The elastic constants of Mg(1-x)AlxB2 have been calculated in the regime 0<x<0.25. The calculations show that the ratio, B/G, between the bulk- and the shear-modulus stays well below the empirical ductility limit, 1.75, for all concentrations, indicating that the introduction of Al will not change the brittle behaviour of the material considerably. Furthermore, the tetragonal elastic constant C’ has been calculated for the transition metal alloys Fe-Co, Mo-Tc and W-Re, showing that if a suitable tuning of the alloying is made, these materials have a vanishingly low C'. Thermal expansion calculations of the 4d transition metals have also been performed, showing good agreement with experiment with the exception of Nb and Mo. The calculated phonon dispersions of the 4d metals all give reasonable agreement with experiment. First principles calculations of the thermal expansion of hcp Ti have been performed, showing that this element has a negative thermal expansion along the c-axis which is linked to the closeness of the Fermi level to an electronic topological transition. Calculations of the EOS of fcc Au give support to the suggestion that the ruby pressure scale might underestimate pressures with ~10 GPa at pressures ~150 GPa. The high temperature bcc phase of the group IV metals has been calculated with the novel self-consistent ab-initio dynamical (SCAILD) method. The results show good agreement with experiment, and the free energy resolution of < 1 meV suggests that this method might be suitable for calculating free energy differences between different crystallographic phases as a function of temperature.

The thermodynamic properties of CO2-mixtures are essential for the design and operation of CO2 Capture and Storage (CCS) systems. A better understanding of the thermodynamic properties of CO2 mixtures could provide a scientific basis to define a proper guideline of CO2 purity and impure components for the CCS processes according to technical, safety and environmental requirements. However the available accurate experimental data cannot cover the whole operation conditions of CCS processes. In order to overcome the shortage of experimental data, theoretical estimation and modelling are used as a supplemental approach.   In this thesis, the available experimental data on the thermodynamic properties of CO2 mixtures were first collected, and their applicability and gaps for theoretical model verification and calibration were also determined according to the required thermodynamic properties and operation conditions of CCS. Then in order to provide recommendations concerning calculation methods for engineering design of CCS, totally eight equations of state (EOS) were evaluated for the calculations about vapour liquid equilibrium (VLE) and density of CO2-mixtures, including N2, O2, SO2, Ar, H2S and CH4.   With the identified equations of state, the preliminary assessment of impurity impacts was further conducted regarding the thermodynamic properties of CO2-mixtures and different processes involved in CCS system. Results show that the increment of the mole fraction of non-condensable gases would make purification, compression and condensation more difficult. Comparatively N2 can be separated more easily from the CO2-mixtures than O2 and Ar. And a lower CO2 recovery rate is expected for the physical separation of CO2/N2 under the same separation conditions. In addition, the evaluations about the acceptable concentration of non-condensable impurities show that the transport conditions in vessels are more sensitive to the non-condensable impurities and it requires very low concentration of non-condensable impurities in order to avoid two-phase problems.   Meanwhile, the performances of evaporative gas turbine integrated with different CO2 capture technologies were investigated from both technical and economical aspects. It is concluded that the evaporative gas turbine (EvGT) cycle with chemical absorption capture has a smaller penalty on electrical efficiency, while a lower CO2 capture ratio than the EvGT cycle with O2/CO2 recycle combustion capture. Therefore, although EvGT + chemical absorption has a higher annual cost, it has a lower cost of electricity because of its higher efficiency. However considering its lower CO2 capture ratio, EvGT + chemical absorption has a higher cost to avoid 1 ton CO2. In addition the efficiency of EvGT + chemical absorption can be increased by optimizing Water/Air ratio, increasing the operating pressure of stripper and adding a flue gas condenser condensing out the excessive water. / QC 20100819

