Tailoring the Holocellulose Fiber/Acrylic Resin Composite Interface with Hydrophobic Carboxymethyl Cellulose to Enhance Optical and Mechanical Properties.

Interface engineering is essential for cellulosic fiber-reinforced polymer composites to achieve high strength and toughness. In this study, carboxymethyl cellulose (CMC) functionalized with hydrophobic quaternary ammonium ions (QAs) were utilized to modify the interface between holocellulose fibers (HF) and acrylic resin. The wet HF/CMC papers were prepared by vacuum filtration, akin to papermaking, followed by cationic ion exchange with different hydrophobic QAs. Subsequently, the modified papers were dried, impregnated with an acrylic resin monomer, and cured to produce transparent composite films. The effect of the hydrophobic QA moieties on the structure and optical and mechanical properties of the HF/CMC/acrylic resin composites were investigated. The composite film with cetyltrimethylammonium (CTA)-functionalized CMC showed high optical transmittance (87%) with low haze (43%), while the composite film with phenyltrimethylammonium (PTMA)-functionalized CMC demonstrated high Young's modulus of 7.6 GPa and high tensile strength of 180 MPa. These properties are higher than those of the composites prepared through covalent interfacial modification strategies. The results highlighted the crucial role of hydrophobic functionalized CMCs in facilitating homogeneous resin impregnation in the HF fiber network, producing a composite with enhanced interfacial adhesion strength, increased optical transparency, and mechanical strength. This facile use of hydrophobic CMCs as interfacial compatibilizers provides an energy-efficient route for preparing transparent, thin, and flexible composite films favorable in optoelectronic applications.

Acetylation of Nanocellulose: Miscibility and Reinforcement Mechanisms in Polymer Nanocomposites.

The improvement of properties in nanocomposites obtained by topochemical surface modification, e.g., acetylation, of the nanoparticles is often ascribed to improved compatibility between the nanoparticle and the matrix. It is not always clear however what is intended: specific interactions at the interface leading to increased adhesion or the miscibility between the nanoparticle and the polymer. In this work, it is demonstrated that acetylation of cellulose nanocrystals greatly improves mechanical properties of their nanocomposites with polycaprolactone. In addition, molecular dynamics simulations with a combination of potential of mean force calculations and computational alchemy are employed to analyze the surface energies between the two components. The work of adhesion between the two phases decreases with acetylation. It is discussed how acetylation can still contribute to the miscibility, which leads to a stricter use of the concept of compatibility. The integrated experimental-modeling toolbox used has wide applicability for assessing changes in the miscibility of polymer nanocomposites.

Coloration and Fire Retardancy of Transparent Wood Composites by Metal Ions.

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 × 100 × 1 (l × b × h) mm3.

Residual Strain and Nanostructural Effects during Drying of Nanocellulose/Clay Nanosheet Hybrids: Synchrotron X-ray Scattering Results.

Cellulose nanofibrils (CNF) with 2D silicate nanoplatelet reinforcement readily form multifunctional composites by vacuum-assisted self-assembly from hydrocolloidal mixtures. The final nanostructure is formed during drying. The crystalline nature of CNF and montmorillonite (MTM) made it possible to use synchrotron X-ray scattering (WAXS, SAXS) to monitor structural development during drying from water and from ethanol. Nanostructural changes in the CNF and MTM crystals were investigated. Changes in the out-of-plane orientation of CNF and MTM were determined. Residual drying strains previously predicted from theory were confirmed in both cellulose and MTM platelets due to capillary forces. The formation of tactoid platelet stacks could be followed. We propose that after filtration, the constituent nanoparticles in the swollen, solid gel already have a "fixed" location, although self-assembly and ordering processes take place during drying.

Ultrastrong Ionotronic Films Showing Electrochemical Osmotic Actuation.

