Optimal Entanglement of Polymers Promotes the Formation of Highly Oriented Fibers

Abstract

Polymer fibers consist of macromolecules oriented along the fiber axis. Better alignment of chains leads to an increased strength of the fiber. It is believed that the key factor preventing formation of a perfectly oriented fiber is entanglement of polymers. We performed large-scale computer simulations of uniaxial stretching of semicrystalline ultrahigh molecular weight polyethylene. We discovered that there is an optimal number of entanglements per macromolecule necessary to maximize chain orientation in a fiber. Polymers that were entangled too strongly formed less oriented fibers. On the other hand, when polymers had too few entanglements per chain, they disentangled during stretching, and the strong fiber was not formed. We constructed a microscopic analytical theory describing both the fiber formation and disentanglement processes. Our work presents a novel view on the role of entanglements during fiber production and predicts the existence of a single universal optimal number of entanglements per chain maximizing the fiber quality: approximately $10^2$ entanglements.