The Equation of State (EoS) of asymmetric nuclear matter has been explored through the study of mid-rapidity fragment dynamics from the 35 MeV/u $^{70}$Zn $^{70}$Zn, $^{64}$Zn $^{64}$Zn, and $^{64}$Ni $^{64}$Ni systems. The experimental data was collected at the Texas A and M Cyclotron Institute using the 4 NIMROD-ISiS array, which provided both event characterization and excellent isotopic resolution of charged particles. The transverse collective flow was extracted for proton, deuteron, triton, 3He, alpha, and 6He particles. Isotopic and isobaric effects were observed in the transverse flow of the fragments. In both cases, the transverse flow was shown to decrease with an increasing neutron content in the fragments. The (N/Z)sys dependence of the transverse flow and the difference betwen the triton and 3He flow were shown to be sensitive to the density dependence of the symmetry energy using the stochastic mean-field model. A stiff parameterization of Esym(p) was found to provide better agreement with the experimental data. The transverse flow for intermediate mass fragments (IMFs) was investigated, providing a new probe to study the nuclear EoS. A transition from the IMF flow strongly depending on the mass of the system, in the most violent collisions, to a dependence on the charge of the system, for the peripheral reactions, was observed. Theoretical simulations were used to show that the relative differences in the IMF flow are sensitive to the density dependence of the symmetry energy. The best agreement between the experiment and theory was achieved with a stiff Esym(p). A new method was developed in which correlations between the projectile-like and mid-rapidity fragments were examined using a scaled flow. Theoretical simulations were used to show that the scaled flow of the particles was connected to their average order of emission. The experimental results suggest that the mid-rapidity region is preferentially populated with neutron-rich light charged particles and the Z=3-4 IMFs at a relatively early stage in the collision. This work presents additional constraints on the nuclear EoS and insight into the mid-rapidity dynamics observed in Fermi energy heavy-ion collisions.

The knowledge of phase equilibrium is essential for the planning and realisation of separation processes in chemical engineering. In this work an equipment for measurement of precise isothermal vapour–liquid equilibria (VLE) using the dynamic method was developed. The pool of experimental data for cyclohexylamine was extended significantly. Isothermal VLE were measured in 3 binary and 4 ternary systems, liquid-liquid equilibria (LLE) were measured in 4 ternary systems and in one quarternary system, in each case for two temperatures, whereas in 2 ternary systems and in the quarternary system even liquid-liquid-liquid equilibria (LLLE) occur. Furthermore, activity coefficients at infinite dilution in 4 binary systems and excess molar volumes in 7 binary systems have been estimated. Binary VLE and LLE data of the components water, octane, cyclohexylamine and aniline of this work and data from literature were fitted with the activity coefficient models NRTL and UNIQUAC, as well as with the equations of state Elliott-Suresh-Donohue (ESD) and Perturbed-Chain-Statistical Associating Fluid Theory (PC-SAFT) which contain both a term to consider explicit hydrogen bonds. In addition, the predictive capabilities of the equations of state (EoS) were investigated. With parameters obtained by simultaneous fitting of VLE and, if available, LLE data similar results with the models NRTL and UNIQUAC could be obtained. Each time the deviations for the vapour pressure were lower than 3 % and lower than 2 % in vapour phase composition. The deviations, in three out of the six systems for vapour pressure and vapour phase composition, were larger with the ESD-EoS than with the activity coefficient models. NRTL, UNIQUAC and ESD delivered similar results with the simultaneously fitted parameters for the LLE, whereas the deviations were lower than 5 %. Comparable results were delivered by the ESD-EoS and PC-SAFT for the fitting and the prediction in the investigated binary systems. Also a fitting for NRTL, UNIQUAC and ESD was carried out, but only to one data set. The intention was to show the effect of parameterization on prediction in ternary systems. Predictions were made for VLE and LLE in ternary systems of the above mentioned components, solely with interaction parameters fitted to binary data. For the models NRTL, UNIQUAC und ESD predictions of simultaneously and separately fitted parameters are presented. It is shown that with parameters simultaneously fitted to several data sets significantly better results could be obtained compared to the parameters separately fitted to a single data set. Additionally, for the equations of state ESD and PC-SAFT predictions for the LL(L)E in ternary systems are compared, but here only with separately fitted parameters. For three out of the four investigated ternary systems a too large miscibility gap is calculated with the models NRTL, UNIQUAC and ESD. In the system water+octane+aniline good results could be obtained for the prediction of the LLLE. In summary the equations of state deliver similar results. In the systems water+octane+CHA and octane+CHA+aniline also too large two phase regions were delivered. Better predictions could be obtained in the systems water+octane+aniline and water+CHA+aniline. The forecasts of the VLE in the ternary systems are good with the simultaneously fitted parameters. The deviations for the vapour phase compositions are as for the vapour pressures under 6 %. Larger deviations occur for the system water+octane+aniline only. As evaluation result for the thermodynamic models can be mentioned that the activity coefficient models NRTL and UNIQUAC deliver somewhat better results for the fitting of the binary data than the equations of state ESD and PC-SAFT however, with a larger number of adjustable parameters. The prediction of the VLE is satisfactorily in the ternary systems and with similar quality of all considered models. Larger deviations occur for the prediction of the LL(L)E in the ternary systems. The results of the ESD-EoS were, with one exception, each time better than those of the activity coefficient models. There is no significant difference between the prediction of the ternary systems for the ESD-EoS and the PC-SAFT.

