Rapid evaluation of oxidation catalysis by gas sensor system: total oxidation, oxidative dehydrogenation, and selective oxidation over metal oxide catalysts

The rapid evaluation of catalysis is an indispensable technology for the success of combinatorial chemistry. A small-sized, less expensive, easily operating screening is desirable for parallel settings which dramatically shortens the evaluation time. Recent advances in gas sensors have enabled us to use them for the rapid evaluation of oxidation catalysis. Three typical catalytic oxidations over metal oxide catalysts were evaluated by gas sensor systems optimized for each catalytic system. The first one is the total oxidation of carbon monoxide in air. Five catalytic combustion-type gas sensors were used in a parallel reactor system to shorten the evaluation time. The second one is the oxidative dehydrogenation (ODH) of ethane over the mixed oxide of nickel and iron. The evaluation of the ODH catalysis was performed by a selective olefin sensor which determines the concentration of C₂H₄ in C₂H₆. The third one is the selective oxidation catalysis of propane over alkali modified Fe/SiO₂. The effluents including CO, CO₂, aldehydes and ketones in propane were analyzed by the CO, CO₂ and semiconductor-type gas sensors selective toward aldehydes and ketones. These evaluation results indicated that gas sensors have a good potential for the rapid evaluation of oxidation catalysts.     

Enhancement of etch rate for preparation of nano-sized ion-track membranes of poly(vinylidene fluoride): Effect of pretreatment and high-LET beam irradiation

We investigated how pretreatment and high-LET beam irradiation affected the ion-track dissolution rate in poly(vinylidene fluoride) (PVDF) films by SEM observations and conductometric analysis in order to develop the preparation methodology of nano-sized ion-track membranes. PVDF thin films irradiated with four types of ion beams were exposed to a 9 mol/dm³ KOH aqueous solution after their storage in air at 120 °C. This heating treatment was found to enhance the etch rate in the latent track, both in the inner core and outer halo regions, without changing that in the bulk, probably due to the formation of parasitic oxidation products facilitating the introduction of the etching agent to improve the etchability. Additionally, the irradiation of heavier higher-LET ions, causing each track to more activated sites (like radicals), was preferable for achieving effective etching.     

A rapid-detection method for radioactive cesium in the air

We propose a method of rapidly detecting radioactive cesium floating in the air for the purpose of alerting people active in the ‘difficult-to-return zone’ of Fukushima to changes in airborne radioactivity. With this purpose in mind, we set requirement specifications and created a new system concept. The targeted detection limit was 30 Bq/m³ and the mandatory level of measurement time was 48 min with a target level of 12 min, and these periods are 10 times faster than those of conventional air monitors. The system consists of a conventional gamma-spectrometer with a novel shaped shield. The targeted peak region of the measured energy spectrum is analyzed. After the basic design and confirmation of feasibility, we perform some experiments in the normal environment of Yokohama city and the difficult-to-return zone of Fukushima. Using the results, we conducted the design improvement and performance evaluation. As a result, the system performance is found to satisfy requirements. We thus conclude that this system is a promising candidate for rapid detection of airborne radioactivity in the difficult-to-return zone of Fukushima.     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Geometric control and tuneable pore size distribution of buckypaper and buckydiscs

The fabrication of buckypaper from unfunctionalised multi-walled carbon nanotubes (MWCNTs) without the aid of surfactants or surface modification techniques is accomplished through a novel and quick frit compression method. The dimensions can be controlled through the size of the syringe housing and the through the mass of carbon nanotubes added. Their thicknesses are typically much larger than surfactant-cast buckypaper and range from 120 μm up to 650 μm; buckypaper with thicknesses larger than 500 μm we call buckydiscs. Buckypaper and buckydiscs are mechanically robust to handle, flexible, stable in solvents and possess larger porosities than Triton-X100 cast buckypaper. They also exhibit a memory effect when bending wetted samples, returning to their former geometry on drying. Buckypaper and buckydiscs were studied by mercury intrusion porosimetry to reveal a defined distribution of mesopores and small macropores that is, along with their density and apparent free volume, dependant on the casting solvent and therefore tuneable. Moreover, the frit compression system also allows control over the 3-dimensional geometry of the buckydiscs during the casting process.     

A novel photoreactive amphiphile of nitrophenylazide for immobilization of bioactive proteins

Monolayers of an amphiphilic nitrophenylazide (ANPA) derivative were prepared and their ability to immobilize a protein molecule by a photochemical binding reaction was demonstrated as a novel means to constitute a biofunctional membrane. Molecular orientations and photoreactions in the ANPA monolayers were investigated by Fourier transform IR spectroscopy. Rapid photolysis of ANPA was observed which reflects decomposition of the azide group to a reactive nitrene radical intermediate. As an enzyme, glucose oxidase (GOD) was immobilized on a monomolecular film of ANPA, coated on a substrate, by means of enzyme adsorption at the solid-solution interface and subsequent photolysis of ANPA. Radioisotope labelling experiments revealed that the enzyme was immobilized at a high surface concentration which corresponds to a closely packed monolayer of GOD. The specific activity of the immobilized enzyme was estimated to be high compared with those of other systems involving the adsorption of this enzyme. The usefulness of the present technique for fabricating biofunctional monolayer assemblies is discussed.     

Experimental and analytical studies of the thermal stratification phenomenon in the outlet plenum of fast breeder reactors

Water and sodium experiments were conducted with scaled models to study the in-vessel thermal stratification. The models simulate the outlet plenum in a loop-type LMFBR with an inner barrel and a closed-type UIS (upper instrumentation structure). An examination of the threshold for thermal stratification, the rising rate of the stratification interface, and the flow regime above the interface has been conducted and is reported in the present paper. In parallel, the phenomenon in the experiments has been evaluated with the multi-dimensional analysis.     

Membrane processing of used frying oils

Studies were conducted with used frying oils in a flat membrane batch cell using five different types of polymeric membranes to decrease the soluble degradation products. During membrane processing, triglycerides permeated preferentially compared to the majority of the polar compounds including oxidation products, polymers, and color compounds. Two of the composite membranes, NTGS-AX and NTGS-2200, selectively rejected polar compounds and oxidation products to the extent of 25–48% and 24–44% respectively. The reduction in Lovibond color values (5R+Y) was in the range of 83–93%. The viscosity of the used frying oil was reduced to the extent of 22%. The composite membranes were effective in reducing the soluble impurities, as well as insoluble particulates, without causing any undesirable changes to the oil. The membrane process appears to improve the life of used frying oils and does not have the disadvantages associated with the active filtration systems, however, for commercial application the permeate flux needs to be improved considerably.