XPS and IR study of electrochemically or chemically redoped poly(3-methylthienylene) films

XPS (X-ray photoemission spectroscopy) and IR (infrared) analyses of poly(3-methylthienylene) films, electrochemically or chemically redoped0 with various chemical species at varying doping levels, have been investigated. On the basis of these results, the major chemical species of dopants have been identified. As a results, the dopant content was determined and the poly(3-methylthienylene) films were classified as light or heavy by doping level. The conductivity ranged from about 10^?12 to 10₂ S cm^?1 for all the films investigated. The conductivity and the activation energy of conduction for the heavily-doped films vary as a function of the dopant content, independent of the different chemical species of dopants. In particular, a sudden change is observed in the dependence of activation energy on dopant content. This sudden change may be associated with the semi-conductor-metal transition. Furthermore, it is shown that the specific absorption bands in the infrared are induced by the doping, intensified with increasing dopant uptake and accompanied by an increase in conductivity.     

Exposure and risk assessment of zinc in Japanese surface waters

In recent years, due to concerns on the potential effects of zinc on aquatic biota, zinc is receiving particular attention from regulatory agencies. A comprehensive exposure and risk assessment of zinc in Japanese surface waters was conducted to provide a scientific basis for developing realistic risk reduction measures for zinc. Emissions from corrosion contribute approximately 37% of the total zinc emissions to surface water in Japan. The zinc concentration distributions estimated using 12 years of monitoring data from 2075 sites by a maximum likelihood method indicated that the mean concentrations have gradually declined. The threshold concentrations (HC5 and PHC5) derived from organism- and population-level species sensitivity distributions were estimated to be 27 and 107 μg/L for total zinc, respectively. The risk characterization identified that during 1991-2002, 14.5-26.8% of the monitoring sites likely exceeded the HC5, whereas only 0.7-3.5% likely exceeded the PHC5. Evaluation of the effect of stormwater runoff to zinc concentrations in a river showed that zinc concentrations in river water increased significantly from roadway drainage flowing into the river. The cost-effectiveness analyses demonstrated that enforcement of the zinc national effluent standard may be effective at a certain level for public water areas in Japan; however, the degree of the effectiveness is highly dependent on the characteristics (e.g., sources and background) of the watersheds. An emissions and exposure assessment along with cost-effectiveness analysis is crucial for developing realistic and appropriate ecological risk management of zinc. The zinc RAD in Japan illustrated that in any “state-of-the science” method used, some degree of ecological risk from zinc can be observed in some Japanese water environments. On the other hand, zinc is a beneficial material for human industrial activities. Because zinc is an element, its role in industrial activities would be difficult to be substituted by other metals with less toxicity. In addition to improving science-based risk assessment methodologies which often focus on the toxicological perspectives, it is important to develop a more robust framework considering a trade-off between a damage in ecosystem and a benefit in human activities. Zinc can be a role model for it.     

Diffusion-limited characteristics of mechanically induced currents in polypyrrole/Au-membrane composites

A mechanically induced current (MIC) in a polypyrrole/Au-coated membrane (PPy/Au-membrane) composite with various surface morphologies was investigated, and the electrolyte conditions were determined in an electrochemical cell. A MIC was induced on porous PPy/Au-membranes with a thin layer of PPy. Conversely, relatively small MICs were observed in non-highly porous films such as freestanding films and PPy/Au-membranes with thick PPy deposits. A MIC smaller by one order of magnitude was also observed in a Au-membrane without PPy. These results indicated that the MICs was due to a charging phenomenon in both the redox and the double layer capacitances. The MIC also varied with supporting electrolyte and their concentration. The MIC was strongly reduced in solutions with diluted electrolytes and with bulky cationic electrolytes, indicating that the number and the penetration speed of mobile ions limited the magnitude of the MIC. These characteristics indicated that the MIC was essentially a diffusion limited current. A two-electrode MIC cell was also configured to investigate a power generation film in a normal saline solution, which can possibly be utilized for biomedical applications.     

Programmed High‐Hole‐Mobility Supramolecular Polymers from Disk‐Shaped Molecules

In this paper a simple, casting solution technique for the preparation of two‐dimensional (2D) arrays of very‐high molecular weight (MW) 1D‐Pc supramolecular inorganic polymers is described. The soluble fluoroaluminium tetra‐tert‐butylphthalocyanine (ttbPcAlF) is synthesized and characterized, which can be self‐assembled to form 2D arrays of very‐high‐MW 1D‐Pc supramolecular inorganic polymers. High‐resolution transmission electron microscopy (HRTEM) demonstrates that the 1D‐ttbPcAlF, having a cofacial ring spacing of ～0.36 nm and an interchain distance of ～1.7 nm, self‐assembles into 2D‐nanosheets (～140 nm in length, ～20 nm in width, and equivalent to MW of 3.2 × 10⁵ g mol^?1). The film cast from a 1,2‐dichloroethane (DCE) solution shows a minimum hole‐mobility of ～0.3 cm² V^?1 s^?1 at room temperature by flash‐photolysis time‐resolved microwave conductivity (TRMC) measurements and a fairly high dark dc‐conductivity of ～1 × 10^?3 S cm^?1.     

