| Abstract: | The effect of pressure on the melting point and volume of fusion of polyethylene was studied by high-pressure dilatometry. Starting materials were crystallized slowly from the melt under pressures of 1500, 3500, 5130 kg/cm2, and 1 atm. It has been shown that the unusual behavior observed at pressures above 4000 kg/cm2 is due to crystallization and melting of two kinds of extended-chain crystals differing in thermal stability. These are designated as ordinary extended-chain and highly extended-chain crystals, respectively. The relation between pressure P and melting temperature Tm of folded-chain, ordinary extended-chain, and highly extended-chain polyethylene was determined precisely. At pressures up to about 3000 kg/cm2, plots of P against Tm for the crystal forms have almost the same curvature and then become parallel. But at pressures above 4000 kg/cm2, ordinary extended-chain crystals show a linear increase of Tm with a constant slope of about 70 atm/deg. Curve for the highly extended-chain crystals changes in slope from 70 to 50 atm/deg at pressures between 3500 and 4300 kg/cm2, and then show a sharp increase of Tm with increasing pressure. Experiments show that the meltingpoint curve of the highly extended-chain crystals overlaps that of the ordinary extended-chain crystals at pressures below 4000 kg/cm2. Annealing experiments with folded-chain and ordinary extended-chain crystals have been made under high pressure. It is suggested that the formation of highly extended-chain crystals occurs stepwise through the formation and reorganization of ordinary extended-chain crystals from the original folded-chain crystals by a mechanism of partial melting and recrystallization at pressures above 4000 kg/cm2. |
