Fabrication study of proton injection layer suitable for electrochromic switchable mirror glass

An electrochromic (EC) switchable mirror glass can change between a reflective state and a transparent state with voltage application. The conventional device has a multilayer of Mg₄Ni/Pd/Al/Ta₂O₅/WO₃/indium-tin oxide on a transparent substrate. A palladium thin film was used as the proton injection layer. For practical use, we attempted to reduce the amount of palladium thin film from the viewpoints of the reduction in total fabrication cost and the efficient use of resources. The thickness of the film was related to the optical switching properties of the device. Although the device with a 1-nm-thick palladium film showed a high transmittance of 63% in the transparent state, its low switching durability was not suitable for practical application.Moreover, we were able to adapt a palladium-based alloy (Pd_0.8Ag_0.2) which is a well-known hydrogen permeation membrane as the proton injection layer to reduce the amount of palladium thin film. As a result, we found that a 4-nm-thick Pd-Ag thin film has good adaptability to the EC switchable mirror.     

Experimental and numerical investigation of effects of particle shape and size distribution on particles’ dispersion in a coaxial jet flow

In this study, an experimental and a numerical investigations are performed to investigate the effect of particle’s shape and size distribution on its dispersion behavior. Firstly, particle dispersion of pulverized coal and spherical polymer particles is observed by Particle Image Velocimetry (PIV) technique in the experiment. Secondly, a simulation is performed to analyze the particle dispersion in detail. Spherical and spheroidal motion models are applied to particle’s movement to investigate the shape effect. Furthermore, monodisperse and polydisperse for particles are applied to investigate the size distribution effect on the dispersion. Experimental results show that in the jet turbulence flow, pulverized coal particles, which have complex shapes and various sizes, have quite different dispersion behavior compared to spherical particles. In terms of the results of the simulation, this difference is mainly caused by the size distribution effect. Although particle’s shape affects the dispersity, it is weakened by the size distribution effect.     

Simple and comprehensive two-dimensional reversed-phase HPLC using monolithic silica columns

Simple and comprehensive two-dimensional (2D)-HPLC was studied in a reversed-phase mode using monolithic silica columns for second-dimension (2nd-D) separation. Every fraction from the first column, 15 cm long (4.6-mm i.d.), packed with fluoroalkylsilyl-bonded (FR) silica particles, was subjected to the separation in the 2nd-D using one or two octadecylsilylated (C(18)) monolithic silica columns (4.6-mm i.d., 3 cm). Monolithic silica columns in the 2nd-D were eluted at a flow rate of up to 10 mL/min with separation time of 30 s that meets the fractionation every 15-30 s at the first dimension (1st-D) operated at a flow rate of 0.4-0.8 mL/min. Three cases were studied. (1) In the simplest scheme of 2D-HPLC, effluent of the 1st-D was directly loaded into an injector loop of 2nd-D HPLC for 28 s, and 2 s was allowed for injection. (2) Two six-port valves each having a sample loop were used to hold the effluent of the 1st-D alternately for 30 s for one 2nd-D column to effect comprehensive 2D-HPLC without the loss of 1st-D effluent. (3) Two monolithic silica columns were used for 2nd-D by using a switching valve and two sets of 2nd-D chromatographs separating each fraction of the 1st-D effluent with the two 2nd-D columns alternately. In this case, two columns of the same stationary phase (C(18)) or different phases, C(18) and (pentabromobenzyloxy)propylsilyl-bonded (PBB), could be employed at the 2nd-D, although the latter needed two complementary runs. The systems produced peak capacity of approximately 1000 in approximately 60 min in cases 1 and 2 and in approximately 30 min in case 3. The three stationary phases, FR, C(18), and PBB, showed widely different selectivity from each other, making 2D separations possible. The simple and comprehensive 2D-HPLC utilizes the stability and high efficiency at high linear velocities of monolithic silica columns.     

Fabrication of vertically aligned diamond whiskers from highly boron-doped diamond by oxygen plasma etching

Conductive diamond whiskers were fabricated by maskless oxygen plasma etching on highly boron-doped diamond substrates. The effects of the etching conditions and the boron concentration in diamond on the whisker morphology and overall substrate coverage were investigated. High boron-doping levels (greater than 8.4 × 10(20) cm(-3)) are crucial for the formation of the nanosized, densely packed whiskers with diameter of ca. 20 nm, length of ca. 200 nm, and density of ca. 3.8 × 10(10) cm(-2) under optimal oxygen plasma etching conditions (10 min at a chamber pressure of 20 Pa). Confocal Raman mapping and scanning electron microscopy illustrate that the boron distribution in the diamond surface region is consistent with the distribution of whisker sites. The boron dopant atoms in the diamond appear to lead to the initial fine column formation. This simple method could provide a facile, cost-effective means for the preparation of conductive nanostructured diamond materials for electrochemical applications as well as electron emission devices.     

