Inconel 738 (IN 738), like other precipitation-hardened nickel-base superalloys that contain a substantial amount of Al and Ti, is very difficult to weld due to its high susceptibility to heat-affected zone (HAZ) cracking during conventional fusion welding processes. The cause of this cracking, which is usually intergranular in nature, has been attributed to the liquation of various phases in the alloy, subsequent wetting of the grain boundaries by the liquid and decohesion along one of the solid-liquid interfaces due to on-cooling tensile stresses. To address the problem of liquation cracking in weldments, recent developments in welding research have resulted in supposedly exclusive solid-state friction joining processes, such as linear friction welding (LFW), for joining crack susceptible structural alloys. The objective of this work was therefore to investigate the weldability of the difficult-to-weld IN 738 superalloy by LFW and to analyze the resulting microstructural changes in the alloy due to the welding process. LFW was performed on Linear Friction Welding Process Development System (PDS) at the Aerospace Manufacturing Technology Centre of the Institute for Aerospace Research, National Research Council (NRC) of Canada. In order to study and decouple the effect of non-equilibrium thermal cycle and imposed compressive stress during the joining, physical simulation of the LFW process was performed by using Gleeble 1500-D Thermo-Mechanical Simulation System at the University of Manitoba. Detailed microstructural study of welded and Gleeble-simulated materials was carried out. Correlation between the simulated microstructure and that of the weldments was obtained, in that, a significant grain boundary liquation was observed in both the simulated specimens and actual weldments due to non-equilibrium reaction of second phase particles, including the strengthening gamma prime phase. These results show that in contrast to the general assumption of LFW being an exclusively solid-state joining process, intergranular liquation, caused by non-equilibrium phase reaction(s), occurred during the process. However, despite a significant occurrence of liquation in the alloy, no HAZ cracking was observed. Nevertheless, the result showed that crack-free welding by linear friction welding is not due to preclusion of grain boundary liquation as has been commonly assumed and reported. Instead, resistance to cracking can be related to the counter-crack-formation effect of the imposed strain and to a concept observed and reported for the first time in this work, which is strain-induced rapid solidification. Furthermore, microstructural evolution during joining cannot be understood without considering the concept of non-equilibrium liquation reaction and strain-induced rapid solidification of the metastable liquid, which are carefully elucidated in this thesis.

Direct compression has gained significant interest since its advent in the late 1950's due to its potential ease compared to wet granulation. The primary prerequisites for powders used in direct compression are (i) good flow properties (ii) good compressibility and (iii) an acceptable dilution potential to accommodate a relative high percentage of active ingredient. Several filler/binders have been manufactured especially for direct compression and co–processing is one of the recent methods used to produce good compressible excipients with acceptable flow properties. In this study, lactose–based filler/binders were used which included simple and modified lactose materials (Granulac, Lactopress, Flowlac and Tablettose) as well as co–processed excipients (Starlac, Cellactose and Microcelac). A comprehensive literature study on direct compression revealed the importance of the physical properties of filler/binders such as interparticle forces, particle shape, particle size and distribution, powder density, particle surface structure and particle packing geometry which influence the flow of powders. All the materials were subjected to the various tests available to evaluate powder flow, namely (i) angle of repose (AoR), (ii) critical orifice diameter (COD), (iii) flow rate and percentage compressibility (%C) in terms of the powders' bulk and tap densities. The results of these tests confirmed the expected flow properties of the various filler/binders, with only one material exhibiting extremely poor flow properties. The following rank order in terms of all flow tests conducted was established; Starlac >> Microcelac ~ Flowlac >> Cellactose > Tablettose > Lactopress >>> Granulac. The co–processed filler/binders presented with superior flow compared to the other lactose–based materials. During the next phase of the study, the compaction properties of the various fillers were evaluated, employing direct compression. Compacts of pure filler were tabletted on an eccentric tablet press at different compression pressures (manipulated by the upper punch setting of the tablet press). The modified lactose filler/binders (Lactopress, Flowlac and Tablettose) exhibited unexpectedly poor compression profiles, where the co–processed filler/binders (Starlac, Cellactose and Microcelac) produced compacts with acceptable appearance and compact properties. Two lubricants (Mg–St or Pruv), which were tested separately in formulations