Microstructure and superconducting properties of rapidly-quenched copper-based alloys containing immiscible lead and bismuth elements

Copper-based superconducting alloys including finely dispersed f c c lead or h c p (Pb- Bi) particles in f c c copper matrix have been obtained by rapid quenching (Cu-M)_100-x Pb_x and (Cu-M)_100-x (Pb_0.6Bi_{0.4 x} (M = aluminium, silicon or tin;x < 10 at%) alloys containing immiscible elements such as lead and bismuth. The particle size and interparticle distance were about 30 to 130 nm and 20 to 200 nm for had particles and about 30 to 60 nm and 30 to 150 nm for (Pb- Bi) particles. The transition temperature,T _c, was in the range of 3.2 to 5.5 K for the Cu-M-Pb alloys and 6.2 to 6.3 K for the Cu-M-Pb-Bi alloys. Critical magnetic field,H _c2, and critical current density,J _c, for the later alloys were 0.47 to 0.93T at 4.2 K and 1.1 × 10⁵ to 2.7 × 10⁵ Am^–2 at zero applied field and 4.21 K. The mechanism of the appearance of such a soft-type superconductivity for the rapidly quenched copper-based alloys was discussed, and inferred to be due to the formation of a percolation path of a superconducting lead or Pb-Bi phase along the grain boundaries, sub-boundaries and/or tangled dislocations where the lead or Pb-Bi phase precipitated preferentially, rather than the proximity effect based on lead or Pb-Bi particles.     

High-field superconductivity in Al-O-Pb and Al-O-Pb-Bi sputtered films

The sputter-quenched Al _x O _y alloys containing lead and bismuth elements, which are insoluble to aluminium; have been found to exhibit a remarkably enhanced upper critical field,H _c2, which is higher by about 6 to 66 times than those of pure lead metal and Pb₆₀Bi₄₀ alloy. The sputtered structure consists of amorphous Al _x O _y and f c c lead or h c p (lead-bismuth) phases. The lead and phases disperse homogeneously in the amorphous matrix and their particle sizes and interparticle distances are about 10 to 20 nm and 5 to 20 nm, respectively, for lead and particles. The superconducting transition temperature,T _c, upper critical magnetic field,H _c2, at 4.3 K, and residual resistivity at 10 K are 7.74 K, 3.3 T and 2.09 × 105cm, respectively, for (Al-O)_92.8 Pb_7.2 and 7.45 K, 8.2 T and 1.70 × 106 cm, respectively, for (Al-O)_86.2(Pb_0.6 Bi_0.4)_13.8. The remarkable enhancement ofH _c2 is interpreted as being mainly due to a remarkable decrease of the coherence length resulting from a large reduction of the effective mean free path of electrons. Additionally, the fluxoid pinning force under applied field has also been markedly enhanced for the duplex structure films than for sputtered lead film, probably because of the change of the dispersed lead phase into a type-II superconductor and an effective fluxoid pinning action at the interface between Al _x O _y and fine lead particles.     

Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.     

The Roles of 3- and 4-Isopropylbiphenyls in the Isopropylation of Biphenyl over a H-Mordenite

The isopropylation of mixtures of 3- and 4-isopropylbiphenyls (3- and 4-IPBPs) was examined over a dealuminated H-mordenite (HM) to elucidate the role of 3- and 4-IPBPs in the isopropylation of biphenyl (BP). 4-IPBP was consumed much faster than 3-IPBP in all cases. 4-IPBP was an exclusive precursor to diisopropylbiphenyls (DIPBs), particularly 4,4-DIPB, and 4,4-DIPB was found in encapsulated products during the reaction. These results show that 4-IPBP can allow establishment of an active complex with propylene and acid site in HM pores, whereas 3-IPBP cannot. It is concluded that the isopropylation of BP over HM occurs through a reactant selectivity mechanism, and through a restricted transition state mechanism, but not through a product selectivity mechanism.     

Graft copolymerization of styrene onto cellulose acetate p-nitrobenzoate by chain transfer reaction

Styrene was grafted onto cellulose acetate p-nitrobenzoate (CANB) by chain transfer reaction of growing polymer radicals to the pendant nitro groups of CANB. A copolymer with a branch for every 17.2 nitro groups was obtained. This result indicates that the pendant aromatic nitro group is more effective in obtaining a graft copolymer by radical mechanism than pendant double bond on the trunk polymer previously reported, where graft copolymers with a branch for several hundred of double bonds are produced.     

