Cui Yan, Xing Yurui, Hou Jingwen, Zhang Hongti, Qiu Huibin
School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China.
School of Physical Science and Technology, Shanghai Key Laboratory of High-Resolution Electron Microscopy, ShanghaiTech University, Shanghai, 201210, China.
Small. 2024 Oct;20(40):e2401432. doi: 10.1002/smll.202401432. Epub 2024 May 31.
Colloidal composites, translating the great potential of nanoscale building bricks into macroscopic dimensions, have emerged as an appealing candidate for new materials with applications in optics, energy storage, and biomedicines. However, it remains a key challenge to bridge the size regimes from nanoscopic colloidal particles to macroscale composites possessing mechanical robustness. Herein, a bottom-up approach is demonstrated to manufacture colloidal composites with customized macroscopic forms by virtue of the co-assembly of nanosized soft polymeric micelles and hard inorganic nanoparticles. Upon association, the hairy micellar corona can bind with the hard nanoparticles, linking individual hard constituents together in a soft-hard alternating manner to form a collective entity. This permits the integration of block copolymer micelles with controlled amounts of hard nanoparticles into macroscopic colloidal composites featuring diverse internal microstructures. The resultant composites showed tunable microscale mechanical strength in a range of 90-270 MPa and macroscale mechanical strength in a range of 7-42 MPa for compression and 2-24 MPa for bending. Notably, the incorporation of soft polymeric micelles also imparts time- and temperature-dependent dynamic deformability and versatile capacity to the resulting composites, allowing their application in the low-temperature plastic processing for functional fused silica glass.
胶体复合材料将纳米级构建单元的巨大潜力转化为宏观尺度，已成为光学、能量存储和生物医学等应用领域新型材料的有吸引力候选者。然而，从纳米级胶体颗粒到具有机械稳健性的宏观复合材料，跨越尺寸范围仍然是一个关键挑战。在此，展示了一种自下而上的方法，通过纳米尺寸的软聚合物胶束和硬无机纳米颗粒的共组装来制造具有定制宏观形态的胶体复合材料。缔合时，多毛的胶束冠层可与硬纳米颗粒结合，以软硬交替的方式将单个硬成分连接在一起形成一个集体实体。这使得能够将含有可控量硬纳米颗粒的嵌段共聚物胶束整合到具有不同内部微结构的宏观胶体复合材料中。所得复合材料在压缩时显示出90 - 270兆帕范围内的可调微观尺度机械强度和7 - 42兆帕范围内的宏观尺度机械强度，在弯曲时为2 - 24兆帕。值得注意的是，软聚合物胶束的加入还赋予所得复合材料时间和温度依赖性的动态可变形性以及多功能性能，使其能够应用于功能性熔融石英玻璃的低温塑性加工。
