<p>This thesis deals with the heat evolution duringsolidification and its relation to the formation of porosity.It intends to improve the current understanding of theformation of porosity in cast materials with special interestin nodular cast iron and the spray forming process. Twodifferent systems, a Fe-based alloy, Cast iron, and a Ni-basedalloy, Inconel 625, are examined. The effect on the heatevolution of the morphology and the processing parameters inspray forming are treated.</p><p>An evaluation of the microstructural features, segregationbehavior and physical properties such as latent heat of fusionis performed byusing thermal analysis under cooling ratesranging from 0.1 to 104 K/s. In order to achieve this amodified differential thermal analysis (DTA) equipment, amirror furnace and levitation casting are used. Results arepresented in terms of the fraction of solidified, the coolingrate and the microstructure observed. The measured latent heatof fusion is not constant throughout the solidificationprocess. Variations in morphology and cooling rate affect therelease of the latent heat.</p><p>A thermodynamic model is used to describe the experimentalobservations and to explain the formation of pores in nodularcast iron by taking into consideration the formation of latticedefects during the liquid/solid transformation. In this casethe formation of porosity is regarded as a consequence ofchanges in the volume fraction ratio graphite/ during thesolidification process.</p><p>A numerical model of the spray forming process is developedby means of CFD modelling and compared with experimentalmeasurements performed in an industrial facility. Stagnationpressure measurements provided information about the gas flowvelocity and an analysis of the overspray powder providedinformation about the particle thermal history. Evaluation ofthe deposit was also performed. It is observed that the processconditions in spray forming promote non-equilibriumsolidification even though solidification at the deposit occursat a lower rate. In this case the porosity formed near theinterface substrate/deposit depends largely on the substratetemperature. The presence of certain reactive elements, such astitanium, affects the porosity levels in the rest of thedeposit.</p><p><b>Keywords:</b>Thermal Analysis, Nodular Cast Iron, Inconel625, CFD, Flow Assesment, Multiphase Flow, Spray Deposition,Microporosity, Superalloys</p>

De nouveaux matériaux métalliques nanoporeux à base d’éléments n’appartenant pas à la famille du Pt ont été synthétisés par le "dealloying" (ou dissolution sélective) d’alliages rapidement solidifiés. L’objectif est d’examiner les propriétés catalytiques en vue d’utilisation dans des piles à combustible alcalines directes ou en tant que substrats actifs pour la spectroscopie SERS. Des surfaces et des matrices nanostructurées de cuivre de morphologie très fines et une forte surface spécifique ont été obtenues respectivement par le dealloying aqueux de rubans CuxCa100-x amorphe (35 <x< 80 % at.) et par le dellaoying chimique d’échantillons massifs de Cu90(HfZr)10. Des substrats nanoporeux d’Ag et de Co ont été produits par dealloying en retirant les phases riches en Cu et Si de rubans M38,75Cu38,75Si22,5 cristallin (avec M = Co ou Ag). En complément des techniques de caractérisations conventionnelles, toutes les structures nanoporeuses ont pu être reconstruites par nanotomographie à partir de découpes FIB. Des outils numériques spécifiques à la nanotomographie de visualisation et de cartographie en 3 dimensions ont permis de révéler la diversité morphologique des trois systèmes avec la porosité traversante. Ces matériaux ont pour la première fois été étudiés pour leur utilisation pratique en tant que catalyseurs anodiques auto-supportés. Cette étude suggére qu’ils constituent une alternative sérieuse aux composites commerciaux instables à base de Pt et supportés par du C. Des essais électrochimiques en demi-cellule ont montré une excellente activité catalytique vis-à-vis de l’oxydation d’un combustible en borane ainsi qu’une stabilité de fonctionnement supérieure dans un environnement alcalin en comparaison d’un catalyseur Pt/C. Le Co nanoporeux a montré dans des conditions similaires une meilleure efficacité mais une stabilité moindre, attribuée à la composition chimique complexe de son réseau poreux. Le Cu nanoporeux n’a pas été étudié pour les applications mentionnées précédemment en raison de sa grande fragilité. Il est suggéré d’améliorer la voie de synthèse de son précurseur pour augmenter sa tenue mécanique. Enfin le comportement mécanique de ces nouveaux matériaux métalliques nanoporeux a été abordé par des mesures de nanoindentation sur des substrats nanoporeux d’Ag. L’étude a permis de proposer un modèle phénoménologique de dépendance entre la charge et le déplacement pour cette classe de matériaux métalliques. / New nanoporous metallic materials based on non-Pt group metals have been synthesized via dealloying of rapidly solidified alloys and aimed to demonstrate competitive catalytic performance in the field of direct alkaline fuel cells and SERS-active substrates. Nanostructured copper surface and nanoporous copper matrix with very fine morphology and specific surface area were obtained by chemical dealloying of bulk Cu90(HfZr)10 and melt-spun amorphous CuxCa100-x (x ranging from 35 to 80 at.