Preparation of oriented β-form poly(L-lactic acid) by solid-state extrusion

• Published in: Journal of polymer science. Part B, Polymer physics Polymer physics, 2002-01, Vol.40 (1), p.95-104
• Main Authors: Sawai, Daisuke, Takahashi, Kazuyo, Imamura, Toshiyuki, Nakamura, Koh, Kanamoto, Tetsuo, Hyon, Suong-Hyu
• Format: Article
• Language: English
• Subjects: Applied sciences; Biopolymers; Crystal orientation; crystal transformation; Crystallization; deformation profiles; Differential scanning calorimetry; Exact sciences and technology; Extrusion; formation of β-form crystals; High pressure effects; Machinery and processing; Melting; Miscellaneous; Molecular weight; Plastics; poly(L-lactic acid); Polycrystalline materials; Polymer industry, paints, wood; Shear deformation; solid-state extrusion; solid-state structure; Technology of polymers
• ISSN: 0887-6266; 1099-0488
• DOI: 10.1002/polb.10076

Melt‐crystallized, low molecular weight poly(L‐lactic acid) (PLLA) consisting of α crystals was uniaxially drawn by solid‐state extrusion at an extrusion temperature (Text) of 130–170 °C. A series of extrusion‐drawn samples were prepared at an optimum Text value of 170 °C, slightly below the melting temperature (Tm) of α crystals (∼180 °C). The drawn products were characterized by deformation flow profiles, differential scanning calorimetry (DSC) melting thermograms, wide‐angle X‐ray scattering (WAXD), and small‐angle X‐ray scattering as a function of the extrusion draw ratio (EDR). The deformation mode in the solid‐state extrusion of semicrystalline PLLA was more variable and complex than that in the extensional deformation expected in tensile drawing, which generally gave a mixture of α and β crystals. The deformation profile was extensional at a low EDR and transformed to a parabolic shear pattern at a higher EDR. At a given EDR, the central portion of an extrudate showed extensional deformation and the shear component became progressively more significant, moving from the center to the surface region. The WAXD intensities of the (0010)α and (003)β reflections on the meridian as well as the DSC melting thermograms showed that the crystal transformation from the initial α form to the oriented β form proceeded rapidly with increasing EDR at an EDR greater than 4. Furthermore, WAXD showed that the crystal transformation proceeded slightly more rapidly at the sheath region than at the core region. This fact, combined with the deformation profiles (shear at the sheath and extensional at the core), indicated that the crystal transformation was promoted by shear deformation under a high pressure rather than by extensional deformation. Thus, a highly oriented rod consisting of only β crystals was obtained by solid‐state extrusion of melt‐crystallized, low molecular weight PLLA slightly below Tm. The structure and properties of the α‐ and β‐form crystals were also studied. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 95–104, 2002