Die Phasengleichgewichte (Flüssigkeit-Dampf und Flüssigkeit-Flüssigkeit) der binären, ternären und quaternären Mischungen bestehend aus Wasser, Toluen, Anilin und Cyclohexylamin wurden experimentell bestimmt und modelliert bzw. vorausberechnet. Die Bestimmung der Flüssigkeit-Dampf-Gleichgewichte erfolgte mit Hilfe der dynamischen Methode, die dafür notwendige Mess- und Regeltechnik wurde erweitert und modernisiert. Die Flüssigkeit-Flüssigkeit-Gleichgewichte wurden durch Trübungstitration und Analyse der koexistierenden Phasen bestimmt. Die Beschreibung der binären Systeme und die Vorausberechnung der Mehrkomponentensysteme erfolgte mit den Aktivitätskoeffizientenmodellen UNIQUAC und NRTL und der Zustandsgleichung, entwickelt von Elliott, Suresh und Donohue (ESD). Die ESD-Zustandsgleichung enthält neben einem Attraktions- und einem Repulsionsterm auch einen Term, der assoziative Wechselwirkungen explizit berücksichtigt. Die Beschreibung der binären Systeme gelingt mit den getesteten Modellen sehr gut. Dabei werden mit den Aktivitätskoeffizientenmodellen bessere Ergebnisse erreicht als mit der ESD-Zustandsgleichung. Diese Bild kehrt sich bei der Vorausberechnung der Mehrkomponentensysteme um. Bei Verwendung der NRTL-Gleichung treten deutlich höhere Abweichungen auf als bei Berechnungen mit der ESD-Zustandsgleichung bzw. der UNIQUAC-Gleichung. Die Erwartung durch explizite Berücksichtigung der Assoziation mit der ESD-Zustandsgleichung einen deutlichen Vorteil in der Vorhersage von Phasengleichgewichten in Systemen mit assoziierenden Komponenten zu erhalten konnte in den untersuchten Mischungen nicht eindeutig bestätigt werden. / Phase equilibria (vapor-liquid and liquid-liquid) of binary, ternary and quaternary systems consisting of water, toluene, aniline and cyclohexylamine were determined experimentally and modeled resp. predicted. Vapor-liquid equilibria were determined by the dynamic method, the necessary measuring and control systems were extended and modernized. Liquid-liquid equilibria were investigated by turbidity titration and analyses of coexisting phases. The calculation of the binary systems and the prediction of the multicomponent systems were performed with the activity coefficient models UNIQUAC and NRTL and the equation of state developed by Elliott, Suresh and Donohue (ESD). The ESD equation of state includes beside an attractive and a repulsive term a term for explicit consideration of associative interaction. The description of the binary systems succeeded very well with the tested models. Better results were achieved with the activity coefficient models than with the ESD equation of state. These findings are inversed in the case of prediction of multicomponent phase equilibria. On application of the NRTL equation the deviations are notable greater than with the ESD equation of state or the UNIQUAC equation. The expectation to get a significant advantage in prediction of phase equilibria in systems with associating components with the ESD equation of state could not be answered definitely.

No description available.

The past decade has witnessed dramatic changes in the oil and gas industry with the drilling and production extending into progressively deeper waters and higher operating pressures, therefore making it essential to gain a better understanding of the behaviour of gas hydrate at high pressure conditions. New experimental 3-phase H−LW−V (Hydrate−Liquid Water−Vapour) equilibrium data for nitrogen and H−LW−V (Hydrate−Liquid Water−Vapour) and H−LW−LHC (Hydrate−Liquid Water−Liquid Hydrocarbon) data for ethane and propane simple clathrate hydrates were generated by a reliable fixed-volume, isochoric, step-heating technique. The accuracy and reliability of the experimental measurements are demonstrated by comparing measurements with reliable literature data from different researchers. Additional experimental data up to high pressure (200 MPa when available) for CH4, C2H6, C3H8, i-C4H10, N2, Ar, Kr, Xe, H2S, O2, CO and CO2 clathrates have been gathered from literature. The Valderrama modification of the Patel-Teja (VPT) equation of state combined with non-density-dependent (NDD) mixing rules is used to model the fluid phases with previously reported binary interaction parameters. The hydrate-forming conditions are modelled by the solid solution theory of van der Waals and Platteeuw. Langmuir constants have been calculated by both Kihara potential as well as direct techniques. Model predictions are validated against independent experimental data and a good agreement between predictions and experimental data is observed, supporting the reliability of the developed model.

