Large amounts of hydrocarbon reserves are trapped in fractured reservoirs where fluid flux is far more rapid along fractures than through the porous matrix, even though the volume of the pore space may be a hundred times greater than the volume of the fractures. These are considered extremely challenging in terms of accurate recovery prediction because of their complexity and heterogeneity. Conventional reservoir simulators are generally not suited to naturally fractured reservoirs’ production history simulation, especially when production processes are associated with large pressure and temperature changes that lead to large redistribution of effective stresses, causing natural fracture aperture alterations. In this case, all the effective processes, i.e. hydraulic, thermal and geomechanical, should be considered simultaneously to explain and evaluate the behavior of stress-sensitive reservoirs over the production period. This is called thermo-hydro-mechanical (THM) coupling. In this study, a fully coupled thermo-hydro-mechanical approach is developed to simulate the physical behavior of fractures in a plane strain thermo-poroelastic medium. A hybrid numerical method, which implements both the finite difference method (FDM) and the displacement discontinuity method (DDM), is established to study the pressure, temperature, deformation and stress variations of fractures and surrounding rocks during production processes. This method is straightforward and can be implemented in conventional reservoir simulators to update fracture conductivity as it uses the same grid block as the reservoir grids and requires only discretization of fractures. The hybrid model is then verified with couple of analytical solutions for the fracture aperture variation under different conditions. This model is implemented for some examples to present the behavior of fracture network as well as its surrounding rock under thermal injection and production. The results of this work clearly show the importance of rate, aspect ratio (i.e. geometry) and the coupling effects among fracture flow rate and aperture changes arising from coupled stress, pressure and temperature changes. The outcomes of this approach can be used to study the behavior of hydraulic injection for induced fracturing and promoting of shearing such as hydraulic fracturing of shale gas or shale oil reservoirs as well as massive waste disposal in the porous carbonate rocks. Furthermore, implementation of this technique should be able to lead to a better understanding of induced seismicity in injection projects of all kinds, whether it is for waste water disposal, or for the extraction of geothermal energy.

Electrical conductive adhesives (ECAs) containing silver filler and polyaniline co-filler were characterized for their electro-mechanical properties. Polyaniline is a conductive polymer and has a moderate conductivity in between those of the silver and epoxy. Incorporation of polyaniline (μm sized) in silver-epoxy facilitated the electrical conduction in ECAs and reduced the percolation threshold- a minimum volume of filler necessary to initiate the conduction. It also prevented the localization of charge carriers due to aggregation of silver filler particles. ‘Bridging effect’ was observed due to addition polyaniline in which the polyaniline enhanced the tunneling of electrons over the silver filler particles. We have investigated the polyaniline co-fillers as a promising alternative way to tune the mechanical and electrical properties of the ECAs and have provided a detailed analysis of the electro-mechanical properties of silver-epoxy (Ag-epoxy) and silver-polyaniline-epoxy (Ag-PANI-epoxy) system in both partially-cured/ viscoelastic and fully-cured states. Analysis of electro-mechanical properties of silver-epoxy and silver-polyaniline-epoxy also provided the insights into electrical contact resistance of ECAs under compressive force. Electro-mechanical properties of ECAs were measured ‘in-situ’ using micro-indentation technique. We also synthesized the electrically conductive and highly crystalline nanotubes of polyaniline by mini-emulsion polymerization of aniline. The motivation behind the synthesis of polyaniline was to propose a potential filler/co-filler for replacement of metallic filler in ECAs. Electrical conductivity of polyaniline nanotubes was tuned by in-situ doping using hydrochloric acid as a dopant. Increase in dopant caused the polyaniline crystallite to grow along (400) plane. Optical, structural, electrical and thermal properties of polyaniline nanotubes are reported with varying amount of dopant. We fabricated the flexible electrically conductive coating of polyaniline tubes with uniform dispersion of polyaniline. Electrical performance of as-synthesized flexible coating is also revealed.

