Gel-glass transformation in the SiO2Fe2O3 system

Gel-glass transformation has been studied by Mössbauer spectroscopy, DTA-TG analyses and X-ray diffractometry for four compositions in the SiO₂Fe₂O₃ system (A: 5 wt% Fe₂O₃, B: 10 wt% Fe₂O₃, C: 20 wt% Fe₂O₃, D: 40 wt% Fe₂O₃).The gels were prepared by the hydrolysis of silicon tetraethoxide and iron triethoxide and successively dried and heated in oxygen in the temperature range 40–1000°C.Samples A and B gave typical amorphous X-ray patterns up to 700°C; heating at higher temperature yielded the precipitation of quartz, cristobalite and hematite in sample A, cristobalite and hematite in sample B. Crystallization was also detected by DTA in sample A for which X-ray diffraction exhibited a larger effect.In samples C and D crystallization took place starting from 300°C with the precipitation of hematite, which remained the only crystalline phase up to 1000°C.The presence of hematite was confirmed by the obtained Mössbauer spectra which showed the characteristic sextet. The apportion of iron ions in the Fe³⁺ and Fe²⁺ oxidation states was also determined, together with the attribution of the probable coordination states for Fe³⁺ ions.Complex magnetic structure appeared in samples treated above 800°C.     

LEED-AES-Untersuchungen der Oxydation von austenitischen Cr-Ni-Stählen an der (100)-Ebene

Oxidation of austenitic stainless steel has been studied on the (100)-face. Temperature region examinated reaches from room temperature to 1000°C. Oxidation begins with formation of chromium oxide (Cr₂O₃). After this iron oxide (Fe₃O₄) covering the chromium oxide arises gradually. At 500°C Fe₃O₄ is destroyed, and a layer of chromium oxide increases. At 700°C the LEED-pattern was observed to represante Cr₂O₃(111), and at 750°C you can prove FeO(111) on that. At 1000°C the oxide layer is destroyed. All the oxides grow in form of islands.     

Amorphous iron-chromium oxide nanoparticles prepared by sonochemistry

Amorphous Fe₂O₃ and Fe_1.9Cr_0.1O₃ materials have been prepared by sonochemical method. X-ray diffraction patterns, transmission electron microscopy, Raman and infrared spectra, differential scanning calorimetry, Mössbauer and magnetic measurements revealed many interesting behaviors of the samples. Reaction to form the materials only occurred at the preparation temperatures of 70 °C or above. Upon heating, the sample prepared at 70°C presented a strong ferromagnetic behavior due to the presence of the magnetite phase coexisting with the hematite phase whereas the samples prepared at higher temperatures presented only the existence of the hematite phase. Thermal analyses of the sample prepared at 80°C revealed three exothermic peaks which were corresponding to the phase changes of dehydroxylation, crystallization of the maghemite phase and maghemite–hematite transition, respectively. The activation energies of the phase changes deduced from the thermal analyses showed that the presence of Cr enhanced the activation energy which can slow down the ageing effect of the amorphous state when being used in practice.     

Characterization of alkoxy-derived iron silicate

Amorphous iron silicates, x Fe₂O₃ · (1 ? x) SiO₂ (0.1 ? x ? 0.4), were prepared by calcining alkoxy-derived gels obtained by the hydrolysis of metal alkoxide mixtures. Structural studies based on X-ray diffratometry. Mössbauer effect and infrared spectroscopy indicated that the materials were indeed amorphous up to 500°C in the composition range x ? 0.3 and that the structure is formed by SiOFe bonds. Crystallization took place on calcining the samples with the composition x ? 0.3 above 600°C. Fayalite deposited at 600°C and hematite and α-cristobalite deposited above 700°C. In the case of the composition x = 0.4 the product was amorphous up to 300°C and only hematite was detected above 400°C.     

