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Water containing low amounts of cellulose nanofiber (CNF) is widely used as a thickening agent owing to its three unique properties: high transparency, viscosity, and controllable viscosity based on the shear rate. CNF dry powders are used to reduce the transportation and storage costs or expand applications as a thickening agent. Herein, the preparation of CNF dry powders that can be used to obtain redispersions while maintaining the aforementioned properties is reported. In this regard, the dehydration and vaporization procedures for a CNF water dispersion without using additives are discussed. When dry powders are prepared by removing water by boiling, their redispersions do not exhibit all their unique properties because of dense aggregations. However, when their redispersions are vigorously stirred to break the dense aggregations, they become transparent, although they do not recover their initial viscosity. Freeze-dried powders recover all their initial properties after redispersion. Nevertheless, their large volume does not reduce the transportation and storage costs. When the liquid is evaporated from the solvent-exchanged CNF organogels, their redispersions also fully recover all their properties. Furthermore, the evaporative dry powders with dense small volumes and good handling contribute to reducing the transportation and storage costs.
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Nanofibras , Água , Pós , Viscosidade , CeluloseRESUMO
Dehydration of a cellulose nanofiber (CNF)/water dispersion requires large amounts of energy and time due to the high hydrophilicities and high specific surface areas of the CNFs. Various dehydration methods have been proposed for CNF/water dispersions; however, an efficient dehydration method for individually dispersed CNFs is needed. Here, electrodeposition of CNFs was evaluated as a dehydration method. Electrodeposition at a DC voltage of 10 V on a 0.2 wt% CNF/water dispersion resulted in a concentration of â¼1.58 wt% in 1 h. The dehydration energy efficiency was â¼300 times greater than that of dehydration by evaporation. The concentrated CNF hydrogels recovered after electrodeposition were redispersed with a simple neutralization process, and clear transparent films were obtained by drying after redispersion. This work provides a new method for dehydration and reuse of individually dispersed CNF/water dispersions and provides new insights into control of the hierarchical structures of CNFs by electrodeposition.
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We formulate copper salt (copper formate/acetate/oleate) precursor inks for photonic sintering using high-intensity pulsed light (HIPL) based on the ink's light absorption ability. The inks can be developed through controllable crystal field splitting states (i.e., the ligand weights and their coordination around the metal centers). The inks' light absorption properties are extremely sensitive to the carbon chain lengths of the ligands, and the ink colors can drastically change. From the relationship between the ratios of C/Cu and the required sintering energies, it is possible to ascertain that the integral absorbance coefficients are strongly correlated with the photonic sintering behavior. These results suggest that the ink absorbance properties are the most important factors in photosintering. The wires formed by sintered copper formate complex ink via the HIPL method showed good electronic conduction, achieving a low resistivity of 5.6 × 10(-5) Ω cm. However, the resistivity of the wires increased with increasing contains carbon chain length of the inks, suggesting that large amounts of residual carbon have negative effects on both the wire's surface morphology and the electrical conductivity. We find in this study that high light absorptivity and low carbon inks would lead to a lower environmental load in future by reducing both energy usage and carbon oxide gas emissions.
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Ultrastrong, transparent, conductive and printable nanocomposites were successfully prepared by mixing single-walled carbon nanotubes (CNTs) with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with abundant sodium carboxyl groups on the crystalline nanocellulose surfaces. The surface-anionic cellulose nanofibrils had reinforcing and nanodispersing effects on the CNTs both in water used as the dispersed medium and in the dried composite film, providing highly conductive and printable nanocomposites with a small amount of CNTs. TOCNs are therefore expected as an effective flexible matrix that can be used as an alternative to conventional polymers for various electrical materials, when nanocomposited with CNTs and also graphene. Our findings provide a promising route to realize green and flexible electronics.
