Understanding nanoscale moisture interactions is fundamental to most applications of wood, including cellulosic nanomaterials with tailored properties. By combining X-ray scattering experiments with molecular simulations and taking advantage of computed scattering, we studied the moisture-induced changes in cellulose microfibril bundles of softwood secondary cell walls. Our models reproduced the most important experimentally observed changes in diffraction peak locations and widths and gave new insights into their interpretation. We found that changes in the packing of microfibrils dominate at moisture contents above 10-15%, whereas deformations in cellulose crystallites take place closer to the dry state. Fibrillar aggregation is a significant source of drying-related changes in the interior of the microfibrils. Our results corroborate the fundamental role of nanoscale phenomena in the swelling behavior and properties of wood-based materials and promote their utilization in nanomaterials development. Simulation-assisted scattering analysis proved an efficient tool for advancing the nanoscale characterization of cellulosic materials.
Keywords: Cell wall nanostructure; Cellulose crystallinity; Molecular dynamics; Wood-water interactions; X-ray scattering.