Influence of shearing history on the rheological properties and processability of branched polymers. III. An amorphous long-chain branched polymer

Viscoelastic properties of branched polymers vary with their shearing history; notwithstanding, their primary molecular parameters do not change. According to a recent study, such viscoelastic variation was believed to be observed only with crystalline long-chain branched polymers such as low-density polyethylene or polyacetal. That is, the origin of the viscoelastic variation was attributed to the presence of specific entanglements at the branching points, which was formed during the crystallization process. However, the viscoelastic variation of the long-chain branched polymers is the phenomenon at temperatures well above their melting points, namely, it is considered that whether the long-chain branched polymers are crystalline or not is not essential for the occurrence of the viscoelastic variation. Thus, the influence of the shearing history on the rheological properties of an amorphous long-chain branched polymer was investigated in this paper, and it was found that, irrespective of their crystallinity, the viscoelastic properties of long-chain branched polymers vary according to their shearing history.     

Grafting of branched polymers onto nano-sized silica surface: Postgrafting of polymers with pendant isocyanate groups of polymer chain grafted onto nano-sized silica surface

To control the surface wettability of nano-sized silica surface, the postgrafting of hydrophilic and hydrophobic polymers to grafted polymer chains on the surface was investigated. Polymers having blocked isocyanate groups were successfully grafted onto nano-sized silica surface by the graft copolymerization of methyl methacrylate (MMA) with 2-(O-[1′-methylpropylideneamino]caboxyamino)ethyl methacrylate (MOIB) initiated by azo groups previously introduced onto the surface. The blocked isocyanate groups of poly(MMA-co-MOIB)-grafted silica were stable in a desiccator, but isocyanate groups were readily regenerated by heating at 150 °C. The hydrophilic polymers, such as poly(ethylene glycol) (PEG) and poly(ethyleneimine) (PEI), were postgrafted onto the poly(MMA-co-MOIB)-grafted silica by the reaction of functional groups of PEG and PEI with pendant isocyanate groups of poly(MMA-co-MOI)-grafted silica to give branched polymer-grafted silica. The percentage of grafting increased with increasing molecular weight of PEG, but the number of postgrafted chain decreased, because of steric hindrance. The hydrophobic polymers, such as poly(dimethylsiloxane) were also postgrafted onto poly(MMA-co-MOI)-grafted silica. It was found that the grafting of hydrophobic polymer and the postgrafting of hydrophilic polymer branches readily controls the wettability of silica surface to water.     

Multijunction thermal converter with improved frequency characteristics between 10 Hz and 1 MHz

A new multijunction thermal converter (MJTC) for precision AC–DC transfer standard has been developed. A U‐shaped heater pattern was sputter‐deposited onto an AlN plate in order to reduce thermoelectric effect, which causes the frequency‐independent AC–DC transfer difference. Both low‐frequency and high‐frequency characteristics improved as a result of the new configuration, and the AC–DC transfer difference of the MJTC was evaluated to be <1 µV/V between 10 Hz and 100 kHz and <10 µV/V up to 1 MHz. © 2012 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

粉末冶金结构零件材料的泊松比

研究了粉末冶金机械零件使用的烧结材料的杨氏模量、切变模量及泊松比与孔隙度的关系.制备了三种钢粉,在不同条件下进行了压制、烧结与热处理.孔隙度对杨氏模量、切变模量及泊松比的影响最大.特别是泊松比还受孔隙形状的影响,而孔隙形状随粉末类型、烧结温度与烧结气氛及热处理条件而变化.对于大部分实际应用的粉末组成来说,烧结气氛对经烧结和热处理后材料的泊松比影响不大.对于部分预合金化粉末(Fe4%Ni1.5%Cu0.5%Mo)+0.8%石墨,只有在孔隙度低于20%时,烧结温度对泊松比与孔隙度的关系才有影响.在这种情况下.提出了烧结与热处理试样泊松比与孔隙度关系的较简单近似方程:在烧结温度1 423K下,v=0.300-0.266P+0.579P2;在烧结温度1 523K下,v=0.304-0.264P+0.548P2.     

Twist form of teleocidin derivatives is active in in vivo tumor promotion by (-)-benzolactam-V8-310

Two patients, both 70 years old, operated for differentiated thyroid cancer with foci of undifferentiated tumor (one papillary containing pseudosarcomatoid foci, the other with insular pattern containing undifferentiated foci) suddenly died. In both cases, for both of them metastatic involvement of the myocardium and endocardium. These original findings suggest that elderly patients suffering rom well differentiated thyroid cancer, containing undifferentiated foci, therefore suspected to have metastasized, would benefit from non-invasive cardiac work-up (sonogram) in order to plan their multidisciplinary treatment.     

