Droplet suction on porous media

We study the forced aspiration of small ( mm) and large ( cm) liquid drops, deposited on prewetted porous membranes, and pumped mechanically with a constant current J. Two kinds of membranes are used where the pores are i) disconnected, cylindrical and calibrated or ii) interconnected “sponge-like”. Whatever the size of the drops and the intensity J of the current, two suction regimes are observed versus time: 1) a “locked” regime, when the drop is pinned, with a dynamic contact angle decreasing from advancing () to finite receding () contact angle; 2) an “unlocked” regime, where the contour line recedes with a constant contact angle closed to . In both regimes, the shape of the drop remains quasistatic, during the suction process, i.e. a spherical cap for small drops and a flat “gravity pancake” for large ones. Received 19 January 2000     

Percolation in two-scale porous media

Two-scale porous media are generated by filtering a Gaussian random correlated field with a random correlated threshold field. The percolation threshold and the critical exponent ν are derived with the help of a finite-size scaling method. The percolation threshold for the three-dimensional media is a decreasing function of the variance and correlation length of the threshold field. A simplified model predicts these trends in 3d; moreover, it suggested some effects in 2d which were all numerically verified. Received 17 August 2000     

Pore size distribution in porous glass: fractal dimension obtained by calorimetry

By differential Scanning Calorimetry (DSC), at low heating rate and using a technique of fractionation, we have measured the equilibrium DSC signal (heat flow) J _q ⁰ of two families of porous glass saturated with water. The shape of the DSC peak obtained by these techniques is dependent on the sizes distribution of the pores. For porous glass with large pore size distribution, obtained by sol-gel technology, we show that in the domain of ice melting, the heat flow J_q is related to the melting temperature depression of the solvent, ΔT _m , by the scaling law: J _q ⁰∼ΔT _m ^{- (1 + D)}. We suggest that the exponent D is of the order of the fractal dimension of the backbone of the pore network and we discuss the influence of the variation of the melting enthalpy with the temperature on the value of this exponent. Similar D values were obtained from small angle neutron scattering and electronic energy transfer measurements on similar porous glass. The proposed scaling law is explained if one assumes that the pore size distribution is self similar. In porous glass obtained from mesomorphic copolymers, the pore size distribution is very sharp and therefore this law is not observed. One concludes that DSC, at low heating rate ( q? 2^°C/min) is the most rapid and less expensive method for determining the pore distribution and the fractal exponent of a porous material. Received 23 July 1999 and Received in final form 16 February 2001     

Tracer dispersion in power law fluids flow through porous media: Evidence of a cross-over from a logarithmic to a power law behaviour

An analytical model is presented to describe the dispersion of tracers in a power-law fluid flowing through a statistically homogeneous and isotropic porous medium. The model is an extension of Saffman's approach to the case of non-Newtonian fluids. It is shown that an effective viscosity depending on the pressure gradient and on the characteristics of the fluid, must be introduced to satisfy Darcy's law. An analytical expression of the longitudinal dispersivity is given as a function of the Peclet number Pe and of the power-law index n that characterizes the dependence of the viscosity on the shear rate . As the flow velocity increases the dispersivity obeys an asymptotic power law: . This asymptotic regime is achieved at moderate Peclet numbers with strongly non-Newtonian fluids and on the contrary at very large values when n goes to 1 ( for n=0.9). This reflects the cross-over from a scaling behaviour for towards a logarithmic behaviour predicted for Newtonian fluids (n=1). Received: 22 July 1997 / Revised and Accepted: 2 July 1998     

Dynamical scaling and kinetic roughening of single valued fronts propagating in fractal media

We consider the dynamical scaling and kinetic roughening of single-valued interfaces propagating in 2D fractal media. Assuming that the nearest-neighbor height difference distribution function of the fronts obeys Lévy statistics with a well-defined algebraic decay exponent, we consider the generalized scaling forms and derive analytic expressions for the local scaling exponents. We show that the kinetic roughening of the interfaces displays intrinsic anomalous scaling and multiscaling in the relevant correlation functions. We test the predictions of the scaling theory with a variety of well-known models which produce fractal growth structures. Results are in excellent agreement with theory. For some models, we find interesting crossover behavior related to large-scale structural instabilities of the growing aggregates. Received 22 May 2002 Published online 19 November 2002     

