Co‐Assembly of Soft and Hard Nanoparticles into Macroscopic Colloidal Composites with Tailored Mechanical Property and Processability

Abstract 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.