Microstructure and Physicochemical Studies of Pure and Zinc-Substituted Lithium Ferrites Sintered above 1000°C

The effects of sintering temperature above 1000°C and of cooling rate on the microstructual development of pure and Zn-substituted spinel lithium ferrites are discussed. The strong dependence of microstructural features on cooling rate can be explained on the basis of the precipitation of α-Fe₂O₃ or the formation of a solid solution of ferrite phase with Fe₃O₄ occurring during sintering above 1000°C. These two phenomena are studied by detailed characterization analyses: SEM, XRD, magnetization, and ac electrical resistivity measurements.     

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.     

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.     

Microwave-Hydrothermal Synthesis of Monodispersed Nanophase α-Fe2O3

Synthesis of monodispersed nanophase α-Fe₂O₃ (hematite) powder to be used as a red pigment in porcelains was investigated using microwave-hydrothermal and conventional-hydrothermal reactions using 0.018 M FeCl₃·6H₂O and 0.01 M HCl solutions at 100°–160°C. Acicular and yellow β-FeOOH (akaganite) particles 300 nm in length and 40 nm in thickness were dominantly formed at 100°C after 2–3 h, while spherical α-Fe₂O₃ particles 100–180 nm in diameter were preferentially formed after 13 h using a conventional-hydrothermal reaction. However, a microwave-hydrothermal reaction at 100°C led to monodispersed and red α-Fe₂O₃ particles 30–66 nm in diameter after 2 h without the formation of β-FeOOH particles. In this paper, the effect of microwave radiation during hydrothermal treatment at 100°–160°C on the formation yield, kinetics, morphology, phase type, and color of α-Fe₂O₃ was investigated.     

Synthesis of Pure and Manganese-, Nickel-, and Zinc-Doped Ferrite Particles in Water-in-Oil Microemulsions

In recent years, the materials research focuses toward synthesis of finer and finer microstructural features. The unique properties of nanosized particles outweigh their higher production costs. Precipitation in microemulsion is one technique, which promises to produce small particles of controlled size and morphology at reasonable cost. The present study demonstrates the synthesis of nanocrystalline α-Fe₂O₃(hematite), Mn_0.5Zn_0.5Fe₂O_4, and Ni_0.5Zn_0.5Fe₂O₄ particles in a reverse micellar microemulsion system [water–iso-octane–AOT (sodium di-2ethylhexylsulfosuccinate)]. The synthesis of α-Fe₂O₃ is performed to obtain baseline data for the synthesis of Mn_0.5Zn_0.5Fe₂O₄ and Ni_0.5Zn_0.5Fe₂O₄ in the microemulsion system. Nanosized, spherical α-Fe₂O₃, Ni-Zn ferrite, and Mn-Zn ferrite particles (20–80 nm) with very narrow particle size distribution are synthesized. Crystallization of the particles is obtained at temperatures as low as 300°C.     

Studies in the System Li2O–Al2O3–Fe2O3-H2O

Subsolidus equilibrium relations in a portion of the system Li2O-Fe₂O₃-Al₂O3 in the temperature range 500° to 1400°C. have been determined near po₂ = 0.21. Of particular interest in this system is the LiFe₅O₈-LiAl₅O₈ join, which shows complete solid solution above 1180°C. Below this temperature the solid solution exsolves into two spinel phases. At 600°C. approximately 15 mole % of each compound is soluble in the other. The high-temperature solid solution and the low-temperature exsolution dome extend into the ternary system from the 1:5 join. There is no appreciable crystalline solubility of LiFeO₂ or of α-Fe₂O₃ in LiFe₅O₈. An attempt to confirm HFe₅O₈ as the correct formulation of the magnetic ferric oxide "γ-Fe₂O₃" was inconclusive, but in the absence of positive evidence, the retention of γ-Fe₂O₃ is recommended. All the metallic oxides of the Group IV elements increase the temperature of the monotropic conversion of -γ-Fe₂O₃ to α-Fe₂O₃. Silica and thoria have a greater effect on this conversion than does titania or zirconia.     

Lowering Crystallization Temperatures by Seeding in Structurally Diphasic Al2O3-MgO Xerogels

Thermal reactions in 93% Al₂O₃-7% MgO and 95.8% Al₂O₃-4.2% MgO gels seeded with α-Al₂O₃, MgAl₂O₄, α-Fe₂O₃, and SiO₂, sols were investigated by differential thermal analysis to determine the extent of nucleation catalysis of solid-state reactions. Seeding with α-Al₂O₃ lowered the α-Al₂O₃ crystallization temperature in these xerogels by 100° to 150°C. Spinel seeds have much less effect on the γ-α transition, and α-Fe₂O₃ and SiO₂ seeds do not affect it significantly. Isostructural seeding of gels may therefore permit lower ceramic processing temperatures.     

