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.     

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.     

Structural behavior of laser-irradiated γ-Fe2O3 nanocrystals dispersed in porous silica matrix : γ-Fe2O3 to α-Fe2O3 phase transition and formation of ε-Fe2O3

The effects of laser irradiation on γ-Fe₂O₃ 4 ± 1 nm diameter maghemite nanocrystals synthesized by co-precipitation and dispersed into an amorphous silica matrix by sol-gel methods have been investigated as function of iron oxide mass fraction. The structural properties of γ-Fe₂O₃ phase were carefully examined by X-ray diffraction and transmission electron microscopy. It has been shown that γ-Fe₂O₃ nanocrystals are isolated from each other and uniformly dispersed in silica matrix. The phase stability of maghemite nanocrystals was examined in situ under laser irradiation by Raman spectroscopy and compared with that resulting from heat treatment by X-ray diffraction. It was concluded that ε-Fe₂O₃ is an intermediate phase between γ-Fe₂O₃ and α-Fe₂O₃ and a series of distinct Raman vibrational bands were identified with the ε-Fe₂O₃ phase. The structural transformation of γ-Fe₂O₃ into α-Fe₂O₃ occurs either directly or via ε-Fe₂O₃, depending on the rate of nanocrystal agglomeration, the concentration of iron oxide in the nanocomposite and the properties of silica matrix. A phase diagram is established as a function of laser power density and concentration.     

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.     

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.     

Synthesis of α-Fe2O3 via oxidative hydrolysis of iron(II) sulphate

The influence of the main reaction parameters (temperature, pH and concentration) in the oxidative hydrolysis of iron (II) sulphate in an acid medium on the properties of the obtained -Fe₂O₃ and its applicability in ferrite production has been studied. The addition of manganese(II) ions catalyses the process in the homogeneous phase, probably by activation of oxygen. The obtained results are discussed within the framework of the assumed reaction mechanism, which includes an homogeneous reaction and a heterogeneous one with the participation of the oxidative hydrolysis product -FeOOH.     

Titanium-doped γ-Fe2O3: Reduction and oxidation properties

Titanium-doped -Fe₂O₃ has been prepared by the calcination of a solid formed by the addition of aqueous ammonia to an aqueous solution of titanium- and iron-containing salts and boiling the precipitate under reflux. As compared to pure -Fe₂O₃ made by similar methods, titanium-doped -Fe₂O₃ showed a higher surface area and a greater stability to reduction, thermal conversion to an -Fe₂O₃-related structure and the maintenance of a higher surface area during oxidation-reduction cycling.     

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.     

Photoelectrochemical activity of as-grown, α-Fe2O3 nanowire array electrodes for water splitting

Undoped hematite nanowire arrays grown using plasma oxidation of iron foils show significant photoactivity (~0.38 mA cm(-2) at 1.5 V versus reversible hydrogen electrode in 1 M KOH). In contrast, thermally oxidized nanowire arrays grown on iron exhibit no photoactivity due to the formation of a thick (>7 μm Fe(1-x)O) interfacial layer. An atmospheric plasma oxidation process required only a few minutes to synthesize hematite nanowire arrays with a 1–5 μm interfacial layer of magnetite between the nanowire arrays and the iron substrate. An amorphous oxide surface layer on hematite nanowires, if present, is shown to decrease the resulting photoactivity of as-synthesized, plasma grown nanowire arrays. The photocurrent onset potential is improved after removing the amorphous surface on the nanowires using an acid etch. A two-step method involving high temperature nucleation followed by growth at low temperature is shown to produce a highly dense and uniform coverage of nanowire arrays.     

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.     

Study on the effects of Cr2O3 on the reduction behavior of γ-Fe2O3

XRD and TG reduction analysis show that -Fe₂O₃ Fe-Cr catalysts, which contains 0.0 to 14.0 wt %. Cr₂O₃ and prepared by coprecipitating method, consist of crystalline -Fe₂O₃ and non-crystalline Fe₂O₃. Between 150–450 °C, three reduction stages are observed in the catalyst. The first stage is non-crystalline Fe₂O₃ reduced to non-crystalline Fe₃O₄, the second is crystalline -Fe₂O₃ to crystalline Fe₃O₄ and the third is non-crystalline Fe₂O₃ reduced to non-crystalline FeO. About 5 wt %. Cr₂O₃ can enter the lattices of -Fe₂O₃ to form solid solution. With the increasing of Cr₂O₃ content, the relative abundance of non-crystalline Fe₂O₃ and the amount of soluble Cr₂O₃ in non-crystalline increases, while the crystalline size of -Fe₂O₃ decreases.     

