Cutting processability of metal-ion-containing cellulose nanofibril films by continuous wave laser.

Understanding the cutting processability of cellulose nanofibril (CNF) films by continuous wave laser is important for precise shape processing that closely follows the design pattern. In this study, laser cutting of films made of surface-carboxylated CNFs with various counterionic species was performed to explore the factors that control the cutting processability. The cut width and the thermally affected width are mainly controlled by the laser irradiation energy per unit length. The processed cross section is tapered and rises above the film thickness. NMR analysis suggests that the pyrolysates contain water-soluble cello-oligosaccharides, the molecular weight of which varies with the type of CNF film. We consequently demonstrated that the COOH-type CNF film is preferable to the COONa-type CNF film for reducing the coloration residue and for processing the film into a shape that best follows the designed processing pattern.

Strong attractive interaction between finite element models of twisted cellulose nanofibers by intermeshing of twists.

Analysis of the attractive interaction between intrinsically twisted cellulose nanofibers (CNFs) is essential to control the physical properties of the higher-order structures of CNFs, such as paper and spun fiber. In this study, a finite element model reflecting the typical morphology of a twisted CNF was used to analyze the attractive interaction forces between multiple approaching CNF models. For two parallel CNF models, when one of the CNF models was rotated 90° around the long-axis direction, the twisting periods meshed, giving the maximum attraction force. Conversely, when the two CNF models were approaching diagonally, the CNF models were closest at an angle of -3.2° (i.e., in left-handed chirality) to give the most stable structure owing to the right-handed twist of the CNF models themselves. Furthermore, the two nematic layers were closest when one nematic layer was approached at an angle of -2° (i.e., in left-handed accumulation chirality), resulting in the greatest attraction. The results characterize the unique distribution of the attractive interaction forces between twisted CNF models, and they underscore the importance of chiral management in CNF aggregates, especially intermeshing of twists.

Tunability of the thermal diffusivity of cellulose nanofibril films by addition of multivalent metal ions.

Discovering principles to tune the heat-transport properties of cellulose nanofibril (CNF) films will open the door for the development of biomass-derived heat-transfer materials and break away from existing petroleum-based polymer composites. In this study, we added various multivalent metal ions to CNF films with surface carboxy groups formed by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidation and measured their thermal diffusivities in the dry state by an original method to verify the tunability of the thermal diffusivity. We found that the in-plane thermal diffusivity of the film is inversely proportional to the ionic radius and directly proportional to the Pauling electro-negativity. The CNF film with proton-neutralized carboxyl groups showed the highest level of thermal diffusivity among the films with various metal ions. Molecular dynamics simulations clarified that the spatial distribution of the introduced ions is determined by the closest distance between the cation and carboxylate oxygen atom of the TEMPO-oxidized CNF surface.

Thermal Diffusion Films with In-Plane Anisotropy by Aligning Carbon Fibers in a Cellulose Nanofiber Matrix.

For highly efficient heat dissipation of thin electronic devices, development of film materials that exhibit high thermal conductivity in the in-plane direction is desired. In particular, it is important to develop thermally conductive films with large in-plane anisotropy to prevent thermal interference between heat sources in close proximity and to cool in other directions by diffusion. In this study, we developed flexible composite films composed of a uniaxially aligned carbon-fiber filler within a cellulose nanofiber matrix through liquid-phase three-dimensional patterning. The film exhibited a high in-plane thermal conductivity anisotropy of 433%, with combined properties of a thermal conductivity of 7.8 W/mK in the aligned direction and a thermal conductivity of 1.8 W/mK in the in-plane orthogonal direction. This remarkable thermal conductivity and in-plane anisotropy showed the ability to significantly cool powder electroluminescent devices formed on the composite film and also to cool two heat sources in close proximity without thermal interference. In addition, the carbon-fiber filler could be extracted from the composite films by heat treatment at 450 °C and reused as a thermally conductive material.

Nanocellulose Paper Semiconductor with a 3D Network Structure and Its Nano-Micro-Macro Trans-Scale Design.

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.

