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Dense polymeric films based on network-forming cellulose nanofibrils (CNFs) have excellent mechanical properties but are limited by moisture sensitivity. Here, interfibrillar effects from CNF surface properties are investigated. TEMPO-oxidized CNFs and two native CNFs are prepared with a similar length and width, to exclude geometrical effects. The CNFs have different surface properties in terms of sorbed hemicellulose content, hemicellulose molar mass, and surface charge. Moisture sorption, structural changes, and mechanical properties at different relative humidities are characterized. The presence of sorbed hemicelluloses in the interfibrillar interphase has favorable effects on the mechanical tensile properties. Surface-charged carboxyls increased moisture sorption and film thickness swelling and reduced the mechanical properties. A comparison with biaxially oriented polyethylene terephthalate films provides a perspective into the structure and properties of CNF films. The present study shows the importance of the interfibrillar interface and interphase region for mechanical film properties, including moisture effects.

2,2,6,6-Tetramethylpiperidin-1-yl oxyl (TEMPO)-oxidized beta-chitin nanofibrils (T-ChNF) are novel nanofibrils of high strength and stiffness and can also enhance the adsorption of chitosan in mate ...

The interfacial bonding and structure at the nanoscale in the polymer–clay nanocomposites are essential for obtaining desirable material and structure properties. Layered nanocomposite films of cellulose nanofibrils (CNFs)/montmorillonite (MTM) were prepared from the water suspensions of either CNFs bearing quaternary ammonium cations (Q-CNF) or CNFs bearing carboxylate groups (TO-CNF) with MTM nanoplatelets carrying net surface negative charges by using vacuum filtration followed by compressive drying. The effect of the ionic interaction between cationic or anionic charged CNFs and MTM nanoplatelets on the structure, mechanical properties, and flame retardant performance of the TO-CNF/MTM and Q-CNF/MTM nanocomposite films were studied and compared. The MTM nanoplatelets were well dispersed in the network of TO-CNFs in the form of nanoscale tactoids with the MTM content in the range of 5–70 wt %, while an intercalated structure was observed in the Q-CNF/MTM nanocomposites. The resulting TO-CNF/MTM nanocomposite films had a better flame retardant performance as compared to the Q-CNF/MTM films with the same MTM content. In addition, the effective modulus of MTM for the TO-CNF/MTM nanocomposites was as high as 129.9 GPa, 3.5 times higher than that for Q-CNF/MTM (37.1 GPa). On the other hand, the Q-CNF/MTM nanocomposites showed a synergistic enhancement in the modulus and tensile strength together with strain-to-failure and demonstrated a much better toughness as compared to the TO-CNF/MTM nanocomposites.

Holocellulose fibers produced by mild delignification form strong fiber networks, without beating or dry-strength agents. Recently, sequential batch delignification using peracetic acid (PAA) on finely cut wood sticks resulted in high-quality holocellulose fibers. Here, single step PAA delignification is developed for wood chips, which is simpler and can be used for larger fiber batches (400 g) with similar, high yield (60%). Such fibers have 1.4% lignin, 25% hemicelluloses content and well-preserved cellulose and hemicellulose molar mass. The corresponding paper sheet materials with a porosity of ~ 50%, have a Young’s modulus of 9 GPa and a strength of 90 MPa. Holocellulose fibers can now be readily investigated for use in larger scale paper, molded fiber and polymer biocomposite materials applications, or for cellulose nanofibril preparation.

The freeze-drying technique is employed for the production of novel strontium bromide/graphite/nanocellulose composites for thermochemical heat storage application. The aim is to obtain a better control and stability of salt organization within the composite, while maximizing the air/salt and salt/graphite interfacial areas and enhancing mass and heat transfer associated to the salt hydration and dehydration. A comparison with a conventional wet impregnation method is also reported. The morphology was investigated by means of scanning electron microscopy. Differential scanning calorimetry was employed to evaluate the energy storage density, while hydration kinetics were evaluated at 23 °C and 50% RH. The wet impregnation approach delivered materials with a limited porosity while freeze-drying produced highly porous structures with oriented channels for moisture transport across the composite. The organic binder provided an active contribution to the energy storage process, producing energy storage densities up to 764 kJ/kg, 48% greater than the theoretical value. Freeze-dried nanocellulose composites evidenced a significant increase of 54% in the hydration kinetics, compared to the pristine salt. Based on these results, the freeze-drying of ternary composites based on salt hydrate, graphite and nanocellulose is envisaged as a promising route for the production of fast charge and discharge thermochemical storage systems.

