O₃ was investigated by observing the change of volume ratio of 3CaOSiO₂ (C₃S) to 2CaOSiO₂ (C₂S) + CaO (C) in the sintered material with the increase of SO₃ content. The primary phase volume of C₃S in the quaternary phase diagram shrank with the increase of SO₃ and disappeared when the SO₃ content exceeded 2.6 wt% in the sintered material. Changes in the peritectic reaction relationship between CaO (C), 2CaOSiO₂ (C₂S), 3CaOSiO₂ (C₃S), 3CaOAl₂O₃ (C₃A), 4CaOAl₂O₃Fe₂O₃ (C₄AF), and liquid were also observed and discussed.     

Phase Equilibrium Relationships at Liquidus Temperatures in the System FeO–Fe2O3–Al2O3–SiO2

Phase equilibrium data at liquidus temperatures are presented for mixtures in the system FeO–Fe₂O₃–Al₂O₃–SiO₂. The volume located between the 1 and 0.2 atm. O₂ isobaric surfaces of the tetrahedron representing this system was studied in detail. Scattered data were obtained at lower O₂ pressures. Results obtained in the present investigation were combined with data in the literature to construct a phase equilibrium diagram, at liquidus temperatures, for the entire system FeO–Fe₂O₃–Al 2 O₃–SiO₂. Methods for interpretation of the diagram are explained.     

Kinetics of the α-to-α'H Polymorphic Phase Transition of Ca2SiO4 Solid Solutions

The α-to-α'_H transition of Ca₂SiO₄ solid solutions (C₂S(ss)) is a nucleation and growth process. This process was shown on time–temperature–transformation (TTT) diagrams for C₂S(ss) with different concentrations of foreign oxides (Na₂O, Al₂O₃, and Fe₂O₃). The kinetic cutoff temperature and the activation energy for growth of the α'_H phase increase steadily with increasing concentration of impurities. The activation energy for nucleation also increases above 950°C. The α'_H phase, which exists in equilibrium with the α phase at 1280°C, is formed at a maximum rate at around 1100°C regardless of the chemical composition. The TTT diagrams enable us to predict, as a function of cooling rate, the phase constitution of C₂S(ss) at ambient temperature.     

Phase Stability Study on the Remelting Reaction in Ca2SiO4 Solid Solutions

A pseudobinary phase equilibrium diagram has been established for the P₂O₅-bearing Ca₂SiO₄-CaFe₄O₇ system to confirm the occurrence of remelting reaction in α-Ca₂SiO₄ solid solutions (C₂S(ss)). The reaction started at 1290°C immediately after the α-to-α'_H transition and finished at 1145°C. The reaction products were made up of about 1 wt% of liquid and 99 wt% of solid α'_H-C₂S(ss). The liquid exsolved at 1290°C was rich in Fe₂O₃, consisting of about 30 wt% of Ca₂SiO₄ and 70 wt% of CaFe₄O₇. The liquid coexisting with α-C₂S(ss) precipitated new α'-phase crystals in association with the remelting reaction.     

Activity–Composition Relations in FeCr2O4–FeAl2O4 and MnCr2O4–MnAl2O4 Solid Solutions at 1500° and 1600°C

Activity–composition relations of FeCr₂O₄–FeAl₂O₄ and MnCr₂O₄–MnAl₂O₄ solid solutions were derived from activity–composition relations of Cr₂O₃–Al₂O₃ solid solutions and directions of conjugation lines between coexisting spinel and sesquioxide phases in the systems FeO–Cr₂O₃–Al₂O₃ and MnO–Cr₂O₃–Al₂O₃. Moderate positive deviations from ideality were observed.     