Polydopamine Doping and Pyrolysis of Cellulose Nanofiber Paper for Fabrication of Three-Dimensional Nanocarbon with Improved Yield and Capacitive Performances.

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.

Enhancement of Luminance in Powder Electroluminescent Devices by Substrates of Smooth and Transparent Cellulose Nanofiber Films.

Powder electroluminescent (EL) devices with an electric field type excitation are surface light sources that are expected to have a wide range of practical applications, owing to their high environmental resistance; however, their low luminance has hindered their use. A clarification of the relationship between the properties of the film substrates and the electroluminescence is important to drastically improve light extraction efficiency. In this study, powder EL devices with different substrates of various levels of surface roughness and different optical transmittances were fabricated to quantitatively evaluate the relationships between the substrate properties and the device characteristics. A decrease in the surface roughness of the substrate caused a clear increase in both the current density and the luminance. The luminance was found to have a direct relationship with the optical transmittance of the substrates. The powder EL device, which was based on a cellulose nanofiber film and was the smoothest and most transparent substrate investigated, showed the highest luminance (641 cd/cm2) when 300 V was applied at 1 kHz.

Thermal Conductivity Analysis of Chitin and Deacetylated-Chitin Nanofiber Films under Dry Conditions.

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.

Irregular and suppressed elastic deformation by a structural twist in cellulose nanofibre models.

The elastic responsiveness of single cellulose nanofibres is important for advanced analysis of biological tissues and their use in sophisticated functional materials. However, the mechanical responsiveness derived from the twisted structure of cellulose nanofibres (CNFs) has remained unexplored. In this study, finite element simulations were applied to characterize the deformation response derived from the torsional structure by performing tensile and bending tests of an unconventionally very long and twisted rod model, having the known dimensional parameters and properties of CNFs. The antagonistic action of two types of structural elements (a contour twist and a curvilinear coordinate) was found to result in an irregular deformation response but with only small fluctuations. The contour twist generated rotational displacements under tensile load, but the curvilinear coordinate suppressed rotational displacement. Under bending stress, the contour twist minimized irregular bending deformation because of the orthotropic properties and made the bending stress transferability a highly linear response.

Direct determination of the degree of fibrillation of wood pulps by distribution analysis of pixel-resolved optical retardation.

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.

High-Speed Fabrication of Clear Transparent Cellulose Nanopaper by Applying Humidity-Controlled Multi-Stage Drying Method.

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.

Checkered Films of Multiaxis Oriented Nanocelluloses by Liquid-Phase Three-Dimensional Patterning.

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.

Thermal diffusivity modulation driven by the interfacial elastic dynamics between cellulose nanofibers.

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 ∼15% 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.

Cellulose paper support with dual-layered nano-microstructures for enhanced plasmonic photothermal heating and solar vapor generation.

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.

"Return to the Soil" Nanopaper Sensor Device for Hyperdense Sensor Networks.

A nanopaper sensor device that combines humidity sensing, wireless information transmission, and degradability has been fabricated using wood-derived nanopaper as the substrate and dielectric layers. The nanopaper shows excellent suitability for capacitor dielectric layers because of its high dielectric constant, insulating properties suitable for thin-film formation, and lamination properties. A wireless transmission circuit containing the nanopaper capacitor can transmit radio signals in the megahertz band, and the relative humidity change can be output as a change in the radio signal owing to the humidity sensitivity of the nanopaper capacitor. More than 95% of the total volume of the nanopaper sensor device decomposes in soil after 40 days. Because the nanopaper sensor device does not need to be recovered, it is expected to greatly contribute to a sustainable society through realization of hyperdense observation networks by mass installation of sensor devices.

Paper-Based Disposable Molecular Sensor Constructed from Oxide Nanowires, Cellulose Nanofibers, and Pencil-Drawn Electrodes.

