Reassessment of Electrical and Dielectric Properties in the Borophosphate Glass System: A Promising Solid Electrolyte for High-Temperature Batteries.

This study investigates the conduction mechanism of ternary sodium borophosphate glass 30Na2O-(70 - x)B2O3-xP2O5 with 0 ≤ x ≤ 35 mol % from a different perspective, focusing on previously unreported high-temperature electrical and dielectric properties for potential solid electrolytes in high-temperature batteries. The glass composition with B2O3/P2O5 = 1 exhibits a conductivity of approximately 10-4 S/cm at 250 °C. Dielectric analysis supports this improved conduction, showing higher dielectric values and minimal energy dissipation during storage, indicating promising conductivity and favorable dielectric properties. This enhancement is attributed to the large-polaron (QMT) model, deduced from the power law exponent, due to the creation and spreading of lattice distortion of a long-range order with interconnected B4-O-P1 and B4-O-P2 linkages. Contrary to previous results, the glass transition temperature does not vary coherently with the conductivity and activation energy, displaying a discontinuity at 14 mol %. This discontinuity is caused by the initial extreme depolymerization of P2O5, leading to an increase in nonbridging oxygens (NBOs) within the glass network and forming B4-O-P0 linkages. Despite this, the ionic mobility of Na+ is continuously enhanced, correlated with the increase in the molar volume. This new perspective highlights the significant impact of both free volume expansion and reduced Coulombic effects on conduction improvement.

Insight into the structure-elastic property relationship of calcium silicate glasses: a multi-length scale approach.

Based on a combination of molecular dynamics simulations, and Raman and Brillouin light scattering spectroscopies, we investigate the structure and elastic properties relationship in an archetypical calcium silicate glass system. From molecular dynamics and Raman spectroscopy, we show that the atomic structure at the short and intermediate length scales is made up of long polymerized silicate chains, which adjusts itself by closing the Si-O-Si angles and leaving more space to [CaO]n edge shared polyhedra to strengthen the glass. Using Brillouin spectroscopy, we observe an increase of elastic constants of the glass with the calcium content, as the cohesion of the glass structure is enhanced through an increase of the binding between the cross-linked calcium-silicate frameworks. This result, albeit being simple in its nature, illustrates for the first time the implication of the calcium framework in the elastic behavior of the glass and will contribute substantially to the understanding of the composition-structure-property relationships in multi-component industrial glasses.

Fingerprint of local disorder in long range ordered isometric pyrochlores.

The detailed characterization of local order and disorder in isometric A2B2O7 crystalline pyrochlores is of significant importance in view of their wide range and sensitive technological applications. Nevertheless, much remains to be understood concerning their atomic scale structures. Here we specifically pinpoint local order and disorder in four stoichiometric Ln2Zr2O7 (Ln = La, Nd, Sm and Eu) pyrochlores using a combination of three standard easily available laboratory techniques: XRD, 17O solid-state MAS NMR and Raman spectroscopy. The evolution of the oxygen sub-lattice identifies specific features (extra 17O NMR signals and Raman bands) which undoubtedly reveal local oxygen order and disorder in these stoichiometric long range ordered crystalline pyrochlores. These results complete the understanding of the atomic scale in these stoichiometric pyrochlores necessitating the need for new microscopic structural models.

On the Role of the Electrical Field in Spark Plasma Sintering of UO2+x.

The electric field has a large effect on the stoichiometry and grain growth of UO2+x during Spark Plasma Sintering. UO2+x is gradually reduced to UO2.00 as a function of sintering temperature and time. A gradient in the oxidation state within the pellets is observed in intermediate conditions. The shape of the gradient depends unequivocally on the direction of the electrical field. The positive surface of the pellet shows a higher oxidation state compared to the negative one. An area with larger grain size is found close to the positive electrode, but not in contact with it. We interpret these findings with the redistribution of defects under an electric field, which affect the stoichiometry of UO2+x and thus the cation diffusivity. The results bear implications for understanding the electric field assisted sintering of UO2 and non-stoichiometric oxides in general.

