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.     

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.     

Permeability changes in granite with crack growth during immersion in hot water

Permeability tests and observation of induced, as well as inherent, cracks have been carried out to quantitatively explain permeability changes in granite taking place during a weathering test in terms of micro-structure by cracks. To this end, permeability tensors were estimated from observations of crack systems using the Replica Method and of the crack apertures with a scanning electron microscope. The following conclusions were reached: the drastic increase in permeability around an immersion of 1000 d in 90°C water could not be explained by the existence of a percolation threshold because all the specimens were percolative in the sense that the traces of crack tensor were above the critical density for percolation. On the other hand, SEM observation revealed that, with immersion, crack apertures widened and their distribution spread. Permeability estimated using the third (not the first) moment of observed apertures showed the increase in measured permeability well. When evaluating the connectivity parameter λ to give a quantitative accordance between measured and estimated permeability, it had a constant value as low as 0.17, irrespective of the immersion period, in spite of the higher density of micro-cracks than the percolation threshold. It can be said that, in considering the natural three-dimensional crack system, the third moment of physical apertures plays a more important role in predicting the permeability and λ is greatly affected by the spread of crack apertures.     

The effect of Ca doping on the properties of melt-processed Gd-based bulk superconductors

The effect of Ca doping to melt-processed Gd-based bulk superconductors fabricated by the oxygen-controlled melt growth (OCMG) method was studied. First, we simply added CaCO₃ to the starting materials to dope Ca and observed an increase in the trapped field and the critical current density (J_c) up to, at least, 0.31 wt.% CaCO₃. However, an additional oxygen annealing resulted in a decrease of J_c in magnetic fields and in a monotonous exponential-like field dependence ofJ_c. This suggests that oxygen deficiency had caused the enhancement of J_c, although the same annealing process as the non-doped sample was applied. We also prepared samples by adding not only CaCO₃ but also BaCO₃ and CuO in a molar ratio of Ca:Ba:Cu = 1:2:3, and observed a large peak effect of J_c up to at least 0.31 wt.% CaCO₃. It is likely that this large peak effect is also caused by oxygen defects, although the superconducting transition temperature was significantly large. These results indicate that J_c at 77 K can be significantly enhanced by introducing a proper amount of oxygen deficiency and compensating at the same time the decrease of carrier density by Ca doping.     

Motion of Crystal Particles by the Electromagnetic Vibrations in Mg-Cu-Y Bulk Metallic Glasses

The method for producing Mg-Cu-Y and Fe-Co-B-Si-Nb bulk metallic glasses using electromagnetic vibrations is effective in forming the metallic glass phase. Disappearance or decrement of clusters by the electromagnetic vibrations applied to the liquid state is considered to cause suppression of crystal nucleation, because the electromagnetic vibrations vibrate the clusters vigorously in the melt. The purpose of this study was to investigate motion of the crystal particles by the electromagnetic vibrations in Mg-Cu-Y bulk metallic glasses. The electromagnetic vibration force vibrated the crystal particles or the clusters that become crystal nuclei in the melt, because the electric current for the electromagnetic vibrations concentrates in those. Thus, the electromagnetic vibrations were found to select vibration particles from the melt. Moreover, it was considered that composites for which second phases or other compounds are dispersed into the metallic glass phase or a nanostructure phase can be produced by the electromagnetic vibration process. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Adaptive control of maximum thermal stress in a smart piezocomposite disk

In this paper, an adaptive control problem of the maximum thermal stress in a smart composite disk is analyzed. The disk consists of a transversely isotropic structural layer onto which piezoelectric sensor and actuator layers are bonded. It is considered that an unknown heating temperature distribution acts on the structural layer and a thermally induced voltage distribution is measured on the sensor layer. The unknown heating temperature distribution is inferred from the knowledge of the measured voltage distribution. Applied voltages to electrodes arranged on every actuator layer are determined by optimization so that the maximum thermal stress in the structural layer is minimized and stress constraints imposed on the piezoelectric layers are satisfied. Finally, the suppression ratio of the maximum thermal stress is discussed based on numerical results.     

