L’intérêt grandissant envers les nanomatériaux a base des métaux de transition 3d comme le cobalt, le nickel et le fer trouve son origine dans les propriétés intrinsèques de ces éléments (forte aimantation du fer et constante magnétocristalline élevée du cobalt) combinées aux propriétés particulières offertes par la taille nanométrique et l’anisotropie de ces alliages. Parmi les nombreuses voies de synthèse dites de chimie douce, le procède polyol permet l’élaboration de plusieurs classes de matériaux inorganiques a l’état finement divises (oxydes, hydroxydes et métaux) grâce aux réactions de réduction et d’hydrolyse qui peuvent être conduites et contrôlées dans les milieux polyols. Le premier axe de ce travail a consisté à tirer profit de l’état finement divise des oxydes et hydroxydes élabores en milieu polyol pour l’obtention de métaux et alliages correspondants, au moyen d’une réduction ménagée a l’état solide sous flux d’hydrogène. Il a alors été possible d’aboutir a des particules de CoFe2, CoFe, NiFe, Ni3Fe et Fe ferromagnétiques avec une température de blocage supérieure a 300 K. Le deuxième axe de travail a trait a l’élaboration d’objets anisotropes. Pour ce faire, une nouvelle approche est proposée : la synthèse en milieu polyol assistée par l’application d’un champ magnétique. Ce type de synthèse mené a des nanofils d’akaganeite β-FeOOH et a des nanoparticules d’oxydes spinelles. Une réduction relativement douce (300 °C) des nanofils d’akaganeite permet de l’obtention de phases spinelles de même morphologie et avec des propriétés magnétiques en accord avec la composition chimique et le caractère nanométrique des particules (comportement superparamagnétique avec une température de blocage proche de 300 K, Ms élevée et Hc dépendant de la nature de l’élément M se trouvant dans le spinelle MFe2O4 : élevé dans le cas du cobalt et faible dans le cas du fer et du nickel). / The growing interest in nanomaterials based on 3d transition metals such as cobalt, iron and nickel finds its origin in the intrinsic properties of these elements (high magnetization of iron and high magnetocristalline constant of cobalt) combined with particular property due to nanometric size and anisotropy of these alloys. Among the numerous synthetic routes, the polyol method which belongs to the chimie douce routes allows the elaboration of several finely divided inorganic materials (oxides, hydroxides, metals) by means of reduction or forced hydrolysis reactions conducted in polyol medium. The main first contribution of this work was to take advantage of these finely divided oxides and hydroxides elaborated in polyol medium to obtain metals and alloys, through a controlled reduction in solid form under hydrogen flow. Ferromagnetic particles of CoFe2, CoFe, NiFe, Ni3Fe and Fe with a blocking temperature above 300 K were obtained. The second main contribution of this work relates elaboration of anisotropic objects. Further, a new approach is proposed: forced hydrolysis in polyol medium assisted by applying a magnetic field. This type of synthesis leads to akaganeite β7&eOOH nanowires and spinel oxides nanoparticles. A relative mild reduction (300 °C) of akaganeite nanowires allows to obtain spinels phase with same morphology and magnetic properties in agreement with the chemical composition and the particles nanoscale (superparamagnetic behavior with blocking temperaturenear 300 K, high Ms and Hc dependent on the nature of the M element in the spinel MFe2O4, high in the case of cobalt and low for nickel and iron).

This thesis describes the synthesis of ruthenium based molecular clusters and their characterisation. Chapter 2 introduces the concept that the very large zero-field splitting (D = 2.9 cm–1) in the S = 5/2 ground state of [Ru2Mn(μ3-O)(tBuCO2)6(py)3] can be modelled by antisymmetric exchange effects. This is supported by measurement of the single ion D values from the Fe2Mn analogue. The same model is applied to the Ru2Ni analogue to describe the zero-field splitting in the S = 1 ground state, (DGS = +8.0 cm–1 from DNi = -4.0 cm–1) in Chapter 3.Chapters 3 and 4 give the full characterisation of each of the two families, [MIII2MII(μ3-O)(tBuCO2)6(py)3] (MIII = Ru or Fe, MII = Mn, Co, Ni or Zn), through IR, electronic absorption and NMR spectroscopy and are structurally characterised by X-ray diffraction. The total spin ground states and zero-field splitting of those ground states have been ascertained by SQUID magnetometry and EPR spectroscopy. Due to the redox activity of the Ru2M complexes chemical oxidations led to the isolation of [RuIII2CoIIIO(tBuCO2)6(py)3]+ (5) and [RuIIIRuIVNiIIO(tBuCO2)6(py)3]+ (6); the locus of their oxidation was determined with the aid of X-ray absorption spectroscopy (XAS).Chapter 5 shows that due to the ease of the substitution of the terminal ligand in Ru2M they can be linked to other molecular clusters with N-donor ligands, in this case [Cr7NiF8(tBuCO2)15(O2CC5H4N)][NH2Pr2] in order to synthesise [Ru2NiO(tBuCO2)6(py)(Cr7NiF8(tBuCO2)15(O2CC5H4N))2][NH2Pr2]2. In situ oxidation experiments have also been carried out to assess the switchabilty of the redox active linker. Chapter 6 demonstrates a new structural archetype for tetranuclear ruthenium mixed-metal complexes, with the formula, [Ru2M2(µ3-OH)2(tBuCO2)7(py)4], where M is either Co (1) or Ni (2). SQUID magnetometry and EPR spectroscopy have determined the spin ground states as, Seff = 1/2 in 1 and S = 3/2 in 2. The magnetic anisotropy in 2 has been determined as +2.02 cm–1 for the S = 3/2 ground state.

