Unconventional natural gas resources, particularly tight gas sands, constitute a significant percentage of the natural gas resource base and offer abundant potential for future reserves and production. The premise of this research is that several unique characteristics of these rocks are the consequence of post depositional diagenetic processes including mechanical compaction, quartz and other mineral cementation, and mineral dissolution. These processes lead to permanent alteration of the initial pore structure causing an increase in the number of isolated and disconnected pores and thus in the tortuosity. The objective of this research is to develop a pore scale model of the geological processes that create tight gas sandstones and to carry out drainage simulations in these models. These models can be used to understand the flow connections between tight gas sandstone matrix and the hydraulic fractures needed for commercial production rates. We model depositional and diagenetic controls on tight gas sandstones pore geometry such as compaction and cementation processes. The model is purely geometric and begins by applying a cooperative rearrangement algorithm to produce dense, random packings of spheres of different sizes. The spheres are idealized sand grains. We simulate the evolution of these model sediments into low-porosity (3% to 10%) sandstone by applying different amount of ductile grains and quartz precipitation. A substantial fraction of the original pore throats in the sediment are closed by the simulated diagenetic alteration. Thus, the pore space in typical tight gas sandstones is poorly connected, and is often close to being completely disconnected, with significant effect on flow properties. The drainage curves for model rocks were computed using invasion percolation in a network taken directly from the grain-scale geometry and topology of the model. The drainage simulations show clear percolation behavior, but experimental data frequently do not. This implies that either network models based on intergranular void space are not a good tool for modeling of tight gas sandstone or the experiments are not correctly done on tight gas samples. In addition to reducing connectivity, the porosity-reducing mechanisms change pore throat size distributions. These combined effects shift the drainage water relative permeability curve toward higher values of water saturation, and gas relative permeability shifts toward smaller values of gas. Comparison of simulations with measured relative permeabilities shows a good match although same network fail to match drainage curves. This could happens because the model gives the right fluid configuration but at the wrong values of curvature and saturation. The significance of this work is that the model correctly predicts the relative permeabilities of tight gas sandstones by considering the microscale heterogeneity. The porosity reduction due to ductile grain deformation is a new contribution and correctly matches with experimental data from literature. The drainage modeling of two-phase flow relative permeabilities shows that the notion of permeability jail, a range of saturations over which both gas and water relative permeabilities are very small, does not occur during drainage. / text

Lower Cambrian Eriboll Formation sandstones of the Ardvreck Group that crop out in the Hebridean foreland west of the Paleozoic Moine Thrust Zone (MTZ) in the Northwest Highlands of Scotland contain five sets of opening-mode fractures with varying degrees of quartz deposits (cement) and topographically prominent but small displacement (mostly less than 10 m) northeast-striking faults. The faults crosscut and in some places displace the MTZ. I interpret these faults to post-date the MTZ and consider them to be late structures (kinematically unrelated to MTZ emplacement). Sparse slip lineations on fault surfaces and offset patterns are evidence for strike-slip to oblique slip. Using geologic mapping I show that relative to their lateral and vertical extents, the faults display small amounts of offset (less than 5 to 10 m). My research documented the patterns and petrology of fractures in a well exposed section of the foreland, documented for the first time fracture patterns adjacent to and within the post-MTZ fault zones, and proposes an account of how fault and fracture patterns developed and their probable effects on fluid flow. Fractures are barren (joints), partially filled (quartz lined), or completely filled (veins). Older fracture sets are typically completely filled, whereas younger sets may be lined with a thin veneer of quartz cement or are barren. Listed in order from oldest to youngest fractures containing quartz strike north, NW to WNW, NE, west, and north (sets A through E respectively). Previously proposed relative ages of the sets were confirmed using crosscutting relationships and preferred orientations of macro- and microfractures (Laubach and Diaz-Tushman, 2009). This study focuses on late northeast-striking fractures (set C) which I interpret to be related to the formation of the small-offset faults. Many of the attributes of late fractures and faults in the Eriboll Formation resemble those found in core from highly quartz cemented sandstone natural gas reservoirs ("tight gas sandstones"). I demonstrate that the well exposed fracture patterns I documented are good analogs for tight gas sandstones, by investigating fracture characteristics such as network configurations and connectivity, fracture intensity (abundance), fracture scaling, fracture length and spacing, and the degree of quartz cement deposits in fractures and cataclastic fault rock. Many of the narrow macroscopic fractures and microfractures I documented using CL methods contain varying amounts of quartz deposits. The excellent preservation of Eriboll outcrops is probably a manifestation of little or no fracture pore space preservation in many of the numerous fractures that are apparent in outcrop. Set C fracture abundance is not distributed in a uniform envelope (or "halo") around the late faults. Using scanlines, I show that set C fracture distribution is heterogeneous and highly variable over short lateral distances (tens of centimeters to meters). I also investigate wing crack assemblages (secondary opening-mode fractures) that are locally associated with set C fractures. The assemblages accommodate small amounts of the distributed displacement (a few millimeters) adjacent to fault zones and are locally responsible for increased amounts of fracture connectivity by linking neighboring fractures. Variations in fracture pattern complexity appears to be related to the presence (or absence) of wing crack assemblages. Localized wing crack development on closely spaced, en echelon set C fractures also leads to precursory development of fragmented lozenges of highly deformed volumes of rock (damage zones) that resemble geometries similar to those seen in preserved Eriboll fault cores. Fault-related deformation in the Eriboll Formation is markedly different than that in the underlying Late Proterozoic Torridonian Applecross Formation (subarkose fluvial sandstone), which is characterized by simple halos fault-related fracture arrays surrounding the same late (post-MTZ) faults. In addition to composition, the Eriboll and Applecross differ in mechanical layer thickness (centimeters versus > tens of meters), mechanical properties (high versus low brittleness), and greater propensity for fractures to be filled with quartz cement in Eriboll sandstones owing to quartz cement growth being impaired by the abundance of non-quartz substrate (feldspar and clay minerals) along fracture walls in the Applecross Formation. Although the Eriboll sandstones are more highly fractured than the older Applecross sandstones, Eriboll fractures are more prone to be filled by quartz cement. In this thesis I also report previously unrecognized early (set A; pre-MTZ) minor normal faults, sandstone petrography and rock mechanical properties of selected Eriboll sandstone samples, and the influence of fractures on the glacial geomorphology of the area. I also describe a previously unmapped igneous dyke. I describe previously unrecognized vugs that are partly strata bound and partly localized along fractures. The attributes of these vugs and a review of the literature suggests that these features could represent evidence of pre-glacial silici-karst in Eriboll quartzites. / text

