Effect of modifier cation size on the structure, properties and nickel speciation in BK7 type alkali borosilicate glasses

Q1 Physics and Astronomy

Journal of Non-Crystalline Solids: X Pub Date : 2023-03-01 DOI:10.1016/j.nocx.2023.100161

Brian Topper , Lucas Greiner , Randall E. Youngman , Darren Stohr , Efstratios I. Kamitsos , Doris Möncke

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引用次数: 2

Abstract

Alkali-borosilicate glasses 16M₂O–10B₂O₃–74SiO₂ were studied for M = Li to Cs. ¹¹B NMR showed 57% four-fold coordinated boron for Li, but 88 to 97% for M = Na to Cs. The fraction of neutral borate triangles decreases from Na to Cs. Vibrational spectroscopy shows significant non-bridging oxygen on silicate species for Li, decreasing to a low level from Na to Cs. The glass transition temperature is highest for M = Cs and correlates with increasing network connectivity. Sub-liquidus phase separation and homonuclear bonding was observed for M = Li, while M = Na to Cs show good linking of silicate with borate tetrahedra. Raman spectroscopy reveals a maximum of danburite rings for M = K, the glass with the highest packing density. Glasses doped with Ni₂O₃ changed color from yellow (Li) to purple (Na), to blue in samples of higher optical basicity (K, Rb, Cs). Tetrahedral Ni²⁺ likely coexists with trivalent nickel, Ni³⁺, in blue glasses, while higher coordinated Ni²⁺ prevails in the yellow Li-sample.

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改性剂阳离子尺寸对BK7型碱硼硅酸盐玻璃结构、性能及镍形态的影响

用16m20 - 10b2o3 - 74sio2碱硼硅酸盐玻璃对M = Li - Cs进行了研究。11B核磁共振显示，Li为57%的四重配硼，而M = Na - Cs为88 - 97%。中性硼酸盐三角形的比例从Na到Cs逐渐减少。振动光谱显示，在硅酸盐中，Li的非桥氧含量显著增加，从Na到Cs的氧含量降低到较低。玻璃化转变温度在M = Cs时最高，并且与网络连通性的增加有关。M = Li和M = Na ~ Cs均表现出良好的硅酸盐与硼酸盐四面体的键合。拉曼光谱显示M = K的玻璃有最大的丹布里岩环，其填充密度最高。掺杂Ni2O3的玻璃颜色从黄色(Li)变为紫色(Na)，在光学碱度较高的样品(K, Rb, Cs)中变为蓝色。在蓝色玻璃中，四面体Ni2+可能与三价镍Ni3+共存，而在黄色锂样品中，更高配位的Ni2+普遍存在。

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