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PHOTOREFRACTIVE THIN FILMS AND POLYMERS FOR USE IN ORGANIC-INORGANIC HYBRID CELLSBuller, Steven Harris 02 April 2012 (has links)
No description available.
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Electrochemical patterning of tantalum and tantalum oxide thin filmsElSayed, Hany 08 1900 (has links)
<p> Nanoscale patterning research is motivated by two objectives: (i) tool development and (ii) scientific opportunities at small length scales. The first objective focuses on designing techniques that can be used to fabricate features as small as possible. Synthetic strategies of nanomaterials can be classified into two categories; bottom-up and top-down. The top-down approach involves reducing the size of a bulk material into nanoscale patterns, while the bottom-up approach refers to the build up of a material from the bottom, i.e. particle-by-particle. This particle maybe an atom, a molecule or even a cluster. In this work, two different top-down approaches were applied to create patterns in the nanoscale. </p> <p> Direct selective metal deposition on semiconductors is of interest to electronic device technology, in particular for interconnects and Schottky devices. In this study, we investigated selective Cu electrodeposition on patterned tantalum oxide thin films. Cyclic voltammetry studies showed that tantalum oxide thin films of thicknesses higher than a certain critical value have insulating properties while oxide films of thicknesses less than this value are semiconductors. For the purpose of this study, tantalum oxide patterns of different thicknesses were created by electrochemical oxidation. Based on the aforementioned behavior of insulating and semiconducting tantalum oxide films, Cu lines were selectively electrodeposited on the tantalum oxide thin films patterns forming Schottky junctions. The process demonstrated in this work is compatible to standard processes for semiconductor device fabrication while permitting flexible prototyping for research at the nanoscale. </p> <p> The second method used to pattern nanoscale features on tantalum lead to the discovery of the first highly ordered nanoporous metal (template) prepared by electrochemical oxidation. The nanoporous tantalum has pores not only of high regularity and high diameter monodispersity, but also of tunable diameters in the range 27-55 nm. The template that has the highest hardness among other porous templates can be used for nanoparticles fabrication. The compatibility of the new porous tantalum template with semiconductor industry makes it a candidate for many potential technological applications. </p> / Thesis / Master of Science (MSc)
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Electro-optic Properties of Semiconductor Nano-crystals And Electro-optic Polymers And Their ApplicationsZhang, Fajian 29 October 2002 (has links)
In recent years, electro-optic polymers have been used to make various optical devices in the telecommunication field due to several advantages, such as large and fast electro-optic (EO) response. Semiconductor nano-crystals promise even higher response speed due to the unique quantum confinement mechanism, and they also show very high EO response because of surface and quantum size effects.
Many investigative efforts have been made in the area of semiconductor nano-clusters. These efforts mainly focus on synthesizing high quality particles, and their physical and chemistry properties (luminescence spectra, nonlinear optical, and other effects), but their electro-optic properties and potential uses in devices have not been fully investigated, so there is still much work to do in this aspect. For application of electro-optic polymers in electro-optic devices, the challenges are to develop more stable electro-optic polymers with higher electro-optic coefficients.
The electrostatic self-assembly (ESA) technique has many advantages over traditional polymer electro-optic film synthesis processes, such as spin coating. For ESA-generated EO films, no poling field is needed, high orientation of the EO polymer can be obtained which does not degrade with time, so the films can be very stable, and this processing is easily compatible with semiconductor VLSI technology. This is a very attractive technique.
The goal of this research is to develop new electro-optic materials by means of ESA techniques and to use them to form improved performance next generation electro-optic devices, with emphasis on two kinds of electro-optic materials: nano-sized II-VI semiconductors (CdS, CdSe), and electro-optic active polymers (chromophores), and their potential use in electro-optic devices.
