Synthesis of novel hexamolybdenum cluster-functionalized copper hydroxide nanocomposites and its catalytic activity for organic molecule degradation.

A novel heterogeneous catalytic nanomaterial based on a molybdenum cluster-based halide (MC) and a single-layered copper hydroxynitrate (CHN) was first prepared by colloidal processing under ambient conditions. The results of the elemental composition and crystalline pattern indicated that CHN was comprehensively synthesized with the support of the MC compound. The absorbing characteristic in the ultraviolet and near-infrared regions was promoted by both of the ingredients. The proper chemical interaction between the materials is a crucial reason to modify the structure of the MCs and only a small decrease in the magnetic susceptibility of CHN. The heterogeneous catalytic activity of the obtained MC@CHN material was found to have a high efficiency and excellent reuse when it is activated by hydrogen peroxide (H2O2) for the degrading reaction of the organic pollutant at room temperature. A reasonable catalytic mechanism was proposed to explain the distinct role of the copper compound, Mo6 compound, and H2O2 in the production of the radical hydroxyl ion. This novel nanomaterial will be an environmentally promising candidate for dye removal.

Waterproof, thin, high-performance pressure sensors-hand drawing for underwater wearable applications.

Wearable sensors, especially pressure sensors, have become an indispensable part of life when reflecting human interactions and surroundings. However, the difficulties in technology and production-cost still limit their applicability in the field of human monitoring and healthcare. Herein, we propose a fabrication method with flexible, waterproof, thin, and high-performance circuits - based on hand-drawing for pressure sensors. The shape of the sensor is drawn on the pyralux film without assistance from any designing software and the wet-tissues coated by CNTs act as a sensing layer. Such sensor showed a sensitivity (~0.2 kPa-1) while ensuring thinness (~0.26 mm) and flexibility for touch detection or breathing monitoring. More especially, our sensor is waterproof for underwater wearable applications, which is a drawback of conventional paper-based sensors. Its outstanding capability is demonstrated in a real application when detecting touch actions to control a phone, while the sensor is dipped underwater. In addition, by leveraging machine learning technology, these touch actions were processed and classified to achieve highly accurate monitoring (up to 94%). The available materials, easy fabrication techniques, and machine learning algorithms are expected to bring significant contributions to the development of hand-drawing sensors in the future.

Environmentally friendly recycling system for epoxy resin with dynamic covalent bonding.

Recycling of epoxy resin and its composites is extremely difficult due to its thermoset nature. In this study, we proposed the environmentally-friendly recycling system of epoxy resin with dynamic covalent bonding in the assistance of cysteine-containing tripeptide, so-called glutathione. The glutathione attached on the epoxy resin and resulted in the cleavage of dynamic disulfide bonds of epoxy resin through thiol-disulfide exchange reaction between the thiol group of glutathione and disulfide bonding of epoxy resin, followed by the scission of epoxy networks. Therefore, the degraded epoxy residue was dissolved into chloroform. Finally, this resulting product could be reused as reagent for preparation the new epoxy materials with approximately 90% of initial mechanical strength via regeneration of disulfide bonding through heating. This work demonstrated the different aspect to understand the decomposition and recycling of thermosetting networks and the wide application under more environmentally friendly condition.

Phase equilibria among η-Fe2Al5 and its higher-ordered phases.

Phase equilibria among the η-Fe2Al5 phase and its higher-ordered phases with the η framework structure were determined experimentally. The solubility range of the η phase at elevated temperature does not differ remarkably from that in previous studies, but this phase is found to undergo complicated phase transformations upon cooling. Four phases are present, namely η', η", η"' and η m, with higher-order atomic orderings in the c-axis chain sites of the orthorhombic crystal structure of the parent η phase. The η" and η"' phases form on the Al-poor and Al-rich sides, respectively, in equilibrium with the ζ-FeAl2 phase below ~415°C and θ-Fe4Al13 phase below ~405°C. The η' and η m phases become stable below 312°C and 343°C with the peritectoid reactions η' → η m + Î·"' and η m → η + Î·", respectively. The η phase is not stable below 331°C with the eutectoid reaction of η m + Î·"' → η. On the basis of these findings, we unraveled the phase equilibria among the η-Fe2Al5 phase and its higher-ordered phases with the η framework structure.

Flexible wearable sensors - an update in view of touch-sensing.

