Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

Left versus right canonical Wiener-Hopf factorization and realization

For an arbitrary rational matrix function, not necessarily analytic at infinity, the existence of a right canonical Wiener-Hopf factorization is characterized in terms of a left canonical Wiener-Hopf factorization. Formulas for the factors in a right factorization are given in terms of the formulas for the factors in a given left factorization. All formulas are based on a special representation of a rational matrix function involving a quintet of matrices.     

Complexation thermodynamics of free and graft oligomers with complementary polymers

The dilute solution complexation equilibrium between linear macromolecules and smaller complementary oligomers is considered when: (1) the oligomers are free in solution; and (2) the oligomers are covalently attached at one end to the polymer. A general statistical mechanical framework is developed and is illustrated using a simple random walk model for polymer conformation. The statistical mechanical partition functions are formulated using a generating function technique, allowing thermodynamic averages in the complexed state to be calculated. Loops, trains, and tails of all possible length are allowed in the conformation of a complexed oligomer. Simulation results for the free oligomer case are compared with those obtained for oligomers covalently attached to the polymeric molecular. The model provides a theoretical explanation for the experimentally observed enhancement of complexation of oligomers grafted to the complementary polymers.     

Ein Beitrag über Oxide vom Typ AMO4 (A = Ti3+, Cr3+; M = Nb5+, Ta5+)

A Contribution on Ternary Oxides of the AMO₄-Type (A = Ti³⁺, Cr³⁺; M = Nb⁵⁺, Ta⁵⁺ ) CrNbO₄, CrTaO₄, TiNbO₄, and TiTaO₄ were prepared by CO₂-laser technique. X-ray single crystal investigations show a random distribution of the metal ions in Rutil type structure, space group D–P4₂/mnm. Calculations of the free energy of reaction between Ti₂O₃ and Nb₂O₅ show higher stability of TiO₂ beside NbO₂. In TiNbO₄ both metals exhibit the oxidation state +4.     

Bacterial Reduction of Chromium

A mixed culture was enriched from surface soil obtained from an eastern United States site highly contaminated with chromate. Growth of the culture was inhibited by a chromium concentration of 12 mg/L. Another mixed culture was enriched from subsurface soil obtained from the Hanford reservation, at the fringe of a chromate plume. The enrichment medium was minimal salts solution augmented with acetate as the carbon source, nitrate as the terminal electron acceptor, and various levels of chromate. This mixed culture exhibited chromate tolerance, but not chromate reduction capability, when growing anaerobically on this medium. However, this culture did exhibit chromate reduction capability when growing anaerobically on TSB. Growth of this culture was not inhibited by a chromium concentration of 12 mg/L. Mixed cultures exhibited decreasing diversity with increasing levels of chromate in the enrichment medium. An in situ bioremediation strategy is suggested for chromate contaminated soil and groundwater.