The strong weak convergence of the quasi-EA

In this paper, we investigate the convergence of a novel simulation scheme to the target diffusion process. This scheme, the Quasi-EA, is closely related to the Exact Algorithm (EA) for diffusion processes, as it is obtained by neglecting the rejection step in EA. We prove the existence of a myopic coupling between the Quasi-EA and the diffusion. Moreover, an upper bound for the coupling probability is given. Consequently we establish the convergence of the Quasi-EA to the diffusion with respect to the total variation distance.     

Functional Polymers by Cationic Techniques

Extensive studies on the mechanism of carbocationic polymerization initiation and particularly termination yielded information useful for the synthesis of a variety of new mono- and difunctional (telechelic) polymers. Unraveling aspects of initiation has opened new avenues toward the synthesis of novel cationic graft copolymers. Understanding details of termination has led among other products to cyclopentadiene-ended polyisobutylene and cyclopentadienylated rubbers. The latters crosslink by Diels-Alder addition and produce thermally reversible networks. Combination of controlled initiation and termination yielded telechelic products e. g., α, ω-diene-polyisobutylene. The use of Cl₂/BCl₃ combinations led to the synthesis of α, ω-dichloropolyisobutylenes.     

Die Analyse von Gemischen von Parazetaldehyd und Azetal

Ohne Zusammenfassung     

A monomeric three-coordinate magnesium bis(amide)

The metallation reaction between di­butyl­magnesium and 2,6-diiso­propyl-N-(tri­methyl­silyl)­aniline gives the unusual monomeric three-coordinate complex (diethyl ether-κO)­bis­[2,6-diiso­propyl-N-(tri­methyl­silyl)­anilido-κN]­magnesium(II), [Mg(C₁₅H₂₆NSi)₂(C₄H₁₀O)] or [Mg{(Me₃Si)(2,6-ⁱPr₂C₆H₃)N}₂(Et₂O)]. This low-coordinate species has a distorted trigonal-planar coordination environment, with an additional short Mg—C_ipso contact of 2.799 (2) Å.     

Experimental and numerical investigation of a capacitively coupled low-radio frequency nitrogen plasma

A capacitively coupled nitrogen discharge driven at a frequency of 40 kHz was analyzed using a particle-in-cell (PIC) code, electrical probe measurements and optical emission spectra (OES). The configuration studied is used to generate plasmas for surface modification of polymer webs and consists of a pair of coplanar electrodes spaced several centimeters from the web plane and housed in a grounded shield. Both the probe measurements and the simulations indicate the presence of a group of high-energy electrons in concentrations of order 0.1% of the bulk electron concentration. Furthermore, bulk electron temperatures from the simulations are less than 1 eV. The energetic electrons and the low temperature of the bulk electrons are both characteristics of discharges operating in the gamma regime, where secondary electron emission from ion bombardment of the cathode sustains the ionization in the discharge. Because ions can respond to the instantaneous potential at the low-driving frequency used, half of the current at the electrode location is ion current. (In contrast, displacement current from the electron motion dominates at significantly higher driving frequencies.) The energetic electrons can provide a valuable source of N⁺ ions through dissociative ionization. The formation of the N⁺ ion was not included in the simulation, but was detected by the OES measurements. The atomic nitrogen ions and neutrals, together with the high-energy electrons, may be responsible for the formation of nitrogen-containing species in the surface region of polymer films treated with nitrogen plasmas using the configuration studied in this work.     

DyNi2Mn—magnetisation and M?ssbauer spectroscopy

The physical properties of DyNi₂Mn doped with ⁵⁷Fe have been investigated by X-ray diffraction, magnetisation (10–300?K) and ⁵⁷Fe M?ssbauer spectroscopy measurements (5–300?K). DyNi₂Mn(⁵⁷Fe) crystallizes in the MgCu₂-type cubic structure (Fd^??3m space group). The ordering temperature is found to be T_C?=?99(2) K, much higher than those of DyNi₂ (～22?K) and DyMn₂ (～35?K). Analyses of isothermal M–H curves and the related Arrott plots confirm that the magnetic phase transition at T_C is second order. The magnetic entropy change around T_C is 4.0?J/kg?K for a magnetic field change of 0?T to 5?T. The spectra above T_C exhibit features consistent with quadrupolar effects while below T_C the spectra exhibit magnetic hyperfine splitting. The Debye temperature for DyNi₂Mn has been determined as θ_D?=?200(20) K from a fit to the variable temperature isomer shift IS(T).     

