Chemical modification of regenerated cellulose fibres by cellulose nano-crystals: Towards hierarchical structure for structural composites reinforcement

A simple and innovative new route, with less negative impact on the environment, for depositing and hope-grafting cellulose nano-crystals onto the surface of regenerated cellulose fibres (Cordenka 700 Super 3), using γ-methacryloxypropyltrimethoxysilane as coupling agent, is presented. Hierarchical cellulosic structure involving micro-scale fibres and nano-scale cellulose crystal network was created as verified by the scanning electron microscopy. The fibres were initially oxidised by optimized concentration of cerium ammonium nitrate to generate radicals on the cellulose backbone in order to polymerize the coupling agent at the surface. Infrared spectroscopy and scanning electron microscopy confirmed the chemical polymerisation of MPS onto regenerated cellulose fibres without enabling to show the chemical bonding between silane and nano-crystals. However, tensile test which was performed to study the impact of different treatments on mechanical properties of regenerated cellulose fibres, revealed that the modification by silane decreased the stiffness and strength of fibres (22% and 10% decrease, respectively) while the strain at failure was increased. These changes were attributed to the treatment conditions which may have induced the disorder and the misalignment of the structure of cellulose fibres (e.g. axial orientation of molecular chains and crystalline phase of the fibre has been reduced). This assumption is supported by the results from successive loading-unloading test of the fibre bundle. However, after depositing cellulose nano-crystals onto the fibre's surface, the stiffness was recovered (20% increase in comparison to MPS treated fibres) while the strength and strain at failure remained at the same order of magnitude as for fibres treated only by the coupling agent.