Determination of the Fe2+/Fe3+ Ratio in Nuclear Waste Glasses

The Fe²⁺/Fe³⁺ ratios of 47 simulated nuclear waste glass samples with ratios varying from 0.01 (oxidized) to 1.6 (reduced) were determined by wet-chemical and Mössbauer spectral analyses. The wet-chemical method involved the spectrophotometric determination of Fe²⁺ and total iron using remote spectroscopy with fiber optic chemical sensing. Interferences from other species present in these glasses were examined and alternative analytical techniques were investigated. Results of wet-chemical and Mössbauer spectral analysis were comparable; however, the wet-chemical method is probably preferable for the analysis of highly radioactive glasses until such glasses have been shown to have satisfactory Mössbauer spectra.     

Occurrence of Ti3+ and Fe2+ in Mullite

Electron paramagnetic studies showed that Ti³⁺ and Fe²⁺ occur in mullites taken from a refractory material which was fused-cast under a reducing atmosphere. Exposure of the mullite samples to temperatures >1600°C caused oxidation of Ti³⁺ and Fe²⁺ to Ti⁴⁺ and Fe³⁺, respectively.     

The Iron-Oxygen Equilibrium in Glass: Effect of Platinum on the Fe2+/Fe3+ Equilibrium

A number of experiments were performed on iron-containing sodium disilicate melts in air. It was found that it was not possible to obtain an equilibrium between Fe²⁺ and Fe³⁺ in platinum crucibles owing to the reaction between platinum and iron, whereas in alumina crucibles the equilibrium was rapidly established. Thermodynamic calculations of the reaction 2FeO (in Na²O-2SiO²) +½O² (g) = Fe²O³ (in Na²O-2SiO²) showed that the equilibrium went more and more to the right with increasing temperature. The standard free energy, enthalpy, and entropy for the reaction were calculated.     

Effect of Fe4+ in the System SrFeO3-SrTiO3

Perovskites of the system SrFeO₃-SrTiO₃ were prepared, and measurements were made of their magnetic and electrical behavior. Chemical analysis showed that the percentage of Fe⁴⁺ varied from 72.5% for SrFeO_2.86 to about zero for Sr(Fe_0.1Ti_0.9)O_2.95; the remainder of the iron was in the Fe³⁺ state and electrical balance was achieved by oxygen loss. Sr(Fe_{1- x} Ti _x )O₃ was antiferromagnetic between x = 0 and x = 0.9, with a Néel temperature below 60°K. A parasitic ferromagnetic component developed when these compounds were cooled in a magnetic field, the magnitude of this component being dependent on the cooling field. The conductivity of these perovskites ranged from 10⁻⁸ ohm⁻¹ cm⁻¹ for x = 1.0 to 10⁻² for x = 0.0 and showed a marked change at x = 0.8. The break corresponded to a change in slope of the lattice parameter and the disappearance of Fe⁴⁺. The Fe⁴⁺ content depended on the heat treatment and atmosphere during formation.     

Nucleation and Growth of Magnesioferrite in MgO Containing 0.9% Fe3+

The initial stage of precipitation of magnesioferrite from a supersaturated solid solution of 0.9 cation % Fe³⁺ in MgO at 500 °C was studied by fitting the magnetization curves to 7000 Oe at low temperatures with the Brillouin function. The averase umber of Fe³⁺ ions in a precipitate particle, increased monotonically with aging time from 9 in the as-quenched condition to 88 after 16 h. The average spin quantum number per Fe³⁺ ion decreased to near its final value at an aging time corresponding to = 50. Thus the volume fraction of precipitate is near the final value when the average particle size is only about three unit cells of magnesioferrite.     

Polymorphism of BaTiO3 Acceptor Doped with Mn3+, Fe3+, and Ti3+

The effect of Mn doping on the cubic to hexagonal phase transition temperature in BaTiO₃ has been determined by quenching samples with different Mn contents from a range of temperatures. Under conditions of equilibrating samples in air over the range 1000°–1400°C, cubic solid solutions BaTi_{1− x} Mn _x O_3−δ form over the range 0≤ x ≤0.015(5), whereas hexagonal solid solutions form for x ≥0.02, depending on the temperature. The results are compared with those on doping BaTiO₃ with Fe³⁺ and observations made concerning acceptor doping with Ti³⁺.     

