Controlled radical polymerization with polyolefin macroinitiator: a convenient and versatile approach to polyolefin-based block and graft copolymers

This paper introduces the new synthetic methodology of polyolefin-based block and graft copolymers with polar segments [e.g., polystyrene and poly(meth)acrylates]. Various brominated polyolefins were prepared by bromination of polyolefins with N-bromosuccinimide. The resulting brominated polyolefins were able to initiate the controlled radical polymerization of polar monomers, such as methyl methacrylate, ethyl acrylate, t-butyl acrylate, styrene and 2-(dimethylamino)ethyl acrylate, using a CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalyst system, leading to a variety of polyolefin-based copolymers with a different content of the corresponding polar segment. Because of the accessible synthesis of polyolefin macroinitiators, this synthetic methodology is expected to result in the preparation of a wide range of polyolefin-based block and graft copolymers.     

Theoretical estimation of dielectric loss of oxide glasses using nonequilibrium molecular dynamics simulations

To theoretically explore amorphous materials with a sufficiently low dielectric loss, which are essential for next-generation communication devices, the applicability of a nonequilibrium molecular dynamics simulation employing an external alternating electric field was examined using alkaline silicate glass models. In this method, the dielectric loss is directly evaluated as the phase shift of the dipole moment from the applied electric field. This method enabled us to evaluate the dielectric loss in a wide frequency range from 1 GHz to 10 THz. It was observed that the dielectric loss reaches its maximum at a few THz. The simulation method was found to qualitatively reproduce the effects of alkaline content and alkaline type on the dielectric loss. Furthermore, it reasonably reproduced the effect of mixed alkalines on the dielectric loss, which was observed in our experiments on sodium and/or potassium silicate glasses. Alkaline mixing was thus found to reduce the dielectric loss.     

Characterization of alternative plasticizers in poly(vinyl chloride) sheets for blood containers

This study aimed to optimize the ratio of dioctyl 4‐cyclohexene‐1,2‐dicarboxylate (DOTH) and di‐isononyl‐cyclohexane‐1,2‐dicarboxylate (DINCH^®) for use as plasticizers in poly(vinyl chloride) (PVC) sheets. We also evaluated the biological safety of DOTH for its potential to be part of a safe PVC‐based blood container. The suppression of hemolysis in mannitol‐adenine‐phosphate / red cell concentrates (MAP/RCC) with DOTH/(DINCH^®‐PVC) sheets and the elution of plasticizers from the sheets increased with higher DOTH compositions. The properties of the PVC sheet containing DOTH and DINCH^® in the ratio of 25:33 parts against PVC 100 parts as a weight were almost identical to the PVC sheet made of di(2‐ethylhexyl) phthalate. From a subchronic toxicity test, DOTH did not show any adverse effects on all organs, including the testes, epididymis, liver, and kidneys. The no‐observed‐adverse‐effect level was 300 mg/kg body weight/day in a rat. These results suggest that DOTH/DINCH^® (25:33) is a promising candidate for the replacement of di(2‐ethylhexyl) phthalate in blood containers. J. VINYL ADDIT. TECHNOL., 22:520–528, 2016. © 2015 Society of Plastics Engineers     

Mixing mechanism of three‐tip kneading block in twin screw extruders

In recent years, twin screw extruders have been applied to various kinds of polymer processing. It has been important to find their optimum geometrical configurations and operational processing conditions for the best performance of extrusions and products. Many engineers have been evolving numerical and the experimental methods to characterize the mixing performance for twin screw extruders. We have carried out three‐dimensional flow simulations of kneading blocks in intermeshing co‐rotating twin screw extruders by using the finite element method to quantify their ability in distributive and dispersive mixing. We discuss their performance in distributive mixing for three different type of kneading blocks in terms of the residence time distribution and the nearest distance between markers at various periods of time, by using the marker tracking method. Those numerical techniques and applications of mixing indices have enabled us to quantify and evaluate their abilities in distributive mixing of kneading blocks in twin screw extruders.     

Enzymatic Properties of β‐1,3‐Glucanase from Streptomyces sp Mo.

Streptomyces sp Mo endo‐β‐1,3‐glucanase was found to have hydrolyzing activity toward curdlan and released laminarioligosaccharides selectively. The molecular weight was estimated to be 36000 Da and its N‐terminal amino acid sequence was VTPPDISVTN. The optimal pH was 6 and the enzyme was found to be stable from pH 5 to 8. The optimal temperature was 60 °C and the activity was stable below 50 °C. The enzyme hydrolyzed selectively curdlan containing only β‐1,3 linkages. The enzyme had 89% relative activity toward Laminaria digitata laminarin, which contains a small amount of β‐1,6 linkages compared with curdlan, while Eisenia bicyclis laminarin with a higher amount of β‐1,6‐linkages, was not hydrolyzed. Mo enzyme adsorbed completely on curdlan powder. The enzymatic hydrolysis of curdlan powder resulted in the accumulation of laminaribiose (yield 81.7%). Trisaccharide was inevitably released from the hydrolysis of laminarioligosaccharides with 5 to 7 degrees of polymerization (DP). Although the enzyme cleaved off disaccharide (DP 2) from tetrasaccharide (DP 4), the reaction rate was lower than those of DP 5 to 7. The results indicated that the active site of Mo endo‐β‐1,3‐glucanase can efficiently recognize glucosyl residue chain of greater than DP 5 and hydrolyzes the β‐1,3 linkage between the 3rd and 4th glucosyl residue.     