Nowadays, much of user interface is based on touch and the touch sensors have been common for displays, Internet of things (IoT) projects, or robotics. They can be found in lamps, touch screens of smartphones, or other wide arrays of applications as well. However, the conventional touch sensors, fabricated from rigid materials, are bulky, inflexible, hard, and hard-to-wear devices. The current IoT trend has made these touch sensors increasingly important when it added in the skin or clothing to affect different aspects of human life flexibly and comfortably. The paper provides an overview of the recent developments in this field. We discuss exciting advances in materials, fabrications, enhancements, and applications of flexible wearable sensors under view of touch-sensing. Therein, the review describes the theoretical principles of touch sensors, including resistive, capacitive, and piezoelectric types. Following that, the conventional and novel materials, as well as manufacturing technologies of flexible sensors are considered to. Especially, this review highlights the multidisciplinary approaches such as e-skins, e-textiles, e-healthcare, and e-control of flexible touch sensors. Finally, we summarize the challenges and opportunities that use is key to widespread development and adoption for future research.

Extraordinarily large kinetic isotope effect on alkene hydrogenation over Rh-based intermetallic compounds.

A series of Rh-based intermetallic compounds supported on silica was prepared and tested in alkene hydrogenation at room temperature. H2 and D2 were used as the hydrogen sources and the kinetic isotope effect (KIE) in hydrogenation was studied. In styrene hydrogenation, the KIE values differed strongly depending on the intermetallic phase, and some intermetallic compounds with Sb and Pb exhibited remarkably high KIE values (>28). An extraordinarily high KIE value of 91, which has never been reported in catalytic reactions at room temperature, was observed particularly for RhPb2/SiO2. RhPb2/SiO2 also showed high KIE values in the hydrogenation of other unsaturated hydrocarbons such as phenylacetylene and cyclohexene. The density functional theory calculation focused on the surface diffusion of hydrogen suggested no contribution of the quantum tunneling effect to the high KIE values observed. A kinetic study revealed that the dissociative adsorption of H2 (D2) was the rate-determining step in the styrene hydrogenation over RhPb2/SiO2. We propose that the large KIE originates from the quantum tunneling occurring at the hydrogen adsorption process with the aid of the specific surface structure of the intermetallic compound and adsorbate alkene.

Heterogeneous structural changes correlated to local atomic order in thermal rejuvenation process of Cu-Zr metallic glass.

In this study, we investigated the atomistic mechanism of structural excitation in a thermal process (thermal rejuvenation) of metallic glass. In a molecular dynamics framework, Cu-Zr metallic glass was rejuvenated by a thermal process composed of an isothermal heat treatment at a temperature above the glass transition temperature T g , followed by fast cooling. Atomistic analyses of the local rearrangement, potential energy, and geometrical structure revealed structural changes correlating to the local atomic order in the rejuvenation process. In the early stage of the heat treatment for thermal rejuvenation, the structural excitation exhibited spatial heterogeneity at the nanometer scale. More-excited regions (i.e., regions with large atomic non-affine and affine transformations) exhibited low-ordered structures and vice versa, implying that the local structural excitation is significantly correlated with the local atomic order. The structural excitation transitioned from partial to whole as the isothermal process proceeded above T g . Although rejuvenation decreased the ordered structure, the calculation results suggested the formation of newly ordered local structures and newly disordered local structures correlated to local structural excitations and atomic dynamics in the thermal process. These results indicate that the heterogeneous structure evolution of the rejuvenation process induces a redistribution of the local atomic order in the microstructure of metallic glasses.

Gigacycle fatigue in high strength steels.

This paper reviews the research results to date on gigacycle fatigue caused by internal fractures in high strength steels. Firstly, accelerated fatigue testing was realized using ultrasonic fatigue testing at 20 kHz, which completes 109 cycles in one day, unlike the 3-4 months needed for conventional fatigue testing. Although the frequency effect was anticipated to be problematic, it proved negligible under conditions in which internal fractures occurred. Later, many unique characteristics of internal fractures were elucidated. For example, hydrogen has dramatically greater effects on internal fractures than on conventional surface fractures. Mean stress effects are more serious in titanium alloys than in high strength steels. Size effects were notable in high strength steels. These distinctive characteristics required a unique model to be able to predict gigacycle fatigue strength, which first required elucidation of its mechanisms. To this aim, the author attempted to measure the crack growth rates of small internal cracks using the beach mark method. The results revealed that the crack growth of small internal cracks controls internal fractures. In calculating the crack growth life, however, it was found that the conventional crack growth law overestimates the effects of inclusion size. To rectify this problem, a new model using a new crack growth law was proposed, which predicts more realistic fatigue life curves. As a result, predictions were derived for several grades of high strength steels.

