One-pot synthesis of magnetic γ-Fe2O3 nanoparticles in ethanol-water mixed solvent

Maghemite (γ-Fe₂O₃) nanoparticles were synthesized via a low-temperature solution-based method using ferric chloride hexahydrate and ferrous chloride tetrahydrate as precursors in the mixed solvent of ethanol and water. X-ray diffraction, energydispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy revealed that the obtained product was pure γ-Fe₂O₃. Transmission electron microscopy showed the morphology of the nanoparticles to be approximately spherical in shape with an average diameter of 11 nm. Magnetization measurements indicated the dry powders exhibit ferromagnetic behavior with a maximum saturation magnetization of 41.1 emu/g at room temperature.     

Solvothermal synthesis and characterization of acicular α-Fe2O3 nanoparticles

Nanometer-sized α-Fe₂O₃ particles have been prepared by a simple solvothermal method using ferric acetylacetonate as a precursor. The products were characterized by X-ray diffraction (XRD), energy dispersive X-ray microanalysis (EDAX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transition electron microscopy (TEM), infrared spectroscopy (IR) and thermal analysis (TG-DTA). XRD indicates that the product is single-phase α-Fe₂O₃ with rhombohedral structure. Bundles of acicular shaped nanoparticles are seen in TEM images with an aspect ratio ～ 12; typically 8–12 nm wide and over 150 nm long. The α-Fe₂O₃ nanoparticles posses a high thermal stability, as observed on thermal analysis traces.     

Green synthesis of α-Fe2O3 nanoparticles for photocatalytic application

In this study, the preparation of α-Fe₂O₃ nanoparticles using curcuma and tea leaves extract are reported. The curcuma and tea leaves are acted as a reductant and stabilizer. The crystal structure and particle size of the as-synthesized materials were measured through X-ray diffraction. X-ray diffraction patterns revealed that the as-prepared samples were α-Fe₂O₃ nanoparticles with well-crystallized rhombohedral structure and the crystallite sizes of the α-Fe₂O₃ nanoparticles are 4 and 5 nm. Scanning electron microscopy images showed that the prepared samples have spherical shape. The purity and properties of the as-synthesized α-Fe₂O₃ nanoparticles were measured by Raman spectroscopy. The chemical compositions of the as-prepared α-Fe₂O₃ nanoparticles have been analyzed by Fourier transform infrared spectroscopy. The absorption edge of the α-Fe₂O₃ nanoparticles are 561 and 551 nm. The photocatalytic activity of the α-Fe₂O₃ nanoparticles was measured by degradation of methylene orange and the α-Fe₂O₃ nanoparticles showed the excellent photocatalytic performance.     

β-Ga2O3 crystal growing from its own melt

The applicability of several nonnoble materials for growing of β-Ga₂O₃ crystals using free crystallization in a crucible has been studied. The possibility of growing β-Ga₂O₃ crystals in crucibles made of single crystal sapphire has been demonstrated. Main features of the growth and properties of the obtained crystals have been investigated.     

Mechanochemical preparation and thermal stability of γ-Fe2O3 derived from γ-FeOOH

The dehydration process of lepidocrocite, γ-FeOOH, induced by wet grinding procedures has been studied. Microcrystals of maghemite, γ-Fe₂O₃, are found in the product of ball-milling in hexane and cyclohexane media. In contrast, grinding in air leads to hematite α-Fe₂O₃. This change is accompanied by the development of a characteristic texture in which a slit-shaped porous system is present. On the other hand, mechanochemically prepared maghemite increases in its thermal stability. This fact has been attributed to the higher crystallinity of ground microcrystals as revealed by the values of crystallite size and microstrains.     

Characterization of oxygen passivated iron nanoparticles and thermal evolution to γ-Fe2O3

Nanocrystalline iron powders have been prepared by the inert gas evaporation method. After preparation the material has been passivated by pure oxygen and air exposure. In the present paper we describe new characterization studies of this sample by Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), X-ray Absorption Spectroscopy (XAS), Electron Energy Loss Spectroscopy (EELS) and Mössbauer Spectroscopy (MS), giving a complete chemical and structural characterization of the nanocomposite material in order to correlate its microstructure with its singular magnetic behavior.This nanocomposite was later heated following different thermal treatments. It was found that the sample heated successively in high vacuum (10^–7 torr) at 383 K for 1 h and under a residual oxygen pressure of 4 × 10^–4 torr at 573 K for 3 h, results in a powder formed by nanoparticles of -Fe₂O₃ as stated from XRD, XAS and MS. This material is stable during several years and behaves almost totally like superparamagnetic at room temperature.     

