Molecular changes on drawing isotopic blends of polyethylene and ethylene copolymers: 1. Static and time-resolved sans studies

Small angle neutron scattering (sans) has been used to observe changes in molecular orientation on deformation of isotopic, melt quenched blends of linear polyethylene and copolymers with butyl and hexyl branches, using uniaxial drawing. In no case was there evidence of significant isotopic fractionation either before or during deformation. Samples left clamped in the neutron beam following deformation showed no evidence of molecular relaxation, while significant changes in molecular orientation with time were observed for samples unclamped after deformation. This latter behaviour could be fitted adequately by a single exponential decay and the relaxation time was found to be of the order of tens of minutes. This relaxation time increased with both increasing molecular weight and the presence of branching. For samples drawn to draw ratios of up to 3.0, the anisotropy in the radius of gyration was compared with predictions for affine deformation. Only in the cases of linear labelled guest molecules in either a linear or copolymer host were significant departures from the affine model observed: no such departures were found for copolymer guest molecules. This is interpreted in terms of a delay in crystallite disruption until higher draw ratios for copolymer guest molecules with respect to linear guest.