%) family of alloys accordingly. Nanoporous silver and cobalt substrates were produced by dealloying of M38.75Cu38.75Si22.5 crystalline ribbons (M = Co and Ag) as a result of the removal of Cu and Si-rich phases. In addition to conventional characterization methods, all nanoporous structures have been reconstructed by FIB-nanotomography, clearly exposing the morphological diversity of the three systems with transversal porosity when visualized and color-mapped in 3D by a special numerical tomography tool. It is for the first time that a practical significance of these materials has been explored in the scope of self-supported anodic catalysts, suggested throughout this study as an alternative to the unstable Pt-based carbon-supported commercial composites. Half-cell electrochemical tests demonstrated an excellent catalytic activity towards the oxidation of a borane fuel and superior stability of functioning in the alkaline environment compared to Pt/C catalyst. In similar conditions, nanoporous Co showed higher efficiency but lower stability, attributed to the complex chemical composition of its porous scaffold. Nanoporous Cu has not been exploited for the mentioned applications due to its high brittleness and is suggested to go through improvements on the step of precursor synthesis. Lastly, while exploring the mechanical behavior of the NPMs by instrumented nanoindentation of different nanoporous Ag substrates, a load-displacement dependence phenomenological model has been suggested for this class of metallic materials

Les carbonates microporeux sont caractérisés par une importante hétérogénéité de faciès (texture, composition) qui se traduit généralement par une très grande variation des (1) propriétés physiques (porosité, perméabilité, vitesses acoustiques), et (2) du comportement mécanique. Ces hétérogénéités rendent souvent difficile les prédictions en termes de stockage géologique, de qualité de porosité ou perméabilité des réservoirs d'eau souterraine ou d'hydrocarbures lors de l'exploration ou production. Cette étude intégrée apporte de nouveaux éléments de réflexion quant aux facteurs de contrôles microstructuraux sur les propriétés physiques et mécaniques des roches carbonatées microporeuses.(1) Une centaine d'échantillons de carbonates a été prélevée tous les 2m environ le long du forage EST205 au niveau de la plate-forme oxfordienne de Meuse/Haute-Marne. Un objectif appliqué de ce travail, vise à mieux contraindre les variations verticales des propriétés pétrophysiques et pétrographiques qui régissent en grande partie les circulations aquifères actuelles dans cette formation. D'un point de vue fondamental, un résultat majeur est la mise au point d'une nouvelle méthode de rock-typing pour les réservoirs microporeux, et l'établissement d'un lien entre matrice micritique et les propriétés physiques. Les propriétés de transport (perméabilité, conductivité électrique) sont grandement influencées par la réduction ou l'augmentation progressive de la microporosité intercristalline selon le type de matrice micritique considéré. L'augmentation des vitesses d'ondes acoustiques peut être vue comme le reflet d'une cimentation progressive des particules de micrites, qui rend l'ensemble de la matrice plus rigide et cohérente. La dispersion des valeurs de vitesses est expliquée grâce à la théorie de la poroélasticité. Les calculs réalisés avec les équations de Biot-Gassmann [Biot, 1956 ; Gassmann, 1951] mettent en évidence une population de microcracks (crack porosity), qui affecte les vitesses de propagation des ondes. Enfin, une origine possible des niveaux poreux oxfordiens est une dissolution précoce des particules de micrites via la circulation d'eau météorique sous saturée par rapport à la calcite, lors de courtes phases d'émersion de la plate-forme.