<p>Mass transfer in a porous solid, partially saturated with asingle solvent and multicomponent liquid mixtures, has beenexperimentally and theoretically studied. A porous materialcontaining single liquids and mixtures of organic solvents wasisothermally dried. Experiments were performed using a jacketedwind tunnel, through which a humidity andtemperature-controlled air stream flowed. The wetted porousmaterial was placed in a cylindrical vessel, whose top isexposed to the air stream until the material became dried to acertain extent. Drying experiments with the single solventswater, methanol, ethanol and 2-propanol, were performed atdifferent temperatures and transient liquid content profileswere determined. In isothermal drying experiments with liquidmixtures,the transient concentration profiles of thecomponents along the cylindrical sample as well as the totalliquid content were determined. The liquid mixtures examinedwere water-methanolethanol and isopropanol-methanol-ethanol.Two different temperatures and initial compositions were usedin the experiments. Mathematical models that describe nonsteadystate isothermal drying of a solid containing single liquidsand multicomponent liquid mixtures were developed. In the solidwetted with a single liquid, capillary movement of the liquidwas the main mechanism responsible for mass transfer. In thesolid containing liquid mixtures, interactive diffusion inliquid phase was superimposed to the capillary movement of theliquid mixture. In addition, interactive diffusion of thevapours in empty pores was considered. The parameters todescribe the retention properties of the solid and thecapillary movement of the liquid were determined by comparingtheoretical and experimental liquid content profiles obtainedduring drying of the solid wetted with single liquids. Tosimulate the transport of the liquid mixtures these parameterswhere weighed according to liquid composition. A fairly goodagreement between theoretical and experimental liquidcomposition profiles was obtained if axial dispersion isincluded in the model when the moisture consists of amixture.</p><p><b>Keywords:</b>Internal mass transfer, capillary flow,multicomponent, diffusion, solvent mixtures</p>

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This research addresses a number of fundamental issues concerning convective mass transfer across fluid-fluid interfaces in porous media. Mass transfer to/from distributed sinks/sources is considered for i) the slow dissolution of liquid filaments of a wetting non-aqueous phase liquid (NAPL) held in the corners of angular pores or throats and ii) the fate of gas bubbles generated during the flow of a supersaturated aqueous phase in porous media. 1. Effects of the stability of NAPL films on wetting NAPL dissolution Wettability profoundly affects the distribution of residual NAPL contaminants in natural soils. Under conditions of preferential NAPL wettability, NAPL is retained within small pores and in the form of thick films (liquid filaments) along the corners and crevices of the pore walls. NAPL films in pore corners provide capillary continuity between NAPL-filled pores, dramatically influencing the behaviour of NAPL dissolution to the flowing aqueous phase by convection and diffusion. A pore network model is developed to explore the dissolution behaviour of wetting NAPL in porous media. The effects of initial NAPL distribution and NAPL film stability on dissolution behaviour are studied using the simulator. NAPL phase loses continuity and splits into disconnected clusters of NAPL-filled pores due to rupture of NAPL films. Quasi-state drainage and fingering of the aqueous phase into NAPL-filled pores is treated as an invasion percolation process and a stepwise procedure is adopted for the solution of flow and solute concentration fields. NAPL film stability is shown to critically affect the rate of mass transfer as such that stable NAPL films provide for more rapid dissolution. The network simulator reproduces the essential physics of wetting NAPL dissolution in porous media and explains the concentration-tailing behaviour observed in experiments, suggesting also new possibilities for experimental investigation. 2. Convective Mass Transfer across Fluid Interfaces in Straight Angular Pores Steady convective mass transfer to or from fluid interfaces in pores of angular cross-section is theoretically investigated. The model incorporates the essential physics of capillarity and solute mass transfer by convection and diffusion in corner fluid filaments. The geometry of the corner filaments, characterized by the fluid-fluid contact angle, the corner half-angle and the interface meniscus curvature, is accounted for. Boundary conditions of zero surface shear (???perfect-slip???) and infinite surface shear (???no-slip???) at the fluid-fluid interface are considered. The governing equations for laminar flow within the corner filament and convective diffusion to or from the fluid-fluid interface are solved using finite-element methods. Flow computations are verified by comparing the dimensionless resistance factor and hydraulic conductance of corner filaments against recent numerical solutions by Patzek and Kristensen [2001]. Novel results are obtained for the average effluent concentration as a function of flow geometry and pore-scale Peclet number. These results are correlated to a characteristic corner length and local pore-scale Peclet number using empirical equations appropriate for implementation in pore network models. Finally, a previously published ???2D-slit??? approximation to the problem at hand is checked and found to be in considerable error. 3. Bubble evolution driven by solute diffusion during the process of supersaturated carbonated water flooding In situ bubble growth in porous media is simulated using a pore network model that idealizes the pore space as a lattice of cubic chambers connected by square tubes. Evolution of the gas phase from nucleation sites is driven by the solute mass transfer from the flowing supersaturated water solution to the bubble clusters. Effects of viscous aqueous phase flow and convective diffusion in pore corners are explicitly accounted for. Growth of bubble clusters is characterised by a pattern of quasi-static drainage and fingering in the gas phase, an invasion percolation process controlled by capillary and gravitational forces. A stepwise solution procedure is followed to determine the aqueous flow field and the solute concentration field in the model by solving the conservation equations. Mobilization of bubbles driven by buoyancy forces is also studied. Results of bubble growth pattern, relative permeability and macroscopic mass transfer coefficient are obtained under different gas saturations and aqueous flow conditions.