Initial Sintering of α-Cr2O3

Since the difference between oxygen-ion and cation diffusion coefficients is greater for α-Cr₂O₃ than for α-Fe₂O₃ or α-Al₂O₃, a study of initial-sintering kinetics was undertaken to show unequivocally which species is rate controlling. Fine powders of α-Cr₂O₃, obtained by thermal decomposition of reagent-grade (NH₄)₂Cr₂O₇, were lightly compacted and their isothermal rates of shrinkage were determined between 1050° and 1300°C. Resultant data follow volume-diffusion sintering models, and calculated diffusion coefficients agree with, those measured for oxygen ions in α-Cr₂O₃. There is little evidence that oxygen diffusion along grain boundaries becomes so enhanced that chromium ions are left in control of the process.     

Kinetics of Nickel Ferrite Formation

The rate of nickel ferrite formation is influenced by the milling technique and in the case of wet milling by the type of liquid media used. The reactivity of different types of α-Fe₂O₃ of spherical shape decreases with an increase of the surface area ratio of α-Fe₂O₃ to NiO. The particle shape of the iron oxides also affects their reactivity; cubical α-Fe₂O₃ has the least reactivity in the formation of nickel ferrite. The validity of Jander's equation in ferrite formation is reviewed. Based on present findings the rate of ferrite formation is best represented by the equation dx / dt = ( a - x) / t , in which x is the percentage of ferrite formed, t the time, and a the kinetic isothermal reaction rate coefficient which is related to the surface area ratio of the reacting oxides. The application of the foregoing equation to the formation of magnesium ferrites from data found in the literature is also satisfactory.     

Transformation, Microstructure Development, and Densification in α-Fe2O3-Seeded Boehmite-Derived Alumina

Addition of α-Fe₂O₃ seed particles to alkoxide-derived boehmite sols resulted in a 10-fold increase in isothermal rate constants for the transformation of γ- to α-Al₂O₃. Changes in porosity and surface area with sintering temperature showed no effect of seeding on coarsening of the transition alumina gels, but the 200-fold decrease in surface area associated with transformation to α-Al₂O₃ occurred ∼ 100°C lower in seeded gels compared with unseeded materials. As a result of high nucleation frequency and reduced microstructure coarsening, fully transformed seeded alumina retained specific surface areas >22 m²/g and exhibited narrow pore size distributions, permitting development of fully dense, submicrometer α-Al₂O₃ at ∼ 1200°C.     

FTIR Spectra, Lattice Shrinkage, and Magnetic Properties of CoTi-Substituted M-Type Barium Hexaferrite Nanoparticles

Single-phase BaCoTiFe₁₀O₁₉ (BaCoTi-M) nanoparticles were prepared by a modified sol–gel process, using metallic chlorides as starting materials. The physical chemistry process of BaCoTi-M formation, the interdependences between composition, technological conditions, microstructure, and magnetic properties were studied by X-ray diffraction (XRD), Fourier transform-infrared (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). XRD and FTIR results show that BaCoTi-M nanoparticles formed directly from γ-Fe₂O₃, spinel ferrite, and barium salts without the formation of α-Fe₂O₃ and BaFe₂O₄. The lattice shrinkage of BaCoTi-M nanoparticles that occurred on increasing the calcining temperature from 973 to 1173 K under holding for 2 h or on increasing the holding time in the range 0–2 h at 1173 K was discovered by analyzing the dependences of lattice parameters on the heat-treatment conditions. The shrinkage led to a relatively higher concentration of magnetic Fe³⁺ cations in the unit cell, and resulted in an increase of specific saturation magnetization under the corresponding conditions. Microstructural characterization shows that the evolutions of coercivity, remnant magnetization, and squareness ratio depended on the crystal growth and the reduction of structural defect as well as a decrease of grain boundary.     

Phase Diagram of a Nickel-Zinc Ferrite of Composition Ni0.685Zn0.177Fe2.138O4+γ

The oxygen content of Ni_0.685Zn_0.177Fe_2.138O_4+γ was determined gravimetrically at atmospheric pressure in varying Po₂ , 3.5 × 10⁻⁴ to 1.0 atm at 600° to 1450°C. The phase boundary associated with the precipitation of α-Fe₂O₃ was determined from the change in slope of γ vs T plots observed on heating. Metastability is particularly evident for curves observed on cooling. Isacompositional lines (0.002 < γ < 0.045) are shown on a plot of log PO₂ vs 1/T. An enthalpy of -21.6 kcal/mol is calculated for the oxidation of Fe²⁺.     

