Yoshihiko Ninomiya

Applications of TiO2 film for environmental purification deposited by controlled electron beam-excited plasma

Abstract Taking advantage of the remarkable features of controlled electron beam-excited plasma (EBEP), the composition and the thickness of TiO 2 film could be directly controlled by the EBEP accelerating voltage V A and discharge current I D , respectively. Experiments were conducted on the dissolving effect on NO x (NO, NO 2 ) gas using glass beads coated with a TiO 2 film deposited by EBEP. With a bead sample size of 20 g and an NO gas flow rate of 100 ml/min, the NO dissolvable amount was approximately 10 −4 mol/m 2 for 120 min. Using a glass plate, glass beads and zeolites coated with TiO 2 film, the experiments succeeded in dissolving water-soluble ink and in obtaining a hydrophilic effect.

Synchrotron-based XANES speciation of chromium in the oxy-fuel fly ash collected from lab-scale drop-tube furnace.

Speciation of chromium (Cr) in the fly ash collected from oxy-firing of Victorian brown coal has been reported for the first time to address the potential formation of toxic Cr(VI) and the variation of the quantities of Cr(III)-bearing species with flue gas composition. Synchrotron-based X-ray absorption near-edge structure (XANES) was employed for Cr speciation. Apart from a pure O(2)/CO(2) mixture (27/73, v/v) versus air, the O(2)/CO(2) mixtures doped with SO(2), HCl, and steam individually or together to simulate real flue gas have also been tested. Under all of the conditions tested here, the fractions of Cr(VI) in the fly ashes are insignificant, constituting no more than 5% of the total Cr. The test of Cr-doped brown coal in pyrolysis further confirmed that the Cr(VI) formation preferentially occurred through a local oxidation of Cr(III) at the oxygen-containing functions sites within coal matrix, rather than through an oxidation by external bulk O(2). This reaction is also highly temperature-dependent and slower than the interaction between Cr(III) and other metals such as iron oxide. Increasing temperature to 1000 °C inhibited the oxidation of Cr(IIII) to Cr(VI). Shifting the combustion gas from air to O(2)/CO(2) exerted little effect on the Cr(VI) formation. Instead, the formation of iron chromite (FeCr(2)O(4)) was facilitated in O(2)/CO(2), probably due to a strong reducing microenvironment formed by the CO(2) gasification reaction within the char matrix. The accumulation of HCl in flue gas favored the vaporization of chromium as gaseous chloride/oxychloride, as expected. The coexistence of SO(2) inhibited this phenomenon by promoting the formation of sulfate. The presence of steam was even beneficial for the inhibition of water-soluble Cr sulfate through stabilizing the majority of Cr into alumino-silicate which is in the slagging phase.

Use of Synchrotron XANES and Cr-Doped Coal to Further Confirm the Vaporization of Organically Bound Cr and the Formation of Chromium(VI) During Coal Oxy-Fuel Combustion

Through the use of synchrotron XANES and Cr-doped brown coal, extensive efforts have been made to clarify the volatility of organically bound Cr during oxy-fuel combustion and the mode of occurrence and leachability of Cr in resulting fly ashes. As the continuation of our previous study using raw coal, the Cr-doped coal has been tested in this study to improve the signal-to-noise ratio for Cr K-edge XANES spectra, and hence the accuracy for Cr(VI) quantification. As has been confirmed, the abundant CO(2) as a balance gas for oxy-firing has the potential to inhibit the decomposition of organically bound Cr, thereby favoring its retention in solid ash. It also has the potential to promote the oxidation of Cr(III) to Cr(VI) to a minor extent. Increasing the oxygen partial pressure, particularly in the coexistence of HCl in flue gas, favored the oxidation of Cr(III) into gaseous Cr(VI)-bearing species such as CrO(2)Cl(2). Regarding the solid impurities including Na(2)SO(4) and CaO, Na(2)SO(4) has proven to preferentially capture the Cr(III)-bearing species at a low furnace temperature such as 600 °C. Its promoting effect on the oxidation of Cr(III) to Cr(VI), although thermodynamically available at the temperatures examined here, is negligible in a lab-scale drop tube furnace (DTF), where the particle residence time is extremely short. In contrast, CaO has proven facilitating the capture of Cr(VI)-bearing species particularly oxychloride vapors at 1000 °C, forming Ca chromate with the formulas of CaCrO(4) and Ca(3)(CrO(4))(2) via a direction stabilization of Cr(VI) oxychloride vapor by CaO particle or an indirect oxidation of Cr(III) via the initial formation of Ca chromite. The fly ash collected from the combustion of Cr-doped coal alone has a lower water solubility (i.e., 58.7%) for its Cr(VI) species, due to the formation of Ba/Pb chromate and/or the incorporation of Cr(VI) vapor into a slagging phase which is water-insoluble. Adding CaO to coal increased the water-solubility of both Cr(VI) and Cr(III) by forming Ca chromite and chromate, respectively.

