Jiménez José A, Hayes Dugan, Antolini Cali, Reinhart Benjamin J
Department of Biochemistry, Chemistry, and Physics, Georgia Southern University, Statesboro, GA 30460, USA.
Department of Chemistry, University of Rhode Island, Kingston, Rhode Island 02881, USA.
Phys Chem Chem Phys. 2023 Dec 6;25(47):32688-32698. doi: 10.1039/d3cp04784a.
Barium phosphate glasses were prepared with 0.5 mol% TbO added alongside SnO up to 5 mol% with the purpose of evaluating the resulting terbium and tin oxidation states and their impact on glass structural, thermal, and luminescent properties. Following material synthesis by melt-quenching, the composition-structure-property investigation was pursued encompassing measurements by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, differential scanning calorimetry (DSC), dilatometry, and photoluminescence (PL) spectroscopy. While XRD confirmed the amorphous nature of the glasses, results from XANES indicated that terbium occurs as terbium(III) with a predisposition for tin to exist as tin(IV) which decreased at high SnO content. The structural as well as the thermal properties appeared to be mostly impacted by the presence of tin(IV). Specifically, glass depolymerization was indicated to be induced by Sn ions, and their concentration was observed to correlate with glass transition and softening temperatures. On the other hand, the tin(II) remnants were observed to exert an impact on the luminescent properties shifting light emission from the green towards the blue-green (cyan). It is indicated that TbO reacting to produce TbO supports the oxidation of tin(II) to tin(IV) which in turn dominates the physical properties. However, this was somewhat circumvented at the highest SnO content wherein tin(IV) appeared to be lower.
制备了添加0.5 mol% TbO以及高达5 mol% SnO的磷酸钡玻璃，目的是评估所得铽和锡的氧化态及其对玻璃结构、热学和发光性能的影响。通过熔融淬火进行材料合成后，开展了成分-结构-性能研究，包括通过X射线衍射（XRD）、X射线吸收近边光谱（XANES）、拉曼光谱、差示扫描量热法（DSC）、热膨胀法和光致发光（PL）光谱进行测量。虽然XRD证实了玻璃的非晶态性质，但XANES结果表明铽以铽（III）形式存在，锡倾向于以锡（IV）形式存在，且在高SnO含量下这种倾向会降低。结构和热学性能似乎主要受锡（IV）的存在影响。具体而言，表明Sn离子会引起玻璃解聚，并且观察到它们的浓度与玻璃转变温度和软化温度相关。另一方面，观察到锡（II）残余物对发光性能有影响，使发光从绿色向蓝绿色（青色）转变。表明TbO反应生成TbO有助于将锡（II）氧化为锡（IV），而锡（IV）反过来主导了物理性能。然而，在最高SnO含量时这种情况有所规避，此时锡（IV）含量似乎较低。