(2) La vitesse de propagation des ondes P dans la formation de l'Oolithe Blanche (Grainstone Oolithique, Jurassique Moyen, Basin de Paris) est très largement contrôlée par la structure de l'espace poreux (porosité annulaire ou uniforme dans les grains ; Type A) et par la présence ou l'absence d'un ciment isopaque autour des grains (Type B) (Makhloufi et al., 2013 ; Casteleyn et al., 2010, 2011). Plusieurs essais de déformation triaxiale ont été réalisées sur des échantillons de Type A et B afin d'investiguer le rôle de telles microstructures sur la réponse mécanique des roches carbonatées poreuses. Cette étude est essentielle à la compréhension générale de l'Oolithe Blanche, qui présente un fort potentiel géothermique et représente une cible potentielle pour la séquestration de CO2.Les échantillons comparés présentent des textures et faciès équivalent (porportion de ciment de blocage, granulométrie), ainsi que des propriétés pétrophysiques très similaire (porosité, perméabilité) ; afin que le paramètre microstructural soit le seul à varier.Deux comportements distincts sont mis en évidence :Type A: les échantillons avec une microporosité uniforme dans les grains ont un comportement ductile, tandis que les échantillons à porosité annulaire sont caractéristiques du domaine fragile.Type B: les échantillons avec des ciments isopaques autour des grains ont un comportement fragile. En revanche, les échantillons dépourvu de tels ciments présentent un comportement mécanique relevant plus du domaine ductile.Ces résultats montrent que les structures de porosité et les ciments jouent un rôle important sur la réponse mécanique des roches carbonatées microporeuses. / This integrated study provides significant insight into parameters controlling (1) the acoustic and reservoir properties of microporous limestone and (2) the mechanical behavior of such rocks. This work improves the knowledge of the relationships among rock physic and rock mechanic on one hand, and the microstructural content on the other hand.(1) Petrophysical properties measured from laboratory and logging tools (porosity, permeability, electrical conductivity and acoustic properties) have been coupled with thin section and SEM observations on the EST205 borehole from the Oxfordian limestone aquifer of the Eastern part of the Paris Basin. A major achievement is the establishment of the link between micrite microtexture types (particle morphology and nature of inter-crystal contacts) and the physical response. Fluid-flow properties are enhanced by the progressive augmentation of intercrystalline microporosity and associated pore throat diameter, as the coalescence of micrite particle decreases between relatively coarser tight morphologies and microporous morphologies. The slow increase of P-wave velocity can be seen as a reflection of crystal size and growing contact cementation leading to a more cohesive and stiffer micrite microtexture. By applying poroelasticity theory on our samples, we show that velocity dispersion can be a very useful tool for data discrimination in carbonates. Finally, a possible origin of high porous levels in neritic limestones is a mineralogical dissolution of carbonates through freshwater-related diagenesis during subaerial exposure time.(2) Regarding rock mechanic, conventional triaxial experiments were performed on samples from the Oolithe Blanche formation (Middle Jurassic Limestone, Paris basin) to investigate the effect of different microstructural parameter on the mechanical behavior of microporous carbonate rocks. Type A samples display two different microporosity distributions within the grains (uniform versus rimmed microporosity) and type B samples are based on the presence/absence of an isopachous cement around the ooids. This work is of primary importance since the Oolithe Blanche formation, a deep saline aquifer, is a possible target for CO2 sequestration and geothermal production in the center of the Paris Basin. Experiments were performed under saturated state with respectively two sets of experimental conditions: (1) a 5 MPa pore pressure and a 28 MPa confining pressure with a temperature of 55°C for Type A carbonates to mimic in-situ conditions in the Center of the Paris Basin; and (2) a 0.5 MPa pore pressure and a 1.5 MPa confining pressure for Type B samples. Sample types have similar facies and composition (oolithic microporous grainstone with a 500µm average grain size), and porosity ranges from 17% to 20%. Permeability values are also very similar and range from 10-2 mD to 10-1 mD.(1) Type A samples with a rimmed porosity display a typical behavior of the brittle failure regime with stress-strain curves reaching a peak (138 MPa) beyond which strain softening was recorded, and strain localization on a shear fracture. (2) Type A samples with a uniform porosity display a ductile behavior with no localization of the deformation.(2) Type B samples with isopachous cement show a brittle behavior with stress drop (16 MPa to 18 MPa) and localization on a shear fracture. When isopachous cements are absent, a more ductile type of behavior is observed. Our set of data suggests that those two microstructural parameters have a significant control on the mechanical behavior of carbonate rocks.

