Abstract
The paper addresses the crystallization behavior of homogeneous branched polyethylenes, where the branches cannot be incorporated within the lattice. The polymer was chosen to investigate the morphology achievable by polymers where the chains cannot extend, which is considered to be a requisite to minimize the surface free energy. Pressure−temperature conditions similar to those necessary to form extended chain crystals in linear polyethylenes are applied. In-situ wide-angle X-ray diffraction and Raman spectroscopy are used to follow the structural and conformational changes during crystallization. The hexagonal phase is not observed in these polymers unlike in linear polyethylene. However, crystallization at elevated pressures results in a structural organization of the interphase and the fold surface; this provides adjacent reentry, where the branches will also possess structural order. Crystallization of these components leads to the formation of an incompressible open-orthorhombic phase (a = 7.56 A, b...
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