Solid Wood Modification toward Anisotropic Elastic and Insulative Foam-Like Materials.

The methods used to date to produce compressible wood foam by top-down approaches generally involve the removal of lignin and hemicelluloses. Herein, we introduce a route to convert solid wood into a super elastic and insulative foam-like material. The process uses sequential oxidation and reduction with partial removal of lignin but high hemicellulose retention (process yield of 72.8%), revealing fibril nanostructures from the wood's cell walls. The elasticity of the material is shown to result from a lamellar structure, which provides reversible shape recovery along the transverse direction at compression strains of up to 60% with no significant axial deformation. The compressibility is readily modulated by the oxidation degree, which changes the crystallinity and mobility of the solid phase around the lumina. The performance of the highly resilient foam-like material is also ascribed to the amorphization of cellulosic fibrils, confirmed by experimental and computational (molecular dynamics) methods that highlight the role of secondary interactions. The foam-like wood is optionally hydrophobized by chemical vapor deposition of short-chained organosilanes, which also provides flame retardancy. Overall, we introduce a foam-like material derived from wood based on multifunctional nanostructures (anisotropically compressible, thermally insulative, hydrophobic, and flame retardant) that are relevant to cushioning, protection, and packaging.

Multiphase Under-Liquid Biofabrication With Living Soft Matter: A Route to Customize Functional Architectures With Microbial Nanocellulose.

The growth of aerobic microbes at air-water interfaces typically leads to biofilm formation. Herein, a fermentative alternative that relies on oil-water interfaces to support bacterial activity and aerotaxis is introduced. The process uses under-liquid biofabrication by structuring bacterial nanocellulose (BNC) to achieve tailorable architectures. Cellulose productivity in static conditions is first evaluated using sets of oil homologues, classified in order of polarity. The oils are shown for their ability to sustain bacterial growth and BNC production according to air transfer and solubilization, both of which impact the physiochemical properties of the produced biofilms. The latter are investigated in terms of their morphological (fibril size and network density), structural (crystallinity) and physical-mechanical (surface area and strength) features. The introduced under-liquid biofabrication is demonstrated for the generation of BNC-based macroscale architectures and compartmentalized soft matter. This can be accomplished following three different routes, namely, 3D under-liquid networking (multi-layer hydrogels/composites), emulsion templating (capsules, emulgels, porous materials), and anisotropic layering (Janus membranes). Overall, the proposed platform combines living matter and multi-phase systems as a robust option for material development with relevance in biomedicine, soft robotics, and bioremediation, among others.

Wood-based superblack.

Light is a powerful and sustainable resource, but it can be detrimental to the performance and longevity of optical devices. Materials with near-zero light reflectance, i.e. superblack materials, are sought to improve the performance of several light-centered technologies. Here we report a simple top-down strategy, guided by computational methods, to develop robust superblack materials following metal-free wood delignification and carbonization (1500 °C). Subwavelength severed cells evolve under shrinkage stresses, yielding vertically aligned carbon microfiber arrays with a thickness of ~100 µm and light reflectance as low as 0.36% and independent of the incidence angle. The formation of such structures is rationalized based on delignification method, lignin content, carbonization temperature and wood density. Moreover, our measurements indicate a laser beam reflectivity lower than commercial light stoppers in current use. Overall, the wood-based superblack material is introduced as a mechanically robust surrogate for microfabricated carbon nanotube arrays.

Composites based on electrospun fibers modified with cellulose nanocrystals and SiO2 for selective oil/water separation.

Membranes for water remediation require structural stability, efficient operation, and durability. In this work, we used cellulose nanocrystals (CNC) to reinforce hierarchical nanofibrous membranes based on polyacrylonitrile (PAN). Hydrolysis of the electrospun nanofibers (H-PAN) enabled hydrogen bonding with CNC and provided reactive sites for grafting cationic polyethyleneimine (PEI). In a further modification, anionic silica particles (SiO2) were adsorbed on the fiber surfaces, obtaining CNC/H-PAN/PEI/SiO2 hybrid membranes, which developed swelling resistance (swelling ratio of 6.7 compared to 25.4 measured for a CNC/PAN membrane). Hence, the introduced hydrophilic membranes contain highly interconnected channels, they are non-swellable and exhibit mechanical and structural integrity. By contrast with untreated PAN membranes, those obtained after modification displayed high structural integrity and allowed regeneration and cyclic operation. Finally, wettability and oil-in-water emulsion separation tests demonstrated remarkable oil rejection and separation efficiency in aqueous media.