were added since no compacts could be produced from the pure filler/binders. None of the modified lactose filler/binders, in combination with a lubricant, were able to produce an acceptable compact, since lamination occurred during compression. The co–processed filler/binders produced satisfactory compacts with the addition of a lubricant, but lactose–cellulose fillers (Cellactose and Microcelac) also required the inclusion of a disintegrant (Ac–Di–Sol) to induce satisfactory compact disintegration. Poor compressible active ingredients (paracetamol), which exhibit very poor flow properties, are usually difficult to use during direct compression. Many excipients (tested in this study) are formulated to accommodate these drugs and produce acceptable functional tablets. After identifying the best filler/binders (co–processed fillers), according to their flow and compressible properties, paracetamol was added to the formulations. During a pilot study, the percentage paracetamol these fillers could accommodate in a 400 mg tablet was determined. Both Microcelac and Cellactose could accommodate 24.5% w/w paracetamol, whilst Starlac could only accommodated 19.5% w/w. Paracetamol is well known for its tendency to cause tablet capping and lamination. An acceptable upper punch setting range (20–22) was chosen for tabletting, followed by quality control tests done. All three formulations produced suitable tablets for testing and exhibited good tablet properties. All tablets disintegrated within two minutes, with hardness profiles between 120 N and 148 N and friability percentages less than 1%. Dissolution studies, however, are probably the ultimate test to distinguish between the capability of filler/binders to release the optimum percentage drug after disintegration. Dissolution studies were done on all three formulations using the AUC (area under the curve) and IDR (initial drug release) as parameters to evaluate drug release. All tablets exhibited high initial dissolution rates (between 0.018 - 0.023 mg/min/ml) and 100% drug release was observed. Starlac presented with a lower amount of drug released compared to the other two, but can be explained by the lower percentage (19.5%) paracetamol present in the formulation. It was once again confirmed that the physical and compressible properties of potential directly compressible filler/binders play a major role in direct compression. It was concluded that co–processed filler/binders (Starlac, Microcelac and Cellactose) definitely exhibited better tabletting properties during direct compression. They were able to accommodate a certain percentage of paracetamol, although it was expected that they would accommodate a higher amount (at least 50% of total tablet weight). / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2011.

The Electrochemical Quartz Crystal Microbalance (EQCM) was used as the main investigation tool coupled with other conventional electrochemical methods to study the electrocatalytic properties of polycrystalline Pt electrodes, including two separate projects. The first project studied the early stage of oxide film formation on the Pt surfaces and the inhibition of the catalytic properties by the oxide film. The inhibition of the fast electrode reaction of small molecules by the growth of oxide film allows those molecules to be used as probes for the nature of the oxide film. The hydrogen oxidation current, jox calculated by differencing the cyclic voltammetry currents with and without H₂ present showed a characteristic plateau-to-plateau profile, which implies a transition from the free Pt surface to the Pt surface completely covered by oxide film. This method allows determination of the onset potential for oxide formation and also the critical potential where a full monolayer of oxide is formed. This method applies to other fast surface reactions such as oxygen reduction reaction (ORR), and the results are enhanced by forced convection in the rotating disk electrode (RDE) experiments. The initial oxidation species was identified by charge and EQCM frequency analysis. Our results support the formation of a species with stoichiometry Pt₂O, for example, with an oxygen atom in the bridging position between two adjacent Pt atoms. In the second project, the stability of the Pt electrodes in acid media with Ag⁺ present was investigated. A substantial frequency drift (8.3 Hz cycle⁻¹, or 44 ng cm⁻² cycle⁻¹) was observed during Ag electrodeposition and stripping on the bare polycrystalline Pt surface. Cyclic voltammograms in pure HClO₄ solution showed nearly no frequency drift while the addition of 10⁻³ mol L⁻¹ Ag⁺ resulted in an immediate and characteristic frequency drift. The frequency drift appeared to be consistent with loss of material from the electrode surface and the ICP-MS detected a maximum Pt concentration of 2.3×10⁻⁶ mol L⁻¹ in solution due to Pt dissolution. The Pt concentration calculated from the EQCM frequency drift matched the ICP-MS results. This allowed the EQCM for direct investigation of Pt dissolution at different system temperatures, sweep rates, and potential ranges. The much higher rate of dissolution with Ag present than that in pure HClO₄ solution can be explained by the formation of Pt-Ag alloy during Ag underpotential deposition and the co-dissolution of Pt and Ag.

