The synthetic freedom to operate is highly dependent on the final application. In polymer science, scalable reactions, simple purification, and the ideal use of renewable and relevant precursors are relied on. This work explores the ring-opening of oxiranes with acrylic acid (AA) toward β-hydroxy acrylates; great care is given to the synthetic aspects of the transformation. In addition to its simplicity, and high yield (isolated yield 68%–87%), the methodology is scalable, atom-economic, and associated with simple purification. Dependent on the initial oxirane, access to a wide range of polymeric properties with a modulus ranging from 0.3 to 630 MPa, strength from 0.3 to 19 MPa, and elongation-at-break from 3% to 170% is demonstrated. All four polymers explored are thermally stable above 250 °C and highly transparent. This work emphasizes the potential of AA as a nucleophile for direct access to monomers for a wide range of polymer applications.

The cradle-to-cradle philosophy is desirable for semi-structural cellulose biocomposites. Selective chemical recycling of a thermoset matrix back to reusable monomers was realized while avoiding cellulose fiber degradation. A fully biosourced, PLA-based (polylactic acid) thermoset polymer was molecularly designed for chemical recycling and for curing in chemically heterogeneous plant fiber networks. Curing was by stepwise polymerization of 4-arm functional prepolymers of PLA in a cellulosic wood fiber network of high fiber content. FT-IR data supported covalent fiber/matrix interface bonding. These eco-friendly biocomposites showed high modulus (24 GPa) and high optical transmittance. The matrix was selectively degraded back to the initial building block, lactic acid monomer, under alkali conditions. This progressed without apparent damage to the cellulosic fibers. The green metrics of the synthesis showed strong potential for this material concept in a circular economy.

Translucent wood fiber composites offer new functions to stiff composites. Most "eco-friendly" thermoset resins are only partially biobased. Poly(limonene acrylate), PLIMA, can be fully biobased and is combined with hot-pressed softwood fibers (WF) by liquid resin impregnation and curing. Fibers are random-in-plane or strongly oriented and have different lignin characteristics. Microstructure-mechanical property relationships are compared for hot-pressed WF networks and WF/PLIMA biocomposites from the same fibers. Stress transfer in WF/PLIMA biocomposites is enhanced with a modulus of up to 16.7 GPa and a tensile strength of up to 139 MPa, compared to transparent plastics like poly(methyl methacrylate) (modulus similar to 3 GPa, tensile strength similar to 70 MPa). Optical transmittance is high, even at 35 vol % fiber content, suggesting translucent panels or lighting applications. Eco-indicators show that the PLIMA matrix accounts for similar to 80% of biocomposite cumulative energy demand (CED, cradle to gate) of 60 MJ/kg, compared to similar to 120 MJ/kg for glass fiber/thermoset composites.

Increased use of multi-phase, wood-based biocomposites may contribute to sustainable development. The porous microstructure offers unique possibilities for modification, but global properties are often predicted based on simplified unit cells and homogenization. For materials design, simulations based on complex 3D microstructures with statistical variability are alternatives to better understanding physical properties. Parametric models are developed in a distortion-map-based method to represent 3D wood microstructures. Basic structures of uniform tubular cells and other features are generated followed by distortion mapping. These maps are highly adaptable and can generate realistic features and variability. Fibers, vessels, and ray cells are realistically distributed. The models are realistic, versatile, and scalable, as well as can be used to simulate the mechanical, optical, and hydrodynamic properties of complex composites. The model is promising for generating large sets of data to train deep learning networks for multi-physics research.

Transparent wood composites (TWs) offer the possibility of unique coloration effects. A colored transparent wood composite (C-TW) with enhanced fire retardancy was impregnated by metal ion solutions, followed by methyl methacrylate (MMA) impregnation and polymerization. Bleached birch wood with a preserved hierarchical structure acted as a host for metal ions. Cobalt, nickel, copper, and iron metal salts were used. The location and distribution of metal ions in C-TW as well as the mechanical performance, optical properties, and fire retardancy were investigated. The C-TW coloration is tunable by controlling the metal ion species and concentration. The metal ions reduced heat release rates and limited the production of smoke during forced combustion tests. The potential for scaled-up production was verified by fabricating samples with a dimension of 180 x 100 x 1 (l x b x h) mm(3).

