Porous materials are essential to our everyday lives, for example as an effective catalyst in the cracking of crude oil, or as water softeners in washing powder. When developing novel functional porous materials, it is necessary to fully understand their structure-property relationships to maximise their ability to be used in industrially relevant settings. This thesis aims to understand the mechanical and adsorption properties of a class of porous solids metal-organic frameworks (or MOFs), which have many potential applications owing to their tuneable structures. Due to the inherent 3-D crystalline structure of MOFs, a wide range crystallographic techniques were used to determine structure-property relationships. To achieve maximum in-depth structural knowledge, both classical and quantum theoretical approaches were also applied to complement the understanding of both the energetics and structural details. Chapters One and Two begin with an overview of the state of the art studies carried out on MOFs, focusing on the use of high-pressure crystallography to understand their properties. In addition, there is emphasise on the importance of complementary computational methods that are used in the characterisation of MOFs. In Chapter Three, an isostructural series of MOFs (zeolitic imidazolate frameworks, or ZIFs) were studied for methanol adsorption by employing both experimental and molecular simulation techniques. These frameworks are gating materials, where the imidazole linker rotates upon adsorption of guest, and it was found that through ligand substitution the gate opening angle and onset pressure to gating could be tuned. By using high-pressure Xray crystallography the structure of the ZIFs were studied upon the uptake of guest and the degree of ring rotation quantified. In combination with periodic DFT and grand canonical Monte Carlo simulations the energy barrier to rotation and energies of adsorption could be calculated, respectively. Chapter Four focuses on one ZIF in particular, ZIF-8 ((Zn6(MeIm)12, MeIm = 2- methylimidazole) and details the adsorption of a selection of gases into the pores. The experimental method of cryogenic gas loading into a diamond anvil cell in this chapter is novel to MOFs. This method, in combination with molecular crystallography, is used to determine the structural response of the framework to guest-uptake as well as the crystallographic positions of the adsorption sites. In combination with in silico methods, the adsorption energies of guest-sites could be calculated, detailing which interactions drive the gating behaviour. The method of cryogenic loading highlighted how extreme conditions can be used to extract useful information about structural behaviour of MOFs on uptake of gas molecules into the pores, and when used in combination with computational methods, we have a powerful tool to analyse both positions and energies of adsorption sites. With this information, progress can be made in developing MOFs to maximize favourable interactions and lead to the development of MOFs with better selective gas storage properties. Chapter Five focuses on the synthesis and characterisation of the physical properties of a series of Zr-containing MOFs, called UiO-MOFs. The high valency of Zr(IV) and 12-fold coordination of the metal cluster in these materials, are associated with high shear and bulk moduli, which surpass those of other MOFs. A combination of single-crystal nano-indentation, high-pressure X-ray diffraction studies, density functional theory (DFT) calculations, and first-principles molecular dynamics (MD) simulations were used to determine the compressibility, elasticity and hardness of these materials, whose mechanical robustness was correlated to their different structural features, in-particular, how using non-linear linkers between the metal clusters stabilises the framework to compression. Chapter Six expands upon the series of Zr-MOFs in Chapter Five, and looks at how the mechanical properties of these MOFs are affected upon increasing the linker length. The experimentally determined elastics modulus of one of the frameworks, UiO-sdc (Zr6O4(OH)4(sdc)6 where sdc =4,4’-stillbene dicarboxylate), was found to lie above those of other highly porous MOFs. In addition, the elastic modulus was found to decrease linearly as a function of increasing the linker length, extending the structure-property relationships determined in Chapter Five.

