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Acta Cryst. (2014). A70, C744
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Glass ceramics containing fluoride crystals such as BaF2 or CaF2 with crystallite sizes in the range from 5 to 100 nm are potential candidates for numerous photonic applications. Glass ceramics containing rare-earth-doped fluoride crystals are candidates for laser materials. The size distribution plays an important role and often a narrow size distribution is required for photonic applications. In the last years a hindered growth effect leading to a more narrow size distribution was observed during the crystallization of BaF2 as well as CaF2 nanocrystals in oxy-fluoride glasses. The aim of this study is a detailed quantitative structural and nano-chemical analysis of the formation of BaF2 or CaF2 in two glass ceramics by Anomalous Small-Angle X-ray Scattering (ASAXS) to reveal and understand the mechanism of hindered growth. Nanocrystals of BaF2 precipitate during heat treatment of a silicate glass of composition 69.6SiO2-7.52Al2O3-15.04K2O-1.88Na2O-4BaF2-2BaO. X-ray diffraction measurement proved the formation of BaF2 crystals in the glass matrix. High resolution TEM showed the formation of spherical particles of sizes in range from 10-40 nm surrounded by a layer enriched with SiO2. SAXS reveal the growth of nanocrystals with increasing annealing time and temperatures. ASAXS experiments are done at four energies close to the Ba-L3 X-ray absorption edge (5247eV). The ASAXS curves for the sample annealed at 5400C for 20h revealed a spherical core-shell model. It turned out that the layer surrounding the BaF2 crystals is enriched with SiO2. Sizes and compositions of these layers are analyzed quantitatively. Furthermore, the ASAXS analysis reveals the presence of very small nucleates of size of about 3 nm in the as melted glass sample already [1]. A precipitation of CaF2 nanoparticles takes place during heat treatment of glasses of composition 7.65Na2O-7.69K2O-10.58CaO-12.5CaF2-5.77Al2O3-55.8SiO2 up to 40 hours. SAXS experiments and especially ASAXS near the Ca-K edge proves the formation of CaF2 nanoparticle surrounded with SiO2 enriched layers, quantitatively. The ASAXS effect is very pronounced at this untypical low energy for ASAXS studies at the Ca-K edge. The ASAXS result reveals crystal sizes between 10-20 nm surrounded by a shell of lower electron density. Additional very small heterogeneities are found after long annealing with diameters of about 1.6 nm [2].
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