Role of α-Fe2O3 Morphology on the Color of Red Pigment for Porcelain

To produce a new red pigment for Japanese porcelains, some hematite (α-Fe₂O₃) powders produced by different methods were investigated by mixing them with lead-free frit powders and firing them on white porcelain plates at 800°C. Commercial hematite powders and uniform α-Fe₂O₃ powders 155 and 53 nm in diameter which were prepared using conventional- and microwave-hydrothermal reactions, respectively, were used as sources of red pigments. The morphology and dispersion of the above α-Fe₂O₃ powders were found to have a significant effect on the tone of red color for porcelain pigment.     

Kinetic Study of Black Fe2O3-Cr2O3 Pigment Synthesis: I, Influence of Synthesis Time and Temperature

A study was undertaken of the kinetics of the black Fe-Cr oxide pigment synthesis process based on the oxide constituents (Fe₂O₃ and Cr₂O₃). A kinetic model is proposed which enables correlating the degree of transformation advance, expressed as the mass fraction of the arising solid solution (of the same composition as the starting oxide mixture), with synthesis time and temperature. The model is valid for raw materials, range of starting compositions, and operating conditions similar to those used in black Fe-Cr oxide pigment processing in industry.     

Imaging and Diffraction Study of Continuous α-Fe2O3 Films on (0001)Al2O3

Continuous α-Fe₂O₃ films grown on bulk (0001)Al₂O₂ substrates by low-pressure chemical vapor deposition have been studied by transmission electron microscopy and the observations compared to those obtained from discontinuous films at an earlier stage of the growth process. Plan-view specimens revealed significant thermal stress in the continuous films, while cross-sectional specimens showed that cracking occurs in thicker films. The free surface of the film and the film/substrate interface appeared sharp and flat, apart from growth ledges and steps. Weak-beam imaging revealed a hexagonal misfit dislocation network consisting of perfect edge dislocations. Fine structure in the selected-area diffraction patterns which corroborates these observations is also discussed. The misfit network of partial dislocations previously observed in the discontinuous films was not observed for the continuous films, indicating an effect of film thickness, growth rate, or surface preparation on the Fe₂O₃/(0001)Al₂O₃ interface structure.     

Oxygen Diffusion in MgO and α-Fe2O3

Oxygen-diffusion coefficients were determined in single crystals of MgO and α-Fe₂O₃ by exchanging the samples with ¹⁸O enriched gas at 1 atm and measuring ¹⁸O profiles using a proton activation technique. For MgO, in the temperature range 1580 to 1820 K, the diffusion coefficient is represented by:         

Atomistic Simulation of Defect Structures and Ion Transport in α-Fe2O3 and α-Cr2O3

Computer-modelling techniques are applied to the calculation of defect formation and migration energies in α-Fe₂O₃ and α-Cr₂O₃: both electronic and lattice defects are considered. The results are used to predict Arrhenius energies for cation and anion migration in different composition and temperature regimes and show reasonable agreement with experimental data where these are available.     

Microstructure and Humidity-Sensitive Characteristics of α-Fe2O3 Ceramic Sensor

The microstructure and humidity-sensitive characteristics of α -Fe₂O₃ porous ceramic were investigated. Microporous α -Fe₂O₃ powders were obtained by controlling the topotactic decomposition reaction of α -FeOOH. Water vapor adsorption thermogravimetrical experiments were carried out in the relative humidity (rh) range 0% to 95% on the α -Fe₂O₃ powder and the 900°C sintered compact. The microstructure was investigated by SEM, TEM, Hg intrusion, and N₂ adsorption porosimetry techniques. The humidity sensitivity was investigated by the impedance measurements technique in 0% to 95% rh on the compacts sintered at 50°C steps in the 850° to 1100°C range. Humidity response was found to be affected by the microstructure, i.e., the characteristics of the precursor powders and sintering temperatures.     

Oxygen Mobility in Polycrystalline NiCr2O4 and α-Fe2O3

Oxygen diffusion coefficients have been determined for polycrystalline samples of NiCr₂O₄ and α-Fe₂O₃ by exchange measurements with oxygen gas containing the stable isotope¹⁸O, using mass spectrometer analysis. Oxygen diffusion in NiCr₂O₄ can be represented by the equation D = 0.017 exp (-65,400/RT); oxygen diffusion in α-Fe₂O₃ can be represented by the equation D = 1 × 10¹¹ exp (-146,000/RT). The large difference between D₀ and activation energy for these materials suggests that different diffusion mechanisms are involved.     

Synthesis of Nanosize-Necked Structure α- and γ-Fe2O3 and its Photocatalytic Activity

Highly dispersed nanometer-sized α-Fe₂O₃ (hematite) and γ-Fe₂O₃ (maghemite) iron oxide particles were synthesized by the combustion method. Ferric nitrate was used as a precursor. X-ray diffractometer study revealed the phase purity of α- and γ-Fe₂O₃. Both the products were characterized using field emission scanning electron microscope and transmission electron microscope for particle size and morphology. Necked structure particle morphology was observed for the first time in both the iron oxides. The particle size was observed in the range of 25–55 nm. Photodecomposition of H₂S for hydrogen generation was performed using α- and γ-Fe₂O₃. Good photocatalytic activity was obtained using α- and γ-Fe₂O₃ as photocatalysts under visible light irradiation.     

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.     