The increasing trend of world-wide energy consumption emphasizes the importance of ongoing optimization of new and existing technologies. In this dissertation, two energy–intensive systems are simulated and optimized. Advanced estimation, optimization, and control techniques such as a moving horizon estimator and a model predictive controller are developed to enhance the profitability, product quality, and reliability of the systems. An enabling development is presented for the solution of complex dynamic optimization problems. The strategy involves an initialization approach to large–scale system models that both enhance the computational performance as well as the ability of the solver to converge to an optimal solution. One particular application of this approach is the modeling and optimization of a batch distillation column. For estimation of unknown parameters, an L1-norm method is utilized that is less sensitive to outliers than a squared error objective. The results obtained from the simple model match the experimental data and model prediction for a more rigorous model. A nonlinear statistical analysis and a sensitivity analysis are also implemented to verify the reliability of the estimated parameters. The reduced–order model developed for the batch distillation column is computationally fast and reasonably accurate and is applicable for real time control and online optimization purposes. Similar to estimation, an L1-norm objective function is applied for optimization of the column operation. Application of an L1-norm permits explicit prioritization of the multi–objective problems and adds only linear terms to the problem. Dynamic optimization of the column results in a 14% increase in the methanol product obtained from the column with 99% purity. In a second application of the methodology, the results obtained from optimization of the hybrid system of a cryogenic carbon capture (CCC) and power generation units are presented. Cryogenic carbon capture is a novel technology for CO2 removal from power generation units and has superior features such as low energy consumption, large–scale energy storage, and fast response to fluctuations in electricity demand. Grid–level energy storage of the CCC process enables 100% utilization of renewable power sources while 99% of the CO2 produced from fossil–fueled power plants is captured. In addition, energy demand of the CCC process is effectively managed by deploying the energy storage capability of this process. By exploiting time–of–day pricing, the profit obtained from dynamic optimization of this hybrid energy system offsets a significant fraction of the cost of construction of the cryogenic carbon capture plant.

Le développement des lasers de fortes puissances réalisé au cours des dix dernières années a ouvert de nouveaux champs de recherche dans de nombreux domaines tels que la production de faisceaux de particules chargées. Lors de l'interaction d'un faisceau laser avec une cible, il est en effet possible de générer un faisceau d'ions ou d'électrons d'une large gamme énergétique dépendant de la puissance du laser et de la nature de la cible.Les physiciens qui étudient les interactions laser-matière montrent un grand intérêt à pouvoir réaliser des expériences avec une cible d'hydrogène pure de l'ordre d'une dizaine de micromètres d'épaisseur. Lors d'une telle interaction, un faisceau constitué uniquement de protons accélérés est produit. La protonthérapie est l'une des applications phares qui utilise les propriétés particulières des protons accélérés pour détruire des tumeurs cancéreuses. Cette technique, plus légère et moins coûteuse, pourrait remplacer dans les années à venir les gros accélérateurs de particules, situés en sous-sol des hôpitaux. Les travaux menés durant cette thèse ont permis de développer un moyen d'obtenir et de caractériser de telles cibles, et ce en utilisant un nouveau procédé d'extrusion.L'extrusion d'hydrogène solide requiert des fortes pressions (100 à 400 bar) et des basses températures (inférieures à 13 K). Les fortes pressions sont obtenues à l'aide des propriétés thermodynamiques du fluide. Dans un premier temps, de l'hydrogène est introduit puis solidifié dans la cellule expérimentale jusqu'à remplir celle-ci. La cellule est alors fermée et chauffée en partie haute afin de liquéfier l'hydrogène qui s'y trouve. La dilatation qui résulte du changement de phase, génère une pression sur l'hydrogène solide qui est situé sous le liquide. Cette pression permet d'obtenir la force nécessaire à l'extrusion qui est réalisée au travers d'une buse se situant à l'extrémité basse de la cellule. La principale différence avec un procédé classique d'extrusion est l'absence de parties mobiles.Des premiers rubans d'hydrogène d'une largeur de 1 mm et d'une épaisseur de 100 µm ont été obtenus et ont donné lieu à publication en mars 2014. Une évolution de la cellule et du cryostat a ensuite été réalisée dans le but d'atteindre des épaisseurs de rubans plus faibles (25 et 50 µm).Une buse cylindrique d'un diamètre de 140 µm a également permis d'obtenir de longs cylindres d'hydrogène solide et de comprendre le comportement de