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Nanocompostos/química , Nanotubos de Carbono/química , Celulose/química , Óxidos N-Cíclicos/química , Condutividade Elétrica , Resinas Sintéticas/químicaRESUMO
Optically transparent materials that are air permeable have potentially numerous applications, including in wearable devices. From the perspective of sustainable development, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibers with widths of 3-4 nm have attracted considerable attention as starting materials for the preparation of clearly transparent nanofiber paper (denoted as conventional nanopaper). However, conventional nanopaper that is prepared from a water dispersion of TEMPO-oxidized cellulose nanofibers by direct drying exhibits poor air permeability owing to its densely packed layered structure. In this study, we prepared a clearly transparent and air-permeable nanopaper by applying filtration-based solvent exchange from high-surface-tension water to low-surface-tension ethanol and hexane, followed by drying under continuous vacuum filtration. The resulting hexane-exchanged nanopaper had a porous structure with individually dispersed and thin nanofiber networks and interlayer pore spaces. Owing to the tailored porous structures, the hexane-exchanged nanopaper provides similar clear transparency (total light transmittance and haze at 600 nm: 92.9% and 7.22%, respectively) and 106 times higher air permeability (7.8 × 106 mL µm m-2 day-1 kPa-1) compared to the conventional nanopaper. This study will facilitate the development of clearly transparent and air-permeable nanopapers to extend their functional applications.
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Remarkable progress has been made in the development of carbonized chitin nanofiber materials for various functional applications, including solar thermal heating, owing to their N- and O-doped carbon structures and sustainable nature. Carbonization is a fascinating process for the functionalization of chitin nanofiber materials. However, conventional carbonization techniques require harmful reagents, high-temperature treatment, and time-consuming processes. Although CO2 laser irradiation has progressed as a facile and second-scale high-speed carbonization process, CO2-laser-carbonized chitin nanofiber materials and their applications have not yet been explored. Herein, we demonstrate the CO2-laser-induced carbonization of chitin nanofiber paper (denoted as chitin nanopaper) and investigate the solar thermal heating performance of the CO2-laser-carbonized chitin nanopaper. While the original chitin nanopaper was inevitably burned out by CO2 laser irradiation, CO2-laser-induced carbonization of the chitin nanopaper was achieved by pretreatment with calcium chloride as a combustion inhibitor. The CO2-laser-carbonized chitin nanopaper exhibits excellent solar thermal heating performance; its equilibrium surface temperature under 1 sun irradiation is 77.7 °C, which is higher than those of the commercial nanocarbon films and the conventionally carbonized bionanofiber papers. This study paves the way for the high-speed fabrication of carbonized chitin nanofiber materials and their application in solar thermal heating toward the effective utilization of solar energy as heat.
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Sustainable biomass-derived carbons have attracted research interest because of their ability to effectively absorb and convert solar light to thermal energy, a phenomenon known as solar thermal heating. Although their carbon-based molecular and nanoporous structures should be customized to achieve enhanced solar thermal heating performance, such customization has insufficiently progressed. In this study, we transformed a chitin nanofiber/water dispersion into paper, referred to as chitin nanopaper, with subwavelength nanoporous structures by spatially controlled drying, followed by temperature-controlled carbonization without any pretreatment to customize the carbon-based molecular structures. The optimal carbonization temperature for enhancing the solar absorption and solar thermal heating performance of the chitin nanopaper was determined to be 400 °C. Furthermore, we observed that the nitrogen component, which afforded nitrogen-doped carbon structures, and the high morphological stability of chitin nanofibers against carbonization, which maintained subwavelength nanoporous structures even after carbonization, contributed to the improved solar absorption of the carbonized chitin nanopaper. The carbonized chitin nanopaper exhibited a higher solar thermal heating performance than the carbonized cellulose nanopaper and commercial nanocarbon materials, thus demonstrating significant potential as an excellent solar thermal material.
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Elastic carbon aerogels show great potential for various applications but are often hindered by structure-derived fatigue failure, weak elasticity with low compressibility, and low stress and height retention. Herein, we demonstrate a super-elastic and fatigue-resistant nanochitin-derived carbon honeycomb with honeycomb-like anisotropic microstructures and carbon-based molecular structures, which was tailored by optimizing the nanochitin concentrations and carbonization temperatures. The carbon honeycomb fabricated at a nanochitin concentration of 1.0 wt % and a carbonization temperature of 900 °C demonstrated anisotropic honeycomb channels, nanofibrous network channel walls with few cracks, and weak interactions between the carbonized nanochitin, which afforded high compressibility with up to 90% strain and complete recovery. In particular, the carbon honeycomb provided good fatigue resistance with high stress and height retentions of 87 and 94%, respectively, after more than 10,000 compression cycles at 90% strain. Moreover, the tailored anisotropic honeycomb channels and molecular structures endowed the carbon honeycomb with elasticity even under severe conditions, such as exposure to flame (approximately 1000 °C) and liquid nitrogen (approximately -196 °C). Owing to these properties, the nanochitin-derived carbon honeycomb could act as a high-sensitivity pressure sensor for a wide working pressure range of 0-185.5 kPa and ultrawide temperature range of -196-600 °C. This study can provide a promising route to develop all-biomass-derived, super-elastic, and fatigue-resistant carbon materials for pressure sensing under harsh conditions and for versatile electronic applications.