Synthesis and properties of α‐Fe2O3 nanorods

We report synthesis of α‐Fe₂O₃ (hematite) nanorods by reverse micelles method using cetyltrimethyl ammonium bromide (CTAB) as surfactant and calcined at 300 °C. The calcined α‐Fe₂O₃ nanorods were characterized by X‐ray diffraction (XRD), high‐resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer (VSM). The result showed that the α‐Fe₂O₃ nanorods were hexagonal structure. The nanorods have diameter of 30‐50 nm and length of 120‐150 nm. The weak ferromagnetic behavior was observed with saturation magnetization = 0.6 emu/g, coercive force = 25 Oe and remanant magnetization = 0.03 emu/g. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Precipitation of zinc ferrite nanoparticles in the Fe2O3–ZnO–SiO2 glass system

Glass materials in the ZnO–Fe₂O₃–SiO₂ system, containing zinc ferrite nanoparticles, were prepared by the sol–gel method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, AC- and DC-magnetization techniques. The gel samples, dried at 130 °C, were further heat treated in air at 500 and 800 °C. At 500 °C zinc ferrite and hematite nanoparticles, with an average size of approximately 24 nm, were precipitated in the brown and opaque 10ZnO–10Fe₂O₃–80SiO₂ and in the ruby colored transparent 5ZnO–5Fe₂O₃–90SiO₂ and 2.5ZnO–2.5Fe₂O₃–95SiO₂ glass matrices. In the 5ZnO–5Fe₂O₃–90SiO₂ sample the nanoparticles exhibited ferro or ferrimagnetic interactions combined with superparamagnetism with a blocking temperature of approximately 14 K. Heating at 800 °C seems to cause partial dissolution of the zinc ferrite and hematite particles in all the investigated compositions. Accordingly at 800 °C the 5ZnO–5Fe₂O₃–90SiO₂ glass shows a paramagnetic behavior down to 2 K.     

Dark-degradation of reactive brilliant blue X-BR in aqueous solution using α-Fe2O3

The precursor of Fe₂O₃ was prepared by chemical precipitation method with sodium hydroxide (NaOH) and iron chloride hexahydrate (FeCl₃ · 6H₂O). The samples annealed at different temperature were characterized by means of X-ray diffraction (XRD) and infrared absorption spectroscopy (IR). Degradation of reactive dye in aqueous solution was used to evaluate the catalytic performance of the Fe₂O₃. The experiments of degradation had been done in dark place. The experimental results indicated that the catalytic property of the precursor of α-Fe₂O₃ was excellent. The mechanism of the degradation of reactive dye in aqueous solution was investigated by comparing the data in the absence and presence of oxygen. The precursor of α-Fe₂O₃ annealed at 300 °C was the best. The degradation rate of reactive brilliant blue X-BR could exceed 95% in 8 min at 25 °C when the concentration of the precursor of α-Fe₂O₃ was 0.1 g/L. The mechanism of the catalytic oxidation reaction was investigated by comparing the X-BR catalytic oxidation data in the absence and presence of oxygen.     

The study of interactions between iron and vanadium ions in semiconducting barium-vanadate glasses doped with Fe2O3

Semiconducting barium-vanadate glasses doped with Fe₂O₃ ranging from 0.1 to 10 wt% were studied. We made attempts to understand features of an incorporation of the impurity ions into the host matrix. EPR, magnetic susceptibility, dc-conductivity and the Mössbauer effect were investigated.It was established that iron entered into the host as Fe³⁺·Fe³⁺ and V⁴⁺ ions formed associates coupled by dipole-dipole interactions for low Fe₂O₃ contents in the glass. The V⁴⁺?Fe³⁺ and Fe³⁺?Fe³⁺ pairs co-existed for all glasses. The contribution of Fe³⁺?Fe³⁺ interactions increased with increasing Fe₂O₃ content. The deviation from paramagnetic behaviour was observed for glasses with 8–9 wt% Fe₂O₃. It was attributed to presence of fine crystalline magnetic particles.The iron impurity induces no considerable changes in the dc-conductivity of the glass. The concentration dependence of dc-conductivity exhibits a minimum of about 5–6 wt% Fe₂O₃.     