La connaissance du comportement hydrodynamique et du transfert de matière de la bulle est importante car elle fournira des indications pour la sélection des conditions de fonctionnement et la conception du réacteur dans de tels processus. Cette thèse a réalisé une étude expérimentale pour les bulles d’air isolées en ascension dans diverses solutions de polymères (Breox, Polyacrylamide (PAAm) and Xanthan gum) qui peuvent simuler les propriétés des eaux usées. Les travaux sont divisés en trois parties: Tout d’abord, en dressant l’état de l'art sur les techniques de visualisation pour le transfert de matière, trois techniques ont été testées pour les bulles d’air (diamètre équivalent ≈ 1 mm) en ascension dans l'eau, notamment la fluorescence induite par plan laser (PLIF, fluorophore: résorufine fluorescente), la PLIF avec inhibition (fluorophore: complexe de ruthénium) et techniques colorimétriques (colorant: résorufine rose), respectivement. Par la suite, sur la base des images capturées par une caméra haute vitesse, le comportement hydrodynamique des bulles d'air (diamètres équivalents: 0,7 à 7 mm) s'élevant dans les solutions de polymères (PAAm et Xanthan) a été étudiée, notamment la vitesse, la trajectoire et la forme de la bulle. Enfin, appliquant la technique PLIF-I, les phénomènes de transfert de matière et de diffusion dans le sillage de bulles d'air (diamètre équivalent 1 ≈ mm) dans différentes solutions aqueuses de polymères (PAAm et Breox) ont été étudiés. / The knowledge on the hydrodynamic property and mass transfer of bubbles is important since it will give guidelines for selecting the operation condition and for reactor design in such processes. For this purpose, this PhD manuscript has implemented an experimental investigation of single air bubbles rising in various polymer solutions (Breox, Polyacrylamide (PAAm) and Xanthan gum) which can simulate the property of the sewage. The works can divided into three parts: Firstly, with a review of the current visualization techniques for mass transfer, three techniques have been tested for air bubble (equivalent diameter ≈ 1 mm) rising in water including traditional Planar Laser Induced Fluorescent (PLIF, dye: fluorescent resorufin), Fluorescent quenching technique (PLIF with Inhibition, dye: ruthenium complex) and colorimetric techniques (dye: pink resorufin), respectively. Secondly, based on images captured by a high speed camera, the hydrodynamics of the bubble single air bubbles (equivalent diameters: 0.7-7 mm) rising in the polymer solutions (PAAm and Xanthan) have been investigated including the bubble velocity, trajectory and bubble shape. Finally, based on PLIF-I technique, the mass transfer and diffusion phenomena in the wake of single air bubbles (equivalent diameter ≈ 1 mm) rising in various aqueous polymer solutions (PAAm and Breox) are investigated.

