Effect of Oxygen Partial Pressure on the Creep of Polycrystalline Al2O3 Doped with Cr, Fe, or Ti

Steady-state creep was studied in hot-forged polycrystalline Al₂O₃ (3 to 42 μm) of nearly theoretical density doped with≤1 cation % of Fe, Ti, or Cr. Tests were conducted at stresses between 10 and 550 kg/cm² at 1375° to 1525°C under O₂ partial pressures of 0.88 to 10⁻¹⁰ atm. Except in the 10-μm Fe-doped material tested at very small stresses, slightly nonviscous creep behavior was generally observed. The effects of P _o2 on the creep rate indicated that increased concentration of a divalent (Fe²⁺) or quadrivalent (Ti⁴⁺) impurity in solid solution enhances the creep rate of polycrystalline Al₂O₃. The activation energies for the creep of Fe- and Ti-doped Al₂O₃ samples (148 and 145 kcal/mol, respectively) were significantly higher than that for Cr-doped material (114 kcal/mol). Taking into account the effects of P_o2, temperature, and grain size, it was concluded that the steady-state creep of transition-metal-doped Al₂O₃ is controlled by cation lattice diffusion.     

Phase Diagram of the System BaO-Fe2O3

The phase diagram of the system BaO-Fe₂0₃ was determined by X-ray diffraction, melting-point measurement, and microscopic methods. Since the reduction of Fe³⁺ to Fe²⁺ was observed by chemical analysis in the samples heated at high temperature, especially in molten samples, the samples were heated at 1 atmosphere pressure of oxygen in the temperature region in which the liquid was in equilibrium; 1 atmosphere pressure of oxygen was su5cient to restrain the reduction of Fe³⁺. In the temperature region of solid-solid equilibrium, the dissociation was not observed even when the samples were heated in air. BaO - 6Fe₂O₃ formed a solid solution with BaO.Fe₂0₃. The BaO:Fe₂0₃ ratio of the solid solution was BaO.4.5Fe₂0₃ at 1350°C. and BaO. 5.0Fe₂0_a at 800°C. The precipitation micro-structures of each primary solid solution were observed.     

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.     

Microstructural Characterization of ZrO2 Particles Prepared by Reaction of Gaseous ZrCl4 with Fe2O3

The microstructure of ZrO₂ fine particles produced by a novel synthesis method at 450° and 950°C has been studied. The fundamentals of the synthesis method, which involves both chemical and diffusion phenomena, are presented. The method is based on mass transport through the gaseous phase between metallic zirconium and Fe₂O₃ powder. The mass-transporting chemical species are zirconium and iron chlorides. This article focuses on the microstructure and structure of ZrO₂ particles formed by the reaction between gaseous ZrCl₄ and solid Fe₂O₃, which is a relevant reaction step that occurs during the synthesis process. The resulting ZrO₂ crystals grown on Fe₂O₃ particles have been analyzed using transmission electron microscopy. Microstructural characterization has been complemented by X-ray diffractometry analysis. Tetragonal-ZrO₂ is produced at 450°C and monoclinic-ZrO₂ single crystals are produced at 950°C.     

High-Temperature Creep Behavior of Polycrystalline SrZrO3

The high-temperature creep behavior of sintered polycrystalline SrZrO₃ containing 1.35 wt% Fe₂O₃ was investigated as a function of temperature, stress, grain size, and strain level over the ranges 1160° to 1275°C, 780 to 3110 psi, 0.45 to 2.04 μm, and 0.0014 to 0.014, respectively. A constant-load 4-point (pure bending) method was used to load the specimens. The creep rate is time-dependent, decreasing exponentially with strain, i.e.     , where the decay constant (β=118, measured at the 1560 psi stress level over the strain range 0.0014 to 0.014) is independent of temperature and grain size. No significant grain growth occurred during creep. The activation energy of 169±10 kcal/mol obtained for creep is relatively independent of temperature, stress, grain size, and strain level over the ranges investigated. The creep rate is directly proportional to the cube of the stress and the reciprocal of the grain size; this result is consistent with nonviscous creep theories based on dislocation generation and climb as the rate-controlling deformation mechanism.     

