Photosensitive Characteristics of Dopant-Free, Ultraviolet-Sensitive Calcium Aluminate Glasses

Calcium aluminate glasses show high sensitivity to ultraviolet radiation without the doping of optically active components. In this paper, photosensitive characteristics and the cause of UV-induced coloring were investigated for these glasses. Ultraviolet rays below 270 nm were effective for inducing the coloring. The most effective wavelength agreed with that of the apparent absorption edge. In the ternary system with SiO₂ or GeO₂, the sensitivity was monotonically reduced with the amount of the third component and almost vanished for the compositions containing 40 mol%. On the basis of the establishment of a close correlation between two optical absorption bands and two electron spin resonance signals induced by UV illumination, the UV-induced coloring was concluded to be due to the emergence of an aluminum-oxygen hole center (Al-OHC) and an ozonide (O₃^-).     

Iron Diffusion in Iron-Aluminate Spinels

The diffusion coefficient of ⁵⁹Fe in iron-aluminate spinels (Fe₃O₄-FeAl₂O₄) was measured by serial sectioning. The results were analyzed with a defect model, assuming that the predominant defects were cation vacancies and interstitials. At 1380°C, diffusion occurs in Fe₃O₄ and Fe(Fe_1.51Al_0.49))O₄ by an interstitial mechanism at low P_O2 and a vacancy mechanism at high P_O2* Diffusion of iron is by the vacancy mechanism for higher hercynite concentrations, except that the results for the end-member, FeAl₂O₄, suggest an interstitial mechanism. At 10⁻⁶ atm O₂, an Arrhenius plot of D _Fe exhibits a minimum for Fe₃O₄ and Fe(Fe_1.51 A1_0.49)O₄. This effect is explained in terms of a mechanism change. The D _Fe is essentially independent of temperature in Fe(Fe_1.03Al_0.97)O₄ and Fe(Fe_0.54Al_1.46)O₄.     

Equilibrium Studies of Fe in Alkali Phosphate Glasses

The Fe²⁺-Fe³⁺ equilibrium in binary Na₂O-P₂O₅, glasses was studied by equilibrating glass melts at different temperatures in air. The enthalpy change (δH) of the reaction 1/2Fe₂O₃⇌FeO+1/4O₂ was calculated for 4 glasses. The results indicate that (1) the equilibrium shifts toward the oxidized state as the Na₂O content of the glass increases (plots of log ([Fe²⁺]/[Fe³⁺]) vs mol% alkali were linear) and (2) Δ H values for glasses of different composition are nearly equal but differ from the standard (calculated) value for the reaction. The experimental ΔH values were nearly equal to that for the reaction FePO₄→1/3 Fe₃(PO₄)²+ 1/6P₂O₅+1/4O₂, indicating that Fe forms phosphate or polyphosphate configurations in the Na₂O-P₂O₅ glasses. In certain of the glasses studied a faint-pink solid precipitated; its X-ray diffraction pattern indicated that its principal component is crystalline Na₂Fe¹¹¹P₃O₁₀.     

Sodium Diffusion and Leaching of Simulated Nuclear Waste Glass

Oxides such as CaO, ZnO, Fe₂0O₃, and Zr0O₂ were substituted for Si0O₂ into a 14 Na₂0-10 B₂0O₃-76 Si0O₂ (wt%) glass in proportion to their weight percent in PNL-7668 simulated nuclear waste glass. No correlation was found between the Na diffusion coefficient (D_Na) in the bulk glass and sodium leaching in water for any of the iron-containing borosilicate glasses. Effective diffusion coefficients calculated from the sodium leach rates in deionized water were 500 to 2000 times larger than D_Na. The experimental leaching data agreed with a diffusion-convection model where the convective term was a measured "phase-boundary" velocity moving into the glass.     

