Ethylenically unsaturated polycarbosiloxanes for novel silicone hydrogels: synthesis,end‐group analysis,contact lens formulations,and structure–property correlations

A series of novel mono‐ethylenically unsaturated polycarbosiloxanes macromonomers as compatibilizer materials for soft silicon hydrogels were prepared from the anionic ring‐opening polymerization (AROP) of 2,2,5,5‐tetramethyl‐2,5‐disila‐1‐oxacyclopentane followed by methacrylation. The characterization was performed by end‐group analysis and included the determination of molecular weight, molecular weight distributions, end‐group functionality, and impurity profiles using gas chromatography‐mass spectrometry, gel permeation chromatography, nuclear magnetic resonance, and matrix‐assisted laser desorption/ionization time of flight mass spectrometry. The synthetic procedure was optimized to minimize the formation of any dimer that would have the potential to act as a low molecular weight cross linker. In addition, the novel di‐ethylenically unsaturated polycarbosiloxanes were synthesized by cationic polymerization. Use of these silicone derivatives was explored in the formulation of contact lenses, and the structure–property relationship was examined. When copoymerized with hydrophilic monomers, these were able to give transparent and wettable films with desired properties, particularly a low moduli for contact lenses. Contact lens with high modulus is often shown to impart a higher degree discomfort when worn upon the eye. It was clear from the structure–property relationship that the modulus and the tensile strength of the formulated material depend on the nature and length of the polycarbosiloxane used and may be tuned for the purpose as needed. Copyright © 2013 John Wiley & Sons, Ltd.     

Singular nature of nonlinear macroscale effects in high-rate flow through porous mediaNature singulière des effets macroscopiques non linéaires dans un écoulement à hautes vitesses en milieux poreux

The quadratic law of laminar flow through porous media at high Reynolds numbers, which is well confirmed by the multiple experimental data, is shown to give rise to three fundamental paradoxes. All them can be resolved by assuming the singular structure of flow. The singularity is produced by the formation of jet brunches which invade the stagnant zones and sharply loss their kinetic energy. The numerical simulation confirms this effect. To cite this article: M. Panfilov et al., C. R. Mecanique 331 (2003).     

Coupled Groundwater Flow and Transport in Porous Media. A Conservative or Non-conservative Form?

A new formulation for the modeling of density coupled flow and transport in porous media is presented. This formulation is based on the development of the mass balance equation by using the conservative form. The system of equations obtained by coupling the flow and transport equations using a state equation is solved by a combination of the mixed hybrid finite element method (MHFEM) and the discontinuous finite element method (DFEM). The former is applied in order to solve the flow equation and the dispersive part of the transport equation, whilst the latter is used to solve the advective part of the transport equation. Although the advantages of the MHFEM are known (efficiency calculation of velocity field and continuity of fluxes from one element to an adjacent one), its application in a classical development form (volumetric fluxes as unknowns) leads to the non-conservative version of the mass balance equation. The associated matrix of the system of equations obtained by hybridization is positive definite but non-symmetrical. By using a new approach (mass fluxes as unknowns) the conservative form of the continuity equation is preserved and the associated matrix of the system of equations obtained by hybridization becomes symmetrical. When applied to Elder's problem involving a strong density contrast, this new approach, with a lower calculation cost, leads to similar or identical results to those found in the specialized literature. The comparison between the conservative and non-conservative formulations solved with the same MHFEM and DFEM combination emphasizes the rigor and the pertinence of this new approach. Furthermore, we show the existence of a limit refinement defining the stability of the numerical solution for Elder's problem.     

Transport with a Very Low Density Contrast in Hele–Shaw Cell and Porous Medium: Evolution of the Mixing Zone

The optimal concentration of a blue dye solution with 'tracer' properties, enabling a pollutant to be marked was determined by the use of numerical, theoretical and experimental approaches. Experimental investigations were performed on a transparent Hele–Shaw cell and the concentration distribution was analyzed using an optical technique based on dye light absorption properties. The injected optimal concentration was established thanks to a theoretical and experimental study carried out on the output signal dynamics. Using the same experimental conditions, numerical simulations were performed. The very good agreement between the data (experimental and numerical) clarified that: (i) the choice of the blue dye optimal concentration was valid and (ii) the concentration-dependent density should not be neglected in flow and transport equations even if it concerns a so-called 'tracer'. Following this remark, a theoretical aspect was developed in order to determine the analogous conditions between a Hele–Shaw cell and a porous medium for the variable density transport phenomenon. The structure of the concentration-dependent dispersion tensor used in the numerical code was obtained by homogenizing the Stokes flow of a bi-component mixture. The numerical results show that, as long as the tracer density does not exceed a certain value, it is not necessary to take into account a density contrast in terms of the dispersion tensor. The classical form of the Taylor dispersion tensor can be used successfully.     

