ABSTRACT
Wood is increasingly considered in sustainable structural materials development due to its hierarchical structure, including an oriented reinforcing cellulose phase combined with carbon capturing and renewability. Top-down manufacturing techniques can provide direct access to this hierarchical cellulose scaffold for use in new functional materials. For high-performance load-bearing wood-based materials, the volume content of the reinforcing phase needs to be increased to much higher fiber volume contents (FVCs). This has been achieved by structure-retaining delignification followed by densification. The obtained matrix-free materials possess high tensile stiffness due to preservation of hierarchical fiber alignment; however, they demonstrate low mechanical properties in bending and cannot be used in moist conditions due to their propensity for water absorption. In order to address these two challenges, an interpenetrating wood polymer phase composite is developed using a delignified wood scaffold as a continuous reinforcing phase and epoxy resin as the interconnected matrix phase. We utilize the continuous flow channels in delignified wood for vacuum-assisted matrix infiltration in a condition of open continuous porosity in the wood scaffold. Prior to matrix curing, the material is densified in order to increase the FVC, decrease porosity, and reduce density variations in the wood scaffold. Due to the compressibility of delignified cellulose fibers, interpenetrating phase composites (IPCs) with very high FVCs of up to 80% could be produced, leading to exceptionally high tensile stiffness and strength of up to 70 GPa and 600 MPa. The obtained stiffness values far exceed the upper limit of the rule of mixtures due to an enhanced stress transfer through mechanically interlocked fiber-fiber interfaces combined with the stiffness providing matrix phase that further aids stress transfer between neighboring wood cells via their pits. This new approach paves the way for an efficient production of high-performance sustainable materials that can be used as alternative for glass fiber reinforced composites or natural fiber composites.
ABSTRACT
The hierarchical structure of wood is composed of a cellulose skeleton of high structural order at various length scales. At the nanoscale and microscale the specific structural features of the cells and cell walls result in a lightweight structure with an anisotropic material profile of excellent mechanical performance. By being able to specifically functionalize wood at the level of cell and cell walls one can insert new properties and inevitably upscale them along the intrinsic hierarchical structure, to a level of large-scale engineering materials applications. For this purpose, however, precise control of the spatial distribution of the modifying substances in the complex wood structure is needed. Here we demonstrate a method to insert methacryl groups into wood cell walls using two different chemistry routes. By using these methacryl groups as the anchor points for grafting, various polymers can be inserted into the wood structure. Strikingly, depending on the methacryl precursor, the spatial distribution of the polymer differs strongly. As a proof of concept we grafted polystyrene as a model compound in the second modification step. In the case of methacryloyl chloride the polymer was located mainly at the interface between the cell lumina and the cell wall covering the inner surface of the cells and being traceable up to 2-3 µm in the cell wall, whereas in the case of methacrylic anhydride the polymer was located inside the whole cell wall. Scanning electron microscopy, Fourier transform infrared spectroscopy and especially Raman spectroscopy were used for an in-depth analysis of the modified wood at the cell wall level.
