A new type of high reinforcement content clay-cellulose-thermoset nanocomposite was proposed, where epoxy precursors diffused into a wet porous clay-nanocellulose mat, followed by curing. The processing concept was scaled to > 200 µm thickness composites, the mechanical properties were high for nanocomposites and the materials showed better tensile properties at 90% RH compared with typical nanocellulose materials. The nanostructure and phase distributions were studied using transmission electron microscopy; Young’s modulus, yield strength, ultimate strength and ductility were determined as well as moisture sorption, fire retardancy and oxygen barrier properties. Clay and cellulose contents were varied, as well as the epoxy content. Epoxy had favorable effects on moisture stability, and also improved reinforcement effects at low reinforcement content. More homogeneous nano- and mesoscale epoxy distribution is still required for further property improvements. The materials constitute a new type of three-phase nanocomposites, of interest as coatings, films and as laminated composites for semi-structural applications.

A critical aspect in materials design of polymer nanocomposites is the nature of the nanoparticle/polymer interface. The present study investigates the effect of manipulation of the interface between cellulose nanofibrils (CNF) and poly(methyl methacrylate) (PMMA) on the optical, thermal, and mechanical properties of the corresponding nanocomposites. The CNF/PMMA interface is altered with a minimum of changes in material composition so that interface effects can be analyzed. The hydroxyl-rich surface of CNF fibrils is exploited to modify the CNF surface via an epoxide-hydroxyl reaction. CNF/PMMA nanocomposites are then prepared with high CNF content (similar to 38 wt %) using an approach where a porous CNF mat is impregnated with monomer or polymer. The nanocomposite interface is controlled by either providing PMMA grafts from the modified CNF surface or by solvent-assisted diffusion of PMMA into a CNF network (native and modified). The high content of CNF fibrils of similar to 6 nm diameter leads to a strong interface and polymer matrix distribution effects. Moisture uptake and mechanical properties are measured at different relative humidity conditions. The nanocomposites with PMMA molecules grafted to cellulose exhibited much higher optical transparency, thermal stability, and hygro-mechanical properties than the control samples. The present modification and preparation strategies are versatile and may be used for cellulose nanocomposites of other compositions, architectures, properties, and functionalities.

Polyurethane (PU) nanocomposites utilizing cellulose nanocrystals (CNCs) as nanofiller and amorphous PU matrix were synthesized in a novel solvent-free bulk process. A green nanofiller, CNCs, was studied as reinforcement and was further modified by grafting poly(ethylene glycol) (PEG) on the CNC surface (CNC-PEG). Transmission electron microscopy revealed an excellent dispersion of the PEGylated CNC nanoparticles in the PU matrix, whereas as-received CNCs formed agglomerates. The results indicated strong improvements in tensile properties with Young's modulus increasing up to 50% and strength up to 25% for both, PU/CNC and PU/CNC-PEG nanocomposites. The enhanced tensile modulus was attributed to stiff particle reinforcement together with an increase in glass transition temperature.

Nanoscale building blocks of many materials exhibit extraordinary mechanical properties due to their defect-free molecular structure. Translation of these high mechanical properties to macroscopic materials represents a difficult materials engineering challenge due to the necessity to organize these building blocks into multiscale patterns and mitigate defects emerging at larger scales. Cellulose nanofibrils (CNFs), the most abundant structural element in living systems, has impressively high strength and stiffness, but natural or artificial cellulose composites are 3-15 times weaker than the CNFs. Here, we report the flow-assisted organization of CNFs into macroscale fibers with nearly perfect unidirectional alignment. Efficient stress transfer from macroscale to individual CNF due to cross-linking and high degree of order enables their Young's modulus to reach up to 86 GPa and a tensile strength of 1.57 GPa, exceeding the mechanical properties of known natural or synthetic biopolymeric materials. The specific strength of our CNF fibers engineered at multiscale also exceeds that of metals, alloys, and glass fibers, enhancing the potential of sustainable lightweight high-performance materials with multiscale self-organization.

