Zheng Zhaoliang, Schenderlein Matthias, Huang Xing, Brownbill Nick J, Blanc Frédéric, Shchukin Dmitry
Stephenson Institute for Renewable Energy, Department of Chemistry, University of Liverpool , Crown Street, Liverpool, L69 7ZD, United Kingdom.
Max-Planck Institute of Colloids and Interfaces , 14424, Potsdam, Germany.
ACS Appl Mater Interfaces. 2015 Oct 21;7(41):22756-66. doi: 10.1021/acsami.5b08028. Epub 2015 Oct 6.
Feedback coating based on pH-induced release of inhibitor from organosilyl-functionalized containers is considered as a compelling candidate to achieve smart self-healing corrosion protection. Four key factors that determine the overall coating performance include (1) the uptake and release capacity of containers, (2) prevention of the premature leakage, (3) compatibility of containers in coating matrix, and (4) cost and procedure simplicity consideration. The critical influence introduced by organosilyl-functionalization of containers is systematically demonstrated by investigating MCM-41 silica nanoparticles modified with ethylenediamine (en), en-4-oxobutanoic acid salt (en-COO(-)), and en-triacetate (en-(COO(-))3) with higher and lower organic contents. The properties of the modified silica nanoparticles as containers were mainly characterized by solid-state (13)C nuclear magnetic resonance, scanning and transmission electron microscopy, N2 sorption, thermogravimetric analysis, small-angle X-ray scattering, dynamic light scattering, and UV-vis spectroscopy. Finally, the self-healing ability and anticorrosive performances of hybrid coatings were examined through scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS). We found that en-(COO(-))3-type functionalization with content of only 0.23 mmol/g performed the best as a candidate for establishing pH-induced release system because the resulting capped and loaded (C-L) functionalized silica nanocontainers (FSNs) exhibit high loading (26 wt %) and release (80%) capacities for inhibitor, prevention of premature leakage (less than 2%), good dispersibility in coating matrix, and cost effectiveness.
基于pH诱导抑制剂从有机硅官能化容器中释放的反馈涂层被认为是实现智能自修复腐蚀防护的有力候选材料。决定涂层整体性能的四个关键因素包括:(1)容器的吸收和释放能力;(2)防止过早泄漏;(3)容器在涂层基质中的兼容性;(4)成本和操作简便性的考量。通过研究用乙二胺(en)、en-4-氧代丁酸盐(en-COO(-))和en-三乙酸盐(en-(COO(-))3)改性的具有较高和较低有机含量的MCM-41二氧化硅纳米颗粒,系统地证明了容器有机硅官能化所带来的关键影响。作为容器的改性二氧化硅纳米颗粒的性能主要通过固态(13)C核磁共振、扫描和透射电子显微镜、N2吸附、热重分析、小角X射线散射、动态光散射和紫外可见光谱进行表征。最后,通过扫描振动电极技术(SVET)和电化学阻抗谱(EIS)研究了混合涂层的自修复能力和防腐性能。我们发现,仅含0.23 mmol/g的en-(COO(-))3型官能化作为建立pH诱导释放系统的候选材料表现最佳,因为所得的封端和负载(C-L)官能化二氧化硅纳米容器(FSN)对抑制剂具有高负载量(26 wt%)和释放量(80%)、防止过早泄漏(小于2%)、在涂层基质中具有良好的分散性以及成本效益。