Design and synthesis of zero–zero-birefringence polymers in a quaternary copolymerization system

We designed and synthesized quaternary copolymers of methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (TFEMA), benzyl methacrylate (BzMA), and 3,3,5-trimethylcyclohexyl methacrylate (TMCHMA) and we investigated their birefringence, thermal properties, and other optical properties. When the copolymer composition was MMA/TFEMA/BzMA/TMCHMA = 50:38:8:4, 40:30:7:23, or 30:21:7:42 (wt%), a zero–zero-birefringence polymer that exhibited neither orientational nor photoelastic birefringence was obtained. We demonstrated that such zero–zero-birefringence polymers with a variety of compositions could be successfully prepared in the quaternary system by using the same compensation method as applied in ternary random copolymerization. We also demonstrated that the glass-transition temperature (T_g) and refractive index (n_D) of these copolymers could be controlled with high accuracy while retaining their zero–zero-birefringence property. We can therefore predict the type of birefringence, the T_g, and the n_D of a particular copolymer before polymerization. Zero–zero-birefringence polymers with the most appropriate characteristics can then be synthesized selectively by quaternary copolymerization.     

Fabrication of discrete polystyrene nanoparticle arrays with controllable their structural parameters

We have demonstrated the fabrication of two-dimensionally periodic non-close packed arrays of spherical polystyrene nanoparticles with controllable their structural parameters including diameter and interpartcile distance. The principle of this procedure relies on stepwise integration of spin-coat-assisted colloidal self-assembly of the single layer of close-packed polystyrene nanoparticle on a substrate, and subsequent etching of the particle under atmospheric pressure helium plasma. The plasma process converted the close-packed nanoparticle array into non-close-packed arrangement remaining with unchanged their original spherical shape and periodicity. Owing to the etching process underwent isotropically, the structural parameters could be controlled with nanometric accuracy by the treatment time. The etching rate strongly depended on the working pressure conditions, and the etching rate under 250 Torr was ca. 3 times faster than that of the 760 Torr. The effects of the working pressure indicated the neutral helium radicals and photons diffused from the plasma might be primarily responsible for the etching.     

A novel method to improve low‐voltage ride‐through capability of wind turbine generators

With increasing penetration of wind farms, power grids have responded by developing specific grid codes to maintain their stability. One of the main grid codes is the low‐voltage ride‐through (LVRT) capability, which requires the wind generator to remain connected when the grid voltage sags for a certain time period. A wind farm with squirrel cage induction generators suffers this LVRT problem the most because of their direct connection to the grid and reactive power consumption. In this paper, a new method is proposed to solve this problem by shunt‐connecting a motor‐driven mechanical load to the cage wind generator. For driving mechanical loads, the induction motor is most widely used in industries. This paper studies the terminal voltage holding effect of an induction machine during grid voltage sag due to the magnetic flux holding effect and the saturation characteristic. Taking advantage of this effect, the induction motor that is used for driving mechanical load is then proposed to improve the LVRT capability of wind turbine generators. Furthermore, the change of the rotating speed or slip of the induction machine is found to have a great impact on improving the LVRT. By adding some inertia to the motor‐driven mechanical load, an enhanced voltage holding effect, and therefore LVRT improvement, is expected for the wind farm. Both simulation and experimental results prove the effectiveness of the proposed method. © 2013 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

The dependence of hydrofluoric acid concentration during anodization on photoluminescence of porous silicon

The mixture of hydrofluoric (HF) acid and ethanol is used as an electrolyte during anodization of silicon. We investigated the effect of the ratio of HF acid to ethanol on photoluminescence. It is concluded that porous silicon anodized with the electrolyte containing 35 or 40% HF acid provides strong photoluminescence. The fact implies the existence of a chemical reaction including ethanol during anodization other than electrochemical reaction.     

