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.     

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.     

Synthesis of Single Crystalline Hematite Polyhedral Nanorods Via a Facile Hydrothermal Process

Single-crystalline α-Fe₂O₃ nanorods with a polyhedral configuration have been successfully synthesized via a facile hydrothermal process at 180°C. X-ray powder diffraction, transmission electron microscopy observations, field emission scanning electron microscopy, and selected area electron diffraction patterns were used to characterize the as-synthesized samples. The result reveals that goethite nanorods were first generated and then transformed into hematite via dehydration in the successive hydrothermal treatment, in which the α-Fe₂O₃ inherited the rod-like morphology of the goethite precursor. The effect of surfactant and treatment time on the phase and morphology of the final products has been studied, and a possible growth mechanism is proposed.     

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.     

Effects of Lithium and Oxygen Losses on Magnetic and Crystallographic Properties of Spinel Lithium Ferrite

The effects of sintering temperature and cooling rate on the magnetic and crystallographic properties of lithium ferrite were studied. The magnetic moments and lattice parameters increased with increasing sintering temperature; these increases result from correlated oxygen and lithium oxide losses. Either annealing at lower temperatures or slow cooling under O₂ causes reoxidation of the Fe²⁺ formed at higher temperatures with attendant decreases in moment and lattice parameter and gradual precipitation of α-Fe₂O₃ as a second phase. The products formed on rapid cooling are equivalent to solid solutions of spinel lithium ferrite with Fe₃O₄, and those formed on slow cooling, to solid solutions of lithium ferrite and γ-Fe₂O₃ with precipitation of α-Fe₂O₃. Lithium losses and α-Fe₂O₃ precipitate amounts are calculated. The magnetic moment of stoichiometric lithium ferrite at 25°C is 3736±20 G; the lattice parameter at 28°C is 8.3296±0.0005 Å.     

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.     

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.     

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.     

Nanocrystalline Maghemite (γ-Fe2O3) in Silica by Mechanical Activation of Precursors

γ-Fe₂O₃ nanocrystallites dispersed in an amorphous silica matrix have been successfully prepared for the first time by mechanical activation of a chemistry-derived precursor at room temperature. The initial 10 h of mechanical activation triggered the formation of nanocrystallites of Fe₃O₄ in a highly activated matrix. Increasing the mechanical-activation time led to a phase transformation from Fe₃O₄ to γ-Fe₂O₃. The γ-Fe₂O₃ phase was well established after mechanical activation of the precursor for 30 h. Further increasing the mechanical-activation time to 40 h induced the formation of α-Fe₂O₃. The mechanical-activation-grown γ-Fe₂O₃ nanocrystallites were ∼10–12 nm in size and well dispersed in the silica matrix, as observed using TEM. They demonstrated superparamagnetic behavior at room temperature when measured using a Mössbauer spectrometer and a vibrating sample magnetometer (VSM). In addition, the γ-Fe₂O₃ derived from 30 h of mechanical activation exhibited a value of saturation magnetization as high as 62.6 emu/g.     

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.     

Facile Fabrication of Pure α-Fe2O3 Nanoparticles via Forced Hydrolysis Using Microwave-Assisted Esterification and their Sensing Property

In this paper we firstly demonstrate a facile approach for the rapid fabrication of α-Fe₂O₃ using microwave-assisted esterification. In situ -generated water leads to the forced hydrolysis of Fe³⁺. Microwave irradiation greatly promotes the growth of α-Fe₂O₃ nanoparticles compared with conventional solvothermal approach, and agitation can assure the obtainment of pure hematite phase. The akaganeite phase is preserved without stirring. The BET specific surface area reaches 83 m²/g although high concentration of FeCl₃ is adopted. Our approach can assure the very rapid acquisition of hematite nanoparticles. Electrochemical studies indicate that our product can function as a candidate for high-performance sensor.     

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.     

DC Electrical Resistivity and Magnetic Property of Single-Phase α-Fe2O3 Nanopowder Synthesized by a Simple Chemical Method

Nanocrystalline pure α-Fe₂O₃ powder, with an average particle size of 35 nm, has been synthesized by using an aqueous solution-based synthetic route. DC electrical resistivity of the synthesized material was measured with respect to temperature by the two-probe method from 28° to 225°C. Room temperature resistivity of the nanopowder was ∼10⁸Ω·cm. Magnetic hysteresis measurement revealed that the synthesized α-Fe₂O₃ nanopowder exhibited ferromagnetic behavior at room temperature. The hysteretic features are high saturation magnetization of 5.1 emu/g, high remanence of 2.2 emu/g, and coercivity of 200.5 Oe.     

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.     

Optical Properties of Hydrothermally Synthesized Hematite Particulate Pigments

Iron oxide hematite particles with various shapes (platelet, polyhedron, pseudocube, and peanut-like) have been synthesized by hydrothermal treatment of a Fe(OH) _x O _y precursor under various conditions. The size and shape of hematite particles can be adjusted by carefully controlling the processing parameters such as holding time, temperature, and adsorption ions present in the system. The nearly monosized α-Fe₂O₃ platelets possess face diameters of approximately 3 μm and a thickness of 0.5 μm under a scanning electron microscope. The apparent color of the particles changes as particle size and shape varies. Munsell color notation was employed to compare the color of hematite particles with various sizes and shapes. Diffuse reflectance spectra show that a "red-shift" of 40 nm is observed in platelet, pseudocube, and peanut-like particles compared with conventional particles. The band at 850 nm for the ⁶A₁→⁴T₁ transition was split in the pseudocubic and peanut-like particles. Raman spectra of the hematite particles also reveal that the vibrational modes of α-Fe₂O₃ particles diminish as particle size decreases, and dependence of vibrational band intensity on frequency is also observed. The spectral profiles demonstrate significant difference as excitation radiation lines changes from blue (457 nm) to red (647 nm). Possible mechanisms responsible for the optical properties of hematite particles are postulated based on the findings of the experiments.     

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.     

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.     

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.     

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.     

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.