Understanding the Structural Evolution and Redox Mechanism of a NaFeO2–NaCoO2 Solid Solution for Sodium‐Ion Batteries

Na‐ion batteries have become promising candidates for large‐scale energy‐storage systems because of the abundant Na resources and they have attracted considerable academic interest because of their unique behavior, such as their electrochemical activity for the Fe³⁺/Fe⁴⁺ redox couple. The high‐rate performance derived from the low Lewis‐acidity of the Na⁺ ions is another advantage of Na‐ion batteries and has been demonstrated in NaFe_1/2Co_1/2O₂ solutions. Here, a solid solution of NaFeO₂‐NaCoO₂ is synthesized and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of operando X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and density functional theory (DFT) calculations for Na_{1– x} Fe_1/2Co_1/2O₂ reveals that the O3‐type phase transforms into a P3‐type phase coupled with Na⁺/vacancy ordering, which has not been observed in O3‐type NaFeO₂. The substitution of Co for Fe stabilizes the P3‐type phase formed by sodium extraction and could suppress the irreversible structural change that is usually observed in O3‐type NaFeO₂, resulting in a better cycle retention and higher rate performance. Although no ordering of the transition metal ions is seen in the neutron diffraction experiments, as supported by Monte‐Carlo simulations, the formation of a superlattice originating from the Na⁺/vacancy ordering is found by synchrotron X‐ray diffraction for Na_0.5Fe_1/2Co_1/2O₂, which may involve a potential step in the charge/discharge profiles.     

Single-Component Pheromone Consisting of Bombykal in a Diurnal Hawk Moth, <Emphasis Type="Italic">Neogurelca himachala sangaica</Emphasis>

Recent work has suggested that hawk moths share pheromone components but are sexually separated by qualitative and quantitative differences in their pheromone blends. During field assays on the sex pheromones of other species, a diurnal hawk moth, Neogurelca himachala sangaica (Lepidoptera: Sphingidae), was frequently captured, but the composition of the sex pheromone of this species was not known. Analysis of hexane extracts of the pheromone glands of calling female by gas chromatography (GC) using an electroantennographic detector (EAD) revealed two components that elicited EAD responses from male moth antennae. These components were identified by their mass spectra and retention indices on two GC columns as (10E,12Z)-10,12-hexadecadienal (E10,Z12–16:Ald) and a trace of its (10E,12E)-isomer (E10,E12–16:Ald) in 98:2 ratio. In field experiments, E10,Z12–16:Ald alone attracted male moths, and addition of E10,E12–16:Ald significantly reduced the attractiveness, even at the naturally-occurring ratio. Analysis of the data using a generalized linear mixed model showed that E10,Z12–16:Ald positively contributed to attractiveness, whereas E10,E12–16:Ald did so negatively, and it was concluded that the sex pheromone of N. himachala sangaica consists solely of E10,Z12–16:Ald, bombykal. The negative effect of E10,E12–16:Ald on attractiveness could promote the species-specificity of this single-component pheromone system.     

Oily Grime Formed on Hard Surfaces of Kitchen Appliances: Chemical Composition and Oxidation Mechanism

The cooking of oil-containing food products at high temperatures results in an insoluble, unsightly, greasy layer of grime on appliance surfaces in residential and commercial kitchens. Over time, adsorbed grime becomes difficult to remove using normal dishwashing detergents. A number of studies have focused on the deterioration and oxidation of oils and the harmful effects that volatile compounds associated with such processes have on human health. Little attention, however, has been paid to kitchen grime. The present study examined grime obtained from the surfaces of appliances such as sirocco fans, filters, and range hoods in residential kitchens in Tokyo. The grime was characterized by X-ray fluorescence spectroscopy (XRF), Fourier-transform infrared spectroscopy (FT-IR), size exclusion chromatography (SEC), thermal hydrolysis methylation–gas chromatography–mass spectroscopy (THM–GCMS), and nuclear magnetic resonance (NMR) techniques. The chemical composition and structure of the grime differed from those of the edible oils. The grime consisted mainly of polymerized and oxidized triacylglycerols. Bridging between unsaturated acyl groups of triglycerols occurred through thermal oxidation and aging in air, yielding their dimers, trimers, and highly polymerized products while also transforming unsaturated acyl groups into saturated ones. Cross-linking reactions involving dibasic acids also caused polymerization. Those polymerized products strongly adhered to the hard surfaces of the appliances. Small amounts of cellulose fibers from air or towel may also play a role in mechanically stabilizing the dirt structure.

Measurements of fiber bundle interfacial properties of three-dimensionally reinforced carbon/carbon composites up to 2273 K

Experimental techniques for evaluating the interfacial properties between fiber bundles and the matrix of three-dimensionally reinforced carbon/carbon composites were examined. Specially arranged fiber bundle push-out and pull-out tests were conducted up to 2273 K in vacuum. In these tests, a fiber bundle in the specimens was extruded or pulled out by external compressive or tensile loads. Post-fracture observations revealed that a shear fracture was successfully induced within the carbon matrices at the loaded fiber bundle interface. The interfacial shear strength and initial sliding stress of the fiber bundle monotonically increased with the test temperature. The relief of residual thermal stress and increases in the frictional resistance and anchor effect at the fiber bundle interface were considered to be the major mechanisms that caused the enhancements. An increase in the heat treatment temperature during the processing of the composites resulted in a significant decrease in and .