Chemical wood cellulose fiber modification is performed with the purpose to improve compatibility and induce nanofibrillation of the fibers during melt compounding of thermoplastic biocomposites. C...

Highly porous, strong aerogels with anisotropicstructural properties are of great interest for multifunctionalmaterials for applications including insulators in buildings,filters for oil cleanup, electrical storage devices,etc. Contem-porary aerogels are mostly extracted from fossil resources andsynthesized from bottom-up techniques, often requiring addi-tional strategies to obtain high anisotropy. In this work, auniversal approach to prepare porous, strong, anisotropicaerogels is presented through exploiting the natural hierarchicaland anisotropic structure of wood. The preparation comprisesnanoscale removal of lignin, followed by dissolution−regener-ation of nanofibers, leading to enhanced cell wall porosity with nanofibrillated networks occupying the pore space in thecellular wood structure. The aerogels retain structural anisotropy of natural wood, exhibit specific surface areas up to 247 m2/g, and show high compression strength at 95% porosity. This is a record specific area value for wood aerogels/foams and evenhigher than most cellulose-based aerogels for its assigned strength. The aerogel can serve as a platform for multifunctionalcomposites including scaffolds for catalysis, gas separation, or liquid purification due to its porous matrix or as binder-freeelectrodes in electronics. To demonstrate the multifunctionality, the aerogels are successfully decorated with metalnanoparticles (Ag) and metal oxide nanoparticles (TiO2)byin situsynthesis, coated by the conductive polymer(PEDOT:PSS), and carbonized to yield conductive aerogels. This approach is found to be a universal way to prepare highlyporous anisotropic aerogels. QC 20200918

Here we investigate the relationship between thermomechanical properties and chemical structure of well-characterized lignin-based epoxy resins. For this purpose, technical lignins from eucalyptus and spruce, obtained from the Kraft process, were used. The choice of lignins was based on the expected differences in molecular structure. The lignins were then refined by solvent fractionation, and three fractions with comparable molecular weights were selected to reduce effects of molar mass on the properties of the final thermoset resins. Consequently, any differences in thermomechanical properties are expected to correlate with molecular structure differences between the lignins. Oxirane moieties were selectively introduced to the refined fractions, and the resulting lignin epoxides were subsequently cross-linked with two commercially available polyether diamines (Mn = 2000 and 400) to obtain lignin-based epoxy resins. Molecular-scale characterization of the refined lignins and their derivatives were performed by 31P NMR, 2D-NMR, and DSC methods to obtain the detailed chemical structure of original and derivatized lignins. The thermosets were studied by DSC, DMA, and tensile tests and demonstrated diverse thermomechanical properties attributed to structural components in lignin and selected amine cross-linker. An epoxy resin with a lignin content of 66% showed a Tg of 79 °C from DMA, Young's modulus of 1.7 GPa, tensile strength of 66 MPa, and strain to failure of 8%. The effect of molecular lignin structure on thermomechanical properties was analyzed, finding significant differences between the rigid guaiacyl units in spruce lignin compared with sinapyl units in eucalyptus lignin. The methodology points toward rational design of molecularly tailored lignin-based thermosets.

In the cellulose scientific community, hydrogen bonding is often used as the explanation for a large variety of phenomena and properties related to cellulose and cellulose based materials. Yet, hydrogen bonding is just one of several molecular interactions and furthermore is both relatively weak and sensitive to the environment. In this review we present a comprehensive examination of the scientific literature in the area, with focus on theory and molecular simulation, and conclude that the relative importance of hydrogen bonding has been, and still is, frequently exaggerated.

Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) usually demands intermediate-scale or full-scale testing. A bench-scale test is presented as a practicable and efficient method to assess how different fire protective systems improve the structural integrity of CFRPs during fire. The direct flame of a fully developed fire was applied to one side of the CFRP specimen, which was simultaneously loaded with compressive force. Three different approaches (film, non-woven, and coatings) were applied: paper with a thickness in the range of μm consisting of cellulose nanofibre (CNF)/clay nanocomposite, nonwoven mats with thickness in the range of cm and intumescent coatings with a thickness in the range of mm. The uncoated specimen failed after just 17 s. Protection by these systems provides fire stability, as they multiply the time to failure by as much as up to 43 times. The reduced heating rates of the protected specimens demonstrate the reduced heat penetration, indicating the coatings’ excellent heat shielding properties. Bench-scale fire stability testing is shown to be suitable tool to identify, compare and assess different approaches to fire protection.

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.

Many polymers, including polyethylene, feature a relatively low melting point and hence must be cross-linked to make them viable for applications that demand a high stiffness and creep resistance at elevated temperatures. The resulting thermoset plastics cannot be recycled, and therefore alternative materials with a reconfigurable internal network structure are in high demand. Here, we establish that such a thermoset-like yet recyclable material can be realized through the addition of a nanocellulose reinforcing agent. A network consisting of cellulose nanocrystals, nano- or microfibrils imparts many of the characteristics that are usually achieved through chemical cross-linking. For instance, the addition of only 7.5 wt % of either nanocellulose material significantly enhances the melt stiffness of an otherwise molten ethylene-acrylate copolymer by at least 1 order of magnitude. At the same time, the nanocellulose network reduces the melt creep elongation to less than 10%, whereas the neat molten matrix would rupture. At high shear rates, however, the molten composites do not display a significantly higher viscosity than the copolymer matrix, and therefore retain the processability of a thermoplastic material. Repeated re-extrusion at 140 °C does not compromise the thermomechanical properties, which indicates a high degree of recyclability. The versatility of dynamic nanocellulose networks is illustrated by 3D printing of a cellulose composite, where the high melt stiffness improves the printability of the resin.

A molecularly engineered water-borne reactive compatibilizer is designed for tuning of the interface in melt-processed thermoplastic poly(caprolactone) (PCL)-cellulose nanocomposites. The mechanical properties of the nanocomposites are studied by tensile testing and dynamic mechanical analysis. The reactive compatibilizer is a statistical copolymer of 2-(dimethylamino)ethyl methacrylate and 2-hydroxy methacrylate, which is subsequently esterified and quaternized. Quaternized ammonium groups in the reactive compatibilizer electrostatically match the negative surface charge of cellulose nanofibrils (CNFs). This results in core-shell CNFs with a thin uniform coating of the compatibilizer. This promotes the dispersion of CNFs in the PCL matrix, as concluded from high-resolution scanning electron microscopy and atomic force microscopy. Moreover, the compatibilizer "shell" has methacrylate functionalities, which allow for radical reactions during processing and links covalently with PCL. Compared to the bio-nanocomposite reference, the reactive compatibilizer (

An environmentally friendly, energy-efficient method for cellulose nanofibre (CNF) production from softwood holocellulose utilising oxidative enzymes, lytic polysaccharide monooxygenases (LPMOs).

Molecular dynamics (MD) simulations of 13C NMR longitudinal relaxation (T1) distributions were recently established as a powerful tool for characterizing moisture adsorption in natural amorphous polymers. Here, such computational-experimental synergy is demonstrated in a system with intrinsically high structural heterogeneity, namely crystalline cellulose nanofibrils (CNFs) in highly hydrated aggregated state. In such a system, structure-function properties on the nanoscale remain largely uncovered by experimental means alone. In this work, broadly polydispersed experimental 13C NMR T1 distributions could be successfully reproduced in simulations and, for the first time, were decomposed into contributions from distinct molecular sources within the aggregated CNFs, namely, (i) the core and (ii) the less-accessible and accessible surface regions of the CNFs. Furthermore, within the surface groups structurally different sites such as (iii) residues with different hydroxymethyl orientations and (iv) center and origin chains could be discerned based on their distinct molecular dynamics. The MD simulations unravel a direct correlation between dynamical and structural heterogeneity at an atomistic-level resolution that cannot be accessed by NMR experiments. The proposed approach holds the potential to enable quantitative interpretation of NMR data from a range of multicomponent high-performance nanocomposites with significantly heterogeneous macromolecular structure.

