Rarefied Pure Gas Transport in Non-isothermal Porous Media: Validation and Tests of the Model

Viscous flow, effusion, and thermal transpiration are the main gas transport modalities for a rarefied gas in a macro-porous medium. They have been well quantified only in the case of simple geometries. This paper presents a numerical method based on the homogenization of kinetic equations producing effective transport properties (permeability, Knudsen diffusivity, thermal transpiration ratio) in any porous medium sample, as described, e.g. by a digitized 3D image. The homogenization procedure—neglecting the effect of gas density gradients on heat transfer through the solid—leads to closure problems in for the obtention of effective properties; they are then simplified using a Galerkin method based on a 21-element basis set. The kinetic equations are then discretized in space with a finite- volume scheme. The method is validated against experimental data in the case of a closed test tube. It shows to be coherent with past approaches of thermal transpiration. Then, it is applied to several 3D images of increasing complexity. Another validation is brought by comparison with other distinct numerical approaches for the evaluation of the Darcian permeability tensor and of the Knudsen diffusion tensor. Results show that thermal transpiration has to be described by an effective transport tensor which is distinct from the other tensors.     

Non-linear normal modes,invariance, and modal dynamics approximations of non-linear systems

Non-linear systems are here tackled in a manner directly inherited from linear ones, that is, by using proper normal modes of motion. These are defined in terms of invariant manifolds in the system's phase space, on which the uncoupled system dynamics can be studied. Two different methodologies which were previously developed to derive the non-linear normal modes of continuous systems — one based on a purely continuous approach, and one based on a discretized approach to which the theory developed for discrete systems can be applied-are simultaneously applied to the same study case-an Euler-Bernoulli beam constrained by a non-linear spring-and compared as regards accuracy and reliability. Numerical simulations of pure non-linear modal motions are performed using these approaches, and compared to simulations of equations obtained by a classical projection onto the linear modes. The invariance properties of the non-linear normal modes are demonstrated, and it is also found that, for a pure non-linear modal motion, the invariant manifold approach achieves the same accuracy as that obtained using several linear normal modes, but with significantly reduced computational cost. This is mainly due to the possibility of obtaining high-order accuracy in the dynamics by solving only one non-linear ordinary differential equation.     

Direct modeling of flow of FENE fluids

Direct simulations of macromolecular fluids are carried out for flows between parallel plates and in expanding and contracting channels. The macromolecules are modeled as FENE dumbbells with soft disks or Lennard-Jones dumbbell-dumbbell interactions. The results are presented in terms of profiles and contour plots of velocity, pressure, temperature, density, and flow fields. In addition the data for potential energy, shear stress, and the normal components of the stress tensor are collected. In general, an excellent agreement is found between the simulated profiles and the well-known flow structures, such as flow separation and formation of viscous eddies, indicating that micro-hydrodynamics is a viable tool in linking macroscopic phenomena with the underlying physical mechanisms. The simulations are performed in the Newtonian regime, for medium-size systems comprising up to 3888 dumbbells. This number is sufficiently large to control boundary and particle number effects. The flow is induced by gravity. The traditional stochastic (thermal) and periodic boundary conditions are employed. Also, diffusive boundary conditions, which could include a stagnant fluid layer and repulsive potential walls, are developed. The scaling problems, which are related to the application of a large external force in a microscopic system (of the size of the order 100 Å), result in extreme pressure and temperature gradients. In addition, the viscosity and thermal conductivity coefficients obtained from velocity and temperature profiles of the channel flow are presented. These results are confirmed independently from modeling of Couette flow by the SLLOD equations of motion and from the Evans algorithm for thermal conductivity.     

Rheological characterization of a solder paste for surface mount applications

Solder pastes used in surface mount soldering techniques (SMT) are very complex suspensions containing high volumes of metallic powder in a carrier fluid. The rheological complexity results largely from the carrier fluid itself, which is a suspension of colloidal particles. In this work, we have characterized the rheological properties of a typical carrier fluid and its solder paste containing 64 vol.% metallic powder. A six-blade vane geometry was used to avoid wall slip and sample fracture. All measurements were carried out following pre-shearing and rest time in order to obtain reproducible results. Steady shear experiments showed that the solder paste was highly shear-thinning and thixotropic. In oscillatory shear, the linear viscoelastic domain was found to be very narrow for both the suspending fluid and the paste. Frequency sweep tests in the linear domain revealed a gel-like structure with a nearly constant G′ for the suspending fluid and a slightly increasing G′ for the solder paste. From creep experiments, a yield stress of about 40 Pa was determined for the suspending fluid at temperatures between 25 and 40°C, and of 100 Pa at 4°C. A much larger yield stress, 480 Pa, was determined for the solder paste at 25°C.     