Stability Domains of TiO2–Ti3O5–Ti2O3–TiC/Ti(CN) Systems During Reduction Process

The phase domain of Ti₃O₅–Ti₂O₃–Ti(CO) at 1580 K was determined from the formation energies of Ti(C _x O _y ), as calculated via the Gibbs–Duhem equation. An extensive Ti(CO) domain is attributed to the high affinity between TiC and TiO. The phase domain of Ti₃O₅–Ti₂O₃–Ti(CN) was obtained at 1673 K using the formation energies of Ti(C _x N _y ). This study shows that the stable region for Ti₂O₃ is significantly small in the Ti₃O₅–Ti₂O₃–Ti(CN) phase domain. It demonstrates the absence of TiO and Ti₂O₃ in the normal syntheses of TiC and Ti(CN) from TiO₂, respectively.     

Homogeneous Fabrication of Al2O3–ZrO2–SiC Whisker Composite by Surface-Induced Coating

Al₂O₃–ZrO₂–SiC whisker composites were prepared by surface-induced coating of the precursor for the ZrO₂ phase on the kinetically stable colloid particles of Al₂O₃ and SiC whisker. The fabricated composites were characterized by a uniform spatial distribution of ZrO₂ and SiC whisker phases throughout the Al₂O₃ matrix. The fracture toughness values of the Al₂O₃–15 vol% ZrO₂–20 vol% SiC whisker composites (∼12 MPa.m^1/2) are substantially greater than those of comparable Al₂O₃–SiC whisker composites, indicating that both the toughening resulting from the process zone mechanism and that caused by the reinforced SiC whiskers work simultaneously in hot-pressed composites.     

Thermodynamic Modeling of the Isomorphous Phase Diagrams in the Al2O3–Cr2O3 and V2O3–Cr2O3 Systems

The phase diagrams in the Al₂O₃–Cr₂O₃ and V₂O₃–Cr₂O₃ systems have been assessed by thermodynamic modeling with existing data from the literature. While the regular and subregular solution models were used in the Al₂O₃–Cr₂O₃ system to represent the Gibbs free energies of the liquid and solid phases, respectively, the regular solution model was applied to both phases in the V₂O₃–Cr₂O₃ system. By using the liquidus, solidus, and/or miscibility gap data, the interaction parameters of the liquid and solid phases were optimized through a multiple linear regression method. The phase diagrams calculated from these models are in good agreement with experimental data. Also, the solid miscibility gap and chemical spinodal in the V₂O₃–Cr₂O₃ system were estimated.     

Influence of the Characteristics of Spinels on the Slag Resistance of Al2O3–MgO and Al2O3–Spinel Castables

The XRD patterns at ambient temperature and at 1500°C showed that the spinel in the Al₂O₃–MgO castables fired at 1500°C for 3 h has the higher peak intensity, compared to those in Al₂O₃–spinel castables; the interplanar distance in the set (311) is 2.43 Å for the spinel in Al₂O₃–MgO castables as well as the spinels in Al₂O₃–spinel castables using spinels containing 73, 90, and 94 wt% Al₂O₃, respectively. The corresponding alumina contents of the spinels in these castables were estimated to be around 75 wt%. The smaller grain size of the spinel in Al₂O₃–MgO castables compared to that in Al₂O₃–spinel castables is evidenced by the recrystallization of the in situ spinel only occurring in Al₂O₃–MgO castables as revealed by the XRD patterns at ambient temperature and at 1500°C. The larger amount and smaller grain size of the in situ spinel in the matrix mostly account for the better slag resistance of Al₂O₃–MgO castables, compared to Al₂O₃–spinel castables.     