From colloidal aggregation to spinodal decomposition in sticky emulsions

Aggregation mechanisms of emulsions at high initial volume fractions () is studied using light scattering. We use emulsion droplets which can be made unstable towards aggregation by a temperature quench. For deep quenches and , the aggregation mechanism is identified as diffusion-limited cluster aggregation (DLCA). An ordering of the clusters, which is reflected by a peak in the scattering intensity, is shown to result from the intercluster separation, exhibiting different scaling than that observed at lower volume fractions. This manifests an increasing similarity to spinodal decomposition observed as is increased. For and shallow quenches, different mechanisms, closer to spinodal decomposition, are observed. These results allow the subtle boundaries between DLCA and spinodal decomposition to be explored. Received: 7 April 1998 / Revised: 19 August 1998 / Accepted: 21 August 1998     

Ageing of random porous media following fluid deterministic displacement, freezing, thawing

This paper introduces and investigates a simple model of random porous media degradation via several fluid displacing, freezing, and thawing cycles. The fluid transport is based on the deterministic method. The result shows that the topology and the geometry of porous media have a strong effect on displacement processes. The cluster size of the viscous fingering (VF) pattern in the percolation cluster increases with the increase of iteration parameter n. When iteration parameter , the VF pattern does not change with n. When and , the peak value of the distribution increases as n increases; is the normalized distribution of throat sizes after different displacement-damage but before the freezing. The distribution of throat size N(r) after displacement but before freezing damage, shows that the major change, after successive cycles, happens at r>0.9. The peak value of the distribution reaches a maximum when and r=1, where is the normalized distribution of the size of invaded throats for different iterations. This result is different from invasion percolation. The distribution of velocities normal to the interface of VF in the percolation cluster is also studied. When , the scaling function distribution is very sharp. The sweep efficiency E increases along with the increasing of iteration parameter n and decreases with the network size L. And E has a minimum as L increases to the maximum size of the lattice. The VF pattern in the percolation cluster has one frozen zone and one active zone. Received 30 March 1999 and Received in final form 8 August 1999     

Eden growth model for aggregation of charged particles

The stochastic Eden model of charged particles aggregation in two-dimensional systems is presented. This model is governed by the following two parameters: screening length of electrostatic interaction, , and short-range attraction energy, E. Different patterns of finite and infinite aggregates are observed. They are of the following morphology types: linear or linear with bending, worm-like, DBM (dense-branching morphology), DBM with nucleus, and compact Eden-like. The transition between the different modes of growth is studied and phase diagram of the growth structures is obtained in co-ordinates. The detailed aggregate structure analysis, including analysis of their scaling properties, is presented. The scheme of the internal inhomogeneous structure of aggregates is proposed. Received 2 September 1998 and Received in final form 15 January 1999     

Investigation of self-assembled fractal porous-silica over a wide range of length scales using a combined small-angle scattering method

The unique structure of a set of self-assembled porous silica materials was characterized through a combined small-angle scattering (CSAS) method using small- and ultra-small angle neutron scattering as well as small-angle X-ray scattering. The porous silica specimens investigated were prepared by a sol-gel method under the presence of alkylketene dimer (AKD) template particles and through calcination, which leads to the development of porous silica having a mass-fractal structure over length scales from ~ 100 nm to ~ 10 μm. Furthermore, the specimens posses a hierarchical structure, which consist of a fractal porous structure, and also contain primary silica particles less than 10 nm in size, which form a continuous silica matrix. To characterize these complex structures, observation over a broad range of length scales is indispensable. We propose a CSAS technique that serves this purpose well.     

A multi-species lattice-gas automaton model to study passive and reactive tracer migration in 2D fractures

We developed a numerical model based on a multi-species lattice gas cellular automaton to study passive and reactive tracer migration in saturated geological media. The model was made of multiple lattice gases interacting via a two-species collision rule. For a binary mixture, the model displayed a negative deviation from Raoult's law and therefore behaved as a real solution. By biasing the initial two-species collision rule, our model was made to obey the tracer assumption which requires that the tracer species does not affect the velocity of the vehicle fluid. In a 2D fracture, we checked the Taylor-Aris relation. An irreversible adsorption between the tracer and the solid phase was numerically added to perform filtration of the colloids. A good agreement was found with the solution of the filtration equation. An attachment efficiency was defined and was found to bear a linear relationship to the filtration coefficient. We added a third species to study the potential role of colloids in the transport of contaminants. Contaminant migration was enhanced when contaminants were bound to colloids and was slightly reduced when colloids were allowed to adsorb on the solid phase. Received 14 January 1999 and Received in final form 8 June 1999     

