The influence of Fe2O3 and B2O3 additions on the thermal properties,crystallization kinetics and durability of a sodium aluminum phosphate glass

A sodium aluminum phosphate glass, identified as a potential encapsulating phase for radioactive wastes, has been noted to be thermally unstable, crystallizing upon heat treatment to yield a variety of phases which may be detrimental to the longer term properties of the final wasteform. In an attempt to improve the thermal stability and overall resistance of this glass to crystallization, the influence of various oxide additions including Fe₂O₃ and B₂O₃ has been investigated. It has been shown that quite small additions of B₂O₃ are extremely effective in improving the stability, with ⩾2 mol% B₂O₃ almost completely suppressing crystallization whilst only marginally affecting the excellent chemical durability of the ternary glass, at least at the lower B₂O₃ concentrations. In contrast, addition of Fe₂O₃ or B₂O₃/Fe₂O₃ mixtures does not lead to significant improvements in the thermal stability, although durability relative to that of the ternary composition is improved significantly with increasing Fe₂O₃ content.     

Structural and magnetic properties of nanometric Zn0.5Co0.5Fe2O4 prepared by hydrothermal method

ABSTRACT

The study of the structural, morphology and magnetic properties of Zn_0.5Co_0.5Fe₂O₄ ferrite is the objective of this work. The sample was prepared by hydrothermal method and was characterized by X-ray diffraction (XRD), (SEM) and (TEM) micrographs and magnetization measurements.

The magnetic hysteresis loops, field cooling (FC) and zero field cooling (ZFC) curves, in temperature range (0-400K), were measured using XL-SQUID magnetometer and the values of blocking temperatures (T_B) were determined. The results indicated that Zn_0.5Co_0.5Fe₂O₄ sample were formed in a single spinel phase and gives the value for the lattice parameter (8.3952 Å) and nanosizes of particles (13.8 nm) were compared with these obtained from ZnFe₂O₄ sample prepared also by synthesis method (8.4261 Å and 14 nm). Although, the superparamagnetic behaviour for Co-Zn ferrite has observed at 350K with a blocking temperature (T_B = 300K), that is maximum at the value obtained in the case of Zn-ferrite (T_B = 12K).     

The vibrational spectra of B2O3-GeO2 glasses

Infrared and Raman spectra were measured for a series of glass compositions in the binary B₂O₃-GeO₂ system at room and elevated temperatures. No coordination changes were detected from spectral analysis for either boron or germanium with concentration or temperature changes. Interpretation of the vibrational spectra indicated that both boroxol rings and BO₃-triangular units were present as the basic units in glasses with higher B₂O₃ concentrations. Only BO₃-triangular units were detected as the basic units in glasses with lower B₂O₃ concentrations. Raman spectra of glasses measured at higher temperatures (>T_g) indicated that their boroxol ring concentrations decreased as a function of temperature. The enthalpy for ring rupture in 35GeO₂–65B₂O₃ glass was 7.7 kcal/mol. Also, spectral analysis indicated that the boroxol ring concentrations of these glasses at room temperature were dependent upon their previous heat treatments.     

Effect of boron addition on the structure and properties of iron phosphate glasses

Effects of boron addition on the glass forming characteristics, structure and properties of iron phosphate glasses with nominal compositions of xB₂O₃-(40−x)Fe₂O₃-60P₂O₅ (x = 2-20, mol%) and xB₂O₃-(100−x)[Fe₂O₃-60P₂O₅] (x = 2-20, mol%) have been investigated by DTA, XRD, IR and Mössbauer spectroscopy. Although there were some weak local surface crystallizations on especially most of the glasses in group B, all of the compositions formed glass. DTA spectra showed two exothermic peaks corresponding to crystallizations along with an endothermic glass transition peak. T_g increased with increasing B₂O₃ content for the glasses in the first series which indicates that the addition of B₂O₃ increases the thermal stability of glasses in this series while the opposite is observed in the second series. The dissolution rates of boron containing bulk glasses were found to be around 10⁻⁹ gr/cm² min which are comparable to that of the base iron phosphate glass. When the B₂O₃ content was above 14%, new bands related to BO₄ tetrahedral groups have been observed in the IR spectra. The Mössbauer isomer shift values of boron doped glasses were found to be a little lower than that of base glass but both iron ions had distorted octahedral coordination in all glasses. The fraction of Fe²⁺ ions in glasses (Fe²⁺/∑(Fe²⁺ + Fe³⁺)) was found to be 23% for the base glass while it was 10-22% for the boron doped glasses.     