CO2 Sensing Property of CuO-BaTiO3 Mixed Oxide Film Prepared by Self-Assembled Multibilayer Film as a Precursor

Preparation of CuO-BaTiO₃ mixed oxide thin film by the decomposition of a self-assembled multibilayer film as a molecular template was investigated in this study. Furthermore, CO₂ sensing property of the resultant thin film was investigated as a capacitive type sensor. The self-assembled bilayer film of few 1000 layers thickness can be obtained easily by casting an aqueous suspension consisting of dimethyldihexadecylammoiun bromide (DC1-16), Cu(ClO₄)₂, Ba(TiO(C₂H₄)₂), 2,6-dimetyle-3,5heptadione (DHP), and polyvinyl alcohol. Divalent copper ion (Cu²⁺)) which is associated with 2 DHP molecules was incorporated into the molecular bilayer film and BaTiO₃ precursor exists at the interspace of molecular bilayer film by coordinating with polyvinyl alcohol. Upquenching the organic-inorganic film at 1173 K leads to the uniform film of CuO-BaTiO₃ oxide mixture. Although operating temperature shifted to higher temperature, the resultant film exhibits the capacitance change upon exposure to CO₂. Consequently, it is concluded that the mixed oxide film of CuO-BaTiO₃ prepared by the decomposition of multibilayer film was also an appropriate capacitive type CO₂ sensor.     

The Effects of Conventional Stabilizers and Phenol Compounds Used as Antioxidants on the Stabilization of Nitrocellulose

The thermal behavior of nitrocellulose (NC) containing diphenylamine (DPA), 2‐nitrodiphenylamine (2‐NO₂‐DPA), N‐nitrosodiphenylamine (N‐NO‐DPA), ethyl centralite (EC), akardite II (AKII), 1,1,3‐tri‐(2‐methyl‐4‐hydroxy‐5‐tert‐butyl‐phenyl)‐butane (BP_less), 3‐(3,5‐di‐tert‐butyl‐4‐hydroxy‐phenyl)‐propionic acid octadecyl ester (BP_hin), and 3‐(3‐tert‐butyl‐4‐hydroxy‐5‐methyl‐phenyl)‐propionic acid 2‐(9‐{2‐[3‐(3‐tert‐butyl‐4‐hydroxy‐5‐methyl‐phenyl)‐propionyloxy]‐1,1‐dimethyl‐ethyl}‐2,4,8,10‐tetraoxa‐spiro [5.5] undec‐3‐yl)‐2‐methyl‐propyl ester (BP_semi) was observed during isothermal storage at 393 K using a C80 microcalorimeter. The results indicate that each stabilizer decreased NC's maximum heat release rate and increased the induction period of heat release. We also observed that the maximum heat release rate and the induction period were dependent on the amount of stabilizer. DPA decreased the maximum heat release rate to the greatest extent, with the other stabilizers having similar effects on the decrease of maximum heat release rate. AKII prolonged the induction period of heat release most. The order of prolongation of the induction period was AKII>2‐NO₂‐DPA≈DPA>N‐NO‐DPA≈EC>BP_less≈BP_semi≈BP_hin.     

Partial oxidation of n-hexadecane and polyethylene in supercritical water

In this study, we show the results of partial oxidation experiments of n-hexadecane (n-C₁₆) and polyethylene (PE) in supercritical water (SCW). The experiments were carried out at 673 or 693 K of reaction temperature and 5 or 30 min of reaction time using a 6 cm³ of a batch type reactor. Water density ranged from 0.1 to 0.52 g/cm³ (water pressure: 20–40 MPa). The loaded amount of oxygen was set to 0.3 of the ratio of oxygen atom to carbon atom. Some experiments were made using CO instead of oxygen for the partial oxidation of n-C₁₆ and PE to explore the effect of water gas shift reaction. In the results of partial oxidation of n-C₁₆, the yield of CO and some compounds containing oxygen atoms, such as aldehydes and ketones increased with increasing water density. Moreover, 1-alkene/ n-alkane ratio in the products decreased with increasing water density. The 1-alkene/n-alkane ratio was lower than that of pyrolysis in SCW. Also for the case of PE experiments, in dense SCW (0.42 g/cm³), the 1-alkene/n-alkane ratio in partial oxidation was lower than that in SCW pyrolysis. In the case of CO experiments for n-C₁₆ and PE, 1-alkene/n-alkane ratio was a little lower than that of pyrolysis in SCW. These results show that the yield of n-alkane, which is a hydrogenated compound, was higher through water gas shift reaction in SCW and also through partial oxidation in SCW. Therefore, these results suggest the possibility of hydrogenation of hydrocarbon through partial oxidation followed by the water gas shift reaction.     