Discoloration of Fired Kaolinitic Clays (Study of Fe3+ Coordination by Mössbauer and UV-ViS-NIR Spectroscopy)

The final color of a ceramic body is generally determined by the contents of Fe³⁺ ions. The Central European market accepts kaolinitic clays for the production of tableware, electro-insulators, and wall tiles only if the Fe₂O₃ in chemical analyses of the kaolin does not exceed 1.0 wt%. The chemical analyses calculate the content of all iron components as if they were in the form of Fe₂O₃ and then their quantity excludes even good-quality clay from the ceramic industry of white bodies. We found that oxidizing firing of the samples fired at over 1180°C changes the color in cases where the initial Fe³⁺ component is in the form of hydro ferric oxide [FeO(OH)] or if the ferric ions were added to the white kaolin samples in the form of ferric nitrate [Fe(NO₃)₃·9H₂O]. The Mössbauer spectroscopy confirms the presence of only diluted Fe³⁺ ions. The UV-ViS-NIR spectroscopy confirms that even if the concentration of Fe₂O₃ is above 3.0 wt%, these ions of Fe³⁺ in the case of their initial hydro ferric oxide formed in clay are incorporated into the mullitic structure in tetrahedral coordination. The iron-coloring effect depends on the coordination of Fe³⁺ ions with the studied discoloring effect of fired bodies—the very small and well-distributed particles enter into the formatted mullitic structure.     

Structural and Optical Characterization of Flower-Like Rutile Nanostructures Doped with Fe3+

Flower-like agglomerates with sizes of 200–400 nm of pure and Fe³⁺-doped TiO₂ with rutile crystalline structure were synthesized by the coprecipitation method. The morphology of the agglomerates was determined by electron microscopy (TEM and HRTEM). TiO₂ agglomerates consist of nanorods with clearly visible crystalline faces, parallel to the axis of elongation whose direction was along the [101] direction of pure TiO₂ and the [111] direction of doped TiO₂. Furthermore, nanorods consist of "chains" of spherical particles, most likely interconnected through the so-called oriented attachment or grain-rotation-induced grain coalescence (GRIGC) process. UV/Vis reflection measurements revealed that the absorption of pure TiO₂ was significantly shifted from UV toward the visible spectral region upon the incorporation of Fe³⁺ into the TiO₂ host.     

Glass Formation in the System SiO2–PbO Containing Transition-Metal Oxides

Glass-forming regions, valence states, and viscosities in SiO₂–PbO systems containing various transition-metal oxides as a third component were investigated. The glasses were prepared by melting in an open atmosphere. The glass-forming regions ranged as follows: MnO≡ZnO > FeO_1.5>NiO. The ratios Fe²⁺/(Fe²⁺+ Fe³⁺) and Mn³⁺/ (Mn³⁺+ Mn²⁺) in the glasses were determined by chemical analysis. The Fe²⁺/ (Fe²⁺+ Fe³⁺) ratio in SiO₂–PbO–FeO_1.5 glasses ranged from 0.016 to 0.050. The Mn³⁺/ (Mn³⁺+ Mn²⁺) ratio in SiO₂–PbO–MnO glasses ranged from 0.056 to 0.30. The fraction of manganese (III) ions in the glasses varies considerably with the glass composition. The effects of transitionmetal oxides on the viscosity are discussed.     

Electrical Resistivity Surface for FeO-Fe2O3-P2O5 Glasses

The dc electrical properties and microstructure of x (FeO-Fe₂O₃)-(100 – x )P₂O₅ glasses were investigated up to a maximum of x = 75 mol%. Results indicate that, in general, the minimum resistivity of the glass does not occur at equal Fe^2+] and Fe^3+] concentrations, although for the special case where x = 55 mol% the minimum does occur at Fe^2+]/Fe total = 0.5, as reported by other investigators. Evidence presented shows that the position of the minimum resistivity is a function of total iron content. The minimum shifts to glasses richer in Fe^2+] at higher total iron concentrations.     

Mechanism of the Blue Up-Conversion in Tm3+/Nd3+-doped Calcium Aluminate Glasses

Blue up-conversion fluorescence from the Tm³⁺:¹ G ₄→³ H ₆ (480 nm) transition has been observed from calcium aluminate glass codoped with Tm³⁺/Nd³⁺. The mechanism for the up-conversion process consists of a two-photon process. An excitation beam with a wavelength of 791 nm first excites Tm³⁺ to the ³ H ₄ level, where Tm³⁺ again absorbs the 1060 nm emission from Nd³⁺:⁴ F _3/2→⁴ I _11/2 to attain the Tm³⁺:¹G₄ level. Lifetime and intensity variations with compositions suggest the presence of an efficient energy transfer from Nd³⁺ to Tm³⁺. The highest 480 nm emission intensity has been obtained from the glass with 0.1 mol% of Nd₂O₃ and 0.2 mol% of Tm₂O₃.     

