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.

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.

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.

Small Angle Neutron Scattering Shows Nanoscale PMMA Distribution in Transparent Wood Biocomposites.

Transparent wood biocomposites based on PMMA combine high optical transmittance with excellent mechanical properties. One hypothesis is that despite poor miscibility the polymer is distributed at the nanoscale inside the cell wall. Small-angle neutron scattering (SANS) experiments are performed to test this hypothesis, using biocomposites based on deuterated PMMA and "contrast-matched" PMMA. The wood cell wall nanostructure soaked in heavy water is quantified in terms of the correlation distance d between the center of elementary cellulose fibrils. For wood/deuterated PMMA, this distance d is very similar as for wood/heavy water (correlation peaks at q ≈ 0.1 Å-1). The peak disappears when contrast-matched PMMA is used, indeed proving nanoscale polymer distribution in the cell wall. The specific processing method used for transparent wood explains the nanocomposite nature of the wood cell wall and can serve as a nanotechnology for cell wall impregnation of polymers in large wood biocomposite structures.

Toward Biocomposites Recycling: Localized Interphase Degradation in PCL-Cellulose Biocomposites and its Mitigation.

Recyclable biocomposites based on degradable polymer systems and cellulosic plant fibers are attractive in a sustainable society, because of enhanced polymer properties and also from an end-of-life perspective. Improved understanding is required for how the degradable polymer matrix is affected during compounding in addition to effects from the cellulosic fiber structure and its chemical nature. This work reveals that a poly(ε-caprolactone) matrix undergoes localized, heterogeneous polymer degradation in the fiber-matrix interphase region during melt-compounding. The extent of localized degradation correlates with the initial moisture content in the wood cellulose fiber, where moisture content is controlled by different fiber modification methods by PCL-grafting. As an effect, high moisture content results in a destabilized and degraded fiber-matrix interphase. This was found through careful analysis of how the polymer population changed after compounding, using two different methods: molar mass distribution from SEC and end-group concentration from NMR. The results are important not only with regard to fiber/matrix interface compatibility but also to understand fiber modification for improved biocomposites recycling.

Polymer Grafting Inside Wood Cellulose Fibers by Improved Hydroxyl Accessibility from Fiber Swelling.

Chemical modification of wood cellulose fibers is important for tailored wood-polymer interfaces, reduced moisture sorption, and novel grades of chemical wood pulp. The present study shows how the reaction solvent system influences hydroxyl accessibility during chemical fiber modification. Surface initiated ring-opening polymerization of ε-caprolactone from wood cellulose fibers was investigated in a wide range of solvent systems. The hydrogen bond donor strength of the solvent increased graft density and the amount of grafted polycaprolactone (PCL) on the fiber surface, and on nanoscale fibrils inside the fiber. Specifically, the reaction system with acetic acid as a new, green solvent for cellulose grafting increased graft density 24 times compared to bulk polymerization conditions. The results show relationships between solvent properties, hydroxyl accessibility, and grafting results in cellulosic plant fibers. The study clarifies the opportunities provided by controlling the interior of the cellulosic plant fiber cell wall during chemical modification so that the fiber becomes a swollen cellulose nanofibril gel.

High-Strength Nanostructured Films Based on Well-Preserved α-Chitin Nanofibrils Disintegrated from Insect Cuticles.

The α-chitin nanofibril is an alternative to nanocellulose as a building-block for strong films and other nanomaterials. The hypothesis of high film strength for films based on mildly treated insect cuticles was tested. Fibrils from the cuticle of Ruspolia differens (a long-horned bush cricket grasshopper locally known as senene) are disintegrated by a mild process, subsequently characterized by transmission electron microscopy, NMR, Fourier transform infrared spectroscopy, and XRD, and used to prepare strong and transparent films. A mild process (with 20% NaOH treatment for 2 weeks and at room temperature) was used to largely remove the strongly bound protein associated with chitin. The purpose was to reduce chitin degradation. The native structure of chitin was indeed well preserved and close to the native state, as is supported by data for degree of acetylation, molar mass, crystallinity, and crystallite dimensions. The diameter of the smallest chitin fibrils was as small as 3-7 nm (average 6 nm) with lengths larger than or around 1 µm. A stable and well-dispersed colloidal chitin fibril suspension in water was achieved. A nanostructured chitin film prepared by filtration showed high optical transmittance (∼90%) and very high tensile strength (220 MPa). The high tensile strength was attributed to the well-preserved chitin structure, high intrinsic fibril strength, and high colloidal stability of the fibril suspension. Strong, transparent insect chitin films offer interesting alternatives to nanocellulose films because of different resource origins, surface chemistries, and potential antimicrobial properties.

