No abstract

Melt‐crystallized films of poly(L‐lactic acid) (PLLA) with Mv in the range of 3.8 ∼ 46 × 104 consisting of α‐form crystals were uniaxially drawn by solid‐state coextrusion. The effects of Mv, extrusion draw ratio (EDR), and extrusion temperature (Text) on the crystal/crystal transformation from α‐ to β‐form crystals and the resultant tensile properties of drawn products were studied. The crystal transformation proceeded with EDR and more rapidly for the higher Mv's. Furthermore, the crystal transformation proceeded most rapidly with EDR at a Text around 130 °C, independently of the Mv's. As a result of the optimum combination of processing variables influencing the the crystal transformation (Mv, Text, and drawability), highly oriented films consisting of β‐form crystals alone were obtained by coextrusion of higher Mv samples at Text's slightly below the melting temperature (150 ∼ 170 °C) and at higher EDR's > 11. Both the tensile modulus and strength increased rapidly with EDR. The modulus at a given EDR was slightly higher for the samples with higher Mv's. In contrast, the strength at a given EDR was remarkably higher for the higher M v's. The highest tensile modulus of 8.0 GPa and strength of 500 MPa were obtained with the sample of the highest Mv of 46 × 104 coextruded at 170 °C to the highest EDR of 14.

Morphology and molecular structure of three nascent ultra high molecular weight polyethylene (UHMWPE) powders synthesized on unsupported and supported Ziegler-Natta heterogeneous catalysts were studied with the help of electron microscopy and infrared (IR) spectroscopy. A synthesis was carried out in a slurry process in n-heptane at a temperature of about 70°C, which resulted in production of UHMWPE of one and the same molecular weight, approaching 10 6 g/mol. The morphology of the nascent particles dramatically differed, however, which is evidence of the important role of the catalytic system used. Nascent particles synthesized on unsupported TiCl 4 catalyst with EtAl as the cocatalyst had a globular structure, while those synthesized on supported TiCl 4 /Al 2 O 3 ؒSiO 2 and TiCl 3 ؒ0.3 AlCl 3 /MgCl 2 Ziegler-Natta catalysts with the same cocatalyst demonstrated fibrillar (cobweb) and spiral (wormlike) structures, respectively. As revealed by IR spectroscopy, there was a significant difference in the nature of the crystalline regions formed during the synthesis/crystallization process; in the amount of short trans sequences not included in crystallites (taut tie molecules); in the content of irregular conformers of various types, including typical point de-*Dedicated to Prof. Francisco J. Baltá Calleja on the occasion of his 65th 814 IVAN'KOVA ET AL.fects 2G1 kinks; and so on. The melt-crystallized films produced from the investigated reactor powders were markedly distinguished by their drawability and by the existence and the amount of different molecular conformations despite a sufficiently high recrystallization temperature and prolonged preheating. The difference in molecular structure of the drawn films was retained in a whole range of draw ratios. It is concluded that there is a well-pronounced "memory effect" and the morphology of the original nascent particles depending on the catalyst/synthesis conditions clearly play a role in the properties of the end product.

No abstract