Local out-of-plane deformation of CFRP ablator subjected to rapid heating

This study investigates local out-of-plane deformation of a carbon fiber reinforced phenolic polymer ablator subjected to very rapid heating. Local out-of-plane deformation was measured using a three-dimensional digital image correlation technique at high temperatures. This was achieved by attaching high temperature resistant random patterns on the specimen surface using a ceramic bond. Additionally, blue filters intended for cutting strong infrared radiation from the specimen were also used. This study then discusses the mechanisms of the local out-of-plane deformation under rapid heating conditions in terms of carbonization, pyrolysis gas occurrence, gas pressure storage, and interlaminar debonding due to gas pressure.     

High-Performance Nonvolatile Organic Photonic Transistor Memory Devices using Conjugated Rod–Coil Materials as a Floating Gate

A novel approach for using conjugated rod–coil materials as a floating gate in the fabrication of nonvolatile photonic transistor memory devices, consisting of n-type Sol-PDI and p-type C10-DNTT, is presented. Sol-PDI and C10-DNTT are used as dual functions of charge-trapping (conjugated rod) and tunneling (insulating coil), while n-type BPE-PDI and p-type DNTT are employed as the corresponding transporting layers. By using the same conjugated rod in the memory layer and transporting channel with a self-assembled structure, both n-type and p-type memory devices exhibit a fast response, a high current contrast between “Photo-On” and “Electrical-Off” bistable states over 10⁵, and an extremely low programing driving force of 0.1 V. The fabricated photon-driven memory devices exhibit a quick response to different wavelengths of light and a broadband light response that highlight their promising potential for light-recorder and synaptic device applications.     

Development of a three-dimensional finite element model for a unidirectional carbon fiber reinforced plastic based on X-ray computed tomography images and the numerical simulation on compression

A unidirectional carbon fiber reinforced plastic (CFRP) was scanned by an X-ray computed tomography (CT) system. Based on the X-ray CT images, a three-dimensional model with random fiber waviness was developed. Each fiber location was identified in a sectional CT image. Subsequently, the relative displacement of fibers between adjacent sectional CT images was obtained with a digital image correlation method. This procedure was repeated to obtain fiber waviness along the axial direction. The constructed three-dimensional fiber model showed random waviness of each fiber in the unidirectional CFRP. Finite element analysis was performed using the three-dimensional model. Simulation results showed bending and twisting deformations coupled with axial contractions during axial compression, which developed due to fiber waviness. A reduction of the fiber directional Young’s modulus due to fiber random waviness was quantitatively evaluated.     

Reentrant Spin Glass and Large Coercive Field Observed in a Spin Integer Dimerized Honeycomb Lattice

2D magnetic materials with dimerized honeycomb lattices can be treated as mixed-spin square lattices, in which a quantum phase transition may occur to realize the Bose–Einstein condensation of magnons under reachable experimental conditions. However, this has never been successfully realized with integer spin centers. Herein, a spin integer (S = 2) dimerized honeycomb lattice in an iron(II)-azido compound [Fe(4-etpy)₂(N₃)₂]_n (FEN, 4-etpy = 4-ethylpyridine) is realized. Morphology characterization by transmission electron microscopy, scanning electron microscopy, and atomic force microscopy spectroscopies show that the thinnest place of the sample is ≈13 nm, which is equal to ten layers of the compound. In contrast to the common magnetic properties of long-range magnetic ordering, Mössbauer and polarized neutron scattering studies reveal that FEN exhibits a reentrant spin glass behavior owing to competing ferro- and antiferromagnetic exchange-coupling interactions within the lattice. Two spin glass phases with disparate canting angles are characterized at 39 and 28 K, respectively. By using Curély's model, two exchange-coupling constants (J₁ = +35.8 cm⁻¹ and J₂ = −3.7 cm⁻¹) can be simulated. Moreover, a very large coercive field of ≈1.9 Tesla is observed at 2 K, making FEN a “very hard” van der Waals 2D magnetic material.     

Nanoimprint Lithography Facilitated Plasmonic-Photonic Coupling for Enhanced Photoconductivity and Photocatalysis

Imprint lithography has emerged as a reliable, reproducible, and rapid method for patterning colloidal nanostructures. As a promising alternative to top-down lithographic approaches, the fabrication of nanodevices has thus become effective and straightforward. In this study, a fusion of interference lithography (IL) and nanosphere imprint lithography on various target substrates ranging from carbon film on transmission electron microscope grid to inorganic and dopable polymer semiconductor is reported. 1D plasmonic photonic crystals are printed with 75% yield on the centimeter scale using colloidal ink and an IL-produced polydimethylsiloxane stamp. Atomically smooth facet, single-crystalline, and monodisperse colloidal building blocks of gold (Au) nanoparticles are used to print 1D plasmonic grating on top of a titanium dioxide (TiO₂) slab waveguide, producing waveguide-plasmon polariton modes with superior 10 nm spectral line-width. Plasmon-induced hot electrons are confirmed via two-terminal current measurements with increased photoresponsivity under guiding conditions. The fabricated hybrid structure with Au/TiO₂ heterojunction enhances photocatalytic processes like degradation of methyl orange (MO) dye molecules using the generated hot electrons. This simple colloidal printing technique demonstrated on silicon, glass, Au film, and naphthalenediimide polymer thus marks an important milestone for large-scale implementation in optoelectronic devices.     