For the last two decades, the possibility of using synthetic membranes for industrial gas separations has attracted considerable interest since membrane separation technologies have the advantages of energy efficiency, simplicity and low cost. However, for wider commercial utilization there is still a need to develop membranes with higher permeant fluxes and higher transport selectivities. Conductive polymers, due to their high gas transport selectivities, give rise to a new class of polymeric materials for membrane based gas separation though poor mechanical properties obstruct the applications for this purpose of use. This problem led researches to a new idea of combining the conducting polymers with insulating polymers forming mixed matrix composite membranes. In the previous studies in our group, polypyrrole was chosen as the conductive polymer, and different preparation techniques were tried and optimized for membrane application. As the insulating polymer, previously poly(bisphenol-Acarbonate) was used to support the conductive polymer filler in order to constitute a conductive composite membrane. For this study, as the polymer matrix, hexafluorobisphenol A based poly(arylene ether ketone) was targeted due to its physical properties and temperature resistance which can be important for industrial applications. First of all, permeabilities of N2, CH4, Ar, H2, CO2, and H2 were measured at varying temperatures ranging from 25&deg / C to 85&deg / C through a homogenous dense membrane of chosen polymeric material to characterize its intrinsic properties. Measurements were done using laboratory scale gas separation apparatus which makes use of a constant volume variable pressure technique. The permeability results were used for the calculations of permeation activation energies for each gas. These permeation activation energies were found to be differing slightly for each gas independently from the kinetic diameters of gases. In this study, mixed matrix membranes of conducting polymer, polypyrrole (PPy) and insulating polymer, hexafluorobisphenol A based poly(arylene ether ketone) (PAEK) were also prepared. It was observed that PAEK and PPy form a composite mixed matrix structure, which can function as permselective membrane. The effect of conducting polymer filler content was investigated with two different filler ratios. When comparing with the pure PAEK membranes, meaningful increases for both permeability and selectivity were obtained for some of the gases.

Diss. (sammanfattning) Stockholm : Karol. inst., 2006. / Härtill 4 uppsatser.

Orientador: Walter Katsumi Sakamoto / Banca: José Antônio Malmonge / Banca: Elson Longo da Silva / Banca: Maria Aparecida Zaghete Bertochi / Banca: Paulo Sérgio Varoto / Resumo: No presente trabalho foram preparados filmes compósitos de PZT/PVDF com PAni por mistura mecânica e posterior prensagem a quente. A PAni foi inserida de duas maneiras distintas no compósito: recobrindo parcialmente os grãos cerâmicos; e disposta separadamente aos grãos. Foram controladas as razões volumétricas dos constituintes dos compósitos e a condutividade da PAni que pode ser controlada pelo seu grau de protonação. A grande vantagem de sistemas com grãos recobertos é garantir a proximidade de canais de condução (ou polarização) com o grão, além de impossibilitar a percolação da fase condutora se o compósito exibir conectividade 0-3. Para o caso das amostras preparadas com PAni (dopada) disposta separadamente do grão, quando o limiar de percolação é alcançado, torna-se impossível o processo de polarização. Para compósitos com grãos recobertos, os melhores resultados em relação às propriedades de eletroatividade (e polarização) são encontrados acima da concentração crítica, onde o padrão de conectividade 0-3 já não é válido. As grandes vantagens obtidas usando compósitos com condutividade controlada são principalmente o tempo mais curto e o campo elétrico inferior usado para a polarização. Os resultados mostraram que é possível obter filmes compósitos com baixo conteúdo de cerâmica recoberta, que apresentem boas propriedades de eletroatividade e flexibilidade. Como uma de suas possíveis aplicações, o compósito mostrou boas propriedades como sensor fototérmico. / Abstract: In the present work composite films of PZT-PAni/PVDF were prepared hot pressing the mixture of components mechanically mixed. The PAni was inserted into the composite by two different ways: partially recovering the ceramic grains; and dispersed separately from the ceramic grains. Volumetric ratio of the single phases of the composite and the electrical conductivity of the PAni were controlled. The advantage of systems with ceramic grains partially recovered is that it allow the neighborhood of conduction channels (or poling) with the ceramic grain, besides to prevent the percolation of the conducting phase if the composite exhibit 0-3 connectivity. For the case of samples prepared with doped PAni dispersed separately from the ceramic grain, the poling process is not able when the limiar of percolation is reached. For composites with partially recovered grains the best results concerned to the electroactive properties (and polarization) are obtained over the critical concentration where the 0-3 connectivity pattern is not valid. The advantages obtained using composite with controlled conductivity are mainly the poling short time of polarization and the lower electric field. The results showed the possibility to obtain composite films with low content of recovered ceramic grain, which shows good electroactive property with flexibility. The composite also showed good properties as photothermal sensor / Doutor