Cryogenic study of the magnetic and thermal stability of retained austenite in nanostructured bainite.

First magnetic characterization of a recently developed generation of carbide free bainitic steels, known as Nanobain, has been performed. Stability of its retained austenite at cryogenic temperatures has been studied by means of X-ray diffraction, microscopy, dilatometry and magnetic measurements. Two morphologies for this phase (blocky-type and film-type) appear in a different proportion depending on the chemical composition and the applied thermal treatment. Inhibition of the martensitic transformation, when decreasing the temperature down to -271°C, has been observed in those microstructures with higher proportion of film-type austenite. The paramagnetic state of austenite at room temperature seems to lead to different magnetic behaviors (ferromagnetic, antiferromagnetic) at cryogenic temperatures (TC or TN being around -23°C in all the studied samples), depending on the proportion of such morphological features. Furthermore, irreversibility with temperature on the evolution of such magnetic behaviors has been observed for all the studied bainitic structures and is proposed to be due to a magnetic proximity effect.

Not always what closes best opens better: mesoporous nanoparticles capped with organic gates.

Four types of calcined MCM-41 silica nanoparticles, loaded with dyes and capped with different gating ensembles are prepared and characterized. N1 and N2 nanoparticles are loaded with rhodamine 6G and capped with bulky poly(ethylene glycol) derivatives bearing ester groups (1 and 2). N3-N4 nanoparticles are loaded with sulforhodamine B and capped with self-immolative derivatives bearing ester moieties. In the absence of esterase enzyme negligible cargo release from N1, N3 and N4 nanoparticles is observed whereas a remarkable release for N2 is obtained most likely due to the formation of an irregular coating on the outer surface of the nanoparticles. In contrast, a marked delivery is found in N1, N3, and N4 in the presence of esterase enzyme. The delivery rate is related to the hydrophilic/hydrophobic character of the coating shell. The use of hydrophilic poly(ethylene glycol) derivatives as gating ensembles on N1 and N2 enables an easy access of esterase to the ester moieties with subsequent fast cargo release. On the other hand, the presence of a hydrophobic monolayer on N3 and N4 partially hinders esterase enzyme access to the ester groups and the rate of cargo release was decreased.

Comb-structured triboelectric nanogenerators for multi-directional energy scavenging from human movements.

A triboelectric nanogenerator (TENG) is an emerging energy harvesting technology utilizing multi-directional, wasted mechanical energies stemming from vibrations, winds, waves, body movements, etc. In this study, we report a comb-structured TENG (CTENG) capable of effectively scavenging multi-directional motions from human movements, which include walking, jumping, and running. By attaching CTENG to a person's calf, we obtain a root-mean-square (RMS) power value of 5.28 µW (i.e. 13.12 V and 0.4 µA) for 1 s during mild running action (~5 m/s), which is sufficient for powering 10 light emitting diodes (LEDs). We integrate a CTENG with a simple hand-held pendulum (HHP) system with a natural frequency of 5.5 Hz. The natural frequency and input energy of our HHP system can be easily controlled by changing the holder mass and initial bending displacement, thus producing different output behaviors for the CTENG. Under the optimal HHP-based CTENG system design, the maximum output reaches 116 V at 6.5 µA under 0.1 kg mass and 4 cm bending displacement conditions. The corresponding output energy is 52.7 µJ for an operation time of 10.8 s. Our HHP-CTENG system can sufficiently power 45 LEDs and shows different output performances by varying the driving velocity of a vehicle, thus demonstrating the possibility for a self-powered velocity monitoring system.

Structural properties of ultrathin SrO film deposited on SrTiO3.

The role of epitaxial strain and chemical termination in selected interfaces of perovskite oxide heterostructures is under intensive investigation because of emerging novel electronic properties. SrTiO   3 (STO) is one of the most used substrates for these compounds, and along its < 001 > direction allows for two nonpolar chemical terminations: TiO2 and SrO. In this paper, we investigate the surface morphology and crystal structure of SrO epitaxial ultrathin films: from 1 to about 25 layers grown onto TiO   2 -terminated STO substrates. X-ray diffraction and transmission electron microscopy analysis reveal that SrO grows along its [ 111 ] direction with a 4% out-of-plane elongation. This large strain may underlay the mechanism of the formation of self-organized pattern of stripes that we observed in the initial growth. We found that the distance between the TiO   2 plane and the first deposited SrO layer is 0.27 ( 3 ) nm, a value which is about 40% bigger than in the STO bulk. We demonstrate that a single SrO-deposited layer has a different morphology compared to an ideal atomically flat chemical termination.

