Melt viscosity and flow birefringence of polycarbonate

Melt viscosity and flow birefringence of bisphenol A-type polycarbonate were measured and analyzed by the application of rubber-like photoelastic theory. The melt viscosity in the Newtonian flow region increased with the molecular weight to the power of 3.4. In polycarbonate, the shear stress of the Newtonian flow region was to 10⁶ dyn/cm², whereas in PMMA it was at most 3 = 10⁵ dyn/cm². The flow birefringence δn has a linear relation with shear stress S, that is δn = 5.7 × 10^?10 S. The principal polarization difference of flow unit α₁ – α₂ was 1.62 × 10^?23 cm³, which was obtained by the application of the rubber-like elastic theory. In PMMA, it was 3.9 = 10^?25 cm³; about 1/40 of that was polycarbonate. The anisotropy of polarizability of the flow unit of polycarbonate was also about 40 times larger than that of PMMA. So the anisotropy reflected the large flow birefringence of the polycarbonate.     

Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

Photoelectric properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with polyhedral oligomeric silsesquioxane

4,4′‐(Hexafluoro‐isopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) was synthesized and reacted with polyhedral oligomeric silsesquioxane (POSS) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The solid‐state and optical properties of the resulting copolymers were systematically investigated, and their electronic states were analyzed. As the POSS concentration increased, the transparency across the entire wavelength range increased. In the ABA‐type triblock copolymers, a new transition was observed between the highest occupied molecular orbital in POSS and the lowest unoccupied molecular orbital in 6FDA‐TeMPD because of their high molecular size dispersion. Since the refractive index of 6FDA‐TeMPD decreased linearly as the POSS concentration increased, the refractive index of the ABA‐type triblock copolymers of 6FDA‐TeMPD with POSS could be easily controlled. POLYM. ENG. SCI., 57:1207–1213, 2017. © 2017 Society of Plastics Engineers     

Characterization and CO2 sorption properties of poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane‐ co‐3‐methacryloxypropyltris(trimethylsiloxy)silane]

Poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane (MAPOSS)‐co‐3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA)] was synthesized through free radical polymerization. The physical and carbon dioxide (CO₂) sorption properties of the copolymer membranes were investigated in terms of the MAPOSS content. As the MAPOSS content increases, the membrane density increased, suggesting a decrease in the fractional free volume. In addition, the thermal stability was improved with increasing the MAPOSS content. These are because of the polyhedraloligomericilsesquioxane (POSS) units that restrict the high mobility of poly(SiMA) segments. The glass transition temperature, T_g of the copolymers was single T_g based on the differential scanning calorimetry, suggesting that the copolymers were random and not phase separation. Based on the CO₂ sorption measurement, the POSS units play a role in reducing Henry's dissolution by suppressing the mobility of the poly(SiMA) component, while POSS units increase the nonequilibrium excess free volume, which contributes to the Langmuir dissolution. Based on these results, the introduction of MAPOSS unit is one of the effective ways to improved the thermal stability and CO₂ sorption property due to the enhancement of the polymer rigidity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enzymatic Analysis of Positional Distribution of Fatty Acids in Solid Fat by 1,3-Selective Transesterification with Candida antarctica Lipase B