Lignin-Based Epoxy Resins: Unravelling the Relationship between Structure and Material Properties.

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.

Nanostructural Effects in High Cellulose Content Thermoplastic Nanocomposites with a Covalently Grafted Cellulose-Poly(methyl methacrylate) Interface.

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 (∼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 ∼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.

Dynamic Nanocellulose Networks for Thermoset-like yet Recyclable Plastics with a High Melt Stiffness and Creep Resistance.

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.

Toward Semistructural Cellulose Nanocomposites: The Need for Scalable Processing and Interface Tailoring.

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.

Preserving Cellulose Structure: Delignified Wood Fibers for Paper Structures of High Strength and Transparency.

To expand the use of renewable materials, paper products with superior mechanical and optical properties are needed. Although beating, bleaching, and additives are known to improve industrially produced Kraft pulp papers, properties are limited by the quality of the fibers. While the use of nanocellulose has been shown to significantly increase paper properties, the current cost associated with their production has limited their industrial relevance. Here, using a simple mild peracetic acid (PAA) delignification process on spruce, we produce hemicellulose-rich holocellulose fibers (28.8 wt %) with high intrinsic strength (1200 MPa for fibers with microfibrillar angle smaller than 10°). We show that PAA treatment causes less cellulose/hemicellulose degradation and better preserves cellulose nanostructure in comparison to conventional Kraft pulping. High-density holocellulose papers with superior mechanical properties (Young's modulus of 18 GPa and ultimate strength of 195 MPa) are manufactured using a water-based hot-pressing process, without the use of beating or additives. We propose that the preserved hemicelluloses act as "glue" in the interfiber region, improving both mechanical and optical properties of papers. Holocellulose fibers may be affordable and applicable candidates for making special paper/composites where high mechanical performance and/or optical transmittance are of interest.

Hydration-Dependent Dynamical Modes in Xyloglucan from Molecular Dynamics Simulation of 13C NMR Relaxation Times and Their Distributions.

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 13C NMR longitudinal relaxation times ( T1) 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.

Reinforcement Effects from Nanodiamond in Cellulose Nanofibril Films.

Although research on nanopaper structures from cellulose nanofibrils (CNFs) is well established, the mechanical behavior is not well understood, especially not when CNF is combined with hard nanoparticles. Cationic CNF (Q-CNF) was prepared and successfully decorated by anionic nanodiamond (ND) nanoparticles in hydrocolloidal form. The Q-CNF/ND nanocomposites were filtered from a hydrocolloid and dried. Unlike many other carbon nanocomposites, the Q-CNF/ND nanocomposites were optically transparent. Reinforcement effects from the nanodiamond were remarkable, such as Young's modulus (9.8 → 16.6 GPa) and tensile strength (209.5 → 277.5 MPa) at a content of only 1.9% v/v of ND, and the reinforcement mechanisms are discussed. Strong effects on CNF network deformation mechanisms were revealed by loading-unloading experiments. Scratch hardness also increased strongly with increased addition of ND.

Estimating the Strength of Single Chitin Nanofibrils via Sonication-Induced Fragmentation.

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 ß-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 ß-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.

High-performance and moisture-stable cellulose-starch nanocomposites based on bioinspired core-shell nanofibers.

Moisture stability and brittleness are challenges for plant fiber biocomposites intended for load-bearing applications, for instance those based on an amylopectin-rich (AP) starch matrix. Core-shell amylopectin-coated cellulose nanofibers and nanocomposites are prepared to investigate effects from the distribution of AP matrix. The core-shell nanocomposites are compared with nanocomposites with more irregular amylopectin (AP) distribution. Colloidal properties (DLS), AP adsorption, nanofiber dimensions (atomic force microscopy), and nanocomposite structure (transmission electron microscopy) are analyzed. Tensile tests are performed at different moisture contents. The core-shell nanofibers result in exceptionally moisture stable, ductile, and strong nanocomposites, much superior to reference CNF/AP nanocomposites with more irregular AP distribution. The reduction in AP properties is less pronounced as the AP forms a favorable interphase around individual CNF nanofibers.

Strong Surface Treatment Effects on Reinforcement Efficiency in Biocomposites Based on Cellulose Nanocrystals in Poly(vinyl acetate) Matrix.