Crystal structure and magnetic properties of the LaCo0.5Fe0.5O3 perovskite

The magnetic and crystal structures of the LaCo_0.5Fe_0.5O₃ perovskite are investigated. It is established that the unit cell of this compound at room temperature is characterized by rhombohedral distortions. As the temperature decreases, the compound undergoes a structural phase transition from the rhombohedral phase to the orthorhombic phase in the temperature range 200–300 K. The LaCo_0.5Fe_0.5O₃ perovskite has an antiferromagnetic structure with the G _z spatial orientation of the antiferromagnetic vector. The magnetic properties of the LaCo_0.5Fe_0.5O₃ perovskite are interpreted within a model according to which the ground state of Co³⁺ ions is a low-spin state and the existence of the weak ferromagnetic component is associated with the exchange interactions between the Fe³⁺ ions.     

The effect of B2O3 on the solubility of (YSmLuCa)3(FeGe)5O12 garnet in PbO-B2O3 flux

The paper deals with the solubility of (YSmLuCa)₃ (FeGe)₅O₁₂ garnet in PbO—B₂O₃ flux. An anionic model explaining the effect of B₂O₃ on the solubility of rare earth garnet is suggested. This model is based on the assumption that PbO in the melted mixture of PbO, B₂O₃, Fe₂O₃, R₂O₃, CaO, GeO₂ dissociates into Pb²⁺ and O²⁻. The oxygen anions react with the other oxides under the formation of BO₃³⁻, FeO₃³⁻, RO₆⁹⁻, CaO₂²⁻ and GeO₃²⁻ anions, until the equilibrium is established. The garnet is dissociated into the anions mentioned above. The validity of the model is verified by an agreement of the experimentally determined saturation temperatures of the melts for LPE of garnet layers with the Arrhenius-type expression of the solubility product of garnet where x_i denotes the equilibrium concentrations of the anions in the melt and x° is the Ge content of the garnet film.     

Crystallization of Ba<Subscript>3</Subscript>Fe<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript> and Ba<Subscript>2</Subscript>Fe<Subscript>2</Subscript>GeO<Subscript>7</Subscript> in oxide-fluoride fluxes

Crystallization of trigonal Ba₃Fe₂Ge₄O₁₄ and tetragonal Ba₂Fe₂GeO₇ barium ferrogermanates is investigated in their own fluxes diluted by B₂O₃-BaF₂ and B₂O₃-PbF₂ mixtures, respectively. The ratios of the components at which the properties of the fluxes satisfy the requirements for controlled crystallization of these incongruently melting compounds are determined. Single crystals of Ba₂Fe₂GeO₇ barium ferrogermanate are grown for the first time.     

Structural and magnetic investigations of Fe2O3–TeO2 glasses

A series of tellurite glasses containing Fe₂O₃ with the nominal composition x(Fe₂O₃)–(1−x)(TeO₂), where x = 0.05, 0.10, 0.15, and 0.20, have been synthesized and investigated using X-ray photoelectron spectroscopy (XPS) and magnetization techniques. The Te 3d core level spectra for all glass samples show symmetrical peaks at essentially the same binding energies as measured for TeO₂ indicating that the chemical environment of the Te atoms in these glasses does not vary significantly with the addition of Fe₂O₃. Furthermore, the full-width at half-maximum (FWHM) of each peak does not vary with increasing Fe₂O₃ content which suggests that the Te ions exist in a single configuration, namely TeO₄ trigonal bipyramid (tbp). The O 1s spectra are narrow and symmetric for all compositions such that oxygen atoms in the Te–O–Te, Fe–O–Fe and Te–O–Fe configurations must have similar binding energies. The analysis of the Fe 3p spectra indicates the presence of Fe³⁺ ions only, which is consistent with the valence state of the Fe ions determined from magnetic susceptibility measurements.     

Magnetic properties of Fe-Co-Nd-Y-B magnet prepared by suction casting

The magnetic properties of Fe_67−xCo₁₀Nd₃Y_xB₂₀ (x = 0, 2, 6, 10) alloys prepared by suction casting had been investigated. It was found that a small addition of Y (6%) was very effective in improving glass-forming ability (GFA) of Fe-Co-Nd-Y-B alloys. The as-cast Fe₆₁Co₁₀Nd₃Y₆B₂₀ alloy presented soft magnetic behavior. However, the alloy showed the hard magnetic behavior due to exchange coupling between soft and hard magnetic phases after annealing at 948 K for 30 min. The results provide a promising approach for the production of bulk magnets by the simple process of copper mold casting and subsequent heat treatment.     

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.     

On the Solubility of Garnets in PbO/B2O3 High Temperature Solvents

The paper is concerned with solubility models for Y₃Fe₅O₁₂ (YIG) and Gd₃Ga₅O₁₂ (GGG) solved in PbO/B₂O₃ high temperature solutions containing Fe₂O₃ or Ga₂O₃ in excess. It is shown that a new extended eight-particle model Interprets well the literature data of the solubility of YIG as well as the DTA data of the solubility of GGG. Comparisons of solution enthalpies determined in terms of the single-molecule, eight-particle, and extended eight-particle model are carried out in dependence on the excess concentration of species containing iron or gallium, respectively.     

