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In this study, Fourier transform infrared spectroscopy, synchrotron small-angle and wide-angle X-ray scattering were employed to reveal the underlying mechanism leading to conformational reorganization during mesomorphic-monoclinic phase transition. Results indicated that conformation reorganization occurred from 50 to 130 °C, evidenced by conformational infrared bands at 800 and 841 cm −1 . The conformation reorganization led to an immediate increase in the density fluctuation but not induced phase transition immediately. Only when the long period started to increase quickly from 80 °C, can phase transition occur. This indicated that intrachain conformational ordering occurred prior to crystalline ordering. Moreover, temperature dependence of long period changed before and after phase transition, implying that chain sliding was the main driven force for the phase transition rather than rewinding and translation of single stems. With the new information obtained, a two-step model for phase transition was proposed. Within a single-chain bundle, two adjacent helices with opposite handedness can interlock into double helices with higher density, and urge each other extending to entire stem during moving along opposite directions with the help of chain slipping, resulting in ordered arrangement of helical stems. Afterwards, single-chain clusters coalesce, leading to interchain crystalline ordering. The new model is helpful to understand the phenomena related to mesomorphic iPP. [ABSTRACT FROM AUTHOR]

Abstract: In this work extension induced crystallization of end-linked polyethylene oxide (PEO) network was investigated with in-situ small angle X-ray scattering (SAXS) and rheological measurement. The coupling between crystallinity and stress of crosslinked network makes the morphology time dependent. With a large strain the structure evolution in the stretched network is found to follow a two-stage process: i) crystals with high numerical density and small dimension form first, which laterally correlate with adjacent ones; ii) continuous melting and fusing of adjacent crystal happen after the first nucleation stage, leading to increase of crystal dimension and stability. Decreasing strain a gradual transformation to normal lamellae formation is found. Strain tuned confinement and crystallization induced confinement release is supposed to induce the structural change. [Copyright &y& Elsevier]

Abstract: With three polymers (poly(1-butene), isotactic polypropylene and syndiotactic polypropylene) as model systems, the effect of extensional strain on the nucleation rate was studied using a home-made miniature extensional rheometer and in-situ X-ray scattering. A non-monotonic correlation between nucleation rate and strain is observed around rheological yield point. Increasing strain leads to an increase in nucleation rate as expected when strain is smaller than yield strain, however, it results in a decrease in nucleation rate when strain slightly exceeds yield. We proposed that disentanglement occurs at yield point and thus decelerates flow-induced nucleation. Disentanglement provides freedom for chains to retract and leads to a dissipation of the energy initially imposed by extensional flow, which consequently weakens the effect of flow field on the enhancement of nucleation. [Copyright &y& Elsevier]