Ulf Olsson

Abstract: Coagulation of cellulose solutions is a process whereby many useful materials with variable microstructures and properties can be produced. This study investigates the complexity of the phase separation that generates the structural heterogeneity of such materials. The ionic liquid, 1-ethyl-3-methylimidazolium acetate ([C₂mim][OAc]), and a co-solvent, dimethylsulfoxide (DMSO), are used to dissolve microcrystalline cellulose in concentrations from 5 to 25 wt%. The solutions are coagulated in water or 2-propanol (2PrOH). The coagulated material is then washed and solvent exchanged (water → 2PrOH → butanone → cyclohexane) in order to preserve the generated microstructures upon subsequent drying before analysis. Sweep electron microscopy images of 50 k magnification reveal open-pore fibrillar structures. The crystalline constituents of those fibrils are estimated using wide-angle X-ray spectroscopy and specific surface area data. It is found that the crystalline order or crystallite size is reduced by an increase in cellulose concentration, by the use of the co-solvent DMSO, or by the use of 2PrOH instead of water as the coagulant. Because previous theories cannot explain these trends, an alternative explanation is presented here focused on solid–liquid versus liquid–liquid phase separations. Graphical abstract: [Figure not available: see fulltext.].