Effect of diffusion on rates and molecular weights in graft polymerization

A theoretical analysis has been made of the graft polymerization process in terms of the quantitative interrelationship between the initiation rate R_i, the k_p/k_t^1/ ratio of the monomer, the equilibrium solubility M of the monomer in the polymer, the polymer film thickness L, and the diffusivity D of the monomer in the polymer. It is shown how the values of these parameters in any grafting system interact to lead to diffusion-controlled graft polymerization. Whether graft polymerization is diffusion-free or diffusion-controlled depends on the values of K_p, d, k_p/k_p^1/2, and L as gathered in the parameter A = [(K_p/k_t^1/2)R_i, D,/^1/2] L/2. When the values of the various terms are such that A is less than 0.1 (i.e., D is large while R_i, k_p, and L are small), the reaction is diffusion-free. When A is greater than 3 (i.e., D is small while R_i, k_p, and L are large), the reaction is diffusion-controlled. The derived equations showing the relationship between kinetic and diffusional parameters are theoretically applicable to all grafting systems, i.e., for all monomer-polymer combinations under all conditions of reaction temperature, radiation intensity and polymer film thickness. The theoretical analysis has been verified for the rate and degree of polymerization for the radiation-induced graft polymerization of styrene to polyethylene.     

The effect of the “Inert” support on relative photocatalytic activity in the oxidative decomposition of alcohols on irradiated titanium dioxide composites

Reduced quantum efficiencies for the photocatalytic degradation of cyclohexanol, cyclododecanol, 2-hexanol, and benzyl alcohol are observed on TiO₂ particles included within small pore zeolitic supports suspended in acetonitrile. A modest reduction in photocatalytic activity observed with TiO₂ included within large pore zeolites and pillared clays is attributed to reflective and refractive losses of incident light. No appreciable substrate size selectivity could be observed in this series of supported TiO₂ composites. TS-1, a titanium-containing zeolite with Ti in tetrahedral lattice sites, was photoactive, although ETS-10, a titanium-containing zeolite with Ti in octahedral lattice sites, was less so. The low quantum yield residual photoactivity observed with these alcoholic substrates on unmodified zeolites may derive from surface charge transfer complexation, as suggested by diffuse reflectance absorption measurements.     

A simulation-based genetic algorithm approach for reducing emissions from import container pick-up operation at container terminal

Emissions from idle truck engines are a main source of pollution at container terminals. In this study, we focus on reducing such emission from waiting trucks as well as the related crane operations with a new truck arrival control method that gives individual truck limited time slots for entry. We develop a method to optimize the time slot assignment for individual trucks, aiming at minimizing total emissions from trucks and cranes at import yards. The method applies discrete event simulation to estimate total truck waiting times and crane moving distance, and then applies a genetic algorithm to minimize the generated emissions from these trucks and cranes. The experiment result shows that the truck arrivals should be controlled based on the stacking of import containers, and that such control is necessary for reducing truck idling emissions at a congested container terminal.     

Electronic Structure of N-Bridged High-Valent Diiron-Oxo

Density functional theory (DFT) and an advanced ab initio technique based on density matrix renormalization group (DMRG-CASPT2) were employed to investigate a reactive N-bridged high-valent diiron-oxo species involved in H-abstraction reactions. We studied in detail two important doublet states, the ground state with two iron(IV) centers and a mixed valence Fe^V-Fe^IV excited state. We found that the latter state is low-lying. Furthermore, its electronic structure and spin density imply that it has significantly higher H-abstraction reactivity than the ground state. This low-lying excited state might be the reason behind the high oxidation reactivity of this diiron-oxo species towards methane.     

Comparison of efficiency calibration techniques of HPGe detector for radioactivity measurement of soil sample in Marinelli geometry

Journal of Radioanalytical and Nuclear Chemistry - To keep the accredited category for the gamma spectrometry test in our laboratory, the efficiency curves of a HPGe detector for soil sample in...     

Estimation of radon and thoron caused dose at exraction and processing sites of mineral sand mining area in Vietnam (HA TINH province)

Mineral sands are mined in several countries to supply to the titanium and zircon producing industries. Coastal black mineral sands usually contain, besides ilmenite (FeTiO₃) and rutile (TiO₂), radioactive minerals such as zircon (ZrSiO₄) and monazite (RePO₄). Radon and thoron activity concentration originated from natural radioactive contents of the black mineral sand was monitored at the extraction and processing for black minerals in the coastal areas of Ha Tinh Province, one of the around 40 coastal mineral sand deposits in Vietnam. The survey was carried out with the Raduet chambers made by Radosys Ltd—Hungary. The obtained results for 25 investigated points show that the measured values are not high in the residential houses and in case of the sand extraction site as well. At the titanium processing plant the measured values were higher than outside the facility (Radon: 18–55 Bq/m³ with average of 34 Bq/³ and Thoron 33–118 Bq/m³ with average of 58 Bq/m³) but still comparable to the average concentration of the world published by UNSCEAR. The typical outdoor levels of radon and thoron gas are each of the order of 10 Bq/m³. Although the radon concentrations were low in the zircon and titanium processing plants, the thoron concentrations in the houses for separating rutile and zircon were very high. At zircon processing factory, the thoron concentration could reach 2,931 Bq/m³ and the estimated annual effective dose would be 21.4 mSv/a. Intervention has to be taken in order to reduce the thoron level in this factory since the level of thoron and its progenies corresponding to an annual occupational effective dose is beyond the action level of 6 mSv/a.