具有智能缓蚀与自修复功能的新型水凝胶涂层的设计与研究

The inner wall baseplate of the storage tank in offshore is subjected to marine corrosion-related damage, which causes an amount of economic loss, crude oil leakage, and environmental pollution. The bottom plate corrosion is mainly due to (a) the corrosive sedimentary water deposits on the bottom of the oil tank, and (b) the solid particles mixed in the crude oil are aggressive to destroy the protective coatings under floating and abrasion. The traditional coatings, however, are limited to protect the metals because the uncontrolled corrosion and the erosion by the solid particles can weaken or destroy the coatings. Although the metal corrosion could be inhibited or retarded by adding inhibitors to the solution, the problems still remain such as large does, high cost and environmental pollution. Meanwhile, the traditional self-healing coatings are limited in the corrosive condition. In this work, we propose a smart-corrosion inhibition and self-healing hydrogel coating for improving corrosion resistance and extending the service life of metal plate. By introducing the inhibitors to coatings with electrostatic interaction, the coatings could exhibit the proactive protection with releasing the inhibitors to the corrosion region; meanwhile, by introducing the dynamic bonds to coatings, they could show self-healing performance at both mechanical and anti-corrosive behaviors. The aim of our study is to prepare the intelligent anti-corrosive coatings with smart-releasing inhibitors and self-healing functions and understand their releasing and self-healing mechanism. Such a project will provide a new route for preparing long-term anti-corrosion, cost-saving coatings, which is vital to the petrochemical industry.

近海原油钢制储罐极易在日常的使用中遭受到海洋环境的腐蚀，其中罐底板穿孔占储罐腐蚀事故比率最高，不仅造成严重的经济问题，还会引起原油泄漏，污染附近海域。钢制储罐底板的腐蚀，主要受到底部沉积的腐蚀性物质侵蚀以及原油中固体颗粒物的冲刷、磨损影响等。通常采用添加缓蚀剂和引入自修复材料解决上述两个问题。但是传统缓蚀剂用量大、经济效益低、不够环保；以前自修复材料的设计很少针对腐蚀环境下研究材料自修复效率。针对上述两个问题，本研究提出了制备具有智能缓蚀和自修复功能的水凝胶涂层。利用静电作用在凝胶网络上吸附带负电荷的聚磷酸盐缓蚀剂，在金属局部腐蚀时利用金属离子与聚磷酸盐具有更强的络合能力实现缓蚀剂智能释放，钝化腐蚀区域；同时在水凝胶中构建静电作用和氢键作用等动态键，赋予凝胶涂层损伤后自修复功能。本项目的顺利实施，将为实现防腐涂层的智能化提供理论指导，对提高储罐的服役周期、节约成本提供新的解决方案。

不锈钢作为重要的金属材料被广泛应用，但在海水强电解质和夹杂的泥沙作用下，不锈钢极易诱发腐蚀破坏。为了解决这一问题，通常在不锈钢的表面涂覆一层带有缓蚀剂的防护涂层，以形成物理和化学的双重防护，但缓蚀剂利用率较低、释放后便很难再进行补充。本项目提出一种使用水凝胶负载和释放缓蚀剂的策略。通过凝胶材料中网络的正电荷与带负电的缓蚀剂之间的静电作用实现缓蚀剂的负载；通过金属离子与缓蚀剂之间更强的络合作用实现缓蚀剂的释放；此外，利用腐蚀性的离子在水凝胶基体中的扩散速率要比溶液中扩散慢的特点，在一定程度上实现凝胶对腐蚀性离子的物理阻隔。.本项目利用疏水-静电作用构筑了一系列具有优良力学性能的缓蚀剂负载型水凝胶材料。这种水凝胶材料的优势再在于：（1）具有良好的力学性能，高强度和韧性使其在承受一定物理冲击后不发生破损；（2）广泛的黏附能力、这类水凝胶可以黏附绝大多数金属和高分子材料表面，这便使其在单独作为涂层应用或者与涂层联用时具有很好的兼容性；（3）缓蚀剂的智能释放，缓蚀剂被水凝胶负载后不会因渗透作用流失，只有在外界的金属离子浓度上升时才会通过平衡转移来释放缓蚀剂，会随金属离子浓度的下降而停止。.本项目利用疏水-电解质单体进行共聚制备了一种具有快速光学盐响应性和粘接可调控性的水凝胶柔性传感器。相比于其它同类凝胶，该凝胶的盐响应行为更加快速，且响应阈值更低，还具有高粘接强度及粘接可调控的性质。此外，本项目提出了一种微相分离尺寸在15–30纳米内可调的光学盐响应凝胶的设计策略，所得的水凝胶材料具有快速敏感的响应性。