Li Zha

Nonisocyanate polyurethanes are sustainable alternatives to conventional polyurethanes but often exhibit limited mechanical performance. Here, poly(hydroxyurethane) (PHU)–epoxy hybrid networks were prepared to tune matrix stiffness through covalent cross-linking and reinforced with wood- and tunicate-derived cellulose nanocrystals (CNCs). Increasing epoxy content enhanced Young’s modulus and tensile strength while reducing strain at break. In contrast, incorporation of CNCs into an intermediate PHU–epoxy matrix produced substantial mechanical enhancement at low loadings. Tunicate-derived CNCs, characterized by higher aspect ratios, provided greater reinforcement than wood-derived CNCs and achieved a maximum toughness of ∼27 MJ m–3 at 2 wt %, exceeding both wood-derived CNC nanocomposites (≤17 MJ m–3) and neat PHU–epoxy hybrids (≤16.5 MJ m–3). Scanning electron microscopy confirmed homogeneous CNC dispersion, while Fourier transform infrared spectroscopy indicated extensive hydrogen-bonding interactions. These results demonstrate that epoxy hybridization and high-aspect-ratio CNC reinforcement provide complementary routes to enhance the mechanical performance of biobased PHU materials.

Interfibrillar phases and bonding in cellulose nanofibril (CNF)-based composites are crucial for materials performances. In this study, we investigated the influence of CNF surface characteristics, the guluronic acid/mannuronic acid ratio, and the molecular weight of alginates on the structure, mechanical, and barrier properties of CNF/alginate composite films. Three types of CNFs with varying surface charges and nanofibril dimensions were prepared from wood pulp fibers. The interfacial bonding through calcium ion cross-linking between alginate and carboxylated CNFs (TCNFs) led to significantly enhanced stiffness and strength due to the formation of an interpenetrating double network, compared to composites from alginates and CNFs with native negative or cationic surface charges. Various alginates extracted from Alaria esculenta (AE) and Laminaria hyperborea (LH) were also examined. The TCNF/AE composite, prepared from alginate with a high mannuronic acid proportion and high molecular weight, exhibited a Young's modulus of 20.3 GPa and a tensile strength of 331 MPa under dry conditions and a Young's modulus of 430 MPa and a tensile strength of 9.3 MPa at the wet state. Additionally, the TCNF/AE composite demonstrated protective properties as a barrier coating for fruit, significantly reducing browning of banana peels and weight loss of bananas stored under ambient conditions.

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.

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.

After lytic polysaccharide monooxygenase (LPMO) treatment, colloidally stable and thin cellulose nanofibrils (CNFs) of a uniform width are produced from kraft pulp fibres, which has a higher hemicellulose content than dissolving pulp fibres.

Integrating synthetic low‐dimensional nanomaterials such as metal–organic framework (MOF) nanosheets with a sustainable biopolymer is a promising strategy to endow composites with attractive structural and functional properties for expanded applications. Herein, aggregation‐induced‐emission luminogen (AIEgen)‐based MOF bulk crystals are successfully exfoliated into ultrathin 2D nanosheets. Seaweed cellulose nanofibrils (CNFs) are assembled with low amounts (0.3 to 4.0 wt%) of the 2D nanosheets to generate luminescent composites. The 2D nanosheets are adsorbed onto the CNFs in dilute water suspensions owing to the flexibility of the MOF nanosheets and the high aspect ratio of the CNFs. Transparent films are prepared by solution casting from a water suspension of the CNF‐MOF assembly. The fluorescence emission of the composite films is enhanced because of the favored affinity between MOF nanosheets and CNFs. Remarkably, these films demonstrate excellent UV‐shielding capacity and high optical transmittance at the visible wavelength range. The composite films also show reversible changes in fluorescence emission intensity in response to ambient humidity. The tensile strength and modulus of the composite films are also enhanced owing to the increased adhesion between CNFs through the adsorbed MOF nanosheets. This work provides a novel pathway to fabricate luminescent CNFs‐based composites with tunable optical properties for functional materials.