Influence of ammonium salt on electrowinning of copper from ammoniacal alkaline solutions

In order to develop an energy-saving copper recycling process from wastes, electrochemical measurements were conducted in ammoniacal alkaline solutions containing Cu(I) ions and an ammonium salt of sulfate, chloride or nitrate. The results of each system were then compared. The polarization measurements suggested that the voltage required for the electrode process is lower in the chloride and nitrate systems than that in the sulfate system. The cathode current efficiency during the copper electrodeposition varied from 39 to 97% and increased with current density in the chloride and sulfate systems. In the nitrate system, the lowest cathode current efficiency of 30% was observed because of nitrate ion reduction. Based on these results, the power consumption required for the electrowinning stage of the copper recycling process was calculated. Among these three systems, the chloride system showed the lowest power consumption of 500 kWh t⁻¹ at the current density of 200 A m⁻², which is about 25% of the conventional copper electrowinning process from a copper sulfate-sulfuric acid solution.     

Enhanced growth inhibition of hepatic multicellular tumor spheroids by lactosylated poly(ethylene glycol)-siRNA conjugate formulated in PEGylated polyplexes

PEGylated polyplexes (lac-PEGylated polyplexes) composed of poly(L-lysine) and lactosylated poly(ethylene glycol)-small interfering RNA conjugate, which inhibits the RecQL1 gene product, were revealed to show an appreciable growth inhibition of multicellular HuH-7 spheroids (human hepatocarcinoma cell lines) for up to 21 days (IC(50)=6 nM); this system used as an in vitro three-dimensional (3D) model mimicking the in vivo biology of tumors. The PEGylated polyplexes thus prepared had a size of approximately 110 nm with clustered lactose moieties on their periphery as targeting ligands for the asialoglycoprotein-receptor-expressing HuH-7 cells. In contrast, OligofectAMINE/siRNA (cationic lipoplex) was observed to have almost no growth-inhibitory effect against HuH-7 spheroids, even though the lipoplex showed a stronger growth-inhibitory effect than the lac-PEGylated polyplexes on conventional monolayer-cultured HuH-7 cells. The FITC-tagged conjugate in the lac-PEGylated polyplexes showed smooth penetration into the HuH-7 spheroids compared with that in the lipoplexes, as observed by confocal fluorescence-scanning microscopy. This indicates that the small size of approximately 100 nm and the reduced nonspecific interaction due to the nonionic and hydrophilic lactosylated PEG layer contributes to the smooth penetration of the PEGylated polyplexes into the spheroid interior, eventually facilitating their uptake into the cells composing the spheroids. Cellular apoptosis indicating programmed cell death was also observed in the HuH-7 spheroids treated with the PEGylated polyplexes, revealing that the observed growth inhibition was indeed induced by the RNAi of the RecQL1 siRNA. These data suggest that the smart PEGylated polyplexes can indeed penetrate into the multiple cell layers of 3D tumor masses in vivo, exerting therapeutic effects through the RNAi.     

Structural and hydration properties of amorphous tricalcium silicate

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca₃SiO₅) sample, where Ca₃SiO₅ is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca₃SiO₅. The hydration of the milled Ca₃SiO₅ with D₂O proceeds as follows: the formation of hydration products such as Ca(OD)₂ rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca₃SiO₅ is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca₃SiO₅ for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage.     

Solid-State Polymerization Behavior of 1,3-Bis(3-quinolyl)-1,4-butadiyne

Summary 1,4-Bis(3-quinolyl)-1,3-butadiyne (DQ) is known to be polymerized in solid state to give the corresponding polydiacetylene. However, the polymer yield of DQ bulk crystals is low. Thus, we prepared several types of DQ crystals by different procedures to find the reason for the low polymer yield. We found three modifications of DQ crystals and they were evaluated by spectroscopic measurements and X-ray diffraction. DQ bulk crystals (Crystal I) and thermally grown DQ crystals on Crystal I (Crystal II) have the same structure classified to Type A, which gives regular polydiacetylene structure in low polymer yields. DQ crystals grown on glass plates by sublimation (Crystal III) belong to the second modification of Type B. DQ nanocrystals prepared by the reprecipitation method (Crystal IV) are Type B, and thermally grown DQ crystals on nanocrystals (Crystal V) are Type C. Crystals of Types B and C could be polymerized in low yields without showing excitonic absorption of polydiacetylene indicating irregular polymerization other than 1,4-addition. For crystals of Type A, we found that the 1,4-addition polymerization proceeded only in near-surface portions of the crystals. It can be plausibly explained that mobile monomers in the near-surface portion are only able to take part in their polymerization, resulting in low polymer conversion.     

