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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Performance Informed Technical Cost Modeling for Novel Manufacturing

Robin Joseph Glebes (7443716) 17 October 2019 (has links)
<p>Inaccurate cost estimates contribute to lost implementation opportunity of novel manufacturing technologies or lost revenue due to under-bidding or loss of an over-bid contract. High-volume, long-term orders, such as those the automotive industry begets, are desired as they lock in revenue streams for months into years. However, high-rate composite materials and their manufacturing processes are novel among the industry and traditional costing methods have not advanced at a proportional rate. This research effort developed a method to reduce the complex composite manufacturing systems to fungible, upgradable, and linkable individual processes that derive their manufacturing parameters from the performance part design process. Employing technical cost modeling, this method accurately quantifies the value of pursuing composite manufacturing by integrating impregnation, solidification, heat transfer, kinetics, and additional technical data from computer-aided part design simulation tools to deliver an accurate cost estimate. </p> <p>Cost modeling provides a quantitative result that weighs heavily in the decision making process for adoption of a new manufacturing method. In this dissertation, three case studies were investigated for three different management decision cases: part production management, in-house manufacturing management, and global manufacturing management. </p> <p>Part production management is the decision making process for selecting a certain manufacturing method. A case study with a Tier 1 Part Producer was conducted to provide a comparison of two emerging novel preforming systems versus their in-use, metals based high-rate manufacturing line in manufacturing a structural automotive part. Determining material usage was the primary cost driver focus. Equipment Supplier A’s process operated by seaming single layers of thermoplastic tape into rolls and then stacking prior to consolidation and resulted in a scrap rate of 23-28% with a cost of $32.87-36.01 per kilogram saved depending on the input tape width. Equipment Supplier B’s layup process, essentially a multi-head automatic tape layup machine, resulted in scrap rate of 20-27% with a cost of $34.48-36.67 per kilogram saved depending on the input tape width. This exceeded the Tier 1 Part Producer’s requirement of $6.6-11 per kilogram saved and led to them to abandon this application as a feasible project and instead look for a different part with a higher return regarding cost for weight saved.</p> <p>In-house manufacturing management is the decision making process governing manufacturing operating procedures. A case study for the Manufacturing Design Laboratory’s (MDLab) hybrid molding line was undertaken to determine the manufacturing cost for a composite test coupon. Processing parameters were obtained from three sources: performance design computer aided engineering (CAE), common industry transfer estimation times, and a calculated preform layup time. Compared to a similarly shaped test coupon made of aluminum, highly-automated manufacturing realizes weight savings of 46.25% and cost savings of 16.5%. Low-automation manufacturing captures the same weight savings, but has a cost for weight saved penalty, cost increase, of $9.89 per kilogram, showing how influential the labor contribution is to manufacturing cost. </p> <p>Global manufacturing management is the decision making process governing manufacturing location. Various manufacturing cost drivers are location dependent, thus a dataset was developed to alter these parameters for the U.S. states. Global comparisons are accomplished through indexing of global cost of living allowances and labor rates. Within the U.S., high-automation manufacturing costs in the West Coast/Pacific are 20.1% greater compared to the Midwest and similarly, low-automation costs are 21.2% greater. Globally, high-automation manufacturing costs in North America are 52.1% greater compared to Asia while low-automation costs are 116.5% greater. These variations highlight why we see geographically clustered manufacturing centers within the states and major manufacturing relocations due to cost sensitive and labor sensitive production. </p>
12