Theoretical study on the thermal decomposition of pyridine

Semi-empirical PM3 molecular orbital calculations have been used to investigate the reaction pathways of pyrolysis of pyridine. All the transition states and intermediates of the reaction path were optimized. The probable pathways are estimated from the activation energies calculated and compared with known experimental results. The heats of formation of pyridine radicals are calculated to be 76.1, 80.6, and 79.5 kcal/mol for 2- (2A), 3- (3A) and 4-pyridyl radicals (4A), respectively. The weakest bonds on the radicals were assumed to be broken and gave the decomposition fragments successively.

Sintering Behavior of Metal Powders Involving Microwave-Enhanced Chemical Reaction

Copper powder compacts were sintered by microwave radiation in air. In this procedure, the samples were sintered by microwave in air without using any special atmosphere, only by protecting them in a container filled with ceramic powder. The enhancement of the deoxidation reaction by the microwave was observed. The samples were analyzed by using scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) analysis. The samples were deoxidized on the surface and were well sintered to the edge from the inside throughout the entire cross section. The tensile strength of the copper samples sintered by the microwave in air was higher than that found in conventional sintering in N2 gas. No other differences were noticed between the samples sintered by the microwave under the air-rich conditions and in the conventional furnace in H2+N2 gas. The microwave-sintered copper samples were of good quality; for example, the tensile strength measured throughout the cross section was the same as that for the samples sintered in H2+N2 gas by the conventional method.

Elucidating the mechanism of Cr(VI) formation upon the interaction with metal oxides during coal oxy-fuel combustion

The thermodynamics underpinning the interaction of Cr-bearing species with basic metal oxides, i.e. K2O, Fe2O3, MgO and CaO, during the air and oxy-fuel combustion of coal have been examined. The synchrotron-based X-ray adsorption near-edge spectroscopy (XANES) was used for Cr speciation. For the oxides tested, Cr(VI) formation is dominated by the reduction potential of the metals. The oxides of Ca(2+) with high reduction potential favored the oxidation of Cr(III), same for K(+). The other two basic metals, Fe2O3 and MgO with lower reduction potentials reacted with Cr(III) to form the corresponding chromites at the temperatures above 600°C. Coal combustion experiments in drop-tube furnace have confirmed the rapid capture of Cr vapors, either trivalent or hexavalent, by CaO into solid ash. The existence of HCl in flue gas favored the vaporization of Cr as CrO2Cl2, which was in turn captured by CaO into chromate. Both Fe2O3 and MgO exhibited less capability on scavenging the Cr(VI) vapor. Particularly, MgO alone exhibited a low capability for capturing the vaporized Cr(III) vapors. However, its co-existence with CaO in the furnace inhibited the Cr(VI) formation. This is beneficial for minimizing the toxicity of Cr in the coal combustion-derived fly ash.