Accurate mass measurement by matrix‐assisted laser desorption/ionisation time‐of‐flight mass spectrometry. I. Measurement of positive radical ions using porphyrin standard reference materials

A method for the accurate mass measurement of positive radical ions by matrix‐assisted laser desorption/ionisation time‐of‐flight mass spectrometry (MALDI‐TOFMS) is described. Initial use of a conjugated oligomeric calibration material was rejected in favour of a series of meso‐tetraalkyl/tetraalkylaryl‐functionalised porphyrins, from which the two calibrants required for a particular accurate mass measurement were chosen. While all measurements of monoisotopic species were within ±5 ppm, and the method was rigorously validated using chemometrics, mean values of five measurements were used for extra confidence in the generation of potential elemental formulae. Potential difficulties encountered when measuring compounds containing multi‐isotopic elements are discussed, where the monoisotopic peak is no longer the lowest mass peak, and a simple mass‐correction solution can be applied. The method requires no significant expertise to implement, but care and attention is required to obtain valid measurements. The method is operationally simple and will prove useful to the analytical chemistry community. Copyright © 2010 John Wiley & Sons, Ltd.     

The effects of vacuum annealing on the structure and surface chemistry of iron:nickel alloy nanoparticles

In order to increase the longevity of contaminant retention on the particle surface, a method is sought to improve the corrosion resistance of bimetallic iron nickel nanoparticles (INNP) used for the remediation of contaminated water, and thereby extend their industrial lifetime. A multi-disciplinary approach was used to investigate changes induced by vacuum annealing (<5 × 10^?8 mbar) at 500 °C on the bulk and surface chemistry of INNP. The particle size was determined to increase significantly as a result of annealing and the thickness of the surface oxide increased by 50%. BET analysis recorded a decrease in INP surface area from 44.88 to 8.08 m² g^?1, consistent with observations from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) which indicated the diffusion bonding of previously discrete particles at points of contact. X-ray diffraction (XRD) confirmed that recrystallisation of the metallic cores had occurred, converting a significant fraction of initially amorphous iron nickel alloy into crystalline FeNi alloy. X-ray photoelectron spectroscopy (XPS) indicated a reduction in the proportion of surface iron oxide and a change in its stoichiometry related to annealing-induced disproportionation. This was also evidenced by an increased proportion of Fe(0) and Ni(0) to Fe- and Ni-oxides, respectively. The data also indicated the concurrent development of boron oxide at the metal surfaces, which accounts for the overall increase measured in surface oxide thickness. The improved core crystallinity and the presence of passivating impurity phases at the INNP surfaces may act to improve the corrosion resistance and reactive lifespan of the vacuum annealed INNP for environmental applications.     

Rendering polyureas melt processible

Because of the presence of extensive H‐bonding in the hard segments, polyureas are processed by solution techniques (e.g., dry spinning) by the use of relatively costly and environmentally unfriendly solvents. Thus, the objective of this research was to render polyureas melt processible, (i.e., to reduce their flow temperature, T_flow) without compromising their excellent mechanical properties. We hypothesized and herein demonstrate that by using conventional chain extenders (CEs) in combination with small amounts of H‐bond acceptor chain extenders (HACEs), the T_flow of polyureas can be significantly reduced from ～230 to ～180 °C, and thus melt processible products with excellent mechanical properties can be obtained. We document the synthesis of conventional polytetramethylene oxide‐based and novel polyisobutylene (PIB)‐based polyureas with T_flows ～ 180 °C and excellent mechanicals by the addition of few percents of commercially available HACEs. Products were characterized by various techniques, including Instron (tensile strengths, elongations), durometer (Shore A Hardness), dynamic mechanical thermal analysis (T_flow), and thermal gravimetric analysis (TGA) (thermal weight loss). According to TGA, a polyurea with T_flow of ～180 °C did not degrade up to ～234 °C in air. A micromorphology for melt processible polyureas is proposed that emphasizes flexibilized hard segments in the presence of HACEs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011