Crystallization and melting of inulin crystals. A small angle X-ray scattering approach (SAXS)

Abstract

Summary — Bulk crystallization of the biopolymer inulin from concentrated solutions results in the same macroscopic and microscopic morphologies as those found for synthetic polymers. Optical and electron microscopy confirm the lamellar nature of the crystals and their arrangement into stacks of lamellar crystals in superstructures like axialites and spherulites. There is evidence for the occurrence of folded chain lamellar crystals. These findings justify the attempt to explore the crystallization and melting of inulin by investigating the morphology of inulin crystals by time-resolved small angle X-ray scattering. The thickness of the lamellar crystals observed by SAXS varies with the degree of supercooling — dynamically or isothermally — as observed for synthetic polymers crystallized from the solution. The complex melting behaviour of polydisperse inulin, crystallized from the concentrated solution, as observed by DSC, and previously desribe by the present authors, can be explained by the occurrence of thin lamellae with lower thermal stability (endotherms I and II) together with thicker lamellae composed of the longer chains with a higher melting temperature (endotherms III and IV), the latter lamellae being able to thicken upon annealing by recrystallization or solid state reorganisation. The broad range of molar masses proper to the samples, the different crystallization conditions (temperature, isothermal and dynamic cooling and melting) account for fractionation and the presence of partially overlapping populations of lamellar stacks with different lc‘s and hence different thermal stabilities. The reported experiments are a basis for the exploration of the semi crystalline nature of inulin gels.