基于有机防腐涂层自防护能力的天然纳米管缓蚀剂装载器智能缓释行为调控及相关机制研究

With the implementation of the china's Mega project and the super infrastructure engineering in China, more than 100-year service life has become an essential performance index for many engineering materials and equipment. To develop intelligent and environment friendly organic anticorrosion coatings is a good solution to meet the requirements. In this project, the discussion will be dressed on the release behavior, control technique and related mechanism of inhibitors in the halloysite nanotubes encapsulated by polyelectrolyte with environmental change response ability on aspect of enhancing the self-protection ability and service life of organic anticorrosive coatings. More focus will put on the response behavior of micro vessel on the invasion of water, the change of Cl- concentration and pH value in the organic anticorrosive coatings. The applicant will also study the interaction behaviors between the environmental change response behavior of the micro vessel and self-protection performance of anti-corrosion coating and analyze the related mechanism. An appropriate control technique will be obtained in the end. The applicant will also study the influence of key parameters, such as load and release rate of inhibitor, additive amount and distribution of micro vessel in organic anticorrosion coatings, on self-protection properties and other service performance, and explore the comprehensive interaction mechanism as well. The suitable range of key parameters will be determined. Finally, laboratory evidence and theoretical guidance for design, development and application of the efficient and long life intelligent environment friendly organic coatings will be present.

发展智能有机防腐涂层是实现我国超级工程、超大型基础设施装备材料超高使役性能和超长使役寿命的有效途径。本项目以提升有机防腐涂层自防护能力和使役寿命为目的，开展经聚电解质包覆的具有环境变化响应能力的天然埃洛石纳米管微容器在有机防腐涂层中对缓蚀剂的缓释行为调控及相关机理研究，重点探究微容器对涂层中水的入侵以及氯离子浓度和pH值变化的响应行为，分析上述响应行为对涂层自防护能力的影响规律和微观作用机制，掌握微容器环境变化响应能力与涂层自防护能力匹配性调控技术；研究微容器的缓蚀剂装载量、对缓蚀剂的释放速度以及微容器在有机涂层中的添加量和分布状态对涂层自防护能力和使役寿命的影响规律和作用机制，确定上述各参数的适宜范围，为建立环境敏感型智能有机防腐涂层设计准则提供理论依据，为环境友好的高效长寿命智能有机防腐涂层的研制和推广应用提供可靠的实验室证据。

发展绿色高效多功能一体化智能防护涂层是实现我国超级工程、超大型基础设施装备用金属材料超高使役性能和超长使役寿命的有效途径。本项目以提升有机防腐涂层自防护能力为目标，开展经聚电解质包覆的具有环境变化响应能力的天然埃洛石纳米管在有机防腐涂层中对缓蚀剂的缓释行为调控及相关机制研究，研发微胶囊环境变化响应能力与涂层自防护能力匹配性调控技术，为绿色高效多功能一体化智能涂层的研制和应用提供可靠的实验室证据。研究验证了天然埃洛石纳米管作为缓蚀剂载体的可靠性和可行性，获得了最佳装载工艺；明确了对水、Cl-以及pH值变化具有敏感性、选择性和持久性响应是微胶囊的必备性能，筛选出PDDA/PSS聚电解质对、天然壳聚糖以及天然-聚赖氨酸/海藻酸钠包覆材料，制备了满足上述缓释性能的微胶囊；微胶囊在涂层中均匀分布且核壳结构完好，适量添加微胶囊可显著提升涂层的防腐能力和自修复能力，湿态附着力、强韧性等机械性能也有一定程度的提升，以壳聚糖包覆的微胶囊还可赋予涂层杀菌防污能力。研究明确指出，决定微胶囊缓释行为和环境变化响应能力的关键因素为缓蚀剂的溶解度和聚电解质所含的特征官能团种类，缓蚀剂在不同pH值的水溶液中的溶解度影响了缓蚀剂的扩散速度以及对pH值变化的响应能力，聚电解质所含的特征官能团种类决定了聚电解质膜表面剩余电荷种类和数量以及与缓蚀剂分子间的相互作用情况，剩余电荷种类和数量的改变导致聚电解质膜层孔隙率的变化，最终决定了缓蚀剂的扩散速度，官能团与缓蚀剂分子间相互作用限制了缓蚀剂的向外扩散，综合考量上述因素是调控微胶囊缓释行为的有效途径，适量添加微胶囊可获得理想的防护涂层。成功研制了兼具防潮、防腐和防污能力的智能水性聚氨酯防护涂层和海洋装备用绿色长效防腐防污一体化智能水性环氧涂层，拓宽了水性防腐涂层的使用范围，为金属材料提供了全新的防护手段，也证实了所获研究理论和设计准则的准确性和可靠性。