l'écoulement dans des géométries simples. En parallèle, de nombreuses simulations numériques ont été réalisées dans le but de caractériser ce comportement. Un modèle dédié a ainsi été établi, pour lequel les résultats expérimentaux et les simulations sont en bon accord.Un algorithme de mesure de vitesses d'écoulement, basé sur le suivi de défauts présents dans le film d'hydrogène a également été développé. Celui-ci est basé sur une technique d'inter-corrélation d'images. L'épaisseur du ruban est également obtenue par analyse d'images acquises. Ces résultats sont en adéquation avec la mesure du débit d'hydrogène pompé, réalisée en aval du cryostat.De nombreux laseristes ont alors manifesté leur intérêt autour de ce nouveau procédé et une collaboration a été mise en place avec l'équipe du laser PALS, à Prague, dans le but d'installer une nouvelle version du cryostat, capable de se fixer sur la chambre à vide de leur laser. Cette équipe, qui sera la première à tirer sur des cibles d'hydrogène solide courant novembre 2015, souhaite valider certaines théories et accélérer des protons en utilisant le principe de la TNSA (Target Normal Shealth Acceleration). Les laseristes du LULI (situés à Palaiseau, en France) sont également intéressés pour utiliser de telles cibles et une installation sur leur chambre laser a été planifiée au mois de janvier 2016. En parallèle, des physiciens de l'Institut Lumière Matière du CNRS de Lyon souhaitent également utiliser ces cibles pour générer des rayons X-UV. / The development of very high power lasers in the latest decade opened up new horizons in a various field, such as the production of accelerated ion beams. When a laser beam interacts with a target, the generated beam can contain energetic ions or electrons with a large energy spectrum (1–200 MeV). This energy distribution depends on the laser power and the nature of the target.Physicists studying the interaction between laser and materials are really interested in having very thin (10 µm) ribbons of solid hydrogen that could be used as a target. Indeed, during the interaction between a laser and such a target, a pure proton beam can be created. Protontherapy is one of the main potential applications which uses the special properties of accelerated protons to destroy cancerous tumor. This technique, lighter and cheaper, could replace in the next years huge particle accelerators situated underground the equipped hospitals. This PhD thesis was about developing a way to get and characterize such ribbons, using a new extrusion process.Extrusion of solid hydrogen requires a high pressure (10 MPa to 40 MPa) and a low temperature (below 13K). This is achieved by using the thermodynamic properties of the fluid. First, the cell is filled in with solid H2, then closed. Afterward, the upper part is heated to liquefy the solid. The expansion, resulting from the phase change creates a pressure on the solid hydrogen, located below the liquid. The extrusion is realized through a micron-sized hole at the bottom of the cell. The main difference with a classic extrusion process is the absence of moving parts.First solid hydrogen ribbons (1mm large and 100 microns of thickness) have been obtained in March 2014, leading to an article in a peer review (laser and particle beams (2014) 32,569-575, Continuous production of a thin ribbon of solid hydrogen). The use of a 50 micron nozzle was satisfying but it showed the limitation in the design of the cell, leading to an upgraded one, which will enable to extrude thinner ribbons.A cylindrical nozzle (140 microns diameter) has also been used to obtain long cylinders of solid hydrogen and to be able to understand the solid hydrogen flow in simple geometries. In parallel, several numerical simulations have been carried out to establish the flow behavior of solid hydrogen during the extrusion process. An “home made” model has been developed for which experimental results and numerical calculations fit quite well for different nozzles' geometries.Using small ribbon defaults as velocity tracers, cross-correlation algorithm has also been developed to measure the velocity during the extrusion process. The ribbon thickness is also extracted from image analysis. These results are also correlated by flowmeter measurements and appeared to be accurate.Several laser teams have shown a great interest for these results and a collaboration contract has been signed with the laser PALS team (Prague) to install an updated version of this cryostat, able to be plugged in their vacuum chamber. The team wants to shoot the solid hydrogen target to understand the laser/matter interaction and accelerate proton through the TNSA (Target Normal Sheath Acceleration) principle. It will be the first time such target will be shot. The installation of the cryostat is scheduled by the end of august and the first experiments are planned during november 2015. LULI's laser team at Palaiseau in France is also interested in using these targets and is planning to shoot them in January 2016. In parallel, CNRS physicists of the ILM (Institut Lumière Matière de Lyon) would like to use these targets to generate X-UV radiation.