A new combustion route to γ-Fe2O3 synthesis

A new combustion route for the synthesis of γ-Fe ₂ O ₃ is reported by employing purified a-Fe ₂ O ₃ as a precursor in the present investigation. This synthesis which is similar to a self propagation combustion reaction, involves fewer steps, a shorter overall processing time, is a low energy reaction without the need of any explosives, and also the reaction is completed in a single step yielding magnetic iron oxide i.e. γ-Fe ₂ O ₃ .The as synthesized γ-Fe ₂ O ₃ is characterized employing thermal, XRD, SEM, magnetic hysteresis, and density measurements. The effect of ball-milling on magnetic properties is also presented.     

Chemical synthesis of faceted α-Fe2O3 single-crystalline nanoparticles and their photocatalytic activity

Faceted hematite nanocrystals have been synthesized via a hydrothermal route and their different morphologies can be tuned by appropriate stabilizer molecules. Detailed observation by high-resolution transmission electron microscopy and atomic force microscopy has revealed many terraces, steps, and kinks on the faceted surface of hematite nanoparticles, and thus, one growth mechanism of the terrace-step-kink model has been suggested to play a major role in determining the equilibrium morphology, together with effect of surface chemistry via the interaction between outer surfaces of iron and oxygen ions and functional groups. The photocatalytic activities were evaluated by decomposing rhodamine B dye. It has been shown that polyhedron hematite particles enclosed by high-index surface planes exhibited higher photoactivity. Density functional theory calculations revealed that the higher photoactivity originates from the more flat band edge in directions normal to the surface planes.     

In situ monitoring of NiO–Al2O3 nanoparticles synthesis by thermo-Raman spectroscopy

Simultaneous thermogravimetric analysis and thermo-Raman spectroscopy (TRS) measurements for in situ monitoring of wet chemical reaction of Ni(OH)₂·4H₂O and Al(OH)₃ forming NiO–Al₂O₃ nanoparticles is studied and compared with the solid-state reaction. Herein, a different approach of synthesis and monitoring of NiO–Al₂O₃ by TRS is presented, in which, in situ thermo-Raman spectra are recorded at every degree interval from 25 to 800 °C to understand the structural and compositional changes in NiO–Al₂O₃ as a function of temperature. Slow controlled heating of the sample as in TRS, enables better control over morphology and particle size distribution (～10–20 nm diameter). The X-ray diffraction (XRD) shows that smaller particle size is obtained using wet chemical reaction than the solid-state reaction (～25 nm diameter). TRS studies also reveal that, the bulk NiAl₂O₄ forms at temperatures above 800 °C, although, the onset of formation is around 600 °C. Condensation of Al(OH)₃ forming Al₂O₃ is also monitored, wherein, presence of hydrocarbon is found to contribute to the observed fluorescence background. Based on the TRS and complementary characterizations using XRD, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray analysis, the formation of supported NiO–Al₂O₃ is discussed.     

Microwave Synthesis of γ-Fe2O3

Fine-particle Fe₂O₃ is prepared via microwave processing of Fe(NO₃)₃ · nH₂O, followed by low-temperature annealing. The particle size of the resulting -Fe₂O₃ is 5–6 nm after microwave processing and 80–110 nm after subsequent low-temperature heat treatment.     

Magnetic resonance study of γ-Fe2O3 nanoparticles dressed in oxygen based free radicals

Two composites consisting of γ-Fe₂O₃ (maghemite) nanoparticles covered by two different oxygen-based free radicals derived from a 4-(methylamino)phenol sulphate and 8-hydroxy-1,3,6-trisulfonic trisodium salt acid were prepared and investigated by the magnetic resonance method in the 4–300 K range. Both composites displayed broad and very intense ferromagnetic resonance (FMR) lines originating from γ-Fe₂O₃ agglomerated nanoparticles. The FMR spectrum was fitted satisfactorily at each temperature by two Landau-Lifshitz functions reflecting the existence of magnetic anisotropy in the investigated system. The temperature dependence of the obtained FMR parameters (resonance field, linewidth, integrated intensity) was studied and the results were interpreted in terms of magnetic interactions between free radicals and nanoparticle agglomerates. A comparison with previously studied similar systems containing maghemite nanoparticles was made and conclusions about the role of free radicals were drawn.     

