Self-healing hybrids fabricated by metal complexation with imidazole-containing silsesquioxane nanoparticles
Self-healing hybrids fabricated by metal complexation with imidazole-containing silsesquioxane nanoparticles
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DOI：
10.1039/d0qm00225a
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发表时间：
2020-08
影响因子：
7
通讯作者：
Y. Sasaki;H. Mori
中科院分区：
文献类型：
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作者：
Y. Sasaki;H. Mori
在材料中同时实现自我修复能力和材料硬度是具有挑战性的，因为这些特性是相互矛盾的。在这项研究中，我们设计了基于单臂含咪唑和正烷基团的有机-无机倍半硅氧烷纳米颗粒(SQ-NPs)的自愈杂化材料。咪唑部分通过金属-配体(锌-咪唑)的动态相互作用作为自愈基序，而正烷基官能团作为一个灵活的单元来操纵链的迁移性。通过硫醇-环氧点击反应和酯化反应制备了三种不同正构烷基链的含咪唑的SQ-NPs。X射线衍射仪、扫描力显微镜、热重分析和差示扫描量热仪测量表明，SQ-NPs的形成具有较窄的尺寸分布，没有团聚和可操控的热性能。含咪唑的SQ-NPs与ZnCl2络合制备的锌/咪唑基杂化材料具有很高的可调性(杨氏模数在0.56~2.13 GPA范围内)和良好的自愈效果(在50℃下24 h恢复了80%的固有力学性能)，这归因于锌-咪唑相互作用的快速交换的愈合性质，以及无定形的SQ-NP迁移率。
Simultaneous achievement of self-healing ability and material hardness in materials is challenging because these properties are contradictory. In this study, we designed self-healable hybrids based on organic–inorganic silsesquioxane nanoparticles (SQ-NPs) having imidazole and n-alkyl groups in a single arm. The imidazole moiety acted as a self-healing motif via dynamic metal–ligand (zinc–imidazole) interactions while the n-alkyl functional groups act as a flexible unit to manipulate the chain mobility. Three imidazole-containing SQ-NPs having different n-alkyl chains were prepared by thiol–epoxy click reaction followed by esterification. X-ray diffraction, scanning force microscopy, thermogravimetric analysis, and differential scanning calorimetry measurements revealed the formation of SQ-NPs (< 5 nm) with relatively narrow size distributions and no aggregation and manipulated thermal properties. The zinc/imidazole-based hybrids prepared by the complexation of the imidazole-containing SQ-NPs with ZnCl2 exhibited a high degree of tunability (Young's modulus in the range of 0.56–2.13 GPa) with good self-healing efficacy (recovered 80% of inherent mechanical properties at 50 °C for 24 h), which was attributable to the healing nature of the rapid exchange of zinc–imidazole interactions, in addition to amorphous SQ-NP mobility.