Ce projet vise à développer de nouvelles encres à base de nanofils d’argent et de nanocellulose pour des applications conductrices et transparentes. Les nanocelluloses, nanoparticules issues de la cellulose, sont de deux types : les nanocristaux de cellulose (NCC) et les nanofibrilles de cellulose (NFC) et possèdent des propriétés bien spécifiques. Ce travail a consisté d’une part (i) à utiliser la forme tubulaire et rigide des NCC pour produire des nanotubes d’argents par synthèse chimique, avant leur formulation en encre et d’autre part (ii) à utiliser les propriétés d’enchevêtrement des NFC flexibles pour stabiliser des nanofils d’argent commerciaux, habituellement instables en suspension. Les divers résultats de ce projet ont permis d’aboutir à la formulation brevetée et à la commercialisation d’une encre conductrice à base d’une faible quantité d’argent et de NCC et de deux encres conductrices et transparentes à base de NFC et de nanofils d’argent. Les interactions physico-chimiques et la stabilité colloïdale de ces suspensions hybrides ont été étudiée de manière fondamentale, tout en développant des formulations adaptées à divers procédés d’impression, que ce soit à échelle laboratoire mais aussi industrielle. / This project aims at developing new conductive inks based on nanocellulose and silver nanowires for transparent and conductive applications. Nanocellulose are nanoparticles extracted from the cellulose and two kinds currently exist: the cellulose nanocrystals (CNC) and the cellulose nanofibrils (CNF). This project have evaluated on one hand the ability of using tubular rigid CNC as template for producing silver nanorods, prior their formulation into conductive inks. On the other hand, the ability of using flexible and entangled CNF to stabilize commercial silver nanowires, usually unstable in suspension, was investigated. The results of this project lead to the patented formulation and commercialization of one low silver content conductive ink based on silver and CNC and two conductive transparent ink based on CNF and silver nanowires. Physico-chemical interactions and colloidal stability of such hybrid suspension have been scientifically studied meanwhile printing process adapted formulation have been successfully designed and tested at laboratory scale but also industrial scale.

abstract: The object of this study is to investigate and improve the performance/stability of the flexible thin film transistors (TFTs) and to study the properties of metal oxide transparent conductive oxides for wide range of flexible electronic applications. Initially, a study has been done to improve the conductivity of ITO (indium tin oxide) films on PEN (polyethylene naphthalate) by inserting a thin layer of silver layer between two ITO layers. The multilayer with an optimum Ag mid-layer thickness, of 8 nm, exhibited excellent photopic average transmittance (~ 88 %), resistivity (~ 2.7 × 10-5 µ-cm.) and has the best Hackee figure of merit (41.0 × 10-3 Ω-1). The electrical conduction is dominated by two different scattering mechanisms depending on the thickness of the Ag mid-layer. Optical transmission is explained by scattering losses and absorption of light due to inter-band electronic transitions. A systematic study was carried out to improve the performance/stability of the TFTs on PEN. The performance and stability of a-Si:H and a-IZO (amorphous indium zinc oxide) TFTs were improved by performing a systematic low temperature (150 °C) anneals for extended times. For 96 hours annealed a-Si:H TFTs, the sub-threshold slope and off-current were reduced by a factor ~ 3 and by 2 orders of magnitude, respectively when compared to unannealed a-Si:H TFTs. For a-IZO TFTs, 48 hours of annealing is found to be the optimum time for the best performance and elevated temperature stability. These devices exhibit saturation mobility varying between 4.5-5.5 cm2/V-s, ION/IOFF ratio was 106 and a sub-threshold swing variation of 1-1.25 V/decade. An in-depth study on the mechanical and electromechanical stress response on the electrical properties of the a-IZO TFTs has also been investigated. Finally, the a-Si:H TFTs were exposed to gamma radiation to examine their radiation resistance. The interface trap density (Nit) values range from 5 to 6 × 1011 cm-2 for only electrical stress bias case. For "irradiation only" case, the Nit value increases from 5×1011 cm-2 to 2×1012 cm-2 after 3 hours of gamma radiation exposure, whereas it increases from 5×1011 cm-2 to 4×1012 cm-2 for "combined gamma and electrical stress". / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

abstract: Transparent conductive oxides (TCOs) are used as electrodes for a number of optoelectronic devices including solar cells. Because of its superior transparent and conductive properties, indium (In) tin (Sn) oxide (ITO) has long been at the forefront for TCO research activities and high-volume product applications. However, given the limited supply of In and potential toxicity of Sn-based compounds, attention has shifted to alternative TCOs like ZnO doped with group-III elements such as Ga and Al. Employing a variety of deposition techniques, many research groups are striving to achieve resistivities below 1E-4 ohm-cm with transmittance approaching the theoretical limit over a wide spectral range. In this work, Ga-doped ZnO is deposited using pulsed laser deposition (PLD). Material properties of the films are characterized using a number of techniques. For deposition in oxygen at pressures >1 mTorr, post-deposition annealing in forming gas (FG) is required to improve conductivity. At these higher oxygen pressures, thermodynamic analysis coupled with a study using the Hall effect measurements and photoluminescence spectroscopy suggest that conductivity is limited by oxygen-related acceptor-like defects in the grains that compensate donors, effectively reducing the net carrier concentration and creating scattering centers that reduce electron mobility. Oxygen is also responsible for further suppression of conductivity by forming insulative metal oxide regions at the grain edges and oxygen-related electron traps at the grain boundaries. The hydrogen component in the FG is thought to passivate the intra-grain acceptor-like defects and improve carrier transport across these grain boundaries. Given this deleterious effect of oxygen on conductivity, depositions are performed in pure argon (Ar), i.e., the only oxygen species in the growth ambient are those ejected directly from the PLD solid source target. Ga-doped ZnO deposited in Ar at 200 °C and 10 mTorr have resistivities of 1.8E-4 ohm-cm without the need for post deposition annealing. Average transmittance of the Ga-doped films is 93% over the visible and near infrared (IR) spectral regions, but free carrier absorption is a limiting factor further into the IR. After annealing in FG at 500 °C, a 300 nm Ar film has a Haacke figure of merit of 6.61E-2 sq. ohm. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