It has been shown recently that high-quality epitaxial graphene (EPG) can be grown on the SiC substrate that exhibits interesting physical properties and has great advantages for varies device applications. In particular, the multilayer graphene films grown on the C-face show rotational disorder. It is expected that the twisted layers exhibit unique new physics that is distinct from that of either single layer graphene or graphite. In this work, by combining density functional and tight-binding model calculations, we investigate the electric field and doping effects on twisted bilayer graphene (TBG), multiple layer effects on twisted triple-layer graphene, and wave packet propagation properties of TBG. Though these studies, we obtain a comprehensive description of the interesting interlayer interaction in this twisted multilayer graphene system.

The growth of the Si(001) surface from gas sources such as disilane is technologically important, as well as scientifically interesting. The aspects of growth covered are: the clean surface, its defects and steps; the action of bismuth, a surfactant; the diffusion behaviour of hydrogen in different environments; and the entire pathway for formation of a new layer of silicon from adsorption of fragments of disilane to nucleation of dimer strings. The theoretical methods used, density functional theory and tight binding, are described. Four linear scaling tight binding methods are compared. The construction of the tight binding parameterisations used is also explained. The structure of the most common defect on the Si(001) surface is identified by comparison of the electronic structure with scanning tunneling microscopy (STM) images. The energy and structure of steps is calculated, and their kinking behaviour is modelled, achieving good agreement with experimental results. Two unusual features which form when bismuth is placed on the surface and annealed are investigated. The first has possible applications as a quantum wire, and its structure and growth are described. The second relates to a controversial area in the field; a structure is proposed which fits all available experimental evidence. The behaviour of hydrogen is vital to understanding growth, as large amounts are deposited during disilane growth. After validating the tight binding parameterisation against DFT and experiment for the system of a single hydrogen diffusing on the clean Si(001) surface, the barriers for diffusion on the saturated surface, down a step and away from a defect are found, and prove to be in good agreement with available experimental data. The pathway for the formation of a new layer of silicon from disilane is described step by step, giving barriers and structures for all events. The interaction with experiment is highlighted, and demonstrates that great benefit accrues from such close work, and that the atomistic modelling techniques used in the thesis produce results in close agreement with reality.

This thesis aims to explore the effects of tight budgetary control on employee behavior focusing on employee loyalty, employee satisfaction, job related tension and tendency towards data manipulation in public sectors. The study explores the subject on the population of three countries which includes Sweden, Jordan and Pakistan. In Pakistan and Jordan, no previous study has ever been performed which tried to explore effects of tight budgetary control in employee behavior. Method: Keeping the above fact in view, method derived for this study was the combination of qualitative and quantitative approach. Questionnaires were formulated and sent to employees of the sampled companies receiving 740 responses. For qualitative method, 5 employees were interviewed from entire three countries. Finding: the study revealed that all three countries are experiencing tight budgetary control whereas Jordan and Pakistan are experiencing it on higher level and Sweden is experiencing it in lower level as compared to Pakistan and Jordan. As far employee behavior is concerned, both the method proved that loyalty was negatively related to tight budgetary control for Pakistan and Sweden whereas positively related in case of Jordan. Satisfaction is also negatively related to tight budgetary control for Sweden and Pakistan while positively related for Jordan. Job related tension and tendency towards data manipulation are positively related to tight budgetary control for all three countries. Research type: Master’s thesis.

