Sulfonated poly(aryl ether ketone)s containing naphthalene moieties obtained by direct copolymerization as novel polymers for proton exchange membranes

A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6‐dihydroxynaphthalene with 5,5′‐carbonyl‐bis(2‐fluorobenzenesulfonate) and 4,4′‐difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using ¹H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10^?2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10^?1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004     

Discrete and Continuous Time Modulated Random Walks with Heavy-Tailed Increments

We consider a modulated process S which, conditional on a background process X, has independent increments. Assuming that S drifts to −∞ and that its increments (jumps) are heavy-tailed (in a sense made precise in the paper), we exhibit natural conditions under which the asymptotics of the tail distribution of the overall maximum of S can be computed. We present results in discrete and in continuous time. In particular, in the absence of modulation, the process S in continuous time reduces to a Lévy process with heavy-tailed Lévy measure. A central point of the paper is that we make full use of the so-called “principle of a single big jump” in order to obtain both upper and lower bounds. Thus, the proofs are entirely probabilistic. The paper is motivated by queueing and Lévy stochastic networks.     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

Boron trifluoride-methanol complex—mild and powerful reagent for deprotection of labile acetylated amines

A set of amino-group possessing cyanine dyes is obtained from their N-acetyl derivatives via deprotection with boron trifluoride-methanol complex in good yields.     

Simulation of the Glass Transition of a Thin Aluminum Melt Layer at Ultrafast Cooling under Isobaric Conditions

JETP Letters - It is shown that a sharp increase in viscosity, a change in the decay rate of correlations, and the appearance of nonequilibrium and transverse sound in a thin film of aluminum melt...     

Supersymmetry and cohomology of graph complexes

Letters in Mathematical Physics - I describe a combinatorial construction of the cohomology classes in compactified moduli spaces of curves $$widehat{Z}_{I}in H^{*}left( bar{mathcal...     

Multi-Fluid Hydrodynamics in Charge Density Waves with Collective,Electronic, and Solitonic Densities and Currents

Journal of Experimental and Theoretical Physics - We present a general scheme to approach the space-time evolution of deformations, currents, and the electric field in charge density waves related...     

Localization for a Random Walk in Slowly Decreasing Random Potential

We consider a continuous time random walk X in a random environment on ?⁺ such that its potential can be approximated by the function V:?⁺→? given by $V(x)=\sigma W(x) -\frac {b}{1-\alpha}x^{1-\alpha}$ where σW a Brownian motion with diffusion coefficient σ>0 and parameters b, α are such that b>0 and 0<α<1/2. We show that P-a.s. (where P is the averaged law) $\lim_{t\to\infty} \frac{X_{t}}{(C^{*}(\ln\ln t)^{-1}\ln t)^{\frac{1}{\alpha}}}=1$ with $C^{*}=\frac{2\alpha b}{\sigma^{2}(1-2\alpha)}$ . In fact, we prove that by showing that there is a trap located around $(C^{*}(\ln\ln t)^{-1}\ln t)^{\frac{1}{\alpha}}$ (with corrections of smaller order) where the particle typically stays up to time t. This is in sharp contrast to what happens in the “pure” Sinai’s regime, where the location of this trap is random on the scale ln² t.     

Adaptive efficient estimation for generalized semi-Markov big data models

Annals of the Institute of Statistical Mathematics - In this paper we study generalized semi-Markov high dimension regression models in continuous time, observed at fixed discrete time moments. The...     

Charge density excitations in bilayer graphene in high magnetic field

The charge-density excitations in bilayer graphene at the filling-factor ν 1 at small momenta are considered in the frame of the Hartree-Fock approximation. The presence of small asymmetry of graphene layers is included. The dependence of the magnetoplasmon energy on the bilayer ground state is shown. The energy splitting proportional to $ \sqrt H $ for the symmetric case with half-filled zero-energy levels is found both for bilayer and monolayer graphene.