Structure and surface nanomechanics of poly(l-lactide) from thermally induced phase separation process

The surface morphology, crystalline structure and nanomechanical properties of poly( l -lactide) (PLLA) samples prepared via thermally induced phase separation (TIPS) process have been investigated by scanning electron microscopy (SEM), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), wide-angle X-ray diffraction (WAXD), atomic force microscopy (AFM), force spectroscopy and nanoindentation. Typical nanofibrous scaffold was obtained at −24 °C (NF sample) while a denser matrix with some plateletlike structure was obtained at 15 °C (PL sample). The NF sample has a higher crystallinity with α′-form crystals while the PL sample has α-form crystals embedded in a largely amorphous matrix. The two kinds of samples have differences in the chain conformation with a more restricted backbone vibration and stiffened segmental motion in NF samples. The NF samples have a higher adhesion force although both samples showed a heterogeneous distribution of adhesion force on the surface based on force spectroscopy analysis. The alternating distribution of domains with higher and lower adhesion force exhibited a banded pattern on PLLA nanofibre. This pattern is proposed to reflect the distribution of crystal-rich and amorphous-rich domains in the semicrystalline samples. AFM-based nanoindentation test indicated that the nanofibrous NF samples can have more significant plastic deformation and creep than the largely amorphous PL samples. The sliding of the crystal-rich domains along the fibrils would account for this increased plasticity of the nanofiber.