Lattice Parameters of the α-Fe2O3-Cr2O3 Solid Solution

Lattice parameter-composition relations are shown in the system α-Fe₂O₃-Cr₂O₃. This information is of some value in determining the composition of scales developed during the oxidation of alloys based on Fe-Cr, such as stainless steels.     

Kinetics of Solid-State Reaction of BaO2 and α-Fe2O3

The reaction kinetics of an equimolar mixture of BaO₂ and alpha-Fe₂O₃ were investigated in an ambient atmosphere under isothermal conditions. The volume fraction of products was determined using the integrated X-ray diffraction intensities of the most prominent peaks, and the rate constants of the reaction were calculated with the Jander equation. The apparent activation energy for the formation of BaFeO_{3- x} ( x = 0.02-0.08) was 82 ± 6 kJmol⁻¹, and that for the formation of BaFe₂O₄ was 82 ± 7 kJmol⁻¹.     

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.     

Preferential X-ray line Broadening and Thermal Behavior of γ-Fe2O3

Preferential X-ray line broadenings in γ-Fe₂o₃ samples prepared from γ-FeOOH, α-FeOOH, N₂H₅Fe(N₂H₃-COO)₃-H₂O, FeOOCH₃, and colloidal Fe₃O₄ are compared. Isotropic size and small crystallites are the origin of the uniform and enhanced X-ray line broadening in samples derived from hydrazinate and colloidal Fe₃O₄. Nonuniform line broadening in ex-α-FeOOH and ex-γ-FeOOH is due to an elongated crystallite shape and the presence of stacking faults, respectively. The thermal behavior of samples with low crystallite size and uniform line broadening is characterized by an exothermal recrystallization process simultaneous to the phase transformation γ-Fe₂0₃→α-Fe₂O₃.     

Superparamagnetic Behavior of MnFe2O4 and α-Fe2O3 Precipitated from Silicate Melts

Manganese ferrite and α-Fe₂O₃ particles were precipitated within silicate melt systems to produce very unusual magnetic properties. Assemblies of particles of both kinds behaved super-paramagnetically when the particle size was small enough. As the particle size was increased, the magnetic properties of the ferrite system increased, but those of the α-Fe₂O₃ system decreased; the latter is expected from Néel's theory of a net spontaneous magnetic moment created by uncompensated magnetic sublattices at very small particle sizes. Liquid-in-liquid phase separation was pronounced in the manganese ferrite-glass systems, which may have influenced the precipitation behavior. Room-temperature initial mass susceptibilities were as high as 2 × 10 ⁻² cgs, and specific magnetizations as high as 26 gauss/g were observed. Precipitation of α-Fe₂O₃ particles exhibiting super-paramagnetic behavior was possible only with very low-viscosity melts. Initial mass susceptibility values changed by as much as a factor of 30 between 296° and 77°K.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

Vaporization Studies of the La2O3–Ga2O3 System

The vaporization of the samples of the compositions Ga₂O₃+ LaGaO₃, LaGaO₃+ La₄Ga₂O₉, and La₄Ga₂O₉+ La₂O₃ was investigated using Knudsen effusion mass spectrometry in the temperature range 1494–1937 K. The partial pressures of the gaseous species O₂, Ga, GaO, Ga₂O, and LaO were determined over the samples investigated. The equilibrium partial pressures were used for the calculation of the thermodynamic activities of the components at 1700 K. Gibbs energies of formation of LaGaO₃( s ) and La₄Ga₂O₉( s ) at 1700 K from the component oxides were derived from the thermodynamic activities as −46.4 ± 4.7 and −99.2 ± 7.9 kJ·mol⁻¹, respectively. The results were compared with the literature data obtained using other methods.     

Modification of αAI2O3 Platelet/ZrO2 Matrix Interface by Epitaxial Growth of β-AI2O3 on the α-AI2O3

An epitaxial β-alumina crystal growth method was used to modify α-AI₂O₃ platelet surfaces before inclusion as a reinforcing phase in partially stabilized zirconia (3Y-TZP). The as-grown surface phase was Na-β"-AI₂O₃. This was converted to Ca-β"-AI₂O₃ by ion exchange, as the latter is more temperature-stable at composite sintering temperatures. The conditions of formation, thermal stability, and chemical compatibility of these interfacial phases were examined. α-AI₂O₃ platelets with Ca-β"-AI₂O₃ film were incorporated into 3Y-TZP. The β"-AI₂O₃/ZrO₂ interface was found to promote platelet debonding and pullout, thus enhancing the α-AI₂O₃ platelet/crack interactions during the fracture process.     

Sintering of Nanophase γ-Al2O3 Powder

The sintering of ultrafine γ-Al₂O₃ powder (particle size ∼10–20 nm) prepared by an inert gas condensation technique was investigated in air at a constant heating rate of 10°C/min. Qualitatively, the kinetics followed those of transition aluminas prepared by other methods. Measurable shrinkage commenced at ∼ 1000°C and showed a region of rapid sintering between ∼1125° and 1175°C followed by a transition to a much reduced sintering rate at higher temperatures. Starting from an initial density of ∼0.60 relative to the theoretical value, the powder compact reached a relative density of 0.82 after sintering to 1350°C. Compared to compacts prepared from the as-received powder, dispersion of the powder in water prior to compaction produced a drastic change in the microstructural evolution and a significant reduction in the densification rate during sintering. The incorporation of a step involving the rapid heating of the loose powder to ∼1300°C prior to compaction (which resulted in the transformation to α-Al₂O₃) provided a method for significantly increasing the density during sintering.