Development of shear-induced crystallization precursor structure was studied by in-situ rheo-SAXS (small-angle X-ray scattering) and rheo-WAXD (wide-angle X-ray diffraction) techniques using binary polymer blends of high and low molecular weight polyethylenes near their nominal melting temperatures (120 °C). Two low molecular weight polyethylene copolymers, containing 2 mol % hexene, with weight-average molecular weights (M w) of 50 000 (MB-50K) and 100 000 (MB-100K), and polydispersity of about 2, were used as the noncrystallizing matrices. A high molecular weight polyethylene homopolymer with M w of 250 000 (MB-250K) and polydispersity of about 2 was used as the crystallizing minor component. Two series of model blends, MB-50K/MB-250K and MB-100K/MB-250K, each containing weight ratios of 100/0, 97/3, 95/5, and 90/10, were prepared by solution blending to ensure thorough mixing at the molecular level. At the chosen shear conditions (rate = 60 s-1, duration = 5 s, T = 120 °C), while no flow-induced structures were seen in pure MB-50K and MB-100K melts, the blends in both series showed distinct but different shear-induced structures. Results indicate that the high molecular weight component dominates the formation of crystallization precursor structures in the blend under shear, which can act as a template for further crystallization. A “shish-kebab” structure, detected by both SAXS and WAXD, was observed in the MB-100K/MB-250K (90/10) blend, while only a twisted lamellar structure (kebab) was seen in the rest of the blends under the same shear conditions. These findings suggest that the matrix viscosity plays an important role to influence the formation of crystallization precursor structure of the high molecular component under flow. In the MB-100K/MB-250K (90/10) blend, the length of the shish was estimated from the equatorial streak in SAXS, which showed a noticeable decrease with time, while the corresponding scattering intensity was found to increase. The evolution of the shish-kebab structure from SAXS is consistent with the appearance of the (110) peak in WAXD, which can be explained by the coil−stretch transition induced by flow.

Neutron reflectometry is used to measure polymer mobility over distances less than 200 Å as a function of distance from an attractive solid surface and molecular size. Effective diffusion coefficients, D eff , are determined from the rates of interdiffusion between supported bilayers of deuterated and hydrogenated poly(methyl methacrylate) (PMMA). The thickness of the d-PMMA layer is varied from less than the radius of gyration, R g , of the bulk polymer to 11R g for three molecular weight pairs of polymers. D eff dramatically decreases in samples with d-PMMA layers less than 3R g thick and approaches bulk interdiffusion rates from layers greater than 5R g thick.

Using in situ small-angle X-ray scattering, the electric field induced orientation in a block copolymer having a cylindrical microdomain morphology was investigated. Studies were performed with the copolymer in different initial states. Beginning with a disordered copolymer, composition fluctuations are oriented by the electric field. Following cooling across the disorder-to-order-transition, microdomains are oriented parallel to the applied field. Beginning with a microphase-separated copolymer where the microdomains are oriented normal to the field, the domain orientation becomes unstable at high field strengths, and the microdomains reorient in a piecewise manner.