Preparation of three-dimensional cellulose objects previously swollen in a DMAc/LiCl solvent system

Abstract

Three-dimensionally shaped cellulosic objects were produced via a two-step procedure: swelling of softwood pulp (93 % cellulose; 4.5 % hemicellulose; 54 % crystallinity) in DMAc/LiCl followed by moulding. Swollen cellulose pulp in the form of gel was solidified with two different anti-solvents: distilled water and a combination of 2-propanol and deionized water. The solid cellulose material was further moulded in a custom-built prototype mould. The role of the anti-solvent was to solidify the swollen cellulose fibres and prepare mouldable solid specimens. The anti-solvent was chosen based on the following criteria, viz., recoverability, stable chemical reactivity, availability, cost and previous research in the anti-solvent area. The choice of solidification solvent had a great influence on the structure and mechanical properties of the final cellulose material. Results of different characterisation techniques showed that when the cellulose gel was washed with distilled water, it had a significantly higher number of lithium cations (ICP-MS and Raman), amorphous structure (X-ray) and lower mechanical properties (nanoindentation) compared to samples washed with a combination of 2-propanol and deionized water. An increase in viscosity as previously reported and changes in the NMR and IR spectra of DMAc upon LiCl suggested the formation of an ion-dipol complex, where lithium cations reside adjacent to the oxygen of the carbonyl group of DMAc. The formed macrocation [DMAc_n + Li]⁺ was preserved between cellulose chains in cellulose specimens washed with distilled water and had an essential role in the disruption of initial bonds, thus enhancing mouldability. Electron microscopy (FE-SEM) studies showed that the surface of cellulose after mechanochemical treatment was rough with no presence of fibres.