A multifunctional soft material with high ionic and electrical conductivity, combined with high mechanical properties and the ability to change shape can enable bioinspired responsive devices and systems. The incorporation of all these characteristics in a single material is very challenging, as the improvement of one property tends to reduce other properties. Here, a nanocomposite film based on charged, high-aspect-ratio 1D flexible nanocellulose fibrils, and 2D Ti3 C2 Tx MXene is presented. The self-assembly process results in a stratified structure with the nanoparticles aligned in-plane, providing high ionotronic conductivity and mechanical strength, as well as large water uptake. In hydrogel form with 20 wt% liquid, the electrical conductivity is over 200 S cm-1 and the in-plane tensile strength is close to 100 MPa. This multifunctional performance results from the uniquely layered composite structure at nano- and mesoscales. A new type of electrical soft actuator is assembled where voltage as low as ±1 V resulted in osmotic effects and giant reversible out-of-plane swelling, reaching 85% strain.

Wood xerogel for fabrication of high-performance transparent wood.

Optically transparent wood has been fabricated by structure-retaining delignification of wood and subsequent infiltration of thermo- or photocurable polymer resins but still limited by the intrinsic low mesopore volume of the delignified wood. Here we report a facile approach to fabricate strong transparent wood composites using the wood xerogel which allows solvent-free infiltration of resin monomers into the wood cell wall under ambient conditions. The wood xerogel with high specific surface area (260 m2 g-1) and high mesopore volume (0.37 cm3 g-1) is prepared by evaporative drying of delignified wood comprising fibrillated cell walls at ambient pressure. The mesoporous wood xerogel is compressible in the transverse direction and provides precise control of the microstructure, wood volume fraction, and mechanical properties for the transparent wood composites without compromising the optical transmittance. Transparent wood composites of large size and high wood volume fraction (50%) are successfully prepared, demonstrating potential scalability of the method.

Transparent Wood Biocomposite of Well-Dispersed Dye Content for Fluorescence and Lasing Applications.

Aggregation-induced quenching often restricts emissive performance of optically active solid materials with embedded fluorescent dyes. Delignified and nanoporous wood readily adsorbs organic dyes and is investigated as a host material for rhodamine 6G (R6G). High concentration of R6G (>35 mM) is achieved in delignified wood without any ground-state dye aggregation. To evaluate emissive performance, a solid-state random dye laser is prepared using the dye-doped wood substrates. The performance in terms of lasing threshold and efficiency was improved with increased dye content due to the ability of delignified wood to disperse R6G.

Processing strategy for reduced energy demand of nanostructured CNF/clay composites with tailored interfaces.

Nacre-mimicking nanocomposites based on colloidal cellulose nanofibrils (CNFs) and clay nanoparticles show excellent mechanical properties, yet processing typically involves preparation of two colloids followed by a mixing step, which is time- and energy-consuming. In this study, a facile preparation method using low energy kitchen blenders is reported in which CNF disintegration, clay exfoliation and mixing carried out in one step. Compared to composites made from the conventional method, the energy demand is reduced by about 97 %; the composites also show higher strength and work to fracture. Colloidal stability, CNF/clay nanostructure, and CNF/clay orientation are well characterized. The results suggest favorable effects from hemicellulose-rich, negatively charged pulp fibers and corresponding CNFs. CNF disintegration and colloidal stability are facilitated with substantial CNF/clay interfacial interaction. The results show a more sustainable and industrially relevant processing concept for strong CNF/clay nanocomposites.

Sustainable Thermal Energy Batteries from Fully Bio-Based Transparent Wood.

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.

Strong, Shape-Memory Lignocellulosic Aerogel via Wood Cell Wall Nanoscale Reassembly.