Preparation of Polymer-Based Nanocomposites Composed of Sustainable Organo-Modified Needlelike Nanoparticles and Their Particle Dispersion States in the Matrix

Polymer-based nanohybrid materials were created using sustainable sepiolite clay composed from ubiquitous elements. Although sepiolite is generally recognized as a fibrous natural clay mineral, it turned out to be an acicular microcrystal because of the organo-modification of the outermost surface. Surface modification was performed using phosphonic acid derivatives containing hydrocarbon chains or fluorocarbon chains. Formation of a bidentate bond enhanced the desorption temperature and made nanocomposite preparation possible by melt compounding with polymers having a high melting point. As a result of organo-modification, amphiphilic sepiolite was obtained, and nanodispersion in an organic solvent was achieved. This technology was useful for detailed evaluation of sepiolite morphology. The nanocomposite of crystalline polymers/organo-modified sepiolites achieved uniform dispersion of these nanofillers in the matrix polymer. The introduction of 1 wt% nanofillers did not impair the transparency of the matrix polymer. As a result, a lamellae structure of the polymer developed, the crystallinity increased, and the mechanical properties improved. In addition, the crystallization temperature was improved, indicating that organo-modified sepiolites may act as a nucleating agent. It was found that sepiolite nanofiller with a highly aggregated tendency can achieve a well-nanodispersed state, even in phase-separable fluoropolymers, by applying fluorocarbon modification. POLYM. ENG. SCI., 60:541–552, 2020. © 2019 Society of Plastics Engineers     

Chemical reaction kinetics dataset of Cs-I-B-Mo-O-H system for evaluation of fission product chemistry under LWR severe accident conditions

In order to improve LWR source term under severe accident conditions, the first version of a fission product chemistry database named ‘ECUME’ was developed. The ECUME is intended to include several datasets of major chemical reactions and their effective kinetic constants for representative severe accident sequences. It is expected that the ECUME can serve as a fundamental basis from which fission product chemical models can be elaborated for use in the severe accident analysis codes. The implemented chemical reactions in the first version were those for representative gas species in Cs-I-B-Mo-O-H system from 300 to 3000 K. The chemical reaction kinetic constants were evaluated from either literature data or calculated values using ab-initio calculations. The sample chemical reaction calculation using the presently constructed dataset showed meaningful kinetics effects at 1000 K. Comparison of the chemical equilibrium compositions by using the dataset with those by chemical equilibrium calculations has shown rather good consistency for the representative Cs-I-B-Mo-O-H species. From these results, it was concluded that the present dataset should be useful to evaluate fission product chemistry in Cs-I-B-Mo-O-H system under LWR severe accident conditions, where kinetics effects should be considered.     

Effect of oxygen potential on the sintering behavior of MgO-based heterogeneous fuels containing (Pu, Am)O2−x

The effect of oxygen potential on the sintering behavior of MgO-based heterogeneous fuels containing (Pu, Am)O_2−x was experimentally investigated. Sintering tests in various atmospheres, i.e. air, moisturized 4%H₂-Ar, and 4%H₂-Ar atmosphere, were carried out. The sintering behavior was found to be significantly affected by the oxygen potential in the sintering atmosphere. The sintered density decreased with decreasing oxygen potential. The (Pu, Am)O_2−x phase sintered in a reductive atmosphere had hypostoichiometry. The aggregates of the (Pu, Am)O_2−x phase sintered in the reductive atmosphere grew, in comparison with those in the oxidizing one. The sintering mechanism was discussed in terms of the difference in sintering behavior of (Pu, Am)O_2−x and MgO.