The goal of this research was to quantify the degradation experienced by a polymer electrolyte fuel cell after storage at subzero temperatures ranging from 0 to -40°C. The performance loss was determined by comparing the polarization and other applicable power curves before and after the subzero storage cycle. The causes of this performance degradation were investigated by the use of Scanning Electron Microscope, Energy Dispersive x-ray Spectroscopy, and porosity scanning technologies. It was found that there are two distinct types of degradation experienced by the membrane. The first type was identified as a variance of the actual voltage - current relationship of the cell. The membrane experienced a 2 - 15% power reduction depending on the load applied to the cell. This mode of degradation only pertained to the initial freeze/thaw cycle and was not observed after any number of subsequent cycles. The cause of this type of degradation has been hypothesized to be related to the delamination of the proton exchange, gas diffusion, and micro porous layers. The second type of degradation was only observed during the subsequent cycles, and mainly affected the high power regions of the operating range. A 5% reduction in current density and power output was observed as a result of further freeze/thaw cycles. Mass transport limitations may have been caused by the destruction of the meso-porous gas diffusion and micro-porous layers. The pore size, volume, and membrane surface area were quantified using a B.E.T. porosity scanner. The results showed that the pore diameter of the catalyst and proton exchange layer did not increase significantly. The porosity scanner did indicate that a pore volume increased by a factor of ten and was confirmed by the surface area measurements of the membrane. The S.E.M. investigations allowed visual inspection of the membrane's structural integrity. Physical separation of the catalyst and gas diffusion layers was observed in the experimental sample, while a more homogeneous assembly was seen in the control sample.

NiTi alloys have been the focus of Shape Memory Alloys (SMA) research and applications due their excellent ductility and shape memory properties, and these alloys have been extensively used in automotive, aerospace, and in biomedical applications. The effects of machining on the surface integrity and the corresponding material and mechanical properties of alloys can be best studied by utilizing NiTi alloys as workpiece material since their physical and mechanical properties are highly microstructure dependent. However, due to very poor machining performance of NiTi shape memory alloys, no comprehensive or systematic investigation on this topic has been conducted by researchers as yet. The current study makes a substantial and unique contribution to this area by making the first and significant contribution to studies on machining performance of NiTi shape memory alloys, and by achieving improved surface integrity and machining performance using cryogenic applications, which give significant reductions of tool-wear, cutting forces, and surface roughness. The influence of machining process conditions, including dry, MQL, preheated, cryogenic machining, and the effects of prefroze cryo machining on surface integrity characteristics such as microhardness, phase transformation, phase transformation temperature, depth of plastically deformed layer have been examined extensively, and unique findings have been obtained. The effects of machining process conditions, in particular preheated and cryogenic machining conditions, on thermo-mechanical and shape memory characteristics were identified through thermal cycling and stress-strain tests. For the first time, orthogonal cutting of NiTi shape memory alloys has been carried out in this study to investigate surface integrity comprehensively. Surface integrity and machining performance are compared for dry and prefroze cryogenic cooling conditions under a wide range of cutting speeds. Stress-induced martensitic phase transformation and deformation twinning were found in prefroze cryogenic and dry cutting conditions respectively. The existing microstructure-based constitutive models were used and modified to predict machining-induced phase transformation and resulting volume fraction. The modified model was implemented in commercial FEM software (DEFORM-2D) as a customized user subroutine. The obtained results from simulation and orthogonal cutting tests were compared considering martensitic volume fraction during cutting with various cutting speeds. The model captured the experimental trend of volume fraction induced by various cutting speeds and process variables. Overall, FEM simulation of cutting process of NiTi was successfully presented.