In this work, the problem to disperse cellulose nanocrystals (CNC) in hydrophobic polymer matrices has been addressed through application of an environmentally friendly chemical modification approach inspired by clay chemistry. The objective is to compare the effects of unmodified CNC and modified CNC (modCNC) reinforcement, where degree of CNC dispersion is of interest. Hydrophobic functionalization made it possible to disperse wood-based modCNC in organic solvent and cast well-dispersed nanocomposite films of poly(vinyl acetate) (PVAc) with 1-20 wt % CNC. Composite films were studied by infrared spectroscopy (FT-IR), UV-vis spectroscopy, dynamic mechanical thermal analysis (DMTA), tensile testing, and field-emission scanning electron microscopy (FE-SEM). Strongly increased mechanical properties were observed for modCNC nanocomposites. The reinforcement efficiency was much lower in unmodified CNC composites, and specific mechanisms causing the differences are discussed.

Nanostructural effects on polymer and water dynamics in cellulose biocomposites: (2)h and (13)c NMR relaxometry.

Improved moisture stability is desired in cellulose biocomposites. In order to clarify nanostructural effects, a new approach is presented where water and polymer matrix mobilities are characterized separately. Nanocomposites from cellulose nanofibers (CNF) in the xyloglucan (XG) biopolymer matrix are investigated at different hydration states. Films of XG, CNF, and CNF/XG composites are subjected to detailed (2)H and (13)C NMR relaxation studies. Since the (2)H NMR signal arises from heavy water and the (13)C signal from the polysaccharides, molecular water and polymer dynamics is for the first time investigated separately. In the neat components, (2)H transverse relaxation (T2) data are consistent with water clustering at the CNF fibril surfaces, but bulk spread of moisture in XG. The new method results in a description of water interaction with the nanoscale phases. At low hydration, water molecules at the CNF/XG interface exhibit higher water mobility than in neat CNF or XG, due to locally high water concentration. At the same time, CNF-associated interphase segments of XG show slower NMR-dynamics than that in neat XG.

Holocellulose Nanofibers of High Molar Mass and Small Diameter for High-Strength Nanopaper.

Wood cellulose nanofibers (CNFs) based on bleached pulp are different from the cellulose microfibrils in the plant cell wall in terms of larger diameter, lower cellulose molar mass, and modified cellulose topochemistry. Also, CNF isolation often requires high-energy mechanical disintegration. Here, a new type of CNFs is reported based on a mild peracetic acid delignification process for spruce and aspen fibers, followed by low-energy mechanical disintegration. Resulting CNFs are characterized with respect to geometry (AFM, TEM), molar mass (SEC), and polysaccharide composition. Cellulose nanopaper films are prepared by filtration and characterized by UV-vis spectrometry for optical transparency and uniaxial tensile tests. These CNFs are unique in terms of high molar mass and cellulose-hemicellulose core-shell structure. Furthermore, the corresponding nanopaper structures exhibit exceptionally high optical transparency and the highest mechanical properties reported for comparable CNF nanopaper structures.

Molecular adhesion at clay nanocomposite interfaces depends on counterion hydration-molecular dynamics simulation of montmorillonite/xyloglucan.

Nacre-mimetic clay/polymer nanocomposites with clay platelet orientation parallel to the film surface show interesting gas barrier and mechanical properties. In moist conditions, interfacial adhesion is lowered and mechanical properties are reduced. Molecular dynamic simulations (MD) have been performed to investigate the effects of counterions on molecular adhesion at montmorillonite clay (Mnt)-xyloglucan (XG) interfaces. We focus on the role of monovalent cations K(+), Na(+), and Li(+) and the divalent cation Ca(2+) for mediating and stabilizing the Mnt/XG complex formation. The conformation of adsorbed XG is strongly influenced by the choice of counterion and so is the simulated work of adhesion. Free energy profiles that are used to estimate molecular adhesion show stronger interaction between XG and clay in the monovalent cation system than in divalent cation system, following a decreasing order of K-Mnt, Na-Mnt, Li-Mnt, and Ca-Mnt. The Mnt clay hydrates differently in the presence of different counterions, leading to a chemical potential of water that is highest in the case of K-Mnt, followed by Na-Mnt and Li-Mnt, and lowest in the case of Ca-Mnt. This means that water is most easily displaced from the interface in the case of K-Mnt, which contributes to the relatively high work of adhesion. In all systems, the penalty of replacing polymer with water at the interface gives a positive contribution to the work of adhesion of between 19 and 35%. Our work confirms the important role of counterions in mediating the adsorption of biopolymer XG to Mnt clays and predicts potassium or sodium as the best choice of counterions for a Mnt-based biocomposite design.