Tensile behavior and structural evolution of poly(lactic acid) monofilaments in glass transition region

A series of amorphous poly(lactic acid) (PLA) monofilaments with various D-isomer contents of 1∼9 mol% have been prepared and then elongated uniaxially at 25∼65 °C in the glass transition region. Both initial modulus and maximum strength of PLA monofilaments are appreciably decreased with increasing the temperature, especially at ∼50 °C, and they were somewhat lower for the monofilament with higher D-isomer content. Structural evolution, chain orientation, and thermal properties of PLA monofilaments drawn uniaxially with various draw ratios at 65 °C were then investigated by using wide-angle X-ray diffraction, polarized Raman spectroscopy, and differential scanning calorimetry, respectively. X-ray diffraction patterns clearly exhibited the development of chain orientation and stain-induced crystallization of the monofilaments as a function of draw ratio (DR). The dichroic ratio, a measure of the chain orientation, was quantitatively evaluated from the polarized Raman spectra. It was revealed that the dichroic ratios increased up to DR=4 and decreased slightly at DR>4 owing to the strain-induced crystallization for PLA monofilaments with D-isomer contents of 1 and 4 mol%. The glass transition and cold-crystallization temperatures of PLA monofilaments increased and decreased, respectively, with the increment of DR. The strain-induced enthalpy relaxation endothermic peak appearing in glass transition region became intense with increasing the DR.