Extraction of lanthanide ions from aqueous solution by bis(2-ethylhexyl)phosphoric acid with room-temperature ionic liquids

Extractions of five kinds of lanthanide metal ions by bis(2-ethylhexyl)phosphoric acid (DEHPA) with [1-Cn-3-methylimidazolium][PF₆](Cn = C₂, C₄) or [1-butyl-4-methylpyridinium][PF₆] were carried out under various DEHPA and HNO₃ concentrations from 0 to 1 M and under different temperature conditions from 298 to 333 K. These results were compared with those using the conventional organic solvent, hexane, in terms of their distribution coefficient values. Under all of the conditions in this study, the ionic liquid system shows more than three times greater extractability for lanthanide compared to when hexane was used. The distribution coefficient of lanthanide ions decreased as the length of the alkyl chain increased from the ethyl to the butyl. In addition, the imidazolium cation generally shows a higher distribution coefficient compared to the pyridinium cation in an ionic liquid. The concentration ratio of lanthanides and DEHPA resulted in an extraction affinity transition for lanthanides. Also evaluated in this study were issues related to the selectivity associated with the lanthanide mixture and the dependency of the ionic radius during lanthanide extraction.     

Determination of dissolved natural thorium and uranium in Horonobe and Mizunami Underground Research Laboratory groundwater and its thermodynamic analysis

At two underground research laboratories situated at Horonobe and Mizunami, Japan, trace amounts of natural thorium and uranium dissolved in deep groundwater were investigated with the help of chemical pre-concentration method. The groundwater was sampled from underground boreholes under the geochemical condition of no atmospheric exposure, and the colloid contribution was checked by in situ two size-fractionated ultrafiltration systems. A rough decrease by half in the concentration after in situ filtration suggested the presence of natural colloids and suspended matter that were carriers of a portion of the elements. The Th and U concentrations in groundwater after 10 kDa filtration was evaluated as dissolved species, and was identified thermodynamically using existing hydrogeological and geochemical data, such as the mineral components in the groundwater at a given pH, ionic strength, concentration of co-existing ions, redox potential, and a hypothetical solubility-limiting solid phase. The crystalline solid phase of tetravalent thorium and uranium dioxides made the solubility very low compared with that of the amorphous phase.     

Method for altering deformational characteristics of controlled-clearance piston-cylinders

A new controlled-clearance pressure balance has been developed to improve the hydraulic pressure standard for pressures up to 1 GPa. For several controlled-clearance (CC) piston-cylinders, characterization experiments based on the Heydemann-Welch (H-W) model were performed to estimate the pressure dependence of the effective area. The results of the experiments, specifically, the changes in the piston fall-rate and the generated pressure in response to the applied jacket pressure, are summarized for CC piston-cylinders of different pressure ranges. At pressures higher than a few hundred MPa, the characteristics of some piston-cylinders differed from those predicted by the H-W model. In this paper, a method for altering the deformational characteristics of CC piston-cylinders is examined. It was found that adjusting the area of the outer surface of the cylinder to which the jacket pressure is applied is an effective method for obtaining deformational characteristics that satisfy the conditions of the H-W model.     

Effects of plating factors on morphology and appearance of electrogalvanized steel sheets

Because the lightness, the gloss and the press-formability of electrogalvanized steel sheets change depending on the morphology of deposited Zn, control of this factor is essential to improving these properties. The effects of plating factors on the morphology of deposited Zn were systematically discussed both from the crystallographic viewpoint of epitaxy between Zn and steel and from the electrochemical viewpoint of the overpotential for Zn deposition. Plating factors include crystal orientation of steel substrate, current density, flow rate, temperature, addition of inorganic compounds to the solution and pre-adsorption of organic compounds. These plating factors affect the overpotential for Zn deposition and epitaxy between Zn and steel. The crystal orientation index of the Zn basal plane and the platelet crystal size of Zn are decreased with increasing the overpotential for Zn deposition. They are also decreased with decreasing the epitaxy between Zn and steel, even when the overpotential is kept constant. When the overpotential for Zn deposition is increased, the surface roughness of deposited Zn increases because of an increase in the inclination of the Zn basal plane to the steel substrate. When the epitaxy between Zn and steel is decreased without changing the overpotential, the surface roughness is reduced due to the decrease in platelet crystal size of Zn, although the inclination of the Zn basal plane is somewhat increased. The lightness of deposited Zn is enhanced with decreasing the surface roughness of Zn.     