Student Number : 0318397E - MSc dissertation - School of Chemical and Metallurgical Engineering - Faculty of Engineering and the Built Environment / An experimental study of the effects of a slag phase on mass transport in a onefifth water model of a 100ton CLU-converter was conducted. The study was a follow up to earlier investigations conducted in the absence of a simulated slag phase. Kerosene (10% by volume) was used to represent the slag phase in the cold model experiments. The presence of a slag phase increased the mixing time of a tracer solution in the bath. The mixing time, defined at 99.66% bath homogeneity, was found to increase with bath height and a lowering gas flow rate. The functional relationship, Tmix = 4.39Q-0.73W0.24H1.12, was established as expressing the effect of gas flow rate (Q), bath weight (W), and bath height (H) on the mixing time (Tmix). The mixing time increased by an average of 16.3% after slag inclusion. The mass transfer parameter [(Reloc,r)0.25(Ret)0.32] values obtained in the absence of a slag phase decreased by an average of 32.2% with slag inclusion. Calculated mass transfer coefficients increased with gas flow rate and a decrease in bath height. The relationship, K Q0.08, showing derived mass transfer coefficient (K) dependence on the gas flow rate (Q) was established. The proportionality constant in the equation was observed to vary with bath height, gas flow rate and sample location. Contour maps representing variation of mass transfer coefficients in the bath regions were produced.

A one-dimensional porous media model has been developed to investigate water based fire suppression. The model is for heat and mass transfer in porous materials subjected to external water sprays and radiant heating. In the model, heat transfer inside the material occurs by conduction, convection, and phase change. Mass transfer occurs by gas phase diffusion and convection in the liquid and gas phases. Convective mass fluxes are driven by pressure gradients according to Darcy’s Law. Boundary conditions that are appropriate for a range of cases are presented. The model was used, along with experiments, to investigate two scenarios relevant to water based suppression: spray wetting and radiant heating. Ceramic fiberboard samples were used as a test material. For the wetting tests, the model is shown to be able to reasonably predict the rate of water absorption into the samples. Radiant heating tests were conducted in the cone calorimeter with pre-wetted samples. For the heating tests, the model is shown to reasonably predict the drying behavior that would directly precede an ignition event.

Thesis. 1977. Ph.D.--Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / Ph.D.

Le bouchon en liège aggloméré joue un rôle clé dans la conservation des vins effervescents car c’est de lui que dépendent les échanges de gaz (CO2 et O2) entre le vin et le milieu extérieur. L’objectif de cette thèse est de déterminer les propriétés mécaniques et barrières des bouchons en liège aggloméré afin d’identifier les paramètres de formulation pouvant impacter ces propriétés et mettre en avant des points critiques, qu’il est nécessaire de contrôler au cours de la fabrication.La caractérisation de la structure du liège aggloméré a permis de mettre en évidence une porosité intergranulaire importante, qui est fortement réduite lorsque l’on utilise des granulés de liège de plus petite taille et lorsque le bouchon est comprimé dans le goulot.L’étude des propriétés mécaniques du liège aggloméré montre que l’élasticité du matériau augmente avec le taux d’hydratation du matériau, l’utilisation de granulés de liège de petites tailles et l’emploi d’un polymère adhésif dont la proportion de phase cristalline est faible. En revanche, la teneur en adhésif au sein du liège aggloméré semble ne pas avoir d’impact sur les propriétés mécaniques.Concernant les propriétés de transfert des bouchons pour vins effervescent de type A2R, les coefficients de diffusion du CO2 ont été mesurés, pour la première fois, dans les différents composants du bouchon (manche, film de colle, rondelle de liège). Le transfert est essentiellement régit par un mécanisme de diffusion de surface au travers du réseau d’adhésif. Plus le réseau d’adhésif est homogène au sein du corps aggloméré et entre les deux rondelles, plus les propriétés barrières seront élevées. La compression du bouchon dans le goulot augmente fortement les propriétés barrières.Enfin, il semblerait que les propriétés mécaniques et de transfert du liège aggloméré soient peu impactés par le vieillissement à condition toutefois que le réseau de colle polyuréthane ne soit pas en contact direct avec un milieu très concentré en éthanol car dans ce cas des phénomènes de solvolyse entrainent une forte dégradation des propriétés barrières et mécaniques du matériau.Mots clés : Liège naturel, liège aggloméré, structure, propriétés mécaniques, transfert de gaz, diffusion de surface, vieillissement. / The agglomerated cork stopper plays a key role in the preservation of sparkling wines because the gas exchanges (CO2 and O2) between the wine and the external environment depend on the stopper. The objective of this work is to determine the mechanical and barrier properties of agglomerated cork stoppers in order to identify the formulation parameters that can impact these properties, and highlight several critical points, which must be controlled during the process.The characterization of the agglomerated cork structure has revealed a large intergranular porosity, which is greatly reduced when smaller cork granules are used and when the cork is compressed in the bottleneck.The study of the mechanical properties of agglomerated cork shows that the elasticity of the material increases with the hydration of the material, the use of small cork granules and adhesive polymer with a low proportion of crystalline phase. On the other hand, the adhesive content within the agglomerated cork does not seem to have an impact on the mechanical properties.Concerning the transfer properties of agglomerated cork stoppers for sparkling wines, the CO2 diffusion coefficients were measured, for the first time, in the various parts of the stopper (agglomerated body, adhesive film, cork disc). The diffusion is essentially governed by a surface diffusion mechanism through the adhesive network. The more the adhesive network is homogeneous within the agglomerated body and between the two washers, the higher the barrier properties will be. Compression of the cork in the bottleneck greatly increases the barrier properties.Finally, it seems that the mechanical and transfer properties of agglomerated cork are slightly impacted by the aging provided that the network of polyurethane glue is not in contact with a highly concentrated ethanol medium, due to solvolysis phenomena that can occur and thus cause a strong degradation of the barrier and mechanical properties of the material.Keyword: Natural cork, agglomerated cork, structure, mechanical properties, gas transfer, surface diffusion, aging