Crystal Structure and Microwave dielectric Properties of Ba(Zn1/3Ta2/3)O3–(Sr,Ba)(Ga1/2Ta1/2)O3 Ceramics

The microwave dielectric properties and crystal structure of Ba(Zn_1/3Ta_2/3)O₃– (Sr,Ba)(Ga_1/2Ta_1/2)O₃ ceramics were investigated in the present study. The Q value of Ba(Zn_1/3Ta_2/3)O₃ was improved by adding 5 mol% Sr(Ga_1/2Ta_1/2)O₃. The maximum Q value of Q × f = 162000 GHz was obtained at 0.95Ba(Zn_1/3Ta_2/3)O₃. 0.05Sr(Ga_1/2Ta_1/2)O₃. For this composition, a lattice super structure caused by hexagonal ordering was observed. A further improvement in the Q value was attained when some Sr was replaced with Ba, and 0.95Ba(Zn_1/3Ta_2/3)O₃· 0.05(Sr_0.25Ba_0.75)(Ga_1/2Ta_1/2)O₃ exhibited a maximum Q value such that Q × f = 210000 GHz. Despite the increased Q value with the replacement of Sr by Ba, the c/a value, which indicates the degree of lattice distortion, remained constant near 3/2. The Q value thus improved without lattice distortion in the system Ba(Zn_1/3Ta_2/3)O₃-(Sr,Ba)(Ga_1/2Ta_1/2)O₃, whereas the improvement of Q value increased with lattice distortion in the solid solution system with Ba(Zn_1/3Ta_2/3)O₃ as an end member.     

Oxidation Equilibrium of Iron in Borosilicate Glass

Ferrous/ferric equilibria were determined in alkali-alkaline-earth borosilicate glass as a function of temperature, oxygen partial pressure, and glass composition. Expected linear relations are found between log(Fe²⁺/Fe³⁺) and log( p O₂) or 1/ T . The slopes of the correlation with 10g( p O₂) are near the expected value of -0.25, but are found to decrease with increasing temperature. Reaction enthalpies determined from the correlation with 1/ T of –100 to –116 kJ/mol are similar to those reported for other silicate glasses. The ferroudferric equilibrium is not dependent on total iron content in the range 0.5 to 0.09% Fe₂O₃. More reducing conditions are required at lower temperatures to stabilize the amber chromophore. The ferroudferric equilibria are correlated to the number of bridging and nonbridging oxygen ions in the glass. The results suggest that the oxidation-reduction reaction can be written as: Fe²⁺+ (¹/₄)O₂+ (³/₂)O^2-= FeO₂⁻     

Atomic Resolution Transmission Electron Microscopy of the Microstructure of Ordered Ba(Cd1/3Ta2/3)O3 Perovskite Ceramics

Microstructures of ordered Ba(Cd_1/3Ta_2/3)O₃ perovskite dielectric ceramics with and without a boron additive have been observed by atomic resolution transmission electron microscopy (TEM). The selected area electron diffraction and lattice image show a well-ordered structure with hexagonal symmetry (lattice constants of a ∼5.8 Å and c ∼7.1 Å) in the ordered Ba(Cd_1/3Ta_2/3)O₃ with a boron additive, which is similar to those in ordered Ba(Zn_1/3Ta_2/3)O₃ and Ba(Mg_1/3Ta_2/3)O₃ ceramics. Ordered domains with a twin crystallographic relationship and high-density domain interfaces induced by ordering were observed in the ordered Ba(Cd_1/3Ta_2/3)O₃ without a boron additive sintered at a relatively high temperature. Atomic resolution TEM further revealed the conservative twin boundaries along (001) and (110) planes and non-conservative antiphase boundaries with a projected displacement vector of the type [001] in the ordered Ba(Cd_1/3Ta_2/3)O₃ without a boron additive. Finally, the energetics of different domain interfaces are discussed with the interfacial structures in ordered Ba(Cd_1/3Ta_2/3)O₃ ceramics revealed by an electron microscope.     

