A microphase separation transition (MST) of a thermoplastic elastomer based on soft segments of poly(tetra methylene oxide) and hard crystalline segments of poly(tetra methylene terephthalate) has been studied by means of rheological measurements, differential scanning calorimetry (DSC), and wide-angle X-ray scattering (WAXS), showing that the MST is entirely caused by melting/crystallization, and that no separate segmental mixing/demixing transition is involved. DSC and WAXS measurements show that melting starts at 190°C, leading to crystal reorganization effects up to above 200°C, and that a gradual decrease in crystallinity occurs from below 210°C up to 224°C, above which temperature no crystals are left. Rheological measurements reveal a wide MST(207-224°C) upon heating, which coincides perfectly with the melting range. From this coincidence together with the Maxwell fluid behavior directly following the MST, it is concluded that melting leads to a one-phase liquid, and that no separate segmental mixing transition occurs. Similar results are obtained upon cooling, indicating that crystallization is the driving force for phase separation and that no separate segmental demixing step precedes crystallization. The wide MST implies a large processing window over which the rheological properties change from highly elastic, with a distinct yield stress, to normal pseudoplastic, enabling application in preparation of structured blends.
