Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006     

A two-echelon base-stock inventory model with Poisson demand and the sequential processing of orders at the upper echelon

We consider a two-echelon inventory system with a number of non-identical, independent ‘retailers’ at the lower echelon and a single ‘supplier’ at the upper echelon. Each retailer experiences Poisson demand and operates a base stock policy with backorders. The supplier manufactures to order and holds no stock. Orders are produced, in first-come first-served sequence, with a fixed production time. The supplier therefore functions as an M/D/1 queue. We are interested in the performance characteristics (average inventory, average backorder level) at each retailer. By finding the distribution of order lead time and hence the distribution of demand during order lead time, we find the steady state inventory and backorder levels based on the assumption that order lead times are independent of demand during order lead time at a retailer. We also propose two alternative approximation procedures based on assumed forms for the order lead time distribution. Finally we provide a derivation of the steady state inventory and backorder levels which will be exact as long as there is no transportation time on orders between the supplier and retailers. A numerical comparison is made between the exact and approximate measures. We conclude by recommending an approach which is intuitive and computationally straightforward.     

Anion exchangers based on modified shungites

Modification of shungite with polyamines, followed by corss-linking with epoxy compounds, yielded chemically and thermally stable polyfunctional anion exchangers. The effect of the nature of a polyamine and epoxy compounds and of the carbon content of shungites and the process conditions on the ion-exchange properties of the samples obtained was studied.     

N2O emission in the 4.5 μM region: high excitation of the bending mode transitions v1v2v3→v1v2(v3−1) with (2v1+v2)=5

Eight emission spectra of pure N₂O and N₂O + N₂ + He mixtures excited by a radio frequency discharge were recorded by Fourier Transform Spectroscopy at a resolution of 0.005 and 0.004 cm⁻¹ in the 4.5 μm region. Results (wavenumbers, band centers, and spectroscopic constants) concerning nine new vibrational transitions which have not been observed before, and which occur between highly excited levels of the bending mode are reported. The derived spectroscopic parameters allow us to reproduce the experimental wavenumbers with an RMS error lower than 4.5 × 10⁻⁴ cm⁻¹.     

Coherent backscattering of light from saturated atoms

We survey recent progress achieved in understanding the impact of inelastic processes on coherent backscattering of light from cold atoms that are saturated by a powerful laser field.     

On the interpretation of the racemic states of the B 2 phase of banana-shaped mesogens

We show that the racemic states of the B 2 phase of liquid crystals composed of banana-shaped molecules do not satisfy the Curie principle. Thus it is argued that these states cannot exist in bulk samples and the homochiral states constitute the only stable microscopic structures. A reinterpretation of the racemic states with the same macroscopic optical behaviour is proposed in terms of mixtures of the homochiral structures.     

Depth profiling of latex blends of fluorinated and fluorine‐free acrylates with laser‐induced secondary mass spectrometry

We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003     

Fuel Oil Pyrolysis Initiated by Propane-Butane-Oxygen Flame

The parameters of fuel oil pyrolysis initiated by propane-butane-oxygen flame were studied as influenced by the temperature in the pyrolysis zone, time of the fuel oil contact with the initiating flame, and fuel oil feed rate. The experimental data on thermal and flame-initiated fuel oil pyrolysis were compared.     

Colossal magnetoresistance manganites: A new approach

Manganites of the LA_1−x Ca _x MnO₃ family show a variety of new and poorly understood electronic, magnetic and structural effects. Here we outline a new approach recently proposed by us, where we argue that due to strong Jahn-Teller (JT) coupling with phonons the twofold degeneratee _g states at the Mn sites dynamically reorganize themselves into localised, JT polaronsl with exponentially small inter-site hopping, and band-like, nonpolaronic statesb, leading to anew 2-band model for manganites which includes strong Coulomb and Hund’s couplings. We also discuss some results from a dynamical mean-field theory treatment of the model which explains quantitatively a wide variety of experimental results, including insulator-metal transitions and CMR, in terms of the influence of physical conditions on the relative energies and occupation of thel andb states. We argue that this microscopic coexistence of the two types of electronic states, and their relative occupation and spatial correlation is the key to manganite physics. Dedicated to Professor C N R Rao on his 70th birthday