Un des ingrédients principaux pour la simulation numérique des écoulements des fluides (hydrocarbures, gaz naturel) en milieux poreux est la discrétisation des termes elliptiques anisotropes et hétérogènes. Dans l’industrie pétrolière, la nécessité d’améliorer la précision des simulations dans les régions proches des puits a suscité l’utilisation de maillages non structurés généraux et des tenseurs de perméabilité pleins. Notre défi a été de trouver des discrétisations consistantes et robustes des termes elliptiques anisotropes, hétérogènes sur maillages généraux. Notre recherche s’est focalisée sur des méthodes volumes finis qui soient consistantes, stables sur maillages polyédriques généraux, robustes par rapport à l’anisotropie et l’hétérogénéité du tenseur de perméabilité, qui mènent à des systèmes linéaires bien conditionnés pour lesquels des stratégies de préconditionnement optimales peuvent être conçues et qui donnent un stencil compact pour réduire les communications dans les implémentations parallèles. Pour répondre à cette recherche, nous avons proposé plusieurs schémas tels que MPFA O généralisé, G scheme, CG method, VFSYM, DIOPTRE. Nous avons prouvé également que toutes ces méthodes convergent sous des hypothèses adéquates à la fois sur le tenseur de perméabilité et le maillage / One of the key ingredients for the numerical simulation of Darcy flow in heterogeneous porous media is the discretization of anisotropic heterogeneous elliptic terms. In the oil industry, the need to improve accuracy in near wellbore regions has prompted the use of general unstructured meshes and full permeability tensors. Our effort has therefore been devoted to find consistent and robust finite volume discretizations of anisotropic, heterogeneous elliptic terms on general meshes. Our research was focused on finite volume methods which are consistent and coercive on general polyhedral meshes as well as robust with respect to the anisotropy and heterogeneity of the permeability tensor ; yield well-conditioned linear systems for which optimal preconditioning strategies can be devised ; have a narrow stencil to reduce the communications in parallel implementations. To answer to this search, we have proposed several scemes such that generalized MPFA O, G scheme, CG method, VFSYM, DIOPTRE. We proved also the convergence of all these methods under suitable assumptions on both the permeability tensor and the mesh

EIT is a method of imaging that exists for a century, initially in geophysics and in recent years in medical imaging. Even though the practical applications of EIT go back to the early 20th century the systematic study of the inverse conductivity problem started in the late 1970s, hence many aspects of the problem remain unexplored. In the study of the inverse conductivity problem usually Finite Element Models are used since they can be easily adapted for bodies of irregular shapes. In this work though we use an equivalent approximation, the electrical resistor network, for which many uniqueness results as well as reconstruction algorithms exist. Furthermore resistor networks are important for EIT since they are used to provide convenient stable test loads or phantoms for EIT systems. In this thesis we study the transfer resistance matrix of a resistor network that is derived from n-port theory and review necessary and sufficient conditions for a matrix to be the transfer resistance of a planar network. The so called “paramountcy” condition may be useful for validation purposes since it provides the means to locate problematic electrodes. In the study of resistor networks in relation to inverse problems it is of a great importance to know which resistor networks correspond to some Finite Element Model. To give a partial answer to this we use the dual graph of a resistor network and we represent the voltage by the logarithm of the circle radius. This representation in combination with Duffin’s non-linear resistor network theory provides the means to show that a non-linear resistor network can be embedded uniquely in a Euclidean space under certain conditions. This is where the novelty of this work lies.

