The assembly of nature-based nanomaterials into complex architectures is both a design principle of biological composites, e.g., wood and nacre with outstanding properties and a promising route for developing functional macroscopic materials. This thesis aims to investigate and understand the colloidal and self-assembly behaviour of nanocellulose in aqueous dispersions. Moreover, composite films of nanocellulose and nanoclay/lignin with diverse functionalities, e.g., mechanical and optical properties, are fabricated by tailoring the electrostatic interactions of these building blocks.

The evaporation induced assembly of sulfonated cellulose nanocrystal (CNC) has been followed in either an aqueous droplet on substrates or a levitated droplet by real-time small angle X-ray scattering. The evolution of structural features, e.g., an isotropic phase, biphasic phase, fully liquid crystalline and contracted helical structures of drying CNC dispersions were related to the power-law scaling of the particle separation distance (d) with concentrations (c, from 1 vol% to 38 vol%). Below 2 vol%, CNC dispersions consolidated isotropically with a scaling of d ∝ c^-1/3, while the fully cholesteric liquid crystalline phase showed a unidimensional contraction of the nematic structure (d ∝ c^-1) with increasing concentrations. Competition between gelation and the ordered assembly of CNC was quantitatively evaluated in nanoscale for the first time, which was reflected by a scaling of d ∝ c^-2/3.

The rheology of composite dispersions of carboxylated cellulose nanofibril (CNF) and nanoclay was investigated, which was influenced by the surface charge of CNF, the morphology of nanoclays and interactions between CNF and clay particles. Optically transparent films of synthetic aminoclay (50 wt%) and CNF were fabricated, of which tensile strength and strain to failure (205 MPa and 7.5%) were significantly higher than those of nacre and other nacre-mimicking nanocellulose-based materials, e.g., montmorillonite-CNF films, due to the formation of ionic bonding between the cationic clay and anionic CNF.

Lignin nanoparticles were testified to enhance the colloidal stability and dispersity of carboxylated CNF in dispersions, and showed a remarkable strengthening and stiffening effect on the matrix of CNF. The mechanical properties of lignin-CNF films were superior to previously reported polymer/nanoparticle-CNF composites, such as polyvinyl alcohol-CNF films and even reduced graphene oxide-CNF films.