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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.

Thanakorn Yeamsuksawat, Yoshitaka Morishita, Jun Shirahama, Yintong Huang, Takaaki Kasuga, Masaya Nogi, and Hirotaka Koga, Semicarbonized Subwavelength-Nanopore-Structured Nanocellulose Paper for Applications in Solar Thermal Heating, Chem. Mater. 2022, 34, 16, 7379–7388. ©2022 American Chemical Society., Recently, there has been remarkable progress in solar thermal heating by applying biomass-derived carbons, which can absorb and convert solar light into thermal energy. The design of subwavelength nanoporous and molecular structures of biomass-derived carbons is required for suppressed reflection and enhanced absorption of solar light. However, such designs are difficult because conventional biomass-derived carbons exhibit intrinsic microstructures and are prepared under specific carbonization conditions. In this study, a wood cellulose nanofiber-derived carbon is proposed to tailor both subwavelength nanoporous and molecular structures. Cellulose nanofibers are first constructed into a paper, denoted as "nanopaper", exhibiting subwavelength nanoporous structures by tailoring the pore spaces between cellulose nanofibers. The as-prepared nanopaper is then carbonized at various controlled temperatures to tailor the cellulose molecular structure, i.e., grow graphitic carbon domains. The graphitic carbon domains grown by semicarbonization at 500 °C adequately balance solar absorption and reflection, while the subwavelength nanoporous structures suppress solar reflection. Thus, the semicarbonized nanopaper with tailored nanoporous and molecular structures exhibits superior solar thermal heating to competitive nanocarbons, also affording thermoelectric power generation. This study can guide the structural and functional design of bionanocarbons for solar thermal heating.

Abundant and renewable all-cellulose-derived humidity sensors are fabricated via direct laser writing of patterned electrodes onto TEMPO-oxidized cellulose fiber paper, offering versatile applicability for the “trillion sensor” era.

Biomimicry and the development of sophisticated materials can derive inspiration from the nanoscale component orientation and hierarchical structures found in living organisms. Herein, a simple and flexible strategy to construct a sophisticated hierarchical structure based on electrophoretic and electrochemical deposition is reported. Cellulose nanofibres (CNFs), which were used as model materials, were deposited on anode in an aqueous dispersion and fixed in an oriented state, which could be seamlessly altered from horizontal to vertical orientation relatively to the electrodes depending on the applied voltage between the electrodes. The oriented CNF hydrogels not only exhibited anisotropic mechanical properties but also formed complex orientations and hierarchical structures, such as cartilage- and plant stem-like configurations upon varying the electrode shape and applied voltage. This electrophoretic and electrochemical approach was also applied to achieve control over the drying-related shrinkage of the CNF hydrogels, which enabled the fabrication of highly functional dried moulded materials made of rigid CNFs. This simple and flexible technology has the potential to be applied to various materials and thus is expected to contribute to a wide range of fields, such as biomimicry, the formation of highly functional materials made of nanomaterials, and the production of sustainable and functional mouldings.

Water is detrimental to electronic devices because it easily causes short circuits. The use of sealing to prevent water permeation is considered as the current conventional solution; however, the t...

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.

The design of the three-dimensional (3D) porous and defective molecular structure of nanocarbons can potentially enhance their functionalities for advanced electronic applications by providing a large working volume, rapid transport of electrolytes and reactants, and active sites for electrochemical reactions. Here, we report successful fabrication of 3D porous and defective nanocarbons by direct pyrolysis of crab shell-derived chitin nanofiber paper. The pyrolyzed chitin nanofiber paper has tunable electrical resistivity (1013 to 10−2 Ω cm), 3D porous structures with layered nanofiber networks, and defective nitrogen-doped carbon molecular structures. The pyrolyzed chitin nanofiber paper shows good performance as a photosensor and an energy-storage supercapacitor electrode, proving that the tailored 3D porous and defective carbon structures play key roles in the drastic improvement of the performance. This pioneering approach can be used for fabrication of chitin nanofiber-derived nanocarbons with excellent multiple functions for future sustainable electronics.