Liquid metal and Mxene enable self-healing soft electronics based on double networks of bacterial cellulose hydrogels.

Liquid metal (LM) nanodroplets and MXene nanosheets are integrated with sulfonated bacterial nanocellulose (BNC) and acrylic acid (AA). Upon fast sonication, AA polymerization leads to a crosslinked composite hydrogel in which BNC exfoliates Mxene, forming organized conductive pathways. Soft conducting properties are achieved in the presence of colloidally stable core-shell LM nanodroplets. Due to the unique gelation mechanism and the effect of Mxene, the hydrogels spontaneously undergo surface wrinkling, which improves their electrical sensitivity (GF = 8.09). The hydrogels are further shown to display interfacial adhesion to a variety of surfaces, ultra-elasticity (tailorable elongation, from 1000 % to 3200 %), indentation resistance and self-healing capabilities. Such properties are demonstrated in wearable, force mapping, multi-sensing and patternable electroluminescence devices.

Leakage-proof microencapsulation of phase change materials by emulsification with acetylated cellulose nanofibrils.

We use acetylated cellulose nanofibrils (AcCNF) to stabilize transient emulsions with paraffin that becomes shape-stable and encapsulated phase change material (PCM) upon cooling. Rheology measurements confirm the gel behavior and colloidal stability of the solid suspensions. We study the effect of nanofiber content on PCM leakage upon melting and compare the results to those from unmodified CNF. The nanostructured cellulose promotes paraffin phase transition, which improves the efficiency of thermal energy exchange. The leakage-proof microcapsules display high energy absorption capacity (ΔHm = 173 J/g) at high PCM loading (up to 80 wt%), while effectively controlling the extent of supercooling. An excellent thermal stability is observed during at least 100 heating/cooling cycles. Degradation takes place at 291 °C, indicating good thermal stability. The high energy density and the effective shape and thermal stabilization of the AcCNF-encapsulated paraffin points to a sustainable solution for thermal energy storage and conversion.

High Internal Phase Oil-in-Water Pickering Emulsions Stabilized by Chitin Nanofibrils: 3D Structuring and Solid Foam .

Chitin nanofibrils (NCh, ∼10 nm lateral size) were produced under conditions that were less severe compared to those for other biomass-derived nanomaterials and used to formulate high internal phase Pickering emulsions (HIPPEs). Pre-emulsification followed by continuous oil feeding facilitated a "scaffold" with high elasticity, which arrested droplet mobility and coarsening, achieving edible oil-in-water emulsions with internal phase volume fraction as high as 88%. The high stabilization ability of rodlike NCh originated from the restricted coarsening, droplet breakage and coalescence upon emulsion formation. This was the result of (a) irreversible adsorption at the interface (wettability measurements by the captive bubble method) and (b) structuring in highly interconnected fibrillar networks in the continuous phase (rheology, cryo-SEM, and fluorescent microscopies). Because the surface energy of NCh can be tailored by pH (protonation of surface amino groups), emulsion formation was found to be pH-dependent. Emulsions produced at pH from 3 to 5 were most stable (at least for 3 weeks). Although at a higher pH NCh was dispersible and the three-phase contact angle indicated better interfacial wettability to the oil phase, the lower interdroplet repulsion caused coarsening at high oil loading. We further show the existence of a trade-off between NCh axial aspect and minimum NCh concentration to stabilize 88% oil-in-water HIPPEs: only 0.038 wt % (based on emulsion mass) NCh of high axial aspect was required compared to 0.064 wt % for the shorter one. The as-produced HIPPEs were easily textured by taking advantage of their elastic behavior and resilience to compositional changes. Hence, chitin-based HIPPEs were demonstrated as emulgel inks suitable for 3D printing (millimeter definition) via direct ink writing, e.g., for edible functional foods and ultralight solid foams displaying highly interconnected pores and for potential cell culturing applications.