Effects of the rate of evaporation and film thickness on nonuniform drying of film-forming concentrated colloidal suspensions

In this paper, we report on nonuniform distribution of film-forming waterborne colloidal suspensions above the critical concentration _c of the colloidal glass transition during drying. We found that colloidal suspension films dry nonuniformly when the initial rate of evaporation E and/or the initial thickness l₀ are high. We found that a Peclet number Pe, defined as Pe = El₀/D, where D is the diffusion coefficient of the colloids in the diluted suspensions, does not predict uniformity of drying of the concentrated suspensions, contrary to the reported work on drying of diluted suspensions. Since the colloidal particles are crowded and their diffusive motion is restricted in concentrated suspensions, we assumed that above _c water is transported to the drying surface by hydrodynamic flow along the osmotic pressure gradient. The permeability of water through channels between deforming particles is estimated by adapting the theory of foam drainage. We defined a new Peclet number Pe by substituting the transport coefficient of flow (defined as the permeability divided by the viscosity, multiplied by the osmotic pressure gradient) for the diffusion coefficient. This extended Peclet number predicted the nonuniform drying with a criterion of Pe > 1. These results indicate that the mechanism of water transport to the drying surface in concentrated suspensions is water permeation by osmotic pressure, which is faster than mutual diffusion between water and particles --that has been observed in diluted suspensions and discussed by Routh and Russel. The theory fits well the experimental drying curves for various thicknesses and rates of evaporation. The particle distribution in the drying films is also estimated and it is indicated that the latex distribution is nonuniform when Pe > 1.     

Structure of gels and aggregates of disk-like colloids

The static structure factor (S(q)) of dispersions and gels of disk-like mineral colloids (Laponite) was investigated using time- and ensemble-averaged light scattering. The evolution of S(q) in time after increasing the ionic strength of well-dispersed Laponite suspensions shows that Laponite aggregates and forms fractal clusters. The structure of the aggregates does not depend on the ionic strength, but the rate of growth increases very strongly with the ionic strength. At concentrations below about 3 g/l (0.12% v/v) the aggregates sediment while at higher concentrations space-filling gels are formed. The gels are homogeneous on length scales larger than the correlation length which decreases strongly with decreasing ionic strength and increasing concentration. However, the local structure is the same, independent of the concentration and the ionic strength. Received 6 August 2000 and Received in final form 16 March 2001     

Size and average density spectra of macromolecules obtained from hydrodynamic data

It is proposed to normalize the Mark-Kuhn-Houwink-Sakurada type of equation relating the hydrodynamic characteristics, such as intrinsic viscosity, velocity sedimentation coefficient and translational diffusion coefficient of linear macromolecules to their molecular masses for the values of linear density M_L and the statistical segment length A. When the set of data covering virtually all known experimental information is normalized for M_L, it is presented as a size spectrum of linear polymer molecules. Further normalization for the A value reduces all data to two regions: namely the region exhibiting volume interactions and that showing hydrodynamic draining. For chains without intachain excluded volume effects these results may be reproduced using the Yamakawa-Fujii theory of wormlike cylinders. Data analyzed here cover a range of contour lengths of linear chains varying by three orders of magnitude, with the range of statistical segment lengths varying approximately 500 times. The plot of the dependence of [η]M on M represents the spectrum of average specific volumes occupied by linear and branched macromolecules. Dendrimers and globular proteins for which the volume occupied by the molecule in solution is directly proportional to M have the lowest specific volume. The homologous series of macromolecules in these plots are arranged following their fractal dimensionality.     

Echo tracer dispersion in flows of polymer solutions through porous media: A tool for detecting weak permeability heterogeneities?

