Several naturally occurring biological systems, such as bones, nacre or wood, display hierarchical architectures with a central role of the nanostructuration that allows reaching amazing properties such as high strength and toughness. Developing such architectures in man-made materials is highly challenging, and recent research relies on this concept of hierarchical structures to design high-performance composite materials. This review deals more specifically with the development of hierarchical fibres by the deposition of nano-objects at their surface to tailor the fibre/matrix interphase in (bio)composites. Fully synthetic hierarchical fibre reinforced composites are described, and the potential of hierarchical fibres is discussed for the development of sustainable biocomposite materials with enhanced structural performance. Based on various surface, microstructural and mechanical characterizations, this review highlights that nano-objects coated on natural fibres (carbon nanotubes, ZnO nanowires, nanocelluloses) can improve the load transfer and interfacial adhesion between the matrix and the fibres, and the resulting mechanical performances of biocomposites. Indeed, the surface topography of the fibres is modified with higher roughness and specific surface area, implying increased mechanical interlocking with the matrix. As a result, the interfacial shear strength (IFSS) between fibres and polymer matrices is enhanced, and failure mechanisms can be modified with a crack propagation occurring through a zig-zag path along interphases.

Green treatment of natural fibres is a major issue in paper, textile and biocomposites industries to design innovative and eco-friendly products. In this work, hierarchical structuring of flax woven fabrics by the adsorption of xyloglucan (XG) and cellulose nanocrystals (CNC) is studied. Indeed, CNC have high mechanical properties, high specific surface area and great potential for functionalization. The adsorption of XG and CNC has been investigated in terms of localization by confocal and scanning electron microscopy (SEM) and quantification through adsorption isotherms. Adhesion force measurements have also been performed by Atomic Force Microscopy (AFM). XG and CNC are homogeneously adsorbed on flax fabric and adsorption isotherms reach plateau values around 20 mg /g fibres for both. The pre-adsorption of XG on flax fabric influences the amount of adsorbed CNC in the high concentrations and also creates entanglements and strong interactions between XG and CNC with the formation of an extensible network.