Luminescence of Fe3plus; in Metaphosphate Glasses: Evidence for Four- and Six-Coordinated Sites

Ferric iron-substituted sodium metaphosphate and calcium metaphosphate glasses exhibit a very weak luminescence that can be observed under laser excitation. Broad emission bands at 16 000 cm⁻¹ and at 12 000 cm⁻¹ are assigned to the ⁴T₁→⁶A, transitions of Fe^3plus; in four- and six-coordinated sites respectively. The interpretation is supported by crystal field theory calculations based on known absorption spectra of Fe^3plus;.     

Redox State of Iron and Its Related Effects in the CaO–P2O5–Fe2O3 Glasses

Iron exists in Fe²⁺ and Fe³⁺ states in CaO–P₂O₅–Fe₂O₃ glasses and they impart characteristic optical absorption bands that allow analysis of relative proportion of the two species. This communication reports the redox states of glasses melted under air, argon, and oxygen atmospheres and relates them to the dissolution rates. The dissolution rate was found to be related to the redox state and it is lowered if the glass is melted under oxidizing atmospheres.     

Incorporation of Aliovalent Dopants into the Bismuth-Layered Perovskite-Like Structure of BaBi4Ti4O15

The solid solubility of the aliovalent dopants Fe³⁺ and Nb⁵⁺ in the BaBi₄Ti₄O₁₅ compound, a member of the family of Aurivillius bismuth-based layer-structure perovskites, has been studied using quantitative wavelength-dispersive spectroscopic microanalysis (SEM/EPMA) in combination with X-ray powder diffractometry (XRPD). The samples with nominal (starting) compositions corresponding to the chemical formulas BaBi₄Ti_{4–4 X} Fe_{4 X} O₁₅ and BaBi₄Ti_{4–4 X} Nb_{4 X} O₁₅ were prepared by hot forging a mixture of BaTiO₃ and Bi₄Ti₃O₁₂ with additions of Fe₂O₃ or Nb₂O₅ followed by a long annealing at 1100°C. The study showed that an excess charge introduced into the structure by the substitution of Ti⁴⁺ ions with aliovalent dopants was preferentially compensated by a change in the ratio of Ba²⁺ to Bi³⁺ ions in the host structure according to the general formulas of the solid solutions Ba_{1–4 X} Bi_{4+4 X} Ti_{4–4 X} Fe^'_{4 X} O₁₅ and Ba_{1+4 X} Bi_{4–4 X} Ti_{4–4 X} Nb^·_{4 X} O₁₅.     

Phase Diagram of the System BaO-Fe2O3

The phase diagram of the system BaO-Fe₂0₃ was determined by X-ray diffraction, melting-point measurement, and microscopic methods. Since the reduction of Fe³⁺ to Fe²⁺ was observed by chemical analysis in the samples heated at high temperature, especially in molten samples, the samples were heated at 1 atmosphere pressure of oxygen in the temperature region in which the liquid was in equilibrium; 1 atmosphere pressure of oxygen was su5cient to restrain the reduction of Fe³⁺. In the temperature region of solid-solid equilibrium, the dissociation was not observed even when the samples were heated in air. BaO - 6Fe₂O₃ formed a solid solution with BaO.Fe₂0₃. The BaO:Fe₂0₃ ratio of the solid solution was BaO.4.5Fe₂0₃ at 1350°C. and BaO. 5.0Fe₂0_a at 800°C. The precipitation micro-structures of each primary solid solution were observed.     

Sintering, Crystallization, and Properties of B2O3/P2O5-Doped Li2O·Al2O3·4SiO2 Glass-Ceramics

Sintering, crystallization, microstructure, and thermal expansion of Li₂O·Al₂O₃·4SiO₂ glass-ceramics doped with B₂O₃, P₂O₅, or (B₂O₃+ P₂O₅) have been investigated. On heating the glass powder compacts, the glassy phase first crystallized into high-quartz s.s., which transformed into β-spodumene after the crystallization process was essentially complete. The effects of dopants on the crystallization of glass to high-quartz s.s. and the subsequent transformation of high-quartz s.s. to β-spodumene were discussed. The major densification occurred only in the early stage of sintering time due to the rapid crystallization. All dopants were found to promote the densification of the glass powders. The effect of doping on the densification can fairly well be explained by the crystallization tendency. All samples heated to 950°C exhibited a negative coefficient of thermal expansion ranging from about −4.7 × 10^-6 to −0.1 × 10^-6 K^-1. Codoping of B₂O₃ and P₂O₅ resulted in the highest densification and an extremely low coefficient of thermal expansion.     