Polymer shape-memory aerogels (PSMAs) are prospects in various fields of application ranging from aerospace to biomedicine, as advanced thermal insulators, actuators, or sensors. However, the fabrication of PSMAs with good mechanical performance is challenging and is currently dominated by fossil-based polymers. In this work, strong, shape-memory bio-aerogels with high specific surface areas (up to 220 m2/g) and low radial thermal conductivity (0.042 W/mK) were prepared through a one-step treatment of native wood using an ionic liquid mixture of [MTBD]+[MMP]-/DMSO. The aerogel showed similar chemical composition similar to native wood. Nanoscale spatial rearrangement of wood biopolymers in the cell wall and lumen was achieved, resulting in flexible hydrogels, offering design freedom for subsequent aerogels with intricate geometries. Shape-memory function under stimuli of water was reported. The chemical composition and distribution, morphology, and mechanical performance of the aerogel were carefully studied using confocal Raman spectroscopy, AFM, SAXS/WAXS, NMR, digital image correlation, etc. With its simplicity, sustainability, and the broad range of applicability, the methodology developed for nanoscale reassembly of wood is an advancement for the design of biobased shape-memory aerogels.

An Oxidative Enzyme Boosting Mechanical and Optical Performance of Densified Wood Films.

Nature has evolved elegant ways to alter the wood cell wall structure through carbohydrate-active enzymes, offering environmentally friendly solutions to tailor the microstructure of wood for high-performance materials. In this work, the cell wall structure of delignified wood is modified under mild reaction conditions using an oxidative enzyme, lytic polysaccharide monooxygenase (LPMO). LPMO oxidation results in nanofibrillation of cellulose microfibril bundles inside the wood cell wall, allowing densification of delignified wood under ambient conditions and low pressure into transparent anisotropic films. The enzymatic nanofibrillation facilitates microfibril fusion and enhances the adhesion between the adjacent wood fiber cells during densification process, thereby significantly improving the mechanical performance of the films in both longitudinal and transverse directions. These results improve the understanding of LPMO-induced microstructural changes in wood and offer an environmentally friendly alternative for harsh chemical treatments and energy-intensive densification processes thus representing a significant advance in sustainable production of high-performance wood-derived materials.

Mixed-linkage (1,3;1,4)-ß-d-glucans as rehydration media for improved redispersion of dried cellulose nanofibrils.

Improving the redispersion and recycling of dried cellulose nanofibrils (CNFs) without compromising their nanoscopic dimensions and inherent mechanical properties are essential for their large-scale applications. Herein, mixed-linkage (1,3;1,4)-ß-d-glucan (MLG) was studied as a rehydration medium for the redispersion and recycling of dried CNFs, benefiting from the intrinsic affinity of MLG to both cellulose and water molecules as inspired from plant cell wall. MLG from barley with a lower molar ratio of cellotriosyl to cellotetraosyl units was found homogeneously coated on CNFs, facilitating rehydration of the network of individualized CNFs. The addition of barley MLG did not impair the mechanical properties of the CNF/MLG composites as compared to neat CNFs nanopaper. With the addition of 10 wt% barley MLG, dry CNF/MLG composite film was successfully redispersed in water and recycled with well-maintained mechanical properties, while lichenan from Icelandic moss, cationic starch, and xyloglucan could not help the redispersion of dried CNFs.

Aqueous synthesis of highly functional, hydrophobic, and chemically recyclable cellulose nanomaterials through oxime ligation.

Cellulose nanofibril (CNF) materials are candidates for the sustainable development of high mechanical performance nanomaterials. Due to inherent hydrophilicity and limited functionality range, most applications require chemical modification of CNF. However, targeted transformations directly on CNF are cumbersome due to the propensity of CNF to aggregate in non-aqueous solvents at high concentrations, complicating the choice of suitable reagents and requiring tedious separations of the final product. This work addresses this challenge by developing a general, entirely water-based, and experimentally simple methodology for functionalizing CNF, providing aliphatic, allylic, propargylic, azobenzylic, and substituted benzylic functional groups. The first step is NaIO4 oxidation to dialdehyde-CNF in the wet cake state, followed by oxime ligation with O-substituted hydroxylamines. The increased hydrolytic stability of oximes removes the need for reductive stabilization as often required for the analogous imines where aldehyde groups react with amines in water. Overall, the process provides a tailored degree of nanofibril functionalization (2-4.5 mmol/g) with the possible reversible detachment of the functionality under mildly acidic conditions, resulting in the reformation of dialdehyde CNF. The modified CNF materials were assessed for potential applications in green electronics and triboelectric nanogenerators.

