In situ X-ray diffraction of surface oxide on type 430 stainless steel in breakaway condition using synchrotron radiation

Changes in the crystal structure of type 430 stainless steel and the oxides on its surface were studied in situ at 1373 K using a high-intensity synchrotron X-ray source provided by SPring-8 in Japan. The surface of the steel was initially covered with Cr₂O₃, which was then converted to FeCr₂O₄, and finally Fe₃O₄ and Fe₂O₃ formed on it. These results indicated that the reason for the breakaway oxidation in type 430 stainless steel is Cr depletion beneath Cr₂O₃ layer and the subsequent ionisation of Fe, not the simple mechanical failure of Cr₂O₃.     

A corrosion prediction method for weathering steels

Japanese Specification for Highway Bridges [Japan Road Association: Specification for Highway Bridges—I & II, 2002.3] has been revised in 2002, which clearly states that degradation of bridge members, including those of weathering steels, to occur in prolonged period of time must be taken into account at the design stage to realize long term structural durability. To cope with the revised paradigm, SABI chemistry committee in Japan Society of Corrosion Engineers has proposed durable state concept [SABI Chemistry Committee of Japan Society of Corrosion Engineers, in: Proc. 132nd Symposium for Corrosion and Protection, 2001.6.25, p. 3], which is defined as a condition in which corrosion rate of steel is slow enough not to form thick rust [H. Kihira, K. Shiotani, H. Miyuki, T. Nakayama, M. Takemura, Y. Watanabe, Doboku Gakkai Ronbun-shu (J. Japan Soc. Civil Engineers) No. 745/I-65, 2003.10, pp.77-87]. Since corrosiveness of atmosphere differs by location, a corrosion prediction method for both conventional and advanced weathering steels [H. Kihira, A. Usami, K. Tanabe, M. Ito, G. Shigesato, Y. Tomita, T. Kusunoki, T. Tsuzuki, S. Ito, T. Murata, in: Electrochemical Society Proceedings, vol. 99-26, 2000, pp. 127-136] is needed to ensure structural durability for future. Thus, versatile computational scheme for it has been derived through mathematical modeling based upon the durable state concept.     

Site-specific electronic structure analysis by channeling EELS and first-principles calculations

Site-specific electronic structures were investigated by electron energy loss spectroscopy (EELS) under electron channeling conditions. The Al-K and Mn-L(2,3) electron energy loss near-edge structure (ELNES) of, respectively, NiAl2O4 and Mn3O4 were measured. Deconvolution of the raw spectra with the instrumental resolution function restored the blunt and hidden fine features, which allowed us to interpret the experimental spectral features by comparing with theoretical spectra obtained by first-principles calculations. The present method successfully revealed the electronic structures specific to the differently coordinated cationic sites.     

Peak assignments of ELNES and XANES using overlap population diagrams

The usefulness of overlap population (OP) diagrams for peak assignments of an electron energy loss near-edge structure (ELNES) and an X-ray absorption near-edge structure (XANES) is demonstrated. Mg-K, L(2,3), and O-K edges of MgO are taken as examples. Theoretical calculations are performed using a first-principles orthogonalized linear combination of atomic orbitals (OLCAO) method. A core-hole is included explicitly, and a large supercell is used to minimize artificial interactions among the core-holes in adjacent cells. All experimental spectra are quantitatively reproduced by the calculations. The OP diagrams for a selected pair of atomic orbitals are computed in order to provide proper assignments for each peak in ELNES and XANES. They are interpreted in terms of interactions among Mg-Mg and Mg-O bonds. Results are found to be consistent to our previous conclusion, which was obtained using a cluster method [T. Mizoguchi, et al., Phys. Rev. B 61 (2000) 2180]. The powerful combination of the OP diagram and a high-energy resolution ELNES to obtain fine electronic structures is also demonstrated.     

Mercury and selenium concentrations in the internal organs of toothed whales and dolphins marketed for human consumption in Japan

Small cetaceans (toothed whales odontoceti and dolphins delphinidae) have been traditionally hunted along the coast of Japan and fresh red meat and blubber, as well as boiled internal organs such as liver, kidney, lung and small intestine, are still being sold for human consumption. We surveyed mercury contamination in boiled liver, kidney and lung products marketed in Japan between 1999-2001. The average +/- S.D. of total mercury (T-Hg) was 370 +/- 525 (range: 7.60 approximately 1980, n = 26) microg/g in liver, 40.5 +/- 48.5 (7.30-95.1, n = 15) microg/g in kidney and 42.8 +/- 43.8 (2.10-79.6, n = 23) microg/g in lung. A high correlation was observed between T-Hg and selenium (Se) concentrations in these organs, supporting the formation of a Hg-Se complex. The formation of a Hg-Se complex probably contribute to the detoxification of Hg for cetaceans and allows a very large accumulation of Hg in livers. The provisional permitted level of T-Hg in marine foods set by the Japanese Ministry of Health and Welfare is 0.4 microg/ g, and the provisional permitted weekly intake (PTWI) set by WHO is 5 microg/kg bw/week. The maximal T-Hg detected in boiled liver (1,980 microg/g) exceeds the permitted level by approximately 5,000 times and the consumption of only 0.15 g of liver exceeds the PTWI of 60 kg of body weight of the consumer, suggesting the possibility of an acute intoxication by T-Hg even after a single consumption of the product.     