Comparative study of electron transport mechanisms in epitaxial and polycrystalline zinc nitride films

Zn3N2 has been reported to have high electron mobility even in polycrystalline films. The high mobility in polycrystalline films is a striking feature as compared with group-III nitrides. However, the origins of the high mobility have not been elucidated to date. In this paper, we discuss the reason for high mobility in Zn3N2. We grew epitaxial and polycrystalline films of Zn3N2. Electron effective mass (m*) was determined optically and found to decrease with a decrease in electron density. Using a nonparabolic conduction band model, the m* at the bottom of the conduction band was derived to be (0.08 ± 0.03)m0 (m0 denotes the free electron mass), which is comparable to that in InN. Optically determined intra-grain mobility (μopt) in the polycrystalline films was higher than 110 cm2 V−1 s−1, resulting from the small m*. The Hall mobility (μH) in the polycrystalline films was significantly smaller than μopt, indicating that electron transport is impeded by scattering at the grain boundaries. Nevertheless, μ...

Transparent conducting zinc nitride films

Highly conducting Zn3N2 thin films were reactively sputtered on unheated glass. Well-crystallized polycrystalline films were obtained even though the films were deposited at a low temperature. Nitrogen-deficient Zn3N2 films exhibited n-type conductivity and resistivities of the order of 10−3 Ω cm. All the obtained Zn3N2 films had sufficiently high electron mobilities in the range of 30 to 66 cm2 V−1 s−1. Such high mobilities probably originate from the small electron effective mass of 0.27m0 (where m0 denotes free electron mass), which was confirmed by infrared reflectance measurements. Furthermore, we found that intentional oxygen doping reduced the resistivities of Zn3N2 thin films to 8.9 × 10−4 Ω cm. Optical measurements revealed that the direct optical band gap of the Zn3N2 films was in the range of 2.9–3.1 eV. These results suggest that impurity-doped Zn3N2 is a candidate for a new nitride-based transparent conductor.

Conduction-band effective mass and bandgap of ZnSnN 2 earth-abundant solar absorber

Pseudo III-V nitride ZnSnN2 is an earth-abundant semiconductor with a high optical absorption coefficient in the solar spectrum. Its bandgap can be tuned by controlling the cation sublattice disorder. Thus, it is a potential candidate for photovoltaic absorber materials. However, its important basic properties such as the intrinsic bandgap and effective mass have not yet been quantitatively determined. This paper presents a detailed optical absorption analysis of disordered ZnSnN2 degenerately doped with oxygen (ZnSnN2−xOx) in the ultraviolet to infrared region to determine the conduction-band effective mass (mc*) and intrinsic bandgap (Eg). ZnSnN2−xOx epilayers are n-type degenerate semiconductors, which exhibit clear free-electron absorption in the infrared region. By analysing the free-electron absorption using the Drude model, mc* was determined to be (0.37 ± 0.05)m0 (m0 denotes the free electron mass). The fundamental absorption edge in the visible to ultraviolet region shows a blue shift with increasing electron density. The analysis of the blue shift in the framework of the Burstein-Moss effect gives the Eg value of 0.94 ± 0.02 eV. We believe that the findings of this study will provide important information to establish this material as a photovoltaic absorber.

Effects of Mineral Transformations on the Reduction of PM2.5 during the Combustion of Coal Blends

Two chinese bituminous coals used in coal-fired power plants are combusted under air conditions in a lab-scale drop tube furnace. The effects of minerals transformation on the formation of PM 2.5 are investigated during the combustion of coal blends. The collected PM were subjected to Computer controlled scanning electron microscopy (CCSEM) and High-resolution transmission electron microscopy(HRTEM) coupled with energy dispersive X-ray spectroscopy (EDX) analysis for determination of chemical species within them. The results show that PM 2.5 emissions are not linearly related to the wt.% of the parent coal or coal blends. Transformations of fine Si-Al mineral grains provided by the minerals in coal XQ into coarse particles (>2.5 μm in diameter) are responsible for the reduction of PM1-2.5 during the combustion of coal blending. The transformed fine Si-Al particles are captured by the coarse Ca-Mg-Al-Si provided by the minerals in coal HT to form larger Ca-Mg-Al-Si particles (>2.5 μm in diameter). Increasing Ca and Mg concentration in coal blends enhances the liquid concentration produced during combustion and hence affects the emissions of PM1 and PM1-2.5.Through adjusting the mineral compositions in coal blends, the reduction of PM1 and PM1-2.5 emissions can be achieved during combustion.