Ce travail s’inscrit dans le cadre de nos recherches sur les écoulements à bulles. C’est l’étude expérimentale du mélange d’un traceur très peu diffusif (fluoresceine dans l’eau) dans l’écoulement instationnaire engendré par le passage d’un écoulement uniforme au travers d’un réseau d’obstacles sphériques (2% de fraction volumique) répartis aléatoirement dans l’espace. Cet écoulement reproduit correctement les caractéristiques de l’agitation dans un essaim de bulles en ascension. La vitesse du fluide est mesurée par PIV de manière assez classique. Le traceur est injecté en amont du réseau et l’´evolution de sa concentration est mesurée par PLIF. L’utilisation de la PLIF pour mesurer des champs de grande extension (15 cm) et avec une grande dynamique d’intensité lumineuse fluorescée constitue une contribution importante de ce travail. Les résultats ainsi obtenus montrent que, à petit nombre de Reynolds, le mélange est régi par les forts gradients de vitesse qui existent dans le voisinage des sphères. A grand nombre de Reynolds, il est maîtrisé par la turbulence qui se développe alors. L’analyse des résultats comporte deux parties principales : (1) une analyse statistique des profils de concentration aboutissant à la détermination d’un coefficient de diffusion effectif et (2) une description de la distribution spectrale des fluctuations de vitesse et de concentration. / This research is a part of our research about bubbly flows. Experiments are performed about mixing of a high Schmidt scalar component (fluorescein in water) by the agitation generated by the flow through a random array of fixed spheres (at high Re and with a volume fraction of solid equal to 2%). This flow mimics for a great part the agitation in the liquid phase of a bubble swarm rising in a liquid otherwise at rest. The velocity of the liquid is estimated from PIV measurements. The scalar is injected through a point source in the array and the evolution of its concentration is estimated by PLIF method. An important part of this research is the measurement of large fields of concentration (15 cm) with a good precision by PLIF. The results show that, at moderate Reynolds number (100), mixing is controled by the steep velocity gradients located near the spheres, while, at large Reynolds number, it is controled by the turbulence that develops. The analysis of the results is composed of two parts : (1) the statistical analysis of the spatial distribution of scalar concentration, and the determination of an effective diffusion coefficient, (2) a spectral analysis of the velocity and concentration fields.

Estimation of effective diffusion coefficients is essential to be able to describe the diffusive transport of solutes in porous media. It has been shown in theory that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by their tortuosity (tensor). To estimate the apparent diffusion coefficients, the values of tortuosity and porosity should be known first. In contrast with calculation of porosity, which can be easily obtained, estimation of tortuosity is intricate, particularly with increasing micro-geometry complexity in porous media. Moreover, many engineering materials (e.g, clays and shales) are characterized by electrical surface charges on particles of the porous material which can strongly affect the diffusive transport properties of ions. For these materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying microscale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters. / In the first part of this thesis a numerical method based on a recently proposed up-scaled Poisson-Nernst-Planck type of equation (PNP) and its microscale counterpart is employed to estimate the tortuosity and thus the effective and apparent diffusion coefficients in thin charged membranes. Beside this, a new mathematical approach for estimation of tortuosity is applied and validated. This mathematical approach is also derived while upscaling of micro-scale Poisson-Nernst-Planck system of equations using the volume averaging method. A variety of different pore 2D and 3D micro-geometries together with different electrochemical conditions are studied here. To validate the new approaches, the relation between porosity and tortuosity has been obtained using a multi-scale approach and compared with published results. These include comparison with the results from a recently developed numerical method that is based on macro and micro-scale PNP equations. / Results confirm that the tortuosity value is the same for porous media with electrically uncharged and charged particles but only when using a consistent set of PNP equations. The effects of charged particles are captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this ratio allows to consistently take into account electro-chemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations. / Steady-state diffusion studies dominate this thesis; however, understanding of transient ion transport in porous media is also important. The last section of this thesis briefly introduces transient diffusion through bentonite. To do so, the micro Nernst-Planck equation with electro-neutrality condition (NPE) is solved for a porous medium which consists of compacted bentonite. This system has been studied before in another research using an experimental approach and the results are available for both transient and steady-state phases. Three different conditions are assumed for NPE governing equations and then the numerical results from these three conditions are compared to the experimental values and analytical phenomenological solution. The tortuosity is treated as a fitting parameter and the effective diffusion coefficient can be calculated based on these tortuosity values. The results show that including a sorption term in the NPE equations can render similar results as the experimental values in transient and steady state phases. Also, as a fitting parameter, the tortuosity values were found varying with background concentration. This highlights the need to monitor multiple diffusing ion fluxes and membrane potential to fully characterize electro-diffusive transport from fundamental principles (which have been investigated in first part of this thesis) rather than phenomenological equations for predictive studies. / This research has lead to two different journal articles submissions, one already accepted in Computers and Geotechnics (October 22, 2009, 5-yrs Impact Factor 0.884) and the other one still under review.