Koga H., Nagashima K., Suematsu K., et al. Nanocellulose Paper Semiconductor with a 3D Network Structure and Its Nano-Micro-Macro Trans-Scale Design. ACS Nano, 16(6), 8630-8640, 2022. https://doi.org/10.1021/acsnano.1c10728., 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.

K. Uetani, S. Izakura, H. Koga and M. Nogi. Thermal diffusivity modulation driven by the interfacial elastic dynamics between cellulose nanofibers Nanoscale Adv., 2020, 2, 1024. https://doi.org/10.1039/C9NA00734B., 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.

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.

Heat dissipation has become increasingly important in electronics. Conventional convection cooling systems have significant material and dimensional constraints, and they have difficulty meeting the heat dissipation, miniaturization, and flexibility requirements of next-generation smart electronics. Here, we used kirigami (the traditional art of paper cutting) with a thermally conductive cellulose nanofiber film to propose a flexible cooling system through convective heat dissipation. By stretching the Amikazari (net decoration) pattern produced by kirigami and allowing air convection through its aperture at 3.0 m/s, the thermal resistance was reduced to approximately one-fifth of that without kirigami and convection. The kirigami apertures defined the outlet air velocity, resulting in a significant increase in the heat-transfer coefficient. Our kirigami heat dissipation concept enables the design of electronics using a variety of film materials as shape-variant cooling structures, which will inspire a wide range of thermal engineering and electronics applications. A shape-variant heat dissipation system using kirigami was proposed using the thermally conductive cellulose nanofiber films. By stretching the Amikazari (net decoration) pattern produced by kirigami and allowing air convection through its aperture at 3.0m/s, the thermal resistance was reduced to approximately one-fifth of that without kirigami and convection. The periodic apertures of kirigami defined the outlet air velocity of convection, resulting in a significant increase in the heat-transfer coefficient. We further demonstrated the effective cooling of the kirigami-processed powder electroluminescent device during the emission of light.

Wearable devices with excellent mechanical stretchability, comparable to that of human skin, are highly desirable for preventing discomfort and dermatitis. Composite material systems that use metal particles and elastomers are promising for realizing intrinsic stretchable electrodes with high conductivity and enhancing mechanical flexibility of wearable devices. However, it is challenging to achieve stable device performance under mechanical deformation using stretchable electrodes. In this study, stretchable electrodes with enhanced conductivity and stretchability are developed and integrated with organic transistors to fabricate a stretchable printed circuit board (PCB) that acts as a voltage amplifier under large strains. The stretchable electrodes are composed of silver microparticles, a small quantity of silver nanowires (AgNWs), and an elastomer matrix, which demonstrated a conductivity of 8.5 × 103 S cm−1 at a curing temperature of 100 °C. The observed conductivity was 3.6 times higher than that of electrodes without AgNWs. Owing to the addition of AgNWs, the durability strain in cyclic stretching increased from 10% to 75%; the increment can be attributed to the suppression of microcrack propagation. Moreover, the proposed stretchable PCB was applied to fabricate a voltage amplifier, which enabled stable amplification by 14 times under 0% and 75% strain owing to a mechanical rigid-soft patterning designed into the substrate according to the rigidness of the mounted components. The stabilization technologies in the proposed stretchable PCB can contribute to the development of wearable devices for long-term usage to assist the early detection of diseases.

Takaaki Kasuga, Hitomi Yagyu, Kojiro Uetani, Hirotaka Koga, and Masaya Nogi. “Return to the Soil” Nanopaper Sensor Device for Hyperdense Sensor Networks. ACS Applied Materials & Interfaces 2019 11 (46), 43488-43493. https://doi.org/10.1021/acsami.9b13886., 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.

