摘 要

陶瓷墙地砖是釉面砖的一种，在建筑陶瓷领域中发挥着巨大的作用，随着我国生产陶瓷墙地砖所需要的优质原材料日益枯竭，导致陶瓷墙地砖的生产成本日益增高，因此亟需开发出新的陶瓷原料来解决这一关键问题。本文以新开发的木鱼石为主要原材料制备陶瓷墙地砖坯体，确定了陶瓷墙地砖坯体的烧成温度范围和最优坯体配方；然后选用锆白釉料、透明釉料和2004釉料，对性能最优的陶瓷墙地砖坯体进行了施釉，制备了木鱼石质陶瓷墙地砖，探究了坯釉结合性机理。本文采用X射线衍射仪和扫描电子显微镜等现代测试仪器对样品的物理性能、相组成以及显微结构等进行了测试分析，研究样品配方组成和制备工艺对陶瓷墙地砖性能的影响。主要研究成果如下：以山东新开发的木鱼石为主要原材料，复配焦宝石、黏土、钾长石、钠长石、石英和滑石等矿物原料，设计了A系列陶瓷墙地砖坯体配方，并采用喷雾造粒、半干压成型和常压烧成等制备工艺，成功制备了陶瓷墙地砖坯体样品。研究结果表明： A系列陶瓷墙地砖坯体的最佳烧成温度范围为1080~1120 ℃，且样品的吸水率均达到了国家标准《陶瓷砖》（GB/T4100-2015）中对瓷质砖的性能要求。经1100 ℃和1080 ℃烧成的A系列陶瓷墙地砖坯体的相组成为石英、钙长石、歪长石和顽灰石，这些晶体在玻璃相的包裹中相互交织在一起，在样品中还存在大量的孤立闭气孔，两者共同作用，赋予样品良好的性能。当木鱼石、焦宝石、黏土、钾长石、钠长石、石英和滑石添加量分别为50 wt%、15 wt%、10 wt%、5 wt%、5 wt%、5 wt%和10 wt%时，经1080 ℃烧成的陶瓷墙地砖坯体样品性能最优，样品的吸水率为0.06%，抗折强度为93.66 MPa，均达到了国家标准《陶瓷砖》（GB/T4100-2015）中对瓷质砖的性能要求。

以A系列样品中最优样品（木鱼石含量为50 wt%，经1080 ℃烧成）为坯体，在其表面分别施以锆白釉料、透明釉料和2004釉料，以RbCl为添加剂，成功制备了CaO-MgO-Al₂O₃-SiO₂系陶瓷墙地砖。研究结果表明：上述三种釉料与坯体的坯釉结合性良好。施加上述三种釉料的墙地砖样品的釉面显微硬度均随着RbCl含量的增加而逐渐增大。RbCl对锆白釉面光泽度影响不大，而透明釉面和2004釉面两种釉面的光泽度随着RbCl含量的增加而逐渐加强。

关键词：木鱼石；氯化铷；陶瓷墙地砖；坯釉适应性；吸水率

Abstract

Ceramic wall and floor tiles are a kind of glazed tiles, which plays a huge role in the field of architectural ceramics. As the high-quality raw materials required for the production of ceramic wall and floor tiles are increasingly exhausted in China and the production cost of ceramic wall and floor tiles is increasing. New ceramic preparation materials need to be developed to solve this problem. In this paper, the ceramic wall and floor tiles body were prepared by using muyu stone from Shandong Province as the main raw materials, determined the firing temperature range of ceramic wall and floor tiles and the optimum body formula. Then the muyu stone ceramic wall and floor tiles were prepared by glazing the optimal ceramic wall and floor tile body with glaze, then explore the mechanism of the glaze bonding with ceramic wall and floor tiles body. In this paper, the physical properties, phase composition and microstructure of the samples were tested by X-ray diffractometer and scanning electron microscope. The influence of sample composition and preparation process on the properties of ceramic wall and floor tiles were studied. The results of the study were as follows.