The oxidative dissolution of chalcopyrite in ferric media often produces incomplete copper recoveries. The incomplete recoveries have been attributed to inhibition caused by the formation of a metal deficient sulphide and the deposition of elemental sulphur and jarosite. Although these phases have been qualitatively identified on the surface of chalcopyrite, none have been quantitatively identified. The aim of the project was to quantitatively analyse the surface before and after oxidative dissolution, with X-ray photoelectron spectroscopy (XPS), and to use the phases identified as the basis for mechanisms of dissolution and inhibition. / XPS analysis was performed on chalcopyrite massive fractured under anaerobic atmosphere and chalcopyrite massive and concentrate oxidised in 0.1 M ferric sulphate (pH 1.9) and 0.2 M ferric chloride (pH 1.6) at 50, 65 and 80ºC. Quantitative XPS analysis of the chalcopyrite surfaces required the development of programs that accounted for the observed XPS spectra. The output of these programs was used to construct profiles of the chalcopyrite surfaces and the deposited phases. These surface profiles were correlated with copper recoveries determined for chalcopyrite concentrate dissolution under the same conditions. / The surface of chalcopyrite before oxidative dissolution reconstructs to form a `pyritic' disulphide phase. This phase is oxidised in ferric media to form thiosulphate via the incorporation of oxygen atoms from the hydration sphere. The thiosulphate reacts in the oxidising conditions of low pH to form elemental sulphur, sulphite and sulphate. The sulphate complexes with ferric to produce hydronium jarosite. This reaction occurs at the surface during the initial stages of dissolution and in the bulk solution during the latter stages. This precipitation of hydronium jarosite during the latter stages of dissolution corresponds to inhibition of the dissolution reaction. It is therefore concluded hydronium jarosite is responsible for inhibiting the oxidative dissolution of chalcopyrite in ferric media. / The identification of hydronium jarosite as the inhibiting phase is consistent with the industrial practice of removing `excess' iron from the ferric solution before oxidative dissolution. However, additional iron and sulphate are generated at the chalcopyrite surface during oxidative dissolution. These high iron and sulphate concentrations combine with the low pH and high temperatures favoured for the oxidative dissolution of chalcopyrite to produce ideal conditions for jarosite precipitation. Therefore, pH must be lowered further to prevent jarosite precipitation and enhance copper recoveries from chalcopyrite in ferric media.

Lors du dimensionnement des ouvrages en terre : remblais, digues, on observe que la plupart des matériaux sont compactés à l’optimum Proctor ou coté humide. En général, ce compactage implique que le sol se trouve dans un état où le degré de saturation est très élevé. Cruz et al (1985) ont montré qu'à un degré de saturation élevé (supérieur à 85%, voire 90% dans le cas de certains sols), la phase liquide est continue alors que l’air présent sous forme de bulles est occlus ; ce qui rend le comportement du sol complexe. L’élaboration d’un modèle de comportement pour ce type de sols nécessite une compréhension approfondie des phénomènes physico-mécaniques intervenant au sein de l’air occlus, de l'eau liquide contenant de l'air dissous et du squelette solide. Dans ce sens, un nouveau modèle hydromécanique a été développé. Ce modèle prend en compte le comportement physico-mécanique et la cinématique propre de chacun des constituants du milieu polyphasé (eau liquide, air dissous, air sous forme gazeuse et matrice solide). En particulier, dans ce modèle, nous tenons compte de la tension de surface, de la migration des phases gazeuse et liquide qui ont des impacts importants sur le comportement mécanique des sols. Le développement du modèle conduit à un système d’équations aux dérivées partielles fortement non linéaire qui peut être résolu numériquement en utilisant la méthode des éléments finis. Ce nouveau modèle a été implémenté dans un code de calcul écrit en C++ « Hydromech », développé à l'origine par Pereira (2005), qui permet de simuler les essais oedométriques suivant différents trajets de chargement hydromécanique. En particulier, ce code de calcul permet de simuler de façon cohérente la transition entre différents régimes de saturation, aussi bien dans l'espace (translation progressive d'une frontière entre deux régimes voisins) que dans le temps (passage d'un régime à l'autre en un point donné) ; ce qui constitue un problème de modélisation difficile. Les études numériques réalisées montrent que ce modèle donne des résultats cohérents et mettent en évidence sa capacité à simuler avec précision le comportement hydromécanique des sols quasi-saturés comportant de l'air occlus. / The behaviour of quasi-saturated materials is an important factor to be considered when designing cuttings and embankments in which earthwork materials are compacted to the optimum proctor density. Typically, soil compaction is performed at the optimum Proctor or on the wet side of the optimum, which means that the soil is in a highly saturated state. Cruz et al (1985) have shown that at a high degree of saturation (greater than 85% or even 90% in the case of certain soils), the liquid phase is continuous whereas the gas phase in the form of entrapped air bubbles is discontinuous. It is the presence of the entrapped air bubbles which makes the soil behaviour complex. The construction of a theoretical model for this type of soils requires the consideration of various physical-mechanical phenomena and their couplings occurring within the tri-phasic medium consisting of the solid grains, liquid water containing dissolved air and the entrapped air bubbles. In this sense, a new hydromechanical model has been developed that takes into account the physical-mechanical interactions between different phases as well as the kinematics of each constituent (liquid water, dissolved air, gaseous air and solid grains). In particular, the model accounts for the interfacial tension, migration of gaseous and liquid phases, which have important impacts on the mechanical behaviour. The development leads to a system of highly non-linear partial differential equations which can be solved numerically using the finite element method. This new model has been implemented in a numerical code “Hydromech” written in C++, developed originally by Pereira (2005) that has been used to simulate oedometer tests with different hydromechanical loading paths. In particular, this code allows to simulate consistently the transition across different regimes of saturation, both with respect to space (progressive translation of a boundary between two neighbouring regimes) and to time (transition of one regime to another at a fixed material point); which constituted a difficult modelling problem at the start. Numerical studies carried out show that this model gives consistent results providing a clear demonstration of its ability to simulate with precision the hydro-mechanical behaviour of quasi-saturated soils containing entrapped air.

