General capillary pressure and relative permeability expressions for through-plane fluid transport in thin fibrous sheets

The rate of fluid transport in partially saturated porous media depends on the media's instantaneous (function of saturation) relative permeability, k_r(S), and capillary pressure, P_c(S). Obtaining functional relationships for relative permeability and capillary pressure is only possible via experimentation or expensive microscale simulations, and needs to be repeated for different media having different fiber diameters, thicknesses, or porosities. In this concern, we conducted series of 3-D microscale simulations to investigate the effect of the above parameters on the relative permeability and capillary pressure of fibrous porous sheets. The results of our parameter study are utilized to develop general expressions for k_r(S) and P_c(S). Our general expressions are based on the existing empirical correlations of two-phase flow in granular media, and can easily be included in macroscale fluid transport equations to predict the rate of fluid release from partially saturated fibrous sheets in a time and cost-effective manner.     

Rheological behavior of POM polymer melt flowing through micro-channels

Determination of the rheological behavior of the polymer melt within micro-structured geometry is vital for accurate simulation modeling of micro-molding. The lack of commercial equipment is one of main hurdles in the investigation of micro-melt rheology. In this study, a melt viscosity measurement system for POM melt flowing through micro-channels was established. For measured pressure drop and volumetric flow rate, both capillary and slit flow models were used for the calculation of viscosity. The calculated results were also compared with those of PS resin to discuss the effect of morphology structure on the viscosity characteristics of polymer within micro-channels. It was found that the measured POM viscosity values in the test ranges are significantly lower (about 29-35% for a channel size of 150 μm) than those obtained with a traditional capillary rheometer. Meanwhile, the percentage reduction in the viscosity value and the ratio of slip velocity relative to mean velocity all increase with decreasing micro-channel size, but less significantly when compared with PS resin. In the present study we emphasize that the rheological behavior of the POM resin in microscopic scale is also different from that of macroscopic scale as PS resin but displays a less significant lower. It also revealed that the wall slip occurs more easily for the PS resin within micro-channels than POM resin due to enlarge the effect of molecular weight.     

Temperature dependence of liquid epoxy resin impregnation through polyester non-woven fabric

The temperature dependence of liquid epoxy resin impregnation under atmospheric pressure was measured under the condition that the impregnation was through polyester non-woven fabric sheets, sandwiched between two circular glass plates. It was expected that impregnation would take place to a small extent, because the pressure in the sheet increases to more than atmospheric pressure in the course of impregnation from the perimeter of the circular sheet toward its center, but the liquid resin impregnates to a great extent and impregnating velocity increases with a rise in temperature. This phenomenon can be analyzed by the Kozeny-Carman equation improved by the introduction of the theoretically calculated capillary force in the modeled fiber bed structure and a parameter to postulate gas solubility and diffusion into the liquid resin. An increase in the impregnating velocity with the temperature rise is caused by decrease in the resin viscosity, by increase of the capillary force pressure and by decrease in the gas pressure corrected by a parameter.     

The rheology of pseudoplastic fluids in porous media using network modeling

This paper considers the rheology of pseudoplastic (shear thinning) fluids in porous media. The central problem studied is the relationship between the viscometric behavior of the polymer solution and its observed behavior in the porous matrix. In the past, a number of macroscopic approaches have been applied, usually based on capillary bundle models of the porous medium. These simplified models have been used along with constitutive equations describing the fluid behavior (usually of power law type) to establish semiempirical macroscopic equations describing the flow of non-Newtonian fluids in porous media. This procedure has been reasonably successful in correlating experimental results on the flow of polymer solutions through both consolidated and unconsolidated porous materials. However, it does not allow an interpretation of polymer flow in porous media in terms of the flows on a microscopic scale; nor does it allow us to predict changes in macroscopic behavior resulting from variations at a microscopic level in the characteristics of the porous medium such as pore size distribution. In this work, we use a network approach to the modeling of non-Newtonian rheology, in order to understand some of the more detailed features of polymjer flow in porous media. This approach provides a mathematical bridge between the behavior of the non-Newtonian fluid in a single capillary and the macroscopic behavior as deduced from the pressure drop-flow rate relation across the whole network model. It demonstrates the importance of flow redistribution within the elements of the capillary network as the overall pressure gradient varies. As an example of a pseudoplastic fluid in a porous medium, we consider the flow of xanthan biopolymer. This polymer is important as a displacing fluid viscosifier in enhanced oil recovery applications and, for that reason, a considerable amount of experimental data has been published on the flow of xanthan solutions in various porous media.     