Bibliography: leaves 114-119.

While clinical transplantation of islets of Langerhans for the treatment of insulin dependent Diabetes Mellitus has shown significant promise in recent years, there remains a need for procedural optimizations to improve cell viability, functionality and ultimately, graft longevity. One of the most critical factors to islet cell survival is the proper oxygenation of these highly metabolic cellular aggregates. In culture, islets experience suboptimal oxygen profiles delimited by steep gradients across culture media. When retransplanted, they are subjected to extremes of hypoxia and anoxia, resulting in pronounced graft dysfunction and cell loss, which is further exacerbated when these cells are immunoisolated in polymer matrices. This study examined the effects of improving both in-vitro culture and immunoisolation of islet cells by optimizing oxygen mass transfer via oxygen carriers in the form of perfluorocarbons. Specifically, new systems for these applications were developed utilizing perfluoromoeities and conventional culture (polydimethylsiloxane) and immunoisolation (sodium alginate) matrices. During in vitro culture of islet cells, the use of perfluoro-impregnated PDMS culture platforms enhanced cell recovery, viability and function over the culture period. Additionally, marginal mass transplants of the islets cultured in these novel platforms functioned better in recipients than relevant controls. In immunoisolation, the optimization of perfluorocarbon emulsions was performed investigating the effects of combinations of surfactants and perfluorocarbons on oxygen mass transfer and cell viability. Emulsions were well characterized using particle size analysis by dynamic light scattering, perfluorocarbon inclusion by gravimetry and oxygen diffusivity measurements utilizing fluorescent optodes. A novel method was developed for the assessment of dissolved oxygen content of these emulsions. Optimal emulsions, as determined by predicted/measured oxygen transfer enhancement over relevant controls, were utilized in alginate matrices for microencapsulation of cell lines, initially, and then, islets of Langehans. The effects of these potential improvements were assessed by in-vitro potency assays, including a novel method for assessing glucose stimulated insulin release, and in transplantation efficacy in rodent marginal mass models. While the improvements in culture were promising in cell line studies, the observed benefit did not translate in islet culture. The cause was found to be related to permeability impediments generated from the surfactant components utilized in emulsion manufacture. In addition to the development of several new methods for the characterization of oxygen containing solutions and the potency assessment of isolated islets of Langerhans, the impact of these studies is important in the field of polymer engineering. We observed that the use of Polyethylene glycol (PEG) based materials may limit transport of nutrients and oxygen critical to cells. Additionally, we developed cell culture platforms that enhance the viability, number and function of cultured islet cells, potentially impacting the clinical realm where cell preservation is critical to transplant outcome.