Complex melting of semi-crystalline chicory (Cichorium intybus L.) root inulin

Abstract When concentrated solutions (30–45% by weight) of inulin (degree of polymerization 2–66, number average degree of polymerization 12) are cooled at 1 °C/min or 0.25 °C/min from 96 °C to 20 °C, suspensions of semi-crystalline material in water are formed. A thermal nucleation process was detected by optical microscopy: the 8-like shaped crystallites resulting from primary nucleation at higher temperature are larger than those resulting from secondary nucleation at lower temperature. Differential scanning calorimetry (DSC) thermograms display melting profiles with three to four partly overlapping endotherms that vary as a function of concentration, cooling rate during crystallization and storage time at 25 °C of the crystallite suspension. Recrystallization during melting was observed. The wide-angle X-ray scattering patterns of the samples at 25 °C correspond to those of the hydrated crystal polymorph. The structural changes during melting indicated the existence of a single crystal polymorph throughout melting. A periodicity of 95 A, arising from alternating regions of different electron density, is detected in the small angle X-ray scattering patterns at 25 °C. The stepwise increase of the long period upon heating is related to the existence of two types of lamellar stacks: one with a higher long period, resulting from the primary nucleation and thus crystallized at high temperature, and a second one with a smaller long period, formed by crystallization at lower temperature. The lamellae formed at low temperature melt at a lower temperature than those formed at high temperature, explaining the existence of the two DSC-endotherms.