Modeling the Dielectric Response and Relaxation Spectra of Relaxor Ferroelectrics

A multi-Debye relaxation model that is based upon the Boltzmann superposition principle has been used to determine the frequency-dispersion behavior of Pb(Mg_1/3-Nb_2/3)O₃ (PMN) and Pb_0.88La_0.08(Zr_0.65Ti_0.35)O₃ (PLZT 8/65/35) relaxor ferroelectrics. For PMN, relaxation times on the order of seconds contribute to the dispersive character of the dielectric properties. A defect-relaxation mechanism that involves Mg cation hopping in a structure that is composed of interpenetrating 〈111〉 chains of ordered Pb(Mg_1/2Nb_1/2)O₃ is proposed for PMN. Motion of the Mg cations results in destruction and reconstruction of these ordered chains, which contributes to the dispersive character of PMN.     

Dielectric Properties of Ceramics in Ba (Co1/3 Nb2/3)O3–Ba(Zn1/3Nb2/3)O3 Solid Solution

The dielectric properties of the Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ system were determined. Ba (Co_1/3 Nb_2/3)O₃–Ba(Zn_1/3Nb_2/3)O₃ has a complex perovskite structure, a high dielectric constant, a low dielectric loss, and a low temperature coefficient of the resonant frequency. A solid-solution ceramic with 0.7Ba (Co_1/3 Nb_2/3)O₃·0.3 Ba(Zn_1/3Nb_2/3)O₃ has a dielectric constant of K=33.5, Q=11000 at 6.5 GHz, and a temperature coefficient of the resonant frequency of τ_f=0 ppm/°C. The temperature coefficient of resonant frequency can be varied by changing the composition. The Q values of the ceramics can be increased by annealing in a nitrogen atmosphere. These ceramics can be used for resonant elements and stabilized oscillators.     

Point Defects and Chromium(IV) Formation Mechanism in Gallia- and Alumina-Based Oxide Glasses

Point defects were found in as-quenched GeO₂, 65CaO35Al₂O₃, and 65SrO35Ga₂O₃ glasses on the basis of electron paramagnetic resonance (EPR) measurements. These defects were identified as Ge É centers in GeO₂ glass and O^-₂, O^-₃, and M-OHC (oxygen hole center) (where M = Al, Ga) in 65CaO35Al₂O₃ and 65SrO35Ga₂O₃ glasses. The formation of Ge É centers in as-quenched GeO₂ glass was due to the thermodynamic stability of GeO at the melting temperature. The latter oxygen-excess defects are supposed to be formed by excess oxygen ions derived from the modifiers in the aluminate and gallate glasses during the formation of these glasses. To investigate some of the properties of the oxygen-excess defects in the calcium aluminate and strontium gallate glasses, chromium ions were doped in these glasses as a probe and the relationship between the valency state of the chromium ion and the defects was determined. We conclude that the peroxy bonding (-O-O-) oxidizes the Cr³⁺ species to Cr⁴⁺. Similar defects have been identified in host compounds that are used for Cr⁴⁺ tunable lasers. These results reveal that the point defects are necessary to stabilize the Cr⁴⁺ ions in glasses and crystals.     

Microwave Characteristics of A(B3+1/2B5+1/2)O3 Ceramics (A = Ba, Ca, Sr; B3+= La, Nd, Sm, Yb; B5+= Nb, Ta)

Dielectric properties of A(B³⁺_1/2B⁵⁺_1/2)O₃ (A = Ba, Ca, Sr; B³⁺= La, Nd, Sm, Yb; B⁵⁺= Nb, Ta) ceramics have been investigated at microwave frequencies. Sr(B³⁺_1/2B⁵⁺_1/2)O₃ and Ca(B³⁺_1/2B⁵⁺_1/2)O₃ ceramics have relative dielectric constants (ε _r ) above 20 and negative temperature coefficients of resonant frequency (T _f ). In the group of Ba(B³⁺_1/2B⁵⁺_1/2)O₃ ceramics, T _f changes from + 118 ppm/° to nearly zero according to the kinds of B-site ions. Among the ceramics investigated, Sr(Sm_1/2Ta_1/2)O₃ ceramics have the highest Q values at microwave frequencies. For Sr(Sm_1/2Ta_1/2)O₃ ceramics Q = 7000, ε _r = 27.7, and T _f =−62.5 ppm/° at 8.5 GHz. The microstructure of Sr(Sm_1/2Ta_1/2)O₃ ceramics is composed of a matrix of the ternary compound (Sr-Sm-Ta-O system) and secondary phase grains of the binary compound (Sm-Ta-O system).     

