Elevation of flow temperature of poly(l-lactic acid) gel by controlling its morphology and crystal form

Complex crystals (ε-crystals) of poly(l-lactic acid) (PLLA) with solvents such as N,N-dimethylformamide (DMF) induce gelation of PLLA by forming fibrous structure. Three procedures to elevate the flow temperature of the PLLA gel were described: formation of an additional network by immersion of a DMF solution of PLLA with lower molecular weight, changing the crystal form from ε-crystal to α-crystal by heating the gel at 46 °C, and increasing the concentration of the solution to form the gel followed by heating. Field emission electron microscopy and X-ray diffraction measurements were carried out to elucidate the structural change and driving force of the elevation of the flow temperature. Densification of the fibrous structure and change of the crystal form from ε-crystals to α-crystals with lower solubility at higher temperatures were observed in the gel after the formation of an additional network by immersion in a DMF solution of PLLA. The procedure to elevate the flow temperature, which has been developed in this study, can broaden the application of PLLA gels.