Microstructure Control of Thermally Sprayed Co-Based Self-Fluxing Alloy Coatings by Diffusion Treatment

This article describes microstructure control aimed for wear-resistance improvement of Co-based (Co-Cr-W-B-Si) self-fluxing alloy coating by diffusion treatment. The diffusion treatments of thermally sprayed Co-based self-fluxing alloy coating on steel substrate were carried out at 1370-1450 K for 600-6000 s under an Ar gas atmosphere. Microstructural variations of the coating and the interface between the substrate and the coating were investigated in detail. A proper diffusion treatment precipitates two kinds of fine compounds in Co-based matrix. X-ray diffractometer (XRD) and electron probe microanalyzer (EPMA) analysis revealed these precipitates to be a chromium boride dissolving cobalt and a tungsten boride containing cobalt and chromium. The size of each precipitate became larger with increasing treatment temperature and time. A coating with the proper size borides showed a superior wear-resistance. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Note: high-pressure generation using nano-polycrystalline diamonds as anvil materials

Nano-polycrystalline diamonds (NPDs) consist of nanosized diamond grains oriented in random directions. They have high toughness and isotropic mechanical properties. A NPD has neither the cleavage feature nor the anisotropy of hardness peculiar to single-crystal diamonds. Therefore, it is thought to be useful as a diamond anvil. We previously reported the usefulness of a NPD as an anvil for high-pressure development. In this study, some additional high-pressure generating tests using diamond anvils of various shapes prepared from NPDs were conducted to investigate the advantage of using NPDs for anvil applications. The results revealed that the achievable pressure value of a NPD anvil with a culet size of more than 300 μm is about 1.5 to 2 times higher than that of single-crystal diamond anvils, indicating that NPD anvils have considerable potential for large-volume diamond anvils with large culet sizes.     

A wind-tunnel study on exhaust gas dispersion from road vehicles—Part I: Velocity and concentration fields behind single vehicles

By a reduced-scale model in a wind tunnel, we investigate the dispersion behavior of exhaust gas from automobiles. Two types of vehicles are considered, a passenger car and a small-size truck. Tracer gas experiments show that the exhaust gas dispersion is enhanced significantly by the vehicle wake compared to the case when the vehicle body is absent. The passenger car and the truck promote dispersion in the horizontal and the vertical direction, respectively. The wake field is analyzed by particle image velocimetry (PIV), and the distribution of the mean and the fluctuation fields is found to conform to the concentration field of the exhaust gas. The buoyancy of the exhaust gas has minor effect except on the vertical spread behind the truck whose wake flow amplifies the vertical displacement generated near the pipe exit.     

The effect of gas atmospheres on resistivity of indium tin oxide films at high temperature

The effects of heat treatment in Q₂, O₂ and N₂, and Ar gases on the high temperature (500 C) electrical resistivity of indium tin oxide (ITO) film 52 nm thick prepared by chemical spray pyrolysis method were studied. The partial oxygen pressure effect on the resistivity was found to be to . The resistivity changes for cyclic exchange of O₂ by Ar gas at 500 C. These lead to the conclusion that chemisorption of oxygen atoms in the film surface is dominant for this thin film, for thicker films such as 640 nm oxygen diffusion is found to occur. The Langmuir model of the monolayer isothermal adsorption of oxygen atoms in the surface is applicable to the rapid change of resistivity.     

Structure and electrochemical applications of boron-doped graphitized carbon nanofibers

Boron-doped graphitized carbon nanofibers (CNFs) were prepared by optimizing CNFs preparation, surface treatment, graphitization and boron-added graphitization. The interlayer spacing (d???) of the boron-doped graphitized CNFs reached 3.356 ?, similar to that of single-crystal graphite. Special platelet CNFs (PCNFs), for which d??? is less than 3.400 ?, were selected for further heat treatment. The first heat treatment of PCNFs at 2800?°C yielded a d??? between 3.357 and 3.365 ?. Successive nitric acid treatment and a second heat treatment with boric acid reduced d??? to 3.356 ?. The resulting boron-doped PCNFs exhibited a high discharge capacity of 338 mAh g?1 between 0 and 0.5 V versus Li/Li? and 368 mAh g?1 between 0 and 1.5 V versus Li/Li?. The first-cycle Coulombic efficiency was also enhanced to 71-80%. Such capacity is comparable to that of natural graphite under the same charge/discharge conditions. The boron-doped PCNFs also exhibited improved rate performance with twice the capacity of boron-doped natural graphite at a discharge rate of 5 C.