The newly developed muyu stone from Shandong Province as the main raw materials, mixed gemstone, clay, K-feldspar, Na-feldspar, quartz and talc mineral raw materials, the blank formula of ceramic wall and floor tiles were designed firstly, and then the ceramic wall and floor tiles were prepared by processes of spray granulation, semi-dry pressing and pressureless firing. The results show that the firing temperature range of series A ceramic wall and floor tiles ranges is 1080~1120 ℃, and the water absorption and porosity of the samples both meet the requirements of national standard "ceramic tiles" (GB/T4100-2015). The main phase composition of the series A ceramic wall and floor tiles body fired at 1100 ℃ and 1080 ℃ are mainly quartz, anorthite, anorthoclase and enstatite. Under the bonding of the glass phase, these crystal phases are intertwined in the sample, in addition, there are many isolated and uniform closed pores in the samples, which can give the samples good performance. When the content of muyu stone, gemstone, clay, K-feldspar, Na-feldspar, quartz and talc is 50 wt%, 15 wt%, 10 wt%, 5 wt%, 5 wt%, 5 wt% and 10 wt% respectively and the firing temperature at 1080 °C, the ceramic wall and floor tiles samples are the best, and the water absorption is 0.06%, and the flexural strength is 93.66 MPa, which meets the requirements of the national standard "ceramic tiles" (GB/T4100-2015).

The ceramic wall and floor tiles were prepared successfully by taking the best samples of series A of samples (muyu stone content of 50 wt%, fired at 1080 ℃) as the blank body, with zirconium white glaze, transparent glaze and 2004 glaze was glazed on the surface, and RbCl as additive. The results show that the three glazes have good adhesion to the ceramic wall and floor tiles bodys. The glazed microhardness of the wall and floor tiles samples with zirconium white glaze, transparent glaze and 2004 glaze increases with the increase of RbCl content. RbCl had little influence on the gloss of zirconium white glaze, but the gloss of transparent glaze and 2004 glaze was gradually increased with the increase of RbCl content.

Key Words：muyu stone, RbCl, wall and floor tiles, glaze adaptability, water absorption

目 录

摘 要 I

Abstract II

第1章 绪论 1

1.1课题研究的目的及意义 1

1.2与课题相关的国内外研究进展 2

1.2.1国内外墙地砖发展趋势 2

1.2.2含钙硅酸盐在陶瓷坯体中的作用 3

1.2.3新开发的陶瓷原料 4

1.2.4添加剂对陶瓷微观结构、性能的影响 5

1.3本文研究的主要内容 6

第2章 结构与性能表征方法 7

2.1样品烧成线收缩的测试 7

2.2样品吸水率、气孔率及体积密度的测定 7

2.3样品抗折强度的测定 7

2.4 X射线衍射分析（XRD） 8

2.5扫描电子显微研究（SEM） 8

2.6釉面色度的测定 8

2.7釉面显微硬度的测定 9

第3章 CaO-MgO-Al₂O₃-SiO₂系陶瓷墙地砖坯体的研究 10

3.1实验 10

3.1.1实验原料 10

3.1.2样品配方组成设计 10

3.1.3样品的制备 11

3.2结果分析与讨论 12

3.2.1影响样品烧成线收缩的因素 12

3.2.2影响样品吸水率、气孔率及体积密度的因素分析 13

3.2.3影响样品抗折强度的因素分析 16

3.2.4样品的相组成分析 17

3.2.5样品的显微结构研究 19

3.3本章小结 33

第4章 CaO-MgO-Al₂O₃-SiO₂系陶瓷墙地砖釉面装饰的研究 34

4.1实验 34

4.1.1实验所需的原料及配方组成 34

4.1.2样品的制备 35

4.2结果分析与讨论 36

4.2.1影响釉面显微硬度的因素分析 36

4.2.2影响釉面色度的因素分析 37

4.2.3釉面显微结构研究 38

4.2.4 坯釉结合机理分析 40