Transforming biomass derived components to materials with controlled and predictable properties is a major challenge. Current work describes the controlled synthesis of starcopolymers with functional and degradable arms from the Lignoboost® process. Macromolecular control is achieved by combining lignin fractionation and characterization with ring-opening copolymerization (ROCP). The cyclic monomers used are e-caprolactone (eCL) and a functional carbonate monomer, 2-allyloxymethyl-2-ethyltrimethylene carbonate (AOMEC). The synthesis is performed at ambient temperature, under bulk conditions, in an open flask, and the graft composition and allyl functionality distribution are controlled by the copolymerization kinetics. Emphasis is placed on understanding the initiation efficiency, structural changes to the lignin backbone and the final macromolecular architecture. The present approach provides a green, scalable and cost effective protocol to create well-defined functional macromolecules from technical lignins.

Chitin nanofibrils (ChNF) are interesting high-value constituents for nanomaterials due to the enormous amount of waste from the seafood industry. So far, the reported ChNFs are substantially modified and chemically degraded (shortened) during extraction from the organisms. Here, highly individualized and long native-state β-chitin nanofibrils from Illex argentinus squid pens are prepared. A mild treatment was developed to preserve the molar mass, aspect ratio, degree of acetylation and crystallite structure. The fibrils show a uniform diameter of 2-7 nm, very high aspect ratio (up to 750), high degree of acetylation (DA = 99%), and high molar mass (843 500 dalton). The powder X-ray diffraction analysis showed the preserved crystallite structure after protein removal. These "high quality" ChNFs were used to prepare nanostructured films via vacuum filtration from stable hydrocolloids. The effects of well-preserved "native" fibrils on morphology, and film properties (mechanical and optical), were studied and compared with earlier results based on coarser and shorter, chemically degraded chitin fibrils.

For the successful commercialisation of microfibrillated cellulose (MFC) it is of utmost importance to carefully characterise the constituent cellulose particles. This could for instance lead to th ...

Chitin nanofibers are an interesting biological nanomaterial for advanced applications, for example, in medicine, electronics, packaging and water purification. The challenge is to separate chitin ...

Olive stone is an important biomaterial waste product generated in large amount. As a lignocellulose material, olive stone could be a sustainable resource for biosorbents. In this work, olive stone powder delignification using sodium chlorite (NaClO2) was performed to enhance metal ion adsorption capacity. The influence of the treatment on olive stone powder physical-chemical properties was studied, including specific surface area, surface chemistry, morphology, etc. The white, delignified olive stone powder was applied for metal ions (Fe3+, Cu2+, and Zn2+) adsorption. Olive stone delignification not only increases the accessibility of the olive stone powder but also broadens the applications to materials design with optical functions by the generation of a white powder.

Nanocomposites from native cellulose with low 2D nanoplatelet content are of interest as sustainable materials combining functional and structural performance. Cellulose nanofibril–graphene oxide (CNF–GO) nanocomposite films are prepared by a physical mixing–drying method, with a focus on low GO content, the use of very large GO platelets (2–45 μm) and nanostructural characterization using synchrotron X-ray source for WAXS and SAXS. These nanocomposites can be used as transparent coatings, strong films or membranes, as gas barriers or in laminated form. CNF nanofibrils with random in-plane orientation, form a continuous non-porous matrix with GO platelets oriented in-plane. GO reinforcement mechanisms in CNF are investigated, and relationships between nanostructure and suspension rheology, mechanical properties, optical transmittance and oxygen barrier properties are investigated as a function of GO content. A much higher modulus reinforcement efficiency is observed than in previous polymer–GO studies. The absolute values for modulus and ultimate strength are as high as 17 GPa and 250 MPa at a GO content as small as 0.07 vol%. The remarkable reinforcement efficiency is due to improved organization of the CNF matrix; and this GO-induced mechanism is of general interest for nanostructural tailoring of CNF-2D nanoplatelet composites.