In this paper, transparent electrodes with dense Cu@Ag alloy nanowires embedded in the stretchable substrates are successfully fabricated by a high-intensity pulsed light (HIPL) technique within one step. The intense light energy not only induces rapid mutual dissolution between the Cu core and the Ag shell to form dense Cu@Ag alloy nanowires but also embeds the newly formed alloy nanowires into the stretchable substrates. The combination of alloy nanowires and embedded structures greatly improve the thermal stability of the transparent electrodes that maintain a high conductivity unchanged in both high temperature (140 °C) and high humidity (85 °C, 85% RH) for at least 500 h, which is much better than previous reports. The transparent electrodes also exhibit high electromechanical stability due to the strong adhesion between alloy nanowires and substrates, which remain stable after 1000 stretching-relaxation cycles at 30% strain. Stretchable and transparent heaters based on the alloyed and embedded electrodes have a wide outputting temperature range (up to 130 °C) and show excellent thermal stability and stretchability (up to 60% strain) due to the alloy nanowires and embedded structures. To sum up, this study proposes the combination of alloying and embedding structures to greatly improve the stability of Cu nanowire-based stretchable transparent electrodes, showing a huge application prospect in the field of stretchable and wearable electronics.

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Applied Materials and Interfaces, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acsami.9b01287., 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.

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.

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.

Li, C.; Kasuga, T.; Uetani, K.; Koga, H.; Nogi, M. High-Speed Fabrication of Clear Transparent Cellulose Nanopaper by Applying Humidity-Controlled Multi-Stage Drying Method. Nanomaterials 2020, 10, 2194. https://doi.org/10.3390/nano10112194., 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.

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.

Y. Huang, Y. Morishita, K. Uetani, M. Nogi and H. Koga. Cellulose paper support with dual-layered nano–microstructures for enhanced plasmonic photothermal heating and solar vapor generation. Nanoscale Adv., 2020, 2, 2339. https://doi.org/10.1039/D0NA00163E., 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.

Flexible and wearable electronics have recently attracted increasing attention, because they can open up new possibilities for next-generation portable devices. Cellulose paper serves various purposes in daily life, including in writing, printing, wrapping, and packaging applications. Since paper materials are sustainable, mass produced, inexpensive, biocompatible, recyclable, lightweight, and flexible, the use of paper has recently been extended to flexible electronic applications. In this chapter, we describe cellulose-based flexible paper electronics. Wood-derived cellulose pulp or nanocellulose is composited with conductive nanomaterials such as silver nanowires, carbon nanotubes, and graphene. The as-prepared paper composites are successfully applied as transparent conductive paper, paper antenna, paper sensor, and paper supercapacitor. These paper devices demonstrated both high device performance and flexibility compared with the state-of-the-art polymer-based flexible devices. Our findings provide a promising route to realize green and flexible paper electronics.

Electrochemical techniques were employed to study the electrochemical corrosion behavior of Sn-9Zn-xTi (x = 0, 0.05, 0.1, 0.2 wt.%) lead-free solders in neutral 0.5M NaCl solution, aiming to figure out the effect of Ti content on the corrosion properties of Sn-9Zn, providing information for the composition design of Sn-Zn-based lead-free solders from the perspective of corrosion. EIS results reveal that Ti addition was involved in the corrosion product layer and changed electrochemical interface behavior from charge transfer control process to diffusion control process. The trace amount of Ti addition (0.05 wt.%) can refine the microstructure and improve the corrosion resistance of Sn-9Zn solder, evidenced by much lower corrosion current density (icorr) and much higher total resistance (Rt). Excess Ti addition (over 0.1 wt.%) led to the formation of Ti-containing IMCs, which were confirmed as Sn3Ti2 and Sn5Ti6, deteriorating the corrosion resistance of Sn-9Zn-xTi solders. The main corrosion products were confirmed as Sn3O(OH)2Cl2 mixed with small amount of chlorine/oxide Sn compounds.

