Crystallization of Polyethylene at Large Undercooling

Extremely fast crystallization of high-density polyethylene observed for the first time by ultrafast scanning calorimetry. In order to and random copolymers of ethylene with up to 16 mol % 1-octene was account for the inherently high crystallization rate of polyethylenes, in nonisothermal and isothermal crystallization experiments cooling rates up to 1 000 000 K/s and crystallization times as short as 10 pis, respectively, were employed. It was possible to supercool the melt of high-density polyethylene down to 57 degrees C and the melt of a random ethylene/1-octene copolymer with 16 mol % 1-octene down to 33 degrees C, without prior crystallization. At these temperatures,. the characteristic time of the primary crystallization process is of the order of magnitude of 100 mu s. Complete vitrification of the liquid would require cooling even faster than 1 000 000 K/s. Compared to the homopolymer, the cooling-rate dependence of the crystallization temperatures and the temperature dependence of the characteristic time of primary crystallization of random ethylene/1-octene copolymers both are nearly parallel shifted to lower temperatures. Fast crystallization under conditions of reduced linear crystal growth rate is possibly caused by boosting homogeneous nuclei density up to 10(27) m(-3) and urgently requires further investigation.