Development of a novel system to quantify the spatial–temporal parameters for crutch-assisted quadrupedal gait

Abstract

Patients with gait disorders often use bilateral crutches along with their own two legs. It is a kind of quadrupedalism. Crutch-assisted gait is usually described and evaluated qualitatively. In this study, we developed a system to quantify the spatial and temporal parameters for crutch-assisted quadrupedalism. Our system consists of walkway hardware and our originally developed software. We specifically extended the measurable area to 1200 mm × 4800 mm, large enough to measure crutch gait. Using our system, we could describe crutch gait precisely. Our system has a capability to evaluate differences between patients and changes within a patient.     

Various spectroelectrochemical cells for in situ observation of electrochemical processes at solid–liquid interfaces

In the last several decades, a variety of surface analysis techniques which can probe the geometric/electronic/molecular structures of the interfaces, as well as the elemental composition, have been developed and applied for the investigation of electrochemical processes taking place at solid–liquid interfaces. Designing spectroelectrochemical cells is one of the big challenges for utilization of those techniques to a variety of electrochemical interfaces because the thickness of solution layers, materials used as a window, geometry of the photon source, sample, and spectrometer/analyzer/detector need to be optimal for the electrochemical reaction of interest and photons used in the individual techniques. To date, various unique spectroelectrochemical cells have been used for in situ electrochemical studies on interfacial processes even by using the techniques which intrinsically require vacuum. In this paper, recent progress on in situ spectroelectrochemical cells, especially used for X-ray photoelectron spectroscopy, is reviewed.     

Characteristics and Reactivity of Lignin in Acacia and Eucalyptus Woods

The chemical characteristics of lignin, including the Klason lignin content, acid-soluble lignin content, proportion of the aromatic ring types [syringyl ratio = syringyl/(syringyl + guaiacyl)], and proportion of the diastereomeric forms for the β-O-4 structure [erythro ratio = erythro/(erythro + threo)], and pulpability were investigated for 28 wood samples belonging to the genera Acacia and Eucalyptus. Although the lignin characteristics of these 28 woods varied widely, the chemical characteristics of the two genera could be categorized in two clearly distinguished groups on the basis of the syringyl ratio. Clear negative correlations were observed between both the syringyl and erythro ratios and the total lignin content (sum of the Klason and acid-soluble lignin contents) within each genus. In addition, the syringyl ratio correlated positively with the erythro ratio and acid-soluble lignin content, regardless of the genus. The existence of a clear, high correlation between the syringyl and erythro ratios supports the hypothesis that the aromatic ring type (syringyl ratio) is a decisive factor for controlling the diastereomeric forms of the β-O-4 structure (erythro ratio). Each of the wood samples was also subjected to Kraft pulping, and it was demonstrated that the woods with higher syringyl ratios were easier to delignify. This tendency is reasonably attributed to the high reactivity of the erythro-rich and syringyl-rich β-O-4 structures, and the low lignin content of these syringyl-rich woods.     

Chemical Factors Underlying the More Rapid β-O-4 Bond Cleavage of Syringyl than Guaiacyl Lignin under Alkaline Delignification Conditions

This study aimed to clarify why the β-O-4 bond cleavage of syringyl lignin is more rapid than that of guaiacyl lignin under alkaline pulping conditions. We examined whether or not three chemical factors, acidity of the α-hydroxy group, nucleophilicity of the generated α-alkoxide, and leaving ability of the leaving phenoxide, are different between syringyl and guaiacyl lignins and control the rate of the alkaline-induced β-O-4 bond cleavage, employing dimeric non-phenolic β-O-4-type lignin model compounds (LMCs) and novel methods for estimating these three factors. The results indicated that the α-hydroxy groups of syringyl-type LMCs are relatively more acidic than those of guaiacyl-type and that syringyl nucleus is a better leaving group than guaiacyl nucleus in the β-O-4 bond cleavage. These factors result in the β-O-4 bond of syringyl lignin being more prone to the alkaline-induced cleavage than that of guaiacyl lignin.     

Stereo-Preference in the degradation of the erythro and threo isomers of β-O-4-type lignin model compounds in oxidation processes. part 2: In the reaction with hydroxyl and oxyl anion radicals under hydrogen peroxide bleaching conditions

We examined which isomer, the erythro or threo, of non-phenolic β-O-4-type lignin model compounds is stereo-preferentially attacked by hydroxyl radical and its conjugate base, oxyl anion radical, generated by the decomposition of hydrogen peroxide in the presence of ferric ion and its precipitates under hydrogen peroxide bleaching conditions. The intrinsic stereo-preference of oxyl anion radical was slightly toward the erythro isomer, while hydroxyl radical had a further smaller stereo-preference. These stereo-preferences can be explained by our prior knowledge that oxyl anion radical preferentially attacks the side-chain of the lignin model compounds rather than the aromatic nucleus. The amount of the degraded lignin model compounds became less great with decreasing pH, but reversely and intensively greater in the pH range below 10. This phenomenon can be attributed to the change in the decomposition mechanism of hydrogen peroxide accompanying the pH variation.