Abstract The sustainable development of functional energy-saving building materials is important for reducing thermal energy consumption and promoting natural indoor lighting. Phase-change materials embedded in wood-based materials are candidates for thermal energy storage. However, the renewable resource content is usually insufficient, the energy storage and mechanical properties are poor, and the sustainability aspect is unexplored. Here a novel fully bio-based transparent wood (TW) biocomposite for thermal energy storage, combining excellent heat storage properties, tunable optical transmittance, and mechanical performance is introduced. A bio-based matrix based on a synthesized limonene acrylate monomer and renewable 1-dodecanol is impregnated and in situ polymerized within mesoporous wood substrates. The TW demonstrates high latent heat (89 J g?1) exceeding commercial gypsum panels, combined with thermo-responsive optical transmittance (up to 86%) and mechanical strength up to 86 MPa. The life cycle assessment shows that the bio-based TW has a 39% lower environmental impact than transparent polycarbonate panels. The bio-based TW holds great potential as scalable and sustainable transparent heat storage solution.

Transparent wood (TW) biocomposites combine high optical transmittance and good mechanical properties and can contribute to sustainable development. The safety against fire is important for building applications. Here, a "green" bleached wood reinforcement is impregnated by water soluble and flame-retardant melamine formaldehyde (MF) in a scalable process, for a wood content of 25 vol%. FE-SEM is used for characterization of optical defects and EDX to examine MF distribution at nanoscale cell wall pore space. Curing (FTIR-ATR), mechanical properties, optical transmittance (74% at 1.2 mm thickness) and flame-retardant properties are also characterized (self-extinguishing behavior and cone calorimetry), and scattering mechanisms are discussed. The fire growth rate of transparent wood was less than half the values for neat wood. Transparent wood/MF biocomposites show interesting wood-MF synergies and are of practical interest in building applications. Critical aspects of processing are analyzed for minimization of optical defects.

Design of nanocellulose-based composite materials suitable for selective disintegration, recovery and recycling of individual components is of great scientific and technical interest. Cellulose nanofiber/epoxy (CNF/EP) composites are candidate bio-based substitutes for petroleum-based materials. However, chemical recovery of such intimately mixed nanocomposites has not been addressed, due to the limited chemical stability of nanocellulose and due to the covalently crosslinked epoxy network. In this work we develop CNF/EP composites designed for selective disintegration. Deconstruction is achieved by including two types of labile linkages to the polymer network; acetals and esters. Besides enabling recycling of the CNF reinforcement, the thermoset constituents were further depolymerized into valuable monomeric units in 63-95% yield. In addition, the preparation of both; epoxy monomers and final composite materials is performed using solely bio-derived materials and solvents. 

The optical response of hierarchical materials is convoluted, which hinders their direct study and property control. Transparent wood (TW) is an emerging biocomposite in this category, which adds optical function to the structural properties of wood. Nano- and microscale inhomogeneities in composition, structure and at interfaces strongly affect light transmission and haze. While interface manipulation can tailor TW properties, the realization of optically clear wood requires detailed understanding of light-TW interaction mechanisms. Here we show how material scattering and absorption coefficients can be extracted from a combination of experimental spectroscopic measurements and a photon diffusion model. Contributions from different length scales can thus be deciphered and quantified. It is shown that forward scattering dominates haze in TW, primarily caused by refractive index mismatch between the wood substrate and the polymer phase. Rayleigh scattering from the wood cell wall and absorption from residual lignin have minor effects on transmittance, but the former affects haze. Results provide guidance for material design of transparent hierarchical composites towards desired optical functionality; we demonstrate experimentally how transmittance and haze of TW can be controlled over a broad range.

Cellulose nanofibril (CNF) hybrid materials show great promise as sustainable alternatives to oil-based plastics owing to their abundance and renewability. Nonetheless, despite the enormous success achieved in preparing CNF hybrids at the laboratory scale, feasible implementation of these materials remains a major challenge due to the time-consuming and energy-intensive extraction and processing of CNFs. Here, we describe a scalable materials processing platform for rapid preparation (<10 min) of homogeneously distributed functional CNF-gibbsite and CNF-graphite hybrids through a pH-responsive self-assembly mechanism, followed by their application in gas barrier, flame retardancy, and energy storage materials. Incorporation of 5 wt % gibbsite results in strong, transparent, and oxygen barrier CNF-gibbsite hybrid films in 9 min. Increasing the gibbsite content to 20 wt % affords them self-extinguishing properties, while further lowering their dewatering time to 5 min. The strategy described herein also allows for the preparation of freestanding CNF-graphite hybrids (90 wt % graphite) that match the energy storage performance (330 mA h/g at low cycling rates) and processing speed (3 min dewatering) of commercial graphite anodes. Furthermore, these ecofriendly electrodes can be fully recycled, reformed, and reused while maintaining their initial performance. Overall, this versatile concept combines a green outlook with high processing speed and material performance, paving the way toward scalable processing of advanced ecofriendly hybrid materials.