Kaletra® (lopinavir e ritonavir) é uma combinação fixa de dois inibidores da protease do vírus da imunodeficiência humana (VIH) indicada para o tratamento da infecção pelo VIH em associação com outros anti-retrovirais. Esta classe de fármacos inibe a protease do VIH evitando a clivagem da poliproteina gag-pol, levando à produção de vírus imaturos, incapazes de infectar outras células. Este trabalho teve como objetivo estabelecer o perfil de dissolução in vitro baseado nos dados in vivo, avaliar a estabilidade térmica do lopinavir e do ritonavir cápsulas, determinar a cinética de reação, isolar e identificar os principais produtos de degradação do ritonavir. Método por CLAE indicativo de estabilidade foi desenvolvido e validado para a quantificação do lopinavir e do ritonavir cápsulas. Método alternativo por espectrometria derivada também foi desenvolvido. Os resultados demonstraram uma correlação nível A entre o perfil de dissolução in vitro e a absorção in vivo nas condições propostas. O método por CLAE para a quantificação desta associação demonstrou ser específico, linear exato, preciso e robusto. O teste t demonstrou que houve diferença significativa entre o método CLAE e UV derivada. Os estudos de estabilidade térmica demonstraram que o lopinavir foi estável nas condições testadas enquanto que o ritonavir foi sensível ao calor, seguindo uma cinética de degradação de primeira ordem. De acordo com os resultados da RMN os principais produtos de degradação do ritonavir são os compostos de fórmula molecular C33H45N5O5S e C25H33N3O6. / Kaletra® (lopinavir and ritonavir) is a combination of two human immunodeficiency virus (HIV) protease inhibitors indicated as part of a multi drug therapy along with other antiretroviral agents. This class of drugs inhibits the HIV protease preventing cleavage of the gag-pol polyprotein, reducing the probability of viral particles reaching a mature, infectious state. The objective of this work was: to establish the in vitro dissolution profile based on in vivo data; to determine their thermal stability in the dosage form; to determine their kinetics of degradation and to isolate and identify their major products of degradation. A stability indicating method was developed and validated for simultaneous quantitation of both drugs in Kaletra®, using liquid chromatography. An alternative method using UV-derivative spectrometry was also proposed. The result showed a level A correlation between the in vitro dissolution profile and in vivo absorption under the proposed conditions. The LC method was fully validated and have shown to be stability indicating. The UV-derivative method showed not to be equivalent (t-test) to the LC method. Thermal stability studies have shown that lopinavir was very stable under the conditions tested while ritonavir was sensitive to heat, following a first order degradation kinetic. According to NMR results ritonavir the main degradation products have the molecular formula C33H45N5O5S and C25H33N3O6.