The research presented in this dissertation involves the synthesis, characterization, and application of novel anionic and cationic chiral molecular micelles in capillary electrophoresis (CE) for the separation of diverse chiral compounds. Chapter 1 presents brief overview of the surfactants, micelle polymer, CE and micellar electrokinetic chromatography (MEKC). Chapter 2 describes the simultaneous enantioseparation of eight single chiral center â-blockers using two novel leucine and isoleucine based polymeric surfactants. The simultaneous enantioseparation of multichiral center bearing â-blockers, nadolol and labetalol is described in chapter 3. A synergistic approach, using a combination of polysodium N-undecenoxycarbonyl-L-isoleucinate (poly-L-SUCIL) and sulfated â-CD showed dramatic enantioseparation of four stereoisomers of nadolol. On the other hand for labetalol, enantiomeric separation remains unaffected using the dual chiral selector system. Chapter 4 deals with the enantiomeric separation of the binaphthyl derivatives that was found to be influenced by pH, type and concentration of the background electrolyte as well as concentration of the polymeric surfactant. In chapter 5, characterization of five alkenoxy leucine-based surfactants with variations in chain length (C8-C11), polymerization concentration and degree of polymerization showed significant effects on the chiral resolution and efficiency of hydrophobic â-blockers. The synthesis and characterization of two positively charged amino acid derived chiral ionic liquids (ILs) and their corresponding polymers is presented in chapter 6. Chiral separation of two acidic analyte (difficult to resolve with anionic micelles) can be achieved with both monomers and polymers of ILs. In chapter 7, the synthesis and detailed characterization of three pH independent amino acids derived (L-leucinol, L-isoleucinol and L-valinol) sulfated chiral polymeric surfactants is presented. These chiral sulfated surfactants are thoroughly characterized and the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The work clearly demonstrates for the first time the superiority of chiral separation in MEKC coupled to mass spectrometry at low pH. Finally, in chapter 8, six amino acid derived chiral surfactants with carboxylate and sulfate head groups were compared for enantioseparation of broad range of structurally diverse racemic compounds at neutral and basic pH conditions.

When increasing magnetic resonance imaging (MRI) resolution into the micron scale, image signal-to-noise ratio (SNR) can be maintained by using small radiofrequency (RF) coils in close proximity to the sample being imaged. Micro-scale RF coils (microcoils) can be easily fabricated on chip and placed adjacent to a sample under test. However, the high series resistance of microcoils limits the SNR due to the thermal noise generated in the copper. Cryo-cooling is a potential technique to reduce thermal noise in microcoils, thereby recovering SNR. In this research, copper microcoils of two different geometries have been cryo-cooled using liquid nitrogen. Quality-factor (Q) measurements have been taken to quantify the reduction in resistance due to cryo-cooling. Image SNR has been compared between identical coils at room temperature and liquid nitrogen temperature. The relationship between the drop in series resistance and the increase in image SNR has been analyzed, and these measurements compared to theory. While cryo-cooling can bring about dramatic increases in SNR, the extremely low temperature of liquid nitrogen is incompatible with living tissue. In general, the useful imaging region of a coil is approximately as deep as the coil diameter, thus cryo-cooling of coils has been limited in the past to larger coils, such that the thickness of a conventional cryostat does not put the sample outside of the optimal imaging region. This research utilizes a scheme of microfluidic cooling (developed in the Texas A&M NanoBio Systems Lab), which greatly reduces the volume of liquid nitrogen required to cryo-cool the coil. Along with a small gas phase nitrogen gap, this eliminates the need for a bulky cryostat. This thesis includes a review of the existing literature on cryo-cooled coils for MRI, as well as a review of planar pair coils and spiral microcoils in MR applications. Our methods of fabricating and testing these coils are described, and the results explained and analyzed. An image SNR improvement factor of 1.47 was achieved after cryo-cooling of a single planar pair coil, and an improvement factor of 4 was achieved with spiral microcoils.