Adverse changes in the Earth's climate are thought to be due to the output of carbon dioxide from power stations. This has led to the development of many new materials to remove CO2 from these gas streams. Polymers of intrinsic microporosity (PIMs) are a novel class of polymers that are rigid with sites of contortion. These properties result in inefficient packing and so lead to large pore volumes and high surface areas. The inclusion of Tröger’s base, a contortion site made up of two nitrogen atoms, is thought to lead to increased uptake of CO2. The combination of electrostatic interactions with strong van der Waals forces should interact favourable with the quadrupole moment of CO2.Here a molecular simulation study of a selection of these polymers is presented. The study begins by developing a quick screening method on single polymer chains. This shows that the high surface area and adsorption affinity are a result of the contorted nature of PIMs along with the inclusion of groups such as Tröger’s base.The creation of atomistic models that reproduce the space packing ability of these polymers is also explored. Methods developed for PIMs in literature are investigated along with a new method developed during this study. GCMC simulations are then used to investigate the adsorption of CO2. In this study it is seen that that these polymers possess a well percolated network of both ultramicropores and supermicropores with a significant fraction of these pores being close to the kinetic diameter of CO 2. It is posited that these pores may be the result of the inclusion of Tröger’s base. It is also shown that this produces a particularly favourable site for adsorption. The phenomenon of swelling as a result of CO2 adsorption is also investigated using a variety of methods that make use of the output from the GCMC simulations. It was found that swelling is negligible for pressures of up to 1 bar. This result is important as swelling in the polymer can lead to a reduction in selectivity and an increase in permeability, which can affect the overall material’s performance.

The polymer of intrinsic microporosity PIM-1 was synthesized following various procedures: (i) from fluoro-monomer by the conventional method, (ii) from fluoro-monomer by a high temperature, high shear mixing method and (iii) from chloro-monomer. For a more complete understanding of the structure of the resultant products of a series of polymerizations under different reaction conditions, a multi-detector gel permeation chromatography (GPC) method was established and validated. A procedure for fractionating PIM-1 using chloroform methanol solvent mixtures was established and validated. A combination of multi-detector GPC and matrix-assisted laser desorption/ionization-time of flight (MALDI-ToF) masss pectrometry was used for the determination of molar mass distribution and to identify structural differences between fractions and between the products from different synthetic procedures. High molar mass samples tended to have broader molar mass distributions. Both Mark-Houwink plots and hydrodynamic volume plots showed deviation from linearity at Mw= 200000 g mol-1, which was attributed to branching. A low cost route for the preparation of PIM-1 from chloro-monomer was successfully established, though samples prepared by this route had broader polydispersities than those prepared from fluoro-monomers. It was found that stable flexible membranes were formed from samples with Mw > 83000 g mol -1. In addition, a comparison of two analytical methods for extraction and determination of additives in HDPE, LLDPE and PP polymers of interest to Saudi Basic Industries Corporation was performed. A comparison of dissolution with ultrasonic assisted extraction methods for the determination of anti-oxidant additives in polyolefins was performed. Ultrasound assisted extraction methods were found to be superior for HDPE and LLDPE, where conventional dissolution was preferred for PP.