Physical Properties and Structure of rf-Sputtered Amorphous Films in the System Al2O3–Y2O3

Amorphous films in the system Al₂O₃–Y₂O₃ were prepared by the rf sputtering method in the range of 0–76 mol% Y₂O₃, and their density, refractive index, and elastic constants were measured. All of the physical properties of the amorphous Al₂O₃–Y₂O₃ films had a similar compositional dependence; that is, they increased continuously, but not linearly with increasing Y₂O₃ content. To confirm the coordination states of aluminum and yttrium ions in the amorphous Al₂O₃–Y₂O₃ films, the Al K α X-ray emission spectra and the X-ray absorption near edge structures (XANES) were measured. The average coordination number of aluminum ions in the amorphous films containing up to about 40 mol% Y₂O₃ content was 5, that is a mixture of 4-fold- and 6-fold-coordinated states. In the region of more than about 50 mol% Y₂O₃, the fraction of the 6-fold-coordinated aluminum ions increased with increasing Y₂O₃ content, while the results led to the conclusion that the coordination number of yttrium ions was always 6, regardless of composition. These results indicate that, in amorphous films in the system Al₂O₃–Y₂O₃, the change of the coordination state of aluminum ions has an important effect on physical properties.     

Effect of Alkali Metal Oxide Addition on the Sinterability of MgO–B2O3–Al2O3 Glass–Al2O3 Filler Composites

The sintering of a composite of MgO–B₂O₃–Al₂O₃ glass and Al₂O₃ filler is terminated due to the crystallization of Al₄B₂O₉ in the glass. The densification of a composite of MgO–B₂O₃–Al₂O₃ glass and Al₂O₃ filler using pressureless sintering was accomplished by lowering the sintering temperature of the composite. The sintering temperature was lowered by the addition of small amounts of alkali metal oxides to the MgO–B₂O₃–Al₂O₃ glass system. The resultant composite has a four-point bending strength of 280 MPa, a coefficient of thermal expansion (RT—200°C) of 4.4 × 10⁻⁶ K⁻¹, a dielectric constant of 6.0 at 1 MHz, porosity of approximately 1%, and moisture resistance.     

Sliding Wear of Al2O3–SiC–(Al,Si) Composites against a Steel Counterface

The sliding-wear behavior of Al₂O₃–SiC–Al composites prepared by melt oxidation against a steel counterface has been recorded in a pin-on-disk machine. At high speeds and pressures (10 m/s, 20 MPa), friction and wear appear to be principally controlled by the in-situ formation of an interfacial film that consists of a layer of Fe₃O₄. The formation of this film is examined as a function of sliding speed, lubrication, and composite microstructure. A model is proposed in which high surface temperatures cause the preferential extrusion of aluminum from the composite onto the pin/disk interface. This promotes the adhesive pickup of iron and its oxidation to form a stable tribologically beneficial layer of Fe₃O₄.     

Phase Relations in the System Al2O3–B2O3–Nd2O3

The phase relations at a temperature below "subsolidus" in the system Al₂O₃–B₂O₃–Nd₂O₃ are reported. Specimens were prepared from various compositions of Al₂O₃, B₂O₃, and Nd₂O₃ of purity 99.5%, 99.99%, and 99.9%, respectively, and fired at 1100°C. There are six binary compounds and one ternary compound in this system. The ternary compound, NdAl₃(BO₃)₄ (NAB), has a phase transition at 950°C ± 15°C. The high-temperature form of NAB has a second harmonic generation (SHG) efficiency of KH₂PO₄ (KDP) of the order of magnitude of the form which has been used as a good self-activated laser material, and the low-temperature form of NAB has no SHG efficiency.     

Spray Pyrolysis of Fe3O4–BaTiO3 Composite Particles

Fe₃O₄–BaTiO₃ composite particles were successfully prepared by ultrasonic spray pyrolysis. A mixture of iron(III) nitrate, barium acetate and titanium tetrachloride aqueous solution were atomized into the mist, and the mist was dried and pyrolyzed in N₂ (90%) and H₂ (10%) atmosphere. Fe₃O₄–BaTiO₃ composite particle was obtained between 900° and 950°C while the coexistence of FeO was detected at 1000°C. Transmission electron microscope observation revealed that the composite particle is consisted of nanocrystalline having primary particle size of 35 nm. Lattice parameter of the Fe₃O₄–BaTiO₃ nanocomposite particle was 0.8404 nm that is larger than that of pure Fe₃O₄. Coercivity of the nanocomposite particle (390 Oe) was much larger than that of pure Fe₃O₄ (140 Oe). These results suggest that slight diffusion of Ba into Fe₃O₄ occurred.     