Magnetic properties and phase diagram of Ni50Mn50−xGax ferromagnetic shape memory alloys

We present the magnetic properties and the magnetic phase diagram of Ni₅₀Mn_50?xGa_x ferromagnetic shape memory alloys across a wide concentration range. Martensitic transformation, intermediate transformation, B2–L2₁ order–disorder transformation, Néel and Curie temperatures are determined for the prepared samples. The martensitic transformation temperature decreases with increasing Ga concentration and bends two times when crossing the Curie temperature and the intermediate-phase transformation temperature. Spontaneous magnetization and its composition dependence were also investigated. Composition dependence of the transformation temperatures and the spontaneous magnetization in the martensite phase of Ni₅₀Mn_50?xGa_x are compared with those of Ni₅₀Mn_50?xIn_x and Ni₅₀Mn_50?xSn_x, revealing a similarity in the NiMn-based alloy systems.     

Selective oxidation of alcohols using novel crystalline Mo-V-O oxide as heterogeneous catalyst in liquid phase with molecular oxygen

Catalytic selective oxidation of benzyl alcohol with molecular oxygen under mild conditions was carried out over novel crystalline Mo-V-O oxide. The present research is focused on investigation of recycling, reusability and stability of the crystalline oxide in the liquid-phase reaction. The Mo-V-O oxide catalyst was used at least four times with comparable activities to that of fresh catalyst. The separation of the catalyst from reaction medium can stop the conversion of benzyl alcohol, and the addition of the catalyst to the reaction medium can trigger the reaction immediately. The catalytic oxidation of 2,3,6-trimethylphenol as a reference reaction suggested that there were no leached active species in the reaction mixture. The results of the ICP–MS analysis, XRD, and SEM characterization confirmed that the structure and composition of the catalyst were stable. Besides, the Mo-V-O oxide can catalyze the oxidation of a series of alcohols with high selectivities for corresponding carbonyl compounds.     

Framework for Performance-Based Design of Building Structures

Abstract:   This article proposes a new framework for performance-based design (PBD) of building structures. This framework was proposed under the 3-year Japanese Government Comprehensive Research and Development Project on "Development of a New Engineering Framework for Building Structures" launched in the fiscal year of 1995. The primary objective of the project is to create a system in which the performance of buildings is clearly stated, and consumers, that is, occupants, are well informed of how their buildings will perform and how much it will cost to maintain their performance. The framework emphasizes the establishment of target performance, the performance evaluation, and the performance statement as the main three elements. It also stresses that an institutional framework and support systems need to be provided to enable PBD to be practiced efficiently. The implementation of the proposed framework is also expected to promote engineering innovation, progress in building engineering, and globalization. The new framework will also bring other benefits, such as improved design techniques, greater design flexibility, and international harmonization. It is also important for building structural performance to become one of the most important indexes for consumers to define a building's value. The Japanese building code was changed to the performance-based code, based in the clear and comprehensive manner proposed in this article. In the United States, "Vision 2000" ( SEAOC, 1995 ) was published, then many research activities were conducted simultaneously.     

Gibbs Energy Change of Carbothermal Nitridation Reaction of Al2O3 to Form AlN and Reassessment of Thermochemical Properties of AlN

The experimental method for the high-temperature reaction equilibria in the AlN-Al₂O₃ system has been established. The equilibrium N₂-CO gas compositions coexisting with AlN- Al₂O₃-graphite have been successfully measured by quadrupole mass spectrometry and gas chromatography. From the obtained results, the standard Gibbs energy change of the forming reaction of AlN by carbothermal nitridation is determined at temperatures ranging from 1723 to 1899 K:
From the obtained result, the standard Gibbs energy of formation of AlN and the third-law enthalpy of formation of AlN at 298.15 K are derived as
The disagreement between the present results and values in the NIST–JANAF thermodynamic table is discussed.     

Performance of ternary PtRuRh/C electrocatalyst with varying Pt:Ru:Rh ratio for methanol electro-oxidation

Highly dispersed ternary PtRuRh/C anode catalysts for direct methanol fuel cells were prepared with various contents and their electro-catalytic activities towards methanol oxidation at 25 °C and 60 °C were examined to investigate the influence of the catalyst composition. Electrocatalysts were prepared by a co-impregnation method using ethanolic solutions of metal precursors and carbon black followed by pyrolysis under reducing conditions. X-ray diffraction analysis revealed that the fcc peaks shifted to higher diffraction angles with increasing Rh content, indicating the alloying of Rh into the fcc structure. In terms of the mass specific current density, the activity towards methanol oxidation differed significantly depending on the catalysts composition and cell temperature. The catalyst prepared at a ratio of Pt:Ru:Rh = 1:1:2 exhibited the highest activity at 60 °C of 155 A (g-Pt)⁻¹ at 0.5 V vs. RHE.