Magnetic behaviour of 20Fe2O380[3B2O3(1−χ)PbOχAs2O3] glasses

The results of magnetic measurements performed on 20Fe₂O₃80[3B₂O₃(1?χ)PbOχAs₂O₃] glasses, in the temperature range 4.2 to 300 K are reported. By decreasing the temperature a downward curvature of reciprocal susceptibility is observed for T<50 K. The composition dependence of the paramagnetic Curie temperatures and Curie constants is discussed.     

EPR study of disorder processes in the ternary vanadate Zn2FeV3O11−x compound

Two samples of the Zn₂FeV₃O₁₁ compound were synthesized using different preparation routes: a solid state reaction of the ZnO–Fe₂O₃–V₂O₅ oxides and a direct reaction of the Zn₂V₂O₇ and FeVO₄ vanadates. In both cases the temperature dependences of the EPR spectra revealed a dominant contribution of antiferromagnetically coupled Fe³⁺ ions in the high-spin state. Specific differences in the EPR spectra of the two samples were recorded at all the investigated temperature intervals. A short range, or less likely, partial magnetic order involving a fraction of the Fe³⁺ distributed on the two octahedral crystallographic sites appeared to take place below 50 K. The differences observed between the EPR spectra of the two Zn₂FeV₃O₁₁ samples might suggest the existence of small variations in the cation disorder phenomena of Fe³⁺ and Zn²⁺ ions or the presence of an oxygen deficiency process.     

Spectroscopic studies on vitreous and polycrystalline heavy metal gallium–bismuthates

Local order changes determined by Fe₂O₃ (0–20 mol%) addition to Bi₂O₃–Ga₂O₃ matrix in glass and vitroceramic samples were investigated by X-ray diffraction (XRD), electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) spectroscopies. Glass samples were prepared using the melt-quench technique. The vitroceramic samples were obtained by crystallization, as a result of the heat treatment applied on glass samples. The glass network mainly consists of [BiO₆] octahedral units. After heat treatment induced crystallization, [BiO₃] pyramidal units are predominant in samples. As evidenced by electron spin resonance, the Fe³⁺ ions surrounding is characterized by low crystal fields, excepting the vitreous sample with the lowest Fe₂O₃ content, wherein the Fe³⁺ ions occupy sites of low symmetry, characterized by high crystal fields.     

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.     

Structural properties of Cr2O3–Fe2O3–P2O5 glasses,Part I

The structural properties of xCr₂O₃–(40 − x)Fe₂O₃–60P₂O₅, 0 ⩽ x ⩽ 10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr₂O₃ does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q¹, units. This is in accordance with O/P ≈ 3.5 for these glasses. The increase in glass density and T_g that occurs with increasing Cr₂O₃ suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe²⁺/Fe_tot ratio increases from 0.13 to 0.28 with increasing Cr₂O₃ content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr₂O₃–30Fe₂O₃–60P₂O₅ (mol%) sample was partially crystallized and contained crystalline β-CrPO₄ and Fe₃(P₂O₇)₂. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe₂O₃ (39.6 mol%) and P₂O₅ (54.9 mol%), but contained only 5.5 mol% of Cr₂O₃. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr₂O₃.     

Crystal structure of the rhombohedral phase of Fe<Subscript>3</Subscript>B<Subscript>7</Subscript>O<Subscript>13</Subscript>Br

The crystal structure of the rhombohedral phase of Fe₃B₇O₁₃Br was determined and compared with the structures of Fe₃B₇O₁₃Cl and Fe₃B₇O₁₃I. The influence of the ionic radii of the halogen atom on the structural features of the crystals of the boracite family is discussed.     

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.     

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.     

Crystal structure and magnetic properties of nanosized Mg(Fe0.8Ga0.2)2O4-δ films on Si substrates

Film samples of nominal Mg(Fe_0.8Ga_0.2)₂O_4-δ composition were obtained on Si(100) substrates by oxygen-ion-beam sputtering of a Mg(Fe_0.8Ga_0.2)₂O_4-δ ceramic target. The film thicknesses were ～200 and ～400 nm. Field dependences of the specific magnetization of ～200-nm films annealed at different temperatures (800–1000°C) have been measured. The crystal structure, surface morphology, and magnetic characteristics of films of different thicknesses (～200 and ～400 nm) are investigated. The reasons for the discrepancy between the specific magnetizations of the films obtained and their ceramic analog are discussed.