Influence of CaCO3 on the Hydration of 3CaO·Al2O3

The influence of CaCO₃ on the hydration of 3CaO Al₂O₃ containing about 90% C₃A is studied with compacts of their mixtures proportioned to 0, 2.5, 10, 20, and 50 wt% CaCO₃. The compacts are exposed to H₂O in liquid and in vapor phase, the attendant expansion being measured as a function of time. Differential thermal analysis, infrared absorption, and X–ray diffraction are used in conjunction with this technique. It is shown that the hydration reaction of 3 CaO · Al₂O₃ is suppressed by CaCO₃ additions and that this is due primarily to the formation of the low form of calcium carboaluminate on the surface of the C₃A grains. Expansion measurements of the compacts during the reactions show that this technique indicates the progress of hydration and detects the formation of the carboaluminate at an early stage of the reaction. Using the same technique, a study at 50% relative humidity provides the basis for the conclusion that C₃A reacts with CaCO₃ under these conditions by a direct mechanism.     

Experimental Establishment of the CaAl2O4–MgO and CaAl4O7–MgO Isoplethal Sections within the Al2O3–MgO–CaO Ternary System

The isoplethal sections CaAl₂O₄–MgO and CaAl₄O₇–MgO of the Al₂O₃–MgO–CaO ternary system have been experimentally established at 1 bar total pressure and air of normal humidity. The sections obtained provide new data and information that are in disagreement with thermodynamic evaluations and optimizations of the Al₂O₃–MgO–CaO ternary system published to date. These differences arise mainly from the inclusion, or exclusion, of the binary compound Ca₁₂Al₁₄O₃₃, mayenite, as a stable phase in the reported studies of the system. The presence or absence of this compound within the system has an important impact on the solid state and melting relationships of the whole ternary system. The present study confirms the solid-state compatibility CaAl₂O₄–MgO and CaAl₂O₄–MgO–MgAl₂O₄ up to 1372°± 2°C, the peritectic melting point of the later mentioned subsystem.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Electroconductive Al2O3–NbN Composites

Electroconductive Al₂O₃–NbN ceramic composites were prepared by hot pressing. Dense sintered bodies of ball-milled Al₂O₃–NbN composite powders were obtained at 1550°C and 30 MPa for 1 h under a nitrogen atmosphere. The bending strength and fracture toughness of the composites were enhanced by incorporating niobium nitride (NbN) particles into the Al₂O₃ matrix. The electrical resistivity of the composites decreased with increasing amount of NbN phase. For a 25 vol% NbN–Al₂O₃ composite, the values of bending strength, fracture toughness, Vickers hardness, and electrical resistivity were 444.2 MPa, 4.59 MPa·m^1/2, 16.62 GPa, and 1.72 × 10⁻²Ω·cm, respectively, making the composite suitable for electrical discharge machining.     

Discontinuous Dissolution of Iron Aluminate Spinel in the Al2O3–Fe2O3 System

When sintered 85Al₂O₃–15Fe₂O₃ (in wt%) specimens consisting of corundum grains and spinel particles were annealed at temperature where only a corundum phase was stable, phase transformation of spinel into metastable FeAIO₃ and subsequently complete dissolution of the metastable phase occurred together with the migration of grain boundaries at the surface of the specimens. Since the grain boundary migration was induced by grain boundary diffusion of Fe₂O₃ from the transforming and dissolving particles, the boundary migration by temperature decrease corresponds to a discontinuous dissolution of the spinel particles and a chemically induced grain boundary migration by temperature change. Inside the specimens, however, the transformation—dissolution and the grain boundary migration were suppressed because of unavailable accommodation of the volume expansion due to the transformation.