This paper indicates that changes in chain mobility, heat capacity, WAXS crystallinity, SAXS long period, SAXS peak intensity, specific volume and morphology as a function of increasing temperature, occur in three fairly distinct annealing ranges (I, II and III) that are more or less the same for all crystallized polymers with a lamellar morphology. It is shown that none of the proposed molecular models to date, including the well-known fold surface premelting model, can satisfactorily account for all the experimental data. However, a new molecular interpretation, based primarily on electron microscopy and SAXS studies of changes such as lateral 'melting' from edges of microparacrystallites (mPC) within the lamellae seen at the annealing temperatures can account for the data. With our new molecular interpretation, the effect of temperature increase is established to result in a slight breakup of the laterally aligned mPC within the lamellae at low annealing temperatures in range I, and selective lateral 'melting' of the exposed mPC and recrystallization at higher annealing temperatures in ranges II and III, with the recrystallization being very limited in range II1. Annealing effects seen in cold-or hot-drawn polymers with a fibrillar morphology can also be readily accounted for by this very general molecular mechanism occurring in the same annealing temperature ranges.

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The local deformation of the lamellar microstructure of isothermally melted crystallized u noriented polyethylene has been investigated using microindentation hardness (MH). The polymer can be visualized as a composite material consisting of hard and weak elements. The former, the lamellae, are considered to consist of mosaic blocks with liquidlike lattice distortions (paracrystallites). The latter are the interlamellar "amorphous" regions and the mosaic block lateral grain boundaries. The deformation mechanisms beneath the indenter are discussed in the light of current models of plastic deformation. MH is shown to depend on the packing density of the macromolecules in both phases and, as a result, it can be clearly correlated with the macroscopic density of the material. The unit cell expansion and lattice distortions increase in parallel as a consequence of increasing incorporation of chain defects within the lattice. This provokes a conspicuous decrease in the microhardness of the crystals. The increase in lattice distortions is consistent with the concurrent decrease of lamellar thickness and, hence, of the coherently diffracting lattice volume. These results unambiguously emphasize the physical significance of the mosaic block character of the lamellae in determining the micromechanical properties of the material. Finally it is shown that the strain boundary which defines the zone of crystal destruction under the indenter also depends on the average volume of the paracrystallites and on the volume fraction of crystalline material.

The surface tensions (y) of a branched polyethylene and two side-group liquid-crystalline (lc) polyacrylates were measured in the isotropic, nematic and smectic states by the pendant-drop method. The surface tension vs. temperature characteristics of the lc polyacrylates studied show anomalous behaviour. The slope in the isotropic state is initially negative but changes its sign near the isotropic-nematic transition. The increase of y with decreasing temperature is regained in the nematic phase, until at the nematic-smectic transition the surface tension of the lc polymers discontinuously jumps to higher values and shows a very low temperature coefficient. The observed features have been found to be partly in agreement with the results of surface tension measurements on low-molar-mass liquid crystals, which indicates that the surface properties of the lc polymers are governed by the mesogenic side groups.

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