Optical absorption and photoluminescence studies of Eu-doped phosphate and fluorophosphate glasses

Phosphate (P₂O₅+K₂O+BaO+Al₂O₃+Eu₂O₃) and fluorophosphate (P₂O₅+K₂O+BaO+BaF₂+Al₂O₃+Eu₂O₃) glasses with different Eu³⁺ ion concentrations have been prepared and characterized through optical absorption, photoluminescence and decay times. An intense red luminescence is observed from the ⁵D₀ emitting level of Eu³⁺ ions in these glasses. The relative luminescence intensity ratio of ⁵D₀→⁷F₂→⁵D₀→⁷F₁ transitions has been evaluated to estimate the local site symmetry around the Eu³⁺ ions. The emission spectra of these glasses show a complete removal of degeneracy for the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions. Second and fourth rank crystal-field (CF) parameters have been calculated together with the CF strength parameter by assuming the C_2v symmetry for the Eu³⁺ ions in both the phosphate and fluorophosphate glasses. Judd-Ofelt parameters have been evaluated from the luminescence intensity ratios of ⁵D₀→⁷F_J (J=2, 4 and 6) to ⁵D₀→⁷F₁ transitions. These parameters have been used to derive radiative properties such as transition probabilities, branching ratios, radiative lifetimes and peak stimulated emission cross-sections for the ⁵D₀→⁷F_J transitions. Decay curves of the ⁵D₀ level of Eu³⁺ ions in these two Eu³⁺:glass systems have been measured by monitoring the ⁵D₀→⁷F₂ transition (611 nm) at room temperature. The experimental lifetime of the ⁵D₀ level in the title glasses is found to be higher than Eu³⁺-doped niobium phosphate glasses. The analysis indicates that the lifetime of the ⁵D₀ level is found to be less sensitive to the Eu³⁺ ion concentration and addition of BaF₂ has no significant effect on the optical properties of Eu³⁺-doped phosphate glasses.     

Synthetic metals: Applications of the Mössbauer effect and other methods

A review is given about the current activities in the field of the “synthetic metals”. This nomenclature is used for materials which consist basically of non-metallic components, but reach metallic conductivities by doping or intercalation reactions with additional components acting as donors or acceptors. Typical examples are conducting polymers like doped polyacetylene or graphite intercalation compounds. The contributions of Mössbauer studies in understanding the electronic, magnetic, and structural properties of such systems are outlined. Comparison with other spectroscopic methods is given in selected cases.     

Elektrometrische Bestimmung von Vanadium und Uran allein, gemeinsam und neben Eisen

Ohne Zusammenfassung     

Effect of pressure on luminescence properties of Sm3+ ions in potassium niobate tellurite glass

Emission spectra and decay properties of the ⁴G_5/2 level of Sm³⁺ ions in TeO₂+K₂O+Nb₂O₅ glass have been measured as a function of pressure upto 14.6 GPa at room temperature. A progressive red shift in the barycentres of ⁴G_5/2→⁶H_J (J=9/2, 7/2 and 5/2) emission bands and increase in splitting of these bands have been observed with increasing pressure. The luminescence decay profile of the ⁴G_5/2 level at ambient condition shows a nearly single exponential nature and with increase in pressure it becomes gradually non-exponential associated with a decrease in lifetime. The non-exponential decay curves are well-fitted to the Inokuti–Hirayama model for S=6, indicating that the interaction for cross-relaxation energy transfer between Sm³⁺ ions is of dipole–dipole type. The results obtained after release of pressure reveal that there is a small hysteresis.     

Controlled accessibility Lewis acid catalysed thermal reactions of regenerated cellulosic fibres

A combination of techniques have been used to characterise lyocell regenerated cellulose fibre subjected to low-moisture thermal-catalytic reactions with zinc chloride Lewis acid. Application from non-swelling ethanol reduces catalyst accessibility, but at high temperatures migration takes place through the internal fibre morphology. The extent of chain scission is reduced at lower temperatures, leading to a higher leveling-off degree of polymerisation (LODP). In contrast, application of zinc chloride from water results in a lower LODP, due to the more even distribution of catalyst. The weights of extractable polymer material increase according to two separate rate constants, following established semicrystalline models. A higher Arrhenius activation energy for chain scission is seen for zinc chloride application from ethanol, which may be due to the physical mobilisation of the cellulose polymer at high temperature, associated with a cellulose T_g. This may also aid recrystallisation. Cellulose dehydration endotherms and pyrolysis exotherms are shifted to lower temperature for application of zinc chloride from ethanol compared to water, which may be the result of a higher local concentration of catalyst and a faster reaction onset.     

Mean-field pairing theory for the charge-stripe phase of high-temperature cuprate superconductors

Striped high-T(c) superconductors such as La(2-y-x)Nd(y)Sr(x)CuO(4) and La(2-x)Ba(x)CuO(4) near x = 1/8 show a fascinating competition between spin and charge order and superconductivity. A theory for these systems therefore has to capture both the spin correlations of an antiferromagnet and the pair correlations of a superconductor. For this purpose we present here an effective Hartree-Fock theory incorporating both electron pairing with finite center-of-mass momentum and antiferromagnetism. We show that this theory reproduces the key experimental features such as the formation of the antiferromagnetic stripe patterns at 7/8 band filling or the quasi-one-dimensional electronic structure observed by photoemission spectroscopy.