The nematic structuring of cellulose nanofibers (CNFs) is proposed as a nanostructural engineering tool for exploiting the potential of CNFs in conceptually new "transparent papers". The nematic-structured CNF papers exhibit superior mechanical properties, optical transparency, gas-barrier properties, heat transfer properties and electrical resistivity, compared with conventional randomly-structured CNF papers.

Colloidal dispersions of cellulose nanofibrils (CNFs) are viable ternatives to cellulose II dissolutions used for filament spinning. e porosity and water vapor affinity of CNF filaments make them itable for controlled breathability. However, many textile plications also require water repellence. Here, we investigated the fects of postmodification of wet-spun CNF filaments via chemical vapor position (CVD). Two organosilanes with different numbers of methyl bstituents were considered. Various surface structures were achieved, ther as continuous, homogeneous coating layers or as ree-dimensional, hairy-like assemblies. Such surface features reduced e surface energy, which significantly affected the interactions with ter. Filaments with water contact angles of up to 116 were obtained, d surface energy measurements indicated the possibility of developing phiphobicity. Dynamic vapor sorption and full immersion experiments re carried out to inquire about the interactions with water, whether the liquid or gas forms. Mechanical tests revealed that the wet rength of the modified filaments were almost 3 times higher than that the unmodified precursors. The hydrolytic and mechanical stabilities the adsorbed layers were also revealed. Overall, our results shed ght on the transformation of aqueous dispersions of CNFs into laments that are suited for controlled interactions with water via ncurrent hydrolysis and condensation reactions in CVD, while intaining the moisture buffering capacity and breathability of related ructures.

Cellulose nanocomposites can be considered for semistructural load-bearing applications where modulus and strength requirements exceed 10 GPa and 100 MPa, respectively. Such properties are higher than for most neat polymers but typical for molded short glass fiber composites. The research challenge for polymer matrix biocomposites is to develop processing concepts that allow high cellulose nanofibril (CNF) content, nanostructural control in the form of well-dispersed CNF, the use of suitable polymer matrices, as well as molecular scale interface tailoring to address moisture effects. From a practical point of view, the processing concept needs to be scalable so that large-scale industrial processing is feasible. The vast majority of cellulose nanocomposite studies elaborate on materials with low nanocellulose content. An important reason is the challenge to prevent CNF agglomeration at high CNF content. Research activities are therefore needed on concepts with the potential for rapid processing with controlled nanostructure, including well-dispersed fibrils at high CNF content so that favorable properties are obtained. This perspective discusses processing strategies, agglomeration problems, opportunities, and effects from interface tailoring. Specifically, preformed CNF mats can be used to design nanostructured biocomposites with high CNF content. Because very few composite materials combine functional and structural properties, CNF materials are an exception in this sense. The suggested processing concept could include functional components (inorganic clays, carbon nanotubes, magnetic nanoparticles, among others). In functional three-phase systems, CNF networks are combined with functional components (nanoparticles or fibril coatings) together with a ductile polymer matrix. Such materials can have functional properties (optical, magnetic, electric, etc.) in combination with mechanical performance, and the comparably low cost of nanocellulose may facilitate the use of large nanocomposite structures in industrial applications.

We report on a sustainable route to protective nanocomposite coatings, where one of the components, nanocellulose fibrils, is derived from trees and the glass matrix is an inexpensive sol-gel organic-inorganic hybrid of zirconium alkoxide and an epoxy-functionalized silane. The hydrophilic nature of the colloidal nanocellulose fibrils is exploited to obtain a homogeneous one-pot suspension of the nanocellulose in the aqueous sol-gel matrix precursors solution. The mixture is then sprayed to form nano composite coatings of a well-dispersed, random in-plane nano cellulose fibril network in a continuous organic inorganic glass matrix phase. The nanocellulose incorporation in the sol-gel matrix resulted in nanostructured composites with marked effects on salient coating properties including optical transmittance, hardness, fracture energy, and water contact angle. The particular role of the nanocellulose fibrils on coating fracture properties, important for coating reliability, was analyzed and discussed in terms of fibril morphology, molecular matrix, and nanocellulose/matrix interactions.