Engineering of lignin in wood towards functional materials

Sammanfattning: Through 270 million years of evolution, the finely tuned hierarchical structure of wood has been optimized for efficient nutrient transport and exceptional mechanical stability. Its distinctive orthotropic constitution can provide inspiration and design opportunities for the development of novel functional materials. In recent years, top-down modification approaches have adapted the wood structure for innovative applications, utilizing the hierarchical arrangement at different length scales. In doing so, preserving the structural integrity is of the essence.This thesis explores new top-down modification techniques for the functionalization and structural control of wood-based materials. With the intent of better preserving and utilizing the natural wood organization and native components, two different modification routes were explored on softwood Scots pine: complete lignin removal and in-situ lignin modification. Complete delignification was achieved through preventive crosslinking of the polysaccharide matrix, enhancing intercellular adhesion between tracheids and preventing the disintegration of the cellular arrangement after lignin removal. The second approach focused on chemical modification of lignin by sulfonation as an alternative to complete lignin removal, resulting in wood templates of high negative charge up to 375 µmol g-1 and with well-preserved residual lignin. Hot compression of the delignified wood veneers produced thin wood films with high optical transmittance of 71 % alongside exceptional tensile strength of 449 MPa and Young’s modulus of 50 GPa. Densification of lignin-retaining wood veneers yielded strong and transparent thin films with UV blocking ability. Additionally, these densified films could be easily recycled into discrete wood fibers. The integration of conductive polymers including poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and polypyrrole in in-situ sulfonated wood resulted in bio-composites with high conductivity up to 203 S m-1 and high pseudo-capacitance up to 38 mF cm-2, indicating that tailoring the wood chemistry and activating the redox activity of lignin by sulfonation are important strategies for the fabrication of composites with potential for sustainable energy applications. By tailoring both wood chemistry and morphology, a wood foam with unique microstructure, enhanced permeability, along with high ultimate strength of 9 MPa and Young’s modulus of 364 MPa was obtained. When combined with the conductive polymer PEDOT:PSS, the composite demonstrated uniform conductivity of 215 S m-1 and mechanoresponsive electrical resistance, showing promise in sensing and mechanoresponsive devices.Therefore, in-situ engineering of lignin proved to be a versatile toolkit to obtain wood templates of improved permeability and porosity, greater compliance to densification, and enhanced compatibility with conductive polymers.