Nucleating and Plasticization Effects in Drawn Poly(Lactic Acid) Fiber during Accelerated Weathering Degradation

Changes in the polymer properties of poly(lactic acid) (PLA) fibers during drawing and degradation processes were analyzed using solid-state NMR, with the goal of elucidating morphological changes that influence fiber tensile properties. Combination of X-ray diffraction (XRD) and differential scanning calorimeter (DSC) indicated that the drawn PLA fibers consisted of different proportions of α crystalline and amorphous forms. ¹³C CP-MAS NMR spectra showed amorphous-like broad singlet signals, of which the full width at half maximum (FWHM) decreased with increasing crystallinity and crystal orientation. The T₁H value decreased by interaction with additives and increased with increasing crystal orientation. The interaction with additives also reduced T₁C values, which increased with increasing crystallinity. Use of organic clay enhanced the crystallization of high draw-ratio PLA fibers due to nucleation, which increased tensile strength; this effect gradually decreased with time during accelerated weathering. In contrast, the plasticization due to the addition of flexible polymers increased fiber elongation, which rapidly dropped during the degradation. Changes of FWHM, T₁H, and T₁C values indicated that the degradation occurred at sites within the amorphous portions of the PLA fibers containing organic clay, while the flexible polymers were preferentially degraded if they were present in the PLA fibers.