The Effect of Temperature on the Plasma-Catalytic Destruction of Propane and Propene: A Comparison with Thermal Catalysis

A comparison has been made of plasma-catalysis with thermal-catalysis and plasma alone for the removal of low concentrations of propane and propene from synthetic air using a one-stage, catalyst-in discharge configuration. In all cases, plasma-catalysis produces better hydrocarbon destructions (~40%) than thermal catalysis at low temperatures. At higher temperatures, little difference is observed between plasma-catalytic and thermal-catalytic operation. Plasma operation by itself had a similar effectiveness to plasma-catalysis at low temperatures but was significantly lower (up to 50%) as the temperature was raised. By examining the form of the temperature dependence for the plasma-catalytic destruction processes, it is possible to phenomenologically distinguish two contributions to the destruction; one that is specifically plasma-induced and another (at higher temperatures) in which both plasma and thermal activation have similar mechanisms.     

A systematic study of the microwave and thermal cure kinetics of the DGEBA/DDS and DGEBA/DDM epoxy‐amine resin systems

The microwave and thermal cure processes for the epoxy-amine systems (epoxy resin diglycidyl ether of bisphenol A, DGEBA) with 4,4′-diaminodiphenyl sulphone (DDS) and 4,4′-diaminodiphenyl methane (DDM) have been investigated for 1 : 1 stoichiometries by using fiber-optic FT-NIR spectroscopy. The DGEBA used was in the form of Ciba-Geigy GY260 resin. The DDM system was studied at a single cure temperature of 373 K and a single stoichiometry of 20.94 wt% and the DDS system was studied at a stoichiometry of 24.9 wt% and a range of temperatures between 393 and 443 K. The best values of the kinetic rate parameters for the consumption of amines have been determined by a least squares curve fit to a model for epoxy/amine cure. The activation energies for the polymerization of the DGEBA/DDS system were determined for both cure processes and found to be 66 and 69 kJ mol⁻¹ for the microwave and thermal cure processes, respectively. No evidence was found for any specific effect of the microwave radiation on the rate parameters, and the systems were both found to be characterized by a negative substitution effect. Copyright © 2002 John Wiley & Sons, Ltd.     

Algebraically stable general linear methods and the <Emphasis Type="Italic">G</Emphasis>-matrix

The standard algebraic stability condition for general linear methods (GLMs) is considered in a modified form, and connected to a branch of Control Theory concerned with the discrete algebraic Riccati equation (DARE). The DARE theory shows that, for an algebraically stable method, there is a minimal G-matrix, G ^*, satisfying an equation, rather than an inequality. This result, and another alternative reformulation of algebraic stability, are applied to construct new GLMs with 2 steps and 2 stages, one of which has order p=4 and stage order q=3. The construction process is simplified by method-equivalence, and Butcher’s simplified order conditions for the case p≤q+1.      

On a multistep method approximating a linear sectorial evolution equation

This paper concerns the linear multistep approximation of anabstract dissipative linear sectorial evolution equation ona Banach space X. We study how well the semigroup generatedby a sectorial operator A is approximated by the numerical semigroupgenerated by a q-step, strictly A ()-stable multistep method.An optimal order error bound is obtained.     

Competitive sorption between glyphosate and inorganic phosphate on clay minerals and low organic matter soils

Inorganic phosphate may influence the adsorption of glyphosate to soilsurface sites. It has been postulated that glyphosate sorption is dominatedby the phosphoric acid moiety, therefore, inorganic phosphate could competewith glyphosate for surface sorption sites. We examine sorption of glyphosatein low organic carbon systems where clay minerals dominate the available adsorptionsites using ³²P-labeled phosphate and ¹⁴C-labeled glyphosateto track sorption. We found glyphosate sorption strongly dependent on phosphateadditions. Isotherms were generally of the L type, which is consistent witha limited number of surface sites. Most sorption on whole soils could be accountedfor by sorption observed on model clays of the same mineral type as foundin the soils.     

The use of NMR for determination of new structures in irradiated TFE/PMVE fluoropolymers

The radiation chemistry of two TFE/PMVE copolymers with TFE mole fractions of 0.66 and 0.81 has been studied under vacuum using ⁶⁰Co γ-radiation over absorbed dose ranges up to 4.2 MGy. The radiolysis temperature was 313 K for both TFE/PMVE copolymers. New structure formation in the copolymers was identified by solid-state ¹⁹F NMR and the G-values for new chain ends of 2.1 and 0.5 and for branching sites of 0.9 and 0.2 have been obtained for the TFE/PMVE with TFE mole fractions of 0.66 and 0.81, respectively. The relative yields of –O–CF₃ and –CF₂–CF₃ chain ends were found to be proportional to the copolymer composition, but the yields of the –CF₂–CF₃ chain ends and –CF– branch points were not linearly related to the composition, rather they were correlated with the radical yields measured at 77 K.     

HPLC Coupled with in-line photolysis, hydride generation and flame atomic-absorption spectrometry for the speciation of tin in natural waters

The use of an in-line photolysis coil in a continuous-flow system of high-performance liquid chromatography coupled with hydride generation and flame atomic-absorption spectrometry for the speciation of tin in natural waters is described. Irradiation with ultraviolet light is shown to convert tributyltin into organic tin(IV), from which a volatile hydride can be produced in the conventional way. The effect of various conditions on the analytical performance is discussed. A detection limit of 2 ng for tin was obtained, and the tin species could be completely separated within 6 min. Use of the technique for quantification of tributyltin compounds in local coastal waters is described.     

EUV Lithography optics contamination and lifetime studies

In this paper we discuss surface phenomena leading to contamination of multilayer optics designed for Extreme Ultraviolet (EUV) lithography. Experimental data supported by calculations indicate dramatic influence of resonance structure of EUV mirror on the secondary electron yield. These low energy electrons play an important role in radiation chemistry at the mirror surface. We also discuss the dependence on the partial pressure of admitted gas of equilibrium surface coverage and contamination rate under EUV irradiation.     

Vicinal Dinitridoruthenium‐Substituted Polyoxometalates γ‐[XW10O38{RuN}2]6− (X=Si or Ge)

Reaction of the divacant polyoxometalate K₈[γ‐XW₁₀O₃₆] (X=Si, Ge) with two equivalents of the metal‐nitrido precursor Cs₂[Ru^VINCl₅], at room temperature in water, produces K₂(Me₂NH₂)₂H₂[γ‐XW₁₀O₃₈{RuN}₂], X=Si ( DMA ‐ 1 a ) or Ge ( DMA ‐ 1 b ). The X‐ray crystal structures of both complexes show monomeric complexes with highly unusual vicinal terminal metal‐nitrido units. The Ru?N bond lengths are 1.594(10) and 1.612(11) Å in 1 a and 1 b , respectively. EXAFS studies confirmed the key structural assignments from X‐ray crystallography. The XANES spectrum of DMA‐1 a , diamagnetism, NMR (²⁹Si and ¹⁸³W) chemical shifts, voltammetric behavior, reductive titrations with [PW₁₂O₄₀]^4?, and computational data are all consistent with d² Ru^VI centers in these complexes. The FT‐IR and Raman spectra show the expected vibrational modes of the {γ‐XW₁₀} unit and the Ru?N stretch at 1080 cm^?1, respectively. Interestingly, reduction of DMA‐1 a by 4 equivalents of [PW₁₂O₄₀]^4? produces NH₃ in nearly quantitative yield. Cyclic voltammetry versus pH and calculations provide the energetics for the possible two‐electron reduction and two‐proton addition processes in this reaction.