Search for a reliable methodology for PSD determination based on a combined molecular simulation-regularization-experimental approach: The case of PHTS materials

We present here a methodology for searching a robust pore size distribution (PSD) for adsorbent materials. The method is based on a combination of individual adsorption isotherms, obtained from Grand Canonical Monte Carlo simulations, a regularization procedure to invert the adsorption integral equation (Tikhonov regularization solved by singular value decomposition), and the needed experimental adsorption isotherm. The selection of several parameters from the available choices to start the procedure are discussed here: the size of the kernel (number of individual pores and number of experimental adsorption points to be included), the fulfillment of the Discrete Picard condition, and the L-curve criteria, all leading to find a reliable and robust PSD. The procedure is applied to plugged hexagonal templated silicas (PHTS), synthesized, and characterized in our laboratory.     

Thermal diffusion of envelope solitons on anharmonic atomic chains

We study the motion of envelope solitons on anharmonic atomic chains in the presence of dissipation and thermal fluctuations. We consider the continuum limit of the discrete system and apply an adiabatic perturbation theory which yields a system of stochastic integro-differential equations for the collective variables of the ansatz for the perturbed envelope soliton. We derive the Fokker-Planck equation of this system and search for a statistically equivalent system of Langevin equations, which shares the same Fokker-Planck equation. We undertake an analytical analysis of the Langevin system and derive an expression for the variance of the soliton position Var[x _s ] which predicts a stronger than linear time dependence of Var[x _s ] (superdiffusion). We compare these results with simulations for the discrete system and find they agree well. We refer to recent studies where the diffusion of pulse solitons were found to exhibit a superdiffusive behaviour on longer time scales.Received: 28 June 2004, Published online: 26 November 2004PACS: 05.10.Gg Stochastic analysis methods - 05.45.Yv Solitons - 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian motion - 05.50. + q Lattice theory and statistics     

Electronic transport properties of bismuth nanobridges through silicon-nitride membranes

The electronic transport through nanostructured bismuth nanobridges has been investigated at low temperatures (T<2 K) and in magnetic fields B up to 8.5 T. The samples show reproducible resistance fluctuations as a function of B, superimposed on a large magnetoresistance of up to 50%. In addition, time-dependent resistance fluctuations in zero magnetic field demonstrate the presence of bistable scatterers in the constriction region of our samples, which are described by two-level systems. Their dynamics are shown to be sensitive to subtle modifications of the static scatterer configuration in their vicinity, which cannot be detected in the sample magnetofingerprint.     

Mathematical modelling of the oxidation of nickel titanium alloys

A one-dimensional bulk reaction model for the oxidation of nickeltitanium is formulated, with preferential oxidation of titaniumbeing included. The modelling is directed at the better understandingof the dominant mechanisms involved in the oxidation processand their significance for the biocompatibility of the alloy.Two different regimes for the relative diffusivities of oxygenand the metals are investigated. By assuming fast bulk reactions,different asymptotic structures emerge in different parameterregimes and the resulting models take the form of moving boundaryproblems. Different profiles of nickel concentration are obtained:in particular a nickel-rich layer (observed in practice) ispresent below the oxide/metal interface for the case when oxygenand the metals diffuse at comparable rates.     

Exciton Molecules in Quantum Wells: Influence of the Well Width Fluctuations

The influence of the well width fluctuations on the dependence of the binding energy of excitonic complexes in quantum wells is studied by using the path-integral Monte-Carlo technique. The results are compared with available experimental data and a good agreement is found.Postdoctoral researcher of FWO-Vlaanderen     

The “corset effect” of spin-lattice relaxation in polymer melts confined in nanoporous media

Linear polyethylene oxides with molecular weightsM _w of 1665 and 10170 confined in pores with variable diameters in a solid methacrylate matrix were studied by proton field-cycling nuclear magnetic resonance relaxometry. The pore diameter was varied in the range of 9–57 nm. In all cases, the spin-lattice relaxation time shows a frequency dependence close toT ₁∞ v^3/4 in the range ofv=3·10^?1-2·10¹ MHz as predicted by the tube-reptation model. This protonT ₁ dispersion essentially reproduces that found in a previous deuteron study (R. Kimmich, R.-O. Seitter, U. Beginn, M. Möller, N. Fatkullin: Chem. Phys. Lett. 307, 147, 1999). As a feature particularly characteristic for reptation, this finding suggests that reptation is the dominating chain dynamics mechanism under pore confinement in the corresponding time range. The absolute values of the spin-lattice relaxation times indicate that the diameter of the effective tubes in which reptation occurs is much smaller than the pore diameters on the time scale of spin-lattice relaxation experimens. An estimation leads to a valued ^*～0.5 nm. The impenetrability of the solid pore walls, the uncrossability of polymer chains (“excluded volume”) and the low value of the compressibility in polymer melts create the “corset effect” which reduces the lateral motions of polymer chains to a microscopic scale of only a few tenths of a nanometer.     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003