Phase Equilibria in the Spinel Region of the System FeO-Fe2O3-Al2O3

Phase relations in the spinel region of the system FeO-Fe₂O₃-Al₂O₃ were determined in CO₂ at 1300°, 1400°, and 15000°C and for partial oxygen pressures of 4 × 10⁻⁷ and 7 × 10⁻¹⁰ atmospheres at 15OO°C. The spinel field extends continuously from Fe₃O_4-x to FeAl₂O_4+z.     

Thermal Grooving of MgO and Al2O3

High-purity polycrystalline MgO and Al₂O₃ were thermally grooved at 1500° and 1600°C. Accurate techniques were developed for following the growth of a single groove. For high-purity samples growth kinetics were essentially similar to those reported in the literature but were determined to be controlled by volume diffusion. Specimens for thermal grooving were prepared from Al₂O₃ to which transition metal oxides (Fe₂O₃₉, MnO, and TiO₂), which are known to accelerate shrinkage and sintering of Al₂O₃ powder compacts, had been added; the rate of groove growth was increased remarkably by minor amounts of these additives. Control of partial pressure indicated that Fe²⁺ and Ti⁴⁺ are the species active in promoting groove growth. Substantial evidence was found for volume diffusion as the mechanism controlling groove formation.     

X-Ray Study of the Solid Solution of TiO, Fe2O3, and G, O3 in Mullite (3A12O3a2Si02)

A study of the solid solution of TiO₂, Fe₂O₃, and Cr₂0₃ in mullite was made by measuring the changes in lattice parameters and unit-cell volume. Synthetic mullite (3O₃-2SiO₂) was reacted with up to 12 weight % of the oxides at temperatures ranging from 1000° to 17000C. The approximate minimum temperature required for the formation of solid solution was 12000C. for Fe₂0₃ and 1400°C. for Cr₂O₃ and TiO₃. The maximum amount of solid solution found was 2 to 4% TiO₂ at 1600°C., 10 to 12% Fe₂O_s at 1300°C., and 8 to 10% Cr_ZO₃ at 1600OC. Lattice parameters and unit-cell volumes for each solid solution series increased with increasing amounts of foreign oxide. There was good agreement between the calculated and observed increase in cell dimensions for the iron oxide series. Except in the case of titania, there was good agreement between X-ray data and petrographic observations.     

The System MgO-Cr2O3−Fe2O3 at 1300°c in Air

Phase relations in air at 1300°C were determined for the system MgO-Cr₂O₃−Fe₂O₃ by conventional quenching techniques. Details of the phase equilibria were established for: (1) the sesquioxide solid solution between Cr₂O₃ and Fe₂O₃, (2) the spinel solid solution field between MgCr₂O₄ and MgFe₂O₄, and (3) the periclase solid solution field for MgO. Selected tie lines connecting coexisting compositions were established with X-ray diffractometer data. Diffuse reflectance spectra, diffractometer intensity ratios, and lattice parameter measurements were obtained for quenched samples to study the structural inversion in the spinel series MgCr₂O4-MgFe₂O₄.     

Grain Growth in Fe3O4

Sintering and microstructural evolution were studied in Fe₃O₄ as a model system for spinel ferrites. Fe₃O₄ powder, purified by the salt-crystallization method, was sintered to ∼99.5% density in a CO-CO₂ atmosphere. The p _O2 Of the sintering atmosphere drastically affects the microstructure (grain size) of sintered Fe₃O₄ without significantly affecting density. The measured grain-boundary mobilities, M , of Fe₃O₄ fit the equation M=M ₀( T ) p _O2^−1/2 with M ₀( T ) = 2.5×10⁵ exp[-(609kJ·mol-¹/ RT ](m/s)(N/m²)^−l. The grain-boundary migration process appeared to be pore-drag controlled, with lattice diffusion of oxygen as the most likely rate-limiting step.     