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Applied Materials and Interfaces, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acsami.7b14827., Functional molecules play a significant role in the development of high-performance composite materials. Functional molecules should be well dispersed (ideally dissolved) and supported within an easy-to-handle substrate to take full advantage of their functionality and ensure easy handling. However, simultaneously achieving the dissolution and support of functional molecules remains a challenge. Herein, we propose the combination of a nonvolatile ionic liquid and an easy-to-handle cellulose paper substrate for achieving this goal. First, the photochromic molecule, i.e., diarylethene, was dissolved in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([bmim]NTf2). Then, diarylethene/[bmim]NTf2 was supported on cellulose fibers within the paper, through hydrogen bonding between [bmim] cations of the ionic liquid and the abundant hydroxyl groups of cellulose. The as-prepared paper composites exhibited reversible, rapid, uniform, and vivid coloration and bleaching upon ultraviolet and visible light irradiation. The photochromic performance was superior to that of the paper prepared in the absence of [bmim]NTf2. This concept could be applied to other functional molecules. For example, lithium perchlorate/[bmim] tetrafluoroborate supported within cellulose paper acted as a flexible electrolyte to provide a paper-based electrochromic device. These findings are expected to further the development of composite materials with high functionality and practicality.

Electrochemical behavior of Zn- x Sn ( x = 40 wt%,30 wt%,20 wt%) high-temperature lead-free alloys was investigated in aerated 0.5 M NaCl solution by open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. OCP results show that the corrosion state of the alloys working surface reached a relatively dynamic equilibrium after the alloys were immersed in 0.5 M NaCl solution for 100 h. EIS analysis reveals that the total corrosion resistance R t of alloys depended on the amount of Sn, and Zn-40Sn possessed the highest value 2228.2 Ω cm 2 . No passivation behavior was observed during corrosion process by potentiodynamic polarization measurement. The dominant corrosion products were confirmed as Zn 5 (OH) 8 Cl 2 ·H 2 O, ZnO and Zn(OH) 2 . Moreover, the surface and cross-section morphology of corrosion product suggested that the corrosion layer was more homogeneous and denser for higher Sn-content, Zn-40Sn obtained the best protective layer from corrosion product. The results recommend that Zn- x Sn high-temperature solder alloy with higher Sn content appears to be more attractive in terms of superior corrosion properties. The exact corrosion process was also discussed in detail.

H. Koga, N. Namba, T. Takahashi, M. Nogi, Y. Nishina. Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous‐Flow Nanocatalysis. ChemSusChem 2017, 10, 2560. https://doi.org/10.1002/cssc.201700576., Continuous-flow nanocatalysis based on metal nanoparticle catalyst-anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle-anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The “paper reactor” offers hierarchically interconnected micro- and nanoscale pores, which can act as convective-flow and rapid-diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous-flow, aqueous, room-temperature catalytic reduction of 4-nitrophenol to 4-aminophenol, a gold nanoparticle (AuNP)-anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state-of-the-art AuNP-anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP-anchored paper reactors were also demonstrated while high reaction efficiency was maintained.

We propose a potential fluid-measurement technology aimed at supporting biomechanics research of water sports using fluid simulation and motion analysis. Cellulose nanofibers introduced into the water as tracer particles to visualize the movement of water. An optical property of nanofibers, called flow birefringence, makes water flows brighter than their surroundings when placed between right and left circularly polarized plates. We tested the capability of the technology in a water tank and succeeded in using an existing particle-tracking method-particle image velocimetry (PIV)-to measure the flows from a pump in the tank.

Uetani, K.; Izakura, S.; Kasuga, T.; Koga, H.; Nogi, M. Self-Alignment Sequence of Colloidal Cellulose Nanofibers Induced by Evaporation from Aqueous Suspensions. Colloids Interfaces 2018, 2, 71. https://doi.org/10.3390/colloids2040071., Cellulose nanopapers fabricated by drying aqueous colloidal suspensions of cellulose nanofibers (CNFs) have characteristic hierarchic structures, which cause the problem that their optical properties, including their transparency or haze, vary due to the drying processes affecting CNF alignment. It is unclear when and how the colloidal CNFs align in the evaporation–condensation process from the randomly dispersed suspension to form the nanopaper. In this study, we found that the CNFs undergo a self-alignment sequence during the evaporation–condensation process to form chiral nematic nanopaper by observing the birefringence of the drying suspensions from both the top and side for two suspensions with different initial CNF concentrations. The layer structures of the CNFs first form on the surface by condensation of the suspension, owing to water evaporation from the surface. The thickness of the layered structure then increases and the CNFs begin to align within each layer plane, finally forming chiral nematic structures. A birefringence difference also occurs for dried nanopapers with similar transparency or haze because of the initial CNF concentration.