In this research work, II-VI semiconductor nano-clusters have been synthesized, with particle diameters ranging from 4 nm to several tens of nanometers. There is a difference in peak positions of absorption and photo luminescence spectra, related to defects in nano-crystals. Larger CdS particles have larger differences than small CdSe particles. Particle sizes measured by absorption spectrum and by HRTEM methods are very close. Based on quantum mechanical theory, peak spectral shifts as a function of particle size can be predicted, but the theoretical results are typically far from the experimental results, because many complicating factors should be considered. Films fabricated by ESA have much stronger absorption than spin coated films, and exhibit a slight blue shift in peak position wavelength. Photo luminescence spectra also show a blue shift for ESA films with respect to spun films.
Polymeric electro-optic films were also fabricated by the ESA technique. Effects due to applying an external electrical field during the ESA process on film growth and properties have also been investigated. Peak position, optical density and wavelength at maximum absorption, all increase with the number of bilayers, and films made under external fields have lower absorption and peak wavelength than those of films fabricated without an external field. These results are related to the order parameter, and indicate that molecule alignment can be improved by the application of an external field during the process of ESA film growth.
CdSe nano-clusters have a much higher electro-optic coefficient than their bulk crystal counterparts. In comparison with polymers, they have totally different origins in their electro-optic effects. For both nano-cluster-and chromophore based ESA films, electro-optic coefficients are hi gher than those of spin-coated films, and no poling voltage is needed. The reasons have been fully discussed. This result means that the ESA technique is effective to align and hold the dipoles in films and to intensify the electro-optic effect.
CdSe quantum dots need 17. 5 ms to complete their physical orientation due to a rotation of the permanent dipole moment. Therefore, at lower frequencies (<100Hz), electro-optic modulation mainly stems from the orientation of the permanent dipole moment. At frequencies higher than 100 Hz, the electro-optic modulation mainly arises from the induced dipole moment orientation and pure electron movement.
The ratio of the electro-optic coefficients r333/r113 > 3. This means that ESA films cannot be treated as an ideal isotropic system with the C v symmetry, and interactions should be considered. Quadratic Kerr electro-optic coefficients have a similar frequency dependence to that of the linear electro-optic coefficients r333 and r113. This indicates that the orientational distribution of the CdSe quantum dots particularly contributes to the quadratic electro-optic modulation.
From the FT-IR measurement of the films, proton irradiation can break the N=N double bonding in pi-conjugated bridges, leading to damage of the conjugating structure, so causing a decrease of the EO coefficient. But the thermal and temporal stability of ESA films are much better than those of spin coated films; this is a significant feature of ESA technique.
The effect of an external field and film thickness on the optical and electro-optic properties of ESA films has been investigated. Electro-optic coefficient decreases with thickness. Electrical field influences the electronic states of the chromophores.
Based on the properties of electro-optic films, the applications of polymer and nano-cluster electro-optic films are discussed. A nano-cluster CdSe electro-optic film has a higher refractive index than the PS-119 polymer film, and these values they are much lower than that of semiconductor wafers, but slightly higher than optical silica glasses. Accordingly optical silica glasses are the ideal substrates for those films. By analysis, the cutoff thickness was determined, which defines the minimum film thickness required for light propagation. For channel waveguides, the aspect ratio w/t, w, and t are determined versus the refractive index of the electro-optic films. Modulator beam length and modulation index were discussed, for high speed operation. Modulator beam length should be carefully chosen to obtain high modulation index; similarly important is the refractive index match between core, substrate, and cladding layers. For high speed operation, traveling wave electrode designs were considered, based on effective refractive index and impedance matching. The effective dielectric constant and characteristic impedance as a function of electrode configuration (sizes) were diagramed, and this served as a basic design suggestion for traveling wave electrodes. / Ph. D.
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Optical property studies and metalorganic chemical vapor deposition of ferroelectric thin filmsPeng, Chien-Hsiung 06 June 2008 (has links)
Ferroelectric lead zirconate titanate thin films, Pb(ZrxTi 1-x)0 3 or PZT, have aroused considerable interest in recent years for the application in nonvolatile electronic memories because of their excellent ferroelectric properties. In this research, PZT thin films were studied from two aspects: the scientific aspect and the technical aspect.