Synthesis and characterisation of a new composite aluminosilicate bioceramic

Sol–gel derived 60SiO₂·20Al₂O₃·10Fe₂O₃·10Dy₂O₃ (mol%) glass and vitro-ceramic samples obtained after high temperature treatment were investigated with respect to structure, magnetic behaviour, response to simulated body fluid (SBF) and bovine serum albumin (BSA). After heat treatment, the iron preponderantly crystallises as magnetite and hematite. The field-dependent magnetisation measurements support a soft ferrimagnetic, nearly superparamagnetic behaviour. After soaking in SFB/BSA solutions, the analysis of the outermost surface layer by X-ray photoelectron spectroscopy shows the attachment of the protein and the self-assembly of a calcium containing phase.     

Influence of the temperature and the oxygen partial pressure on the phase formation in the system Cu – Fe – O

Copper iron oxides, Cu_1‐xFe_2+xO₄ (0 ≤ x ≤ 0.5), have been synthesized by thermal oxidation of copper ‐ iron mixtures. In this process, the phase formation and the phase stability were investigated as function of the temperature (800°C – 1200°C) and the oxygen partial pressure (1.013 x 10¹ – 1.013 x 10⁵ Pa). The phase formation starts with the reaction of the metallic components to simple oxides (Fe₃O₄, Fe₂O₃, CuO). From these simple oxides, the formation of complex oxides requires a minimum temperature of 800°C. The synthesis of single phase spinel compounds Cu²⁺_1‐2x Cu¹⁺_xFe_2+xO_4±δ is realized for 0.1 ≤ x ≤ 0.5, using specific temperature – p(O₂) – conditions for a given value of x. Remarkably, to achieve our goal, we found that the increase of x implies that of the reaction temperature and/or a decrease of the p(O₂) in the reaction gas stream. Besides, a single phase spinel CuFe₂O₄ does not exist in the temperature / p(O₂)‐field investigated. Using the results of XRD ‐ phase analysis, T ‐ p(O₂) – x – diagrams were constructed. These diagrams allow the prediction of phase compositions expected for different synthesis conditions. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Controllable fabrication and growth mechanism of hematite cubes

Monodispersed and single‐crystalline hematite (α‐Fe₂O₃) cubes have been successfully prepared by a template‐free hydrothermal synthetic route with FeCl₃ and CH₃COONH₄. The influences of the reactant concentration, reaction temperature, and reaction time on the crystal growth were systematically investigated. The results show that the monodisperse hematite cubes with high crystalline and narrow size distribution could be fabricated at the hydrothermal temperature of 160 °C for 24 h while the concentrations of FeCl₃ and CH₃COONH₄ were in the range of 0.03‐0.5 M and 0.05‐0.1 M, respectively. In addition, the formation mechanism of hematite cube is also proposed, where the CH₃COONH₄ plays a role of shape controller in the formation of cube hematite structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Iron redox equilibrium, structure and properties of zinc iron phosphate glasses

Iron redox equilibrium, structure and properties were investigated for the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glasses melted at different temperatures. The structure and valence states of the iron ions in these glasses were investigated using Mössbauer spectroscopy, Raman spectroscopy and differential thermal analysis. Mössbauer spectroscopy indicated that the concentration of Fe²⁺ ions increased in the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glass with increasing melting temperature. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio increased from 0.18 to 0.38 as the melting temperature increased from 1100 to 1300 °C. The measured isomer shifts showed that both Fe²⁺ and Fe³⁺ ions are in octahedral coordination. It was shown that the dc conductivity strongly depended on Fe²⁺/(Fe²⁺ + Fe³⁺) ratio in glasses. The dc conductivity increases with the increasing Fe²⁺ ion content in these glasses. The conductivity arises from the polaron hopping between Fe²⁺ and Fe³⁺ ions which suggests that the conduction is electronic in nature in zinc iron phosphate glasses.     

