Transmission Electron Microscopy of Annealed ZrO2+8 Mol% Sc2O3

The influence of heat treatment (800°C for 200 h) on the micro-structure of 8 mol% Sc₂O₃-ZrO₂ was investigated by XRD and TEM. The starting material was initially characterized and found to contain predominantly cubic-fluorite phase grains, with <5% of the grain containing the rhombohedral β phase. The β phase was positively identified by the analysis of electron diffraction pattern and by quantitative energy dispersive X-ray analysis. On aging, the relative amount of β phase was found to increase to about 15 to 20% by XRD measurement; this was confirmed by TEM observation. The orientation relation between the different variants of the β phase within a grain was determined to be (100)_r||(010)_r, and the geometrical arrangement of these variants within the grain was deduced using a 2¹/₂D imaging electron microscopy technique.     

Thermodynamic Properties of Fe3O4-FeV2O4 and Fe3O4-FeCr2O4 Spinel Solid Solutions

Solid solutions of Fe304-FeV204 and Fe304-FeCr204 were prepared and equilibrated with Pt under controlled streams of CO/CO, gas mixtures at 1673 K. The concentration of Fe in Pt was used to determine the activity of Fe304 in the solid solutions. The activity of the second component was calculated by Gibbshhem integration. From these data, the Gibbs energy of mixing was derived for both systems. The experimental results and theoretical values which are determined from calculated cation distribution compare favorably in the case of vanadite solid solutions but not in the case of chromite solid solutions. The difference is attributed to a heat term arising from lattice distortion due to cation size difference. The positive heat of mixing will give rise to a miscibility gap in the system Fe304-FeCr204 at lower temperatures.     

Dissociation Pressures of Solid Solutions from Fe3O4 to 0.4Fe3O4·0.6CoFe2O4

The dissociation pressures of solid solutions from Fe₃O₄ to 0.4Fe₃O₄·0.6CoFe₂O₄ have been determined as a function of temperature. Within experimental error, solid solutions within this range are thermodynamically ideal.     

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.     

Characterization of Freeze-Dried Al2O3 and Fe2O3

Oxide crystallite formation and growth from freeze-dried sulfates were studied for the representative materials Al₂O₃ and Fe₂O₃. Transmission and scanning electron micrographs showed the formation and growth of chainlike aggregates of crystallites. Aggregation occurred as part of the nucleation and growth of the oxide, and discrete oxide particles were never present. Orientation of the chain aggregates was related to the ice structure formed during freezing. X-ray line broadening data showed that crystallite size is a function of the 1/5 to 1/7 power of time for isothermal treatments. A qualitative analysis of material transport favored the surface diffusion mechanism.     

High-Temperature Cation Distributions in Fe3-FeAl2O4

Cation distribution at 1600 K in the system Fe₃O₄-FeA1₂O₄ was derived from Seebeck coefficient measurements assuming that the aluminum distribution behaved according to the thermodynamic model proposed by O'Neill and Navrotsky. Approximately 10% of the aluminum resides tetrahedrally. This system provides a good test of thermodynamic models.     

Sintering of Acicular Fe2O3 Powder

The sintering of acicular Fe₂O₃ powder has been studied in comparison with an ordinary equiaxed powder. The acicular powder gave a dense material more than 99 % theoretical even from the relatively low green density. Oriented granular structures were observed in the 1200°C compacts. The observed densification behavior has been attributed to the pore configuration in the green compact.     

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.     

Evolution of a Nanocrystalline (Co,Ni)Al2O4 Spinel Phase from Quasicrystalline Precursor

This work reports on the synthesis of a spinel phase from a thermodynamically stable decagonal quasicrystalline Al₇₀Co₁₅Ni₁₅ alloy. The Al₇₀Co₁₅Ni₁₅ alloy, synthesized through slow cooling of the molten alloy, was subjected to milling in an attritor ball mill at 400 rpm for 5, 10, 20, 30, and 40 h with a ball to powder ratio of 20:1 in the hexane medium. The differential thermal analysis, X-ray diffraction, scanning, and transmission electron microscopy techniques have been used for characterization of milled as well as annealed powders. The Voigt function analysis has been used for calculation of the effective crystallite size and relative strain of ball-milled samples. The crystallite size has been found to be ∼14 nm after 40 h of milling along with a lattice strain of 8.1%. The annealing experiments have been carried out under two different conditions: (i) in vacuum and (ii) in air. The results of the present investigation clearly revealed that the nano-decagonal phase was stable in vacuum while annealing at 600°C for 40 h. However, during annealing under a similar condition in air, the formation of a nanospinel of (Ni,Co)Al₂O₄ of size ∼60 nm was identified. The possible structural evolution of the spinel from the quasicrystalline phase has been discussed.     

Kinetics of Solid-State Reaction of Bi2O3 and Fe2O3

Solid-state reactions of equimolar mixtures of Bi₂O₃ and Fe₂O₃ from 625° to 830°C and their kinetics were investigated. The reaction rates were determined from the integrated X-ray diffraction intensities of the strongest peaks of the reactants and products. The activation energy for the formation of BiFeO₃ was 96.6±9.0 kcal/mol; that for a second-phase compound, Bi₂Fe₄O₉, which formed above 675°C, was 99.4±9.0 kcal/mol. Specific rate constants for these simultaneous reactions were obtained. The preparation of single-phase BiFeO₃ from the stoichiometric mixture of Bi₂O₃ and Fe₂O₃ is discussed.     

