Self-Healing Composite Coating Fabricated with a Cystamine Cross-Linked Cellulose Nanocrystal-Stabilized Pickering Emulsion.

A gelled Pickering emulsion system was fabricated by first stabilizing linseed oil droplets in water with dialdehyde cellulose nanocrystals (DACNCs) and then cross-linking with cystamine. Cross-linking of the DACNCs was shown to occur by a reaction between the amine groups on cystamine and the aldehyde groups on the CNCs, causing gelation of the nanocellulose suspension. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize the cystamine-cross-linked CNCs (cysCNCs), demonstrating their presence. Transmission electron microscopy images evidenced that cross-linking between cysCNCs took place. This cross-linking was utilized in a linseed oil-in-water Pickering emulsion system, creating a novel gelled Pickering emulsion system. The rheological properties of both DACNC suspensions and nanocellulose-stabilized Pickering emulsions were monitored during the cross-linking reaction. Dynamic light scattering and confocal laser scanning microscopy (CLSM) of the Pickering emulsion before gelling imaged CNC-stabilized oil droplets along with isolated CNC rods and CNC clusters, which had not been adsorbed to the oil droplet surfaces. Atomic force microscopy imaging of the air-dried gelled Pickering emulsion also demonstrated the presence of free CNCs alongside the oil droplets and the cross-linked CNC network directly at the oil-water interface on the oil droplet surfaces. Finally, these gelled Pickering emulsions were mixed with poly(vinyl alcohol) solutions and fabricated into self-healing composite coating systems. These self-healing composite coatings were then scratched and viewed under both an optical microscope and a scanning electron microscope before and after self-healing. The linseed oil was demonstrated to leak into the scratches, healing the gap automatically and giving a practical approach for a variety of potential applications.

Advances in Smart Photovoltaic Textiles.

Energy harvesting textiles have emerged as a promising solution to sustainably power wearable electronics. Textile-based solar cells (SCs) interconnected with on-body electronics have emerged to meet such needs. These technologies are lightweight, flexible, and easy to transport while leveraging the abundant natural sunlight in an eco-friendly way. In this Review, we comprehensively explore the working mechanisms, diverse types, and advanced fabrication strategies of photovoltaic textiles. Furthermore, we provide a detailed analysis of the recent progress made in various types of photovoltaic textiles, emphasizing their electrochemical performance. The focal point of this review centers on smart photovoltaic textiles for wearable electronic applications. Finally, we offer insights and perspectives on potential solutions to overcome the existing limitations of textile-based photovoltaics to promote their industrial commercialization.

Comparison and assessment of methods for cellulose crystallinity determination.

The degree of crystallinity in cellulose significantly affects the physical, mechanical, and chemical properties of cellulosic materials, their processing, and their final application. Measuring the crystalline structures of cellulose is a challenging task due to inadequate consistency among the variety of analytical techniques available and the lack of absolute crystalline and amorphous standards. Our article reviews the primary methods for estimating the crystallinity of cellulose, namely, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Raman and Fourier-transform infrared (FTIR) spectroscopy, sum-frequency generation vibrational spectroscopy (SFG), as well as differential scanning calorimetry (DSC), and evolving biochemical methods using cellulose binding molecules (CBMs). The techniques are compared to better interrogate not only the requirements of each method, but also their differences, synergies, and limitations. The article highlights fundamental principles to guide the general community to initiate studies of the crystallinity of cellulosic materials.

Tackling the challenge of drying and redispersion of cellulose nanofibrils via membrane-facilitated liquid phase exchange.

It is generally acknowledged that to advance the application of cellulose nanofibrils (CNFs) in product formulations, challenges associated with the drying and redispersion of this material must be addressed. Despite increased research efforts in this area, these interventions still involve the use of additives or conventional drying technologies, which both have the capacity to drive up the cost of the final CNF powders. Herein, we prepared dried and redispersible CNF powders with varying surface functionalities without the use of additives nor conventional drying technologies. Rapid drying in air was achieved after liquid phase exchange from water to isopropyl alcohol. The surface properties, morphology and thermal stabilities were the same for the never-dried and redispersed forms. The rheological properties of the CNFs were also unaffected after drying and redispersion of unmodified and organic acid modified materials. However, for 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-mediated oxidised CNFs with higher surface charge and longer fibrils, the storage modulus could not be recovered to the never-dried state because of the possible non-selective reduction in length upon redispersion. Nevertheless, this method provides an effective and low-cost process for the drying and redispersion of unmodified and surface modified CNFs.

