La problématique de cette thèse est l’identification des phénomènes physico-chimiques se produisant entre les roches encaissantes du gisement de sel gemme de Lorraine et des saumures, puis l’étude de leurs effets sur le comportement mécanique. Une démarche multi-échelle a été entreprise : du minéral à l’échelle d’une exploitation en passant par celle des essais mécaniques. La confrontation de la géologie locale avec la géométrie des cavités de dissolution de sel (logiciel GOCAD) au travers de ces roches encaissantes rend compte d’un délitage relativement rapide lorsque les argilites sont au contact d’une saumure de cavité. A l’inverse, l’anhydrite et la dolomie peuvent constituer le toit de cavité pendant plusieurs années, avant de se rompre. Suite à une caractérisation minéralogique, et microtexturale des roches encaissantes (Marnes irisées inférieures et moyennes), une expérimentation de type batch a été mise en œuvre afin de comprendre ces différences: les faciès lithologiques qualifiés de majeurs ont été immergés dans des saumures pendant plus d’un an. Des analyses chimiques et microscopiques ont permis de suivre les modifications minéralogiques et microtexturales. Au contact de saumures saturées en chlorure de sodium, les faciès argileux se délitent en raison de l’hydratation en gypse du minéral anhydrite. Au niveau de l’anhydrite massive, cette hydratation n’affecte qu’une frange superficielle des échantillons, en raison d’une porosité connectée quasi-nulle. En présence d’une saumure de cavité, l’hydratation est promue par la présence de potassium et de strontium en solution. Ces résultats permettent d’expliquer qualitativement la dilatation voire la rupture des éprouvettes d’argilite lors d’essais de fluage en saumures. Le comportement en flexion de l’anhydrite massive ne semble pas être affecté par la présence de saumure, en raison d’une porosité trop faible pour permettre l’accès de la saumure au site réactionnel que sont les cristaux d’anhydrite / The aim of this study is the understanding of the physico-chemical interactions between saturated brine and the rocks (Marnes Irisées inférieures) enclosing the underground salt workings in Lorraine (eastern France), and also the study of their effect on the mechanical behaviour. A multi-scale study was undertaken, from the mineral scale to the one of a salt working. Whereas anhydrite-rich argillites flake quickly with the presence of saturated brine at the border of solutions cavities, the dolomudstone and massive anhydrite don’t and can constitute the top of cavities for several years. In order to explain this difference, these three lithologies were analysed in terms of mineralogy, micro-texture and porous media. Then, samples of argillites and massive anhydrite were immersed in saturated brines for more than one year. Chemical and microscopic analysis testified the hydration of anhydrite crystals into gypsum. This transformation occurs in a superficial way on massive anhydrite; to the contrary, it is located inside the anhydrite-rich argilites. As this transformation induces a volume increasing of 63%, the anhydrite crystals swell. In saturated brine, the water activity is low enough to prevent the swelling of clays such as smectites. Thus, anhydrite swelling might be the responsible of the argillites splitting in a saturated brine environment. The superficial anhydrite hydration on massive anhydrite can be explained by the low values of connected porosity (less than 1%) for this lithology. This results can explain, in a qualitative way, the dilatant behaviour of argilites samples during creep tests with brine. The bending behaviour of massive anhydrite don’t seem to be affected by the presence of brine for one year or less, probably because of the too low porosity of this lithology

