摘 要

在日常生活中，硅酸盐玻璃得到了普遍的使用，钡钛硅玻璃是其中的一种，由于其具有良好的化学稳定性、较高的强度、电绝缘及定向反光回归（即折射率高）等优异性能。在反光材料领域、交通安全领域、光储存材料领域以及喷墨打印等领域的研究已得到关注。

本篇文章主要研讨的是：对BaO-TiO₂-SiO₂系统玻璃来说，调节各氧化物的含量对其结构和性能的影响，以确定合适的玻璃组分。通过XRD检测了所得到的样品的析晶状况及成玻性能，通过DSC仪器分析获得玻璃样品的转变温度及析晶温度，检测了玻璃的折射率和维氏显微硬度，探究了BaO-TiO₂-SiO₂玻璃在不同二氧化钛摩尔百分含量下结构与性能对应关系。

研究结果表明：（1）通过对样品的XRD衍射分析，得到相应的衍射峰图，本研究所有样品均未见有衍射峰的存在，只存在峰包，说明所制得的玻璃样品均不析出晶体。（2）DSC分析结果表明：在保证氧化钡的摩尔百分含量不变的前提下，玻璃样品的转变温度Tg随着玻璃中二氧化钛的摩尔百分含量的增加而升高；转变温度Tg的变化在一定范围内，分别在720.1 ℃ 到738.9 ℃；析晶状况存在一定差异。（3）折射率的测量结果表明：在确保氧化钡摩尔百分含量不变的条件下，随着二氧化钛摩尔百分含量的增加，折射率也随之升高，并且折射率的增加量与二氧化钛的摩尔百分含量的增加量的比值近常数（图像近一条直线），验证了干福熹等人所提出的折射率加和法则。（4）维氏显微硬度的结果表明：经每样品三个测量点取平均值的情况下，所得的各样品的维氏显微硬度值最低为670 Hv，最高为796.3 Hv，比一般玻璃维氏硬度高（一般玻璃的维氏显微硬度值在500~600 Hv之间）。探索了BaO-TiO₂-SiO₂玻璃的结构和性能在二氧化钛的摩尔百分含量发生变化时的影响，对玻璃样品做了性能测试，结果表明在玻璃组分中二氧化钛的摩尔百分含量在高达35mol%甚至是55mol%情况下，仍然能够成玻不析晶，并对其进行了DSC、折射率、维氏显微硬度的测试，探索了如果选用钡钛硅体系制造玻璃微珠的结构和性能随组成的变化规律。

关键词：高折射率；玻璃微珠；XRD；析晶；DSC；转变温度：加和法则

Abstract

In daily life, silicate glass has been widely used, barium-titanium silicate glass is one of them, because of its good chemical stability, high strength, electrical insulation and directional reflective regression (that is, high refractive index) and other excellent performance. Research in the field of reflective materials, traffic safety, optical storage materials and inkjet printing has been paid attention.

The main research of this article is: for the BaO-TiO₂-SiO₂ system glass, adjust the content of each oxide to its structure and performance of the effect, to determine the appropriate glass components. The crystallization condition and the performance of the obtained samples were detected by XRD. The transformation temperature and crystallization temperature of glass samples were obtained by DSC analysis, the refractive index and Vickers microhardness of glass were detected, and the relationship between structure and properties of BaO-TiO₂-SiO₂ glass under different molar content of titanium dioxide was investigated.

The results show that: (1) by XRD diffraction analysis of the sample, we get the corresponding diffraction peaks, and there is no diffraction peak in all the samples, only the peak package exists, which shows that the glass samples are not precipitated by crystal. (2) The results of DSC analysis show that the molar percent content of barium oxide is unchanged, the transition temperature of glass sample is increased with the increase of molar percent content of titanium dioxide in glass; the change of Tg changes in a certain range, respectively in 720.1 ℃ to 738.9 ℃, and there are some differences in the crystallization condition. (3) The refractive index measurement results show that: in order to ensure that the molar content of barium oxide is unchanged, with the increase of the molar percent of titanium dioxide, the refractive index increases, and the increase of refractive index is near constant (near a straight line) to the increase of molar percent content of titanium dioxide, which verifies the refractive index addition and law proposed by Ganford and others. (4) Vickers microhardness results show that: with the average of three measured points per sample, the lowest Vickers hardness of each sample is $number Hv, the highest is 796.3 Hv, and the Vickers hardness is higher than that of the average glass (the Vickers microhardness of the general glass is between 500~600 Hv). The effects of the structure and properties of BaO-TiO₂-SiO₂ glass on the molar content of titanium dioxide were investigated, and the properties of the glass samples were tested, and the results showed that the molar percent content of titanium dioxide in the glass component was up to 35mol and even 55mol. It can still be made into glassy amorphous, and the DSC, refractive index and Vickers Microhardness are tested, and the structure and properties of the glass beads made by barium-titanium system are studied.

Key Words：High refractive index; glass beads; XRD; crystallization; DSC; transition temperature: addition and law

目 录

摘要 I

Abstract II

第1章 绪论 1

1.1 高折射率玻璃微珠概况介绍 1

1.1.1 高折射率玻璃微珠简介 1

1.1.2 BaO-TiO₂-SiO₂系统玻璃的折射率 1

1.1.3 高折射率玻璃微珠行业现状 1

1.1.4 高折射率玻璃微珠国内外研究情况 3

1.2 高折射率玻璃微珠的应用及其发展 4

1.3 研究的目的及意义 5

1.4 本研究的主要内容 5

第2章 实验方法及测试 6

2.1 实验总体思路 6

2.2 实验方案 6

2.2.1 玻璃形成原理 6

2.2.2 实验仪器 6

2.2.3 玻璃熔制 7

2.3 玻璃组成设计 7

2.4 实验设备 8

2.5 玻璃的结构及性能测试 9

2.5.1 维氏硬度测试 9

2.5.2 示差扫描量热法（DSC）分析 9

2.5.3 X射线衍射分析（XRD） 10

2.5.4 折射率的测定 10

第3章 结果与讨论 12

3.1 XRD分析 12

3.2 差示扫描量热（DSC）分析 12

3.3 折射率分析 14

3.4 维氏硬度结果分析 15

3.5 BaO-TiO₂-SiO₂系统玻璃结构讨论 15

第4章 结论 17

参考文献 18

致谢 20

第1章 绪论

1.1高折射率玻璃微珠概况

1.1.1高折射率玻璃微珠简介

玻璃是由二氧化硅和其他化学物质经熔融后冷却、硬化而得到的具有无规则网络结构的非晶态固体材料。对玻璃的光学性质探究，不管是在理论上还是在实际生产、生活中都是非常重要的。一般玻璃的光折射性能用折射率来表示，玻璃的折射率是最基本的光学性质，它是指真空光速，与介质光速的比值，即折射率n=真空光速c/介质光速v。折射率反映出光在介质中传播受阻碍（速度下降）的程度。高折射率玻璃通常指折射率n在1.8及以上的玻璃材料。此外，光学性能还包括，光反射率，光吸收，透光性和光的色散等^[1]。

作为一种新型材料，玻璃微珠是逆反射材料的主要元件，是制造具有回归反光新型光学功能的复合材料的核心。其具有回归反射，表面光滑，流动性好，不导电,化学稳定性高，耐热性能好及机械强度高等优点^[2]。