The optical properties of PZT solid solutions and the structure development in PZT films were extensively investigated in the scientific aspect. The PZT films used in this part of study were prepared by metalorganic decomposition (MOD) process. The envelope method, with consideration of light intensity loss from the back surface of the substrate, was demonstrated to be a simple and convenient tool for obtaining the optical properties of the PZT films in the medium and weak absorption regions. In the near optical band gap region, both the transmission and reflection spectra were used to successfully calculate the optical constants of the films. The film thickness derived from the envelope method was cross checked by a computer simulation method and was found to have an accuracy better than 2%. An effective, versatile, and nondestructive optical method was developed for the study of the structure development in MOD PZT films. Also, the models for the structure development were proposed and were verified by this optical method. Using this method, the characteristic temperatures (i.e., the initiation and completion temperatures) of each phase can be easily identified. In addition, the volume fraction of the perovskite phase in the pyrochlore-perovskite phase transformation region was obtained from this optical method.
From the technical point of view, ferroelectric PZT films were successfully and reproducibly deposited for the first time by hot-wall metalorganic chemical vapor deposition (MOCVD). One of the problems associated with the MOCVD technique is the availability of the precursors. After intensive studies searching for the most suitable precursors for MOCVD PZT thin films, the safe and stable precursors, namely lead tetramethylheptadione [Pb(thd)2)], zirconium tetramethylheptadione [Zr(thd)4], and titanium ethoxide [Ti(OEt)4] were chosen. The films were deposited at temperatures as low as 55QOC and had pure perovskite phase in the as-deposited state. Also, the films were smooth, specular, crack-free, uniform, and adhered well on the substrates. The stoichiometry of the films can be easily controlled either by varying the individual precursor temperature and/or the flow rate of the carrier gas. Auger electron spectroscopic (AES) depth profile showed good uniformity through the thickness of the films. The AES spectra also showed no carbon contamination in the bulk of the films. As-deposited films were dense and showed uniform and fine grains. The film (Pb/Zr/Ti = 50/41/9) annealed at 6QQOC showed a spontaneous polarization of23.3 pC/cm² and a coercive field of 64.5 kV /em. / Ph. D.
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Synthesis and Characterization of Ferroelectric (1-x)SrBi2Ta2O9-xBi3TaTiO9 thin films for Non-volatile memory ApplicationsRyu, Sang-Ouk 12 May 1999 (has links)
The (1-x)SrBi2Ta2O9-xBi3TaTiO9 thin films fabricated by modified metalorganic solution deposition technique showed much improved properties compared to SrBi2Ta2O9: a leading candidate material for memory applications. A pyrochlore free crystalline phase was obtained at a low annealing temperature of 600 oC and grain size was found to be considerably increased for the (1-x)SrBi2Ta2O9-xBi3TaTiO9 compositions. The film properties were found to be strongly dependent on the composition and annealing temperatures. The measured dielectric constant of the thin films was in the range 180-225 for films with 10-50 mol % of Bi3TaTiO9 content in the solid solution. Ferroelectric properties of (1-x)SrBi2Ta2O9-xBi3TaTiO9 thin films were significantly improved compared to SrBi2Ta2O9. For example, the observed 2Pr and Ec values for films with 0.7SrBi2Ta2O9-0.3Bi3TaTiO9 composition, annealed at 650 oC, were 12.4 micro C/cm2 and 80 kV/cm, respectively. The solid solution thin films showed less than 5 % decay of the polarization charge after 10^10 switching cycles and good memory retention characteristics after about 10^6 s of memory retention.
The size and temperature effect of 0.7SrBi2Ta2O9-0.3Bi3TaTiO9 thin films were studied by determining how the ferroelectric properties vary with film thickness and temperature. It was found that the ferroelectric properties were determined by the grain size, and not by the thickness of the film in our studied thickness range of 80-350 nm. A 80 nm thick film showed good ferroelectric properties similar to the 350 nm thick film. Thermal stability of the 0.7SrBi2Ta2O9-0.3Bi3TaTiO9 thin film was found to be much better compared to the SrBi2Ta2O9 and Pb(Zr,Ti)O9 thin films due to its higher Curie temperature and lower Schottky activation energy according to temperature changes. Also, 0.7SrBi2Ta2O9-0.3Bi3TaTiO9 thin films has shown good ferroelectric properties on multilayer system such as PtRh/PtRhOx/poly-Si suggest their suitability for high density FRAM applications. / Ph. D.