A protocol for the analysis of the positional distribution of fatty acids (FA) in solid triacylglycerols (TAG) was developed using sn-1(3) selective alcoholysis catalyzed by immobilized Candida antarctica lipase B (CALB). One part by weight of solid fat and ten parts by weight of ethanol (99.5 %) were warmed to liquefy the fat. After adding 0.44 parts by weight of CALB, the mixture was shaken at 50 °C for 10 min then at 30 °C for 2.8 h. The recovery of 2-MAG after the 3-h transesterification reaction was ca. 85 % of the maximum theoretical yield (33 mol%), with the loss of 15 % attributable to the acyl migration from sn-2 to sn-1(3). The recovery was similar to that of the solvent-free alcoholysis of structured lipids, 1,3-dipalmitoyl, 2-oleoyl glycerol and 1,3-dioleoyl, 2-palmitoyl glycerol, conducted at 30 °C for 3 h. In contrast, the acyl migration from sn-1(3) to sn-2 was hardly observed. Because the detected acyl migration was only in the direction of sn-2 to sn-1(3), and not vice versa, it is proposed to determine the FA composition of the sn-2 position of TAG by the gas chromatographic analysis of 2-MAG fraction recovered from the enzymatic reaction mixture, and the FA composition of sn-1(3) position by a mass balance using the FA composition of TAG and of the sn-2 position as inputs. The procedure was successfully applied to palm oil and shea butter, and docosahexaenoic acid (DHA)-rich single cell oil from Aurantiochytrium sp. KH105 for the first time.     

Thermoelectric properties of β-FeSi2 with B4C and BN dispersion by mechanical alloying

The B₄C- and BN-dispersed -FeSi₂ thermoelectric materials were synthesized by mechanical alloying and subsequent hot pressing. The effects of the B₄C and BN dispersion on the thermoelectric properties, such as Seebeck coefficient, electrical resistivity and thermal conductivity etc., of the -FeSi₂ were investigated. For the sample with B₄C and BN addition, a larger amount of the residual phase was detected in the X-ray diffraction patterns than the sample without addition. In the case of the BN addition, the Seebeck coefficient was enhanced by BN addition above 700 K, and the electrical resistivity also increased with increasing amount of BN. This is considered to result from doping of a small amount of B into the phase due to partial decomposition of the BN phase. The fine dispersion of BN particles in the phase matrix was quite effective for reducing the thermal conductivity as compared to the B₄C addition over the entire temperature range. The figure of merit, Z, of the -FeSi₂ was significantly enhanced by BN addition.     

A method for calculating the electromagnetic noise of a motor-driven thin blade fan

An urgent need exists to develop a method of predicting the noise level of a blade fan attached to a motor shaft. To satisfy this requirement, we developed a method for calculating the sound generated when a rotating blade is excited by the torque pulsation of a motor. The sound pressure values calculated by the new method for a rotating blade were found to correspond well with experimentally measured ones.     

Role of Stripes in Spin and Charge Dynamics of Underdoped La2−x Sr x CuO4

We investigate the electronic states of underdoped La _2–x Sr _x CuO ₄ (LSCO) by using a microscopic model, i.e., t-t-t-J model, containing charge stripes. The numerically exact diagonalization calculation is employed on small clusters. The physical properties observed in the angle-resolved photoemission and optical conductivity experiments are consistently explained in the model with vertical stripes, but not diagonal ones. These results demonstrate a crucial role of the vertical stripes in underdoped LSCO.     

Effect of anti-IL-4 and anti-IL-5 antibodies on allergic airway hyperresponsiveness in mice

In order to study the role of IL-4 and IL-5 in allergen-induced airway hyperresponsiveness in mice, the effect of the combined administration of anti-IL-4 and anti-IL-5 monoclonal antibodies (mAbs) on IgE response, airway inflammation and airway hyperresponsiveness was studied in sensitized Balb/c mice. Three inhalations of antigen caused an increase in the number of eosinophils in bronchoalveolar lavage fluid and in airway responsiveness to acetylcholine, with a significant elevation in the serum antigen-specific IgE level. Anti-IL-4 mAb inhibited IgE production but did not affect airway eosinophilia or hyperresponsiveness. Moreover, anti-IL-5 mAb inhibited airway eosinophilia but did not affect IgE production or airway hyperresponsiveness. The combined administration of anti-IL4 and anti-IL-5 mAbs, however, inhibited IgE antibody production, airway eosinophilia and hyperresponsiveness. These results suggest that inhibitory action of IL-4 and IL-5 in combination can effectively suppress the onset of antigen-induced airway hyperresponsiveness in mice.