摘 要

日常废弃物和工业矿渣等污染源不仅成为生态环境的重要威胁，制约了人们的生产和生活，也造成了严重的资源浪费。工业尾矿和硅酸盐基废弃物的回收利用将有助于减少其对生态环境的不利影响，降低工艺过程对天然原材料的依赖，节约生产制造中消耗的能源，进而制造出具有高生态价值和经济效益的产品，达到一举多得的效用。

论文主要研究了Fe₂O₃含量和烧结温度对微晶玻璃晶相和磁性的影响。实验选用了来自承德的铁尾矿，适当优化其各组分含量，调节Fe₂O₃含量分别达到20%和30%，经熔融水淬后制成基础玻璃粉，再与电子显像管玻璃（CRT玻璃）进行复合，通过烧结工艺在不同热处理温度下制备了具有磁性的功能化微晶玻璃。通过XRD、SEM、VSM等测试方法分别对样品的晶相组成，微观形貌和磁学性质等进行了表征，结合半定量的晶体谱学分析方法，深入分析了材料在制备过程中的析晶变化。

研究结果表明：高的Fe₂O₃含量更加有利于玻璃析晶，烧结温度的升高引起样品结晶度先增后减，使得辉石矿中的含铁成分以赤铁矿的形式析出，磁性相向非磁性相发生转变。结晶度变化和磁性相向非磁性相的转变导致样品的宏观饱和磁感应强度出现钟形曲线的变化规律。

本文的特色：通过对XRD图谱进行全谱模拟，半定量地标定了个各个晶相的组成和含量，从而研究了热处理工艺对微晶玻璃晶相组成的影响。进一步结合各晶相的磁性，计算了微晶玻璃的磁性相含量以及宏观相对饱和磁矩，解释了其磁学特性随热处理工艺制度的变化。

关键词：磁性微晶玻璃；热处理工艺；铁尾矿；烧结法

Abstract

Pollution sources such as daily waste and industrial slag not only pose an important threat to the ecological environment, which have restricted people's production and life, but also cause a serious waste of resources. Recycling and reuse of industrial tailings and silicate based waste will help to reduce the adverse effects on the ecological environment, reduce the dependence on natural raw materials during the processing, save the energy consumed in the manufacture and create products with high ecological value and economic benefit, so as to achieve the purpose of the utility in one fell swoop.

The effects Fe₂O₃ content and sintering temperature on the crystal structure and magnetic properties were studied in this experiment. The iron tailing selected form Chengde were optimized on its composition to increase the ratio of Fe₂O₃ to 20% and 30% respectively. The optimized iron tailing was melted and quenched with water to prepare base glass, and then sintered with electronic imaging tube (CRT) glass to prepare magnetic functional glass ceramics under different temperature. The crystalline phase composition, microstructure and magnetic properties of samples were characterized XRD, SEM, VSM etc. Combined with semi-quantitative crystallography spectroscopy analysis, we studied the crystallization processes during the preparation of materials in depth.

Experimental result shows the high ratio of Fe₂O₃ content is more conducive to crystallization of the glass. The increase of sintering temperature induces increase and then reduce of crystallinity, which makes the iron containing components in pyroxene mineral precipitate in forms of hematite and turn the magnetic phase into nonmagnetic one. The changes of crystallinity and transformation form magnetic phases into nonmagnetic phases are responsible for the appearance of bell-like curve of saturated magnetic induction.

This paper features on the whole pattern fitting of XRD spectra, we studied the effects of heat treatment on crystal phases and their composition through semi-quantitative analysis. Combined with magnetic properties of each crystal phase, we further calculated the mass ratio of magnetic phases and the overall magnetic moment of the glass ceramics, and explained the changes of its magnetic properties as a function of heat treatment temperature.

Keywords: magnetic glass ceramics；heat treatment process；iron tailing；sintering method

目 录

第1章 绪 论 1

1.1 引言 1

1.2废弃物微晶玻璃的制备工艺和应用 1

1.3磁性微晶玻璃的研究现状 3

1.4本题研究内容及意义 4

第2章 实 验 5

2.1实验的基本思路 5

2.2实验过程 6

2.2.1配料组分的设计 6

2.2.2热处理工艺制度 7

2.3 样品的测试 8

第3章 分析与讨论 10

3.1 样品相组成的确定 10

3.2 样品微观形貌的表征与分析 12

3.3 结晶度的半定量分析 14

3.4 晶相组成的半定量分析 15

3.5 样品磁性能测试与分析 16

第4章 结 论 19

参考文献 20

致 谢 22

第1章 绪 论

1.1 引言

随着人口密度的增长和工业化进程的加快，日常废弃物和工业矿渣等污染源成为生态环境的重要威胁，严重制约着人们的生产和生活，也造成了重要的资源浪费。我国是矿产资源加工大国，矿山开采后遗留的尾矿数量惊人，堆积如山，据统计，我国累计的尾矿堆积总量在100亿吨以上，年产出量达12亿吨^[1]，而铁尾矿在尾矿类废弃物中所占比例最大，数量最多，主要来自于高炉矿渣，钢渣等冶金废渣，目前我国的尾矿综合利用率低，仅有7%左右^[2,3]，如何回收利用长期搁置的尾矿成为我国矿业循环经济的重要部分。另一方面，电子电器产品的迭代换新和日常硅酸盐产品的淘汰也产生了大量的硅酸盐基废弃物。这些尾矿和废弃物露天堆放，在占用土地资源的同时也会析出有机物和金属离子，对土壤和地下水源产生严重的污染^[4]，从而导致次生的公众健康危机。因此，通过现代技术来对废弃物进行安全有效地回收利用成为一个被广泛关注的课题。

除了降低废弃物对环境的影响，废弃材料的循环利用将有助于减少对原材料的依赖，降低工业能耗和污染。从电力行业产生的煤燃烧的渣灰（CCBS）和冶金行业产生的矿渣是最主要的两类再生废弃物，前者可以推广应用在道路建设和水泥行业，后者可回收生产应用型产品如陶瓷玻璃^[5]。碎玻璃等硅酸盐基废弃物可以重新熔炼而得以回收，通过控制添加物的成分和工艺参数可以获得具有催化活性，磁性，电学特性以及光学性质的玻璃，例如通过溶胶凝胶法可以制备具有生物活性的微晶玻璃^[6-8]。相对于使用天然原料生产相同量的产品，二次材料的加工通常需要较少的能源，产生更少的污染，在大大降低微晶玻璃生产成本的同时，也实现了废物利用，变废为宝，促进可持续发展。