AN ABSTRACT OF THE DISSERTATION OFSUMAN SAURABH, for the Doctor of Philosophy degree in Engineering Science, presented on August 30, 2019, at Southern Illinois University Carbondale.TITLE: GEOMECHANICAL STATE OF ROCKS WITH DEPLETION IN UNCONVENTIONAL COALBED METHANE RESERVOIRSMAJOR PROFESSOR: Dr. Satya HarpalaniOne of the major reservoir types in the class of unconventional reservoirs is coalbed methane. Researchers have treated these reservoirs as isotropic when modeling stress and permeability, that is, mechanical properties in all directions are same. Furthermore, coal is a highly sorptive and stress- sensitive rock. The focus of this dissertation is to characterize the geomechanical aspects of these reservoirs, strain, stresses, effective stress and, using the information, establish the dynamic flow/permeability behavior with continued depletion. Several aspects of the study presented in this dissertation can be easily extended to shale gas reservoirs. The study started with mechanical characterization and measurement of anisotropy using experimental and modeling work, and evaluation of how the sorptive nature of coal can affect the anisotropy. An attempt was also made to characterize the variation in anisotropy with depletion. The results revealed that the coals tested were orthotropic in nature, but could be approximated as transversely isotropic, that is, the mechanical properties were isotropic in the horizontal plane, but significantly different in vertical direction. Mechanical characterization of coal was followed by flow modeling. Stress data was used to characterize the changes in permeability with depletion. This was achieved by plotting stress path followed by coal during depletion. The model developed was used to successfully predict the permeability variation in coal with depletion for elastic deformations. As expected, the developed model failed to predict the permeability variation resulting from inelastic deformation given that it was based on elastic constitutive equations. Hence, the next logical step was to develop a generalized permeability model, which would be valid for both elastic and inelastic deformations. Investigation of the causes of coal failure due to anisotropic stress redistribution during depletion was also carried out as a part of this study. It was found that highly sorptive rocks experience severe loss in horizontal stresses with depletion and, if their mechanical strength is not adequate to support the anisotropic stress redistribution, rock failure can result. In order to develop a generalized permeability model based on stress data, stress paths for three different coal types were established and the corresponding changes in permeability were studied. Stress path plotted in an octahedral mean stress versus octahedral shear stress plane provided a signal for changes in the permeability for both elastic as well as inelastic deformations. This signal was used to develop a mechanistic model for permeability modeling, based on stress redistribution in rocks during depletion. The model was able to successfully predict the permeability variation for all three coal types. Finally, since coal is highly stress- sensitive, changes in effective stresses were found to be the dictating factor for deformations, changes in permeability and possible failure with depletion. Hence, the next step was to develop an effective stress law for sorptive and transversely isotropic rocks. For development of an effective stress law for stress sensitive, transversely isotropic rocks, previously established constitutive equations were used to formulate a new analytical model. The model was then used to study changes in the variation of Biot’s coefficient of these rocks. It was found that Biot’s coefficient, typically less than one, can take values larger than one for these rocks, and their values also change with depletion. The study provides a methodology which can be used to estimate the Biot’s coefficient of any rock. As a final step, preliminary work was carried out on the problem of under-performing coal reservoirs in the San Juan basin, where coal is extremely tight with very low permeability. An extension of the work presented in this dissertation is to use the geomechanical characterization techniques to unlock these reservoirs and improve their performance. The experimental data collected during this preliminary study is included in the last chapter of the dissertation.

No description available.

Natural gas and oil from characteristically complex unconventional reservoirs, such as organic shale, tight gas and oil, coal-bed methane; are transforming the global energy market. These conventional reserves exist in complex geologic formations where conventional seismic techniques have been challenged to successfully image the subsurface. To acquire maximum benefits from these unconventional reserves, seismic anisotropy must be at the center of our modeling and inversion workflows. I present algorithms for fast traveltime computations in anisotropic media. Both ray-based and finite-difference solvers of the anisotropic eikonal equation are developed. The proposed algorithms present novel techniques to obtain accurate traveltime solutions for anisotropic media in a cost-efficient manner. The traveltime computation algorithms are then used to invert for anisotropy parameters. Specifically, I develop inversion techniques by using diffractions and diving waves in the seismic data. The diffraction-based inversion algorithm can be combined with an isotropic full-waveform inversion (FWI) method to obtain a high-resolution model for the anellipticity anisotropy parameter. The inversion algorithm based on diving waves is useful for building initial anisotropic models for depth-migration and FWI. I also develop the idea of 'effective elliptic models' for obtaining solutions of the anisotropic two-way wave equation. The proposed technique offers a viable alternative for wavefield computations in anisotropic media using a computationally cheaper wave propagation operator. The methods developed in the thesis lead to a direct cost savings for imaging and inversion projects, in addition to a reduction in turn-around time. With an eye on the next generation inversion methods, these techniques allow us to incorporate more accurate physics into our modeling and inversion framework.