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To shore up the demand of transparent electrodes for wide applications such as organic light emitting diodes and solar cells, transparent electrodes are required as an alternative for indium tin oxide electrodes. Herein the self-assembly method with a bubble template paves the way for cost-effective fabrication of transparent electrodes with high conductivity and transparency using self-assembly of silver nanowires (AgNWs) in a bubble template. AgNWs were first dispersed in water that was bubbled with a surfactant and a thickening agent. Furthermore, these AgNWs were assembled by lining along the bubble ridges. When the bubbles containing the AgNWs were sandwiched between two glass substrates, the bubble ridges including the AgNWs formed continuous polygonal structures. Mesh structures were formed on both glass substrates after air-drying. The mesh structures evolved into mesh transparent electrodes following heat-treatment. The AgNW mesh structure exhibited a low sheet resistance of 6.2 Ω/square with a transparency of 84% after heat treatment at 200 °C for 20 min. The performance is higher than that of transparent electrodes with random networks of AgNWs. Furthermore, the conductivity and transparency of the mesh transparent electrodes can be adjusted by changing the amount of the AgNW suspension and the space between the two glass substrates.
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Nanofios/química , Prata/química , Condutividade Elétrica , Eletrodos , Vidro/química , Temperatura AltaRESUMO
The deformation micromechanics of bacterial cellulose (BC) and microfibrillated cellulose (MFC) networks have been investigated using Raman spectroscopy. The Raman spectra of both BC and MFC networks exhibit a band initially located at ≈ 1095 cm(-1). We have used the intensity of this band as a function of rotation angle of the specimens to study the cellulose fibril orientation in BC and MFC networks. We have also used the change in this peak's wavenumber position with applied tensile deformation to probe the stress-transfer behavior of these cellulosic materials. The intensity of this Raman band did not change significantly with rotation angle, indicating an in-plane 2D network of fibrils with uniform random orientation; conversely, a highly oriented flax fiber exhibited a marked change in intensity with rotation angle. Experimental data and theoretical analysis shows that the Raman band shift rate arising from deformation of networks under tension is dependent on the angles between the axis of fibrils, the strain axis, the incident laser polarization direction, and the back scattered polarization configurations. From this analysis, the effective moduli of single fibrils of BC and MFC in the networks were estimated to be in the ranges of 79-88 and 29-36 GPa, respectively. It is shown also that for the model to fit the data it is necessary to use a negative Poisson's ratio for MFC networks and BC networks. Discussion of this in-plane "auxetic" behavior is given.
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Celulose/química , Gluconacetobacter xylinus/química , Microfibrilas/química , Nanofibras/química , Tamanho da Partícula , Análise Espectral RamanRESUMO
The orientation control and the formation of hierarchical structures of nanoscale components, such as bionanofibers and nanosheets, have attracted considerable research interest with the aim of achieving sophisticated functional materials. Herein, we report a simple and flexible strategy for constructing sophisticated hierarchical structures through electrophoretic and electrochemical deposition. Cellulose nanofibers (CNFs), which are used as model materials, are deposited on an anode in an aqueous dispersion and seamlessly oriented from horizontal to vertical relatively to the electrode by adjusting the applied voltage between the electrodes. The oriented CNF hydrogels not only exhibit anisotropic mechanical properties but also form complex orientations and hierarchical structures, such as cartilage- and plant stem-like configurations in response to electrode shape and applied voltage. This simple and flexible technique is expected to be applicable to various materials and contribute to a wide range of fields that include biomimicry, functional nanomaterials, and sustainable and functional moldings.
