Conformational and microstructural characteristics of poly(L-lactide) during glass transition and physical aging

The glass transition and physical aging processes of poly(L-lactide) (PLLA) were studied by variable-temperature Fourier transform infrared (FTIR) spectroscopy and (13)C solid-state NMR spectroscopy. The glass transition temperature (T(g)) of PLLA can be well determined from the temperature-dependent FTIR intensity. Nearby T(g), a distinct change in the slope of spectral intensity versus temperature plot is detected. FTIR results suggest that the energy-favorable gauche-trans (gt) conformers rearrange into the less energy-favorable gauche-gauche (gg) counterparts with heating over the glass transition region, which becomes more distinct at temperature above T(g). Besides, the 1267 cm(-1) band, which shows different trends of variation from the other bands upon heating, was assigned to be more sensitive to the nu(as)(C-O-C)+delta(CH) vibration mode of the less energy-favorable gg conformers in PLLA. By comparing the FTIR spectra of the aged and deaged PLLA, it was demonstrated that the rearrangement from the high- to low-energy conformers, i.e., gg to gt, occurs with physical aging. (13)C spin-lattice relaxation measurements indicate that the relaxation rate distribution broadens with aging, which agrees with the previous suggestion that the locally ordered domains are formed during physical aging. Because of the larger variation in the conformational state and microstructure, the FTIR intensities vary much more abruptly for the aged sample with heating to nearby T(g).