A Novel Technique for Raman Analysis of Highly Radioactive Samples Using Any Standard Micro-Raman Spectrometer.

A novel approach for the Raman measurement of nuclear materials is reported in this paper. It consists of the enclosure of the radioactive sample in a tight capsule that isolates the material from the atmosphere. The capsule can optionally be filled with a chosen gas pressurized up to 20 bars. The micro-Raman measurement is performed through an optical-grade quartz window. This technique permits accurate Raman measurements with no need for the spectrometer to be enclosed in an alpha-tight containment. It therefore allows the use of all options of the Raman spectrometer, like multi-wavelength laser excitation, different polarizations, and single or triple spectrometer modes. Some examples of measurements are shown and discussed. First, some spectral features of a highly radioactive americium oxide sample (AmO2) are presented. Then, we report the Raman spectra of neptunium oxide (NpO2) samples, the interpretation of which is greatly improved by employing three different excitation wavelengths, 17O doping, and a triple mode configuration to measure the anti-stokes Raman lines. This last feature also allows the estimation of the sample surface temperature. Finally, data that were measured on a sample from Chernobyl lava, where phases are identified by Raman mapping, are shown.

Further insights into the chemistry of the Bi-U-O system.

Cubic fluorite-type phases have been reported in the U(IV)O2-Bi2O3 system for the entire compositional range, but an unusual non-linear variation of the lattice parameter with uranium substitution has been observed. In the current extensive investigation of the uranium(iv) oxide-bismuth(iii) oxide system, this behaviour of the lattice parameter evolution with composition has been confirmed and its origin identified. Even under inert atmosphere at 800 °C, U(IV) oxidises to U(V)/U(VI) as a function of the substitution degree. Thus, using a combination of three methods (XRD, XANES and Raman) we have identified the formation of the BiU(V)O4 and Bi2U(VI)O6 compounds, within this series. Moreover, we present here the Rietveld refinement of BiU(V)O4 at room temperature and we report the thermal expansion of both BiU(V)O4 and Bi2U(VI)O6 compounds.

Structural relaxation dynamics and annealing effects of sodium silicate glass.

Here we report high-precision measurements of structural relaxation dynamics in the glass transition range at the intermediate and short length scale for a strong sodium silicate glass during long annealing times. We evidence for the first time the heterogeneous dynamics at the intermediate range order by probing the acoustic longitudinal frequency in the GHz region by Brillouin light scattering spectroscopy. Or, from in-situ Raman measurements, we show that relaxation is indeed homogeneous at the interatomic length scale. Our results show that the dynamics at the intermediate range order contains two distinct relaxation time scales, a fast and a slow component, differing by about a 10-fold factor below Tg and approaching to one another past the glass transition. The slow relaxation time agrees with the shear relaxation time, proving that Si-O bond breaking constitutes the primary control of structural relaxation at the intermediate range order.

Glasses formation, characterization, and crystal-structure determination in the Bi2O3-Sb2O3-TeO2 system prepared in an air.

A glass-forming domain is found and studied within Bi2O3-Sb2O3-TeO2 system. The glasses composition were obtained in pseudo-binary xSbO1.5, (1-x)TeO2 for 0.05 ≤ x ≤ 0.20. The constitution of glasses in the system Sb2O3-TeO2 was investigated by DSC, Raman, and Infrared spectroscopy. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated based Infrared and Raman studies and showed the transition of TeO4, TeO3+1, and TeO3 units with increasing Sb2O3 content. XRD results reveal the presence of three crystalline: γ-TeO2, α-TeO2, and SbTe3O8 phases during the crystallization process. The density of glasses has been measured. The investigation in the ternary system by the solid state reaction using XRD reveals the existence of a solid solution Bi1-x Sb1-x Te2x O4 isotopic to BiSbO4 with 0 ≤ x ≤ 0.1.