Diamines prevent thermal aggregation and inactivation of lysozyme

Protein aggregation is a major obstacle in both biological applications and biomedical fields involving proteins. In this study, we investigated the essential structure of small additives that function as chemical chaperones. Aggregation-suppressing competent additives were 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane, which suppressed aggregation in the given order; whereas no diols or monoamines prevented the thermal aggregation and the inactivation of lysozyme. The heat-inactivation rate of lysozyme with 1,3-diaminopropane was almost identical to that of lysozyme with spermine and arginine ethylester, which are the most prominent additives reported yet.     

Correlation of optical emission and turbulent length scale in a coaxial jet diffusion flame

This article investigates the correlation between optical emission and turbulent length scale in a coaxial jet diffusion flame. To simulate the H₂O emission from an H₂/O₂ diffusion flame, radiative transfer is calculated on flame data obtained by numerical simulation. H₂O emission characteristics are examined for a one-dimensional opposed-flow diffusion flame. The results indicate that H₂O emission intensity is linearly dependent on flame thickness. The simulation of H₂O emission is then extended to an H₂/O₂ turbulent coaxial jet diffusion flame. Time series data for a turbulent diffusion flame are obtained by Large Eddy Simulation, and radiative transfer calculations are conducted on the LES results to simulate H₂O emission optical images. The length scales of visible structures in the simulated emission images are determined by the procedure proposed by Ivancic and Mayer (2002) [8]. The length scales of emission intensity are compared with the integral length scales of velocity and temperature evaluated from LES flowfield data. The results clearly indicate that the length scale of emission intensity agrees well with the integral length scale of temperature, and is also close to that of the radial velocity component. Finally, the explanation as to why the integral length scale of temperature can be extracted from emission intensity distributions is stated.     

Color and Vanadium Valency in V-Doped ZrO2

The distribution and chemical states of vanadium in V-doped ZrO₂ were studied to clarify the origin of the color of vanadium-zirconium yellow pigment in comparison with vanadium-tin yellow pigment. ESCA data and measurements of lattice constants of V-doped ZrO₂ revealed that vanadium was dissolved mainly as V⁴⁺ substituting for Zr in ZrO₂ lattice, and its solubility limit was 0.5 wt% as V₂O₅. It was found that the yellow color of vanadium-zirconium yellow was produced predominantly by the dissolved vanadium and that the contribution of vanadium oxide on ZrO₂ grains to the yellow color was about 1/30 of that of the dissolved vanadium when compared on the basis of equimolar quantity of vanadium. Most of the undissolved vanadium oxide was in an amorphous or a poorly crystallized state.     

Proposal and development of radial air‐gap coreless generator suitable for small wind turbine used in urban area

Independent distributed power generation using small wind turbines is becoming more widespread as wind power generation increases. Installation of small wind turbines in densely populated urban areas is not only useful from the viewpoint of extracting wind power sources in weak‐wind areas but also for making renewable energy easier to access when power supplies are closer to consumers. It is from this point of view that the authors proposed “urban wind power generation” using a collective system with a number of small vertical wind turbines, and have developed a suitable generator for low‐speed vertical wind turbines such as a Savonius windmill. Based on a standard coreless generator, the proposed generator is designed to make the direction of the magnetic flux radial in order to install the magnets and coils on the outer end of the generator. The change of magnet composition and flux direction maximizes the speed of the flux change and output voltage within a limited space. With the above configuration, the power of the proposed generator is independent of the diameter. In this report, the authors describe and evaluate the fundamental performance of a prototype of the proposed generator. Based on the experiments, a maximum output power of 283 W was obtained. The obtained starting torque is small enough to begin rotation under weak wind conditions of no more than 1 m/s. Therefore, it is clear that the proposed “radial” coreless generator is suitable for self‐starting and producing high power at low wind speed. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 167(1): 26– 34, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20695     

Ti-Containing Silsesquioxane Gels with Tunable Porosity: Preparation and Catalytic Activity for the Epoxidation of Cyclooctene by Aqueous Hydrogen Peroxide

Novel Ti-containing silsesquioxane gel catalysts were prepared by the hydrosilylative condensation of Ti-containing silsesquioxanes together with cubic silsesquioxanes and spherosilicates. The porosity of gels was controlled by changing the composition and the mixing order of the starting materials. Both porous and nonporous gels were found to act as excellent heterogeneous catalysts towards the selective epoxidation of cyclooctene by the use of aqueous hydrogen peroxide as an oxidant.