Living cationic polymerization of vinyl monomers by organoaluminum halides

Summary Well-defined living polymers of isobutyl vinyl ether were obtained in the polymerization initiated with ethylaluminum dichloride (EtAlCl₂) in conjunction with a stoichiometric excess of dioxane (5–10 vol%) in n-hexane at 0°C. Under these conditions, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, while the molecular weight distribution stayed narrow (M_w/M_n = 1.1–1.25). In sharp contrast, the EtAlCl₂-initiated polymerization in the absence of dioxane led to non-living polymers with a broad molecular weight distribution. It was concluded that the propagating carbocation is stabilized not by the counteranion but by an externally added basic compound (dioxane) that strongly interacts with the active end.     

Buoyancy engine developed for underwater gliders

A buoyancy engine with a swashplate-type axial piston pump was developed. Its oil extrusion and drawing properties under high hydraulic pressure were evaluated. This buoyancy engine is now installed in an underwater glider that will achieve long-term monitoring of ocean environments up to 2100 m depth in a designated area with lower operational costs. This bidirectionally functioning pump can control the amount of oil in extrusion and draw operations. When drawing oil under high pressure, the hydraulic pump and the electric motor, respectively, act as a hydraulic motor and an electric generator. The generated electric power is absorbed by a damping resistor. The oil-drawing and extrusion properties were measured using a large hyperbaric chamber that is able to produce an almost identical environment to that of actual operations. Results confirmed stable oil extrusion operations up to 21 MPa. Regarding oil-drawing properties, although it was measured only up to 10 MPa in the hyperbaric chamber, it can be inferred that the system can draw the oil and can control the buoyancy precisely up to 21 MPa by replacing the two-way ball valve with an electromagnetic latching solenoid valve.     

Using selective precipitant for uranyl ions — Fundamental studies for evaluating the precipitant performance

We have developed a simple reprocessing process for spent FBR fuels using N-cyclohexyl-2-pyrrolidone (NCP) which has selective precipitation ability for UO₂²⁺ ions. It was confirmed that NCP has sufficient precipitation ability for UO₂²⁺ ions, decontamination capability (separation of UO₂²⁺ from simulated fission products), and resistance to γ-ray radiation in nitric acid solutions. These findings indicate that NCP is applicable to our reprocessing process. We have also evaluated performances of other precipitants such as N-n-propyl-2-pyrrolidone (NProP), N-n-butyl-2-pyrrolidone (NBP), and N-n-butyl-2-pyridone (NBPyr). It was found that higher decontamination factors (DFs) are obtained by using NProP and NBP. This can be interpreted that the hydrophobicity of NProP and NBP is lower than that of NCP. Furthermore, we have obtained an experimental result that the resistance of NBPyr to γ-ray radiation is superior to that of NCP.     

Calculations from texture of earing in deep drawing for FCC metal sheets

The present study aims to calculate the height at each peripheral position of a cup drawn from polycrystalline sheet using texture data. In the analytical treatment the polycrystalline sheet is simplified to an aggregation of many single crystals with various orientations, and the texture is represented by a three-dimensional crystallite orientation distribution function. The ear is calculated crystallographically using the orientation distribution function as a volume fraction of a certain oriented crystal. In the experiment aluminium, Al-Mg alloy and copper sheets which are treated under various conditions of cold rolling and heat treatment are used. The average textures over the thicknesses of the sheets are measured by the Schulz reflection method. The calculated ears based on the measured textures are compared with the experimental ears for each material. The results show that all the principal features of the ears of drawn cups are predicted satisfactorily by the calculation.     

Deuterium trapping by irradiation damage in tungsten induced by different displacement processes

The deuterium trapping behaviors in tungsten damaged by light ions with lower energy (10 keV C⁺ and 3 keV He⁺) or a heavy ion with higher energy (2.8 MeV Fe²⁺) were compared by means of TDS to understand the effects of cascade collisions on deuterium retention in tungsten. By light ion irradiation, most of deuterium was trapped by vacancies, whose retention was almost saturated at the damage level of 0.2 dpa. For the heavy ion irradiation, the deuterium trapping by voids was found, indicating that cascade collisions by the heavy ion irradiation would create the voids in tungsten. Most of deuterium trapped by the voids was desorbed in higher temperature region compared to that trapped by vacancies. It was also found that deuterium could accumulate in the voids, resulting in the formation of blisters in tungsten.     