Cellulose: A Review of Water Interactions, Applications in Composites, and Water Treatment.

Cellulose is known to interact well with water, but is insoluble in it. Many polysaccharides such as cellulose are known to have significant hydrogen bond networks joining the molecular chains, and yet they are recalcitrant to aqueous solvents. This review charts the interaction of cellulose with water but with emphasis on the formation of both natural and synthetic fiber composites. Covering studies concerning the interaction of water with wood, the biosynthesis of cellulose in the cell wall, to its dispersion in aqueous suspensions and ultimately in water filtration and fiber-based composite materials this review explores water-cellulose interactions and how they can be exploited for synthetic and natural composites. The suggestion that cellulose is amphiphilic is critically reviewed, with relevance to its processing. Building on this, progress made in using various charged and modified forms of nanocellulose to stabilize oil-water emulsions is addressed. The role of water in the aqueous formation of chiral nematic liquid crystals, and subsequently when dried into composite films is covered. The review will also address the use of cellulose as an aid to water filtration as one area where interactions can be used effectively to prosper human life.

Cellulose Iß microfibril interaction with pristine graphene in water: Effects of amphiphilicity by molecular simulation.

Graphene-cellulose interactions have considerable potential in the development of new materials. In previous computational work (Biomacromolecules2016, 16, 1771), we predicted that the model 100 hydrophobic surface of cellulose interacted favourably with pristine graphene in aqueous solution molecular dynamics simulations; conversely, a model of the hydrophilic 010 surface of cellulose exhibited progressive rearrangement to present a more hydrophobic face with the graphene, with weakened hydrogen bonds between cellulose chains and partial permeation of water. Here, we extend this work by simulating the interaction in aqueous solution of the amphiphilic 110 surface of a cellulose Iß microfibril model, comprising 36 chains of 40 glucosyl residues, with an infinite sheet of pristine graphene. This face of the microfibril is of intermediate hydrophilicity and progressively associates with graphene over replicate simulations. As cellulose chains adhere to the graphene surface, forming interactions via its CH and OH groups, we observe a degree of local and global untwisting of the microfibril. Complementary rippling of the graphene surface is also observed, as it adapts to interaction with the microfibril. This adsorption process is accompanied by increased exclusion of water between cellulose and graphene although some water localises between chains at the immediate interface. The predicted propensity of a cellulose microfibril to adsorb spontaneously on the graphene surface, with mutual structural accommodation, highlights the amphiphilic nature of cellulose and the types of interactions that can be harnessed to design new graphene-carbohydrate biopolymer materials.

Stable Sodium-Metal Batteries in Carbonate Electrolytes Achieved by Bifunctional, Sustainable Separators with Tailored Alignment.

Sodium (Na) is the most appealing alternative to lithium as an anode material for cost-effective, high-energy-density energy-storage systems by virtue of its high theoretical capacity and abundance as a resource. However, the uncontrolled growth of Na dendrites and the limited cell cycle life impede the large-scale practical implementation of Na-metal batteries (SMBs) in commonly used and low-cost carbonate electrolytes. Herein, the employment of a novel bifunctional electrospun nanofibrous separator comprising well-ordered, uniaxially aligned arrays, and abundant sodiophilic functional groups is presented for SMBs. By tailoring the alignment degree, this unique separator integrates with the merits of serving as highly aligned ion-redistributors to self-orientate/homogenize the flux of Na-ions from a chemical molecule level and physically suppressing Na dendrite puncture at a mechanical structure level. Remarkably, unprecedented long-term cycling performances at high current densities (≥1000 h at 1 and 3 mA cm-2 , ≥700 h at 5 mA cm-2 ) of symmetric cells are achieved in additive-free carbonate electrolytes. Moreover, the corresponding sodium-organic battery demonstrates a high energy density and prolonged cyclability over 1000 cycles. This work opens up a new and facile avenue for the development of stable, low-cost, and safe-credible SMBs, which could be readily extended to other alkali-metal batteries.

Octylamine-Modified Cellulose Nanocrystal-Enhanced Stabilization of Pickering Emulsions for Self-Healing Composite Coatings.

