Entropy,Free Volume,and Cooperative Relaxation

The high frequency end of the relaxation spectrum for polymer molecules involves the rotation of the segmental bonds. This fast relaxation process, however, cannot take place easily in the condensed state crowded by the densely packed conformers, necessitating the slower cooperatively synchronous relaxation. As the temperature is lowered, the domain of cooperativity grows towards the infinite size at the Kauzmann zero entropy temperature, though actually the system deviates from the equilibrium as the glass transition intervenes typically at 50 K above that temperature. The excess enthalpy and entropy drop faster than predicted by the rotational isomeric states which would reach zero only at 0 K. The real ΔC_P is greater than that of the RIS value. The actual volume in excess of the crystalline lattice volume, however, points towards zero at 0 K. Thus, a polymer with higher T_g typically exhibits a lower density and modulus in the glassy state. Since the configurational entropy associated with the free volume is proportional to the logarithm of the latter, the Kauzmann temperature can be scaled by ln M, where M is the algebraic average of the conformer molecular weight. The temperature dependence of the most dominant, i.e., the largest equilibrium domain size will result in the Adam-Gibbs and Vogel equations for the characteristic relaxation time. The cooperative domain distribution leads to the relaxation spectrum that follows a power law. The relationship between the characteristic relaxation time and the rate of physical aging is derived.     

Electrolyte properties of 1-alkyl-2,3,5-trimethylpyrazolium cation-based room-temperature ionic liquids for lithium secondary batteries

The physicochemical and electrochemical properties of three 1-alkyl-2,3,5-trimethylpyrazolium cation-based room-temperature ionic liquids with various alkyl chain lengths were investigated. The temperature dependences of density, viscosity, and ionic conductivity were obtained by precise measurements. Electrolyte properties of these room-temperature ionic liquids were also examined from the viewpoint of their uses in lithium secondary batteries ([LiCoO₂ positive electrode|electrolyte|lithium metal negative electrode]). It was found that the alkyl chain length affects the charge–discharge performances of cells.     

V–I characteristics of solid polymer electrolytic (SPE) dehumidifier

Measurements of the V–I characteristics of a solid polymer electrolytic (SPE) dehumidifier were done using a modified SPE dehumidifier with four electrodes which included two electrodes to carry the main current and the other two electrodes to measure the voltages applied to the electrical double layer, which are the boundary voltages between the electrodes and the SPE membrane. The measured results were analyzed using the Butler-Volmer equation to examine the validity of the measurements. The current flowing in the dehumidifier is produced by the decomposition of water near the anode. Therefore, under a steady-state condition, the current should be proportional to the supply rate of water to the anode. On the other hand, a two-layer model for the SPE dehumidifier presented in our previous article showed that the current flowing in the dehumidifier was roughly proportional to the water content in the vicinity of the anode. These results were introduced for interpretation of the V–I measurements of the SPE dehumidifier. It was concluded that the dehumidifier current was expressed in the form of a Butler-Volmer equation as a function of the electrode boundary voltages which were the voltages across the boundary between the electrodes and the SPE membrane. An experimental formula for the current under a steady-state condition was developed as a function of the water content near the anode and the boundary voltages.     

Preparation of micrometer‐sized,multifunctional capsule particles for cosmetic by microsuspension polymerization utilizing the self‐assembling of phase separated polymer method

Micrometer‐sized polymer particles with encapsulated ultraviolet (UV) absorbent, fluorescent agent, and blue pigment were successfully prepared by microsuspension polymerization utilizing the Self‐assembling of Phase Separated Polymer method. The particles were characterized by optical microscope and particle size distribution analysis, and they were evaluated on their usefulness for cosmetic using UV spectrometry, colorimetry, VISIA? Evolution, and bioassay. The capsule particles had multifunctional properties, which are very attractive in the cosmetic field, especially in whitening, brightening, the improvement of face‐texture, and less noticeable pores in face, as well as the protection from UV. Moreover, bioactivities of the particles under the UV irradiation, which were examined with the films prepared from capsule components, revealed not only makeup effect but also the activation of human epidermal keratinocytes. The results suggest the importance of blue light in the field of cosmetics. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Reusability, Durability and Treatability of Palladium Catalyst on a Semiconductor Plate: Comparison with Commercially Available Solid-Supported Palladium Catalysts

A palladium catalyst supported on a semiconductor plate underwent the Heck reaction effectively to afford a coupling product. The catalytic plate was easily recovered from the reaction mixture with tweezers and reused several times without any special treatment. Comparison of reusability, durability, and treatability of seven kinds of commercially available solid-supported palladium catalysts and the semiconductor-supported catalyst plate was studied.     

