论文总字数：23651字

摘 要

本文使用熔融法制备Bi₂O₃-B₂O₃-CaO玻璃，而后绘制出该体系的大致的玻璃形成区域并通过掺杂Na₂O、K₂O、Li₂O来改善玻璃性能。通过XRD分析玻璃是否为非晶结构，根据FTIR和Ranman光谱对铋酸盐玻璃网络结构中键的振动进行分析，进而确定玻璃性能与结构之间的关系。所有玻璃样品的密度通过阿基米德法原理测定。利用高温卧式热膨胀仪来测试不同组分的玻璃化转变温度、软化温度和热膨胀系数。通过以上测试方法对Bi₂O₃-B₂O₃-CaO体系和掺杂其他氧化物后玻璃性能和结构进行了考察。 

Bi₂O₃-B₂O₃-CaO玻璃具有广阔的玻璃形成区，其形成区甚至超过图形的2/3。当Bi₂O₃含量不改变时，玻璃样品其密度跟随B₂O₃含量的增多而增加，T_g,T_f逐渐减小，热膨胀系数逐渐增大。当B₂O₃含量增加到35mol%时可能由于“硼反常”现象使得T_g、T_f和热膨胀出现了截然相反的趋势变化。

随着K₂O含量的增加，玻璃网络结构变得疏松，热膨胀系数从初始的7.42×10^-6/℃逐渐增加到9.53×10^-6/℃。随着Li₂O的增加，热膨胀系数先减小后增加，但依据实验数据，在不改变总碱含量的情况下，使用Li₂O来取代体系中的Na₂O后会使玻璃的密度增加，热膨胀系数增加，玻璃化转变温度降低。最终确定了在不改变玻璃热膨胀系数的同时又降低了玻璃特征温度的最优的一组是10mol%Na₂O和5mol%Li₂O的掺杂。

关键词：Bi₂O₃-B₂O₃-CaO 铋酸盐玻璃 Na₂O、K₂O、Li₂O掺杂 结构

Preparation and Modification of Bi₂O₃-B₂O₃-CaO System Glass

Abstract

In this paper, Bi₂O₃-B₂O₃-CaO glass was prepared by melting method, and the glass properties were improved by doping with Na₂O, K₂O, and Li₂O. The structure of the glass was analyzed by XRD, FTIR, and Ranman. According to FTIR and Ranman spectra, the vibration of the bond in the niobate glass network structure was analyzed to determine the relationship between the glass properties and the structure. The density of all glass samples was determined by the Archimedean principle. A high-temperature horizontal thermal dilatometer was used to test the glass transition temperature, softening temperature, and coefficient of thermal expansion of the various components. Through the above test methods, the performance and structure of Bi₂O₃-B₂O₃-CaO system and other oxide-doped glass were investigated.

Bi₂O₃-B₂O₃-CaO glass has a broad glass formation area, and its formation area even exceeds 2/3 of the figure. When the Bi₂O₃ content does not change, the density of the glass sample increases with increasing B₂O₃ content, T_g, T_f gradually decreases, and the thermal expansion coefficient gradually increases. When the B₂O₃ content is increased to 35 mol%, the “boron anomaly” phenomenon may cause diametrically opposite trends in T_g, T_f, and thermal expansion.With the increase of K₂O content, the glass structure becomes loose, and the thermal expansion coefficient increases from 7.42×10^-6/°C to 9.53×10^-6/°C. With the increase of Li₂O, the coefficient of thermal expansion first decreases and then increases. However, in general, using Li₂O instead of Na₂O in the system will increase the density of the glass and increase the coefficient of thermal expansion when the total alkali content is unchanged. The transformation temperature decreases.

Key Words: Bi₂O₃-B₂O₃-CaO;germanate glass;Na₂O、K₂O、Li₂Odoping;structure

目 录

摘 要………………………………………………………………………………I

ABSTRACT………………………………………………………………………II

第一章 绪 论………………………………………………………………………1

1.1引言……………………………………………………………………………1

1.2铋酸盐玻璃概述………………………………………………………………1

1.3铋酸盐玻璃的研究与应用……………………………………………………2

1.4本课题研究的意义……………………………………………………………2

1.5本课题研究内容………………………………………………………………3

第二章Bi₂O₃-CaO-B₂O₃体系玻璃的形成区域及其性能研究…………4

2.1引言……………………………………………………………………………4

2.2实验部分………………………………………………………………………4

2.2.1 实验原料………………………………………………………………4

2.2.2 实验仪器与设备………………………………………………………5

2.2.3 实验方案………………………………………………………………5

2.2.4 实验流程………………………………………………………………6

2.2.5 样品制备………………………………………………………………6

2.2.6 测试与表征……………………………………………………………7

2.3 结果和讨论………………………………………………………………… 8

2.3.1 X射线衍射分析…………………………………………………… 8

2.3.2 玻璃性能研究……………………………………………………… 9

2.3.3 玻璃的密度和摩尔体积的研究……………………………………10

2.3.4 玻璃化转变温度、软化温度及热膨胀系数………………………11

2.3.5 玻璃的红外光谱……………………………………………………12

2.3.6 玻璃的拉曼光谱……………………………………………………13

2.4 本章小结……………………………………………………………………14

第三章 Na₂O、K₂O以及Li₂O掺杂对玻璃的性能及结构的影响……15

3.1 引言…………………………………………………………………………15

3.2 实验部分……………………………………………………………………15

3.2.1 实验原料……………………………………………………………15

3.2.2 实验仪器与设备……………………………………………………16

3.2.3 实验流程……………………………………………………………16

3.2.4 玻璃样品的制备……………………………………………………16

3.2.5 测试与表征…………………………………………………………16

3.3 结果与讨论…………………………………………………………………17

3.3.1 X射线衍射分析……………………………………………………17

3.3.2 玻璃样品的密度和摩尔体积………………………………………18

3.3.3 玻璃样品的转变温度，软化温度以及热膨胀系数………………18

3.3.4 玻璃样品的红外光谱………………………………………………20

3.4 本章小结……………………………………………………………………20

第四章 结论与展望……………………………………………………………22

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