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Observations of a sample of poly(ethylene-co-octene)in a polarizing optical microscope reveal peculiarities in its crystallization behavior. When cooled from the melt to a fixed crystallization temperature, at first a structure of diffuse appearance with variations on the length scale of micrometers forms rapidly. The transformation into the final semi-crystalline state then proceeds in two ways, by a continuous change of the inner structure of microm-sized objects and by the growth of spherulites. Time dependent small angle and wide angle X-ray scattering experiments corroborate the occurrence of the two crystallization mechanisms. Atomic force microscopy indicates that the change of the inner structure of the preformed objects is due to an in-filling of crystallites.

Dilatometric and X-ray scattering experiments of the crystallization kinetics of a sample of poly(ethylene-co-octene) show pronounced melt memory effects, i.e., the shapes of isotherms and characteristic times vary systematically with the temperature of the melt prior to cooling to the crystallization temperature. The temperature range of the effect is limited; crystallization kinetics remains constant below a melt temperature T(m)l and above a melt temperature T(m)h and varies only in-between. Analysis shows that the melt memory effect is caused by a variation of the characteristic time of a first order crystallization process. The process can be assigned to the in-filling of crystallites into objects of a previously generated precursor structure.

Melting points in mixtures of a crystallizable polymer with a low-molar-mass diluent depend on both, the diluent fraction and the crystal thickness. A differentiation of the two factors can be achieved by temperature-dependent SAXS experiments. A corresponding study, complemented by DSC, dilatometry, microscopy and AFM-imaging, was carried out for mixtures of a poly(ethylene-co-octene) with n-C16H34, c-C16H32 and methyl-anthracene, respectively. All diluents lead for a constant crystal thickness to melting point depressions in agreement with Raoult's law. On the other hand, the effect of the diluents on the thickness of the crystals formed at a fixed crystallization temperature varies. While in the presence of the two alkanes thicker crystals form, no effect arises for the methyl-anthracene--as was previously found for the octene-co-units. We consider these observations as a further support for our view that polymer crystallization follows a multi-stage route which includes a passage through an intermediate mesomorphic phase. Under such conditions crystal thicknesses would only be affected if the diluent is still present in the mesomorphic phase and stay invariant if the diluent molecules are already rejected when this intermediate phase forms.