Fabrication and operation limit of lead-free PTCR ceramics using BaTiO3–(Bi1/2Na1/2)TiO3 system

The electric properties of BaTiO₃–(Bi_1/2Na_1/2)TiO₃ (BT–BNT) solid solution ceramics were studied as a lead-free PTCR (positive temperature coefficient of resistivity) thermistor material usable over 130°C. For determining the maximum switching temperature T _s, the phase diagram of BT–BNT binary system was clarified. Two semiconductorization processes and their electric properties are described. The lanthanum(La)-doped BBNT ceramics sintered in air still showed dielectric behaviors, but the niobium(Nb)-doped ones had a low resistivity at room temperature, ρ _RT, on the order of 10³ Ωcm and showed a PTC behavior. Sintering under a low O₂ atmosphere produces BT–BNT ceramics with less than 10² Ωcm compared to those prepared in air. Our current research produced the BBNT ceramics with T _s values around 210°C by increasing the (Bi_1/2Na_1/2) content in the ceramics.     

Biochip with integrated pumps for plug-based sequential exchange of solutions

A novel method for exchanging solutions used in biochemical analyses and a device to carry out the exchange are proposed. An array of plugs formed using six injectors was transported in a microflow channel using a main pump located at one end of the main flow channel. The injectors and main pump were operated on the basis of the change in volume caused by the electrolysis of water. Bubbles were produced from working electrodes; these bubbles caused a diaphragm placed below the injectors to inflate and occlude the inlet of the solution reservoir. Increase in the number of bubbles caused the reservoir to inject the solution into the main flow channel in the form of a plug. Each plug was individually transported downstream to the sensing area by the main pump, which was operated in a similar manner to the injector. The device was used for the detection of a tumor marker, α-fetoprotein (AFP). Plugs of necessary solutions were individually transported to the sensing area with immobilized primary antibodies to allow antigen–antibody binding, cleaning, and detection. The fluorescence intensity from the antibodies showed clear dependence on the concentration of AFP. The immobilization of antibodies could also be carried out on-chip.     

Product mix problems considering several probabilistic conditions and flexibility of constraints

This paper considers product mix problems including randomness of future returns, ambiguity of coefficients and flexibility of upper value with respect to each constraint such as budget, human resource, time and several costs. Particularly, the flexibility is assumed to be a fuzzy goal. Then, several models based on maximizing total future profits under a level of satisfaction to each fuzzy goal are proposed. Furthermore, the model considering preference ranking to each fuzzy goal of constraints is proposed. Since these problems are basically formulated as nonlinear programming problems, the transformations into deterministic equivalent problems are introduced and the efficient solution methods are developed. A numerical example for product mix problem is given to illustrate our proposed models.     

A TEM study on melt-crystallized poly(butylene terephthalate)

A study was made to investigate an optimum condition for ruthenium tetraoxide staining of poly(butylene terephthalate) (PBT) with glass transition temperature as low as ca. 23 degrees C for TEM observation of melt-grown PBT crystals. The morphological study of ultrathin sections prepared based on optimum staining at 25 degrees C for 8 h revealed formation of fringed-micellar crystal nuclei in the early stage and folded-chain fringed-micellar crystals in the later stage of isothermal crystallization at 40 degrees C from melt. The fraction of chain-folded crystals increased with increasing crystallization temperature from the quantitative analysis of crystal thickness in comparison with the reported morphology using the replica method.     

Elevation of plasma levels of L-dopa in transdermal administration of L-dopa-butylester in rats

To increase delivery of L-dopa in its transdermal absorption, a new lipophilic derivative of L-dopa, L-dopa-butylester, was synthesized. An in-vitro study employing two-chamber diffusion cells, in which the excised rat abdominal skin was mounted, revealed that, in the presence of L-menthol and ethanol, L-dopa-butylester penetrated in its original form more effectively than L-dopa. L-Dopa-butylester sheets were made by immersing wiper sheets in methanol containing the compound, and then evaporating the methanol. An extraction study of the compound from the sheets revealed that its stability was maintained for at least 12 weeks. In an in-vivo cutaneous absorption study, an L-dopa-butylester sheet was attached to the shaved rat abdominal skin. A hydrogel containing L-menthol and ethanol was spread on vinyl tape, and this sheet was placed over it. In plasma, the L-dopa level rose linearly between 30 and 180 min after the cutaneous application; L-dopa-butylester was not detected. The L-dopa level was higher than that in which L-dopa was applied. These findings indicated that the lipophilic nature of L-dopa-butylester further increased its penetration through the skin, and that L-dopa-butylester that was taken up into the general circulation system was rapidly converted to L-dopa by hydrolysis in the body.