Linear and Nonlinear Viscoelasticity of a Model Unentangled Polymer Melt: Molecular Dynamics and Rouse Modes Analysis

Summary: Using molecular dynamics simulations, we determine the linear and nonlinear viscoelastic properties of a model polymer melt in the unentangled regime. Several approaches are compared for the computation of linear moduli and viscosity, including Green‐Kubo and nonequilibrium molecular dynamics (NEMD). An alternative approach, based on the use of the Rouse modes, is also discussed. This approach could be used to assess local viscoelastic properties in inhomogeneous systems. We also focus on the contributions of different interactions to the viscoelastic moduli and explain the microscopic mechanisms involved in the mechanical response of the melt to external solicitation.

     

Purification of Hydrogen from CO with Cu/ZSM-5 Adsorbents

The transition to a hydrogen economy requires the development of cost-effective methods for purifying hydrogen from CO. In this study, we explore the possibilities of Cu/ZSM-5 as an adsorbent for this purpose. Samples obtained by cation exchange from aqueous solution (AE) and solid-state exchange with CuCl (SE) were characterized by in situ EPR and FTIR, H₂-TPR, CO-TPD, etc. The AE samples possess mainly isolated Cu²⁺ cations not adsorbing CO. Reduction generates Cu⁺ sites demonstrating different affinity to CO, with the strongest centres desorbing CO at about 350 °C. The SE samples have about twice higher Cu/Al ratios, as one H⁺ is exchanged with one Cu⁺ cation. Although some of the introduced Cu⁺ sites are oxidized to Cu²⁺ upon contact with air, they easily recover their original oxidation state after thermal treatment in vacuum or under inert gas stream. In addition, these Cu⁺ centres regenerate at relatively low temperatures. It is important that water does not block the CO adsorption sites because of the formation of Cu⁺(CO)(H₂O)_x complexes. Dynamic adsorption studies show that Cu/ZSM-5 selectively adsorbs CO in the presence of hydrogen. The results indicate that the SE samples are very perspective materials for purification of H₂ from CO.     

Sensitivity analysis of the differential matrix Riccati equation based on the associated linear differential system

Perturbation bounds are given for the solution of the nth order differential matrix Riccati equation using the associated linear 2nth order differential system. The new bounds are alternative to those existing in the literature and are sharper in some cases. This revised version was published online in June 2006 with corrections to the Cover Date.     

Perron Conditions for Uniform Exponential Expansiveness of Linear Skew-Product Flows

 We present necessary and sufficient conditions for uniform exponential expansiveness of discrete skew-product flows, in terms of uniform complete admissibility of the pair (c ₀(N, X), c ₀(N, X)). We give discrete and continuous characterizations for uniform exponential expansiveness of linear skew-product flows, using the uniform complete admissibility of the pairs (c ₀(N, X), c ₀(N, X)) and (C ₀(R ₊, X), C ₀(R ₊, X)), respectively. We generalize an expansiveness theorem due to Van Minh, R?biger and Schnaubelt, for the case of linear skew-product flows. Received August 10, 2001; in revised form June 25, 2002     

Decay Law of Moving Unstable Particle

Quantum relativistic decay law of moving unstable particle is analytically calculated in the model case of the Breit–Wigner mass distribution. It turns out that Einstein time dilation of the moving particle decay holds approximately at times when the decay is exponential. The related correction is calculated analytically. Being very small at these times it is practically unobservable. It is shown that Einstein dilation fails for large times t when decay is not exponential. An unstable system of the kind of K ₀-meson (which is the superposition of K _s and K _I) is also considered. In this case, the violation of Einstein dilation is shown to be appreciable at all times under some condition     

Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride

This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5.     

Ion-driven ATP pump by self-organized hybrid membrane materials

We report new hybrid organic-inorganic materials, based on macrocyclic receptors 1-3 self-organized in tubular superstructures prepared by sol-gel process. Fourier transform infrared (FTIR) and NMR spectroscopic analyses demonstrate that the self-organization by hydrogen bonding of organogel superstructures of 2 and 3 were preserved in the hybrid materials throughout the sol-gel process. The molecular arrangement of heteroditopic receptors defines a particularly attractive functional transport device for both cation (tubular macrocycles) and anion (sandwich-urea) directional-diffusion transport mechanism in the hybrid membrane material. This system has been employed successfully to design a solid dense membrane, functioning as an ion-powered adenosine triphosphate (ATP(2)(-)) pump, and illustrates how a self-organized hybrid material performs interesting and potentially useful functions.     

A singular control model with application to the goodwill problem

We consider a stochastic system whose uncontrolled state dynamics are modelled by a general one-dimensional Itô diffusion. The control effort that can be applied to this system takes the form that is associated with the so-called monotone follower problem of singular stochastic control. The control problem that we address aims at maximising a performance criterion that rewards high values of the utility derived from the system’s controlled state but penalises any expenditure of control effort. This problem has been motivated by applications such as the so-called goodwill problem in which the system’s state is used to represent the image that a product has in a market, while control expenditure is associated with raising the product’s image, e.g., through advertising. We obtain the solution to the optimisation problem that we consider in a closed analytic form under rather general assumptions. Also, our analysis establishes a number of results that are concerned with analytic as well as probabilistic expressions for the first derivative of the solution to a second-order linear non-homogeneous ordinary differential equation. These results have independent interest and can potentially be of use to the solution of other one-dimensional stochastic control problems.