Efficient growth of aligned SnO2 nanorod arrays on hematite (α-Fe2O3) nanotube arrays for photoelectrochemical and photocatalytic applications

SnO₂ nanorod arrays were fabricated on hematiete nanotube arrays by an efficient hydrothermal method. The hematiete nanotube arrays were prepared by anodization of pure iron foil in an ethylene glycol solution. SnO₂ nanorod arrays grew from the bottom of hematite nanotubes and were firmly combined with the iron foil substrate. The morphology and microstructure of SnO₂ nanorod arrays are investigated by field-emission scanning electron microscopy, grazing incidence X-ray diffraction and UV–Vis absorbance spectra. The sample presented typical SnO₂ nanorod arrays (reacted for 2 h) generally of 400 nm in length and 50 nm in side width showed the best photocatalytic activity and photoelectrochemical response under the UV illumination. It should be attributed to the effective electron–hole separation and the excellent electron transfer pathway along the 1D SnO₂ nanorod arrays and hematiete nanotube arrays.     

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.     

Structure switch between α-Fe2O3, γ-Fe2O3 and Fe3O4 during the large scale and low temperature sol–gel synthesis of nearly monodispersed iron oxide nanoparticles

With same procedure and same starting materials, nearly monodispersed α-Fe₂O₃, γ-Fe₂O₃ and Fe₃O₄ nanoparticles were synthesized on an large scale of about 60 g in a single reaction through a low temperature sol–gel route. The simple preparation process includes the reactions between FeCl₂ and propylene oxide in ethanol solution at boiling point to form a sol and the following drying of the sol. The different iron oxide phases can be obtained just by changing of the drying conditions for the sol solution. The strategy developed in this study offers important advantages over the conventional routes for the synthesis of α-Fe₂O₃, γ-Fe₂O₃ and Fe₃O₄ nanoparticles, showing potential for its application in industrial production of iron oxides.     

Preparation and characterization of ZnO-doped and Li2O-stabilized Na-β″-Al2O3 solid electrolyte via a solid-state reaction method

Journal of Materials Science: Materials in Electronics - In this paper, Na–β"–Al2O3 is prepared using a conventional solid-state method and cost-effective burying and...     

Crystallization of γ-Fe2O3 particles with the aid of barium oxide as a catalyst and the effects on magnetic properties

-Fe₂O₃ particles with BaO additives (up to 20 mol%) have been crystallized by solid state reaction of the stoichiometric compositions containing 20 mol% B₂O₃ as a sintering aid. This markedly effects the crystallization and magnetic properties of -Fe₂O₃. The microstructure of the samples shows growth of crystallites of considerably smaller sizes and with fairly sharp size distribution after the additions. Crystallites as small as 5 m size (normally 25 m) were obtained using 15 to 20 mol% BaO additives in the reaction performed at 1230 °C/20h. This leads to a variation in coercivity over a wide range from 35 to 3500 Oe. Measurements of X-ray diffractometry, magnetization, microstructure and magnetic resonance have been carried out to characterize the magnetic applications of the material. The results are all consistent and elucidate promotion by thermal-treatment of the incorporation of Ba²⁺ into the -Fe₂O₃ particle cores.     

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.     

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.     

Microstructure and superconductivity of highly ordered YBa(2)Cu(3)O(7-δ) nanowire arrays

In order to explore the fundamental properties of one-dimensional nanostructured high-temperature superconductors and enhance their promising applications, a universal and general method for the synthesis of high-quality YBa(2)Cu(3)O(7-δ) (YBCO) nanowire arrays is developed, which involves the combination of a novel sol-gel process to lower the crystallization temperature of YBCO, and porous anodic alumina (PAA) as an effective morphology-directing hard template. Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) results indicate that the as-prepared YBCO nanowires have average diameters of about 50?nm and lengths up to several microns. The structures of the samples were analysed by x-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDX) and inductively coupled plasma (ICP) analysis, which indicate that the nanowires are well crystallized with orthorhombic YBCO-123 structure. The magnetization measurement under zero-field-cooled (ZFC) mode indicates that the superconducting transition temperature (T(c)) of the nanowires is about 92?K, which is in agreement with that of a bulk YBCO sample.     

Effect of zinc on the magnetic properties of acicular cobalt-modified γ-Fe2O3 particles

Acicular -FeOOH particles with a particle length of about 0.35 m and an axial ratio of about 7 were synthesized by the coprecipitation method using the reaction of FeCl₂-NaOH. The (Co, Zn)-modified -F₂O₃ particles were produced by absorbing Co²⁺ and Zn²⁺ ions on the surfaces of -FeOOH particles followed by dehydration, reduction and oxidation. The saturation magnetization and thermal stability of the coercivity of (Co, Zn)--Fe₂O₃ particles were all higher than those of Co--F₂O₃ particles. For the same (Co+Zn) content, the saturation magnetization of (Co, Zn)--Fe₂O₃ particles increased with increasing zinc content but the coercivity decreased.