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.     

Discontinuous Dissolution and Grain-Boundary Migration in Al2O3-Fe2O3 by Oxygen Partial Pressure Change

When sintered 95Al₂O₃-5Fe₂O₃ (wt%) specimens constituting corundum grains and iron aluminate spinel precipitates were annealed under high oxygen partial pressure (P_o2) where only a corundum phase is stable, fast dissolution of particulate spinel precipitates occurred, together with the migration of corundum grain boundaries. Behind the migrating boundaries, a corundum solid solution enriched with Fe₂O₃ formed. Discontinuous dissolution (DD) of particulate spinel precipitates thus occurred by P_o2 increase. In contrast, when 95Al₂O₃-5Fe₂O₃ specimens constituting only corundum grains were annealed under low P_o2 where both corundum and spinel phases are stable, grain boundaries migrated without spinel precipitation, leaving behind a corundum phase depleted of Fe₂O₃, similar to chemically induced grain-boundary migration (CIGM) observed during solute depletion. The volatilization of Fe₂O₃ appeared to cause the boundary migration without precipitation. The observed CIGM and DD would suggest various possibilities of microstructure control in other oxide systems through oxygen partial pressure change.     

High-Temperature Deformation of Polycrystalline Fe2O3

The effects of stress, temperature, grain size, porosity, and O₂ partial pressure on the creep of polycrystalline Fe₂O₃ were studied in the range 770° to 1105°C by tests in 4-point bending and compression. Deformation rates are controlled by the stress-directed diffusion of either oxygen or iron. Diffusion coefficients computed from the Nabarro-Herring formula modified by including an empirical porosity-correction term are also consistent with the values reported for oxygen and iron.     

Subsolidus Reactions in the System Fe2O3- TiO2

A study has been made of the binary system Fe₂O₂-TiO₂ by solid-state reactions under dry and hydrothermal conditions. Under dry conditions only one binary compound, pseudobrookite (Fe₂O₃-TiO₂), was formed and no evidence of solid solution on either side of this compound at temperatures up to 1200°C. was obtained. The system under these conditions is a simple binary with a single binary compound. Under hydrothermal conditions of 300° C. and 1200 Ib. per sq. in. the system is apparently also binary, with a single unstable compound closely resembling, if not identical with, the naturally occurring mineral arizonite (ferric metatitanate, Fe₂(TiO₃)₃).     

Phase Equilibrium Studies in the System Iron Oxide-Al2O3-Cr2O3

Subsolidus phase relations in the system iron oride-Al₂O₂-Cr₂O₃ in air and at 1 atm. O₂ pressure have been studied in the. temperature interval 1250° to 1500°C. At temperatures below 1318° C. only sesquioxides with hexagonal corundum structure are present as equilibrium phases. In the temperature interval 1318° to 1410°C. in air and 1318° to 1495° C. at 1 atm. O₂, pressure the monoclinic phase Fe₂O₃. Al₂O₃ with some Cr₂O₃ in solid solution is present in the phase assemblage of certain mixtures. At temperatures above 1380°C. in air and above 1445°C. at 1 atm. O₂ pressure a complex spinel solid solution is one of the phases present in appropriate composition areas of the system. X-ray data relating d- spacing to composition of solid solution phases are given.     

Phase Relations In The Pseudo-Ternary System La2O3–SrO–Fe2O3

The phase relations in the pseudo-ternary system La₂O₃–SrO–Fe₂O₃ have been investigated in air. Isothermal sections at 1100° and 1300°C are presented based on X-ray diffraction and thermal analysis of annealed samples. Extended solid solubility was observed for the compounds Sr _{n +1− v} La _v Fe _n O_{3 n +1−δ} ( n =1, 2, 3, and ∞) and Sr_{1− x} La _x Fe₁₂O₁₉, while only limited solubility of La in Sr_{4− z} La _z Fe₆O_13±δ was observed. At high Fe₂O₃ content, a liquid with low La₂O₃ content was stable at 1300°C.     