Currently at the Savannah River Site (SRS), there are fifteen single-shell, 3.6-million liter tanks containing High Level Waste. To close the tanks, the sludge must be removed. Mechanical methods have had limited success. Oxalic acid cleaning is now being considered as a new technology. This research uses sample results and chemical equilibrium software to develop a preferred flowsheet and evaluate the acceptability of the system impacts. Based on modeling and testing, between 246,000 to 511,000 l of 8 wt% oxalic acid were required to dissolve a 9,000 liter Purex sludge heel. For SRS H-Area modified sludge, 322,000 to 511,000 l were required. To restore the pH of the treatment tank slurries, approximately 140,000 to 190,000 l of 50 wt% NaOH or 260,000 to 340,000 l of supernate were required. When developing the flowsheet, there were two primary goals to minimize downstream impacts. The first was to ensure that the Resultant oxalate solids were transferred to DWPF, without being washed. The second was to transfer the remaining soluble sodium oxalates to the evaporator drop tank, so they do not transfer through or precipitate in the evaporator pot. Adiabatic modeling determined the maximum possible temperature to be 73.5°C and the maximum expected temperature to be 64.6°C. At one atmosphere and at 73.5°C, a maximum of 770 l of water vapor was generated, while at 64.6°C a maximum 254 l of carbon dioxide were generated. Although tank wall corrosion was not a concern, because of the large cooling coil surface area, the corrosion induced hydrogen generation rate was calculated to be as high as 10,250 l/hr. Since the minimum tank purge exhaust was assumed to be 5,600 l/hr, the corrosion induced hydrogen generation rate was identified as a potential concern. Excluding corrosion induced hydrogen, trending the behavior of the spiked constituents of concern, and considering conditions necessary for ignition, energetic compounds were shown not to represent an increased risk Based on modeling, about 56,800 l of Resultant oxalates could be added to a washed sludge batch with minimal impact on the number of additional glass canisters produced. For each sludge batch, with 1 to 3 heel dissolutions, about 60,000 kg of sodium oxalate entered the evaporator system, with most collecting in the drop tank, where they will remain until eventual salt heel removal. For each 6,000 kg of sodium oxalate in the drop tank, about 189,000 l of Saltstone feed would eventually be produced. Overall, except for corrosion-induced hydrogen, there were no significant process impacts that would forbid the use of oxalic acid in cleaning High Level Waste tanks. / MATHEMATICAL SCIENCES / M. Tech. (Chemical Engineering)

This dissertation examines the figures of the shaman and the cyborg, arguing that both act as intermediaries between the organic world of bodies and the artificial world of culture and machines. Using the sf of Robert Holdstock, David Zindell and Kathleen Ann Goonan as starting points, new forms of embodiment in the context of the cyborg and the shaman's shared narrative of radical boundary dissolution are critically and imaginatively examined. Throughout this thesis, the works of Deleuze and Guattari, Sadie Plant, Manuel De Landa, Erik Davis, Donna Haraway, Terence McKenna, and other speculative theorists who operate at the nexus of technological culture and the shamanic imagination serve as guidelines. / English Studies / M.A.

Entacapona, inibidor da catecol-o-metiltransferase, é utilizada como terapia adjuvante à associação de levodopa + carbidopa no tratamento da doença de Parkinson. No Brasil encontra-se disponível na forma de comprimidos revestidos com o nome comercial de Comtan®. O objetivo desse trabalho foi desenvolver e validar métodos analíticos para o controle de qualidade da entacapona em comprimidos revestidos e método de dissolução, bem como, estudos preliminares de estabilidade durante o desenvolvimento do método indicativo de estabilidade por cromatografia líquida de alta eficiência (CLAE) e na determinação da cinética de fotodegradação. Devido à falta da substância química de referência de entacapona, realizou-se a extração do fármaco a partir dos comprimidos e a caracterização qualitativa e quantitativa por calorimetria diferencial de varredura (DSC), espectrofotometria na região do infravermelho (IV), ressonância magnética nuclear (RMN) e volumetria em meio não-aquoso. Métodos utilizando cromatografia em camada delgada (CCD), espectrofotometria na região do ultravioleta (UV) e CLAE foram utilizados para análise qualitativa de entacapona. A validação dos métodos para determinação quantitativa (UV e CLAE) foi realizada de acordo os parâmetros das principais Guias Oficiais (BRASIL, 2003; ICH, 2005; USP 30, 2007). O método de dissolução foi desenvolvido e validado de acordo com a USP. Os métodos qualitativos e quantitativos descritos nesse trabalho demonstraram-se adequados para determinação de entacapona em comprimidos revestidos. Para o método de dissolução as seguintes condições foram selecionadas: solução tampão acetato pH 5,3 como meio, utilizando pás a 50 rpm. A cinética de fotodegradação em metanol, frente à luz UV indicou reação de segunda ordem. Análises por CLAE-EM/EM sugerem que o produto de fotodegradação formado