Changes in serum pepsinogen, gastrin, and immunoglobulin G antibody titers in helicobacter pylori-positive gastric ulcer after eradication of infection

The feasibility of using the spiral nerve cuff electrode design for recordings of respiratory output from the hypoglossal (HG) and phrenic nerves is demonstrated in anesthetized, paralyzed, and artificially ventilated cats. Raw neural discharges of the HG nerve were analyzed in terms of signal-to-noise ratios and frequency spectra. The rectified and integrated moving average activity of the HG nerve had a peak value of 1.74 +/- 0.21 microV and a baseline value of 0.72 +/- 0.11 microV at elevated respiratory drive induced by increases in CO2 or oxygen deprivation when recorded with 10-mm-long cuffs. The frequency content of the HG electroneurogram extended from several hundred hertz to 6 kHz. Spiral nerve cuff recordings without desheathing of the nerve provided large enough signal-to-noise ratios that allowed them to be used as a measure of respiratory output and had much wider frequency bandwidths than the hook electrode preparations. A major advantage of the cuff electrode over the hook electrode was its mechanical stability, which significantly improved the reproducibility of the recordings both in terms of signal amplitudes and frequency contents.     

Grafting of vinyl polymers onto VGCF surface and the electric properties of the polymer-grafted VGCF

The graft polymerization of vinyl monomers onto vapor grown carbon fibers (VGCF) initiated by the system consisting of molybdenum hexacarbonyl (Mo(CO)₆) and trichloroacetyl (COCCl₃) groups introduced onto the surface was investigated. The introduction of trichloroacetyl groups onto VGCF surface was successfully achieved by the reaction of carboxyl groups on VGCF surface with trichloroacetyl isocyanate. It was found that the radical graft polymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and glycidyl methacrylate (GMA) is successfully initiated by the system consisting of Mo(CO)₆ and COCCl₃ groups introduced onto the surfaces. In the polymerization, the corresponding vinyl polymers were effectively grafted onto the VGCF surface, based on the propagation of polymer from surface radicals formed by the interaction of trichloroacetyl groups and Mo(CO)₆: the percentage of PMMA grafting reached 40%. Polymer-grafted VGCF gave a stable colloidal dispersion in good solvents for grafted polymer. The electric resistance of composite prepared from the polymer-grafted VGCF suddenly increased in organic solvent vapor over 10³ times, and returned to initial resistance when it was transferred into dry air. These results indicate that such composites can be used as novel gas sensors.     

Poly(fluoroalkylsilane-b-dialkylsilane)-based chemosensory material for fluoride with high sensitivity,selectivity and solubility

Poly((i-butyl-n-decylsilane)_x-b-(methyl-3,3,3-trifluoropropylsilane)_1?x) (PSi3) was prepared using a simultaneous block copolymerization with a conventional Wurtz-type condensation reaction. The block-like polysilane copolymer showed high selectivity and sensitivity toward fluoride ion (F^?) even in the coexistence of the halide ions (Cl^?, Br^?, and I^?), and high solubility to common organic solvents with the dielectric constants (?′) between 1.88 (n-hexane) and 9.04 (benzotrifluoride). Such unique characteristics were derived from poly(methyl-3,3,3-trifluoropropylsilane) (PSi1) and poly(i-butyl-n-decylsilane) (PSi2) unit in the copolymer, respectively. In addition, sensitivity to F^? and solubility in organic solvents were successfully optimized by adjusting the composition ratio between PSi1 and PSi2 unit.     

In vitro and in vivo investigations of upconversion and NIR emitting Gd2O3:Er3+,Yb3+ nanostructures for biomedical applications

The use of an “over 1000-nm near-infrared (NIR) in vivo fluorescence bioimaging” system based on lanthanide containing inorganic nanostructures emitting in the visible and NIR range under 980-nm excitation is proposed. It may overcome problems of currently used biomarkers including color fading, phototoxicity and scattering. Gd₂O₃:Er³⁺,Yb³⁺ nanoparticles and nanorods showing upconversion and NIR emission are synthesized and their cytotoxic behavior is investigated by incubation with B-cell hybridomas and macrophages. Surface modification with PEG-b-PAAc provides the necessary chemical durability reducing the release of toxic Gd³⁺ ions. NIR fluorescence microscopy is used to investigate the suitability of the nanostructures as NIR–NIR biomarkers. The in vitro uptake of bare and modified nanostructures by macrophages is investigated by confocal laser scanning microscopy. In vivo investigations revealed nanostructures in liver, lung, kidneys and spleen a few hours after injection into mice, while most of the nanostructures have been removed from the body after 24?h.