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Semiconducting nanomaterials with 3D network structures exhibit various fascinating properties such as electrical conduction, high permeability, and large surface areas, which are beneficial for adsorption, separation, and sensing applications. However, research on these materials is substantially restricted by the limited trans-scalability of their structural design and tunability of electrical conductivity. To overcome this challenge, a pyrolyzed cellulose nanofiber paper (CNP) semiconductor with a 3D network structure is proposed. Its nano-micro-macro trans-scale structural design is achieved by a combination of iodine-mediated morphology-retaining pyrolysis with spatially controlled drying of a cellulose nanofiber dispersion and paper-crafting techniques, such as microembossing, origami, and kirigami. The electrical conduction of this semiconductor is widely and systematically tuned, via the temperature-controlled progressive pyrolysis of CNP, from insulating (1012 Ω cm) to quasimetallic (10-2 Ω cm), which considerably exceeds that attained in other previously reported nanomaterials with 3D networks. The pyrolyzed CNP semiconductor provides not only the tailorable functionality for applications ranging from water-vapor-selective sensors to enzymatic biofuel cell electrodes but also the designability of macroscopic device configurations for stretchable and wearable applications. This study provides a pathway to realize structurally and functionally designable semiconducting nanomaterials and all-nanocellulose semiconducting technology for diverse electronics.
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Biomass-derived three-dimensional (3D) porous nanocarbons have attracted much attention due to their high surface area, permeability, electrical conductivity, and renewability, which are beneficial for various electronic applications, including energy storage. Cellulose, the most abundant and renewable carbohydrate polymer on earth, is a promising precursor to fabricate 3D porous nanocarbons by pyrolysis. However, the pyrolysis of cellulosic materials inevitably causes drastic carbon loss and volume shrinkage. Thus, polydopamine doping prior to the pyrolysis of cellulose nanofiber paper is proposed to fabricate the 3D porous nanocarbons with improved yield and volume retention. Our results show that a small amount of polydopamine (4.3 wt%) improves carbon yield and volume retention after pyrolysis at 700 °C from 16.8 to 26.4% and 15.0 to 19.6%, respectively. The pyrolyzed polydopamine-doped cellulose nanofiber paper has a larger specific surface area and electrical conductivity than cellulose nanofiber paper that without polydopamine. Owing to these features, it also affords a good specific capacitance up to 200 F g-1 as a supercapacitor electrode, which is higher than the recently reported cellulose-derived nanocarbons. This method provides a pathway for the effective fabrication of high-performance cellulose-derived 3D porous nanocarbons.
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We propose a new methodology for direct evaluation of the degree of fibrillation of fibrillating pulp suspensions through the pixel-resolved retardation distribution. Through simple normalization by just injecting a pulp suspension with a certain concentration into a quartz flow channel with a constant cross-sectional shape, the degree of fibrillation (i.e., the degree of bundling of cellulose molecular chains) can be directly mapped by the retardation gradation, reflecting locally high retardation (pulp fibers), smaller retardation (balloons on fibrillating pulps), and much smaller retardation close to water (dispersed nanofibers). Both the average retardation and standard deviation are found to be the direct indicators of the degree of fibrillation. We envision that the proposed methodology will become the future standard for determining the degree of fibrillation by the retardation distribution, and it will pave the way for more precise control of pulp fibrillation and more sophisticated applications of cellulose nanofiber suspensions.
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Celulose/química , Cryptomeria/química , Nanofibras/química , Madeira/química , Birrefringência , Celulose/ultraestrutura , Humanos , Nanofibras/ultraestrutura , Suspensões/química , Água/químicaRESUMO
Chitin, a natural polysaccharide polymer, forms highly crystalline nanofibers and is expected to have sophisticated engineering applications. In particular, for development of next-generation heat-transfer and heat-insulating materials, analysis of the thermal conductivity is important, but the thermal conductivity properties of chitin nanofiber materials have not been reported. The thermal conductivity properties of chitin nanofiber materials are difficult to elucidate without excluding the effect of adsorbed water and analyzing the influence of surface amino groups. In this study, we aimed to accurately evaluate the thermal conductivity properties of chitin nanofiber films by changing the content of surface amino groups and measuring the thermal diffusivity under dry conditions. Chitin and deacetylated-chitin nanofiber films with surface deacetylation of 5.8% and 25.1% showed in-plane thermal conductivity of 0.82 and 0.73 W/mK, respectively. Taking into account that the films had similar crystalline structures and almost the same moisture contents, the difference in the thermal conductivity was concluded to only depend on the amino group content on the fiber surfaces. Our methodology for measuring the thermal diffusivity under conditioned humidity will pave the way for more accurate analysis of the thermal conductivity performance of hydrophilic materials.
