摘 要

硼硅酸盐玻璃由于热膨胀系数低，硬度高，力学性能、热稳定性及耐化学性能优异等等，被广泛应用于太阳能、电光源、电子元器件、传感器、航天、医疗、化工等领域。锌硼硅玻璃作为一种性能优良的硼硅酸盐玻璃，近年来倍受人们青睐。低熔点锌硼硅玻璃粉还可作为无机填料，用于研制高质量、高效能、低成本的耐高温涂料。

本文以锌硼硅玻璃系统为研究对象，以CaO、BaO、MgO三种碱土金属氧化物替代Na₂O，探究RO对锌硼硅玻璃结构和性能的影响。选用红外光谱、DSC测试和热膨胀系数测试分析了玻璃的结构变化，并重点研究了各基本组成对锌硼硅玻璃硬度、化学稳定性能的影响规律。在对锌硼硅玻璃工艺性能的研究上，本文研制了以低熔点锌硼硅玻璃系统作为耐高温涂层的无机填料，研究不同组成玻璃填料对涂层性能的影响。研究结果表明：

以等摩尔质量分数的RO替代Na₂O制备锌硼硅玻璃，玻璃的结构和性能均得到改善。当以RO替代1.5mol%Na₂O时，掺入MgO的玻璃热膨胀系数最小，膨胀软化温度和转化温度最高，硬度和耐碱性最强。掺入BaO的玻璃硬度介于三者中间，热膨胀系数最大，耐碱性最弱。故以这两种配方的玻璃料与色料混合进行涂覆实验时，玻璃料中掺入BaO的涂层表面状况和光泽度优于掺杂MgO的涂层，但其硬度和耐碱性弱于后者。当以RO替代3mol%Na₂O，对比掺杂BaO和CaO的玻璃试样，掺入BaO的玻璃热膨胀系数较小，膨胀软化温度和转化温度较高，硬度和耐碱性较强。

锌硼硅玻璃中掺杂RO后，其部分红外吸收光谱波数向高波数偏移，表明B₂O₃在玻璃中的结构发生变化，部分[BO₃]单元向[BO₄]单元转变，使玻璃的网络结构致密化，从而使玻璃性能发生变化。

由XRD测试分析，涂覆实验所烧结的复合涂层主要由铁橄榄石（Fe₂SiO₄）、Al_0.5Fe_0.5、Fe_2-30Si_0.7O₄组成。

本文特色是通过研究碱土金属氧化物对锌硼硅玻璃的影响，为得到结构和性能最优的锌硼硅玻璃提供理论和实际依据的同时，对无机填料制备耐高温涂层也具有指导意义。

关键字：锌硼硅玻璃；高温涂层；碱土金属氧化物；结构；性能

Abstract

Borosilicate glass which have a low coefficient of thermal expansion, high hardness, good mechanical properties, thermal stability, chemical stability and etal, is widely used in solar, electric light source, medical, chemical, electronic components, sensors, aerospace and other fields. As a kind of boron silicate glass with excellent performance, zinc borosilicate glass has been favored by people in recent years. Zinc borosilicate glass powder with low melting point can be used as an inorganic filler for developing the high tempreture resistant coating which has high quality and efficiency and low cost .

This article regards zinc borosilicate glass system as the research object, raplacing CaO, BaO and MgO with Na₂O, to explore its the influence on zinc borosilicate glass^,s structure and performance . The structure change of the glass was analyzed by IR, DSC test and thermal expansion coefficient test. The influence of the basic composition on the hardness and resistance to acid and alkali of zinc borosilicate glass was intensivley studied. On the study of its process performance, we use the low melting point zinc borosilicate glass system as the inorganic filler to develope high temperature resistance coating, and the effect of different composition of glass filler on the properties of the coating was studied. These results show that:

By replacing Na₂O with RO, The structure and properties of zinc borosilicate glass were improved. When the replacement of 1.5mol%Na₂O to RO, glass doped with MgO showde the minimum thermal expansion coefficient, the highest expansion softening temperature and conversion temperature ,the strongest hardness and the resistance to alkali. Glass doped with BaO showed the middle hardness among the three, the maximum coefficient of thermal expansion and the weakest alkali resistance. So mixing the two formulations of glass material with pigment to conduct the coating experiment, glass doped with BaO coating showde the superior surface condition and glossiness than glass doped MgO coatings, but the weaker hardness and the resistance to alkali. When increasing to 3mol%Na₂O, the dopant contrast BaO and CaO on the glass sample, glass doped with BaO showed the smaller thermal expansion coefficient, higher expansion softening temperature and conversion temperature, stronger hardness and the resistance to alkali.

It was found that part of the infrared absorption spectrum of zinc borosilicate glass which was doped with RO had moved to high wave number. This was mainly because the structure of B₂O₃ changed in the glass for [BO₃] unit partly transformed into [BO₄] so that the spatial structure of glass turnde compacted and some performance of glass got changed.

The composite coating sintered by the coating study is mainly composed of iron olivine (Fe₂SiO₄）、Al_0.5Fe_0.5 and Fe_2-30Si_0.7O_4。

Featured in this study is that by the studies on the impact of the alkaline earth metal oxide to zinc borosilicate glass, providing the theoretical and practical basis for obtaining the optimal structure and performance of Zinc Borosilicate glass, at the same time, for developing high temperature resistant coating with inorganic fillers also has guiding significance.

Key words: zinc borosilicate glass; high tempreture coating; alkaline earth oside; structure;

performance

目录

第1章 绪论 1

1.1研究的目的及意义 1

1.2本课题国内外研究及应用进展 2

1.2.1有关基本组成与性能的研究现状 2

1.2.2低熔点玻璃粉在高温涂料中应用的国内外研究现状 3

1.3本研究的主要内容 4

第2章 锌硼硅玻璃的制备与测试 5

2.1锌硼硅玻璃样品制备 5

2.1.1配方组成设计 5

2.1.2实验仪器与设备 5

2.1.3玻璃制备工艺 5

2.2样品的结构表征与性能测试 6

2.2.1样品结构测试 6

2.2.2样品性能测试 8

第3章 RO对锌硼硅玻璃结构和性能的影响 10

3.1测试分析 10

3.1.1红外光谱测试分析 10

3.1.2差热分析（DSC）测试分析 11

3.1.3热膨胀系数测试分析 12

3.1.4硬度测试分析 14

3.1.5耐碱性测试分析 14

3.2本章小结 15

第4 章 RO对锌硼硅玻璃工艺性能的影响 17

4.1涂覆实验 17

4.1.1涂覆样品的配方组成设计 17

4.1.2制备工艺 17

4.2性能分析 17

4.2.1涂覆试样基本性能 17

4.2.2 XRD分析测试 18

4.2.3化学稳定性分析 19

4.3本章小结 19

第5章 总结 20

参考文献 21

致谢 22

第1章 绪论

1.1研究的目的及意义

　　低熔点玻璃在电子行业中可作为基础材料用于玻璃、陶瓷、金属等材料之间的封接，起到绝缘、密封的作用。此外，低熔点玻璃是研制电子浆料的重要组成成分，在浆料烧结过程中有粘结和降低烧结温度的效用。目前，大多数商用封接玻璃和电子浆料所用低熔点玻璃为高铅玻璃。但铅对环境和人体存在危害，故各种电子元器件均需达到无铅化标准。因此，综合性能良好的无铅低熔点玻璃材料的成功开发对电子行业的发展具有重要意义。

　　目前研究的无铅低熔点玻璃主要有铋酸盐和硼硅酸盐玻璃。但铋酸盐需要的氧化铋量大且价格昂贵，而硼硅酸盐玻璃的热膨胀系数较小，化学性能稳定、热稳定性、光学性能和电学性质较好，机械强度高等优点，在生活中广泛应用^[1]。