Transition metal oxides constitute a large class of materials with variety of very interesting properties and important technological utility. A subset with perovskite structure has been the subject matter of the current theoretical investigation with an emphasis on their electronic and structural behavior. An analytical and a computational method are used to calculate physical entities like lattice parameters, bulk moduli, band structures, density of electronic states and charge density distributions for various topologies. Results are discussed and compared with the available experimental findings.

In 1997, Rogner published a paper containing an estimate of the natural gas in place in unconventional reservoirs for 11 world regions. Rogner's work was assessing the unconventional gas resource base, and is now considered to be very conservative. Very little is known publicly about technically recoverable unconventional gas resource potential on a global scale. Driven by a new understanding of the size of gas shale resources in the United States, we estimated original gas in place (OGIP) and technically recoverable resource (TRR) in highly uncertain unconventional gas reservoirs, worldwide. We evaluated global unconventional OGIP by (1) developing theoretical statistic relationships between conventional hydrocarbon and unconventional gas; (2) fitting these relationships to North America publically available data; and (3) applying North American theoretical statistical relationships to evaluate the volume of unconventional gas resource of the world. Estimated global unconventional OGIP ranges from 83,300 (P10) to 184,200 (P90) Tcf. To assess global TRR from unconventional gas reservoirs, we developed a computer program that we call Unconventional Gas Resource Assessment System (UGRAS). In the program, we integrated a Monte Carlo technique with an analytical reservoir simulator to estimate the original volume of gas in place and to predict production performance. We used UGRAS to evaluate the probabilistic distribution of OGIP, TRR and recovery factor (RF) for the most productive unconventional gas formations in the North America. The P50 of recovery factor for shale gas, tight sands gas and coalbed methane is 25%, 79% and 41%, respectively. Finally, we applied our global OGIP assessment and these distributions of recovery factor gained from our analyses of plays/formations in the United States to estimate global technically recoverable unconventional gas resource. Global technically recoverable unconventional gas resource is estimated from 43,000 (P10) to 112,000 (P90) Tcf.

Diss. (sammanfattning) Stockholm : Karolinska institutet, 2006. / Härtill 4 uppsatser.

In this thesis we describe the development of a real-space implementation of the Bethe-Salpeter equation (BSE) and use it in conjunction with a semi-empirical tight-binding model to investigate the optoelectronic properties of colloidal quantum- confined nanostructures. This novel implementation exploits the limited radial extent and small size of the atomic orbital basis to treat finite systems containing up to ∼4000 atoms in a fully many-body framework. In the first part of this thesis our tight-binding model is initially benchmarked on zincblende CdSe nanocrystals, before subsequently being used to investigate the electronic states of zincblende CdSe nanoplatelets as a function of thickness. The band-edge electronic states are found to show minimal variation for a range of thicknesses and the results of our tight-binding model show good agreement with those predicted using a 14-band k·p model for a nanoplatelet of 4 monolayers (ML) in thickness. Optical absorption spectra were also computed in the independent-particle approximation. While the results of the tight-binding model show good agreement with those of the 14-band k·p model in the low-energy region of the spectrum, agreement with experiment was poor. This reflects the need for a many-body treatment of optical absorption in nanoplatelet systems. In the second part of this thesis we apply our tight-binding plus BSE model to study the excitonic properties of CdSe nanocrystals and nanoplatelets. Simulations performed on CdSe nanocrystals examined an approximation of the BSE equivalent to configuration interaction singles (CIS), and found that both the optical gap and the low-energy spectral features were unaffected by the approximation. A comparison of exciton binding energies with those predicted by CIS demonstrates the sensitivity of results to the exact treatment of dielectric screening and the decision of whether or not to screen exchange. Our model predicts optical gaps that are in strong agreement with average experimental data for all but the smallest diameters, but was not able to reproduce low-energy spectral features that were fully consistent with experiment. This was attributed to the absence of the spin-orbit interaction in the model. Simulations performed on CdSe nanoplatelets investigate the optical gaps and exciton binding energies as a function of thickness. Exciton binding energies were found to reach ∼200 meV for the thinnest system, however, optical gaps were slightly overestimated in comparison to experiment. This is attributed to the reduced lateral dimensions used in our simulations and our bulk treatment of dielectric screening. A two-dimensional treatment of dielectric screening is expected to further increase binding energies. Calculations of the excitonic absorption spectrum reproduce the characteristic spectral features observed in experiment, and show strong agreement with the spectra of nanoplatelets, with thicknesses ranging from 3 ML to 5 ML.

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