LAUSR

Abstract Terahertz time-domain spectroscopy (THz-TDS), which has been proved to show promising application in complex polymer systems, was employed to investigate the polymorphism phenomenon and crystal transformation of polylactide (PLA) in this study. The THz-TDS shows sensitive response on the crystal structure. The α' -form, α -form and stereocomplex crystals exhibit absorption peaks of lattice vibration at 1.82, 2.01 and 2.09 THz, respectively. THz-TDS has no direct chirality identification on the difference between poly ( d -lactide) (PDLA) and poly( l -lactide) (PLLA). However, the PLA stereocomplex shows an extra and distinctive absorption peak at 1.43 THz compared with homo-PLA, and the peak was proved to be stemmed from the collective vibration of L-lactic unit and D-lactic unit pairs connecting by hydrogen bonds. This is the first time that THz-TDS has been proved to be of great potential in identification of polymer stereocomplex crystal. Also, the α' → α crystal transformation of PLA were intuitively investigated at 120 °C using THz-TDS, while the transformation rate was quite slow.