Speciation of Fe(II) and Fe(III) effect on CaCO3 crystallization

The present work was carried out to investigate separately the effect of Fe²⁺ and Fe³⁺ on the precipitation kinetics and the microstructure of CaCO₃. For this an experimental procedure was proposed. Precipitation tests were made by using the dissolved‐CO₂ degassing method. Both air and nitrogen were employed to strip the CO₂ from a Ca(HCO₃)₂ solution initially rich in this gas. At anoxic medium, it was shown that iron (II) prolongs the nucleation step and decelerates the crystalline growth rate. X‐ray diffraction analysis shows that its presence inhibits calcite and promotes aragonite variety. By using air, the reaction medium is rich in oxygen and iron (II) is rapidly oxidized. Seeing the higher solution pH (> 6.5), iron hydroxide forms before the onset of CaCO₃ precipitation and plays a role of seed permitting to initiate CaCO₃ nucleation. So, contrary to the observed effect of iron (II), the presence of iron (III) accelerates the precipitation rate of CaCO₃. As for iron (II), iron (III) inhibits calcite formation but favored the vaterite variety instead of the aragonite one.     

Elektronenmikroskopische Untersuchungen zur Oxidkeimbildung an Reineisenoberflächen

During a high temperature treatment of pure α-iron crystals under vacuum conditions (po₂ = 1 · 10⁻⁴ … 1 · 10⁻⁶ torr) single oxide nuclei originate on the crystal surfaces. The oxide was identified as γ-Fe₂O₃. From the definite shape of the nuclei on (100) oriented α-iron and from their orientations relative to the iron lattice an epitaxial growth may be concluded, following the well-known relation (100)_Fe ∥ (100)_Oxide; [100]_Fe ∥ [110]_oxide. Grown-in dislocations, surface steps and grain boundaries of the matrix were decorated by the oxide nuclei. However, oxide nuclei did not originate at the emergent points of fresh dislocations.     

Effect of ferric ions on the morphology and size of magnetite nanocrystals synthesized by ultrasonic irradiation

Two‐dimensional plate‐like Fe₃O₄ nanocrystals and nanoparticles could be synthesized by a simple one‐step sonochemical method through ultrasonic irradiation in reverse co‐precipitation solution at low temperature. This technique provided a facile and rapid way to prepare Fe₃O₄nanocrystals with different morphology and size. Magnetite nanoplates were synthesized with only ferrous salt adding into alkali solution, and adding ferric ions with low molar ratio in the metal salts solution would lead to the formation of very small magnetite nanoparticles (∼10 nm). The size of as‐prepared magnetite nanoparticles increased with increasing reaction temperature and showed narrow size distribution, the standard deviation less than 2 nm. This investigation indicated that ferric ions had significant influence on the morphology of Fe₃O₄ nanocrystals. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of iron phosphate glasses prepared by microwave heating

Phosphate glasses have been prepared by melting batch materials in electric furnaces, induction furnaces, and in microwave ovens. In the present work mixtures of (NH₄)₂HPO₄ and Fe₃O₄ or Fe₂O₃ were exposed to microwave energy, heated to 1200 °C, and cast to produce iron phosphate glasses. Glasses were also produced in electric furnaces for comparison. The material was analyzed by X-ray diffraction, Mössbauer spectroscopy, and differential thermal analysis. For magnetite-based glasses produced in an electric furnace, the Fe²⁺/(Fe²⁺ + Fe³⁺) ratio is compatible with the value in the batch material. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio is higher for glasses produced in a microwave oven. Glasses with nominal composition 55Fe₃O₄–45P₂O₅ (mol%) produced in an electric furnace present an arranged magnetic phase with hyperfine field that could be associated to hematite (estimated to be 21%). All the glasses submitted to heat treatments for crystallization present the following crystalline phases: FePO₄, Fe₃(PO₄)₂, Fe(PO₃)₃, Fe(PO₃)₂ and Fe₇(PO₄)₆. The amount of these phases depends on the glass composition, and glass preparation procedure. Microwave heating allows to reach melting temperatures at high heating rates, making the procedure easy and economical, but care should be taken concerning the final Fe²⁺/(Fe²⁺ + Fe³⁺) ratio.     

