Year: 2010
Type: preprint
Abstract: Kinetic barriers cause polymers to crystallize incompletely, into nanoscale lamellae interleaved with amorphous regions. As a result, crystalline polymers are full of crystal-melt interfaces, which dominate their physical properties. The longstanding theoretical challenge to understand these interfaces has new relevance, because of accumulating evidence that polymer crystals often nucleate via a metastable, partially ordered "rotator" phase. To test this idea requires a theory of the bulk and interfacial free energies of the critical nucleus. We present a new approach to the crystal-melt interface, which represents the amorphous region as a grafted brush of loops in a self-consistent pressure field. We combine this theory with estimates of bulk free energy differences, to calculate nucleation barriers and rates via rotator versus crystal nuclei for polyethylene. We find rotator-phase nucleation is indeed favored throughout the temperature range where nucleation is observed. Our methods can be extended to other polymers.
Source: arXiv (Cornell University)
Author: Milner, Scott T.
Institution: Pennsylvania State University
Language: English
Subfield: Polymers and Plastics
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2949475810