The gas diffusion layer (GDL) is one of the key components in a polymer electrolyte membrane (PEM) fuel cell. It performs several functions including the transport of reactant gases and product water to and from the catalyst layer, conduction of both electrons and heat produced in the catalyst layer, as well as mechanical support for the membrane. The overarching goal of this work is to thoroughly examine the GDL structure and properties for use in PEM fuel cells, and more specifically, to determine how to characterize the GDL experimentally ex-situ, to understand its performance in-situ, and to relate theory to performance through controlled experimentation. Thus, the impact of readily measured effective water vapor diffusivity on the performance of the GDL is investigated and shown to correlate to the wet limiting current density, as a surrogate of the oxygen diffusivity to which it is more directly related. The influence of microporous layer (MPL) design and construction on the fuel cell performance is studied and recommendations are made for optimal MPL designs for different operating conditions. A method for modifying the PTFE (Teflon) distribution within the GDL is proposed and the impact of distribution of PTFE in the GDL on fuel cell performance is studied. A method for characterizing the surface roughness of the GDL is developed and the impact of surface roughness on various ex-situ GDL properties is investigated. Finally, a detailed analysis of the physical structure and permeability of the GDL is provided and a theoretical model is proposed to predict both dry and wet gas flow within a GDL based on mercury intrusion porosimetry and porometry data. It is hoped that this work will contribute to an improved understanding of the functioning and structure of the GDL and hence advance PEM fuel cell technology.

Rapporten innefattar en jämförande studie mellan olika typer av membran och beläggningar.Främst sker en jämförelse mellan materialens förmåga att andas. Vattentäthet testas på nyamaterial och efter olika sorters nötning så som martindale, flexing och tvätt för att få en ökadförståelse för materialen. Verktyget som används i studien för att mätaånggenomsläppligheten är hudmodellen. Resultatet presenteras med ett Ret-värde vilket är enförkortning på Evaporative resistance of a textile. Metoden används för att på ett bra sättsimulera hur huden svettas.Projektet har utförts på Swerea IVF som är ett forskningsinstitut beläget i Mölndal.Hudmodellen är en av de senaste stora investeringarna på Swereas textil och plast avdelning.Resultatet av studien visar att laminat andas bättre än beläggningar, dock har bärarmaterialetstor inverkan på resultaten. Ett tydligt samband mellan grövre material och sämre andning harobserverats. Många av de material som testats i studien uppvisar god förmåga att andas, därbåde flera av de mikroporösa och hydrofila materialen uppvisar Ret-värden under 13, vilketinnebär mycket god andning. En delstudie har varit att testa hur materialens andande förmågaförändras vid lägre relativ fuktighet. Resultatet blev att mikroporösa material inte påverkaslika mycket som de hydrofila materialen som då får en sämre andning.Efter de resultat studien har visat kan slutsatsen dras att tunna laminat är att föredra då högånggenomsläpplighet är ett krav. Behövs däremot ett högt motstånd mot nötning kan etttjockare material med fördel användas, vilket dock kan leda till högre ångmotstånd.This report is a comparative study between different types of membranes and coatings, thebreathability of the fabrics being the main focus of research. The fabrics' waterproofness wastested on new materials and by abrasion including martindale, flexing and washing. The toolthat has been used to measure water-vapour resistance is the skin model. The result ispresented by a Ret-value, which is short for evaporative resistance of a textile. The method isused to simulate the sweating body in a realistic way. Swerea IVF is the research institutelocated in Mölndal where the project has been carried out. The skin model is one of the latestbig investments at Swereas textile and plastic department.The results of the study shows that laminates breath better than coatings. It is important topoint out, however, that the carrier has great influence on the fabric in question. In addition,the results indicate a relation between thick fabrics and less breathability. Many of thematerials that have been tested show good permeability to breath, including bothmicropourous and hydrophilic materials. Most of them demonstrate a Ret-value less than 13,which means very good breathability. Further tests also show how the breathability changeswith lower relative humidity, indicating that microporous materials are less affected thanhydrophilic materials, thus having a higher resistance to water vapour.The conclusion of the study is that thin laminates is to prefer when high breathability isrequired. If the demand is high resistance to abrasion, a thicker material is prefered, whichalso yields a higher resistance to water permability. / Program: Textilingenjörsutbildningen

