用先进的固态核磁共振方法鉴定氟化镓磷酸盐玻璃的结构特征以及与光物理特性的相关性

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of the American Ceramic Society Pub Date : 2024-08-06 DOI:10.1111/jace.20051

Anuraag Gaddam, Gustavo Galleani, Vitor de Lima Reis, Andrea S. S. de Camargo, Hellmut Eckert

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引用次数: 0

摘要

氟化磷酸镓玻璃具有低折射率、抗高能辐射、宽透射范围以及稀土掺杂物的良好发射特性。为了开发优化的玻璃成分，我们需要从根本上了解玻璃结构的这些特性。我们报告了对 xGa(PO3)3-(40-x)GaF3-20BaF2-20ZnF2-20SrF2（x = 5、10、15、20 和 25 mol%）体系玻璃的核磁共振（NMR）结构研究。与 71Ga 重新偶联的 31P NMR 结果表明，网络结构以 P-O-Ga 链接为主，不存在 P-O-P 链接。71Ga NMR 结果表明，镓主要是六配位，具有氟化物/磷酸盐混合配位的特点。通过 71Ga{31P} 自旋回波双共振（REDOR）测量，获得了镓周围配体分布的定量估计值。光物理特性表明，在低 P/F 比时，Eu(III) 配体的分布朝着以氟化物为主的环境变化，而玻璃网络则主要由桥接氧原子通过 P-O-Ga 连接来维持。

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Structural characterization of gallium fluoride phosphate glasses by advanced solid‐state NMR methods and correlation with photophysical properties

Gallium fluoride phosphate glasses feature low refractive index, high energy radiation resistance, wide transmission range, and favorable emission characteristics of rare‐earth dopants. For the development of optimized glass compositions, a fundamental understanding of these properties in terms of glass structure is sought. We report nuclear magnetic resonance (NMR) structural studies of glasses in the system xGa(PO3)3–(40 − x)GaF3–20BaF2–20ZnF2–20SrF2 (x = 5, 10, 15, 20, and 25 mol%). 31P NMR results with 71Ga recoupling show that the network structure is dominated by P–O–Ga linkages, and no P–O–P linkages exist. 71Ga NMR results show that Ga is mainly six‐coordinated featuring a mixed fluoride/phosphate coordination. Quantitative estimates of this ligand distribution around gallium were obtained by 71Ga{31P} spin echo double resonance (REDOR) measurements. Photophysical properties suggest changes in the Eu(III) ligand distribution toward a fluoride‐dominated environment at low P/F ratio while the glass network is largely sustained by bridging oxygen atoms via P–O–Ga linkages.

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来源期刊

Journal of the American Ceramic Society 工程技术-材料科学：硅酸盐

CiteScore

7.50

自引率

7.70%

发文量

590

审稿时长

2.1 months

期刊介绍： The Journal of the American Ceramic Society contains records of original research that provide insight into or describe the science of ceramic and glass materials and composites based on ceramics and glasses. These papers include reports on discovery, characterization, and analysis of new inorganic, non-metallic materials; synthesis methods; phase relationships; processing approaches; microstructure-property relationships; and functionalities. Of great interest are works that support understanding founded on fundamental principles using experimental, theoretical, or computational methods or combinations of those approaches. All the published papers must be of enduring value and relevant to the science of ceramics and glasses or composites based on those materials. Papers on fundamental ceramic and glass science are welcome including those in the following areas: Enabling materials for grand challenges[...] Materials design, selection, synthesis and processing methods[...] Characterization of compositions, structures, defects, and properties along with new methods [...] Mechanisms, Theory, Modeling, and Simulation[...] JACerS accepts submissions of full-length Articles reporting original research, in-depth Feature Articles, Reviews of the state-of-the-art with compelling analysis, and Rapid Communications which are short papers with sufficient novelty or impact to justify swift publication.