Kinetics and Microstructural Evolution of Heterogeneous Transformation of θ-Alumina to α-Alumina

Ultrafine (<0.1 μm) high-purity θ-Al₂O₃ powder containing 3–17.5 mol%α-Al₂O₃ seeds was used to investigate the kinetics and microstructural evolution of the θ-Al₂O₃ to α-Al₂O₃ transformation. The transformation and densification of the powder that occurred in sequence from 960° to 1100°C were characterized by quantitative X-ray diffractometry, dilatometry, mercury intrusion porosimetry, and transmission and scanning electron microscopy. The relative bulk density and the fraction of α phase increased with annealing temperature and holding time, but the crystal size of the α phase remained ∼50 nm in all cases at the transformation stage (≤1020°C). The activation energy and the time exponent of the θ to α transformation were 650 ± 50 kJ/mol and 1.5, respectively. The results implied the transformation occurred at the interface via structure rearrangement caused by the diffusion of oxygen ions in the Al₂O₃ lattice. A completely transformed α matrix of uniform porosity was the result of appropriate annealing processes (1020°C for 10 h) that considerably enhanced densification and reduced grain growth in the sintering stage. The Al₂O₃ sample sintered at 1490°C for 1 h had a density of 99.4% of the theoretical density and average grain size of 1.67 μm.     

Crystallization of Beta NaFeO2 from a Glass Along the Na2SiO3-Fe2O3 Join

Fine-particle beta sodium ferrite (β-NaFeO₂), rather than α-Fe₂O₃, may be responsible for superparamagnetic behavior in a glass of composition (in mole fractions) 0.37Na₂O-0.26Fe₂O₃-0.37SiO₂. The 700°C isothermal section of the phase diagram of the Na₂O-Fe₂O₃-SiO₂ system is given, showing a three-phase field bounded by Na₂SiO₃-NaFeO₂-Fe₂O₃; there is no evidence for the existence (at 700°C) of compounds of molar composition 6Na₂O-4Fe₂O₃-5SiO₂ or 2Na₂O-Fe₂O₃-SiO₂. The Moessbauer spectrum of β-NaFeO₂ has an internal magnetic field of 487 kOe at room temperature.     

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.     

High-Vacancy-Content Magnetites and Zinc-Bearing Ferrites from Iron(III) Tartrate in Strongly Alkaline Solution

High-vacancy-content magnetites with particle size in the range of 20 to 150 nm can be precipitated as stable products in the clear and strongly alkaline solution of iron(III) tartrate and dextrose at 100°C, although Fe(III) ions in alkaline solution have been reported previously to form only α-FeO(OH) and α-Fe₂O₃. When Zn(II) ions were present in the reaction solutions, high-vacancy-content Zn(II)-bearing ferrites represented by (ZnFe₂O₄)_x-(Fe₃O₄)_y-(γ-Fe₂O₃)_z, where x + y + z = 1, were obtained in the strongly alkaline solutions. The Fe(II) ions, which were formed by the reduction of Fe(III) ions with dextrose, accelerate the crystallization of the spinel structure.     

Magnetoplumbite-Corundum Phase Equilibria in the System Sr─Fe─Al─O at 1100°C

The phase relations in the region of the Fe₂O₃- and Al₂O₃-rich sides of the quaternary system SrO─Fe₂O₃–Al₂O₃–B₂O₃ and the location of conjugation lines between magnetoplumbite solid solution SrO·(6 − x)Fe₂O₃·xAl₂O₃ and corundum (α-Fe₂O₃, α-Al₂O₃) phases were determined at 1100°C in air by using the flux-growth method based on the Ostwald ripening mechanism. Activity–composition relations and the lattice parameters along the magnetoplumbite solid solutions were also obtained.     

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.     

Ion Exchange in Alkali Layers of Potassium β -Ferrite ((1 + x)K2O · 11Fe2O3) Single Crystals

The potassium ions in potassium β-ferrite ((1 + x)K₂O ·11Fe₂O₃) crystals were exchanged with Na⁺, Rb⁺, Cs⁺, Ag⁺, NH₄⁺, and H₃O⁺ in molten nitrates or in concentrated H₂SO₄. On the other hand, spinel and hexagonal ferrites were formed by soaking the crystals in the melt of divalent salts. The crystals of K⁺, Rb⁺, and Cs⁺β-ferrites decomposed to form α-Fe₂O₃ at high temperatures of 800° to 1100°C. In addition, H₃O⁺, NH₄⁺, and Ag⁺β-ferrites decomposed to form α-Fe₂O₃ at relatively low temperatures of 350° to 650°C, in accordance with the stabilities of the inserted ions. The electrical properties of some β-ferrites were measured.     

Mechanosynthesis of Gadolinium Iron Garnet

We investigated the mechanosynthesis of gadolinium iron garnet by high-energy ball milling stoichiometry amounts of α-Fe₂O₃ and Gd₂O₃, followed by short thermal annealings conducted at moderate temperatures. X-ray diffraction and Mössbauer spectroscopy results revealed, for the as-milled samples, the formation of the GdFeO₃ perovskite phase, in relative amounts that depend on the milling time. The formation of the Gd₃Fe₅O₁₂ garnet phase was observed in 1000°C/2 h or 1100°C/3 h as-annealed samples. The occurrence of a milling time was verified in which the relative amount of garnet phase formed by further annealing is maximized.