Functionalized Wood Veneers as Vibration Sensors: Exploring Wood Piezoelectricity and Hierarchical Structure Effects.

Functional wood materials often rely on active additives due to the weak piezoelectric response of wood itself. Here, we chemically modify wood to form functionalized, eco-friendly wood veneer for self-powered vibration sensors. Only the piezoelectricity of the cellulose microfibrils is used, where the drastic improvement comes only from molecular and nanoscale wood structure tuning. Sequential wood modifications (delignification, oxidation, and model fluorination) are performed, and effects on vibration sensing abilities are investigated. Wood veneer piezoelectricity is characterized by the piezoresponse force microscopy mode in atomic force microscopy. Delignification, oxidation, and model fluorination of wood-based sensors provide output voltages of 11.4, 23.2, and 60 mV by facilitating cellulose microfibril deformation. The vibration sensing ability correlates with improved piezoelectricity and increased cellulose deformation, most likely by large, local cell wall bending. This shows that nanostructural wood materials design can tailor the functional properties of wood devices with potential in sustainable nanotechnology.

Highly reinforced and degradable lignocellulose biocomposites by polymerization of new polyester oligomers.

Unbleached wood fibers and nanofibers are environmentally friendly bio-based candidates for material production, in particular, as reinforcements in polymer matrix biocomposites due to their low density and potential as carbon sink during the materials production phase. However, producing high reinforcement content biocomposites with degradable or chemically recyclable matrices is troublesome. Here, we address this issue with a new concept for facile and scalable in-situ polymerization of polyester matrices based on functionally balanced oligomers in pre-formed lignocellulosic networks. The idea enabled us to create high reinforcement biocomposites with well-dispersed mechanically undamaged fibers or nanocellulose. These degradable biocomposites have much higher mechanical properties than analogs in the literature. Reinforcement geometry (fibers at 30 µm or fibrils at 10-1000 nm diameter) influenced the polymerization and degradation of the polyester matrix. Overall, this work opens up new pathways toward environmentally benign materials in the context of a circular bioeconomy.

Nanostructurally Controllable Strong Wood Aerogel toward Efficient Thermal Insulation.

Eco-friendly materials with superior thermal insulation and mechanical properties are desirable for improved energy- and space-efficiency in buildings. Cellulose aerogels with structural anisotropy could fulfill these requirements, but complex processing and high energy demand are challenges for scaling up. Here we propose a scalable, nonadditive, top-down fabrication of strong anisotropic aerogels directly from wood with excellent, near isotropic thermal insulation functions. The aerogel was obtained through cell wall dissolution and controlled precipitation in lumen, using an ionic liquid (IL) mixture comprising DMSO and a guanidinium phosphorus-based IL [MTBD][MMP]. The wood aerogel shows a unique structure with lumen filled with nanofibrils network. In situ formation of a cellulosic nanofibril network in the lumen results in specific surface areas up to 280 m2/g and high yield strengths >1.2 MPa. The highly mesoporous structure (average pore diameter ∼20 nm) of freeze-dried wood aerogels leads to low thermal conductivities in both the radial (0.037 W/mK) and axial (0.057 W/mK) directions, showing great potential as scalable thermal insulators. This synthesis route is energy efficient with high nanostructural controllability. The unique nanostructure and rare combination of strength and thermal properties set the material apart from comparable bottom-up aerogels. This nonadditive synthesis approach is believed to contribute significantly toward large-scale design and structure control of biobased aerogels.

Recyclable nanocomposites of well-dispersed 2D layered silicates in cellulose nanofibril (CNF) matrix.