Hydrazine method of synthesis of γ-Fe2O3 useful in ferrites preparation. Part III – study of hydrogen iron oxide phase in γ-Fe2O3

Direct current electrical conductivity () measurements as a function of temperature have been carried out on -Fe₂O₃ prepared from precursors, iron (II) carboxylatohydrazinates, -FeOOH and hydrazinated -FeOOH. The conductivity variation obeys an Arrhenius equation, _I = \_oe^- E / kT and the plots of log versus 1/T of the as prepared -Fe₂O₃, which are in general linear, during the very first heating up to 350°C and cooling to room temperature (RT) do not overlap. This indicates a hysteresis behavior of conductivity, thereby suggesting involvement of two different conductivity mechanisms. When the heat treated sample was equilibrated in a known partial pressure of moisture at 200°C and then conductivity measured from RT, the log plots during heating and cooling did not overlap and a hysteresis behavior similar to the as prepared -Fe₂O₃ is observed again in the conductivity. Water is considered to be crucial during the synthesis of -Fe₂O₃ through magnetite, Fe₃O₄. Protons, H⁺, are thought to be introduced in the spinel Fe₃O₄ making it defective and the oxidation product of this is -Fe₂O₃ which retains few protons in its spinel structure. From the structural similarity of such proton incorporated -Fe₂O₃ and lithium ferrite, LiFe₅O₈, (Fe³⁺)₈ [Fe³⁺ ₁₂ Li¹⁺ ₄]O₃₂, a formula HFe₅O₈, (Fe³⁺)₈ [Fe³+₁₂H¹+₄]O₃₂ is suggested. A hydrogen iron oxide of formula H_1-xFe_5+x3O₈, where x 0.1 is probably formed as a maximum limit. Protons are removed during the very first heating of the as prepared sample in the present studies and hence the conductivity of proton free -Fe₂O₃ is different and therefore a hysteresis behavior is observed. Moisture equilibration reintroduces the protons. The lithiated samples in the present studies were found to substitute for protons in -Fe₂O₃ and no hysteresis behavior is observed in such samples even after moisture equilibration.     

Room-temperature synthesis of nanometric α-Bi2O3

Nanometric Bi₂O₃ powder was successfully synthesized by applying the method based on self-propagating room temperature reaction (SPRT) between bismuth nitrates and sodium hydroxide. X-ray powder diffraction (XRPD) and Rietveld's structure refinement method were applied to characterize prepared powder. It revealed that synthesized material is a single phase monoclinic α-Bi₂O₃ (space group P2₁/c with cell parameters a = 5.84605(4)Å, b = 8.16339(6) Å, c = 7.50788(6) Å and β = 112.9883(8)). Powder particles were of nanometric size (about 50 nm). Raman spectral studies conformed that the obtained powder is single phase α-Bi₂O₃. Specific surface area of obtained powder was measured by Brunauer-Emmet-Teller (BET) method.     

Hydrazine method of synthesis of γ-Fe2O3 useful in ferrites preparation. Part IV – preparation and characterization of magnesium ferrite, MgFe2O4 from γ-Fe2O3 obtained from hydrazinated iron oxyhydroxides and iron (II) carboxylato-hydrazinates

Electro-magnetic properties and microstructural characterization of MgFe₂O₄ synthesized by a ceramic technique at 1000°C from iron oxides, consisting of mainly -Fe₂O₃ and traces of alpha-Fe₂O₃, prepared from iron ore rejects, are compared with the ferrite obtained from commercial alpha-Fe₂O₃. The sources of -Fe₂O₃ are hydrazinated iron (II) carboxylates and iron oxyhydroxides which autocatalytically decompose giving mainly -Fe₂O₃ of uniform particles of 10–30 nm (by scanning electron microscopy (SEM) studies) having high surface area. The ferrite synthesized from such nanoparticle size -Fe₂O₃ gave a porosity of 25% with grains ranging from 0–3 m. On the other hand, MgFe₂O₄ obtained from commercial alpha-Fe₂O₃ grains (of 1–2 m size) gave particles of 0–6 m with a porosity 42%. Saturation magnetization values 922–1168 G are found for MgFe₂O₄ from -Fe₂O₃ source while the alpha-Fe₂O₃ source gave the lowest value, 609. The Curie temperature, T_c, from magnetic susceptibility, initial permeability and resistivity measurements indicated a highest T_c of 737 K for MgFe₂O₄ from alpha-Fe₂O₃, while lower values are found for the ferrite prepared from -Fe₂O₃.     

