摘要
Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the self-assembly of AB di-block copolymers(di-BCPs)confined in Janus spherical nanocavities using simulations,and explained the structure formation mechanisms.In the case of a strongly selective cavity wall,all the lamella-forming,gyroid-forming,and cylinder-forming di-BCPs can form interfacial frustration-induced Janus concentric perforated lamellar nanoparticles,whose outermost is a Janus spherical shell and the internal is a sphere with concentric perforated lamellar structure.In particular,Janus concentric perforated lamellar nanoparticles with holes distributed only near the equatorial plane were obtained in both lamella-forming and gyroid-forming di-BCPs,directly reflecting the effect of interfacial frustration.The minority-block domain of the cylider-forming di-BCPs may form hemispherical perforated lamellar structures with holes distributed in parallel layers with a specific orientation.For symmetric di-BCPs,both the A and B domains in each nanoparticle are continuous,interchangeable,and have rotational symmetry.While for gyroid-forming and cylinder-forming di-BCPs,only the majority-block domains are continuous in each nanoparticle,and holes in the minority-block domains usually have rotational symmetry.In the case of a weakly selective cavity wall,the inhomogeneity of the cavity wall results in structures having a specific orientation(such as flower-like and branched structures in gyroid-forming and cylinder-forming di-BCPs)and a perforated wetting layer with uniformly distributed holes.The novel nanoparticles obtained may have potential applications in nanotechnology as functional nanostructures or nanoparticles.
基金
supported by the National Natural Science Foundation of China(NSFC)(Nos.22173051,21829301,21774066)
College Discipline Innovation and Intelligence Introduction Program(111 Project(B16027)
the International Cooperation Base(2016D01025)
Tianjin International Joint Research and Development Center。