An investigation of the high-strain-rate mechanical properties, deformation mechanisms, and fracture characteristics of a Zr-based bulk metallic glass (BMG) and its composite with tungsten was conducted through the use of controlled impact experiments and constitutive modeling. The overall objective of this research was to determine the high-strain-rate deformation and failure mechanisms of a BMG and its composite as a function of stress state and strain rate, and describe the mechanical behavior over a range of loading conditions. The research involved performing controlled impact experiments on BMG composites consisting of an amorphous Zr57Nb5Cu15.4Ni12.6Al10 (LM106) with crystalline tungsten reinforcement particles. Monolithic LM106 was also examined to aid in the understanding of the composite. The mechanical behavior of the composite was investigated over a range of strain rates (10^3 s^-1 to 10^6 s^-1), stress states (compression, compression-shear, tension), and temperatures (RT to 600 C) to determine the dependence of mechanical properties and deformation and failure modes (i.e., homogeneous deformation vs. inhomogeneous shear banding) on these parameters. Mechanical testing in the quasi-static to intermediate strain rate regimes was performed using an Instron, Drop Weight Tower, and Split Hopkinson Pressure Bar, respectively. High-strain-rate mechanical properties of the BMG-matrix composite and monolithic BMG were investigated using dynamic compression (reverse Taylor) and dynamic tension (spall) impact experiments performed using a gas gun instrumented with velocity interferometry and high-speed digital photography. These experiments provided information about dynamic strength and deformation modes, and allowed for validation of constitutive models via comparison of experimental and simulated transient deformation profiles and free surface velocity traces. Hugoniot equation of state measurements were performed on the monolithic BMG to investigate the high pressure phase stability of the glass and the possible implications of a high pressure phase transformation on mechanical properties. Specimens were recovered for post-impact microstructural and thermal analysis to gain information about the mechanisms of dynamic deformation and fracture, and to examine for possible shock-induced phase transformations of the amorphous phase.