In this thesis, fluid characteristics and sampling efficiency of high molecular weight cut-off microdialysis are presented, with the aim of improving the understanding of microdialysis sampling mechanisms and its performance regarding extraction efficiency of biological fluid and biomarkers. Microdialysis is a well-established clinical sampling tool for monitoring small biomarkers such as lactate and glucose. In recent years, interest has raised in using high molecular weight cut-off microdialysis to sample macro molecules such as neuropeptides, cytokines and proteins. However, with the increase of the membrane pore size, high molecular weight cut-off microdialysis exhibits drawbacks such like unstable catheter performance, imbalanced fluid recovery, low and unstable molecule extraction efficiency, etc. But still, the fluid characteristics of high molecular weight cut-off microdialysis is rarely studied, and the clinical or in vitro molecule sampling efficiency from recent studies vary from each other and are difficult to compare.   Therefore, in this thesis three aspects of high molecular weight cut-off microdialysis have been explored. The first, the fluid characteristics of large pore microdialysis has been investigated, theoretically and experimentally. The results suggest that the experimental fluid recovery is in consistency with its theoretical formula. The second, the macromolecule transport behaviour has been visualized and semi-quantified, using an in vitro test system and fluorescence imaging. The third, two in vitro tests have been done to mimic in vivo cerebrospinal fluid sampling under pressurization, using native and differently surface modified catheters. As results, individual protein/peptide extraction efficiencies were achieved, using targeted mass spectrometry analysis. In summary, a theory system of the fluid characteristics of high molecular weight cut-off microdialysis has been built and testified; Macromolecular transport of microdialysis catheter has been visualized; In vivo biomolecules sampling has been simulated by well-defined in vitro studies; Individual biomolecular extraction efficiency has been shown; Different surface modifications of microdialysis catheter have been investigated. It was found that, improved sampling performance can be achieved, in terms of balanced fluid recovery and controlled protein extraction efficiency.

Nanoporous carbons have become a material of interest in many applications such as electrochemical double layer capacitors (supercapacitors). Supercapacitors are being studied for their potential in storing electrical energy storage from intermittent sources and in use as power sources that can be charged rapidly. However, a lack of understanding of the charge storage mechanism within a supercapacitor makes it difficult to optimize them. Two components of this challenge are the difficulties in experimentally characterizing the sub-nanoporous structure of carbon electrode materials and the electrical performance of the supercapacitors. This work provides a means to accurately characterize the porous structure of sub-nanoporus carbon materials and identifies the current limitations in characterizing the electrical performance of a supercapacitor cell. Future work may focus on the relationship between the sub-nano porous structure of the carbon electrode and the capacitance of supercapacitors, and on the elucidation of charge storage mechanisms.

Nanoporous carbons have become a material of interest in many applications such as electrochemical double layer capacitors (supercapacitors). Supercapacitors are being studied for their potential in storing electrical energy storage from intermittent sources and in use as power sources that can be charged rapidly. However, a lack of understanding of the charge storage mechanism within a supercapacitor makes it difficult to optimize them. Two components of this challenge are the difficulties in experimentally characterizing the sub-nanoporous structure of carbon electrode materials and the electrical performance of the supercapacitors. This work provides a means to accurately characterize the porous structure of sub-nanoporus carbon materials and identifies the current limitations in characterizing the electrical performance of a supercapacitor cell. Future work may focus on the relationship between the sub-nano porous structure of the carbon electrode and the capacitance of supercapacitors, and on the elucidation of charge storage mechanisms.

