• crystallization;
  • polyolefins;
  • thermal properties


A semicrystalline ethylene-hexene copolymer (PEH) was subjected to a simple thermal treatment procedure as follows: the sample was isothermally crystallized at a certain isothermal crystallization temperature from melt, and then was quenched in liquid nitrogen. Quintuple melting peaks could be observed in heating scan of the sample by using differential scanning calorimeter (DSC). Particularly, an intriguing endothermic peak (termed as Peak 0) was found to locate at about 45 °C. The multiple melting behaviors for this semicrystalline ethylene-hexene copolymer were investigated in details by using DSC. Wide-angle X-ray diffraction (WAXD) technique was applied to examine the crystal forms to provide complementary information for interpreting the multiple melting behaviors. Convincing results indicated that Peak 0 was due to the melting of crystals formed at room temperature from the much highly branched ethylene sequences. Direct heating scans from isothermal crystallization temperature (Tc, 104–118 °C) were examined for comparison, which indicated that the multiple melting behaviors depended on isothermal crystallization temperature and time. A triple melting behavior could be observed after a relatively short isothermal crystallization time at a low Tc (104–112 °C), which could be attributed to a combination of melting of two coexistent lamellar stack populations with different lamellar thicknesses and the melting-recrystallization-remelting (mrr) event. A dual melting behavior could be observed for isothermal crystallization with both a long enough time at a low Tc and a short or long time at an intermediate Tc (114 °C), which was ascribed to two different crystal populations. At a high Tc (116–118 °C), crystallizable ethylene sequences were so few that only one single broad melting peak could be observed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2100–2115, 2008