用于防腐蚀涂料的具有预警功能耐候缓蚀材料的结构设计及宏量制备

The realization of corrosion protection and early warning of corrosion damage are of great significance for prolonging material life and improving production safety. The existing weathering and corrosion resistant materials used as fillers not only need to be improved the anticorrosive performance, but also do not have the function of corrosion warning. In this project, the surface of zinc phosphomolybdate modified with benzotriazole is coated by magnetic metal-doped zinc oxide solid solution through surface modification, solid solution doping and crystal engineering techniques. Hetero-complementary anti-weathering and corrosion resistant materials of core-shell structures with early-warning function are obtained, which provide novel high-efficiency intelligent materials for metal corrosion protection. In situ carbon spot modification technique is used to give material corrosion damage warning function, and combined chemical thinking is used to fit the composition of interface layer, adhesion area, coating thickness, crystal surface defect of core-shell layer, magnetoresistive effect and so on. The correlation between structural stability and weathering and corrosion resistance, which can guide materials to design and synthesis; The ultrasonic hydrothermal preparation technology is used to prepare the material, the preparation mechanism is proved, and the optimum process parameters are obtained, which providing theoretical support and experimental reference for the design of the function and composition of the new weathering and corrosion resistant material with early warning function. The completion of the project is of great significance for improving the performance of existing weathering and corrosion inhibition materials, enriching the theory of corrosion resistance and reducing the ocurrence of corrosion disasters.

实现金属腐蚀防护与局部损伤预警，对于延长材料寿命，提高生产安全意义重大。现作为防腐涂料填料使用的耐候缓蚀材料组成与结构单一，造成耐候缓蚀性能有待提高，且无腐蚀预警功能。本项目拟通过表面修饰、固溶体掺杂等手段，结合晶体工程技术，以苯并三唑修饰的磷钼酸锌材料为核层，在其表面包覆碳点修饰的磁性金属掺杂的氧化锌固溶体，设计合成具有预警功能的异质互补型核壳结构耐候缓蚀材料，为金属防腐蚀领域提供一类高效智能新材料。利用原位碳点修饰技术，赋予材料腐蚀损伤预警功能；利用组合化学思维，深入探讨界面组成、附着面积、包覆厚度、核壳层的晶体缺陷、磁阻效应等因素与预警灵敏性和耐候缓蚀性能之间的相关性，为新型具有预警功能耐候缓蚀材料的组成设计提供理论支持和实验参考；利用超声水热同步工艺宏量制备该材料，探明制备机理，获得最佳工艺参数。该项目完成，有助于丰富耐候缓蚀材料设计理论，实现局部腐蚀损伤预警，减少腐蚀灾害发生。

项目按照计划圆满完成，取得了诸多原创性成果，并在项目实施过程中发现，异质结材料具有更加优异的耐候缓蚀性能，为今后的深化研究指明了方向。项目完成了碳点的制备，并用于修饰硅酸锌材料作为耐候缓蚀材料，探讨了材料的耐候缓蚀性能和预警功能；并将苯并三唑用于材料的修饰，显著提升了材料的耐候缓蚀性能；将金属元素、稀土金属元素作为掺杂原子制备了一系列金属掺杂氧化锌基固溶体，并获得了该类材料制备的关键技术；探索出了多种钼酸锌耐候缓蚀材料制备工艺，并对其耐候缓蚀性能进行了详细探讨。将上述单元材料进行原位复合，获得复合结构耐候缓蚀材料，并可实现材料的宏量制备，课题组已将相关成果用于指导企业的实际生产；详细探究了腐蚀损伤预警机理和耐候缓蚀作用机理，获得了提高预警灵敏性和耐候缓蚀性能的关键因素，获得的原创性结论可以用于指导新型高效智能化耐候缓蚀材料的设计合成。已发表标注基金支持的SCI学术论文24篇，申请国家发明专利6项，培养博士研究生5人，硕士研究生12人，项目获得的研究结果对于金属耐候缓蚀材料的工业化生产及实际应用具有参考价值。