An Additional Insight into the Correlation between the Distribution Ratios and the Aqueous Acidity of the TODGA System

Abstract

Extraction of Eu(III) and Am(III) from HNO₃ into the organic solvents using N,N,N′,N′‐tetraoctyl‐diglycolamide (TODGA) was investigated in order to study the detailed extraction reaction. The chemical species: 1:2 for metal:TODGA complex is present in polar diluents. On the other hand, the metal complexes need three or more TODGA molecules to remain stable in non‐polar diluents. The HNO₃ concentration dependence on the distribution ratio suggests that HNO₃ participates in the metal extraction. Infrared spectra indicate that the carbonyl oxygen coordinates with Eu(III), and luminescence lifetimes suggest that there are no water molecules in the inner coordination sphere of the extracted Eu‐complex.     

Determination of number-average and weight-average molecular weights of polymer sample from diffusion and sedimentation velocity measurements in theta solvent

Several methods to determine number-average molecular weight M_n and weight-average molecular weight M_w, of a polymer sample are proposed from diffusion and sedimentation velocity measurements at the θ point. According to these methods, M_n and M_w are determined from the diffusion constant vs. molecular weight relationship, and also from the equations of Svedberg and Flory–Mandelkern, using the 2nd-order and the –2nd-order diffusion constants. These methods have been applied to four samples of polydisperse polystyrene in the θ solvent, cyclohexane at 35°C. It was experimentally ascertained that M_n and M_w of each sample determined by the present methods were in good agreement with the results of column fractionation, light scattering, and calculated values from molecular weight distribution curve within experimental errors. It is concluded that the present methods are useful for determining M_n and M_w, since the reliabilities of M_n and M_w values, which are fundamental quantities of polymer characterization, can be raised by comparing the experimental data observed by conventional methods such as osmotic pressure, light scattering, and the Archibald method with those observed by the present methods.     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

Corrosion characteristics of reduced activation ferritic steel, JLF-1 (8.92Cr–2W) in molten salts Flibe and Flinak

Static corrosion tests were performed in molten salts, LiF–BeF₂ (Flibe) and LiF–NaF–KF (Flinak), at 500 °C and 600 °C for 1000 h. The purpose is to investigate the corrosion characteristics of reduced activation ferritic steels, JLF-1 (8.92Cr–2W) in the fluids. The concentration of hydrogen fluoride (HF) in the fluids was measured by slurry pH titration method before and after the exposure. The HF concentration determined the fluoridation potential. The corrosion was mainly caused by dissolution of Fe and Cr into the fluids due to fluoridation and/or electrochemical corrosion. Carbon on the surface might be dissolved into the fluids due to the corrosion, and this resulted to the decrease of carbide on the surface. The corrosion depth of the JLF-1 specimen, which was obtained from the weight losses, was 0.637 μm in Flibe at 600 °C and 6.73 μm in Flinak at 600 °C.     

Development of copper beam ducts with antechambers for advanced high-current particle storage rings

There has been continuous progress at the High Energy Accelerator Research Organization (KEK) in R&D on vacuum beam ducts adaptable to future high-current particle storage rings. Here we proposed copper beam ducts with antechambers to deal with the severe issues attributed to the high beam currents. The proposed antechamber scheme can withstand intense synchrotron radiation (SR), provide a beam duct with low beam impedance, and effectively reduce the electron cloud effect (ECE) in positron/proton rings. Several trial models were manufactured by a pressing or cold-drawn method, and assembled with electron beam welding. Special vacuum components, such as connection flanges, distributed pumps, and gate valves, were customized for the beam ducts. TiN coating on the inner surface of the beam duct was also investigated as a mitigating measure for the ECE. Trial models of the copper beam ducts were installed into the KEK B-factory (KEKB), and their performances were evaluated using real positron and electron beams.     

EFFECTS OF OPERATIONAL CONDITIONS ON DRYING CHARACTERISTICS IN CLOSED SUPERHEATED STEAM DRYING

The effects of operational conditions on the drying performance in closed superheated steam drying were examined theoretically and experimentally. The vapor generated from the sample was circulated in the drying chamber. In the theoretical analysis, the replacement of air with vapor in drying chamber and the convective vapor transfer in sample were considered. At the start of drying, the drying chamber was filled with air. As the drying proceeded, the air was replaced with the vapor generated from sample. The calculated results explained the characteristics of experimental data. The pore diameter of sample had little effect on the drying characteristics. During the internal evaporation period, the evaporation occurred in the narrow zone, which moved from the surface to the bottom of sample. The convective vapor transfer in sample had a significant influence on the drying performance. The excess increments in temperature and velocity of drying gas hardly contributed to shortening the drying time.     

LiErO2 formation on Er2O3 in static and natural convection lithium

Er₂O₃ is candidate material for insulating coating to prevent the magnetohydrodynamic (MHD) pressure drop in the self-cooled liquid Li blanket system. Although Er₂O₃ is stable material, detailed chemical behavior in liquid Li is not clear. Corrosion behavior of bulk Er₂O₃ in Li is investigated in static and flowing condition in the present study. After these tests, good compatibility of Er₂O₃ was confirmed and slight formation of LiErO₂ was detected by XRD analysis. This chemical behavior did not change in a static and flowing tests, however some of the corrosion product of LiErO₂ was removed easily by the Li flow. Intensity of LiErO₂ peaks in XRD spectrum suggests that the temperature gradient may affect the reaction rate in the natural convection loop. Since corrosion rate of Er₂O₃ is very small, slight change in state will be important information to evaluate lifetime of coating.     

High‐current lightning discharges in winter

Lightning electric‐field waveforms related to power line faults in winter have been identified. Most of those waveforms appear to be associated with upward lightning discharges with absolute peak currents of over 100 kA. They are quite different from common return‐stroke waveforms, and the lightning discharges which produce these characteristic waveforms are called GC (Ground to Cloud) flashes. These high‐current lightning discharges are distributed around the coastline in different ways depending on their polarities. The spatial distributions of high‐current lightning discharges around Japan are also investigated. It is revealed that the region of Honshu Island along the coastline of the Sea of Japan belongs to the area in which the density of high‐current lightning flashes is the highest in Japan through the year. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 170(1): 8–15, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20874