Automatic steel labeling on certain microstructural constituents with image processing and machine learning tools.

It is demonstrated that optical microscopy images of steel materials could be effectively categorized into classes on preset ferrite/pearlite-, ferrite/pearlite/bainite-, and bainite/martensite-type microstructures with image pre-processing and statistical analysis including the machine learning techniques. Though several popular classifiers were able to get the reasonable class-labeling accuracy, the random forest was virtually the best choice in terms of overall performance and usability. The present categorizing classifier could assist in choosing the appropriate pattern recognition method from our library for various steel microstructures, which we have recently reported. That is, the combination of the categorizing and pattern-recognizing methods provides a total solution for automatic quantification of a wide range of steel microstructures.

Crystal structure of η″-Fe3Al7+x determined by single-crystal synchrotron X-ray diffraction combined with scanning transmission electron microscopy.

The crystal structure of η″-Fe3Al7+x , the low-temperature phase of η-Fe2Al5 with a composition on the Fe-rich side of the solid solubility range, has been determined by synchrotron X-ray single-crystal diffraction combined with scanning transmission electron microscopy. The η″ phase possesses commensurate long-period-ordered superlattice structures (space group Pmcn) based on the parent orthorhombic unit cell of η-Fe2Al5, consisting of twin domains (orientation variants) alternately stacked along the long-periodicity axis. Each of the twin domains possesses a motif structure belonging to the base-centered monoclinic space group C2/m, with a cell volume twice that of the parent orthorhombic unit cell (space group Cmcm). One-fourth of the c-axis chain sites corresponding to Al2- and Al3-sites in the η phase are respectively occupied by both Fe and Al atoms and exclusively by Al atoms in a regular manner. This regularity is disturbed in the twin-boundary region, giving rise to structural/compositional modulation. Because of the different chemical compositions between the motif structure and twin-boundary region, the η″ phase with various compositions can be constructed only by changing the number of the parent orthorhombic unit cells to be stacked along the orthorhombic c-axis, without changing the atomic arrangements for the motif structure or the twin boundary to account for the observed solid solubility range. The chemical formula of the η″ phase can thus be expressed as Fe3Al7+x under a simple assumption on the occupancies for Al/Fe atoms in the c-axis chain sites.

Dynamic modulation of the Fermi energy in suspended graphene backgated devices.

Freestanding (suspended) graphene films, with high electron mobility (up to ~200,000 cm2V-1s-1), good mechanical and electronic properties, could resolve many of the current issues that are hampering the upscaling of graphene technology. Thus far, attempts at reliably fabricating suspended graphene devices comprising metal contacts, have often been hampered by difficulties in exceeding sizes of 1 µm in diameter, if using UV lithography. In this work, area of suspended graphene large enough to be utilized in microelectronic devices, have been obtained by suspending a CVD graphene film over cavities, with top contacts defined through UV lithography with both wet and dry etching. An area of up to 160 µm2 can be fabricated as backgated devices. The suspended areas exhibit rippling of the surfaces which simultaneously introduces both tensile and compressive strain on the graphene film. Finally, the variations of the Fermi level in the suspended graphene areas can be modulated by applying a potential difference between the top contacts and the backgate. Having achieved large area suspended graphene, in a manner compatible with CMOS fabrication processes, together with enabling the modulation of the Fermi level, are substantial steps forward in demonstrating the potential of suspended graphene-based electronic devices and sensors.

Preparation of cubic SiC from δ-Na2Si2O5/carbon nanocomposite using cobalt catalyst.

