Centimeter-scale giant spherulites in mixtures of polar polymers and crystallizable diluents: Morphology, structure, formation and application

Abstract

A series of giant spherulites at centimetre scale were effectively constructed from the mixtures of polyacrylonitrile (PAN)/dimethyl sulfone (DMSO2), although neither PAN nor DMSO2 itself forms spherical morphology during crystallization. A detailed investigation was carried out on the morphology, microstructure, and formation mechanism by polarized optical microscopy, scanning electron microscopy, wide-angle X-ray diffraction, polarized FTIR spectroscopy, and differential scanning calorimetry. These giant spherulites constituted of PAN phase and DMSO2 crystals alternately distributed in divergent patterns. The fast crystallization of DMSO2 dominates the large growth rate and the macroscopic size, while PAN composes the skeleton of the giant spherulites. The cooperative deposition of PAN beside DMSO2 crystals originates from dipole–dipole interaction between the nitrile groups of PAN and the sulfone groups of DMSO2, accounting for the branching and splaying in the giant spherulites. These macroscopic morphologies were universally observed in other mixtures of PAN/dimethyl sulfoxide, PAN/maleic anhydride, poly(vinylidene fluoride)/DMSO2, and cellulose acetate/DMSO2. We propose that the giant spherulites can be formed by introducing suitable diluent crystallization and appropriate polymer–diluent interaction. Furthermore, this spherulitic pattern has been used as a template to direct the oriented growth of calcium carbonate based on the molecular orientation in the giant spherulite.