Kinetics of Nonisothermal Crystallization of Bi2Sr2CaCu2Ox Glasses with Different Copper Valence States

The kinetics of the nonisothermal crystallization process in Bi₂Sr₂CaCu₂O_x glasses with different copper valance states, R(Cu⁺) = Cu⁺/(Cu⁺+ Cu²⁺) = 0.79–0.99, were examined by using differential scanning calorimetry. Four different kinetic equations were used for the data analyses. It was found that the values of activation energy for crystal growth, E _a, decreased with increasing Cu⁺ content. The value of E _a, which was estimated from the modified Ozawa equation, for the glass with R(Cu⁺) = 0.79 was 483 kJ·mol^-1 and for the glass with R(Cu⁺) = 0.99 was 353 kJ·mol^-1. In the former glass, the number of crystal nuclei was almost independent of the heating rate. But, in the latter glass, the number of crystal nuclei varied significantly with the heating rate. The crystallization mechanism in the glasses was closely related to the thermal stability and viscosity of glasses: the glass with R(Cu⁺) = 0.99 showing a high thermal stability and a low activation energy for viscous flow had a small value of E _a. The plot of In ( T _p²/α) against 1/ T _p, where T _p and α are crystallization peak temperature and heating rate, respectively, gave a reasonable value of E _a for the glass with R(Cu⁺) = 0.79 but was unsuitable for the evaluation of E _a for crystal growth of the glass with R(Cu⁺) = 0.99.     

Oxidation-Reduction Equilibria in Molten Na2O.2SiO2 Glass

The oxidation-reduction equilibria in molten glasses having a soda/silica ratio of 1/2 and containing small amounts of variable-valence ions of the transition elements titanium, vanadium, iron, cobalt, and nickel, the post-transition elements tin and antimony, and the rare-earth element cerium were obtained by equilibrating the melts with various atmospheres. The simple mass expression
was always applicable. In the expression, n is the number of electrons involved in the valence change of the metal M. The value of n is 1 for all systems except for the ions of antimony and tin where n is 2. The ions found are those generally accepted as existing in glass melts which are Ti³⁺, Ti⁴⁺; Fez+, Fe³⁺; Ce³⁺, Ce⁴⁺; Mn²⁺, Mn³; Co²⁺, Co³⁺; Ni²⁺, Ni³; Sb³⁺, Sb⁵⁺; and Sn²⁺, Sn⁴⁺. Two mass action expressions were needed for vanadium-containing glasses to describe the equilibria between 5+, 4+, and 3 f species.     

Preparation and Properties of Quenched Li2O-BaO-Nb2O5 Glasses

Glasses were prepared in the wide variety of compositions in the system Li₂O-BaO-Nb₂O₅, which contains no "glass-former," by the twin-roller quenching technique. The crystallization temperature ranges from 500° to 700°C and increases as Li₂O is replaced by BaO. The dielectric constant increases steeply with temperature, reaching an anomalously large value (10⁴) in glasses which contain a large amount of Li₂O. Such a temperature dependence of dielectric constant is very similar to that of conductivity in each glass, indicating that the dielectric behavior is caused by polarization due to the ionic motion in glass. The conductivity at 500 K ranges from 10⁻¹³ to 10⁻⁵Ω⁻¹·cm⁻¹ and the activation energy for conduction from 120 to 40 kJ/mol. The concentration of Li⁺ ions mainly controls the conductivity and the addition of Ba²⁺ ions slightly lowers it.     

2.0 μm Emission Properties and Energy Transfer between Ho3+ and Tm3+ in PbO—Bi2O3—Ga2O3 Glasses

Emission properties of 2.0 μm fluorescence and the energy transfer between Ho³⁺ and Tm³⁺ in 57PbO·25Bi₂O₃·18Ga₂O₃ (mol%) glass codoped with Ho³⁺ and Tm³⁺ were investigated. Cross-relaxation rates in Tm³⁺ increased approximately 5 times when the Tm₂O₃ concentration was increased from 1.0 to 1.5 wt%. Coefficients of the forward Tm³⁺→ Ho³⁺ energy transfer were about 15 times larger than those of the Tm³⁺← Ho³⁺ backward transfer. Analysis of the energy transfer and gain spectra indicated that the highest gain at the 2.0 μm wavelength region could be achieved from the glass with 1.5 wt% of Tm₂O₃ and 0.3 wt% of Ho₂O₃.