Development of surface-engineering strategies, which are facile, versatile, and mild, are highly desirable in tailor-made functionalization of high-performance bioinspired nanocomposites. We herein disclose for the first time a general organocatalytic strategy for the functionalization and hydrophobization of nacre-mimetic nanocomposites, which includes vide supra key aspects of surface engineering. The merging of metal-free catalysis and the design of nacre-mimetic nanocomposite materials were demonstrated by the organocatalytic surface engineering of cellulose nanofibrils/clay nanocomposites providing the corresponding bioinspired nanocomposites with good mechanical properties, hydrophobicity, and useful thia-, amino, and olefinic functionalities.

Careful design of the structures of interfaces between nanofillers and polymer matrices can significantly improve the mechanical and thermal properties of the overall nanocomposites. Here, we investigate how the grafting density on the surface of nanocelluloses influences the properties of nanocellulose/cellulose triacetate (CTA) composites. The surface of nanocellulose, which was prepared by 2,2,6,6-tetramethylpiperidine-1-oxyl oxidation, was modified with long poly(ethylene glycol) (PEG) chains at different grafting densities. The PEG-grafted nanocelluloses were homogeneously embedded in CTA matrices. The mechanical and thermal properties of the nanocomposites were characterized. Increasing the grafting density caused the soft PEG chains to form denser and thicker layers around the rigid nanocelluloses. The PEG layers were not completely miscible with the CTA matrix. This structure considerably enhanced the energy dissipation by allowing sliding at the interface, which increased the toughness of the nanocomposites. The thermal and mechanical properties of the composites could be tailored by controlling the grafting density. These findings provide a deeper understanding about interfacial design for nanocellulose-based composite materials.

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 nanocomposite coatings of a well-dispersed, random in-plane nanocellulose 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.

This work reports the development of a sustainable and green one-step wet-feeding method to prepare tougher and stronger nanocomposites from biodegradable cellulose nanofibrils (CNF)/polycaprolactone (PCL) constituents, compatibilized with reversible addition fragmentation chain transfer-mediated surfactant-free poly(methyl methacrylate) (PMMA) latex nanoparticles. When a PMMA latex is used, a favorable electrostatic interaction between CNF and the latex is obtained, which facilitates mixing of the constituents and hinders CNF agglomeration. The improved dispersion is manifested in significant improvement of mechanical properties compared with the reference material. The tensile tests show much higher modulus (620 MPa) and strength (23 MPa) at 10 wt % CNF content (compared to the neat PCL reference modulus of 240 and 16 MPa strength), while maintaining high level of work to fracture the matrix (7 times higher than the reference nanocomposite without the latex compatibilizer). Rheological analysis showed a...

Macromolecular dynamics in biological systems, which play a crucial role for biomolecular function and activity at ambient temperature, depend strongly on moisture content. Yet, a generally accepted quantitative model of hydration-dependent phenomena based on local relaxation and diffusive dynamics of both polymer and its adsorbed water is still missing. In this work, atomistic-scale spatial distributions of motional modes are calculated using molecular dynamics simulations of hydrated xyloglucan (XG). These are shown to reproduce experimental hydration-dependent 13 C NMR longitudinal relaxation times (T 1 ) at room temperature, and relevant features of their broad distributions, which are indicative of locally heterogeneous polymer reorientational dynamics. At low hydration, the self-diffusion behavior of water shows that water molecules are confined to particular locations in the randomly aggregated XG network while the average polymer segmental mobility remains low. Upon increasing water content, the hydration network becomes mobile and fully accessible for individual water molecules, and the motion of hydrated XG segments becomes faster. Yet, the polymer network retains a heterogeneous gel-like structure even at the highest level of hydration. We show that the observed distribution of relaxations times arises from the spatial heterogeneity of chain mobility that in turn is a result of heterogeneous distribution of water-chain and chain-chain interactions. Our findings contribute to the picture of hydration-dependent dynamics in other macromolecules such as proteins, DNA, and synthetic polymers, and hold important implications for the mechanical properties of polysaccharide matrixes in plants and plant-based materials.

