Atomistic packing models for experimentally investigated swelling states induced by CO2 in glassy polysulfone and poly(ether sulfone)

Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO₂ gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006     

A self-organizing network in the weak-coupling limit

We prove the existence of spatially localized ground states of the diffusive Haken model. This model describes a self-organizing network whose elements are arranged on a d-dimensional lattice with short-range diffusive coupling. The network evolves according to a competitive gradient dynamics in which the effects of diffusion are counteracted by a localizing potential that incorporates an additional global coupling term. In the absence of diffusive coupling, the ground states of the system are strictly localized, i.e. only one lattice site is excited. For sufficiently small non-zero diffusive coupling , it is shown analytically that localized ground states persist in the network with the excitations exponentially decaying in space. Numerical results establish that localization occurs for arbitrary values of in one dimension but vanishes beyond a critical coupling _c(d), when d> 1. The one-dimensional localized states are interpreted in terms of instanton solutions of a continuum version of the model.     

Steady state analysis of an M/G/1 queue with two phase service and Bernoulli vacation schedule under multiple vacation policy

This paper examines the steady state behaviour of a batch arrival queue with two phases of heterogeneous service along and Bernoulli schedule vacation under multiple vacation policy, where after two successive phases service or first vacation the server may go for further vacations until it finds a new batch of customer in the system. We carry out an extensive stationary analysis of the system, including existence of stationary regime, queue size distribution of idle period process, embedded Markov chain steady state distribution of stationary queue size, busy period distribution along with some system characteristics.     

Theory of Non-Equilibrium Stationary States as a Theory of Resonances

We study a small quantum system (e.g., a simplified model for an atom or molecule) interacting with two bosonic or fermionic reservoirs (say, photon or phonon fields). We show that the combined system has a family of stationary states parametrized by two numbers, T ₁ and T ₂ (‘reservoir temperatures’). If T ₁ ≠ T ₂, then these states are non-equilibrium stationary states (NESS). In the latter case we show that they have nonvanishing heat fluxes and positive entropy production and are dynamically asymptotically stable. The latter means that the evolution with an initial condition, normal with respect to any state where the reservoirs are in equilibria at temperatures T ₁ and T ₂, converges to the corresponding NESS. Our results are valid for the temperatures satisfying the bound min (T ₁,T ₂) > g ^{2 + α}, where g is the coupling constant and 0 < α < 1 is a power related to the infra-red behaviour of the coupling functions. Submitted: March 20, 2006. Revised: March 19, 2007. Accepted: May 11, 2007. Marco Merkli: Partly supported by an NSERC PDF, the Institute of Theoretical Physics of ETH Zürich, Switzerland, the Departments of Mathematics of McGill University and the University of Toronto, Canada. Matthias Mück: Supported by DAAD under grant HSP III. Israel Michael Sigal: Supported by NSERC under grant NA7901.     

The case of missing incommensurate smectic A phases

Two binary mixtures of polar liquid crystal materials were previously reported to exhibit three incommensurate smectic A phases predicted for such materials on the basis of phenomenological theory. Results of our recent high-resolution X-ray scattering experiments show that no incommensurate phases exist in the two systems. Wide coexistence regions are found at first order transitions between various frustrated smectic phases of these mixtures. These regions were previously identified as the incommensurate smectic A phases. The phase diagrams of the two systems determined with high-resolution X-ray technique are shown to be in excellent agreement with Baroisa-Prost-Lubensky theory.     

Liquid crystalline hexa-amides and side chain polysiloxanes of azacrown [18]-N6

The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N₆ was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N₆ has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH₂)₁₁ spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N₆ mesogen. The polysiloxanes also display a liquid crystalline phase.