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.     

Size adjustment of spherical temperature-sensitive hydrogel beads by liquid–liquid dispersion using a Kenics static mixer

Temperature-sensitive hydrogel beads were prepared by Kenics static mixer technology. The temperature-sensitive monomer N,N-diethylacrylamide and photo-crosslinkable pre-polymer ENT were used as model hydrogel materials. Drop dispersion of high viscosity polymer material in low viscosity hexadecane was made using the static mixer. Drops of a solution of the mixed materials were rapidly photo-crosslinked by UV irradiation after mixing in the static mixer, and spherical hydrogel beads with narrow, normal size distribution were thus prepared. The Kenics static mixer is a useful device for the preparation of spherical beads of temperature-sensitive hydrogels. The Sauter Mean Diameter of the hydrogel beads swollen in deionized water at 293 K was measured. The experimentally determined dimensionless swollen hydrogel bead diameter was well correlated with the Weber number, degree of swelling and viscosity ratio. The effects of gelation and ENT addition on the bead size were evaluated from the degree of swelling. The correlation equation can be used for size adjustment of temperature-sensitive spherical hydrogel beads.     

Delamination growth mechanisms in woven glass fiber reinforced polymer composites under Mode II fatigue loading at cryogenic temperatures

The purpose of this research is to characterize the cryogenic delamination growth behavior in woven glass fiber reinforced polymer (GFRP) composite laminates subjected to Mode II fatigue loading. Mode II fatigue delamination tests were performed at room temperature, liquid nitrogen temperature (77 K) and liquid helium temperature (4 K) using the four-point bend end-notched flexure (4ENF) test method, and the delamination growth rate data for the woven GFRP laminates were obtained. The energy release rate range was determined by the finite element method. Microscopic examinations of the specimen sections and fracture surfaces were also carried out. The present results are discussed to obtain an understanding of the fatigue delamination growth mechanisms in the woven GFRP laminates under Mode II loading at cryogenic temperatures.     

Timing-Error-Detecting Dual-Edge-Triggered Flip-Flop

This paper presents a construction of timing-error-detecting dual-edge-triggered flip-flops (DET-FFs). The proposed FF is based on a conventional DET-FF and a conventional timing error detection method. While the conventional timing error detection uses a transition detector with relatively large area, the proposed FF uses internal signals in a DET-FF as as an alternative to the transition detector. This paper also shows an evaluation result indicating that the proposed FF has smaller area overhead than the simple combination of the conventional DET-FF and timing error detection methods.     

Antioxidant property of polyhydroxylated naphthoquinone pigments from shells of purple sea urchin Anthocidaris crassispina

Sea urchin gonads are highly priced sushi foodstuff “Uni” in Japanese traditional food, but after removal of them the residual shells with spines are dumped as waste. However, sea urchin shells contain naphthoquinone pigments with several phenolic hydroxyl groups, which were expected to act as potent antioxidant substances by donating hydrogens. Our previous study has evaluated their antioxidant ability to depress lipid peroxidation. This study examined other antioxidant property of the pigments from purple sea urchin shells, which possess larger amount of pigments than those of red and green sea urchins. The pigments as well as known antioxidant, α-tocopherol, exhibited 1,1-diphenyl 2-picryhydrazyl (DPPH) radical scavenging ability. Superoxide anion radical and hydrogen peroxide were also scavenged while hydroxyl radical, one of the most reactive oxygen species, was not significantly inhibited. However, because the pigments had significant activity to scavenge hydrogen peroxide and superoxide anion radical that could be in vivo precursors of hydroxyl radical, sea urchin pigments would be able to depress the generation of its related active oxygen radical species. These results suggested that sea urchin shells, which are still regarded as food waste, would be a new bio-resource for obtaining natural antioxidant.     

Preparation and electrocatalytic activity of palladium-platinum core-shell nanoalloys protected by a perfluorinated sulfonic acid ionomer

Palladium-platinum nanoalloys with a core-shell and nano-network structure were successfully synthesized by a hydrogen sacrificial protective method in an aqueous solution directly using a perfluorinated sulfonic acid (PFSA) ionomer as a protecting agent. The structure, local composition and electrocatalytic activity for the oxygen reduction reaction of the Pd/Pt/PFSA nanoalloys were investigated by transmission electron microscopy (TEM), aberration corrected scanning transmission electron microscopy (Cs-STEM), energy-dispersive X-ray spectrometry (EDS) and voltammetry. The core-shell structure was completed without contaminating reducing agents, organic solvents, useless protecting agents and a mediator. The Pd/Pt/PFSA core-shell nanoalloys realized a high electrochemical surface area and better electrocatalytic mass-activity for the oxygen reduction reaction than the Pt/PFSA nanoparticles.     

Mixing speed-controlled gold nanoparticle synthesis with pulsed mixing microfluidic system

Gold nanoparticles with diameters of a few tens of nanometer and a narrow size distribution were synthesized using a pulsed mixing method with a microfluidic system which consists of a Y-shaped mixing microchannel and two piezoelectric valveless micropumps. This mixing method enables control of the mixing speed of gold salts and reducing agent by changing the switching frequency of the micropumps, which was our focus to improve the particle size distribution, which is an essential parameter in gold nanoparticle synthesis. In the proposed method, the mixing time was inversely proportional to the switching frequency and the minimum mixing time was 95 ms at a switching frequency of 200 Hz. During synthesis experiments, the mean diameter of the synthesized gold nanoparticles was found to increase, and the coefficient of variation of particle size was found to decrease with decreasing mixing time. We successfully improved the coefficient of variation to less than 10% for a mean diameter of around 40 nm.