seja o isômero geométrico de entacapona (Z-entacapona). / Entacapone, inhibitor of the catechol-O-methyltransferase, is used as adjunct with levodopa + carbidopa association in the treatment of Parkinson’s disease. In Brazil it is available in tablets coated with the commercial name of Comtan®. The aim of this work was to develop and validate analytical methods for the quality control of entacapona in coated tablets, as well as, preliminary studies of stability during the development of stability-indicating high-performance liquid chromatography (HPLC) method and determination of photodegradation kinetics. Due to the lack of entacapone reference standard, it was necessary to extract the drug by the tablets and the qualitative and quantitative characterization was carried out by differential scanning calorimetry (DSC), infrared spectroscopy (IR), nuclear magnetic resonance (NMR) and non-aqueous titration of weak acid. Methods using thin-layer chromatography (CCD), ultraviolet spectroscopy (UV) and HPLC were performed to entacapone qualitative analysis. The validation of the methods for quantitative determination (UV and CLAE) was accomplished of agreement the parameters of the main Official Guides (BRASIL, 2003; ICH, 2005; USP 30, 2007). The dissolution test was developed and validate in according by USP. The qualitative and quantitative methods described in this study demonstrated to be adequate to determination of entacapone in coated tablets. For dissolution test the following conditions were selected: buffer acetate pH 5,3 as medium, using paddles at 50 rpm. The photodegradation kinetics in methanol, front to UV light indicated the second-order reaction. LC-MS/MS method results suggest that the photodegration product was the geometric isomer of entacapone (Z-entacapone).

La circulation de l’eau souterraine dans les aquifères contenants des roches évaporitiques peut provoquer des problèmes géo-mécaniques tels que l'affaissement du sol ou l'effondrement. Dans ce travail, nous nous intéressons au développement de modèles numériques permettant de simuler les écoulements dans les milieux poreux et non poreux ainsi que les phénomènes de dissolution et d’évolution des fractures dans le temps. La première partie de cette thèse est consacrée au développement de nouvelles solutions pour la validation des modèles numériques simulant les écoulements densitaires en milieux poreux. La nouvelle procédure consiste à résoudre simultanément les deux systèmes d’écoulement et de transport en utilisant l’algorithme de Levenberg-Marquardt. L’utilisation de cette technique nous a permis de développer, pour la première fois, des solutions semi-analytiques d’intrusion d’eau salée dans le cas de faible diffusion ainsi que dans le cas d’un grand contraste de densité. Dans la deuxième partie de ce travail, nous nous sommes intéressés aux écoulements dans les fractures des roches évaporitiques. Un code de calcul a été développé pour résoudre ce système non linéaire en utilisant des méthodes numériques adaptées. Pour valider ce nouveau modèle, nous avons développé une solution semi-analytique pour les écoulements densitaires de Stokes. La troisième partie de ce travail est consacrée au transport avec dissolution de la roche salée. Dans un premier temps, nous avons étudié l’influence de différents paramètres sur la dissolution du sel dans l’Adler tunnel situé à une profondeur de 160 m dans la région de Bâle en Suisse. Dans un second temps, nous nous sommes intéressés à la simulation de l’évolution dune fracture sous l’effet de la dissolution. Le modèle numérique développé prend en compte les écoulements de Stokes ainsi que le transport de masse avec effets densitaires et la dissolution des parois de la fracture. / The groundwater flow in aquifers contain evaporite rocks can cause problems such as geo-mechanical subsidence or collapse. In this work, we focus on the development of numerical models to simulate the flow in porous and non-porous domains in order to study the dissolution phenomenon and fractures evolution over time. The first part of this thesis is devoted to developing new solutions for the validation of numerical models to simulate density driven flow in porous media. The new procedure consist of solving simultaneously the flow and the transport equations using the Levenberg-Marquardt algorithm. The use of this technique allowed us to develop, for the first time, semi-analytical solutions of saltwater intrusion in the case of small diffusion and in the case of a large density contrast. In the second part of this work, we studied the flow in evaporitic rocks. A numerical code was developed to solve the nonlinear system using advanced numerical methods. To validate this new model, we have developed a semi-analytical solution for the density Stokes flow. The third part of this work is devoted to transport with dissolution of rock salt. As a first step, we studied the influence of various parameters on the dissolution of salt in Adlertunnel located at a depth of 160 m in the region of Basel in Switzerland. In a second step, we are interested in the simulation of the fracture’s evolution as a result of the dissolution. The numerical model takes into account the Stokes flow and mass transport effects and dissolution of the fracture walls.