High Klason lignin content (23 wt%) cellulose nanofibrils (LCNF) were successfully isolated from eucalyptus pulp through catalyzed chemical oxidation, followed by high-pressure homogenization. LCNFs had a diameter of ca. 13 nm according to AFM evaluation. Dense films were obtained through vacuum filtration (nanopaper) and subjected to different drying methods. When drying under heat and mild vacuum (93 °C, 95 kPa) a higher water contact angle, lower roughness and oxygen transmission rate were observed, compared to those drying at room temperature under compression conditions. DSC experiments showed difference in signals associated to Tg of LCNF compared to CNF produced from spruce bleached pulp through enzymatic pre-treatment. The LCNF-based nanopaper showed mechanical properties slightly lower than for those made from cellulose nanofibrils, yet with increased hydrophobicity. In summary, the high-lignin content cellulose nanofibrils proved to be a suitable material for the production of low oxygen permeability nanopaper, with chemical composition close to native wood.

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.

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.

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.

We report the mechanical strength of native chitin nanofibrils. Highly crystalline α-chitin nanofibrils were purified from filaments produced by a microalgae Phaeocystis globosa, and two types of β-chitin nanofibrils were purified from pens of a squid Loligo bleekeri and tubes of a tubeworm Lamellibrachia satsuma, with relatively low and high crystallinity, respectively. These chitin nanofibrils were fully dispersed in water. The strength of individualized nanofibrils was estimated using cavitation-induced tensile fracture of nanoscale filaments in a liquid medium. Both types of β-chitin nanofibrils exhibited similar strength values of approximately 3 GP; in contrast, the α-chitin nanofibrils exhibited a much lower strength value of 1.6 GPa. These strength estimates suggest that the tensile strength of chitin nanofibrils is governed by the molecular packing modes of chitin rather than their crystallinity.

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.

The interfacial adhesion design between "mortar" and "bricks" is essential for mechanical and barrier performance of nanocellulose-based nacre-mimetic nanocomposites, especially at high moisture conditions. To address this fundamental challenge, dopamine (DA) has been conjugated to cellulose nanofibrils (CNFs) and subsequently assembled with montmorillonite (MTM) to generate layered nanocomposite films inspired by the strong adhesion of mussel adhesive proteins to inorganic surfaces under water. The selective formation of catechol/metal ion chelation and hydrogen bonding at the interface between MTM platelets and CNFs bearing DA renders transparent films with strong mechanical properties, particularly at high humidity and in wet state. Increasing the amount of conjugated DA on CNFs results in nanocomposites with increased tensile strength and modulus, up to 57.4 MPa and 1.1 GPa, respectively, after the films are swollen in water. The nanocomposites also show excellent gas barrier properties at high relative humidity (95%), complementing the multifunctional property profile.

Although the anisotropy of wood fibers is reasonably well established, the anisotropy of injection molded wood fiber composites is not well understood. This work focuses on chemo-thermomechanical pulp (CTMP) reinforced polypropylene (PP) composites. A kinetic mixer (Gelimat) is used for compounding CTMP/PP composites, followed by injection molding. Effects from processing induced orientation on mechanical properties are investigated. For this purpose, a film gate mold was designed to inject composites in the shape of plates so that specimens in different directions to the flow could be evaluated. Observations from tensile tests were complemented by performing flexural tests (in different directions) on discs cut from the injected plates. SEM was used to qualitatively observe the fiber orientation in the composites. At high fiber content, both modulus and tensile strength could differ by as much as 40% along the flow and transverse to the flow. The fiber orientation was strongly increased at the highest fiber content, as concluded from theoretical analysis.