An analysis of induced pressure fields in electroosmotic flows through microchannels

Induced pressure gradients are found to cause band-broadening effects which are important to the performance of microfluidic devices, such as capillary electrophoresis and capillary chromatography. An improved understanding of the underlying mechanisms causing an induced pressure gradient in electroosmotic flows is presented. The analysis shows that the induced pressure distribution is the key to understanding the experimentally observed phenomena of leakage flows. A novel way of determining the static pressures at the inlet and outlet of microchannels is also presented that takes account of the pressure losses due to flow contraction and expansion. These commonly neglected pressure losses at the channel entrance and outlet are shown to be important in accurately describing the flow. The important parameters that define the effect of induced pressure on the flows are discussed, which may facilitate the design of improved microfluidic devices. The present model clearly identifies the mechanism behind the experimentally observed leakage flows, which is further confirmed by numerical simulations. Not only can the leakage flow occur from the electric-field-free side channel to the main channel, but also the fluid in the main channel can be attracted into the side channel by the induced pressure gradient.     

Adsorption-Desorption Flow of Condensable Vapors through Mesoporous Media: Network Modeling and Percolation Theory

Flow of condensable vapors in mesoporous media is investigated theoretically and experimentally during adsorption and desorption processes. A typical permeability curve of a condensable vapor is strongly enhanced in the capillary condensation region. This is because additional capillary pressure gradients are imposed on the capillary-condensed pores, which act as "good" conductors compared to the noncondensed pores, which are considered "poor" conductors. The percolation scaling properties that hold for a system of "good" and "poor" conductors are confirmed for the cases examined. As the ratio of gas flow/capillary-enhanced flow decreases, the rise of permeability with pressure becomes sharper. The network connectivity has a strong impact on the maximum permeability value and on the width of the scaling law regions. The contribution of surface flow does not affect the permeability in the peak region, but results in a shrinkage of the scaling law regions. During desorption, a marked hysteresis in the permeability curves is found and it is attributed only to thermodynamic hysteresis. The maximum permeability values in this case are higher and shifted to lower relative pressures. Copyright 2000 Academic Press.     

NEURAL NETWORK ANALYSIS APPLICATION TO PERMEABILITY DETERMINATION OF FIBERGLASS AND CARBON PREFORMS

Preform permeability is an important process parameter in liquid injection molding of composite parts.This parameter is currently determined with time consuming and expensive experimental procedures.This paper presents the application of a back-propagation neural network to predicting fiber bed permeability of three types of reinforcement mats. Resin flow experiments were performed to simulate the injection cycle of a resin transfer molding process.The results of these experiments were used to prepare a ...     

Evaluation of the use of capillary numbers for quantifying the removal of DNAPL trapped in a porous medium by surfactant and surfactant foam floods

The capillary number is used to quantify the mobilization potential of organic phases trapped within porous media. The capillary number has been defined in three different forms, according to types of flow velocity and viscosity used in its definition. This study evaluated the suitability of the capillary number definitions representing surfactant and surfactant foam floods by constructing capillary number-TCE saturation relationships. The results implied that the capillary number should be correctly employed, according to scale and fluid flow behavior. This study suggests that the pore-scale capillary number should be used only for investigating the organic-phase mobilization at the pore scale because it is defined by the pore velocity and the dynamic viscosity. The Newtonian-fluid capillary number using the Darcy velocity and the dynamic viscosity may be suitable for quantifying flood systems representing Newtonian fluid behavior. For viscous-force modified flood systems such as surfactant-foam floods, the apparent capillary number definition employing macroscopic properties (permeability and potential gradient) may be used to appropriately represent the desaturation of organic phases from porous media.     

Electrokinetic coupling in unsaturated porous media

We consider a charged porous material that is saturated by two fluid phases that are immiscible and continuous on the scale of a representative elementary volume. The wetting phase for the grains is water and the nonwetting phase is assumed to be an electrically insulating viscous fluid. We use a volume-averaging approach to derive the linear constitutive equations for the electrical current density as well as the seepage velocities of the wetting and nonwetting phases on the scale of a representative elementary volume. These macroscopic constitutive equations are obtained by volume-averaging Ampère's law together with the Nernst-Planck equation and the Stokes equations. The material properties entering the macroscopic constitutive equations are explicitly described as functions of the saturation of the water phase, the electrical formation factor, and parameters that describe the capillary pressure function, the relative permeability functions, and the variation of electrical conductivity with saturation. New equations are derived for the streaming potential and electro-osmosis coupling coefficients. A primary drainage and imbibition experiment is simulated numerically to demonstrate that the relative streaming potential coupling coefficient depends not only on the water saturation, but also on the material properties of the sample, as well as the saturation history. We also compare the predicted streaming potential coupling coefficients with experimental data from four dolomite core samples. Measurements on these samples include electrical conductivity, capillary pressure, the streaming potential coupling coefficient at various levels of saturation, and the permeability at saturation of the rock samples. We found very good agreement between these experimental data and the model predictions.     

