Facile Morphological Modification of Ba5Nb4O15 Crystals Using Chloride Flux and in Situ Growth Investigation

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• 作者：Tetsuya Yamada ; Yukinori Murata ; Hajime Wagata ; Kunio Yubuta ; Katsuya Teshima
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：July 6, 2016
• 年：2016
• 卷：16
• 期：7
• 页码：3954-3960
• 全文大小：539K
• 年卷期：0
• ISSN：1528-7505

文摘

The cation-deficient layered perovskite oxide Ba₅Nb₄O₁₅ is one of the functional materials that exhibits a microwave-responsive dielectric property and an ultraviolet-active photocatalytic property. Although systematic control of the morphology of Ba₅Nb₄O₁₅ is beneficial for improving these properties, synthesized Ba₅Nb₄O₁₅ usually has a plate-like shape owing to its crystal structure, with a particle size less than 5 μm. For systematic morphological control of Ba₅Nb₄O₁₅, the crystal growth was studied by using a chloride-based flux method. Idiomorphic plate-like Ba₅Nb₄O₁₅ crystals up to 50 μm in size and polyhedron ones ∼10 μm in size were obtained using a BaCl₂ flux by changing the solute concentration to 5–20 mol % and 50 mol %, respectively. The growth of the Ba₅Nb₄O₁₅ crystals was investigated by thermogravimetric and differential thermal analysis and in situ X-ray diffraction analysis. These analyses revealed the flux-growth manner of Ba₅Nb₄O₁₅ as follows: (I) Ba₅Nb₄O₁₅ was formed by a solid-state reaction above ∼650 °C. (II) After the melting of BaCl₂ above ∼962 °C, the Ba₅Nb₄O₁₅ crystals became larger and assumed idiomorphic shapes, indicating that they were somewhat dissolved in the flux and that the crystal growth was promoted. Increasing the holding time yielded an increased number of crystals larger than 28 μm. This indicates that Ostwald ripening effectively yields Ba₅Nb₄O₁₅ crystals up to 50 μm in size. Chloride fluxes with different alkaline or alkaline earth cation fluxes did not produce such large crystals. It is assumed that the common ion effect of Ba²⁺ in the solute and flux provides an effective reaction field to facilitate Ostwald ripening.