This work explores the fabrication and permeability testing of mixed matrix membranes (MMM) utilising a polymer of intrinsic microporosity (PIM-1) and various fillers. PIM-1 has been chosen for this work due to its high apparent surface area and high sorption of gases. PIM-1 also is a good candidate for gas sorption applications due to the film forming properties of the polymer. The fillers utilised in this work are Metal Organic Frameworks (MOFs) and organic cages, which have been chosen due to the gas sorption properties they exhibit. The MOFs used are micro and nanoparticles of Zeolitic Imidazole Framework-8 (ZIF-8), copper based MOF HKUST-1 and chromium based MOF MIL-101. Micro particles of magnesium based MOF Mg-MOF-74 were also looked at as well as cage 3, nano cage 3 and reduced cage 3. Comparable surface areas of the MOFs compared to those quoted in the literature have been obtained. Successful PIM-1/Filler MMMs were synthesised utilising PIM-1 and the fillers outlined above with various loadings of filler. The highest loading achieved was with a 10:6.4 PIM-1/nanoZIF-8 ratio. All MMMs apart from PIM-1/Mg-MOF-74 MMM were homogenous on a macroscale with scanning electron microscopy proving the dispersion of fillers. Gas transport properties of the MMMs were determined using predominantly a time lag method. PIM-1/ZIF-8 MMMs were also tested using a chromatographic method and using a gas sorption experiment. A range of gases were tested including CO2, N2, CH4, O2, He and H2. Ideal selectivities were also calculated with focus on the gas pairs O2/N2, CO2/CH4 and CO2/N2.When comparing the two permeability methods using the PIM-1/nanoZIF-8 MMM, lower permeability results were found from the time lag method. This was concluded to be due to the aging effect brought about by the vacuum used in the time lag method. The chromatographic method produced positive results with high selectivities, breaking Robeson’s upper bound, for the gas pair O2/N2. All other fillers tested showed an increase in permeability and stable selectivity with an increase in the amount of filler. MIL-101 and Cage 3 were the most successful fillers with high permeabilities of 35600 and 37400 Barrer respectively, encroaching on that of PTMSP. Mg-MOF-74 and reduced cage 3 MMM however, had a detrimental effect on the permeability. Aging data was also investigated which showed that for the majority of MMM the permeability followed the trend of PIM-1. microHKUST-1 and cage 3 of 10:3 loading were shown to give promising results with 10000 and 14300 Barrer respectively compared to 7200 Barrer for PIM-1. Although a loss in permeability is seen, it is still above that of PIM-1 at the same point of aging. These results give a positive indication that MMMs have the potential to provide resistance against aging, a major problem in using high free volume polymers in industrial applications.

Ethylene is the most important organic molecule with regard to production volume. Therefore, the energy spent in its separation processes, based on old-fashioned distillation, takes approx. 33% of total operating costs. Membranes do not require significant thermal energy input; therefore, membrane processes may separate hydrocarbons cheaply and just as reliably as distillation columns. Olefin/paraffin separations are the future targets of commercial membrane applications, provided high-performing materials become available at reasonable prices. This thesis addresses the development of advanced carbon molecular sieve (CMS) membranes derived from intrinsically microporous polymers (PIMs). Chronologically, Chapter 4 of this work reports the evaluation of PIMs as potential ethylene/ethane selective materials, while Chapters 5 to 7 propose PIMs as carbonization precursors. The gravimetric sorption studies conducted in this work regarding both the polymers and their heated-derivatives revealed that this separation is entirely controlled by diffusion differences. The pristine polymers examined in this study presented BET surface areas from 80 to 720 m2g-1. Furthermore, the effect of using bromine-substituted PIM-polyimides elucidated a boost in ethylene permeability, but with a significant drop in selectivity. The hydroxyl functionalization of PIM-polyimides was confirmed as a valuable strategy to increase selectivity. Functionalized PMDA-HSBF is the most selective polyimide of intrinsic microporosity known to date (= 5.1) due to its hydrogen-bonded matrix. In spite of their novelty, pristine PIMs based on the spirobisindane moiety were not tight enough to distinguish between the 0.2 Å difference in diameter of the ethylene/ethane molecules. Therefore, they did not surpass the upper bound limit performance of known polymeric membranes. Nevertheless, the carbons derived from these polymers were excellent ethylene/ethane sieves by virtue of their narrow and tight pore distribution around the 3.6- 4.4 Å range. PIM-based carbons were typically 10 times more permeable than their corresponding low free-volume analogues treated after the weight-loss of the sample reached a plateau. Furthermore, carbons derived from PIM-6FDA-OH and PIM-6FDA at 800 ºC were as ethylene separating efficient as their lower free-volume counterparts. The pore sintering mechanism that takes place above 600 ºC during the carbonization procedure of these films reduced the entropic freedom of the molecules, as was observed from separation factors of up to 25 under pure-gas conditions and 2 bar of pressure— The best performing CMS membranes reported to date for ethylene/ethane separation. The mixed-gas separation of 1:1 binary ethylene/ethane mixtures revealed a significant decrease of the pure-gas measurements due to a carbon matrix dilation effect. This localized ultramicroporous dilation caused the ethane permeation rate to increase monotonically as the pressure rose to realistic operating values. Nevertheless, the CMS obtained from PIM-6FDA and PIM-6FDA-OH surpassed any diffusion-controlled polymer or carbon that has been reported to date.