Statistical Analysis of Surface Reconstruction Domains on InAs Wetting Layer Preceding Quantum Dot Formation

Surface of an InAs wetting layer on GaAs(001) preceding InAs quantum dot (QD) formation was observed at 300°C with in situ scanning tunneling microscopy (STM). Domains of (1 × 3)/(2 × 3) and (2 × 4) surface reconstructions were located in the STM image. The density of each surface reconstruction domain was comparable to that of subsequently nucleated QD precursors. The distribution of the domains was statistically investigated in terms of spatial point patterns. It was found that the domains were distributed in an ordered pattern rather than a random pattern. It implied the possibility that QD nucleation sites are related to the surface reconstruction domains.     

Temperature-Dependent Site Control of InAs/GaAs (001) Quantum Dots Using a Scanning Tunneling Microscopy Tip During Growth

Site-controlled InAs nano dots were successfully fabricated by a STMBE system (in situ scanning tunneling microscopy during molecular beam epitaxy growth) at substrate temperatures from 50 to 430°C. After 1.5 ML of the InAs wetting layer (WL) growth by ordinal Stranski–Krastanov dot fabrication procedures, we applied voltage at particular sites on the InAs WL, creating the site where In atoms, which were migrating on the WL, favored to congregate. At 240°C, InAs nano dots (width: 20–40 nm, height: 1.5–2.0 nm) were fabricated. At 430°C, InAs nano dots (width: 16–20 nm, height: 0.75–1.5 nm) were also fabricated. However, these dots were remained at least 40 s and collapsed less than 1000 s. Then, we fabricated InAs nano dots (width: 24–150 nm, height: 2.8–28 nm) at 300°C under In and As₄ irradiations. These were not collapsed and considered to high crystalline dots.     

Influence of the conditions of storage and cooking on growth,invasion and survival of Salmonella enteritidis in eggs

Basal studies for the confirmation of sanitary rules in the kitchen were performed, focusing on preventing an outbreak of food poisoning due to eggs contaminated with Salmonella Enteritidis (SE), using hen and quail eggs. SE did not grow at 5 degrees C but grew markedly at 25 degrees C in eggs. The invasion and growth of SE were marked under very humid conditions regardless of whether the eggshell was damaged. The invasion of SE into egg also occurred when eggs were taken in and out of the refrigerator. Moreover, SE was spread immediately to all non-contaminated eggs when SE-contaminated eggs were cracked into a bowl with non-contaminated eggs. In homemade mayonnaise containing 15% vinegar, sterilization took several hours to occur. On a stainless-steel bowl, SE survived for 2 weeks or more. These findings suggest that it is necessary to pay attention to secondary contamination.     

Atmospheric outflow of anthropogenic semivolatile organic compounds from East Asia in spring 2004

To estimate the emissions of anthropogenic semivolatile organic compounds (SOCs) from East Asia and to identify unique SOC molecular markers in Asian air masses, high-volume air samples were collected on the island of Okinawa, Japan between 22 March and 2 May 2004. Contributions from different source regions (China, Japan, the Koreas, Russia, and ocean/local) were estimated by use of source region impact factors (SRIFs). Elevated concentrations of hexachlorobenzene (HCB), hexachlorcyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and particulate-phase polycyclic aromatic hydrocarbons (PAHs) were attributed to air masses from China. A large proportion of the variation in the current-use pesticides, gas-phase PAHs, and polychlorinated biphenyl (PCB) concentrations was explained by meteorology. Chlordanes showed a technical mixture profile and similar concentrations regardless of source region. alpha/gamma HCH and trans/cis chlordane ratios did not vary significantly with different source regions and had regional averages of 2.5 +/- 1.0 and 1.2 +/- 0.3, respectively. Particulate-phase PAH concentrations were significantly correlated (p value < 0.05) with other incomplete combustion byproduct concentrations, including elemental mercury (Hg0), CO, NOx, black carbon, submicrometer aerosols, and SO2. By use of measured PAH, CO, and black carbon concentrations and estimated CO and black carbon emission inventories, the emission of six carcinogenic particulate-phase PAHs was estimated to be 1518-4179 metric tons/year for Asia and 778-1728 metric tons/year for China, respectively. These results confirm that East Asian outflow contains significant emissions of carcinogenic particulate-phase PAHs.     

Reduction of nitric oxide with activated PAN fibres

The reductive removal of nitric oxide from flue gases by reaction with polyacrylonitrile-based active carbon fibres (PAN-ACF) activated with sulphuric acid has been studied at 423–632 K, using a circulating flow reactor. Nitric oxide (0.67 mmol) was completely removed via reduction with 1 g activated carbon under optimum conditions in 210 and 60 min at 423 and 623 K, respectively. N₂ was formed as NO was removed. Some oxygen remained on the carbon surface at 423 K, but was desorbed as CO or CO₂ on subsequent heating to 623 K. The bimolecular reaction of NO reduction over PAN-ACF, and the possible active sites of oxygen surface groups are discussed in the light of a kinetic study and a comparison of the fibre activation at different temperatures.