The recent trend toward the Internet of Things (IoT) has increased the importance of technologies for the mass production of high-sensitivity flexible antennas for efficient wireless communication. Here, we describe the rapid low-temperature fabrication of high-sensitivity flexible antennas based on hot-water sintering of silver (Ag) precursor-based ink. Ag precursor-based ink was printed on various flexible substrates such as plastic films and cellulose nanofiber paper, followed by pre-drying the ink solvent and then treatment at 80 °C and 95% relative humidity for 2 min. The resulting printed Ag lines achieved a volume resistivity of approximately 6 μΩ cm, providing excellent sensitivity as dipole antennas for wireless communication. This technique enables the mass production of printed high-sensitivity antennas, which will likely be required for a future IoT society.

Reproduced from Ref. Green Chem., 2016,18, pp. 1117-1124. with permission from the Royal Society of Chemistry., Recent progress in portable and wearable electronics has promoted a growing demand for high-performance and flexible energy-storage devices that are abundant and affordable. Because reduced graphene oxide (rGO), originating from inexpensive graphite, serves as a higher-performance energy-storage electrode than conventional activated carbons and carbon nanotubes, research and development of rGO/polymer composite electrodes for flexible supercapacitors have become a center of attraction. However, the fabrication of rGO-based flexible electrodes frequently requires a long time with high-temperature treatment or toxic chemical treatment, resulting in the lack of scalability and eco-friendliness. Here we show a fast, scalable, and environment-compatible route to fabricate a high-performance rGO/cellulose paper supercapacitor electrode. Single-layer graphene oxide (GO) sheets and recycled waste pulp fibers were successfully fabricated into a paper composite by a well-established scalable papermaking process, followed by a room-temperature, additive-free, and millisecond-timescale flash reduction process. The as-prepared rGO/paper electrode had a high specific capacitance, up to 212 F g-1, for an all paper-based flexible supercapacitor, comparable to those of state-of-the-art rGO-based electrodes, while dramatically decreasing the reduction time of GO from the conventional hour timescale to milliseconds. This work will pave the way for green, flexible, and mass-producible energy-storage paper in future wearable electronics.

Uetani, K.; Koga, H.; Nogi, M. Checkered Films of Multiaxis Oriented Nanocelluloses by Liquid-Phase Three-Dimensional Patterning. Nanomaterials 2020, 10, 958. https://doi.org/10.3390/nano10050958., 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.

The transparent electrode based on silver nanowire (AgNW) networks is one promising alternative of indium tin oxide film in particular for advanced flexible and printable electronics. However, the widespread application of AgNW electrode is hindered by its poor long-term reliability. Although the reliability can be improved by applying traditional overcoating layer or the core-shell structure, the transmittance or conductivity is inevitably undermined. In this paper, a novel patterned barrier of photoresist in situ assembled on the nanowire surface realized the reliability enhancement by simply employing AgNWs themselves as the mask in the photolithography process. The patterned barrier selectively covered the nanowires, while keeping the high transmittance and conductivity unchanged and improving the adhesion of AgNW networks on substrate. After 720 h storage in 85 °C/85% relative humidity (RH) environment, the resistance of electrode with patterned barrier only increased by 0.72 times. This study proposes a new way, i.e., the in situ patterned barrier containing light-sensitive substance, to selectively protect AgNW networks, which can be expanded to various metallic networks including nanowires, nanorods, nanocables, electrospun nanofibers, and so on.

Optically transparent cellulose nanopaper is one of the best candidate substrates for flexible electronics. Some types of cellulose nanopaper are made of mechanically or chemically modified cellulose nanofibers. Among these, nanopapers produced from chemically modified cellulose nanofibers are the most promising substrate because of their lower power consumption during fabrication and higher optical transparency (lower haze). However, because their thermal durability is as low as plastics, paper devices using chemically modified nanopaper often do not have sufficiently high performance. In this study, by decreasing the carboxylate content in the cellulose nanofibers, the thermal durability of chemically modified nanopaper was drastically improved while maintaining high optical transparency, low coefficient of thermal expansion, and low power consumption during fabrication. As a result, light-emitting diode lights illuminated on the chemically modified nanopaper via highly conductive lines, which were obtained by printing silver nanoparticle inks and high-temperature heating.

