The Journal of Physical Chemistry B, 2017, vol 121, 27, pp. 6673-6684
In situ small-, ultrasmall-, and wide-angle X-ray scattering measurements were performed to investigate the structural evolution of crystalline lamellae and cavities as a function of deformation ratio during tensile deformation of isothermally crystallized poly(ε-caprolactone). The cavities were modeled as cylinder-shaped objects which are oriented along the stretching direction and randomly distributed in the samples, and their dimensions were evaluated by direct model fitting of scattering patterns. At small deformations, the orientation of these cavities at the onset of cavity formation was related to the isothermal crystallization temperature. Upon further stretching, the cavities were found to cluster in the interfibrillar regions at moderate strains where the long spacing of the newly developed lamellae along the stretching direction remained essentially constant. At large orientations, the cooperative deformational behavior mediated via slippage of fibrils was evidenced, the extent of which depended on the cavity number, which could be traced back to the significantly different coupling forces imposed by chains connecting adjacent fibrils. Furthermore, wide-angle X-ray scattering results revealed that a fraction of the polymer chains with their orientation perpendicular to the stretching direction were still preserved even at large macroscopic strains.