Superconducting nanowire single-photon detectors (SNSPDs) are nanodevices usually made from thin niobium nitride (NbN) films. Operated at liquid helium temperature, they can exhibit high detection efficiency with low dark-counts associated with a fast response time and a low timing jitter. Covering a broad detection range from ultraviolet to mid-infrared, SNSPDs are a very attractive alternative to silicon or gallium arsenide based semiconductor detectors for fiber based telecommunication when single-photon sensitivity and high counting rates are necessary. Efficient packaging and fiber coupling of a SNSPD is in itself a real challenge and is often a limiting factor in reaching high system quantum efficiency. Our approach makes use of a controlled expansion alloy which has been adequately heat treated to enhance its characteristics for cryogenic operation. This insures the integrity of the optical coupling at cryogenic temperatures while done at room temperature. It also provides a good attenuation for electromagnetic interference due to the high relative permeability of the nickel-iron alloy. The small form factor of this pigtailed optical fiber package makes it versatile and could be easily integrated with a commercial cryogen-free system or simply dipped into a standard helium transport Dewar. We report on our theoretical and experimental methodology to evaluate the optical coupling quality and present the optoelectronic characterization of two devices packaged in this way. Electrical simulation is studied to understand the speed limitation factor inherent to these devices and preliminary speed and jitter measurements are reported.

AEGIS (Antimatter Experiment, Gravity, Interferometry and Spectroscopy) isan experiment under development at CERN which will measure earth's gravitationalforce on antimatter. This will be done by creating a horizontal pulsedbeam of low energy antihydrogen, an atom consisting of an antiproton anda positron. The experiment will measure the vertical de ection of the beamthrough which it is possible to calculate the gravitational constant for antimatter.To characterise the production process in the current state of the experimentit is necessary to develop an imaging detector for single excited hydrogenatoms. This thesis covers the design phase of that detector and includes studiesand tests of detector components. Following literature studies, tests and havingdiscarded several potential designs, a baseline design was chosen. The suggesteddetector will contain a set of ionising rings followed by an electron multiplyingmicrochannel plate, a light emitting phosphor screen, a lens system and nallya CCD camera for readout. The detector will be able to detect single hydrogenatoms, measure their time of ight as well as being able to image electronplasmas and measure the time of ight of the initial particles in such a plasma.Tests were made to determine the behaviour of microchannel plates at the lowtemperatures used in the experiment. Especially, the resistance and multiplicationfactor of the microchannel plates have been measured at temperaturesdown to 14 K. / AEGIS

Superconducting nanowire single-photon detectors (SNSPDs) are nanodevices usually made from thin niobium nitride (NbN) films. Operated at liquid helium temperature, they can exhibit high detection efficiency with low dark-counts associated with a fast response time and a low timing jitter. Covering a broad detection range from ultraviolet to mid-infrared, SNSPDs are a very attractive alternative to silicon or gallium arsenide based semiconductor detectors for fiber based telecommunication when single-photon sensitivity and high counting rates are necessary. Efficient packaging and fiber coupling of a SNSPD is in itself a real challenge and is often a limiting factor in reaching high system quantum efficiency. Our approach makes use of a controlled expansion alloy which has been adequately heat treated to enhance its characteristics for cryogenic operation. This insures the integrity of the optical coupling at cryogenic temperatures while done at room temperature. It also provides a good attenuation for electromagnetic interference due to the high relative permeability of the nickel-iron alloy. The small form factor of this pigtailed optical fiber package makes it versatile and could be easily integrated with a commercial cryogen-free system or simply dipped into a standard helium transport Dewar. We report on our theoretical and experimental methodology to evaluate the optical coupling quality and present the optoelectronic characterization of two devices packaged in this way. Electrical simulation is studied to understand the speed limitation factor inherent to these devices and preliminary speed and jitter measurements are reported.