Phase Transition with the Line‐Tension Effect

We make the connection between the geometric model for capillarity with line tension and the Cahn‐Hilliard model of two‐phase fluids. To this aim we consider the energies where u is a scalar density function and W and V are double‐well potentials. We show that the behaviour of F _ε in the limit ε→0 and λ→∞ depends on the limit of ε log λ. If this limit is finite and strictly positive, then the singular limit of the energies F _ε leads to a coupled problem of bulk and surface phase transitions, and under certain assumptions agrees with the relaxation of the capillary energy with line tension. These results were announced in [ABS1] and [ABS2]. (Accepted November 5, 1997)     

Near-wall velocity measurements by particle-shadow tracking

We report a new method to measure the velocity of a fluid in the vicinity of a wall. The method, that we call particle-shadow tracking (PST), simply consists in seeding the fluid with a small number of fine tracer particles of density close to that of the fluid. The position of each particle and of its shadow on the wall are then tracked simultaneously, allowing one to accurately determine the distance separating tracers from the wall and therefore to extract the velocity field. We present an application of the method to the determination of the velocity profile inside a laminar density current flowing along an inclined plane.     

Self-assembled nanoribbons and nanotubes in water: energetic vs entropic networks

We present a comparative investigation of two opposite classes of self-assembled fibrillar networks. Ribbons and tubes having cross-sectional dimensions in the nanoscale can be formed in aqueous solutions of steroids derived, respectively, from deoxycholic (DC) and lithocholic (LC) acids. Rheological features distinguish energetic networks of DC ribbons rigidly fixed in cylindrical bundles and entropic transient networks of LC tubes weakly interacting in shear-sensitive suspensions. The two classes are characterized by their frequency sweep profiles, viscoelastic linear domains, scaling laws of the elastic shear modulus vs concentration, kinetics of formation of the networks, and their optical birefringence aspects. A theoretical context for networks of rigid fibers is used to account for the scaling exponents α in the G’ (and σ*) ∝C ^α laws (α=2.0 and 1.0, respectively, for DC and LC). The evolution observed in DC gels from ribbons to cylindrical fibers with monodisperse sections made up with four ribbons is an indication of an equilibrated balance between face-to-face attractions and untwisting elastic processes of the constitutive ribbons.Paper presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005     

Transfer and Termination Reactions in “Living” Carbocationic Polymerizations

Abstract

The available data concerning the polymerization of three classes of monomers deemed to yield living polymers, vinyl ethers, styrenic monomers and isobutylene, are discussed from the point of view of transfer and termination reaction. In the case of vinylethers, linearity of [Mbar]_n with a yield up to 30,000 has been obtained, but when higher [Mbar]_n are planned, there is evidence for the occurrence of transfer reactions. In the case of isobutylene, indene, and p-Me-styrene, the linearity (up to [Mbar]_n ～ 10⁵) of [Mbar]_n with the amount of monomer polymerized which has been observed (but only at low temperature) is compatible with values of transfer constants to monomer measured in “conventional” systems. In these living systems, irreversible terminations are often not very important but may become significant toward the end of monomer consumption. The main termination process is reversible termination which may lead to narrow molecular weight distributions. The linearity of [Mbar]_n with yield is not conclusive evidence for the absence of transfer and termination and for the presence of particular active centers. The control of the polymerizations achieved up to now can be accounted for by the mechanisms of conventional cationic polymerizations, transfer reactions included.     

How Strain Affects the Reactivity of Surface Metal Oxide Catalysts

Highly dispersed molybdenum oxide supported on mesoporous silica SBA‐15 has been prepared by anion exchange resulting in a series of catalysts with changing Mo densities (0.2–2.5 Mo atoms nm^?2). X‐ray absorption, UV/Vis, Raman, and IR spectroscopy indicate that doubly anchored tetrahedral dioxo MoO₄ units are the major surface species at all loadings. Higher reducibility at loadings close to the monolayer measured by temperature‐programmed reduction and a steep increase in the catalytic activity observed in metathesis of propene and oxidative dehydrogenation of propane at 8 % of Mo loading are attributed to frustration of Mo oxide surface species and lateral interactions. Based on DFT calculations, NEXAFS spectra at the O‐K‐edge at high Mo loadings are explained by distorted MoO₄ complexes. Limited availability of anchor silanol groups at high loadings forces the MoO₄ groups to form more strained configurations. The occurrence of strain is linked to the increase in reactivity.