Abstract
Blends of poly(ethylene oxide) (PEO) and poly(methyl acrylate) (PMA) as well as the respective diblock copolymers PEO-b-PMA form a homogeneous melt and undergo crystallization of PEO upon cooling. Although an identical PEO (Mn = 5000 g/mol) is used in blends and diblock copolymers, crystallization and melting behavior at comparable PMA contents differs strongly as revealed by temperature-resolved small-angle X-ray scattering (TR-SAXS) and differential scanning calorimetry (DSC) measurements. After isothermal crystallization, PEO lamellae in the blends thicken during heating from once-folded to extended chain crystals prior to melting as revealed by TR-SAXS. Contrarily, in PEO-b-PMA a thickening to extended chain lamellae is impossible when the PMA block exceeds an Mn of about 3000 g/mol. This behavior is caused by a balance between the tendency of the crystallizable block to form extended chain crystals, the tendency of the noncrystallizable chains to adopt a maximum in conformational entropy, and the spa...
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