Cellulose nanofibrils as templates for the design of poly(l-lactide)-nucleating surfaces

The abilities of surface-grafted cellulose nanofibrils for the nucleation of poly(l-lactide) (PLLA) were investigated. Cellulose nanofibrils with a width of ∼3 nm were obtained from wood cellulose via the oxidation using 2,2,6,6-tetramethylpiperidiniyl-1-oxyl as a catalyst and successive mechanical treatment. The cellulose nanofibril surfaces were selectively modified with amine-terminated poly(ethylene glycol) chains, via simple ionic bonds. The PEG-grafted cellulose nanofibril/PLLA composite films were prepared using a solvent casting method with chloroform. The isothermal and non-isothermal crystallization kinetics of the PLLA in the composites was studied using differential scanning calorimetry and polarized optical microscopy. The PEG chains were densely immobilized on the surface of the cellulose nanofibril templates, which had extraordinarily large specific surface areas. As a result, the surface-PEG layers effectively increased the rate of crystallization of the PLLA in the composites. Because of the increased degree of crystallinity after the isothermal crystallization, the composites showed better heat resistance than neat PLLA.     

Trap Levels in Eu and other Rare‐Earth Ions Codoped CaAl2O4 Phosphors

Photoluminescence spectrum, trap depths, and densities of trapped carriers of CaAl₂O₄:Eu phosphor crystals doped with rare‐earth elements were studied using the thermally stimulated luminescence technique. Trap depths and densities of the specimens vary with rare‐earth elements doped as the auxiliary activators. Tm and Nd are found to be effective for the strong afterglow phosphorescence peaking at λ = 442 nm for several hours after the excitation. CaAl₂O₄:Eu phosphor crystals doped with Nd and Tm include high density of carriers trapped at E = 0.59 and 0.52 eV, respectively.     

Cavitation erosion resistance of stellite alloy weld overlays

Stellite alloys have excellent cavitation erosion resistance and are often used for liquid machinery, but the erosion properties of various stellite alloys have not been evaluated by a standard method. In this study, we evaluate the erosion resistance for various stellite alloy weld overlays of ST6 and ST21 in a vibrating method and in a cavitating liquid jet method. The grain size of the Co matrix affects the cavitation erosion resistance of stellite alloy weld overlays of ST6. The erosion rate of the maximum rate stage of stellite weld overlay alloys of ST6-1, ST6-2 and ST6-3 were found to be about 1/13 to 1/7 times that of SUS304. Moreover, we clarified the cavitation erosion mechanism of SUS304 and ST6 by scanning electron microscopy. Furthermore, by comparing the erosion behavior in a cavitating liquid jet method with that in a vibratory method, it was found that the erosion rate of the cavitating jet method and the vibratory method have a good correlation.     

Gelation of poly(vinyl alcohol) solutions at low temperatures (20 to −78°C) and properties of gels

The flow points of atactic poly(vinyl alcohol) (a-PVA) gels with H₂O/dimethyl sulfoxide (DMSO) = 90/10 (v/v) chilled at 20 to ?78°C for 24 h depended on the chilling temperature and were 0–30°C for gels with the initial polymer concentrations (C_i) of 2–5 g/dL, whereas those for H₂O/DMSO = 50/50 chilled at 0 to ?78°C were independent of the chilling temperature and were 70–75°C. Syneresis occurred after eight cycles of freezing (?24°C) and thawing (20°C) for a-PVA hydrogels at concentrations above C_i = 4 g/dL and two such cycles for syndiotacticity-rich PVA (s-PVA) hydrogels at concentrations above C_i = 1 g/dL. The extent of syneresis per one cycle for s-PVA hydrogels was higher than that for a-PVA hydrogels at the initial cycles. In the a-PVA hydrogels with an initial polymer concentration of ca. 30 g/dL, syneresis was expected not to occur even after 20 cycles. If all the free water in the gels is assumed to have transuded by syneresis after 20 cycles, the residual water is bound water and is estimated to be six water molecules per one vinyl alcohol monomer unit. © 1994 John Wiley & Sons, Inc.