Coherent crystal branches: the impact of tetragonal symmetry on the 2D confined polymer nanostructure

The symmetry of polymer crystals greatly affects the optical, thermal con­ductivity and mechanical properties of the materials. Past studies have shown that the two-dimensional (2D) confined crystallization of polymer nanorods could produce anisotropic structures. However, few researchers have focused on understanding confined nanostructures from the perspective of crystal sym­metry. In this research, we demonstrate the molecular chain self-assembly of tetragonal crystals under cylindrical confinement. We specifically selected poly(4-methyl-1-pentene) (P4MP1) with a 4(1) or 7(2) helical conformation (usually crystallizing with a tetragonal lattice) as the model polymer. We found a coherent crystal branching of the tetragonal crystal in the P4MP1 nanorods. The unusual 45°- and 135°-{200} diffractions and the meridional 220 diffraction (from 45°-tilted crystals) have shown a uniform crystal branching between the a (1)-axis crystals and the 45°-tilted crystals in the rod long axis, which originates from a structural defect associated with tetragonal symmetry. Surprisingly, this chain packing defect in the tetragonal cell can be controlled to develop along the rod long axis in 2D confinement.