Phase Diagram for the 0.4Pb(Ni1/3,Nb1/3)O3–0.6Pb(Zr,Ti)O3 Solid Solution in the Vicinity of a Morphotropic Phase Boundary

A phase diagram based on dielectric-permittivity-versus-temperature measurements and high-temperature X-ray diffractometry was proposed for 0.4Pb(Ni_1/3,Nb_1/3)O₃- x PbZrO₃-(0.6- x )PbTiO₃ (0.2 lessthan equal to x lessthan equal to 0.32) relaxor-ferroelectric solid solution, and a morphotropic phase boundary that sharply bends toward zirconium-rich compositions was found. A spontaneous normal-to-relaxor ferroelectric transition was also observed when heating was performed for all the compositions tested near the morphotropic phase boundary. Additional considerations about previously published phase diagrams for Pb(Zn_1/3,Nb_2/3)O₃-PbTiO₃ and Pb(Mg_1/3,Nb_1/3)O₃-PbTiO₃ might lead to an extension of the presented diagram to these compositions.     

Ultraviolet Absorption of Pentavalent Vanadium in Binary Alkali Borate Classes

The ultraviolet absorption of vanadium(V) in R₂O-B₂O₃ glasses (R represents Li, Na, or K) and in aqueous buffer solutions was investigated. In glasses of variable R₂O:B₂O₃ ratio, a change in the absorption spectra similar to the [VO₄]³- → [VO₃(OH)]^2- change in aqueous solution was observed. It is suggested that vanadium(V) in these glasses may be present as either [VO₄]^3- or [VO₃O_1/2]^2- (O_1/2 indicates a bridging oxygen ion), depending on the basicity of the melt. The critical R₂O concentration, above which this change in vanadium(V) environment occurs with increasing alkalinity, is 24, 26, and ≅30 mol%, for K₂O, Na₂O, and Li₂O, respectively.     

Outgassing of ZrF4-Based Glasses

The nature and quantities of the chemical species evaporating from the surface of fluorozirconate glasses heated to above T_g were investigated. ZrF4 vaporized from a ZBLAN glass whereas ZrF₃. ZrF₂ and ZrF vaporized from a ZBL glass. Other gases found include HF, HCl, O₂, CO₂, and atomic fluorine.     

Preparation of Cubic Perovskites A(B2/5W3/5)O3 (A=Ba or Sr, B=Na or Li)

Pure cubic perovskites Ba(Na_2/5W_3/5)O₃, Sr(Na_2/5W_3/5)l5)O₃, and Sr(Li_2/5W_3/5)O₃ were prepared by solid-state reaction at 600° to 650°C in air, by starting with oxides or carbonates of the various elements. The cubic forms have an ordered arrangement of the B cations in the ABO₃ structure, and the lattice constants are a =0.8324 nm [Ba(Na_2/5W_3/5)O₃], 0.8136 nm Sr(Na_2/5W_3/5)O₃], and 0.7958 nm [Sr(Li_2/5W_3/5)O₃]     

Formation of Lead Zirconate-Lead Titanate Solid Solutions

Formation of the Pb(Zr,Ti)O₃ solid solution in the system PbO-TiO₂-ZrO₂ was studied by chemical analysis and X-ray powder diffrac-tometry. Only PbTiO₃ and Pb(Zr,Ti)O₃ were found as reaction products. The following three elementary reactions seemed to be reasonable for the formation of the Pb(Zr,Ti)O₃ phase: PbO + TiO₂→ PbTiO₃, PbTiO₃+ PbO + ZrO₂→Pb(Zr_1-λTi_λ)O₃, and Pb(Zr_l-λTi_λ)O₃+ PbTiO₃→ Pb(Zr_1-λ'Ti_λ')O₃ (λ<λ').     

