Diffusion of additives and plasticizers in poly(vinyl chloride): 4. A programmed temperature technique for the determination of the diffusion parameters of three dialkylphthalates

A programmed temperature technique has been developed for the measurement of the self-diffusion coefficients of additives in polymers. This has been applied to the diffusion of three dialkylphthalate plasticizers in poly(vinyl chloride). Values of the self-diffusion coefficients and the calculated activation energies obtained in this way have been compared with values previously obtained from measurements at constant temperature. It has been shown that the programmed temperature technique gives a very rapid method for the estimation of the activation energy of self-diffusion.     

Dispersion of flexible polymer chains in confined geometries

Molecular model approach has been used to predict the dispersion characteristics of flexible polymer chains in confined geometries. The analysis ranges from the early stage dispersion to the steady Taylor dispersion of the simple linear dumbbell model polymer chains. For the early stasje dispersion the ray method was applied; an Aris type moments rnothod was useful for the Taylor dispersion. Two parallel plates were chosen as a confining geometry and the specific initial condition of a point source in the midway of the gap was chosen for simplicity. It was found that the qualitative difference in dispersion properties of deformable polymer chains starts from the early stage compared with those of single Brownian particles. And it turns out that one parameter, which is similar to the relative spacing of the dumbbell to the gap of confining geometries, is useful to see the dispersion characteristics of the dumbbells.     

Catalytic Combustion of Methane over Rare Earth Stannate Pyrochlore

Well-defined Ln₂Sn₂O₇ powders (Ln = La, Sm and Gd) with a phase-pure pyrochlore structure were synthesized by hydrothermal reaction. The catalytic activities of Ln₂Sn₂O₇ powders for methane combustion were measured. Methane oxidation started at 500 °C and increased with oxidation temperature. Catalytic methane combustion is strongly influenced by the presence of oxygen vacancies that form by breaking Sn–O lattice bonds as the temperature increases. Addition of manganese to the rare earth pyrochlores improved methane oxidation activity. Manganese-doped samarium stannate pyrochlore (Sm₂Sn_1.8Mn_0.2O₇) shows highest the catalytic activity. Light-off and complete oxidation temperatures were measured at about 400 and 650 °C, respectively.     

Use of cascade reduction potential for selective precipitation of Au,Cu, and Pb in hydrochloric acid solution

Optimization of reduction potential for electroseparation was studied for the recovery of gold, copper, and lead from acidic solution. A linear sweep voltammetric method enabled us to determine characteristic reduction potentials for each metal and the kinetics of the metal deposition indicated by current-voltage curves. In order to precipitate the metal species sequentially, reduction potentials were examined for the individual and mixed solutions of Au(III), Cu(II), and Pb(II). The three metals were reasonably well isolated from the mixed solutions such as Cu(II)/ Pb(II) and Au(III)/Cu(II)/Pb(II) in the order of the corresponding reduction potentials, in particular, the mass transfer controlled reduction potentials, obtained from linear sweep voltammetry (LSV) measurement.     

Transferring information from one experiment to another

This paper presents a rational method (based on Bayes' Theorem) for transferring information on parameter values from one experiment to another, in situations where the mathematical models for the two experiments share some parameters in common. The uncertainty in the estimates of the parameters, which reflects the experimental error in the initial experiment, is properly transferred as well. The use of the method is demonstrated by applying it to a fairly complicated system, typical in chemical reaction engineering, in which the kinetic parameters in a model for the hydrogenolysis of butane reaction were estimated using data obtained from a bench-scale, integral packed-bed reactor. These parameter estimates were then transferred to a model for a fluidized bed reactor in which the same chemical reaction occurred. Using the fluidized bed data they were updated and two additional parameters in the fluidized bed model were also estimated. This procedure allows a more realistic estimate of the uncertainty in all parameter values in the model for the fluidized bed reactor.     

