Gas transport in surface‐modified low‐density polyethylene films with acrylic acid as a grafting agent

The modification of polyethylene by the grafting of poly(acrylic acid) onto the surface of one of the faces of low‐density polyethylene films with UV radiation is reported. The transport of oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and argon across surface‐modified films containing 3.7% poly(acrylic acid) has been investigated at several temperatures. The layer of poly(acrylic acid) grafted onto the surface of one of the faces of the films reduces the permeability coefficient of the gases by a factor of about 1/6. The sharp drop in the gas permeability as a result of the poly(acrylic acid) layer may arise either from the formation of ordered structures of the grafted chains or from the development of highly crosslinked structures. The values of the polymer–gas enthalpic interaction parameter for the modified film are higher than those for the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2828–2840, 2006     

Basic studies on gas solubility in natural rubber–cellulose composites

This work reports sorption processes of oxygen, carbon dioxide, methane, ethylene, and propylene in films of both vulcanized natural rubber and vulcanized rubber–regenerated cellulose composites. The curves representing the pressure dependence of the concentration of carbon dioxide in the composites clearly exhibit a slight concavity with respect to the abscissa axis as a result of adsorption processes taking place in Langmuir sites located in the glassy cellulose component. Adsorption processes are also detected in the sorption curves of ethylene at low pressures. The concavity with respect to the ordinate axis of the curve concentration of propylene versus pressure at high pressure is pretty well described by the Flory‐Huggins formalism. The solubilities of the other gases mainly obey Henry's behavior, adsorption processes in the glassy component being in most cases negligible. Values of the interaction χ parameter for gas–natural rubber and gas–natural rubber composites are obtained from the comparison of the experimental solubility coefficients with those predicted by the Flory‐Huggins theory. The theory suggests that Henry's constant is a linear function of the boiling temperature of the gases. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2131–2140, 2005     

Chain Dynamics of Polymers with Highly Flexible Side Groups

Summary: The relaxation behaviour of poly(5-acryloxy-5-methyl-2,3-dioxacyclohexne), poly(2,3-dichlorobenzyl methacrylate) and poly(3-chlorobenzyl methacrylate) was thoroughly studied by broadband dielectric spectroscopy with the aim of investigating how the chemical structure affects the response of polymers to electric perturbation fields over a wide temperature window. Retardation spectra calculated from dielectric isotherms utilizing linear programming regularization parameter techniques were used to deconvolute strongly overlapped absorptions. Special attention is paid to both the splitting region and the fitting of the Williams ansatz to the experimental results. Attempts are made to explain the molecular origin of the relaxations observed in the retardation spectra of the polymers.     

Highly Dispersible and Stable Anionic Boron Cluster–Graphene Oxide Nanohybrids

An efficient process to produce boron cluster–graphene oxide nanohybrids that are highly dispersible in water and organic solvents is established for the first time. Dispersions of these nanohybrid materials in water were extraordinarily stable after one month. Characterization of hybrids after grafting of appropriate cobaltabisdicarbollide and closo‐dodecaborate derivatives onto the surface of graphene oxide (GO) was done by FT‐IR, XPS, and UV/Vis. Thermogravimetric analysis (TGA) clearly shows a higher thermal stability for the modified‐GO nanohybrids compared to the parent GO. Of particular note, elemental mapping by energy‐filtered transmission electron microscopy (EFTEM) reveals that a uniform decoration of the graphene oxide surface with the boron clusters is achieved under the reported conditions. Therefore, the resulting nanohybrid systems show exceptional physico‐chemical and thermal properties, paving the way for an enhanced processability and further expanding the range of application for graphene‐based materials.     

Mechanistic Studies on the Rearrangement of 1‐Alkenyl‐2‐alkynylcyclopropanes: From Allylic Gold(I) Cations to Stable Carbocations

An allylic gold(I) cation, proposed as key intermediate in the gold‐promoted rearrangement of 1,5‐enynes bearing a fixed conformation, has been detected and characterized by NMR spectroscopy. Moreover, its participation in the overall transformation was confirmed. Computational studies indicate that the gold‐catalyzed transformation occurs through an uncommon rearrangement. Additionally, this study led us to isolate and characterize a stable homoantiaromatic carbocation.     

A new method of construction of resonances that applies to critical models

We introduce a new method of multi-scale analysis that can be used to study the spectral properties of operators in non-relativistic quantum electrodynamics with critical coupling functions. We utilize our method to prove the existence of resonances of nonrelativistic atoms which are minimally coupled to the quantized (ultraviolet-regularized) radiation field and construct them together with the corresponding resonance eigenvector in case of critical coupling, i.e., without any infrared regularization. This result was first proved in [19] with the ingredient of a suitable Pauli-Fierz transformation. The purpose of the present paper, however, is to demonstrate the power of our new method for the estimation of resolvents that is based on the isospectral Feshbach-Schur map [8]. The reconstruction formula for the resolvent of an operator in terms of the resolvent of its image under the Feshbach-Schur map allows us to use a fixed projection and to compare two resolvents without actually decimating the degrees of freedom. This is in contrast to the renormalization group based on Feshbach-Schur map, developed in [8], [5], that uses a decreasing sequence of ever-smaller projections and successively decimates the degrees of freedom. It is this new method that allows us to treat the critical and physically relevant Standard model of non-relativistic quantum electrodynamics [7] which is intractable by standard methods.     

Optical and magneto-optical properties of Co–SiO<Subscript>x</Subscript> thin films

The optical and magneto-optical properties of hybrid Co–SiO_x systems are studied as a function of Co concentration. The structures were prepared by alternate depositions of SiO_x thin films and layers of 10-nm-diameter Co nanoparticles produced by an Ion Cluster Source. Both optical and magneto-optical constants of the system gradually increase with the amount of Co, though maintaining low optical absorption values in the visible range. The experimental results are well reproduced assuming that the nanoparticles have a cobalt core (7–8 nm in diameter) surrounded by a cobalt oxide shell (1–2 nm thick). The magneto-optical activity versus optical absorption figure of merit of this system is compared with other magneto-optical dielectric systems.