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Processing - structure - property interrelationships of ferroelectric thin films with emphasis on formation kineticsKwok, Chi Kong 19 October 2006 (has links)
Lead zirconate titanate (PZT) is a ferroelectric material which has many interesting properties. Recently, PZT thin films have been considered as one of the most promising materials for the application of nonvolatile electronic memories. In this study, a sol-gel process for PZT film preparation was adopted and greatly modified. PZT films with very desirable electrical properties have been successfully prepared by this modified sol-gel process.
One of the problems of incorporating PZT films into the DRAM devices is the need of high post-deposition annealing temperatures which complicates their integration into the existing semiconductor manufacturing process. In this work, formation kinetics of PZT films were studied and the nucleation was found to be the rate-limiting step in the formation of the perovskite phase. Based on this finding, a seeding process was invented to encourage the nucleation of the perovskite phase. As a result of this seeding process, the transformation temperature has been lowered by as much as 100°C. The seeded PZT films also have good ferroelectric properties.
The ferroelectric domain structures, and the metastable pyrochlore phase including its transformation to the perovskite phase have been investigated by transmission electron microscopy (TEM). The domain structures of the PZT films had the {lID} <110> orientation and most of them were 90° domains. The TEM study of the pyrochlore to perovskite transformation provides valuable insight on the formation of the perovskite phase.
Among all the processing steps, the drying process of the sol-gel films created the highest growth stress. In addition, the thin film stress study was also used to determine the transformation stress and Curie temperature.
The effects of composition, thermal processing conditions, and film thickness on electrical properties have been studied. Some of the notable results are as follow: (1) PZT films with a Zr/Ti ratio of 53/47, the morphotropic boundary (MPB) composition, have the highest remanent polarization and the lowest coercive field. (2) The optimum annealing temperatures for most of the PZT compositions are found to be about 50°C higher than the completion temperature of the perovskite formation (T<sub>c</sub><sup>per</sup>) of the same composition. (3) PZT films with film thicknesses greater than or equal to 170 nm have electrical properties very close to those of the thicker films and are not susceptible to dielectric breakdown at an applied voltage of 5 V. / Ph. D.
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Design and Fabrication of Polymer/Graphene Laminate Thin FilmsCroft, Zacary Lane 05 September 2024 (has links)
The development of graphene-based electronics may produce a new generation of electronic devices with enhanced performance over traditional materials. However, quality graphene electronics will require large-area, continuous graphene film produced by chemical vapor deposition (CVD), which is typically not stable when free-standing. Instead, CVD graphene may be coupled with polymer thin films to produce polymer/graphene laminates (PGLs), which show improved mechanical stability and good electrical conductivity over large areas. For example, single-layer graphene (SLG) has been coupled with polyetherimide (PEI) to produce thin film audio speakers with significantly enhanced energy efficiency compared to traditional speaker designs. However, the poor design and fabrication of PGLs may degrade the interfacial interactions of polymers with graphene and make the interface more susceptible to deformation. Interfacial weakening then limits their long-term reliability and performance in micro- and nano-electromechanical systems (MEMS/NEMS), in which materials are constantly subjected to dynamic loads. In this dissertation, we construct a framework for developing PGL thin films with controlled interfacial properties based on the rational design of polymer substrates and careful consideration of fabrication-induced defects. We evaluate this framework from several angles. First, the design of PEI/SLG film thickness is explored for controlling mechanical mixing and composite Young's modulus. Then, the role of thermal annealing during PEI/SLG fabrication is examined and its effect of mechanical mixing studied. Finally, we investigate mechanical fatigue in PEI/SLG thin films under dynamic loading with different pre-tensions.