This study was to investigate theory and application of Osmotic Distillation (OD). OD is a new novel membrane separation process used for the concentration of aqueous solutions such as fruit juices without the application of heat. The present work was undertaken to investigate flux limitations focusing on feedside, membrane and stripper side characteristics of OD. Once the limiting areas were identified, further studies were undertaken to determine methods of minimizing those limitations without losing the quality and integrity of the liquid feed. A laboratory scale OD system was used to simulate the industrial process which takes place during the production of grape juice concentrate for the fruit juice industry. Results of a UF pretreatment study showed that the use of UF membranes with pore diameters of 0.1 fÝm or less as a pretreatment for the subsequent OD of grape juice resulted in significant increases in OD flux over that observed for juice not subjected to UF. The study of the physical properties of the feed played an important role in the explanation of the OD process. The increase in OD flux was attributed to a reduction in juice viscosity as the result of the removal of protein and other high molecular weight components. Apart from an increase in OD flux, UF pretreatment of the grape juice proved to be beneficial in other areas of the OD process. HPLC measurements showed that the normal concentration of fermentable sugars in standard 68 oBrix concentrate can be achieved at a lower Brix value in feed subjected to UF pretreatment, further reducing the need to handle highly viscous feeds. UF pretreatment also resulted in an increase in juice surface tension consequently reducing the tendency for membrane wet-out to occur. The study of the deoxygenation of the feed solution shows that the removal of dissolved gases by the pre boiling method and the perstraction with chemical reaction (PCR) method both had a positive affect on OD flux. Pre boiling the brine resulted in an indirect reduction in dissolved oxygen in the feed. Pre boiling both the feed and brine, further increased the flux. Throughout the PCR study, it was evident that stripper side mass transfer of O2 was not limited by flowrate but was limited by higher stripper concentration. However, the latter had an insignificant effect when the sulfite-oxygen reaction was catalysed. The use of a catalyst and increase in temperature gave a significant improvement in overall mass transfer coefficient. Ten types of hydrophobic microporous membranes were tested for their influence on OD flux. While the pore diameter is a considerable factor in mass transport of gases through the membrane, it was also noted that the type of membrane material used had an affect on the overall mass transfer. All top three performing membranes had pore diameters of 0.2 x 10-6 m and were made from polytetrafluoroethylene (PTFE). The choice of brine to use as the stripper was based on criteria that were confirmed by the brine studies performed here. The best performing stripper solutions demonstrating the greatest improvement in OD flux over the most commonly used brines, NaCl, CaCl2 and CH3COOK were aqueous solutions of potassium salts of phosphoric acid, pyrophosphoric acid and blends thereof. These salts agreed with all the required characteristics of a suitable brine, demonstrating high solubility rates, supporting the ability to lower water vapour pressure. The study of the corrosion effects of brine salts confirmed the phosphate salts are superior demonstrating some of the lowest corrosion rates and highest pH.