To date there exists a great deal of energetic and economic inefficiency in the separation of olefins from paraffins because the principal means of achieving industrial purity requirements is accomplished with very energy intensive cryogenic distillation. Mitigation of the severe energy intensity of the propylene/propane separation has been identified as one of seven chemical separations which can change the landscape of global energy use, and membranes have been targeted as an emerging technology because they offer scalability and lower capital and operating costs. The focus of this work was to evaluate a new direction of material development for the very industrially relevant propylene/propane separation using membranes. The objective was to develop a rational design approach for generating highly selective membranes using a relatively new platform of materials known as polyimides of intrinsic microporosity (PIM-PIs), the prospects of which have never been examined for the propylene/propane separation. Structurally, PIMs comprise relatively inflexible macromolecular architectures integrating contortion sites that help disrupt packing and trap microporous free volume elements (< 20 Å). To date most of the work reported in the literature on this separation is based on conventional low free volume 6FDA-based polyimides which in the best case show moderate C3H6/C3H8 selectivities (<20) with C3H6 permeabilities too low to garner industrial interest. Due to propylene and propane’s relatively large molecular size, we hypothesized that the use of more open structures can provide greater accessibility to the pores necessary to enhance membrane sieving and flux. It has been shown for numerous key gas separations that introduction of microporosity into a polymer structure can defy the notorious permeability/selectivity tradeoff curve and induce simultaneous boosts in both permeability and selectivity. The cornerstone approach to designing state of the art high performance PIM-PI membranes for the light gas separations involving maximizing the intra-segmental rigidity of the polymer chain was applied to the C3H6/C3H8 separation. A study regarding a stepwise maximization of intra-molecular rigidity and its effects on C3H6/C3H8 permeation was evaluated by conducting systematic structural modifications to high performance PIM-PIs. State of the art increases in performance were observed in pure-gas measurements as there were significant increases in C3H6/C3H8 selectivity and C3H6 permeability upon doing so. However, mixed-gas measurements showed that there were 65% losses in selectivity due to competitive sorption and mainly plasticization. Based on the conclusions drawn, a fundamental departure from conventional PIM design principles was used, instead emphasizing enhancing inter-chain interactions by introduction of a flexible diamine and functionalization with hydroxyl groups to attempt to immobilize the polymer chains. In doing so, the polymer chains may be able to pack more efficiently and upon sub-Tg annealing cause a microstructural reorganization to form a coplanarized configuration due to the combination of inter-chain charge transfer complexes (CTC) and hydrogen bonding networks. This approach successfully mitigated plasticization, but more importantly resulted in a tightening of the microstructure, especially in the ultra-microporous range (<7 Å) thereby yielding significant boosts in C3H6/C3H8 selectivity. Based on the PIM platform and novel polymer design approach thereof, the C3H6/C3H8 upper bound was thrust to new limits and led to the generation of the most selective solution processable polymers reported for the C3H6/C3H8 separation. Although the PIM platform has redefined the polymer upper bound, the permeability/selectivity tradeoff still endures, as the C3H6 permeabilities were on the order of 1 to 3.5 Barrer for the most selective polymers. To bridge that gap in permeability, several different approaches were taken. For the first time attempted for C3H6/C3H8 separation, high temperature heating of a PIM-PI to form thermally-rearranged and carbon molecular sieve membranes was employed. The TR membrane showed increased C3H6 permeability and about 50% losses in C3H6/C3H8 selectivity, while the CMS membrane formed at 600 oC showed modest gains in C3H6/C3H8 selectivity with significant improvements in C3H6 permeability. Finally, hybrid nanocomposite membranes incorporating a metal-organic framework structure into a PIM-PI matrix was used. ZIF-8, which has demonstrated high diffusive selectivities for C3H6/C3H8, was dispersed within the polymer, since previous work by the Koros group indicated that its incorporation into polyimide matrices can facilitate major improvements in both C3H6/C3H8 selectivity and C3H6 permeability compared to the respective neat polymer. Focus was directed towards attempting to improve polymer/nanoparticle