The design of mechanical properties in PGLs is crucial for ensuring long-term stability and operational performance. The Young's modulus is an important mechanical parameter governed by mechanical mixing in PGLs, and better mechanical mixing is facilitated by improved stress transfer efficiency at the polymer/graphene interface. Thus, the control of mechanical mixing through PGL design is an important research topic for developing PGL thin films with good mechanical performance. To this end, we evaluated the design of PEI/SLG thin films with precisely controlled thicknesses to afford control over mechanical mixing and the composite Young's modulus. PEI concentrations of 3–6 wt% were used to spin-coat PEI/SLG films at precisely controlled thicknesses of ~200–1000 nm, which enabled the design of PEI/SLG thin films based on thickness control. The design of PEI/SLG film thickness afforded control over the volume fraction of SLG, which is related to the composite Young's modulus of the films via the well-known mixing rule. To validate this approach, we measured the composite Young's modulus of PEI/SLG films and modelled the relationship between modulus and film thickness (i.e., volume fraction) using the mixing rule. However, we found that linear regression analysis yielded an unexpectedly high effective Young's modulus of 1.12 ± 0.05 TPa for SLG. Further investigation revealed the larger-than-expected value was due to the gradual deterioration of mechanical mixing between SLG and PEI at film thicknesses > 250 nm. Overall, our results demonstrate that the control of mechanical mixing in PGL thin films is achievable through the physical design of film thickness, which fits well within the proposed framework for PGL development.
The fabrication of PGL materials is another important topic for controlling PGL properties. For example, the transfer process required for removing PGL thin films from a CVD substrate is known to introduce mechanical defects and electronic doping if improper processing conditions are used. However, little is known about the impact of thermal annealing on the properties of PGL materials. Normally, thermal annealing is thought to aid in the removal solvent and stress after polymer deposition on SLG, but we show that thermal annealing instead induces substantial structural damage and reduced film properties when poor conditions are used. Specifically, thermally annealing PEI/SLG in air past the Tg of PEI (~217 °C) caused widespread structural damage due to oxidation of the underlying Cu substrate. This conclusion was supported through an in-depth mechanistic investigation of annealing-induced deformation. First, changing the annealing atmosphere to high-purity nitrogen prevented widespread structural deformation from occurring during annealing, regardless of temperature. Second, the onset of film deformation during annealing in air was strongly associated with temperatures above the glass transition temperature of PEI. Finally, Arrhenius analysis yielded an activation energy of 159 kJ/mol for the deformation process, almost twice that associated with Cu oxidation and instead closer in scale to that of glass transitions in amorphous polymers. A physical failure mechanism was proposed based on the in-plane shrinkage of PEI during the glass-to-rubber transition caused by the release of internal stress induced by spin-coating. In-plane contraction of PEI would then cause compression of SLG as internal stress was released, which we confirmed from a significant blue-shift in the 2D band of SLG by ~30 cm-1 after annealing both with and without visible deformation. Importantly, we demonstrate that common secondary processing steps, like thermal annealing, will have critical effects on film properties if conditions are not properly controlled.
The mechanical fatigue and cycling stability of PGL thin films is another topic of interest for developing reliable PGLs with long operational lifetimes. Mechanical failure analysis might be used to evaluate failure mechanisms governing interfacial fatigue in PGL thin films. However, little work has been done understanding mechanical fatigue in PGLs. To this end, we explore the use of mechanical bulge testing for the evaluation of cycling fatigue in PGLs and construct a custom instrument, known as a bulge test apparatus (BTA), to perform fatigue measurements. In general, our BTA test platform provides a means of analyzing different fabrication/design conditions. To test its use, we prepared PEI/SLG thin films with different tensioning weights between 0 and 30 g. Then, the well-established methods for bulge testing were applied to the dynamic loading of PEI/SLG using the BTA. Specifically, the evolution of bulge-test-derived pre-stress in PEI/SLG was monitored as a function of cycle number and tensioning weight, which revealed large fluctuations in pre-stress with mechanical cycling up to ~200k cycles, which was unexpected for these films. To investigate the underlying mechanism, we further employed Raman spectroscopy, optical microscopy, and