Electrochemical corrosion behavior of Sn–Zn solder alloys in aerated and quiescent 0.5 M NaCl solution was investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques, aiming to assess the role of Zn precipitates and Cl− anions in pitting corrosion. The results reveal that increasing in Zn contents leads to increasing in pitting susceptibility, ascribed to the coarsening Zn precipitates with larger intergranular boundaries between Zn-rich precipitates and Sn matrix. The EIS results provide a quantitative description of the electrochemical interface behavior. The mechanism of pitting and the role of Cl− anions are discussed.

This is the peer reviewed version of the following article: Inui, T., Koga, H., Nogi, M., Komoda, N. and Suganuma, K. (2015), A Miniaturized Flexible Antenna Printed on a High Dielectric Constant Nanopaper Composite. Adv. Mater., 27: 1112-1116., which has been published in final form at https://doi.org/10.1002/adma.201404555. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving., A high-dielectric-constant and flexible cellulose nanopaper composite is prepared by mixing a small amount of silver nanowires with cellulose nanofibers. The nanopaper antenna is downsized by about a half when using the nanopaper substrate. The nanopaper antenna has potential in wearable wireless communication devices.

By adding 2 wt% multi-layer graphene oxide (MGO) to an epoxy resin, the thermal conductivity of the compos- ite reached a maximum, 2.03 times that of the epoxy. The presence of 2 wt%MGO percolating chains leads to an unprece- dentedly sharp rise in energy barrier at final curing stage, but an increased epoxy curing degree (!IR) is observed; however, this !IR difference nearly disappears after aging or thermal annealing. These results suggest that the steep concentration gra- dient of -OH, originated from the 2 wt%MGO percolating chains, exerts the vital driving force on the residual isolated/ trapped epoxy to conquer barrier for epoxy-MGO reaction. A modified Shrinking Core Model customized for the special layered-structure of MGO sheet was proposed to understand the resistance variation during the intercalative epoxy-MGO reaction. It shows that the promoted intercalative crosslinking is highly desirable for further improving the thermal conduc- tivity of the composite, but it meets with increased resistance. Guided by the kinetic studies, targeted optimization on the cure processing strategy was accordingly proposed to promote the intercalative crosslinking, a thermal conductivity, 2.96 times that of the epoxy, was got with only a small amount (30°C) increase of the post-heating temperature.

Transparent electrodes based on silver nanowire (AgNW) films have attracted considerable attention owing to their high electrical and thermal conductivity, optical transparency, and flexibility. However, the long-term reliability of AgNW electrodes, has seldom been studied. In this work, the effects of storage environment, such as, natural light and humidity, on the long-term reliability have been investigated in detail. The increase of electrical resistance with storage time greatly depended on the natural light illumination, especially ultraviolet (UV) illumination, and high humidity seriously accelerated the failure of AgNW electrodes. All the results were dependent on the storage temperature. Some over-coating layers have been used to protect the AgNW electrodes from light and humidity in environment and the results showed that an epoxy resin protecting layer exhibited the longest lifetime: over 40 days at 85 °C and 85% relative humidity.

Multi-layer graphene oxide (MGO) has attracted considerable interest in conductive polymer composites. However, in most cases the optimal MGO content is determined using a complex procedure. Avoiding the complicated work of processing polymerized samples followed by testing various properties, here a facile strategy is proposed to directly identify the critical MGO content among formulations for epoxy composites with optimal thermal properties, simply by monitoring the “unusual” nonlinear MGO content-dependent cure behaviors, as well as the “unusual” pattern of double-peak curing curves. The formation mechanism of the double-peak pattern was explored, with emphasis on studying the epoxy/MGO reaction using a modified Shrinking Core Model. The optimal content determined in this work (2 wt% MGO) was verified by the thermal properties (thermal conductivity, structural thermal stability and coefficient of thermal expansion) of MGO/epoxy composites. Based on the inherent relationship between the effect of MGO percolating chains on the thermal polymerization behavior and the resulting thermal properties, this strategy can be easily extended to different kinds of conductive MGO/polymer composites.

