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Smectic–Smectic Phase Segregation Occurring in Binary Mixtures of Long and Short Rigid-Rod Helical Polysilanes

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Small-angle X-ray scattering and atomic force microscopy were used to observe smectic–smectic phase segregation in binary mixtures of rigid-rod-like helical poly[n-decyl-(S)-2-methylbutylsilane] (PDMS) polymers with molecular-weight ratios of 4.82 and narrow… Click to show full abstract

Small-angle X-ray scattering and atomic force microscopy were used to observe smectic–smectic phase segregation in binary mixtures of rigid-rod-like helical poly[n-decyl-(S)-2-methylbutylsilane] (PDMS) polymers with molecular-weight ratios of 4.82 and narrow molecular-weight distributions. Phase segregation is attributed to entropic effects as the homopolymers in the binary mixture differ only in molecular weight. Entropy-driven segregation in smectic phases was theoretically predicted in mixtures of rodlike particles with different lengths under high pressure. Binary mixtures of long and short PDMS with broader molecular-weight distributions, which do not form smectic phases, showed no such segregation, verifying that the driving force for segregation is the entropy gained through smectic-phase formation. The binary mixture of a long PDMS with a narrow molecular-weight distribution and a short PDMS with a broad molecular-weight distribution showed segregation of each component, indicating that the entrop...

Keywords: segregation; smectic phase; phase segregation; binary mixtures; molecular weight

Journal Title: Macromolecules
Year Published: 2019

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