Thesis (Master of Engineering in Mechanical Engineering)--Cape Peninsula University of Technology, 2017. / Transparent conductive oxides (TCOs), which are widely used in transparent electronics, possess a spectral selectivity that is suitable for a solar material absorber. TCO materials have a plasma wavelength in the infrared region. Consequently electromagnetic waves shorter than a plasma wavelength are transmitted through the material, while longer electromagnetic waves are reflected on the surface. In contrast to the opaque solar selective absorbers, the plasma wavelength in TCO materials can be easily tuned by controlling the heavy doping process to match the peak shift of thermal radiation at higher temperatures. Furthermore, the use of TCO in conjunction with a solar absorber relaxes the spectral selectivity of the latter and thus widens the selection of the solar absorber; subsequently the only requirement is a thermally stable black body. Aluminum doped Zinc Oxide (AZO) is a class of TCO materials which is cost effective to manufacture due to abundance ZnO, and Aluminum raw materials. This thesis is based on the synthesis of Al doped ZnO thin films nanostructure using radio frequency RF magnetron sputtering process. The influence of the deposition parameters, including argon working pressure and substrate temperature, on the structural and optical properties of the AZO thin films is investigated by means of X-ray diffraction (XRD) and optical spectroscopy (UV-VIS-NIR). The optical constants of AZO films are extracted from transmittance and reflectance spectra using a combination of Drude and Lorentz dielectric function model. A computer simulation is developed to calculate the radiative properties of Al doped ZnO thin films nanostructure. The thermal emittance and solar absorptance is predicted indirectly from optical reflectance and transmittance of AZO films by invoking Kirchhoff’s law. A Special attention has been paid to the parameters that influence the spectral properties of the AZO films including carrier’s mobility, Al doping concentration and film thickness. Carrier’s mobility turned out to have the most significant influence on the spectrally selective performance of AZO films.

abstract: Nanoporous electrically conducting materials can be prepared with high specific pore volumes and surface areas which make them well-suited for a wide variety of technologies including separation, catalysis and owing to their conductivity, energy related applications like solar cells, batteries and capacitors. General synthetic methods for nanoporous conducting materials that exhibit fine property control as well as facility and efficiency in their implementation continue to be highly sought after. Here, general methods for the synthesis of nanoporous conducting materials and their characterization are presented. Antimony-doped tin oxide (ATO), a transparent conducting oxide (TCO), and nanoporous conducting carbon can be prepared through the step-wise synthesis of interpenetrating inorganic/organic networks using well-established sol-gel methodology. The one-pot method produces an inorganic gel first that encompasses a solution of organic precursors. The surface of the inorganic gel subsequently catalyzes the formation of an organic gel network that interpenetrates throughout the inorganic gel network. These mutually supporting gel networks strengthen one another and allow for the use of evaporative drying methods and heat treatments that would usually destroy the porosity of an unsupported gel network. The composite gel is then selectively treated to either remove the organic network to provide a porous inorganic network, as is the case for antimony-doped tin oxide, or the inorganic network can be removed to generate a porous carbon material. The method exhibits flexibility in that the pore structure of the final porous material can be modified through the variation of the synthetic conditions. Additionally, porous carbons of hierarchical pore size distributions can be prepared by using wet alumina gel as a template dispersion medium and as a template itself. Alumina gels exhibit thixotropy, which is the ability of a solid to be sheared to a liquid state and upon removal of the shear force, return to a solid gel state. Alumina gels were prepared and blended with monomer solutions and sacrificial template particles to produce wet gel composites. These composites could then be treated to remove the alumina and template particles to generate hierarchically porous carbon. / Dissertation/Thesis / Ph.D. Chemistry 2012