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Accuracy in the effective diffusion coefficient of the gas diffusion layer (GDL)/microporous layer (MPL) is important to accurately predict the mass transport limitations for high current density operation of polymer electrolyte membrane (PEM) fuel cells. All the previous studies regarding mass transport limitations were limited to pure GDLs, and experimental analysis of the impact of the MPL on the overall diffusion in the porous GDL is still lacking. The MPL is known to provide beneficial water management properties at high current operating conditions of PEM fuel cells but its small pore sizes become a resistance in the diffusion path for mass transport to the catalyst layer. A modified Loschmidt cell with an oxygen-nitrogen mixture is used in this work to determine the effect of MPL on the effective diffusion coefficients. It is found that Knudsen effects play a dominant role in the diffusion through the MPL where pore diameters are less than 1 μm. Experimental results show that the effective diffusion coefficient of the MPL is only about 21% that of its GDL substrate and Knudsen diffusion accounts for 80% of the effective diffusion coefficient of the GDL with MPL measured in this study. No existing correlations can correlate the effective diffusion coefficient with significant Knudsen contribution.

Accuracy in the effective diffusion coefficient of the gas diffusion layer (GDL)/microporous layer (MPL) is important to accurately predict the mass transport limitations for high current density operation of polymer electrolyte membrane (PEM) fuel cells. All the previous studies regarding mass transport limitations were limited to pure GDLs, and experimental analysis of the impact of the MPL on the overall diffusion in the porous GDL is still lacking. The MPL is known to provide beneficial water management properties at high current operating conditions of PEM fuel cells but its small pore sizes become a resistance in the diffusion path for mass transport to the catalyst layer. A modified Loschmidt cell with an oxygen-nitrogen mixture is used in this work to determine the effect of MPL on the effective diffusion coefficients. It is found that Knudsen effects play a dominant role in the diffusion through the MPL where pore diameters are less than 1 μm. Experimental results show that the effective diffusion coefficient of the MPL is only about 21% that of its GDL substrate and Knudsen diffusion accounts for 80% of the effective diffusion coefficient of the GDL with MPL measured in this study. No existing correlations can correlate the effective diffusion coefficient with significant Knudsen contribution.

The main aim of this thesis is the utilization of simple diffusion techniques for the study on transport properties of copper ions in the systems containing humic acids with respect to the other parameters, which can affect the process (the structure of diffusion environment, the interactions between transported specie and diffusion matrices, selective blocking of binding sites of humic acids). The first part of experimental works was focused on characterization of studied materials (humic acids, humic sol and humic hydrogel). The main part of the thesis was dealing with the optimization of simple diffusion techniques, which were suitable for the study on transport of copper ions in matrices containing humic acids, taking into account the mutual interactions between studied components in the system. The obtained diffusion characteristics were compared to the data determined using sorption experiments. Consequently, the minor goal of the experimental works of this thesis was also the assessment of the influence of basic physico-chemical parameters of studied materials on transport phenomenon.

Presented diploma thesis focuses on the study of diffusion of cupric ions in humic acid gels. A total of fifth different standards of humic acids and one sample humic acid prepared from same source as in bachelor's thesis, on which this thesis continues, were used for preparation solutions of humic acids. Thereafter, these solutions were used for preparation of agarose hydrogels, which were necessary in following diffusion experiments. The objective of the work was to compare transport properties of humic standards between themselves and then compare standards with humic acid prepared from same source as in bachelor's thesis. Measure, which was used to determine the transport properties, was comparison of effective diffusion coefficients. Method of instantaneous planar source diffusion was used to compare them. This method was based monitoring temporal evolution of diffusion profiles of cupric ions in humic hydrogels. Copper ions were selected as diffusing medium because of their high affinity and strong bonds to humic acids.