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Abstract: We report a TEM microstructural and compositional study of proton-conducting (La,Ca)P3O9 (Al-free) and (La,Ca,Al)P3O9 (Al-containing) glass-ceramics, prepared by the crystallization of quenched glass melts. Bright-field Transmission Electron Microscopy imaging, annular dark-field Scanning Transmission Electron Microscopy, and energy dispersive x-ray compositional analysis were used to characterize the structure and chemistry of the glass and crystalline phases of the samples that developed following the treatments at various temperatures, heating-rate and dwell-time. TEM chemical characterization revealed that the crystallized domains were mainly Ca-doped LaP3O9, while the remaining phase was a Ca-rich phosphate glass. Crystallization improved conductivity first (up to a conductivity of nearly 10−4.5 S/cm at 550°C in air). However, the conductivity dropped when the samples were treated at higher temperature or for longer dwell-times, due to a continued Ca-departure from the La-rich crystalline into glass phase. Possible proton transfer mechanisms and strategy to improve conductivity in this doped rare earth metaphosphate glass-ceramic are discussed. [Copyright &y& Elsevier]

Abstract: Al2O3 was added to a 2CaO–La2O3–5P2O5 metaphosphate, to replace 10% of the Ca2+ ions by Al3+, forming a phosphate with the nominal composition 1.8CaO–0.1Al2O3–La2O3–5P2O5. The effect of Al2O3 addition and heat treatment on the microstructure and conductivity of the resulting glass–ceramics was investigated by XRD, SEM, TEM, and AC impedance spectroscopy. Upon transformation from glass to glass–ceramic, conductivities increased significantly. The glasses were isochronally transformed at 700 and at 800 °C for 1 h or 5 h, in air, following heating at 3 or 10 °C/min. With Al2O3 addition, after a heat treatment at 700 °C, 100–300 nm nano-domains of LaP3O9 crystallized from the glass matrix. Annealing at 800 °C produced a further order of magnitude conductivity increase for the Al-free glass, but less so for the Al-containing glass. [Copyright &y& Elsevier]