Mid Sweden University

Cellulose nanofibrils (CNFs) assemble into water-resilient materials in the presence of multivalent counter-ions. The essential mechanisms behind these assemblies are ion–ion correlation and specific ion effects. A network model shows that the interfibril attraction indirectly influences the wet modulus by a fourth power relationship to the solidity of the network ($E_w \propto \varphi^4$). Ions that induce both ion–ion correlation and specific ion effects significantly reduce the swelling of the films, and due to the nonlinear relationship dramatically increase the wet modulus. Herein, this network model is used to explain the elastoplastic behavior of wet films of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized, carboxymethylated, and phosphorylated CNFs in the presence of different counter-ions. The main findings are that the aspect ratio of the CNFs influences the ductility of the assemblies, that the bivalency of phosphorylate ligands probably limits the formation of interfibril complexes with divalent ions, and that a higher charge density increases the friction between fibrils by increasing the short-range attraction from ion–ion correlation and specific ion effects. These findings can be used to rationally design CNF materials for a variety of applications where wet strength, ductility, and transparency are important, such as biomaterials or substrates for bioelectronics.