scanning electron microscopy (SEM) to determine the strain state of SLG before and after cycling and probe for structural changes. Raman measurements revealed that mechanical cycling induced a large redshift in the 2D and G peak positions of SLG by ~25.4 and ~10.1 cm-1, respectively, for 30 g-tensioned PEI/SLG, with similar shifts observed for 20 g-tensioned films. Optical and SEM images showed possible changes in the surface structure of SLG after cycling accompanying the shift in Raman characteristics. We discuss the possibility of interfacial failures involving in-plane slippage and out-of-plane buckling of SLG based on our results. If validated, the use of BTA may provide future insight regarding mechanical fatigue and failure at the PGL interface during dynamic loading. The practical relevance of methods for determining the influence of design and fabrication characteristics in PGLs will no doubt be invaluable for further development. Additional work in this area will be necessary to connect our analytical approach by BTA to underlying failure mechanisms in PGLs. / Doctor of Philosophy / Due to its record-breaking properties, graphene has tremendous promise for use in next-generation consumer electronics, like ultra-thin audio speakers and flexible displays. However, on its own, single-layer graphene (SLG) is not stable enough for practical uses. Therefore, in this dissertation, I construct a framework for developing polymer substrates to stabilize and enhance graphene based on the design and fabrication of polymer/graphene laminates (PGLs). To explore this framework, I design polyetherimide (PEI)/SLG thin films with controlled mechanical properties, evaluate fabrication-induced defects, and develop an analytical approach for measuring mechanical fatigue in these films.
The ability to precisely control thin film mechanics has important implications for the application of PGLs. However, it is challenging in PGL systems to enhance mechanical properties due to the limited amount of graphene that is used. Therefore, I show that the design of PEI/SLG film thickness can effectively control mechanical reinforcement, even at very low loadings of graphene. I further investigate the design of a controlled pre-tensioning in PEI/SLG and show that tensioning can be used to modify the mechanical response. However, using a custom mechanical testing platform, I also determine that mechanical fatigue may increase with pre-tensioning as well.
The impact of fabrication procedures on the properties of PGL thin films is another important aspect of PGL development that is often overlooked. Specifically, thermal annealing may introduce residual contamination and/or structural defects that reduce material properties. Therefore, I present a detailed study of thermal annealing-induced structural failures in PEI/SLG films, which shows that annealing at high temperature induces substrate oxidation and structure damage in the films. The results of this annealing study demonstrate the potential negative effects of fabrication on PGL development. Finally, this dissertation ends by discussing future directions in PGL design and fabrication that will need to be addressed in the coming years for further development of PGL thin film electronics.
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Thinnest uniform liquid films formed at the highest speeds with reverse roll coatingBenkreira, Hadj, Shibata, Yusuke, Ito, K. 11 March 2013 (has links)
No / Reverse roll coating is probably the most widely used coating operation, much less investigated than its counterpart and inherently unstable forward roll coating. A new data to complement earlier work which was limited to large gaps and thus “thick” films is presented. The intention is to assess the feasibility of reverse roll coating to yield very thin films (<10 μm) at high speeds (>1 m/s) for application in the newer technologies, such as the production of solar cells and plastic electronics. The data obtained demonstrate this is possible but at the lowest permissible gap (25–50 μm) with low-viscosity fluids (∼7 mPa s). The study also developed a new understanding of how instabilities are controlled. It was seen that the size of the inertia forces generated by the applicator roller in relation to surface tension, as expressed by the Weber number and not the applicator Capillary number (viscous forces/surface tension) which is the critical parameter.
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Pore-scale Interfacial and Transport Phenomena in Hydrocarbon ReservoirsFang, Chao 10 June 2019 (has links)
Exploring unconventional hydrocarbon reservoirs and enhancing the recovery of hydrocarbon from conventional reservoirs are necessary for meeting the society's ever-increasing energy demand and requires a thorough understanding of the multiphase interfacial and transport phenomena in these reservoirs. This dissertation performs pore-scale studies of interfacial thermodynamics and multiphase hydrodynamics in shale reservoirs and conventional oil-brine-rock (OBR) systems.