Nacre-mimetic biocomposites made from the combination of montmorillonite clay and the hemicellulose xyloglucan give materials that retain much of their material properties even at high relative humidity. Here, a model composite system consisting of two clay platelets intercalated by xyloglucan oligomers was studied at different levels of hydration using molecular dynamics simulations, and compared to the pure clay. It was found that xyloglucan inhibits swelling of the clay at low water contents by promoting the formation of nano-sized voids that fill with water without affecting the material’s dimensions. At higher water contents the XG itself swells, but at the same time maintaining contact with both platelets across the gallery, thereby acting as a physical cross-linker in a manner similar to the role of XG in the plant cell wall.

BACKGROUND: Factor VIIc, fibrinogen, and plasminogen activator inhibitor 1 (PAI-1) are cardiovascular disease (CVD) risk factors and are modulated, in part, by fat type and amount. OBJECTIVE: We evaluated fat type and amount on the primary outcomes: factor VIIc, fibrinogen, and PAI-1. METHODS: In the Dietary Effects on Lipoproteins and Thrombogenic Activity (DELTA) Trial, 2 controlled crossover feeding studies evaluated substituting carbohydrate or MUFAs for SFAs. Study 1: healthy participants (n = 103) were provided with (8 wk) an average American diet [AAD; designed to provide 37% of energy (%E) as fat, 16% SFA], a Step 1 diet (30%E fat, 9% SFA), and a diet low in SFA (Low-Sat; 26%E fat, 5% SFA). Study 2: participants (n = 85) at risk for CVD and metabolic syndrome (MetSyn) were provided with (7 wk) an AAD, a step 1 diet, and a high-MUFA diet (designed to provide 37%E fat, 8% SFA, 22% MUFA). RESULTS: Study 1: compared with AAD, the Step 1 and Low-Sat diets decreased mean factor VIIc by 1.8% and 2.6% (overall P = 0.0001), increased mean fibrinogen by 1.2% and 2.8% (P = 0.0141), and increased mean square root PAI-1 by 0.0% and 6.0% (P = 0.0037), respectively. Study 2: compared with AAD, the Step 1 and high-MUFA diets decreased mean factor VIIc by 4.1% and 3.2% (overall P

Nacre-inspired clay nanocomposites have excellent mechanical properties, combined with optical transmittance, gas barrier properties, and fire retardancy, but the mechanical properties are still be ...

Industries, governments and consumers increasingly request sustainable resources and greener routes for the integration of advanced functional nanocomposites in products and devices. Among renewable biopolymers, cellulose deserves special consideration since it is the most abundant one. While inorganic nanoparticles add functional properties to a nanocomposite, a flexible and porous cellulosic support will facilitate the interaction of the nanoparticles with the surroundings, their handling and recycling. A significant challenge is to develop high strength, flexible nanobiocomposites controlling the nanoparticle properties, their volume fraction and their topographic distribution within the scaffold. A new concept is presented here for multifunctional laminates where layers consist of bacterial cellulose fibrils decorated by inorganic nanoparticles. Each layer can provide a specific function using a different nanoparticle. As model systems, we have selected two metals (Au, Ag) and two semiconductors (TiO2 and Fe2O3). Energy-efficient microwave-assisted synthetic routes have been used to in situ nucleate and grow the inorganic nanocrystals on the cellulose fibrils. Then, functionalized bacterial cellulose films can be arranged as laminates in a millefeuille construct simply by layering and drying the wet films at 60 °C. After drying, they perform as a single integrated and thicker film. Structural, functional and mechanical integrity of the laminates have been investigated. Molecular dynamics simulations were used to compute the surface adhesion energy between two cellulose fibrils and the results are discussed in light of the experimental peel-off data for the separation of the layers in the laminate., Authors acknowledge the financial support from the Spanish Ministry of Science, Innovation and Universities through the MAT2015-64442-R project, the ‘Severo Ochoa’ Programme for Centers of Excellence in R&D (SEV-2015-0496) and the PhD scholarships of S. R. (BES-2016-077533) and I. A. (BE-2016-076734) and the Generalitat de Catalunya for the 2017SGR765 project. D. C. M. is supported by the European Union's horizon 2020 research and innovation programme under Marie Sklodowska-Curie grant agreement No. 6655919. We thank CESGA Supercomputing center for technical support and computer time at the supercomputer Finisterrae II. The Wallenberg Wood Science Center is acknowledged for funding of KTH activities., We acknowledge support of the publication fee by the CSIC Open Access Support Initiative through its Unit of Information Resources for Research (URICI)

Foam-like clay-nanocellulose hybrids are of great interest as load-bearing structural foams with excellent fire retardancy, due to unique effects from clay on thermal cellulose degradation. For the ...