Radiation-induced graft copolymerization of mixtures of styrene and n-butyl acrylate onto cellulose and cellulose triacetate

Mixtures of styrene and n-butyl acrylate of various compositions were grafted onto cellulose and cellulose triacetate fibers preirradiated with γ-rays at 0°C in air. Monomer reactivity ratios of the grafted copolymers were found to be different from those of the nongrafted copolymers or those of AIBN-initiated copolymers. The active species initiating the graft copolymerization were trapped radicals for cellulose and peroxides for cellulose triacetate. Kinetic investigations of the graft copolymerization of styrene onto preirradiated cellulose triacetate fibers were also carried out, and it was found that the kinetic scheme for radical polymerization is also applicable to graft copolymerization in a heterogeneous system.     

Enzymatic modification of canola/palm oil mixtures: Effects on the fluidity of the mixture

The bioreactor system to interesterify edible oils and fats at an ultra-micro aqueous phase of 100 ppm and less was investigated. The adsorption of lecithin, together with lipase onto a carrier, was effective for conducting the interesterifying reaction efficiently for oils and fats in micro aqueous phase. To improve the handling properties of palm oil at rather low temperature, palm oil was blended with canola or soybean oil, and then these blended oils were modified by enzymatic selective interesterification in a solvent-free, ultra-micro aqueous bioreactor system with an immobilized lipase that had 1,3-positional specificity. The effects of enzymatic interesterification were confirmed by triglyceride determination, by solid fat content profiles and by cloud point profiles, which were also compared to products of chemical interesterification. The improvement in the fluidity of blended oils with canola oil by the enzymatic reaction was bigger than with soybean oil, and chemical interesterification had no effects on the fluidity of blended oils.     

Thermal Response and Oxidation of Tyranno™-Fiber-Reinforced Si-Ti-C-O Matrix Composites for a Thermal Protection System in High-Enthalpy Dissociated Air

The thermal response and oxidation of Tyranno™ Lox-M fiber-reinforced Si-Ti-C-O matrix composites in high-enthalpy dissociated air was investigated in an arc jet facility (an arc wind tunnel). The maximum surface temperature reached 1310–1670°C. Catalytic recombination of oxygen and nitrogen on the composite surface under dissociated air was not significant. Surface recession was insignificant below 1600°C surface temperatures and above 5 kPa of oxygen partial pressure at the stagnation point. Passive-to-active oxidation transition of the composite agreed with Balat's theory for monolithic silicon carbide. A glass sealant prevented active oxidation of the composite for short-time exposures.     

An application of the 2-nitrobenzenesulfenyl method to proteomic profiling of human colorectal carcinoma: A novel approach for biomarker discovery

In the development of novel biomarkers, the proteomic approach is advantageous because using it the cancer-associated proteins can be directly identified. We previously developed a 2-nitrobenzenesulfenyl (NBS) method to improve quantitative proteome analysis. Here, we applied this method to proteomic profiling of colorectal carcinoma (CRC) to identify novel proteins with altered expression in CRC. Each pair of tumor and normal tissue specimens from 12 CRC patients was analyzed, and approximately 5000 NBS-labeled paired peaks were quantified. Peaks with altered signal intensities (>1.5-fold) and occurring frequently in the samples (>70%) were selected, and 128 proteins were identified by MS/MS analyses as differentially expressed proteins in CRC tissues. Many proteins were newly revealed to be CRC related; 30 were reported in earlier studies of CRC. Six proteins that were up-regulated in CRC (ZYX, RAN, RCN1, AHCY, LGALS1, and VIM) were further characterized and validated by Western blot and immunohistochemistry. All six were found to be CRC-localized, either in cancer cells or in stroma cells near the cancer cells. These results indicate that the proteins identified in this study are novel candidates for CRC markers, and that the NBS method is useful in proteome mining to discover novel biomarkers.     

High-intensity multi-bunch beam generation by a photo-cathode RF gun

A multi-bunch photo-cathode RF gun system has been developed as an electron source for the production of intense quasi-monochromatic X-rays based on inverse Compton scattering. The desired multi-bunch beam is 100 bunches/pulse with a total charge of 500 nC and a bunch spacing of 2.8 ns. We modified the gun cavity of a ‘BNL-type IV’ RF gun to allow a CsTe cathode plug in the end plate. The system uses a four-dipole chicane beam line to allow the injection of laser light normal to the cathode surface. We compensate the gun cavity beam loading caused by the high-intensity multi-bunch electron beam by injecting the laser pulse before RF power has filled the cavity. We have achieved a total intensity of 220 nC in 100 bunches with a bunch-to-bunch energy spread under 1.3% (peak-to-peak). This paper concentrates on experiments to generate the high-intensity multi-bunch beam with compensation of the bunch-to-bunch energy spread due to heavy beam loading.