Dans ce manuscrit, nous présentons une étude expérimentale d’un gaz de Bose de spin-1 avec des interactions antiferromagnétiques, réalisée pour des atomes de sodium ultra-froids dans l’état hyperfin F=1. Gr au refroidissement évaporatif, nous obtenons un condensat de Bose-Einstein (CBE) spineur, soit dans un piège très confinant (« piège 0D »), soit sous la forme d’un quasi-condensat quasi-unidimensionnel dans un piège très allongé. Les deux systèmes présentent un ordre magnétique a très basse température, qui résulte de la compétition entre les interactions d’échange et l’énergie Zeeman quadratique q dans un champ magnétique externe. Nous étudions dans un premier temps l’ordre magnétique se forme dans le piège 0D. À très bassetempérature deux phases magnétiques sont possible : une phase dite « antiferromagnétique » pour q < Us, ou une phase dite « à aimantation transverse » dans le cas inverse. Dans ce travail, nous nous plaçons près de la température critique. Nous mesurons plusieurs scénarios de condensation séquentielles en changeant la magnétisation et le champ magnétique externe, ou une composante Zeeman condense toujours en premier et ou l’ordre magnétique n’apparait qu’à une seconde température de condensation. Les résultats expérimentaux pour les températures critiques sont bien décrits par une théorie d’Hartree-Fock simplifiée dans les cas ou une seule composante Zeeman est condensée. Dans un second temps, nous étudions l’ordre magnétique du système quasi-unidimensionnel a basse température. On observe la formation de domaines de spin ou les composantes Zeeman se sépare spontanément en domaines disjoints en l’absence de force extérieure (par exemple, un gradient de champ magnétique). On étudie l’état d’équilibre du système en fonction de la magnétisation et du champ magnétique. On observe une transition de phase entre une phase miscible et une phase immiscible ou la composante Zeeman mF = 0 forme un domaine séparé de mF = ±1 dans le centre du piège. L’équation d’état d’un nuage polarisé (atomes dans l’état mF = +1) est utilisée pourmesurer la température du système. Enfin, nous mesurons la réponse mécanique a une force magnétique appliquée pour un système binaire mF = 0, +1. Nous mesures une exaltation de la réponse par rapport a l’attente na basée sur l’effet Zeeman habituel, d’un facteur qui peut varier de plusieurs dizaines a environ cent. La configuration spatiale des domaines est ainsi sensible a de très faibles gradients de champ magnétique inférieurs au mG/cm. / In this thesis we present the experimental study of a spin-1 Bose gas of ultra-cold Na atoms with antiferromagnetic interactions in the F=1 manifold. Thanks to evaporative cooling in optical traps we obtain, depending on the trap geometry, quasi-pure spinor Bose-Einstein condensates (BEC) in 0D traps and quasi-condensates in quasi-1D traps. The quantum-statistical Bose enhancement, typical of BEC, allows inter-component interactions (between the different Zeeman components) to order the system just below the Bose-Einstein condensation temperature. The magnetic ordering of the system is set: by contact interactions, that do not change the Zeeman populations, by spin-exchange interactions (U_s spin-exchange energy), that do, and by the quadratic Zeeman energy q. In particular, for q < U_s the system is in the antiferromagnetic phase while, for q > U_s, is in the transverse magnetised phase. We study first in which order the magnetic ordering appears, in the 0D trap, near to the critical temperature for BEC. We experimentally study different condensations scenarii varying q and magnetisation. The condensation of the different components is sequential and strongly influenced by interactions. We find a good agreement between the experimental data and a simplified Hartree-Fock model.Then we study the magnetic ordering, at T=0, in a quasi-1D trap. The system presents the formation of spin domains. We study the ground state of the system varying magnetisation and q. We observe a transition from the miscible to the immiscible phase, associated with the transition from the antiferromagnetic to the transverse magnetised phase. This is due to the relative strengths of inter-species contact interaction. To measure the temperature of the system, we measure the equation of state for a polarised cloud (all atoms in m_F=+1). Finally, we prepare the system in the immiscible phase m_F=0,+1 and we measure the spin-dipole polarisability of the system.

This thesis is dedicated to the exploration of fluid phases confined in nanoporous materials using Nuclear Magnetic Resonance (NMR) techniques, with an aim to benefit catalysis research. Included in this report are studies of pure fluids and their mixtures, confined in titania and silica catalyst supports. These investigations are conducted at industrially-relevant, high-temperature (≥ 180 °C) and high-pressure conditions (up to 13 bar), made possible by a pilot-scale chemical reactor unit, designed to operate inside the strong magnetic fields of an NMR spectrometer. NMR spectroscopy, relaxation and pulsed field gradient (PFG) diffusion experiments were performed on each of the systems discussed in this report. Cyclohexane was initially studied inside a porous titania catalyst support at 188 °C and various pressures up to 13 bar. The adsorption and desorption processes of the cyclohexane were observed, revealing a number of previously unobserved phenomena. In addition to an overall, averaged diffusion coefficient, a slow diffusion coefficient was observed within the PFG NMR data attributable to surface diffusive processes occurring within the material. Additionally, T1 relaxation studies were found to provide experimental evidence for the differing configurations of adsorbed layers on the adsorption and desorption branch of the isotherm. Cyclohexane was subsequently studied alongside fluorobenzene in a series of silica catalyst supports of 6 nm, 10 nm and 20 nm pore size. In doing this, it was hoped that the multiple phenomena observed in the titania experiments might be deconvoluted, allowing a greater level of insight. The diffusivities of the fluids were found to differ significantly between the materials, and greater evidence was found of the slow-diffusing surface phase in each of the materials. Additionally, concentrations of cyclohexane and fluorobenzene in the gas and adsorbed layers inside the pore space were calculated via the results of the PFG NMR experiments, providing a map of confined phase behaviour. Competitive adsorption effects were found to become more significant, the smaller the pore size of the material. The results of the cyclohexane and fluorobenzene in silica studies were modelled, using approaches available in the literature, which were found to give varying levels of prediction. The data set acquired in this thesis was found to provide a useful standard, against which current and future models of confined phase behaviour might be verified.