【作者】 成茵；

【导师】 肖汉宁；

【作者基本信息】 湖南大学 ， 材料学， 2006， 博士

【摘要】 低熔点封接玻璃以及稀土掺杂铋硼酸盐玻璃是近年来新型硼酸盐功能玻璃研究的热点。研究工作主要集中在对新型玻璃体系的开发和认识以及掺杂稀土元素改变玻璃的光学性能方面,而对新型玻璃的结构形成机理及其与特殊功能的关系还认识不足。如果能从玻璃的形成机理和微观结构的角度来研究组成对玻璃结构和性能的影响,便能更好地解析和预测玻璃的性能,对新型功能玻璃的材料设计和应用开发将具有重要的理论指导意义。本文采用熔融法制备了PbO-B₂O₃,Bi₂O₃-B₂O₃二元系统玻璃以及多组分的低熔点铅硼酸盐玻璃和稀土掺杂铋硼酸盐玻璃。从分析二元系统的玻璃结构出发,进一步分析了新型硼酸盐功能玻璃的网络形成机理,并结合玻璃的析晶特性分析,探讨了组成对玻璃热稳定性、机械性能以及特殊性能的影响。本文通过红外吸收光谱和拉曼散射光谱分析,较系统地研究了PbO-B₂O₃、Bi₂O₃-B₂O₃二元系统玻璃的网络结构。实验结果表明: PbO含量较低时（10mol%≤PbO≤20mol%）在硼酸盐玻璃结构中仅起网络修饰体作用;当PbO含量较高时,PbO逐步进入到玻璃网络中起网络形成体作用。在PbO-B₂O₃玻璃网络中,可能存在三种玻璃结构模型。Bi₂O₃在Bi₂O₃-B₂O₃二元系统玻璃网络中起网络形成体作用,根据Bi₂O₃含量的不同,提出了两种可能的玻璃结构模型。PbO和B₂O₃是低熔点封接玻璃的重要组成。本文设计了不同PbO/B₂O₃的铅硼酸盐封接玻璃配方,并探讨了添加氧化物（ZnO、Bi₂O₃、GeO₂）对玻璃封接温度、热膨胀、化学稳定性以及机械性能的影响,获得了综合性能较好的低熔点铅硼酸盐封接玻璃配方。其中G3配方的封接温度仅400℃,其PbO含量为54mol%左右,与目前商品化封接玻璃铅含量相近,但其封接温度降低了40℃,且没有引入Cd、Hg、Tl等剧毒重金属氧化物;BL10配方的封接温度为440℃,与商品封接玻璃的封接温度相同,但其铅含量大大降低,仅为36mol%。BiBO3晶体的析出是铋硼酸盐玻璃是否具有特殊的非线性光学性能的重要标志。根据对Bi₂O₃-B₂O₃二元系统玻璃的析晶特性分析,结果表明,在50mol%≤Bi₂O₃≤60mol%范围内,玻璃晶化热处理后可析出BiBO3晶体,有望实现非线性光学性能。因此,本文在组成为Bi₂O₃·B₂O₃的铋硼酸盐玻璃基础上,制备了xRE₂O₃·（100-x） （Bi₂O₃·B₂O₃）玻璃（RE3+=La3+、Pr3+、Sm3+、Gd3+、Er3+、Yb3+, x=0.5¹0）。系统地研究了稀土氧化物对玻璃结构、热稳定性、晶体种类以及形貌的影响。研究结果表明,对稀土掺杂铋硼酸盐更多还原

【Abstract】 Low-melting sealing glass and rare-earth doped bismuth borate glass are the important systems of advanced borate glasses. Recently, the studies on advanced borate glasses are focused on developing and realizing new glass systems, few reports were found on the mechanism of glass formation and the relationship between glass structure and properties. Based on the mechanism of glass formation and glass network structure, studies on compositional effects of glass structure and properties should be an available work to understand and forecast properties of advanced borate glasses and consequently have a significant influence on the design and applications of advanced borate glasses.In this work, series of PbO-B₂O₃ glass, Bi₂O₃-B₂O₃ glass, lead borate sealing glass and rare-earth doped bismuth borate glass were prepared by melting-quenching method. Combined with the glass structure and crystallization properties of binary borate glass systems, compositional effects on glass thermal stability, mechanical properties and other properties of advanced borate glasses were investigated.The results of FTIR and Raman analysis indicate that PbO only acts as a network modifier of PbO-B₂O₃ glass in the compositional range of 10 mol%≤PbO≤20mol%, with the further increase of PbO, it tends to play as a glass former. In the system of Bi₂O₃-B₂O₃ glass, Bi₂O₃ was one of the glass former. Three possible structure models and two possible structure models were suggested to explain the effects of PbO and Bi₂O₃ on borate glass networks respectively.Both PbO and B₂O₃ are the important components of low-melting sealing glass. Therefore a series of lead borate sealing glasses with different ratios of PbO/B₂O₃ were designed. Based on the structure and crystallization analysis of PbO-B₂O₃ glass, effects of PbO/B₂O₃ and additive oxides （including ZnO, Bi₂O₃, GeO2） on sealing temperature, thermal expansion property, chemical stability and mechanical property of lead borate sealing glasses were involved. Two successful batches of low-melting sealing glass were obtained named G3 and BL10. The sealing temperature of G3 glass is 400℃, which is 40℃lower than that of commercial sealing glasses. The PbO content of G3 is 54mol% （as the same as in commercial sealing glass） and no toxic component is involved. The sealing temperature of BL10 glass is similar to that of traditional sealing glass （440℃）, while the PbO content is decreased to更多还原