Energy System Modeling towards a Sustainable Future

Yiru Li (8804120) 12 October 2021 (has links)
<div>As the global population approaches 10 billion by the mid-century, supplying all the needs of the human race from the Earth’s limited land area and resources with minimized greenhouse gas emission will be the essential challenge of sustainability. In a sustainable economy, all renewable energy, in combination with carbon sources and other elements from the nature, such as water, air and land, will be used synergistically to produce building blocks for human beings. These building blocks, including electricity, heat, fuels, hydrogen, etc., will enable the production of all the end uses for human beings. The challenge for chemical engineers is to come up with processes and synergistic strategies to enable such a sustainable future.</div><div><br></div><div>Shale gas can serve as both energy resource and chemical feedstock for the transition period towards a sustainable economy, and has the potential to be a carbon source for the long term. Natural gas liquids contained in shale gas provide abundant feedstock for chemical and fuel production and could bring extra value for remote shale gas basins. Unlike current shale gas processing where large scales are preferred, simple and intensified processes with least processing steps and least pieces of equipment are favored for remote shale plays. While conventional shale gas processing usually follows a four-section hierarchy of "gas treatment - NGL recovery - NGL fractionation - NGL activation", four innovative configurations are proposed for simpler and intensified process design, including NGL co-processing, integrated NGL recovery and activation, switched NGL recovery and activation, and eliminated NGL recovery. A two-step conversion of NGLs to liquid hydrocarbons via dehydrogenation followed by oligomerization is used as an example to show how these innovative process designs evolve. Simulation results show that the loss of ethane, the NGL component with the highest concentration, could be largely reduced by the innovative process configurations. At the same time, higher yield of liquid products, fewer processing steps, reduced pieces of equipment and elimination of energy and capital-intensive units can be achieved. The intensification of process here would benefit the modularization of shale gas plants, and make it possible for distributed production of liquid hydrocarbons onsite for remote shale locations. </div><div><br></div><div>While shale gas being the carbon source for a sustainable future, renewable energy, especially solar and wind energy, will become the dominant energy resources for a sustainable economy. However, both solar and wind energy are dilute resources and harvesting them requires vast tracts of land, which could potentially compete with agricultural production for food. As a bookend case study, we investigate the land requirement for a 100% solar economy. The contiguous United States is used as an example and our analysis takes into account several issues that are usually ignored, such as the intermittent solar availability, estimation of future energy demand, actual power production from solar farms and available land types. Results show that it will be difficult for currently available land to meet the energy needs using current solar park designs for the entire contiguous United States and for nearly half of the individual states, which include well over half of the total US population. Barring radical improvements in agricultural output that could greatly reduce the land devoted to agriculture, the competition for land between energy and food seems inevitable, posing a major challenge to a future solar economy. If we extend the study to Germany, the United Kingdom and China, we could see that the challenge exists for both developed and developing countries. </div><div><br></div><div>To resolve the issue, a concept of "Aglectric" farming is proposed, where agricultural land produces electricity without diminishing existing agricultural output. Both wind turbines and photovoltaic (PV) panels can be used to generate electricity on agricultural land. While the use of the current PV panels is known to have a negative impact on crop growth, we propose several innovative PV systems using existing and new materials, innovative installation paradigms and module designs. Through extensive modeling of PV shadows throughout a day, we show that some of our designed PV systems could mitigate the loss of solar radiation while still maintaining substantial power output. Thus, it should be possible to design and install these PV systems on agricultural land to have significant power output without potentially diminishing agricultural production. We also show that PV aglectric farms alone will have the potential of realizing a 100% solar economy without land constraint. Together with regular PV parks and wind aglectric farms, PV aglectric farms will serve as an important option for a renewable future.</div><div><br></div><div>With its high energy density and zero greenhouse gas emission, hydrogen is the key energy carrier in a sustainable future. We introduce a process design strategy for the production of hydrogen by high temperature water electrolysis using concentrated solar thermal energy. At the same time, co-production of hydrogen and electricity is investigated where hydrogen can be produced by both thermochemical cycles and high temperature electrolysis. The process design features the process integration between hydrogen production and power generation. Process simulation is performed in an integrated Matlab and Aspen Plus platform. Efficiencies are analyzed for various processes.</div><div><br></div><div>Synergy is the key feature of all the studies in the dissertation. Process intensification for shale gas conversion and process integration for solar hydrogen production are examples of synergy at the process level. Coproduction of hydrogen and electricity and coproduction of electricity and food are examples of synergy at the building block level. Potential synergistic use of solar, wind and shale resources is an example of synergy at the resource level. Synergy is the keyword of the sustainable future we are pursuing.</div>
13

