碱硼硅酸盐系统陶瓷釉上装饰材料耐磨损与耐污染机理研究

Alkali borosilicate (ABS) system ceramic over-glaze lead-free frits can produce specific phase separation and crystallization when heat treated, which will significantly improve their physical properties, chemical stability, and mechanical strength, etc. The theory, research methods, models, and test standards developed by tribology and modern chemistry can also be used as references for the research of daily-use porcelain. In order to solve the problem of poor abrasion and stain resistance of over-glaze decorated daily-use porcelain, based on the lead-free frits of ABS system in this project, the frit composition will be optimized by the introduction of rare earth and transition metal oxides, network formers, intermediates and modifier oxides. On this basis, different heat treatment processes will be introduced to induce phase separation and crystallization, thereby further improving frit performance.The abrasion and stain resistance of sample is set to be tested and based on test data such as AFM, SEM, TEM, FTIR, etc., a suitable model will be established to predict the friction process. At the same time, the effect of the unique phase separation/crystallization nano-hierarchy structure formed in the previous heat treatment experiment on the abrasion and stain resistance will be studied and a theoretical explanation will be given.. To carry out the research on the abrasion and stain resistance over-glaze decorated daily-use porcelain, explore the mechanism behind it, solve the problem of poor abrasion and stain resistance, and finally form key techniques and standard test methods, all these mothods can be beneficial to the improvement of the quality of daily-use ceramic products and the competitiveness of the industry.

碱硼硅酸盐（ABS）系统陶瓷釉上无铅熔剂经热处理会产生特定形态的分相和析晶，能大幅提高其物理性能、化学稳定性和机械强度等。摩擦学和现代化学所发展的理论、研究方法、模型及试验标准亦能为日用瓷的研究所借鉴。为解决釉上彩装饰日用瓷耐磨性、耐污染性差的问题，本项目在ABS系统无铅熔剂中引入稀土和过渡金属氧化物、网络形成体、中间体和外体氧化物对熔剂组成进行优化，在此基础上，引入不同热处理工艺诱发分相-析晶，从而进一步提高熔剂性能。对样品进行耐磨性和耐污染性测试，以AFM、SEM、TEM、FTIR等测试分析数据为基础，建立合适的模型对摩擦过程进行预测。同时研究前期热处理实验所形成的独特的分相-析晶纳米层级结构对耐磨性和耐污染性的影响，并给出理论解释。本项目开展釉上彩装饰瓷耐磨性和耐污染性研究，解决耐磨、耐污染性差的问题，并最终形成关键技术和标准的测试方法，对提升日用陶瓷产品品质和行业竞争力意义重大。

随着厨房电器洗碗机等机洗设备的普及，碱硼硅酸盐系统(ABS)釉上彩装饰材料的耐磨性与耐污性差的问题凸显。釉上彩颜料中的低温熔剂含量高达70 wt.%，因此提升低温熔剂的性能是解决此问题的关键因素。本课题在ABS无铅熔剂的基础上，研究了熔剂组成、纳米级液-液分相及外掺第二相颗粒等对熔剂性能的影响。揭示了熔剂的分相机制、制品表面形貌以及显微硬度对熔剂耐磨性与耐污性的影响规律，阐释了磨损机理，得到了耐磨等级为3级、耐污性良好的釉上装饰材料。. 首先研究了不同碱金属、碱土金属摩尔比对熔剂耐磨性的影响，然后通过单掺Y2O3、Nb2O5、CeO2等稀土及过渡金属氧化物以及复掺TiO2-Dy2O3，探究其对耐磨性的影响。结果表明，外掺4 wt.%的CeO2，可大幅提高熔剂耐磨性。采用适当的热处理工艺，在连续相中诱导生成孤立纳米级滴状分相，并可有效地调控分相尺寸和体积分数，提高了熔剂的耐磨性和显微硬度，耐磨等级由2级提高至3级。磨损过程中ABS熔剂并没有像其他脆性材料那样受力后出现脆性断裂，而是在表面形成了长约为2~30 μm的取向随机、宽窄与深浅不一的犁坑、微切削以及点坑缺陷，表明样品的磨损模式以冲蚀磨损机理为主。实验还研究了外掺第二相颗粒对熔剂耐磨性和耐污性的影响规律。研究得出，经325~400目筛分所得长径比为11.7的莫来石晶须能显著增强熔剂耐磨性，磨损后表面仅存在少量的长短犁沟，未见微切削和点坑缺陷，表明样品的磨损模式以磨粒磨损机理为主；外加一定长径比的莫来石晶须有效提高了熔剂表面抗冲蚀磨损能力，磨损机制由冲蚀磨损机理转变为磨粒磨损机理。莫来石晶须的加入也增强了熔剂的耐污性，样品经程序A、B、C清洗后KMnO4污染剂绝大部分去除，样品表面污染剂由难至易的去除顺序为KMnO4溶液、AgNO3溶液、油性记号笔、Fe2O3分散液、植物调和油。. 本项目的实施，解决了釉上装饰日用瓷耐磨性与耐污性的难题，可为无公害釉上装饰材料的研发提供理论指导，促进日用陶瓷产品的更新换代，具有极大的经济和社会价值。