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It is essential to build multiaxis oriented nanocellulose films in the plane for developing thermal or optical management films. However, using conventional orientation techniques, it is difficult to align nanocelluloses in multiple directions within the plane of single films rather than in the thickness direction like the chiral nematic structure. In this study, we developed the liquid-phase three-dimensional (3D) patterning technique by combining wet spinning and 3D printing. Using this technique, we produced a checkered film with multiaxis oriented nanocelluloses. This film showed similar retardation levels, but with orthogonal molecular axis orientations in each checkered domain as programmed. The thermal transport was enhanced in the domain with the oriented pattern parallel to the heat flow. This liquid-phase 3D patterning technique could pave the way for bottom-up design of differently aligned nanocellulose films to develop sophisticated optical and thermal materials.
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Thermal transport modulating materials show great potential to address the heat problems in a wide range of engineering fields. However, tuning the thermal conductivity of solid-state materials is practically difficult because it requires specific or extreme stimulation, such as chemical composition change, a phase transition, or large applied fluctuations, to change the internal bulk structures. Here, we report reversible switching of the in-plane thermal diffusivity of densely packed cellulose nanofiber (CNF) films by â¼15% by simple mechanical strain as small as 0.3%. From analysis of the stress relaxation profiles and the different bulk densities of the CNF films, the interfacial elastic dynamics between the strongly hydrogen bonded CNFs were found to exhibit thermal diffusivity modulation by tuning the interfacial thermal resistance, rather than changing the bulk structure of the CNFs. Our concept of interfacial-elasticity-driven thermal diffusivity switching has the potential to enhance the on/off rate and extensibility toward practical use owing to the high designability of the interfacial conditions.
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As a renewable nanomaterial, transparent nanopaper is one of the promising materials for electronic devices. Although conventional evaporation drying method endows nanopaper with superior optical properties, the long fabrication time limits its widely use. In this work, we propose a multi-stage drying method to achieve high-speed fabrication of clear transparent nanopaper. Drying experiments reveal that nanopaper's drying process can be separated into two periods. For the conventional single-stage evaporation drying, the drying condition is kept the same. In our newly proposed multi-stage drying, the relative humidity (RH), which is the key parameter for both drying time and haze, is set differently during these two periods. Applying this method in a humidity-controllable environmental chamber, the drying time can be shortened by 35% (from 11.7 h to 7.6 h) while maintaining the same haze level as that from single-stage drying. For a conventional humidity-uncontrollable oven, a special air flow system is added. The air flow system enables decrease of RH by removing water vapor at the water/air interface during the earlier period, thus fabricating clear transparent nanopaper in a relatively short time. Therefore, this humidity-controlled multi-stage drying method will help reduce the manufacturing time and encourage the widespread use of future nanopaper-based flexible electronics.
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Plasmonic nanoparticles, such as gold nanoparticles (AuNPs), have been actively applied in solar vapor generation for seawater desalination and water purification, owing to their photothermal heating performances. Such nanoparticles have been frequently anchored within porous supporting materials to ensure easy handling and water absorption. However, there has been limited progress in improving the transport efficiency of light to nanoparticles within porous supports to achieve more effective photothermal heating. Here, we show an enhanced light absorption of AuNPs by supporting on a cellulose paper with tailored porous structures for efficient photothermal heating. The paper consists of AuNP-anchored cellulose nanofibers and cellulose pulp as the top and bottom layers, respectively, which provides dual-layered porous nano-microstructures in the perpendicular direction. Then, the bottom layer with pulp-derived microstructures reflects the transmitted light back to AuNPs within the top layer, which improves their light absorptivity. Thus, under 1 sun illumination, the dual-layered paper demonstrates superior performance in photothermal heating (increases from 28 °C to 46 °C) and solar vapor generation (1.72 kg m-2 h-1) compared with the single-layered AuNP-anchored cellulose nanofiber paper even at the same AuNP content. Furthermore, the water evaporation rate per AuNP content of the dual-layered paper is more than 2 times higher than those of the state-of-the-art AuNP-anchored porous materials under the same light irradiation. This strategy enables the efficient use of precious plasmonic nanoparticles for further development of solar vapor generation.
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Chitin nanofibers were prepared from dried crab shells by a simple grinding treatment in a never-dried state under an acidic condition after the removal of proteins and minerals. The obtained nanofibers were observed by FE-SEM and found to have a uniform width of approximately 10-20 nm and high aspect ratio; both these findings were similar to those for nanofibers from prawns. Furthermore, it was confirmed that the nanofibers were extracted from the natural chitin/protein/mineral composites of crab shell in their original state. That is, the N-acetyl group was not removed and the alpha-chitin crystal structure was maintained, as confirmed by elemental analysis data, FT-IR spectra, and X-ray diffraction profiles.