The main goal in seismic exploration is to identify locations of hydrocarbons reservoirs and give insights on where to drill new wells. Therefore, estimating an Earth model that represents the right physics of the Earth's subsurface is crucial in identifying these targets. Recent seismic data, with long offsets and wide azimuth features, are more sensitive to anisotropy. Accordingly, multiple anisotropic parameters need to be extracted from the recorded data on the surface to properly describe the model. I study the prospect of applying a scattering integral approach for multi-parameter inversion for a transversely isotropic model with a vertical axis of symmetry. I mainly analyze the sensitivity kernels to understand the sensitivity of seismic data to anisotropy parameters. Then, I use a frequency domain scattering integral approach to invert for the optimal parameterization. The scattering integral approach is based on the explicit computation of the sensitivity kernels. I present a new method to compute the traveltime sensitivity kernels for wave equation tomography using the unwrapped phase. I show that the new kernels are a better alternative to conventional cross-correlation/Rytov kernels. I also derive and analyze the sensitivity kernels for a transversely isotropic model with a vertical axis of symmetry. The kernels structure, for various opening/scattering angles, highlights the trade-off regions between the parameters. For a surface recorded data, I show that the normal move-out velocity vn, ƞ and δ parameterization is suitable for a simultaneous inversion of diving waves and reflections. Moreover, when seismic data is inverted hierarchically, the horizontal velocity vh, ƞ and ϵ is the parameterization with the least trade-off. In the frequency domain, the hierarchical inversion approach is naturally implemented using frequency continuation, which makes vh, ƞ and ϵ parameterization attractive. I formulate the multi-parameter inversion using the scattering integral method. Application to various synthetic and real data examples show accurate inversion results. I show that a good background ƞ model is required to accurately recover vh. For 3-D problems, I promote a hybrid approach, where efficient ray tracing is used to compute the sensitivity kernels. The proposed method highly reduces the computational cost.

Strain control of correlated electron phenomena has been a theme of condensed matter research in recent years. Two primary areas of investigation have been controllable symmetry breaking and measurements of susceptibility with respect to elastic deformation and in this thesis we present an example of each. In 2H-NbSe₂ explore the effect of lattice anisotropy on the charge-ordered superconductor. Using a novel strain apparatus, we measure the superconducting transition temperature 𝑇_{sc} as a function of uniaxial strain. It is found that 𝑇_{sc} is independent of tensile(compressive) strain below a threshold of 0.2% (0.1%), but decreases strongly with larger strains with an average rate of 1.3𝐊/% (2.5𝐊/%). Transport signatures of charge order are largely unaffected as a function of strain. We employ theoretical considerations to show that the change in the behavior of 𝑇_{sc} with strain coincides with a phase transition from 3𝐐 to 1𝐐 charge order in the material. The spectral weight on one of the Fermi surface bands is found to change strongly as a consequence of this phase transition, providing a pathway to tune superconducting order. In the bilayer ruthenate Ca₃(Ru₁₋ₓTiₓ)₂O₇ a material that is unique among correlated insulators for its hybrid improper ferroelectricity and, at elevated temperatures, transitioning to a polar metallic phase, we investigate phase textures and their susceptibility to strain. Through multi-messenger low-temperature infrared and Kelvin probe nano-imaging, we reveal a spontaneous striped texture of coexisting insulating and metallic domains in single crystals across their insulator-metal phase transition at T=50-100K. Under in situ uniaxial strain, we image anisotropic nucleation and growth of these domains, rationalized through on-demand control of a spontaneous Jahn-Teller distortion. Through spatially correlative transmission electron microscopy and nano-scale strain mapping, we also reveal the selective interplay between this textured phase coexistence and domain boundaries between polar twins in these crystals. We study the strain susceptibility of the striped phase mixture and explain our results in terms of homogeneous phase susceptibilities and the strain susceptibility of domains. We study the anisotropy in bulk response functions (resistivity and elastosusceptibility) and we find that the results are consistent with a network model of the phase texture. We also perform low-temperature infrared nanoimaging and elastosusceptibility of the nonequilibrium current-driven metal-insulator transition in Ca₃(Ru₁₋ₓTiₓ)₂O₇. Our results are consistent with the emerging consensus explanation in terms of Joule heating.

Thesis: M.S., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 1977 / Includes bibliographical references. / M.S. / M.S. Massachusetts Institute of Technology, Department of Materials Science and Engineering