Synthesis of ferrite grade γ-Fe2O3

Iron(II) carboxylato-hydrazinates: Ferrous fumarato-hydrazinate (FFH), FeC₄H₂O₄·2N₂H₄; ferrous succinato-hydrazinate (FSH), FeC₄H₄O₄·2N₂H₄; ferrous maleato-hydrazinate (FEH), FeC₄H₂O₄·2N₂H₄; ferrous malato-hydrazinate (FLH), Fein4H₄O₅·2N₂H₄; ferrous malonato-hydrazinate (FMH), FeC₃H₂O₄·1.5N₂H₄·H₂O; and ferrous tartrato-hydrazinate (FTH), FeC₄H₄O₆·N₂H₄·H₂O are being synthesized for the first time. These decompose (autocatalytically) in an ordinary atmosphere to mainly γ-Fe₂O₃, while the unhydrazinated iron(II) carboxylates in air yield α-Fe₂O₃, but the controlled atmosphere of moisture requires for the oxalates to stabilize the metastable γ-Fe₂O₃. The hydrazine released during heating reacts with atmospheric oxygen liberating enormous energy, N₂H₄ + O₂ → N₂ + H₂O; ΔH₂O = −621 kJ/mol, which enables to oxidatively decompose the dehydrazinated complex to γ-Fe₂O₃. The reaction products N₂ + H₂O provide the necessary atmosphere of moisture needed for the stabilization of the metastable oxide. The synthesis, characterization and thermal decomposition (DTA/TG) of the iron(II) carboxylato-hydrazinates are discussed to explain the suitability of γ-Fe₂O₃ in the ferrite synthesis.     

Some magnetic properties of γ-Fe2O3 synthesized from ferrous fumarate half-hydrate

-Fe₂O₃ synthesized from ferrous fumarate half-hydrate was studied by measurements of D.c. electrical conductivity, Seebeck coefficient, initial magnetization and magnetic hysteresis, and by Mössbauer spectroscopy and scanning electron microscopy. The phase transformation observed by electrical conductivity measurements matched well with the phase transformation observed by the variation with temperature of initial magnetization measurements of -Fe₂O₃; this magnetic study also established the single-domain character of -Fe₂O₃. The magnetic hysteresis values of the -Fe₂O₃ synthesized indicated improved values over that of a -Fe₂O₃ sample synthesized by established procedures. The scanning electron micrographs showed that the -Fe₂O₃ particles were acicular in shape and the Mössbauer spectrum showed a well-resolved six-band spectrum. The presence of a hydrogen ferrite phase was also confirmed by the electrical and magnetic measurements.Deceased, 10 October, 1985.     

Sintering of pseudo-boehmite and γ-Al2O3

Sintering of pseudo-boehmite, acicular-Al₂O₃ produced by dehydration of pseudo-boehmite, and-Al₂O₃ ex alum was investigated. The sintering process was studied by X-ray diffraction, transmission electron microscopy with selected area electron diffraction and BET surface area measurements. The solid state reaction to-Al₂O₃ causes a steep drop of the surface area to less than 10 m²g^–1. The acicular pseudo-boehmite and-Al₂O₃ supports exhibit an intermediate state where the acicular particles assume a rod-like shape and the surface area falls from about 300 to 100 m²g^–1. It was established that reaction to -Al₂O₃ and, hence, sintering proceeds via a nucleation and growth mechanism. The rate-limiting step is nucleation of -Al₂O₃. Consequently, the contacts between the elementary alumina particles dominate the sinter process. The contact between the acicular elementary particles of pseudoboehmite and-Al₂O₃ studied leads to the reaction to -Al₂O₃ to be almost complete after keeping samples for 145 h at 1050 °C. Decomposition of alum produces very small particles showing negligible mutual contacts. Consequently an elevated thermal stability is exhibited. Treatment of the alumina ex alum with water and drying results in a xerogel in which contact between elementary particles is much more intimate. Accordingly, treatment at 1050 °C causes a sharp drop in surface area.     

Microwave sintering of nanocrystalline γ-Al2O3

The densification and phase transformation behavior of gas condensation synthesized nanocrystalline γ-A1₂O₃ sintered with microwave radiation has been studied. The polymorphic nucleation and growth phase transformations which occurred as the material was heated through the temperature range of 800–1300°C present significant obstacles in the achievement of specimens which possess high bulk densities. These phase transformations are accompanied by a change in particle morphology, crystallite size, and surface area. Alumina derived from a chemically synthesized boehmite precursor has been shown to exhibit the same nucleation and growth phase transformation behavior when conventionally heated. It is concluded that nanocrystalline γ or δ alumina will not be a viable starting material for the production of dense bodies with grain sizes of less than 100 nm.