N. Isobe, T. Kasuga and M. Nogi. Clear transparent cellulose nanopaper prepared from a concentrated dispersion by high-humidity drying. RSC Adv., 2018, 8, 1833. https://doi.org/10.1039/C7RA12672G., Optically transparent cellulose nanopaper is a promising candidate for flexible device substrates because of its light weight, surface smoothness, and high dimensional stability with respect to temperature. Conventionally, clear transparent nanopaper has been fabricated from cellulose nanofiber dispersions with quite low concentration: less than 0.5 wt%. However, this diluteness leads to several problems, such as huge energy consumption and long operation time for drying. Therefore, nanopaper should be fabricated from a concentrated dispersion to mitigate these problems. In this study, transparent nanopaper was fabricated from cellulose nanofiber dispersions with various concentrations (0.24-1.81 wt%). Optical experiments revealed that the haze of the transparent nanopaper increased monotonically with cellulose nanofiber dispersion concentration, when the cellulose nanofiber dispersion was prepared from holocellulose pulp and conventional over-drying was applied. Based on our insight into the origin of this increase in the haze of transparent nanopaper, we developed high-humidity drying, which successfully produced clear transparent nanopaper from a concentrated dispersion without prolonged drying time.

Transparent electrode based on silver nanowires (AgNWs) emerges as an outstanding alternative of indium tin oxide film especially for flexible electronics. However, the conductivity of AgNWs transparent electrode is still dramatically limited by the contact resistance between nanowires at high transmittance. Polyvinylpyrrolidone (PVP) layer adsorbed on the nanowire surface acts as an electrically insulating barrier at wire–wire junctions, and some devastating post-treatment methods are proposed to reduce or eliminate PVP layer, which usually limit the application of the substrates susceptible to heat or pressure and burden the fabrication with high-cost, time-consuming, or inefficient processes. In this work, a simple and rapid pre-treatment washing method was proposed to reduce the thickness of PVP layer from 13.19 to 0.96 nm and improve the contact between wires. AgNW electrodes with sheet resistances of 15.6 and 204 Ω sq−1 have been achieved at transmittances of 90 and 97.5 %, respectively. This method avoided any post-treatments and popularized the application of high-performance AgNW transparent electrode on more substrates. The improved AgNWs were successfully employed in a capacitive pressure sensor with high transparency, sensitivity, and reproducibility. Electronic supplementary material The online version of this article (doi:10.1007/s40820-014-0018-0) contains supplementary material, which is available to authorized users.

Single- and multi-layer transparent conductive oxide (TCO) thin films exhibiting high performance, good packing density and low surface/interface roughness are deposited on silica glass substrates by the sol–gel method. The crystal and microstructural properties of the TCO thin films are evaluated as an alternate to films prepared by ultra-high vacuum deposition. Tin-doped indium oxide (ITO) thin films produced using a two-step drying process showed low surface roughness because of dense packing structure not only horizontal but also vertical directions. As a result, electrical conductivity, carrier concentration, carrier mobility, and optical transmittance of 2.3 × 103 S/cm, 8 × 1020 cm−3, 18 cm2/Vs, and over 98% at 500 nm, respectively, were achieved. A multilayer ZnO/ITO stacked structure was also fabricated using the sol–gel process. Our findings suggest that solution-based methods show promise as an alternative to existing ultra-high vacuum methods to fabricate TCO thin films.

Silver nanowires >60 μm and even 100 μm in length have been synthesized using a polyol process by adjusting the stirring speed at 130 °C. The length is over three times longer than that of normal AgNWs. These wires have a uniform ∼60 nm diameter, independent of the stirring speed. At 91% transmittance at 550 nm, AgNW films fabricated at room temperature achieved 25 Ω per square sheet resistance, which is superior to that of expensive ITO films.