Soap‐free emulsion copolymerization of perfluoroalkyl acrylates in the presence of a reactive surfactant

Soap‐free emulsion copolymerization of perfluoroalkyl acrylate (FA)/methyl methacrylate (MMA)/n‐butyl acrylate (n‐BA) was carried out in the presence of sodium 2‐acrylamide‐2‐methyl propanesulfonate (AMPSNa) as a reactive surfactant and potassium persulfate (KPS) as an initiator. An analysis of the effects of concentration of AMPSNa, KPS, FA as well as polymerization temperature on the kinetic features (rate of polymerization) and colloidal characteristics (mean particle diameter, particle disperse index, particle numbers, and surface charge density) was followed. NMR, FTIR, AFM, and fluorine‐selective electrode analysis were used to characterize the composition and morphology of the FA copolymers. Both AFM analysis and contact angle measurements strongly implied that the fluorinated segments migrated to the outmost surface and created films with lower surface energy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2438–2444, 2007     

Effects of estrogen-induced hyperlipidemia on the erythrocyte membrane in chicks

The effects of estrogen-induced hyperlipidemia on plasma lipid peroxidation, fatty acid composition and osmotic fragility of erythrocytes in chickens were studied. Young male chickens implanted with estrogen for three wk developed a marked hyperlipidemia. Plasma levels of triglyceride, cholesterol and phospholipid were elevated 68-, four- and 24-fold, respectively, over controls. There was also a two-fold increase in plasma lipid peroxidation measured by the thiobarbituric acid test. Vitamin E supplement (1,000 IU/kg diet) reduced the plasma lipid peroxidation to the control level, but had no effect on the plasma lipid content. Estrogen-induced hyperlipidemia resulted in changes in the fatty acid composition of membrane lipids of erythrocytes. The major changes were an increase in oleic acid from 10.0% to 14.2% and a decrease in linoleic acid from 31.3% to 26.0%. The erytrocytes with an altered membrane fatty acid composition were found to have an increased osmotic fragility. It was apparent that there was a direct correlation between the oleic acid content and the osmotic fragility of erythrocytes.     

Effect of adsorptive gaseous reactant on non-isothermal behavior for gas-solid reactions

The effect of adsorptive species on non-isothermal gas-solid reactions is studied on the basis of Langmuir-Hinshelwood kinetics. The concept of an effectiveness factor provides good information to ascertain the effect of adsorptive species and the transition of the rate controlling regime, in connection with the parameters, generally used in the analysis of non-isothermal behavior. For highly exothermic reactions, the effectiveness factor-Thiele modulus curves with multiple solutions are presented with respect to the modified adsorption equilibrium constant. The variations of the rate-controlling regime by the effect of adsorptive species are also discussed.     

Enhanced utilization bound of Rate-Monotonic scheduling in Controller Area Networks

When priorities to message streams are assigned using Rate Monotonic (RM) for a Controller Area Network (CAN), the utilization bound is known to be about 25% for CAN 2.0A and 29% for CAN 2.0B. In this letter, we present a higher utilization bound than the existing ones with a reasonable constraint. The new utilization bounds are approximately 34% for CAN 2.0A and 41% for CAN 2.0B if no single message stream's utilization exceeds 46% or 27% of the total utilization for CAN 2.0A or CAN 2.0B, respectively.     

Semi-annual cycle of sea-surface temperature in the East/Japan Sea and cooling process

Semi-annual cycles of the sea-surface temperature (SST) in the East/Japan Sea (EJS) and their forcings were examined by analysing National Oceanic and Atmospheric Administration/Advanced Very-High-Resolution Radiometer data, scatterometer wind vectors, and heat flux data. The semi-annual cycle contributed to the total variance of the SST by 8% and amounted to 25% of the amplitudes of the annual SST cycle, particularly in the Tatarskiy Strait and along the continental shelf off Russia. The lowest phase, corresponding to the minimum SST, occurred during early November and 6 months earlier in May or June depending on the position. The forcings of the semi-annual cycle were not semi-annual but substantially annual with a lag of 6 months, which gave rise to SST cooling in spring and autumn. Our analyses illustrated that SST cooling in autumn was caused by direct, local atmospheric wind forcings, whereas the cooling with large amplitudes of the semi-annual cycle in spring was caused by the non-local, remotely forced cold water advection of the Liman Current associated with sea-ice melting in the Tatarskiy Strait. The phase lag of 1–2 months between the complete melting of the sea ice in the Tatarskiy Strait and the surface cooling along the Russian continental shelf was related to the advection of cold water from sea ice in the form of the Liman Cold Current. The semi-annual cycle also resulted from asymmetry of the time series of the SST due to a long cold winter and a short warm summer. To understand how SST curves are distorted and asymmetric, we suggested two mathematical parameters of kurtosis and skewness. In addition, we suggest that the ratio of the semi-annual amplitude to the annual amplitude of SST harmonics can be used as a typical indicator of the asymmetry in year-to-year SST variations.