Experimental validation of the tetrahedral skeleton model pressure drop correlation for silica monoliths and the influence of column heterogeneity

This paper describes the use of computational fluid dynamics for the calculation of the flow resistance through computer-generated models resembling silica monoliths. This study was undertaken to determine the effect of skeleton heterogeneity on the flow resistance and, more precisely, to test the hypothesis that increased skeleton heterogeneity decreases the flow resistance. To evaluate the proposed model, 24 real silica monoliths have been prepared using the same method, covering a wide range of skeleton sizes (2.2 microm < d(s) < 8 microm) and porosities (0.47 < epsilon < 0.66). The permeability of these monoliths was determined by pressure drop measurements, and structural information was obtained by image analysis of laser scanning confocal microscopy-generated 3D images of the skeleton structure. The results indicate that the presence of preferential flow paths due to an increased heterogeneity of the flow through pore space reduces the flow resistance of monolithic media. It is also shown that the pore size is hence a much better suited scaling dimension than the skeleton size to reduce the permeability of monolithic columns.     

Effective Dissolution of Platinum by Using Chloride Salts in Recovery Process

Platinum (Pt) is typically recovered by employing dissolution processes in aqueous solutions; however, these processes require a long processing time and considerable quantities of acids with strong oxidants owing to the high chemical stability of Pt. In order to develop an efficient dissolution process, we studied chlorination treatments for Pt prior to dissolution. Chlorination was carried out at 673?K to 873?K (400?°C to 600?°C) using copper(II) chloride (CuCl₂) as a chlorine source. While pure Pt was insoluble in hydrochloric acid (HCl(aq)), the entire Pt component of the treated sample dissolved in HCl(aq) under certain conditions. Therefore, the proposed method can be used as a new, environmental friendly Pt recovery process.     

Preparation of Lanthanum Nickel Oxide-Coated Ni Sheet Anodes and Their Application to Electrolytic Production of (CF3)3N in (CH3)4NF·4.0HF Melt

A new process for electrolytic production of a perfluorinated compound, (CF₃)₃N, using lanthanum nickel oxide-coated Ni sheet anode in the (CH₃)₄NF·4.0HF melt at room temperature, was developed. Thin films of the lanthanum nickel oxides were prepared on Ni sheets by sol-gel coating method using polyvinlylpyrrolidone(PVP). The main components of the thin films were La₂O₃, LaNiO₃, and La₂NiO₄ at 500, 750 and 1000 °C, respectively. The anode performance in the (CH₃)₄NF·4.0HF melt depends greatly on the main component of the thin film, and the LaNiO₃-coated Ni sheet anode gives the best anode performance. The potential of LaNiO₃-coated Ni sheet anode remains constant at 5.9 V during electrolysis at 20 mA·cm⁻² in the (CH₃)4NF·4.0HF melt for 100 h. This is because LaNiO₃ and NiF₃, and/or Ni₂F₅, the latter of which was formed during electrolysis, in the film give a high electronic conductivity to the surface film during electrolysis. The maximum mole fraction of (CF₃)₃N (21.4%) was obtained at 20 mA·cm⁻² in (CH₃)₄NF·4.0HF melt using the LaNiO₃-coated Ni sheet.     

A molecular model for the d chain of the giant haemoglobin from Lumbricus terrestris and its implications for subunit assembly

We have previously reported that rhodacyanine dyes, such as 1 and 2, exhibited a potent inhibitory effect on the growth of several tumor cells and that 4-oxothiazolidine (rhodanine) was an essential moiety for antitumor activity. On the basis of our foregoing work, two types of rhodacyanine dyes, which categorized into class I and II depending on the methine length, were synthesized and evaluated as a novel antitumor agent. Attention was particularly focused on the structure-activity study of two heteroaromatic rings. In class I, where the A rings were conjugated to rhodanine via two methine groups, compounds 1, 20, 23, and 24 were found to be efficacious in tumor-bearing nude mice model study, but they did not have the chemical properties (stability, solubility) suitable for clinical use. In contrast, in class II, where the A rings were directly conjugated to rhodanine, compounds 13 and 25, which possessed a benzothiazole moiety for the A ring, exhibited the favorable biological and chemical properties. Therefore, we decided to have a benzothiazole moiety as the A ring and introduce various heterocyclic groups for the B ring. As a result, the pyridinium ring was selected as the optimal moiety for the B ring (compound 13). Further, the variation of counteranion had a profound effect on solubility in water without influence on antitumor activity. Chloride anion was selected as the favorable anion with respect to synthetic method as well as solubility in water. Our study finally led us to the identification of compound 3 (MKT 077, 1-ethyl-2-[[3-ethyl-5-(methylbenzothiazolin-2-ylidene)-4-oxothi azolidin-2 -ylidene]methyl]pyridinium chloride) as the candidate for clinical trials and is currently subjected to further investigation as a potent antitumor agent in phase I clinical trial for the treatment of solid tumors.     

Boron removal by titanium addition in solidification refining of silicon with Si-Al melt

In order to effectively remove B from Si for its use in solar cells, a process involving B removal by solidification refining of Si using a Si-Al melt with Ti addition was investigated. For clarifying the effect of Ti addition on B removal from the Si-Al melt, TiB₂ solubilities in Si-64.6 at. pct Al melt at 1173 K and Si-60.0 at. pct Al melt at 1273 K were determined by measuring the equilibrium concentrations of B and Ti in the presence of TiB₂ precipitates. The small solubilities of TiB₂ in the Si-Al melt indicate the effective removal of B from the Si-Al melt by Ti addition. Further, solidification experiments of Si-Al alloys containing B by Ti addition were performed, and the effect of Ti addition on the solidification refining of Si with the Si-Al melt was successfully confirmed.