Influence of Iron Doping on the Microstructure of YBa2(Cu1−xFex)3O7−δ Ceramics

Porosity, grain growth, phase composition, and microstructural defects were studied in sintered YBa₂ (Cu_1−x)₃O_7−x ceramics for x values up to 0.3. The porosity of the samples, related to the sintering mechanism, was independent of iron concentration. A linear dependence of the grain size with the inverse of the iron concentration was found, strongly suggesting grain boundary segregation of iron. The solubility limit was estimated to be x = 0.18 at 950°C in O₂. Beyond this limit, a new microstructural component was found consisting of YBa₂(Cu_1−xFe_x)₃O_7−δ, YBaCuFeO₅ and Ba(Cu,Fe)O₂. The transition from an orthorhombic twin to an orthorhombic tweed phase and a tetragonal phase was detected by polarized light microscopy.     

Decolorisation of textile effluent using homogeneous photochemical oxidation processes

In this paper, the results of COD and colour removal from textile effluent using homogeneous photochemical oxidation processes in a batch mode are presented. The results show that the best result was obtained using a combined O₃/H₂O₂/UV process, with 97% removal for COD and 99% removal for colour. Optimum conditions for pH and hydrogen peroxide dosage for this process was determined as 3 and 25 mg/l, respectively. Both H₂O₂/UV and O₃/UV combinations were found to result in similar levels of COD and colour removal efficiencies (over 91% removal for COD and 96% for colour). In addition, the associated operating costs of the various advanced oxidation processes were determined in this study. Received: 21 February 2005; Accepted: 14 June 2005.     

Contribution of Structure to Temperature Dependence of Resonant Frequency in the (1 −x)La(Zn1/2Ti1/2)O3·xATiO3 (A = Ca, Sr) System

The crystal structure and microwave dielectric properties of the (1 − x ) La(Zn_1/2Ti_1/2)O₃· x SrTiO₃ and (1 − x )La(Zn_1/2Ti_1/2)O₃· x CaTiO₃ system were investigated. X-ray powder diffraction showed that cation ordering disappeared at x > 0.3 for both systems. However, infrared spectra demonstrated that short-range cation ordering could exist at x = 0.4. Permittivity and the temperature coefficient of the resonant frequency (τ_f) of both systems exhibited nonmonotonic variations with composition. Both systems exhibited a τ_f of zero at the same composition of x = 0.5 although the τ_f of SrTiO₃ was about two times larger than that of CaTiO₃. The behavior of the permittivity and τ_f were described by the tilting of oxygen octahedra and cation ordering. The relation between τ_f and cation ordering of La(Zn_1/2Ti_1/2)O₃ was discussed in conjunction with the experimental results on metal halides. It is suggested that cation ordering induced a negative τ_f and suppressed the increase of permittivity for compositions between x = 0 to x = 0.5 for (1 − x )La(Zn_1/2Ti_1/2)O₃· x SrTiO₃ and (1 − x )La(Zn_1/2Ti_1/2)O₃· x CaTiO₃ systems.     

Solubility and Transport of NiO Cathodes in Molten Carbonate Fuel Cells

Equilibrium NiO solubility measurements were made in Li₂CO₃/K₂CO₃ mixtures as a function of temperature, ambient gas environment, and salt composition for gases containing 3.1% H₂O. The equilibrium solubility was found to increase with increasing temperature, CO₂ partial pressure, and cation fraction Li⁺ and to decrease slightly with increasing O₂ partial pressure. These results were coupled with theoretical predictions of (1) O₂, H₂, and CO₂ activities and (2) compositional gradients which develop across the electrolyte structure of an operating carbonate fuel to explain the two distinct regions of nickel precipitation across the fuel cell. Precipitation occurs near the cathode because NiO solubility decreases commensurate with electrolyte compositional gradients, whereas the second region deeper within the electrolyte matrix results from a decreased O₂ activity.