Progress toward the concept of "a trillion sensor universe" requires sensor devices to become more abundant, ubiquitous, and be potentially disposable. Here, we report a paper-based disposable molecular sensor device constructed from a nanowire sensor based on common zinc oxide (ZnO), a wood-derived biodegradable cellulose nanofiber paper substrate, and a low-cost graphite electrode. The ZnO nanowire/cellulose nanofiber composite structure is embedded in the surface of the cellulose nanofiber paper substrate via a two-step papermaking process. This structure provides a mechanically robust and efficiently bridged network for the nanowire sensor, while ensuring efficient access to target molecules and allowing reliable electrical contact with electrodes. The as-fabricated paper sensor device with pencil-drawn graphite electrodes exhibits efficient resistance change-based molecular sensing of NO2 as a model gas. The performance of our device is comparable to that of noble metal electrodes. Furthermore, we demonstrate cut-and-paste usability and easy disposal of the sensor device with its uniform in-plane sensing properties. Our strategy offers a disposable molecular sensing platform for use in future sensor network technologies.

Estimation of the Intrinsic Birefringence of Cellulose Using Bacterial Cellulose Nanofiber Films.

The intrinsic birefringence of cellulose is one of the most fundamental optical parameters for analyzing and developing various cellulosic materials. However, the previously reported values greatly vary depending on the problems occurred due to the measured cellulose sample or method, and it is still a challenge to evaluate the intrinsic birefringence of cellulose using suitable cellulose samples and methodologies by taking account into the recent knowledge and techniques. Here, we estimated the intrinsic birefringence of cellulose to be 0.09 by a procedure with three valid factors: (1) bacterial cellulose nanofibers consisting of extended chain crystals of cellulose are used, (2) films with relatively small orientation degrees are fabricated, and (3) the in-plane retardation maps are measured. The resultant eigenvalue is greater than those reported for cellulose and many petroleum-based polymers. Therefore, cellulose could be used to develop high-performance light compensation films with large optical anisotropies for use in future optoelectronic devices.

Thermal conductivity analysis and applications of nanocellulose materials.

In this review, we summarize the recent progress in thermal conductivity analysis of nanocellulose materials called cellulose nanopapers, and compare them with polymeric materials, including neat polymers, composites, and traditional paper. It is important to individually measure the in-plane and through-plane heat-conducting properties of two-dimensional planar materials, so steady-state and non-equilibrium methods, in particular the laser spot periodic heating radiation thermometry method, are reviewed. The structural dependency of cellulose nanopaper on thermal conduction is described in terms of the crystallite size effect, fibre orientation, and interfacial thermal resistance between fibres and small pores. The novel applications of cellulose as thermally conductive transparent materials and thermal-guiding materials are also discussed.

In-Plane Anisotropic Thermally Conductive Nanopapers by Drawing Bacterial Cellulose Hydrogels.

We developed flexible polymeric "heat-guiding materials" by simply drawing bacterial cellulose (BC) hydrogels to align the cellulose nanofibers and form "nanopapers" with anisotropic thermal conductivity. The in-plane anisotropy of thermal conductivity between the drawn and transverse directions increased as the draw ratio increased. For the drawn BC nanopapers, the coefficient of thermal expansion was found to be inversely correlated with the thermal diffusivity. We fabricated a planar spiral sheet by assembling the drawn BC strips to visualize the "heat flux controllability". The coexistence of heat-diffusing and heat-insulating capacities within the single nanopaper plane could help to cool future thin electronics.

Crystallite Size Effect on Thermal Conductive Properties of Nonwoven Nanocellulose Sheets.

The thermal conductive properties, including the thermal diffusivity and resultant thermal conductivity, of nonwoven nanocellulose sheets were investigated by separately measuring the thermal diffusivity of the sheets in the in-plane and thickness directions with a periodic heating method. The cross-sectional area (or width) of the cellulose crystallites was the main determinant of the thermal conductive properties. Thus, the results strongly indicate that there is a crystallite size effect on phonon conduction within the nanocellulose sheets. The results also indicated that there is a large interfacial thermal resistance between the nanocellulose surfaces. The phonon propagation velocity (i.e., the sound velocity) within the nanocellulose sheets was estimated to be ∼800 m/s based on the relationship between the thermal diffusivities and crystallite widths. The resulting in-plane thermal conductivity of the tunicate nanocellulose sheet was calculated to be ∼2.5 W/mK, markedly higher than other plastic films available for flexible electronic devices.