Particle correlations in e + e − → W + W − events

Preliminary results are reported on the two-particle correlation function R(Q) in hadronic Z decays, fully hadronic WW decays, and mixed hadronic-leptonic WW decays using data collected by the DELPHI detector at LEP at energies between 189 and 206 GeV. Evidence for Bose-Einstein correlations was observed in all three cases. The event mixing technique was used to determine correlations between particles arisingfrom different W bosons in fully hadronic WW decays. An excess of like-sign particle pairs with low four-momentum difference in fully hadronic WW events is observed, consistent with the effect expected from correlations between identical particles from different W bosons.     

Pretransition state and structural transition in a deformed crystal

Physics of the Solid State - It is shown theoretically that a deformed crystal exhibiting structural instability can be treated as a quantum system of pseudospins. The quantum behavior of atoms...     

Synthesis and association of poly(N,N‐dimethylacrylamide) copolymers with perfluorocarbon pendent groups connected through polyethylene‐glycol tethers

The synthesis is reported of copolymers of N,N‐dimethylacrylamide (DMA) and methacrylates containing 2,2′‐dihydroperfluorodecanoyl (RF) groups separated from the methacrylate by long polyethylene glycol (PEG) tether groups (between 1000 and 14,000 Da). At concentrations of between 1 and 8 wt % the copolymers with macromonomer contents of 1 mol % or less give gels in organic solvents such as dioxane, THF, or methanol, as well as in water. Given the low molecular weights, this indicates very efficient association of very low numbers of RF groups. Association and gel formation is enormously enhanced in the presence of longer PEG tethers. This is consistent with smaller poly(N,N,‐dimethylacrylamide) (PDMA) intermolecular excluded volume effects that are mediated by the longer PEG tethers and possibly by the incompatibility of PEG and PDMA that may lead to the formation of PEG microdomains. This increases the local concentrations of the RF groups in the PEO domains that are not diluted by the PDMA chains, as would be the case in the absence of PEG tethers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 360–373, 2004     

Photopolymerization of 1,6‐hexanedioldiacrylate initiated by three‐component systems based on N‐arylphthalimides

Three‐component photoinitiators comprised of an N‐arylphthalimide, a diarylketone, and a tertiary amine were investigated for their initiation efficiency of acrylate polymerization. The use of an electron‐deficient N‐arylphthalimide resulted in a greater acrylate polymerization rate than an electron‐rich N‐arylphthalimide. Triplet energies of each N‐arylphthalimide, determined from their phosphorescence spectra, and the respective rate constants for triplet quenching by the N‐arylphthalimide derivatives (acquired via laser flash photolysis) indicated that an electron–proton transfer from an intermediate radical species to the N‐arylphthalimide (not energy transfer from triplet sensitization) is responsible for generating the initiating radicals under the conditions and species concentrations used for polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4009–4015, 2004     

Novel dinitroxide mediating agent for stable free‐radical polymerization

A novel dinitroxide mediating agent that was suitable for stable free‐radical polymerization was synthesized and used in the block copolymerization of styrene and t‐butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6‐hexamethylene diisocyanate and 4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy were obtained. Various experimental parameters, including the nitroxide‐to‐initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated stable free‐radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two‐step synthesis of triblock copolymers of styrene and t‐butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain‐end decomposition kinetics, and the determined observed rate constant (5.89 × 10^?5 s^?1) for decomposition agreed well with previous studies for other dinitroxide mediating agents. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1547–1556, 2004     

Atom transfer radical polymerization of methyl methacrylate by copper(I)‐pyridine‐2‐carboximidate catalysts

Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [k_obs = (1.19 vs 0.56) × 10^?4 s^?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]_o/[ 1d ]_o/[ethyl 2‐bromoisobutyrate]_o/[MMA]_o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr₂. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004     

Strain hardening of polycarbonate in the glassy state: Influence of temperature and molecular weight

This study is concerned with the temperature and molecular weight dependence of the strain-hardening behavior of polycarbonate. It is shown that the strain-hardening modulus reduces with increasing temperature and decreasing molecular weight. This result is interpreted in terms of temperature accelerated relaxation of the entanglement network. Moreover, it is shown that frozen-in orientations, induced by homogeneous deformations above the glass transition temperature, lead to anisotropic yield behavior that can be fully rationalized (and modelled) in terms of a superimposed stress contribution of the prestrained network. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2041–2049, 2004     

Announcement of Proficiency Testing Schemes

Accreditation and Quality Assurance -     

Rheological and physical properties of aliphatic hyperbranched polyesters

The effects of the size (pseudo‐generation number) and nature of end groups on physical and rheological properties were investigated for a series of hyperbranched polyesters based on an ethoxylated pentaerythritol core and 2,2‐bis‐(hydroxymethyl)propionic acid repeat units. The observed linear dependence of the melt viscosity on the molar mass in the high pseudo‐generation‐number limit indicated that entanglement effects were substantially absent. Moreover, the marked influence of end capping of the end groups on the physical and rheological properties suggested that intermolecular interactions were dominated by contacts between the outer shells of the molecules, in which the end groups were assumed to be concentrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1218–1225, 2004     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004