In shale gas reservoirs, the imbibition of water through surface hydration into gas-filled mica pores was found to follow the diffusive scaling law, but with an effective diffusivity much larger than the self-diffusivity of water molecules. The invasion of gas into water-filled pores with width down to 2nm occurs at a critical invasion pressure similar to that predicted by the classical capillary theories if effects of disjoining pressure and diffusiveness of water-gas interfaces are considered. The invasion of oil droplets into water-filled pores can face a free energy barrier if the pressure difference along pore is small. The computed free energy profiles are quantitatively captured by continuum theories if capillary and disjoining pressure effects are considered. Small droplets can invade a pore through thermal activation even if an energy barrier exists for its invasion.
In conventional oil reservoirs, low-salinity waterflooding is an enhanced oil recovery method that relies on the modification of thin brine films in OBR systems by salinity change. A systematic study of the structure, disjoining pressure, and dynamic properties of these thin brine films was performed. As brine films are squeezed down to sub-nanometer scale, the structure of water-rock and water-oil interfaces changes marginally, but that of the electrical double layers in the films changes greatly. The disjoining pressure in the film and its response to salinity change follow the trend predicted by the DLVO theory, although the hydration and double layer forces are not simple additive as commonly assumed. A notable slip between the brine film and the oil phase can occur.
The role of thin liquid films in multiphase transport in hydrocarbon reservoirs revealed here helps lay foundation for manipulating and leveraging these films to enhance hydrocarbon production and to minimize environmental damage during such extraction. / Doctor of Philosophy / Meeting the ever-increasing energy demand requires efficient extraction of hydrocarbons from unconventional reservoirs and enhanced recovery from conventional reservoirs, which necessitate a thorough understanding of the interfacial and transport phenomena involved in the extraction process. Abundant water is found in both conventional oil reservoirs and emerging hydrocarbon reservoirs such as shales. The interfacial behavior and transport of water and hydrocarbon in these systems can largely affect the oil and gas recovery process, but are not well understood, especially at pore scale. To fill in the knowledge gap on these important problems, this dissertation focuses on the pore-scale multiphase interfacial and transport phenomena in hydrocarbon reservoirs. In shales, water is found to imbibe into strongly hydrophilic nanopores even though the pore is filled with highly pressurized methane. Methane gas can invade into water-filled nanopores if its pressure exceeds a threshold value, and the thin residual water films on the pore walls significantly affect the threshold pressure. Oil droplet can invade pores narrower than their diameter, and the energy cost for their invasion can only be computed accurately if the surface forces in the thin film formed between the droplet and pore surface are considered. In conventional reservoirs, thin brine films between oil droplet and rock greatly affect the wettability of oil droplets on the rock surface and thus the effectiveness of low-salinity waterflooding. In brine films with sub-nanometer thickness, the ion distribution differs from that near isolated rock surfaces but the structure of water-brine/rock interfaces is similar to their unconfined counterparts. The disjoining pressure in thin brine films and its response to the salinity change follow the trend predicted by classical theories, but new features are also found. A notable slip between the brine film and the oil phase can occur, which can facilitate the recovery of oil from reservoirs.
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I. Solubility and blend studies of nitrocellulose II. Relaxation properties of thin film coatings: the role of surface topographyBalcells, Eduardo January 1988 (has links)
In the first part of this two part thesis, interaction parameters of nitrocellulose with various solvent systems were investigated by Inverse Gas Chromatography. From these data, the solubility parameters of nitrocellulose were determined at a series of nitration levels which were used to guide the selection of suitable plasticizers for nitrocellulose films. Subsequent dynamic mechanical experiments were then used to evaluate the effectiveness of the blend formulations in broadening the glass transition dispersion of the nitrocellulose blended films; in addition, stress-strain experiments were done in order to evaluate the tensile modulus of the nitrocellulose blends.
In the second part of this thesis, both dynamic mechanical thermal analysis and dielectric thermal analysis were used to evaluate the relaxation properties of thin film polysulfone coatings and the effect of substrate surface topography on these properties. Both dynamic mechanical and dielectric thermal analysis revealed that the topographical nature of the substrate influenced the linear viscoelastic properties of the thin film coatings and that the extent of this influence was dependent on the coating thickness. / Master of Science
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