adhesion by enhancing the interactions between the polymer and filler particles to mitigate the interfacial defects notorious in mixed-matrix membranes (MMM). To do so, ZIF-8 was dispersed into one of the best performing hydroxyl functionalized PIM-PI for the C3H6/C3H8 separation. The highest loaded mixed-matrix membrane in a glassy polymer to date of 65% (w/w) was achieved. The membranes showed pure-gas selectivities ranging from 34 with 10 Barrer at 30% loading to 43 with 38 Barrer at 65% loading. Strong performance and plasticization resistance were sustained in mixed-gas experiments even to feed pressures approaching the vapor pressure of the C3H6/C3H8 mixture, as selectivities well over 20 were achieved with high permeabilities, thereby demonstrating the potential commercial viability. Based on the work reported in this dissertation, we hope to help lay a framework to be able to tailor membrane performance and future membrane design to meet the demands of the different applications of the propylene/propane separation and hence show that there can be a marketplace for membranes in the separation. These include the debottlenecking of cryogenic distillation towers for production of polymer-grade propylene (99.5%) to reduce the associated extensive energy load, production of chemical-grade propylene (92-95% propylene), or for the recovery and recycling of olefins from reactor purges of petrochemical processes.

Gas separation membranes are proving to be a sustainable method to mitigate climate change given the rising energy demand. Polymers of intrinsic microporosity (PIMs) have emerged as a novel material class for such application. Physical aging is a major concern for the growth and commercialization of these glassy polymers. Several factors play an important role in determining the effects of physical aging for a PIM film; one important parameter is its thickness. Gas transport properties of PIM-Trip-TB films of thicknesses between 20-150 µm were monitored over 150 days for physical aging and its dependence on film thickness. Over this period, thicker films had generally higher permeability, and thinner films aged faster. Although fresh films showed higher selectivity during the initial tests, no correlation was found between film thickness and selectivity after aging. In addition, physical aging was more severe and independent of film thickness for larger-sized gases. Film storing environment affected the physical aging of multiply tested samples significantly, whereas films which were not tested periodically showed very minimal aging. A more systematic approach is required to fully analyze and comprehend factors yielding this phenomenon.

Sub-seismic meter-scale interwell depositional facies heterogeneity and microporosity are critical components behind properties and fluid flow heterogeneities of many Middle eastern giants and supergiants carbonate reservoirs. The Hanifa reservoir is one of the most petroliferous Arabian carbonate strata that hosts the notoriously heterogenous stromatoporoid/coral facies. Paradoxically, the 3D geometry, architecture, and subsurface implication of these facies are poorly understood or completely ignored in most studies. The lower part of the Arab-D reservoir is dominated by microporosity. However, studies that investigate the influence of microcrystals that host microporosity to petrophysical properties and upscale it to reservoir simulation grid-block scale are modicum. This dissertation aims to bridge this paucity by performing an advanced three-dimensional outcrop analog investigation and multiscale microporosity studies of these formations. We document the 3D morphology and spatial distribution of the stromatoporoid/coral facies part of the Hanifa reservoir outcrop analog in Wadi Birk, Saudi Arabia, using 3D drone-based digital outcrop model, cores, near-surface geophysical measurements, and deep-learning methodology. We construct a high-fidelity outcrop analog reservoir model from these observations and utilize it for dynamic simulation during waterflood. Further, based on the Upper Jubaila Formation outcrop analog in Wadi Laban, Saudi Arabia, we investigate the influence of microcrystals that host microporosity on petrophysical properties. We upscale the relationships and utilize seismic-derived acoustic-impedance data to arrive at reservoir grid block-scale microporosity distribution. Our results provide a novel and valuable insight into the growth morphology of the stromatoporoid/coral buildups and their relationship with subsurface fluid flow previously unknown for the Hanifa reservoir. The results demonstrate that sweep efficiency is greatly influenced by the interaction between the buildup clusters with the background strata. Our results also provide a practical method to integrate key sub-grid scale micro and macro heterogeneities into reservoir grid block-scale property models.