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A thermodynamic prediction of tie chain length distribution in drawn semicrystalline polymers
Author(s) -
Popli Rakesh,
Roylance David
Publication year - 1985
Publication title -
polymer engineering and science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.503
H-Index - 111
eISSN - 1548-2634
pISSN - 0032-3888
DOI - 10.1002/pen.760251307
Subject(s) - materials science , polymer , crystallinity , thermodynamics , gaussian , distribution (mathematics) , statistical physics , composite material , computational chemistry , chemistry , physics , mathematics , mathematical analysis
The mechanism underlying fracture of many oriented semicrystalline polymers is hypothesized to be a thermally activated, stress‐aided rate process in which the tie chains connecting crystalline units suffer thermomechanical dissociation. Some previous numerical models based on this concept have assumed a Gaussian distribution of tie chain contour lengths which are ruptured progressively by successively higher specimen strains, and have used electron spin resonance (ESR) spectroscopy to obtain the numerical parameters of the distribution. The distribution of tie chain lengths in the intererystalline region is calculated theoretically in this paper, based on minimization of free energy. Our results, although in basic agreement with earlier models, suggest a reinterpretation of some of the ESR findings with regard to molecular fracture processes.