Linseed oil-in-water Pickering emulsions are stabilized by both sulfated CNCs (sCNCs) and octylamine-modified CNCs (oCNCs). oCNCs with hydrophobic moieties grafted on the surfaces of otherwise intact nanocrystals provided emulsions exhibiting stronger resistance to creaming of oil droplets, compared with unmodified sCNCs. sCNCs were not able to completely stabilize linseed oil in water at low CNC concentrations while oCNCs provided emulsions with no unemulsified oil residue at the same concentrations. Oil droplets in oCNC emulsions were smaller than those in samples stabilized by sCNCs, corresponding with an increased hydrophobicity of oCNCs. Cryo-SEM imaging of stabilized droplets demonstrated the formation of a CNC network at the oil-water interface, protecting the oil droplets from coalescence even after compaction under centrifugal force. These oil droplets, protected by a stabilized CNC network, were dispersed in a water-based commercial varnish, to generate a composite coating. Scratches made on these coatings self-healed as a result of the reaction of the linseed oil bled from the damaged droplets with oxygen. The leakage and drying of the linseed oil at the location of the scratches happened without intervention and was accelerated by the application of heat.

Lightweight, strong, moldable wood via cell wall engineering as a sustainable structural material.

Wood is a sustainable structural material, but it cannot be easily shaped while maintaining its mechanical properties. We report a processing strategy that uses cell wall engineering to shape flat sheets of hardwood into versatile three-dimensional (3D) structures. After breaking down wood's lignin component and closing the vessels and fibers by evaporating water, we partially re-swell the wood in a rapid water-shock process that selectively opens the vessels. This forms a distinct wrinkled cell wall structure that allows the material to be folded and molded into desired shapes. The resulting 3D-molded wood is six times stronger than the starting wood and comparable to widely used lightweight materials such as aluminum alloys. This approach widens wood's potential as a structural material, with lower environmental impact for buildings and transportation applications.

Postsynthesis Self- And Coassembly of Enzymatically Produced Fluorinated Cellodextrins and Cellulose Nanocrystals.

The design of new functional materials and devices substantially relies on self-assembly of hierarchical structures. Formation of 2D platelets is known in the enzymatic synthesis of cellulose-like polymers. Here we demonstrate the feasibility of postsynthesis assembly of novel fluorinated cellodextrins. Highly ordered 2D structures of large lateral dimensions, unattainable in the polymerization process, can be formed because of postsynthesis assembly of the cellodextrins. These cellodextrins were also involved in coassembly with cellulose nanocrystals (CNCs) leading to hybrid systems. The hybrid architectures obtained depend on the content of fluorine atoms in the fluorinated cellodextrins. Monofluorinated cellodextrins coassemble with CNCs into a nanoweb, while multifluorinated cellodextrins assemble around the CNCs.

Natural Fibres as a Sustainable Reinforcement Constituent in Aligned Discontinuous Polymer Composites Produced by the HiPerDiF Method.

Sustainable fibre reinforced polymer composites have drawn significant attention in many industrial sectors as a means for overcoming issues with end-of-life regulations and other environmental concerns. Plant based natural fibres are considered to be the most suitable reinforcement for sustainable composites since they are typically from renewable resources, are cheap, and are biodegradable. In this study, a number of plant based natural fibres-curaua, flax, and jute fibres-are used to reinforce epoxy, poly(lactic acid) (PLA), and polypropylene (PP) matrices to form aligned discontinuous natural fibre reinforced composites (ADNFRC). The novel HiPerDiF (high performance discontinuous fibre) method is used to produce high performance ADNFRC. The tensile mechanical, fracture, and physical (density, porosity, water absorption, and fibre volume fraction) properties of these composites are reported. In terms of stiffness, epoxy and PP ADNFRC exhibit similar properties, but epoxy ADNFRC shows increased strength compared to PP ADNFRC. It was found that PLA ADNFRC had the poorest mechanical performance of the composites tested, due principally to the limits of the polymer matrix. Moreover, curaua, flax (French origin), and jute fibres are found to be promising reinforcements owing to their mechanical performance in epoxy and PP ADNFRC. However, only flax fibre with desirable fibre length is considered to be the best reinforcement constituent for future sustainable ADNFRC studies in terms of mechanical performance and current availability on the market, particularly for the UK and EU.

Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials*.