Nanocomposites based on components from nature, which can be recycled are of great interest in new materials for sustainable development. The range of properties of nacre-inspired hybrids of 1D cellulose and 2D clay platelets are investigated in nanocomposites with improved nanoparticle dispersion in the starting hydrocolloid mixture. Films with a wide range of compositions are prepared by capillary force assisted physical assembly (vacuum-assisted filtration) of TEMPO-oxidized cellulose nanofibers (TOCN) reinforced by exfoliated nanoclays of three different aspect ratios: saponite, montmorillonite and mica. X-ray diffraction and transmission electron micrographs show almost monolayer dispersion of saponite and montmorillonite and high orientation parallel to the film surface. Films exhibit ultimate strength up to 573 MPa. Young's modulus exceeds 38 GPa even at high MTM contents (40-80 vol%). Optical transmittance, UV-shielding, thermal shielding and fire-retardant properties are measured, found to be very good and are sensitive to the 2D nanoplatelet dispersion.

Nanocellulose Xerogel as Template for Transparent, Thick, Flame-Retardant Polymer Nanocomposites.

Cellulose nanofibers (CNFs) have excellent properties, such as high strength, high specific surface areas (SSA), and low coefficients of thermal expansion (CTE), making them a promising candidate for bio-based reinforcing fillers of polymers. A challenge in the field of CNF-reinforced composite research is to produce strong and transparent CNF/polymer composites that are sufficiently thick for use as load-bearing structural materials. In this study, we successfully prepared millimeter-thick, transparent CNF/polymer composites using CNF xerogels, with high porosity (~70%) and high SSA (~350 m2 g-1), as a template for monomer impregnation. A methacrylate was used as the monomer and was cured by UV irradiation after impregnation into the CNF xerogels. The CNF xerogels effectively reinforced the methacrylate polymer matrix, resulting in an improvement in the flexural modulus (up to 546%) and a reduction in the CTE value (up to 78%) while maintaining the optical transparency of the matrix polymer. Interestingly, the composites exhibited flame retardancy at high CNF loading. These unique features highlight the applicability of CNF xerogels as a reinforcing template for producing multifunctional and load-bearing polymer composites.

Sustainable Development of Hot-Pressed All-Lignocellulose Composites-Comparing Wood Fibers and Nanofibers.

Low-porosity materials based on hot-pressed wood fibers or nanocellulose fibrils (no polymer matrix) represent a new concept for eco-friendly materials with interesting mechanical properties. For the replacement of fossil-based materials, physical properties of wood fiber materials need to be improved. In addition, the carbon footprint and cumulative energy required to produce the material also needs to be reduced compared with fossil-based composites, e.g., glass fiber composites. Lignin-containing fibers and nanofibers are of high yield and special interest for development of more sustainable materials technologies. The present mini-review provides a short analysis of the potential. Different extraction routes of lignin-containing wood fibers are discussed, different processing methods, and the properties of resulting fiber materials. Comparisons are made with analogous lignin-containing nanofiber materials, where mechanical properties and eco-indicators are emphasized. Higher lignin content may promote eco-friendly attributes and improve interfiber or interfibril bonding in fiber materials, for improved mechanical performance.

Sustainable Wood Nanotechnologies for Wood Composites Processed by In-Situ Polymerization.

The development of large, multifunctional structures from sustainable wood nanomaterials is challenging. The need to improve mechanical performance, reduce moisture sensitivity, and add new functionalities, provides motivation for nanostructural tailoring. Although existing wood composites are commercially successful, materials development has not targeted nano-structural control of the wood cell wall, which could extend the property range. For sustainable development, non-toxic reactants, green chemistry and processing, lowered cumulative energy requirements, and lowered CO2-emissions are important targets. Here, modified wood substrates in the form of veneer are suggested as nanomaterial components for large, load-bearing structures. Examples include polymerization of bio-based monomers inside the cell wall, green chemistry wood modification, and addition of functional inorganic nanoparticles inside the cell wall. The perspective aims to describe bio-based polymers and green processing concepts for this purpose, along with wood nanoscience challenges.