Dispersion de Taylor généralisée à un fluide à propriétés physiques variablesGeneralized Taylor dispersion for heterogeneous fluid

The investigation of non-reactive miscible solute dispersion in a vertical Hele–Shaw cell is considered. An asymptotic method is used to extend Taylor model to the case of the fluid density, the dynamic viscosity and the molecular diffusion coefficient are solute concentration-dependent. It is demonstrated that the averaged variables over the gap are governed by a convection–dispersion equation in which the dispersion tensor is concentration-dependent. To cite this article: C. Felder et al., C. R. Mecanique 332 (2004).     

DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

Numerical Simulations for Saltwater Intrusion by the Mixed Hybrid Finite Element Method and Discontinuous Finite Element Method

The proposed numerical code simulates the displacement of two miscible fluids through a saturated porous medium (2D configuration). Coupling between flow and transport is carried out by an equation of state. In the mixing zone, the density is assumed to vary as a function of concentration. The model uses a combination of the mixed hybrid finite element method and the discontinuous finite element method.Applied in its classical development, the mixed hybrid finite element method leads to a non-conservative formulation of the mass balance equation. However, one of the main reasons for using this technique is the ability to conserve mass cell-by-cell. Consequently, a new formulation that makes it possible to hold the conservative form of the continuity equation and so preserve the mass cell-wise is proposed. Although the pertinence of these approaches could have also been tested on other standard benchmarks, e.g., Elder's problem or salt dome problem, we have voluntarily limited ourselves to Henry's problem (1964). This choice was dictated by the possibility of a comparison with a semi-analytical solution. Contrary to previous numerical results, the comparison is made for the whole mixing zone. The very good agreement between our results and the semi-analytical solution shows the robustness and the efficiency of this approach for the seawater intrusion problems.     

Transport in Porous Media: Contents of Volume 48

Volume Contents

Transport in Porous Media: Contents of Volume 48     

Redox control of rotary motions in ferrocene-based elemental ball bearings

Rotational motions of ferrocene-based carousels have been achieved by electron transfer centered on π-dimerizable 4,4'-bipyridinium substituents introduced on both cyclopentadienyl rings through covalent linkers of different size, geometry, and flexibility. Detailed spectroscopic, electrochemical, and theoretical analyses demonstrate that rigid and fully conjugated linkers allow the quantitative formation of intramolecular π-dimers resulting from optimized orbital overlaps within the HOMO of the electrochemically generated bis-radical species. The tetra-cationic "charge-repelled" conformers, the self-assembled π-dimers, and their electron triggered interconversions have been investigated by UV-vis, NMR, and ESR spectroscopy, electrochemistry, X-ray diffraction analysis, and theoretical calculations. These studies support the conclusion that the rotation of both cyclopentadienyl rings in ferrocene can be controlled electrochemically using noncovalent reversible interactions arising from π-radical coupling processes.     

Infiltration of Salt Solute in Homogeneous and Saturated Porous Media – An Analytical Solution Evaluated by Numerical Simulations

In many cases various land disposal activities (e.g. infiltration, injection wells) constitute an important potential source of groundwater contamination. Using a 2D physical model, the behaviour of the infiltration of a salt solute, locally injected in a homogeneous and saturated porous medium, has been analysed. Under various experimental conditions (density effects, injection flow rate) the salt solute penetrates the porous media and leads to a steady-state regime inside the mixing zone. By using experimental observations, the basic equations describing the flow and transport phenomena can be simplified and an analytical solution obtained. Its validity is subject to numerical verification. The numerical model, based on the development of the mass balance equation expressed by its conservative form, uses a combination of the mixed hybrid finite element (MHFE) and discontinuous finite element (DFE) methods. The efficiency of this numerical model was previously verified on standard benchmarks, for example Elder's problem and Henry's problem. In the first step, the qualitative good agreement between the experimental and numerical results enabled us to use the numerical model in order to verify some hypotheses resulting from visual observations. Thus, the numerical results reveal the existence of a steady-state regime inside the mixing zones. Nevertheless, both its vertical and longitudinal extensions are less than those observed in the physical model. In the second step, the numerical results enable to establish the validity domain as well as the accuracy of the proposed analytical solution.