Silicon carbide (SiC) was prepared by carbothermal reduction of a crystalline-layered sodium silicate (δ-Na2Si2O5)/carbon nanocomposite (LCN), which contained a stacked carbon film embedded with cobalt between the silicate layers. Subsequent sintering of this mixture for 3 h at 1000-1350°C resulted in the formation of graphitic carbon and SiC. Meanwhile, sintering without a cobalt catalyst resulted in the formation of graphitic carbon, regardless of the temperature. The use of a cobalt catalyst allowed the formation of a pure SiC phase at 1350°C. The formed SiC had an irregular worm-like morphology, with a particle size of ~5 µm. The Brunauer-Emmett-Teller surface areas of graphitic carbon and SiC were 28-150 and ~7.0 m2/g, respectively. We concluded that graphite and SiC were produced at this low sintering temperature because of the cobalt catalyst, which facilitated nanomixing of carbon and SiO2 by sandwiching the carbon films between the silicate layers.

Structure-property relationship of a model network containing solvent.

For the application of polymer gels, it is necessary to control independently and precisely their various physical properties. However, the heterogeneity of polymer gels hinders the precise control over the structure, as well as the verification of theories. To understand the structure-property relationship of polymer gels, many researchers have tried to develop a homogeneous model network. Most of the model networks were made from polymer melts that did not have a solvent and had many entanglements in the structure. Because the contribution of entanglements is much larger than that of chemical crosslinking, it was difficult to focus on the crosslinking structure, which is the structure considered in conventional theories. To overcome such a situation, we have developed a new model network system that contains much solvent. Specifically, we fabricated the polymer gel (Tetra-PEG gel) by mixing two types of solutions of tetra-armed poly(ethylene glycol) (Tetra-PEG) with mutually reactive end groups (amine (-PA) and activated ester (-HS)). Because the existence of a solvent strongly reduces the effect of entanglements, the effect of the crosslinking structure on the physical properties can be extracted. In this review, we present the structure-property relationship of Tetra-PEG gel. First, we show the structural homogeneity of Tetra-PEG gels. Then, we explain gelation reaction, elastic modulus, fracture energy and kinetics of swelling and shrinking of Tetra-PEG gels by comparing the theories and experimental results.

New development of atomic layer deposition: processes, methods and applications.

Atomic layer deposition (ALD) is an ultra-thin film deposition technique that has found many applications owing to its distinct abilities. They include uniform deposition of conformal films with controllable thickness, even on complex three-dimensional surfaces, and can improve the efficiency of electronic devices. This technology has attracted significant interest both for fundamental understanding how the new functional materials can be synthesized by ALD and for numerous practical applications, particularly in advanced nanopatterning for microelectronics, energy storage systems, desalinations, catalysis and medical fields. This review introduces the progress made in ALD, both for computational and experimental methodologies, and provides an outlook of this emerging technology in comparison with other film deposition methods. It discusses experimental approaches and factors that affect the deposition and presents simulation methods, such as molecular dynamics and computational fluid dynamics, which help determine and predict effective ways to optimize ALD processes, hence enabling the reduction in cost, energy waste and adverse environmental impacts. Specific examples are chosen to illustrate the progress in ALD processes and applications that showed a considerable impact on other technologies.

Twinning behavior of orthorhombic-α" martensite in a Ti-7.5Mo alloy.

Deformation microstructure of orthorhombic-α" martensite in a Ti-7.5Mo (wt.%) alloy was investigated by tracking a local area of microstructure using scanning electron microscopy, electron back-scattered diffraction, and transmission electron microscopy. The as-quenched α" plates contain {111}α"-type I transformation twins generated to accommodate transformation strain from bcc-ß to orthorhombic-α" martensite. Tensile deformation up to strain level of 5% induces {112}α"-type I deformation twins. The activation of {112}α"-type I deformation twinning mode is reported for the first time in α" martensite in ß-Ti alloys. {112}α"-type I twinning mode was analyzed by the crystallographic twinning theory by Bilby and Crocker and the most possible mechanism of atomic displacements (shears and shuffles) controlling the newly reported {112}α"-type I twinning were proposed.

Stress dependence of indentation modulus for carbon fiber in polymer composite.

Elastic modulus measured through atomic force microscopy (AFM)-based indentation on single carbon fiber (CF) is found with dependence on lateral applied stress. An in situ indentation experiment inside a high-resolution transmission electron microscope was performed to quantitatively understand this phenomenon by observing microstructure change in the indented area. Change of graphitic basal plane misalignment angle during indentation was linked to a continuous change of modulus with the help of finite element simulation. The established relationship between modulus and indentation force was further used to calculate residual stress distribution in CF imbedded in a CF reinforced polymer composite using the AFM indentation technique. The stress-induced formation of nanoscale defects in the CF and their transformation into fracture were directly characterized.