Understanding the fine details of the self-assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft-matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self-assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site-selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis. Bearing in mind the potential disruption of the hydrogen-bond network of cellulose II, we have prepared and characterised a multiply 6-fluorinated cellodextrin. In addition, a series of single site-selectively fluorinated cellodextrins was synthesised to assess the structural impact upon the addition of one fluorine atom per chain. The structural characterisation of these materials at different length scales, combining advanced NMR spectroscopy and microscopy methods, showed that a 6-fluorinated donor substrate yielded multiply 6-fluorinated cellodextrin chains that assembled into particles presenting morphological and crystallinity features, and intermolecular interactions, that are unprecedented for cellulose-like materials.

Beyond What Meets the Eye: Imaging and Imagining Wood Mechanical-Structural Properties.

Wood presents a hierarchical structure, containing features at all length scales: from the tracheids or vessels that make up its cellular structure, through to the microfibrils within the cell walls, down to the molecular architecture of the cellulose, lignin, and hemicelluloses that comprise its chemical makeup. This structure renders it with high mechanical (e.g., modulus and strength) and interesting physical (e.g., optical) properties. A better understanding of this structure, and how it plays a role in governing mechanical and other physical parameters, will help to better exploit this sustainable resource. Here, recent developments on the use of advanced imaging techniques for studying the structural properties of wood in relation to its mechanical properties are explored. The focus is on synchrotron nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray tomographical imaging, Raman and infrared spectroscopies, confocal microscopy, electron microscopy, and atomic force microscopy. Critical discussion on the role of imaging techniques and how fields are developing rapidly to incorporate both spatial and temporal ranges of analysis is presented.

Hydrophobized cellulose nanocrystals enhance xanthan and locust bean gum network properties in gels and emulsions.

Locust bean/xanthan gum (LBG/XG) synergistic networks have previously been well studied, with evidence that junction zones between the two polymers result in hydrophobic domains. Here we report on the effect of both hydrophilic and hydrophobic cellulose nanocrystals (CNCs) on the rheological properties of the individual gums, the gum networks, and emulsion gels consisting of the gum network and corn oil. We also take advantage of differences in the autofluorescent spectra for each of the components to map their distribution within the gel and emulsion gel systems. Whilst both types of CNC confer thermal stability to the systems, hydrophilic CNCs induce minor changes in rheological properties of synergistic gels and prove to be detrimental to the stability of the emulsion gels. In contrast, hydrophobic CNCs associate with the LBG/XG network, affecting the rheological response. Their inclusion in the emulsion gel system results in smaller, more homogeneously distributed oil droplets with a resultant increase in the storage modulus by an order of magnitude compared to the CNC-free and hydrophilic CNC systems. We conclude that hydrophobic CNCs play a critical role in stabilising LBG/XG network gels and emulsions.

Employing photoluminescence to rapidly follow aggregation and dispersion of cellulose nanofibrils.

Photoluminescence of cellulose, and other polysaccharides, has long been presumed to be due to contamination of the material by other autofluorescent compounds - such as lignin, or proteins. This is attributed to the lack of known fluorescent chemical groups present in the molecular structure of polysaccharides and the weak emission intensity when compared to typical fluorophores. However, recent research suggests that the observed luminescence may actually be due to transitions involving the n orbitals containing lone electron pairs present in oxyl groups, stabilised by the molecular forces between the polysaccharide chains. Here we investigate this theory further by varying the physicochemical environment (concentration and pH) of oxidised cellulose nanofibril suspensions and observing the resultant fluorescent spectra using multi-channel confocal laser scanning spectroscopy. We confirm that both factors affect the material photoluminescence, specifically changing the intensity ratio between two localised emission maxima, supporting current theories. Furthermore, we demonstrate that this variation enables the determination of critical aggregation concentrations and the apparent pKa values of hydroxyl groups that undergo deprotonation within the examined pH range, enabling use of the technique to track rapid changes in the fibril physicochemical environment.

Characterisation of Natural Fibres for Sustainable Discontinuous Fibre Composite Materials.

Growing environmental concerns and stringent waste-flow regulations make the development of sustainable composites a current industrial necessity. Natural fibre reinforcements are derived from renewable resources and are both cheap and biodegradable. When they are produced using eco-friendly, low hazard processes, then they can be considered as a sustainable source of fibrous reinforcement. Furthermore, their specific mechanical properties are comparable to commonly used, non-environmentally friendly glass-fibres. In this study, four types of abundant natural fibres (jute, kenaf, curaua, and flax) are investigated as naturally-derived constituents for high performance composites. Physical, thermal, and mechanical properties of the natural fibres are examined to evaluate their suitability as discontinuous reinforcements whilst also generating a database for material selection. Single fibre tensile and microbond tests were performed to obtain stiffness, strength, elongation, and interfacial shear strength of the fibres with an epoxy resin. Moreover, the critical fibre lengths of the natural fibres, which are important for defining the mechanical performances of discontinuous and short fibre composites, were calculated for the purpose of possible processing of highly aligned discontinuous fibres. This study is informative regarding the selection of the type and length of natural fibres for the subsequent production of discontinuous fibre composites.

