Understanding chain folding morphology of semicrystalline polymers based on a rod–coil multiblock model

Abstract

We employ a rod–coil multiblock molecular chain model to investigate chain folding behavior, which is a significant characteristic in semicrystalline polymers, by using the method of self-consistent field theory (SCFT). Polymer chains with different conformations in crystalline and amorphous regions are described by rigid rod chains and flexible Gaussian chains, respectively. At present, we concentrate on the thermodynamic behaviors of polymer semi-crystals after the formation of the initial lamellar crystals. A new mechanism for lamellar thickening is proposed to realize that the end of lamellar thickening depends on the crystallinity degree. In other words, it is impossible for lamellae to develop into extended-chain crystals by means of lamellar thickening if crystallinity is limited to a certain degree. We further discuss the competition between crystalline and amorphous regions and its influence on crystallization behaviors, such as the formation of double lamellae, chain tilt, the anomalies and adjacent re-entry. The synergistic influences of the driving force of crystallization, interfacial energy and crystallinity degree on chain folding behavior are also investigated when the density anomalies in amorphous regions are excluded. Our model demonstrates advantages in accurately describing the mesoscopic layered structures of semicrystalline polymers based upon a microscopic chain model and provides at least a semi-quantitative thermodynamic picture for chain folding.