A flow injection-capillary electrophoresis system with high-voltage contactless conductivity detection for automated dual opposite end injection

The system comprises two flow injection-capillary electrophoresis interfaces into which the opposite ends of the separation capillary are inserted. The electrolyte solution flows through both interfaces by use of hydrostatic pressure. The injection of the samples into the electrolyte flow is accomplished by a rotary-type chromatographic valve at the grounded side and by a pinch-valve injector at the high-voltage side that provides sufficient isolation from the high electric field. The system allows a fully automated dual-injection sequence of samples from both capillary ends and simultaneous electrophoretic separation of anions and cations in the samples. The analytes are detected by a high-voltage contactless conductometric detector positioned approximately in the middle of the separation capillary. The parameters of the system were evaluated. The repeatability of the flow injection-capillary electrophoresis system for the simultaneous determination of anions and cations was evaluated for ten consecutive injections and relative standard deviation (RSD) values for peak areas were better than 1.0%. The sample throughput for total ionic analysis was estimated to be 25 samples per hour. The system was used for automated simultaneous analysis of anions and cations in various real samples. Using a short separation capillary, rapid total ionic analysis in less then 1 min is demonstrated.     

The transport of condensible vapors through a microporous vycor glass membrane

The flow of condensible vapors through microporous Vycor glass was investigated experimentally as well as theoretically. In porous materials, adsorbable gases frequently exhibit higher permeability than predicted from the flow of nonadsorbable gases. This enhanced flow has been attributed to the surface diffusion of adsorbed molecules along the surface of the porous media or to the viscous flow of capillary condensate at high relative pressures. In the present investigation, a new flow model of condensible vapors through microporous material was developed by considering the blocking effect of the adsorbed phase on the basis of a cylindrical capillary structure. Six different flow modes were considered depending on the pressure distribution and the film thickness of the adsorbed layer. Experimental measurements were also conducted on the transport of condensible vapors (Freon-113 and water) through microporous Vycor glass at steady state in the entire range of relative pressure. The maximum peak and scattering phenomena of permeabilities were observed. The estimated values of permeability from the developed model were compared with the experimental results. Also, it was attempted to explain the maximum peak and scattering phenomena of the experimentally observed permeabilities.     

Coupling CE with atmospheric pressure photoionization MS for pharmaceutical basic compounds: optimization of operating parameters

The use of CE coupled with MS (CE-MS) has evolved as a useful tool to analyze charged species in small sample volumes. Because of its sensitivity, versatility and ease of implementation, the ESI interface is currently the method of choice to hyphenate CE to MS. An alternative can be the atmospheric pressure photoionization (APPI) source, however, numerous parameters must be optimized for its coupling to CE. After evaluation of the sheath liquid composition and the CE capillary outlet position, an experimental design methodology was assessed for optimizing other ionization source parameters, such as sheath liquid flow rate, drying gas flow rate and temperature, nebulizing gas pressure, vaporizer temperature, and capillary voltage. For this purpose, a fractional factorial design (FFD) was selected as a screening procedure to identify factors which significantly influence sensitivity and efficiency. A face-centered central composite design (CCD) was then used to predict and optimize sensitivity, taking into account the most relevant variables. Sensitivity was finally evaluated with the optimized conditions and height-to-noise ratios (H/N) around 10 were achieved for an injection of 200 ng/mL of each analyte.     

Forced imbibition-a tool for separate determination of Laplace pressure and drag force in capillary filling experiments

When a very thin capillary is inserted into a liquid, the liquid is sucked into it: this imbibition process is controlled by a balance of capillary and drag forces which are hard to quantify experimentally, particularly considering flow on the nanoscale. By computer experiments using a generic coarse-grained model, it is shown that an analysis of imbibition forced by a controllable external pressure independently quantifies the Laplace pressure and Darcy's permeability as relevant physical parameters governing the imbibition process. From the latter one may then compute the effective pore radius, effective viscosity, dynamic contact angle and slip length of the fluid flowing into the pore. In determining all these parameters independently, the consistency of our analysis of such forced imbibition processes is demonstrated.     

A network model for the permeability of condensable vapours through mesoporous media

The paper aims at introducing a discrete (network) approach to modelling transport of condensable vapours in mesoporous structures. Such models possess the potential for improving the understanding of the mechanisms responsible for the observed transport behaviour. The basic elements of a typical pore network representing a mesoporous medium are summarized and the current state concerning the simulation of the related phenomena is given. The main processes involved (adsorption, mass diffusion, surface flow, capillary condensation) are simulated over the entire range of relative pressure. Finally, the effects of material structural parameters (average pore radius, pore size distribution and standard deviation, pore connectivity) and other relevant factors (relative pressure, temperature, resistance to surface flow, total pressure drop) on vapour permeability are presented and the future research directions are pointed out.     

