Crystallization of linear polyethylene from melt in isothermal compression

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Abstract
Crystallization and primary nucleation of linear polyethylene has been studied by means of a custom‐made miniature pressure apparatus. It has been shown that during isothermal compression of linear polyethylene melt at a constant rate crystallization occurs. In the range of fastest conversion rates the crystallization assumes isobaric character. The level of pressure at which the crystallization occurs increases with the increase of the crystal‐lization temperature and/or with the increase of the compression rate. The crystallization has a spherulitic character up to the highest pressure achieved in the apparatus (approx. 600 MPa). Surprisingly, there are no dependencies of average spherulite size, degree of crystallinity, and lamellae thickness on the pressure and the temperature of crystallization during melt compression, but there is a strong relation to the compression rate. Below 250 MPa and above 300 MPa the crystallization proceeds under pressure, ensuring a constant undercooling. The undercooling for the pressure above 300 MPa is approximately 10°C lower than that for the pressure below 250 MPa. For the pressure 250–300 MPa a change in a primary nucleation and spherulite crystallization has been observed that is connected with the transformation from orthorhombic to pseudohexagonal symmetry of crystals. No noticeable effect of molecular weight of linear polyethylene on crystallization during iso‐thermal melt compression has been observed.