State of Fe3+ ion and Fe3+ −F− interaction in calcium fluorosilicate glasses

The state of Fe³⁺ ions and Fe³⁺ ?F^? interaction in calcium fluorosilicate glasses xCaF₂·(1- x)CaO·SiO₂) (0 ≤ x ≤ 0.3) containing a small amount of iron were investigated by ESR spectroscopy. Two resonances observed near g = 2.0 and g = 4.3 were assigned to dipole-dipole interacted Fe³⁺ ions and Fe³⁺ ions in a rhombic crystal field, respectively. The fraction of Fe³⁺ ions in a rhombic crystal field decreased and that of dipole-dipole interacted Fe³⁺ ions increased with increasing Fe₂O₃ content. It was found that the quantity of dipole-dipole interacted Fe³⁺ ions depends on the negative partial charge of fluorine ions and shows a maximum at 10 mol% CaF₂ (x = 0.2). The maximum is attributed to the largest difference between absolute values of the ionic potentials of ferric and fluorine ions which is caused by the smallest negative partial charge of flourine at 10 mol% CaF₂.     

Luminescence of Y2O3:Eu and Gd2O3:Eu Depending on Precursor and Activation Temperature

The activation of Y₂O₃, Gd₂O₃and (Y_0.7,Gd_0.3)₂O₃ with Eu³⁺ ions at temperatures lower than 1000 °C is studied using different starting compounds. The activator ions are introduced during the crystallization or precipitation of the precursor. Phosphors prepared from hydroxides and activated at 900 °C exhibit luminescence with high efficiency under 254 nm Hg-line excitation. Strong emission is observed even in samples activated at 700 °C. Luminescence intensity, emission and excitation spectra are compared to these of Y₂O₃:Eu produced by the industry.     

Spinel ferrite-silica glass obtained by splat quenching

The compositions (in mol%) 40 MnFe₂O₄, 60 SiO₂, and 42.8 CoFe₂O₄, 57.1 SiO₂ have been melted and splat-quenched. The resulting materials have been analyzed using X-ray diffraction, transmission electron microscopy, scanning transmission electron microscopy, and room temperature Mössbauer spectroscopy.The quenched Mn-containing material was completely amorphous. Its Mössbauer spectrum contains two doublets, indicating Fe²⁺ and Fe³⁺ in distorted octahedral sites.The quenched Co-containing composition contained (Co, Fe)₂SiO₄ (olivine and (Co, Fe)₂O₄ (spinel) precipitates, 150–400 Å in diameter, in a glassy matrix. The Mössbauer spectrum contains three doublets, indicating octahedral Fe²⁺ in the olivine, distorted octahedral Fe²⁺ in the glass, and distorted octahedral Fe³⁺ in the glass. The spectrum also shows trace hyperfine splitting, attributed to the spinel ferrite.     

X-Ray Studies of Some Europium Compounds at Elevated Temperatures

The temperature variation of the lattice constants of europium iron garnet (Eu₃Fe₅O₁₂), europium sulphide (EuS) and europium fluoride (EuF₂) has been studied using an X-ray powder diffractometer. The lattice constant of Eu₃Fe₅O₁₂ increases linearly upto 800 °C with an expansion coefficient of 10.4 × 10⁻⁶ °C⁻¹. In the case of EuS, the lattice constant increases non-linearly with temperature. At room temperature the expansion coefficient has a value of 14.3 × 10⁻⁶ °C⁻¹. In EuF₂ the lattice constant increases non-linearly upto 140 °C. At higher temperatures, the lattice constant decreases with increasing temperature with a negative expansion coefficient of −29 × 10⁻⁶ °C⁻¹ over the range 170–235 °C. The cause of the anomalous behaviour observed in EuF₂ is yet to be understood.