Sintering of (Cu0.25Ni0.25Zn0.50)Fe2O4 Ferrite

A study has been conducted on the sintering of a ceramic ferrite having the composition (Cu_0.25Ni_0.25Zn_0.50)Fe₂O₄. The study analyzes the evolution of ferrite relative to density and microstructure with peak sintering temperature and dwell time at peak temperature. The densification and grain-growth rates are correlated with average grain size, relative density, and temperature. Corresponding rate-controlling diffusion mechanisms are proposed.     

Equilibrium Cation Distribution in NiAl2O4, CuAl2O4, and ZnAl2O4 Spinels

Stoichiometric NiAl₂O₄, CuAl₂O₄, and ZnAl₂O₄ spinels were prepared and equilibrated at temperatures from 600° to 1400°C. The parameters u and x , denoting the oxygen position and fraction of divalent cations on tetrahedral sites, respectively, were determined from a detailed X-ray diffraction analysis. In NiAl₂O₄, x increased from 0.07 at 595° to 0.26 at 1391°C; in CuAl₂O₄, x decreased from 0.68 at 613° to 0.64 at 1195°C; and in ZnAl₂O₄, x decreased from 0.96 at 905° to 0.94 at 1197°C. The form of the temperature dependence of x could not be described using theoretically based equations advanced in the literature. A more general equation which allows for a non-distributional contribution to the configurational entropy was derived and observed to properly describe the temperature dependence; the results indicate that short-range order is of definite significance in these intermediate aluminate spinels.     

Phase Relations in the System Fe2O3–Fe3O4–YFeO3 in Air

Measurements were made of temperature and ternary composition for coexisting liquid and crystalline phases on the air isobar in the system Fe₂O₃-Fe₃O₄-YFeO₃ with particular regard to the stability range and compositional limits of yttrium iron garnet. Phase equilibrium relations were determined by conventional quenching techniques combined with measurements of loss in weight at the reaction temperature to locate true ternary compositions. The intersection of the air isobar with the ternary univariant boundary curve for coexisting magnetite, garnet, and liquid phases results in a eutectic-type situation at the composition Y_0.27Fe_1.73 O_2.87 and 1469°± 2°C. A similar intersection of the isobar with the boundary curve for coexisting garnet, orthoferrite, and liquid phases gives rise to a peritectic-type reaction at 1555° 3°C. and Y_0.44Fe_1.56 O_2.89 The yttrium iron garnet crystallizing from liquids within these temperature and composition limits contains up to 0.5 mole % iron oxide in excess of the stoichiometric formula in terms of the starting composition 37.5 mole % Y₂O₃, 62.5 mole % Fe₂O₃. At 1470° C. the garnet phase in equilibrium with oxide liquid contains 2 mole % FeO in solid solution. The small solubility of excess of iron oxide and partial reduction of the garnet phase in air are unavoidable during equilibrium growth from the melt.     

Microstructure of (Fe0.2Co0.8)0.8(Fe2.38Co0.62O4): A Magnetic Oxidation Resistant Composite Formed by Coprecipitation

The metal–ferrite composite (Fe_0.2Co_0.8)_0.8(Fe_2.38Co_0.62O₄) has been studied by X-ray diffractometry measurements and high-resolution transmission electron microscopy. Spinel ferrite occurs in highly crystalline domains 100–150 nm in size, and the iron–cobalt alloy occurs in smaller and less-crystalline domains (10–20 nm). Both phases are heterogeneous in composition. The metal is embedded in the spinel phase, located near the edges, and overlaid by a poorly crystallized layer or misshapen regions containing small spinel crystals and amorphous phases. By annealing under vacuum up to 800°C, the misshapen regions disappear and the size of the metallic regions increases. The concentration of iron in the metallic regions decreases and their structure changes to face-centered cubic, while the spinel becomes enriched in iron.     

In Situ Formation of Hexaferrite Magnets within a 3Y-TZP Matrix: La2O3–ZnO–Fe2O3 and BaO–Fe2O3 Systems

The in situ formation of magnetoplumbite-type (M-type) hexaferrites within a 3Y-TZP matrix was examined for the La₂O₃–ZnO–Fe₂O₃ and BaO–Fe₂O₃ systems. The formation of barium hexaferrite (Ba-M) was rapid enough at a temperature of 1300°C for 2 h to result in a uniform dispersion of fine Ba-M particles in a tetragonal zirconia polycrystal (TZP) matrix. However, the formation of lanthanum-substituted hexaferrite (La-M) was rather sluggish, despite the existence of a charge-compensating divalent oxide. The 3Y-TZP/20-wt%-BaFe₁₂O₁₉ in situ composite possessed good magnetic properties, as well as moderately good mechanical properties.     

Solid-State Reactions between CaO Powder and Fe2O3

Diffusion couples are used to study the reaction between CaO powder and Fe₂O₃ All heat treatments were performed in air. The growth and morphology of calcium ferrites is studied at different temperatures. It is shown that CaO·2Fe₂O₃, starts to form at about 1125°C, while the accepted phase diagram for equilibrium with air predicts a temperature of 1155°C.     

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.     

Thermal Stability of Gallium Orthoferrite in the System Fe2O3-FeO-Ga2O3

Gallium orthoferrite (Ga_{2- x} Fe _x O₃) has a maximum thermal stability which coincides roughly with liquidus temperatures at oxygen pressures near atmospheric. As a result, changes in ambient oxygen pressure between 0.2 and 10 atm have a pronounced effect on equilibria. The compound exhibits a wide range in Ga:Fe ratio on both sides of the stoichiometric GaFeO₃ but is essentially invariant in oxygen content to 1500°C in air. The orthoferrite bears many similarities to the corresponding aluminum compound Al₂- _x Fe _x O₃.