The present work was undertaken to develop a composite osmotic distillation (OD) membrane consisting of a thin hydrogel coating on a microporous hydrophobic substrate for the concentration of aqueous feeds containing surface-active agents. The range of OD applications using the hydrophobic membrane alone have been severely limited by the propensity for membrane wet-out when contacted by amphiphilic agents such as oils, fats and detergents. Wet-out allows the feed solution to track freely through the membrane pores with a resulting loss of solutes and a decrease in selectivity. The rationale for the approach taken was based on the hypothesis that the high water selectivity of the hydrophilic coating would maintain good water mass transfer to the underlying hydrophobic substrate but exclude other components including surface-active agents. The first stage of this work involved the identification of potential coating materials and the fabrication and structural characterization of films of these materials to determine their suitability. The second stage involved the development of techniques to facilitate adhesion of the hydrophilic coatings to the hydrophobic substrate, and the testing of the resulting composite membranes for OD performance and resistance to wet-out by surface-active agents. Sodium alginate was selected as the major coating component on the basis of its non-toxicity and its potential for stable hydrogel formation. Structural characterization of noncrosslinked films and films crosslinked using a water-soluble carbodiimide (WSC) was carried out using differential scanning calorimetry (DSC), Fourier Transform infrared spectroscopy (FT-IR) and swelling measurements. Maximum crosslinking through esterification of hydroxyl and carboxylic acid groups on adjacent polymer strands using the film immersion method was achieved with a non-solvent (ethanol) concentration of 60 vol % and a WSC concentration of 100 mM at pH 4. These conditions resulted in a hydrogel with an equilibrium water content of 60 wt %. DSC measurements of noncrosslinked and crosslinked alginate films showed an increase in crystallinity and hence rigidity on crosslinking. Therefore, several coatings were prepared as blends of sodium alginate and amorphous highly flexible carrageenan gum in order to meet the flexibility requirements of a membrane subjected to varying operating pressures in an industrial OD plant. Structural characterization with respect to polymer blend ratio was carried out using scanning electron microscopy (SEM), DSC, X-ray diffraction (XRD). The optimisation for crosslinking conditions was undertaken as for sodium alginate alone. Optimum conditions for film preparation were 20 wt % carrageenan content and a crosslinking medium containing 60 vol % non-solvent (ethanol) and 120 mM WSC at pH 4. These conditions produced a hydrogel with an equilibrium water content of 85 wt %. Two different techniques were employed to anchor the coatings on substrate PTFE membranes. For membranes with a nominal diameter of 0.2 µm, the technique involved surface tension adjustment of the coating solution by ethanol addition in order to enhance penetration of the coating solution meniscus into the substrate pores. This was followed by polymer precipitation by the selective removal of water using OD to provide structural interlocking. T-peel strength measurements showed that this technique resulted in a ten-fold increase in adhesion strength when compared with a coating cast without surface tension adjustments. For membranes with a nominal diameter of 0.1µm, an interfacial bonding agent, myristyltrimethylammonium bromide (MTMA), was used. This technique gave a three-fold increase in adhesion strength relative to that of coating cast without the use of MTMA. The composite membranes were tested in extended OD trials using pure water and feeds containing limonene, the major surface-active components of orange oil. The sodium alginate-carrageenan blend membrane, which was the preferred membrane based on flexibility and water sorption considerations, was also tested against full-cream milk and an industrial detergent, sodium dodecylbenzene sulfonate (DBS). The results indicated that the coatings offered little resistance to water transport and were effective in providing protection against membrane wet-out. Durability trials showed that the composite membranes retained their integrity in water for a minimum of 30 days. Overall, this study has expanded the potential applications of OD to include many important industrial concentration steps that are currently being undertaken by conventional processes with unsatisfactory results. These include the concentration of citrus juices, full-cream milk and nuclear power plant liquid waste. These feeds contain limonene, fats and detergents respectively, all of which wet out unprotected hydrophobic membranes.

This thesis combines synthetic studies for isotopic enrichment with solid-state characterisation techniques to investigate two classes of microporous materials: zeolites and metal-organic frameworks (MOFs). These materials have a wide range of successful applications, from industrial catalysis to medicine, resulting in the increasing need for both a complete understanding of their unique structural features and synthetic methods to target new frameworks. Nuclear magnetic resonance (NMR) spectroscopy, thanks to its sensitivity to the local, atomic-scale, environment and its element specificity, is applied, in combination with powder X-ray diffraction (PXRD), electron microscopy, N2 adsorption and mass spectrometry, to the study of these materials. Oxygen atoms play a crucial role in the structure and chemistry of zeolites and MOFs, making 17O NMR an excellent tool for chemical and structural investigations. However, the low natural abundance of this isotope (0.037%) and the cost of 17O-enriched reactants require the development of atom-efficient synthetic processes for isotopic enrichment. In the first part of this work, the unconventional assembly-disassembly-organisation-reassembly (ADOR) method is applied to the Ge-doped UTL framework and optimised in reduced-volume conditions for economic enrichment to obtain 17O- and 29Si-enriched UTL-derived zeolites. In situ and ex situ solid-state characterisation studies show that isotopic enrichment not only enables a more detailed spectroscopic investigation, but also provides new insights into the mechanism of the ADOR process and its sensitivity to experimental conditions. In the second part of this work, dry gel conversion synthesis and a novel steaming procedure are studied as cost-effective 17O-enrichment pathways for Al, Ga and Sc mixed-metal terephthalate MOFs. 17O solid-state NMR spectroscopy, in combination with PXRD and electron microscopy, is employed to investigate cation disorder and 17O NMR spectra are shown to be sensitive to substitution of metal centers and conformational changes upon interaction with guest molecules.

No description available.