Hydrophobization of Cellulose Nanocrystals for Aqueous Colloidal Suspensions and Gels.

Surface hydrophobization of cellulose nanomaterials has been used in the development of nanofiller-reinforced polymer composites and formulations based on Pickering emulsions. Despite the well-known effect of hydrophobic domains on self-assembly or association of water-soluble polymer amphiphiles, very few studies have addressed the behavior of hydrophobized cellulose nanomaterials in aqueous media. In this study, we investigate the properties of hydrophobized cellulose nanocrystals (CNCs) and their self-assembly and amphiphilic properties in suspensions and gels. CNCs of different hydrophobicity were synthesized from sulfated CNCs by coupling primary alkylamines of different alkyl chain lengths (6, 8, and 12 carbon atoms). The synthetic route permitted the retention of surface charge, ensuring good colloidal stability of hydrophobized CNCs in aqueous suspensions. We compare surface properties (surface charge, ζ potential), hydrophobicity (water contact angle, microenvironment probing using pyrene fluorescence emission), and surface activity (tensiometry) of different hydrophobized CNCs and hydrophilic CNCs. Association of hydrophobized CNCs driven by hydrophobic effects is confirmed by X-ray scattering (SAXS) and autofluorescent spectroscopy experiments. As a result of CNC association, CNC suspensions/gels can be produced with a wide range of rheological properties depending on the hydrophobic/hydrophilic balance. In particular, sol-gel transitions for hydrophobized CNCs occur at lower concentrations than hydrophilic CNCs, and more robust gels are formed by hydrophobized CNCs. Our work illustrates that amphiphilic CNCs can complement associative polymers as modifiers of rheological properties of water-based systems.

Rapid Determination of the Distribution of Cellulose Nanomaterial Aggregates in Composites Enabled by Multi-Channel Spectral Confocal Microscopy.

There is increased interest in the use of cellulose nanomaterials for the mechanical reinforcement of composites due to their high stiffness and strength. However, challenges remain in accurately determining their distribution within composite microstructures. We report the use of a range of techniques used to image aggregates of cellulose nanocrystals (CNCs) greater than 10 µm2 within a model thermoplastic polymer. While Raman imaging accurately determines CNC aggregate size, it requires extended periods of analysis and the limited observable area results in poor reproducibility. In contrast, staining the CNCs with a fluorophore enables rapid acquisition with high reproducibility, but overestimates the aggregate size as CNC content increases. Multi-channel spectral confocal laser scanning microscopy is presented as an alternative technique that combines the accuracy of Raman imaging with the speed and reproducibility of conventional confocal laser scanning microscopy, enabling the rapid determination of CNC aggregate distribution within composites.

Characterization of pulp derived nanocellulose hydrogels using AVAP® technology.

Bioinspiration from hierarchical structures found in natural environments has heralded a new age of advanced functional materials. Nanocellulose has received significant attention due to the demand for high-performance materials with tailored mechanical, physical and biological properties. In this study, nanocellulose fibrils, nanocrystals and a novel mixture of fibrils and nanocrystals (blend) were prepared from softwood biomass using the AVAP® biorefinery technology. These materials were characterized using transmission and scanning electron microscopy, and atomic force microscopy. This analysis revealed a nano- and microarchitecture with extensive porosity. Notable differences included the nanocrystals exhibiting a compact packing of nanorods with reduced porosity. The NC blend exhibited porous fibrillar networks with interconnecting compact nanorods. Fourier transform infrared spectroscopy and X-ray diffraction confirmed a pure cellulose I structure. Thermal studies highlighted the excellent stability of all three NC materials with the nanocrystals having the highest decomposition temperature. Surface charge analysis revealed stable colloid suspensions. Rheological studies highlighted a dominance of elasticity in all variants, with the NC blend being more rigid than the NC fibrils and nanocrystals, indicating a double network hydrogel structure. Given these properties, it is thought that these materials show great potential in (bio)nanomaterial applications where careful control of microarchitecture, surface topography and porosity are required.