A new type of high reinforcement content clay–cellulose–thermoset nanocomposite is proposed, where epoxy precursors diffuse 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. A more homogeneous nano- and mesoscale epoxy distribution is still required for further property improvements. The materials constitute a new type of three-ph...

Wide-spread use of cellulose nanofibril (CNF) biocomposites and nanomaterials is limited by CNF moisture sensitivity due to surface hydration. We report on a versatile and scalable interface tailor ...

CNFs (cellulose nanofibers) based on holocellulose have a pure cellulose fibril core, with a hemicellulose coating. The diameter is only around 6–8 nm and the hemicellulose surface coating has anio ...

Role of hydrogen bonding in cellulose deformation : the leverage effect analyzed by molecular modeling

Chitin nanofibers of unique structure and properties can be obtained from crustacean and fishery waste. These chitin nanofibers have roughly 4 nm diameters, aspect ratios between 25–250, a high degree of acetylation and preserved crystallinity, and can be potentially applied in hydrogels. Hydrogels with a chitin nanofiber content of 0.4, 0.6, 0.8, 1.0, 2.0, and 3.0 wt % were successfully prepared. The methodology for preparation is new, environmentally friendly, and simple as gelation is induced by neutralization of the charged colloidal mixture, inducing precipitation and secondary bond interaction between nanofibers. Pore structure and pore size distributions of corresponding aerogels are characterized using auto‐porosimetry, revealing a substantial fraction of nanoscale pores. To the best of our knowledge, the values for storage (13 kPa at 3 wt %) and compression modulus (309 kPa at 2 wt %) are the highest reported for chitin nanofibers hydrogels.

ObjectivesLipoprotein(a) [Lp(a)] is mainly similar in composition to LDL, but differs in having apolipoprotein (apo) (a) covalently linked to apoB-100. Our purpose was to examine the individual metabolism of apo(a) and apoB-100 within plasma Lp(a).Materials and methodsThe kinetics of apo(a) and apoB-100 in plasma Lp(a) were assessed in four men with dyslipidemia [Lp(a) concentration: 8.9-124.7nmol/L]. All subjects received a primed constant infusion of [5,5,5-(2)H3] L-leucine while in the constantly fed state. Lp(a) was immunoprecipitated directly from whole plasma; apo(a) and apoB-100 were separated by gel electrophoresis; and isotopic enrichment was determined by gas chromatography/mass spectrometry.ResultsMulticompartmental modeling analysis indicated that the median fractional catabolic rates of apo(a) and apoB-100 within Lp(a) were significantly different at 0.104 and 0.263 pools/day, respectively (P=0.04). The median Lp(a) apo(a) production rate at 0.248nmol/kg·day(-1) was significantly lower than that of Lp(a) apoB-100 at 0.514nmol/kg·day(-1) (P=0.03).ConclusionOur data indicate that apo(a) has a plasma residence time (11days) that is more than twice as long as that of apoB-100 (4days) within Lp(a), supporting the concept that apo(a) and apoB-100 within plasma Lp(a) are not catabolized from the bloodstream as a unit in humans in the fed state.

Optically transparent wood (TW) with transmittance as high as 85% and haze of 71% was obtained using a delignified nanoporous wood template. The template was prepared by removing the light-absorbing lignin component, creating nanoporosity in the wood cell wall. Transparent wood was prepared by successful impregnation of lumen and the nanoscale cellulose fiber network in the cell wall with refractive-index-matched prepolymerized methyl methacrylate (MMA). During the process, the hierarchical wood structure was preserved. Optical properties of TW are tunable by changing the cellulose volume fraction. The synergy between wood and PMMA was observed for mechanical properties. Lightweight and strong transparent wood is a potential candidate for lightweight low-cost, light-transmitting buildings and transparent solar cell windows.