Tracer dispersion in Newtonian and shear-thinning fluids (scleroglucan-water polymer solutions) flowing through single and double porosity grain packings has been studied experimentally using both classical transmission dispersion and echo dispersion (in the latter, the concentration variation front is pumped back through a detector at the inlet after penetrating for a chosen distance into the sample). Transmission dispersion increases markedly in both types of samples with the shear thinning index of the fluid at all Péclet numbers (except when molecular diffusion is dominant). Echo and transmission experiments give nearly identical dispersivity values for Newtonian fluids while echo dispersivity is lower than transmission for shear thinning ones. The normalized dispersivity difference has same order of magnitude for single and double porosity samples and increases with the shear thinning exponent α (by a factor of 2 between α = 0.35 and α = 0.60). This difference may be due to heterogeneities inducing permeability variations of small amplitude over distances of the order of the sample section : their influence on tracer dispersion is partly reversible with respect to a change of the flow direction and is only detectable if it is amplified by the shear-thinning properties of the fluid. Received 19 September 2001     

An universal relation between fractal and Euclidean (topological) dimensions of random systems

It is shown that a dimension-invariant form for fractal dimension D of random systems (where d is Euclidean dimension of the embedding space) is in good agreement with results of numerical simulations performed by different authors for critical (p=p _c ) and subcritical (p<p _c ) percolation, for lattice animals, and for different aggregation processes. Received: 9 July 1998 / Revised and Accepted: 12 July 1998     

Can one hear the shape of an electrode? II. Theoretical study of the Laplacian transfer

The flux across resistive irregular interfaces driven by a force deriving from a Laplacian potential is computed on a rigorous basis. The theory permits one to relate the size of the active zone to the derivative of the spectroscopic impedance with respect to the surface resistivity r through: . It is shown that the macroscopic transfer properties through a system of arbitrary shape are determined by the characteristics of a first-passage interface-interface random walk operator . More precisely, it is the distribution of the harmonic measure (or normalized primary current) on the eigenmodes of this linear operator that controls the transfer. In addition, it is also shown that, whatever the dimension, the impedance of a weakly polarizable electrode for any irregular geometry scales under a homothety transformation as L^d-1, L being the size of the system and d its topological dimension. In this new formalism, the question addressed in the title is transformed in a open mathematical question: “Knowing the distribution of the harmonic measure on the eigenmodes of the self-transport operator, can one retrieve the shape of the interface?” Received 3 November 1998     

Thermal and chemical nanofractal relaxation

We studied shape relaxation of nano-fractal islands, during annealing, after their growth from antimony cluster deposition on graphite surface. Annealing at 180^°C shows evidence of an increase of the fractal branch width with time followed by branch fragmentation, without changing the fractal dimension. The time evolution of the width of the arm suggests the surface self-diffusion mechanism as the main relaxation process. With Monte Carlo simulations, we confirmed the observed behavior. Comparison is done with our previous results on fragmentation of nano-fractal silver islands when impurity added to the incident cluster promotes rapid fragmentation by surface self-diffusion enhancement [1].     

Edison revisited: Electro mechanical effects in wet porous materials

Edison discovered that the coefficient of friction between a metallic plate and a porous material moistened with a dilute electrolyte could be modulated by an electric field. In experiments on the same kind of contacts (clays or chalks on carbon or metals) but without continuous tangential relative motion we measure two electro-mechanical effects at frequencies of the order of 10 kHz. An alternating field induces an alternating normal force between the porous material and the conducting base. The force is lagging by versus the field. A forced normal relative motion induces through the contact a current nearly in phase with the motion. For an explanation we start from Helmholtz theory of stationary electrophoretic phenomena. We present a model in which liquid motions obey the Helmholtz laws. It explains decently the phase relations between causes and effects, and approximately the values of the effects. In optical experiments on contacts between a wet clay and the transparent conducting coating of a glass plate we measure in the frequency range 1-100 kHz a modulation of reflecting power induced by an alternating potential. The decrease of reflecting power is lagging by an angle close to behind the field. We think the modulation observed is induced by a modulation of the amount of liquid in the film present between glass and clay. In friction experiments this alternating liquid lubrication acting exclusively at the very places where friction occurs may have significant effect. Received: 22 July 1997 / Revised: 21 October 1997 / Accepted: 21 November 1997     

Number of arm selection in two-dimensional diffusion processes

We introduce an algorithm to generate two-dimensional diffusion-limited star-branched aggregates (DLSA)attaching bi-functional monomers successively to a central colloidal particle with any desired number of reactive sites. The proposed algorithm produces star-shaped aggregates that grow forever and show a power law polydispersity in the chemical length of the arms near the central colloid. More interestingly, it gives rise to a number of arm selection consisting in that only a small number of arms (around five) define the final structure at relatively large distances from the central colloid, independently of the initial number of reactive sites and the size of the central colloid. We characterize the structure of the aggregates by means of the particle-particle correlation function, analyze its scaling properties and obtain the fractal dimension.