Dynamique des écoulements en milieux poreux double échelle

Simple mathematical models with two time constants are used to study the dynamics of pressure variation during permeability measurements on dual porosity saturated media. We think that these transient phase dynamic aspects, which Darcy's Law cannot explain, are a macroscopic image of flows in macro and micropores.     

Formation of coffee stains on porous surfaces

During the drying of drops of nanoparticle suspensions, segregation can occur by internal fluid flows toward the contact line, if the contact line is pinned. This leads to a characteristic ring deposit or coffee stain. On solid substrates coffee staining can be eliminated through the use of solvent mixtures that promote Marangoni flows to oppose these drying-induced flows. Here it is shown that a suspension, optimized to eliminate the formation of coffee stains on a range of solid surfaces, shows coffee staining on a number of porous surfaces. This behavior is shown to be consistent with a mechanism of fluid removal through capillary flow (draining) of the solvent into the porous substrate, combined with filtration of the particles by the small pore size, in addition to the flow from solvent evaporation. The extent of capillary driven coffee staining is a function of substrate pore size: if the pore size is small, capillary flow is slow, reducing the observed coffee staining. However, if the pore size is too large, the nanoparticles are absorbed into the material along with the draining solute and no deposition of particles is observed.     

Viscous flow of a volatile liquid on an inclined heated surface

We investigate the effects of evaporation on a gravity-driven flow of a viscous liquid on a heated solid surface. Vapor molecules are adsorbed on the dry areas of the solid and form a microscopic adsorbed film. The thickness of this film is calculated from the formulas for disjoining pressure and the principles of equilibrium thermodynamics. A lubrication-type approach is used to derive an evolution equation capable of describing both the macroscopic shape of the vapor-liquid interface and the adsorbed film on the vapor-solid interface. Under the conditions of negligible evaporation, the numerical solution of the evolution equation predicts translational motion and formation of capillary ridge, in agreement with previous investigations. Moderate evaporation is shown to slow down the flow and decrease the height of the capillary ridge, which implies a stabilizing effect of evaporation on the well-known instability observed in gravity-driven thin film flows. We also study the combined effects of evaporation and thermocapillary stresses and show that the latter act to reduce the velocity of the downward motion, but increase the height of the capillary ridge. Apparent contact angles are found from the solution and shown to increase with evaporation and contact line speed. For strong evaporation, steady state solutions are found such that evaporation balances the downward motion of the interface under the action of gravity.     

The identification and determination of selected 1,4-benzodiazepines by an optimised capillary electrophoresis-electrospray mass spectrometric method

An optimised capillary electrophoresis-electrospray mass spectrometric method is presented for the identification and determination of diazepam and its metabolites N'-desmethyldiazepam, oxazepam and temazepam. By investigating constituent parts of the capillary electrophoresis-electrospray mass spectrometric interface and optimising their function, a relatively fast and reproducible method is described for the identification and determination of selected 1,4-benzodiazepines. Optimisation of sheath and auxiliary gas flows, capillary tip tapering, capillary tip positioning, sheath liquid composition and flow rate and pressure application during the separation step have led to acceptable relative standard deviation (RSD) values for migration time and peak area, correlation coefficients and limits of detection. This has been achieved as a result of stabilising the electrospray current prior to analysis, a procedure that takes a matter of minutes when using the method described. Sequential product ion fragmentation (MS(n)) characterisation of 15 1,4-benzodiazepines is also presented and mechanisms for the observed fragmentation patterns proposed.     

Application of a capillary‐assembled microfluidic system for separation of cephalosporins

This paper demonstrates a simple and easy setting up of a fused‐silica capillary‐assembled microfluidic system (μCE). This system incorporates a split‐flow pressure injection of the sample into a microfluidic system made from PDMS and a short (～20 cm) length of fused‐silica capillary as a separation unit. The on‐capillary detection was carried out by fiber optic spectrometry. A mixture of six cephalosporin antibiotics was separated in the μCE system and the obtained results were compared to those achievable by conventional CE. The six components could be separated within 8.5 min with the number of theoretical plates around 10 000.     

Dramatic selectivity changes on carrier gas flow change in a series-coupled GC capillary tandem

We describe the polarity of selectivity of a GC separation system in terms of Retention Index data. In a series-coupled capillary system having stationary phases of differing polarity even slight (independent!) carrier gas flow changes in one part of the capillary series result in a dramatic change of selectivity. “Dramatic” is a relative term! Using a simple electronically controlled flow changing device we found retention index changes of several hundred units for polar test compounds such as phenols on a SE30/Carbowax tandem. This means: The classical theoretical model for understanding retention (and selectivity) in chromatography must be corrected. We propose a very simple approach involving addition of the expression RESIDENCE TIME to the chromatographic vocabulary. Instead of using flow resistors, one can just add a pressure regulator to the coupling point. A powerful analytical concept is now in easy reach.