Phase Equilibria in the Ferrite Region of the System FeO-MgO-Fe2O3

Phase equilibria in the ferrite region of the system FeO–MgO–Fe₂O₃ have been investigated up to 1300°C. over an oxygen-pressure range of 1.0 to 0.01 atmospheres. The five most important features of the equilibria in this system are as follows: (1) The spinel phase can exist with a deficiency of oxygen in the high-magnesium compositions, (2) Mg++ replaces Fe⁺⁺ in Fe₃O₄ beyond the "stoichiometric MgFe₂O₄," corresponding to the formula (MgO)_xMgFe₂O₄, where x = 0.092 ± 0.004 and is independent of temperature, (3) the spinel field does not include single-phase composition corresponding to Mg-Fe₂O₄, (4) the lattice constant of spinels in this system depends on cation distribution, and the extent of distribution changes as a function of temperature in turn depends on the magnesium concentration in the spinel, and (5) the spinel field near its terminus has little or no width.     

Phase Relations in the System Iron Oxide—Cr2O3 in Air

The quenching method has been used to determine approximate phase relations in the system iron oxide-Cr₂O₃ in air. Only two crystalline phases, a sesquioxide solid solution (Fe₂O₃–Cr₂O₃) with corundum structure and a spinel solid solution (approximately FeO ·Fe₂O₃–FeO – Cr₂O₃), occur in this system at conditions of temperature and O₂ partial pressure (0.21 atm.) used in this investigation. Liquidus temperatures increase rapidly as Cr₂O₃ is added to iron oxide, from 1591°C. for the pure iron oxide end member to a maximum of approximately 2265°C. for Cr₂O₃. Spinel(ss) is the primary crystalline phase in iron oxide-rich mixtures and sesquioxide (ss) in Cr₂O₃–rich mixtures. These two crystalline phases are present together in equilibrium with a liquid and gas (po₂= 0.21 atm.) at approximately 2075°C.     

Co2+-Substitution Effect in Ce-TZP/La M-type Hexaferrite Composites

A Ce-TZP/platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was synthesized in situ while sintering from a mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO powders. Platelike La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ crystals were grown in a dense Ce-TZP matrix after sintering at temperatures of 1200°–1350°C. The temperature range for sintering Ce-TZP/La(Fe,Al)₁₂O₁₉ composites was expanded widely by substituting Co²⁺ ions for Fe²⁺ ions in its structure. The highest value of the bending strength of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composites was 880 MPa, which was higher than that of the Ce-TZP/La(Fe,Al)₁₂O₁₉ composite (780 MPa) and Ce-TZP (513 MPa). The saturation magnetization of the Ce-TZP/La(Co(Fe_0.9Al_0.1)₁₁)O₁₉ composite was a constant value of 7.7 emu/g after the composite was sintered at 1200°–1350°C.     

Grain Size Distributions and Grain Growth in MgO and MgO-Fe2O3 Solid Solutions

The Cahn-Fullman method was used to determine three-dimensional grain size distributions from experimentally measured two-dimensional chord distributions in high-purity MgO and magnesiowustite (0.10 and 0.48 wt% Fe₂O₃). Using the standard deviation of the three-dimensional distributions, the constant which relates average three- and two-dimensional grain sizes was evaluated by the procedure of Mendelson. The characteristics of the grain size distributions were correlated with steady state, abnormal, and terminal grain growth in MgO and magnesiowustite from 1300° to 1500°C. The distribution parameters were particularly useful in characterizing anomalous (i.e. abnormal and terminal) grain growth behavior.