Intrinsic deformation behavior of semicrystalline polymers

The influence of crystallinity and lamellar thickness on the intrinsic deformation behavior of a number of semicrystalline polymers is studied: a poly(ethylene terephthalate) and two different molecular weight grades of polyethylene and polypropylene. The crystallinity and lamellar thickness are altered by varying the rate of crystallization from the melt and by cold crystallization (annealing) at elevated temperatures above T-g but below the melting point. Crystallinity and lamellar thickness are determined by wide-angle X-ray diffraction and small-angle X-ray scattering measurements. Uniaxial compression tests are performed to obtain the large strain intrinsic deformation behavior, e.g., yield stress, strain softening, and strain hardening modulus. The yield stress is found to be proportional to lamellar thickness, whereas the strain hardening modulus is shown not to depend on crystallinity or lamellar thickness. Over the strain range experimentally covered, the strain hardening modulus appears to be well described by a simple neo-Hookean relation and appears to be related to the chain entanglement density. Am affirmation for this relation arises from the observation that slowly melt crystallized samples exhibit a lower strain hardening, resulting from a lower chain entanglement density, which is expected to be caused by reeling in of the molecular chains in such a slow crystallization process. The similarity in the results observed on all polymers tested supports the conclusion that the crystalline phase does not contribute to strain hardening, which is primary controlled by the chain entanglement density.