陶瓷激光打印用球形超细陶瓷色料的微-纳结构控制与其固态流变性研究

The development of ceramic laser-printing technology has become an inevitable tendency to overcome the drawbacks of inkjet printing which to plug easily the nozzle and break through the technological barriers of domestic ceramic printing. The ultrafine ceramic powder with high solid flowability is the core of ceramic laser printing technology. To understand the relationship between the solid flowability and the special surface properties (hydrophobicity, charge, in-situ curing) of spherical ultrafine ceramic pigment, the series of ZrSiO4-based ceramic pigment are the research objects. The ultra-fine ceramic pigments with high solid flowability are prepared by a hard microemulsion method. The micro-nano structure of spherical ultrafine ceramic pigments is controlled through the optimization of hard microemulsion parameters. The adsorption rules of the hydrophobicity and the photosensitive polymer on the surface of superfine powder to be mastered. The key factors affecting the quality of laser printing pattern are studied by the further research on the sintering process of superfine ceramic pigments with each other and glaze. The above research results will contribute to the preparation technology development of the ultrafine ceramic powders with high solid flowability, provide the knowledge and experimental basis for the next generation of ceramic decoration technology, promote to achieve leapfrog development in the domestic ceramic decoration technology, which has an important economic and social benefit.

发展陶瓷激光打印技术成为克服喷墨打印易堵塞喷头的弊端和突破国内陶瓷印刷技术壁垒的必然趋势。高固态流动性超细色粉是陶瓷激光打印技术的核心。为深入认识球形超细陶瓷色料的固态流动性和特殊表面性质（憎水、荷电、原位固化）的影响因素，以ZrSiO4基系列陶瓷色料为研究对象，通过优化硬微乳液法制备条件控制球形超细陶瓷色料的微-纳结构，掌握憎水性和紫外光敏性高分子在超细粉体表面的吸附规律，获得高固态流动性超细色粉。进而研究煅烧过程中超细陶瓷色料间及其与釉料的界面作用，掌握影响激光打印图案质量的关键因素。上述研究成果将有助于发展高固态流动性的超细陶瓷色料的制备技术，为下一代陶瓷装饰技术提供知识基础和实验依据，还可促进国内陶瓷装饰技术实现跨越式发展，具有重要的经济和社会效益。

发展高固态流动性超细色粉是陶瓷激光打印技术的核心。为深入认识球形超细陶瓷色料的固态流动性和特殊表面性质（憎水、荷电、原位固化）的影响因素，以ZrSiO4基系列陶瓷色料为研究对象，研究了球形超细陶瓷色粉的微-纳结构控制；球形超细陶瓷色粉的憎水性和紫外光敏性表面修饰；球形超细陶瓷色粉的固态流动性影响因素以及烧结对混合超细陶瓷色粉呈色的影响。发展了多种制备超细陶瓷色料的方法：（1）溶胶-凝胶-微乳液-水热法(S-G-M-H)制备了高性能的亚微米ZrSiO4粉体。研究了矿化剂阳离子种类、粒度以及离子掺杂对色料呈色的影响。（2）介孔塌陷法制备ZrSiO4包裹炭黑，炭黑被致密的锆石完全包裹。经900℃空气煅烧除去可能的未包覆炭黑后，得到的颜料仍呈深黑色(L* = 24.14)。（3）溶胶-凝胶-微乳液法(S-G-M)制备了超细球形Pr-ZrSiO4颜料，具有均匀的球形颗粒，平均粒径约为0.785 μm。（4） 微乳液-沉淀法制备超细球形钴蓝色料，色料的平均粒径为0.3 μm，着色性能远优于商业钴蓝颜料。采用微乳液-水热沉淀法(M-H-P)制备了球形海胆状CoAl2O4颜料。采用氟硅烷偶联剂对陶瓷色料进行表面改性后，色料未改性时，水接触角仅为32°。改性后色料的接触角大幅度提升至110°。采用电荷调节剂N24加入量为4wt%，摩擦时间为5min时改性钴蓝色料的静电荷Q/M值能够达到最大值-17.41µC/g。但相应的静电荷Q/M值还未满足实际应用要求。项目通过优化制备条件获得球形超细陶瓷色料的微-纳结构，掌握憎水性和紫外光敏性高分子在超细粉体表面的吸附规律，认识了煅烧过程中超细陶瓷色料间及其与釉料的界面作用，掌握影响激光打印图案质量的关键因素。项目发表学术论文25篇，其中SCI&EI收录论文12篇。授权发明专利3项，培养硕士研究生4名。上述研究成果有助于发展下一代陶瓷装饰技术。