Highly efficient electrochemical valence control of uranium using microfluidic chip equipped with microelectrodes

We have developed a novel microchip equipped with a microchannel and Pt microelectrode array for electrochemically controlling valences of actinide (An) species. The square wave voltammograms of the redox reaction of potassium hexacyanoferrate(II) in the microchannel were measured. We found that the fabricated Pt microelectrode array has superior performances for the detection of the electrochemically active species in the microchannel. Therefore, the potentiostatic electrolysis experiments of uranium ions were carried out in the microchannel, and the concentration changes of uranium ions accompanied by the potentiostatic electrolysis were examined using thermal lens microscope. The results showed that the redox reactions between U(VI) and U(IV) can be performed completely in a microchannel in a few minutes, that is, the microscale reaction is accelerated by a factor of more than 10 compared with the bulk solution reactions taking hours mostly. The developed microchip was found to have enough performances for realizing rapid and highly efficient redox reactions for An species, which are impossible in the bulk reactions.     

Morphology and breaking of latex particle deposits at a cylindrical collector in a microfluidic chamber

We report an analysis for the morphology and breaking behavior of deposits of spherical latex particles (1 and 3.6 μm in diameter) at a cylindrical collector in a microfluidic channel fabricated by soft-lithography. In-situ observation of particle deposition over a large range of flow rate conditions evidence the relationship between deposit morphology and mode of particle transport toward the collector. For low Pe?clet number (Pe), particle deposits are nearly uniform all over the collector surface except at the rear where particles do not attach. Upon increase of Pe, deposits gradually adopt a columnar morphology at the collector stagnation point. These results are qualitatively consistent with previously reported Monte Carlo simulations of deposits formation in stagnation point flow systems. However, these simulations fail to quantitatively predict the observed deposition at the rear of the collector for sufficiently high flow rate. Additional deposit breaking experiments together with numerical evaluations of particle flux around the collector suggest that such "anomalous" deposition at large Pe is significantly governed by concomitant detachment of deposited particles at the stagnation point and the presence of recirculation flow at the collector rear. Finally, kinetics of deposition are discussed in connection with particle size-dependence of deposit breaking features.     

Transmission electron microscopic observations of nanobubbles and their capture of impurities in wastewater

Unique properties of micro- and nanobubbles (MNBs), such as a high adsorption of impurities on their surface, are difficult to verify because MNBs are too small to observe directly. We thus used a transmission electron microscope (TEM) with the freeze-fractured replica method to observe oxygen (O₂) MNBs in solutions. MNBs in pure water and in 1% NaCl solutions were spherical or oval. Their size distribution estimated from TEM images close to that of the original solution is measured by light-scattered methods. When we applied this technique to the observation of O₂ MNBs formed in the wastewater of a sewage plant, we found the characteristic features of spherical MNBs that adsorbed surrounding impurity particles on their surface.     

Biocatalytic Synthesis of Nitriles through Dehydration of Aldoximes: The Substrate Scope of Aldoxime Dehydratases

Nitriles, which are mostly needed and produced by the chemical industry, play a major role in various industry segments, ranging from high‐volume, low‐price sectors, such as polymers, to low‐volume, high‐price sectors, such as chiral pharma drugs. A common industrial technology for nitrile production is ammoxidation as a gas‐phase reaction at high temperature. Further popular approaches are substitution or addition reactions with hydrogen cyanide or derivatives thereof. A major drawback, however, is the very high toxicity of cyanide. Recently, as a synthetic alternative, a novel enzymatic approach towards nitriles has been developed with aldoxime dehydratases, which are capable of converting an aldoxime in one step through dehydration into nitriles. Because the aldoxime substrates are easily accessible, this route is of high interest for synthetic purposes. However, whenever a novel method is developed for organic synthesis, it raises the question of substrate scope as one of the key criteria for application as a “synthetic platform technology”. Thus, the scope of this review is to give an overview of the current state of the substrate scope of this enzymatic method for synthesizing nitriles with aldoxime dehydratases. As a recently emerging enzyme class, a range of substrates has already been studied so far, comprising nonchiral and chiral aldoximes. This enzyme class of aldoxime dehydratases shows a broad substrate tolerance and accepts aliphatic and aromatic aldoximes, as well as arylaliphatic aldoximes. Furthermore, aldoximes with a stereogenic center are also recognized and high enantioselectivities are found for 2‐arylpropylaldoximes, in particular. It is further noteworthy that the enantiopreference depends on the E and Z isomers. Thus, opposite enantiomers are accessible from the same racemic aldehyde and the same enzyme.