The Design of Continuous Chromatography for Separation and Purification

David M Harvey (8782685) 30 April 2020 (has links)
Continuous chromatography is an attractive alternative to traditional batch chromatography because it can have higher productivity, solvent efficiency, and product concentrations. However, several barriers prevent further use of continuous chromatography. There are many operating parameters that must be determined when designing continuous systems making it difficult to achieve high purity, yield, and productivity. Through the identification and strategic combination of the key dimensionless groups that control a continuous separation, it is possible to design highly productive systems that produce products with high yield and high purity. In this dissertation, three examples were selected to demonstrate the significance of a model-based method when designing continuous chromatography systems. (1) The Speedy Standing Wave Design and simulated moving bed splitting strategies for the separation of ternary mixtures with linear isotherms. (2) The Standing-wave Design of Three-Zone open-loop non-isocratic SMB for purification. (3) The Continuous Ligand-Assisted Displacement for the separation of Rare Earth Elements.<div>In the first example, the Speedy Standing Wave Design equations were developed for multicomponent separations with linear isotherms and a systematic splitting strategy was developed for the design of multiple sequential Simulated Moving Beds (SMBs). By performing the easiest split first, the overall productivity and solvent efficiency can be significantly improved. Rate model simulations were used to verify that the SSWD equations achieved target yields and purities. In systems where only one component is desired, the sorbent should be selected such that this component is the most or least retained so that it can be separated in a single SMB.</div><div>In the second example, the Standing Wave Design method was extended to non-isocratic three zone open loop SMBs. The standing wave design equations were derived and then verified using rate model simulations. In two case studies it was shown that non-isocratic SMBs designed using the standing wave design method show an order of magnitude higher productivity than a comparable batch system when the impurities are weakly adsorbing. When the impurities are competitive, the SWD method produces SMB systems with 2 orders of magnitude higher productivity than comparable batch systems. Because the design is based on dimensionless groups, the resulting designs are easily scalable and no rate model simulations are required to design high yield, high purity, and high productivity SMBs.</div><div>In the third example, the constant pattern design method was extended to continuous LAD systems. A continuous operation mode was developed that reduced the cycle time of LAD systems to further increase the productivity. In cases where the feed was equimolar, the continuous configuration increased the productivity between 20-50%. A multizone continuous LAD configuration was developed for the separation of a complex mixture of Dy, ND, and Pr that simulated a crude magnet feed. The resulting overall productivity for this system was 190 kg/m<sup>3</sup>day which was two orders of magnitude higher than a single column batch system and 70% higher than a multizone batch system. The robustness of the constant pattern design method was demonstrated through a simulated case study and it was determined that adding a safety factor through the reduction of the flowrate was more effective than reducing the design length.</div><div>Using a model-based design allows for the consistent design of continuous chromatography systems. The effects of a change in a feed or operating condition can be more easily understood through the lens of the model. This means that adjustments can be made pre-emptively when necessary and the new designs can be tested with virtual experiments before being implemented. The understanding of key dimensionless groups allows for designs that meet key design criteria at all scales of operation and thus allows for the easy transition from one scale to another.</div>
14

THE THERMAL SAFETY UNDERSTANDING OF MXENE ANODES IN LITHIUM-ION BATTERIES

Lirong Cai (9174149) 29 July 2020 (has links)
<p>Rechargeable lithium ion batteries (LIBs) are widely used in various daily life applications including electronic portable devices, cell phones, military applications, and electric vehicles throughout the world. The demand for building a safer and higher volumetric/gravimetric energy density LIBs has increased exponentially for electronic devices and electric vehicles. With the high energy density and longer cycle life, the LIBs are the most prominent energy storage system for electric vehicles. Researchers are further exploring for new materials with a high specific capacity, the MXene has been a promising new anode material for LIBs. The typical MXene material Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> has 447mAh/g theoretical capacity, which is higher than traditional graphite (372 mAh/g for LiC<sub>6</sub>) based anode.</p> <p>Though LIBs are used in most of the portable energy storage devices, LIBs are still having thermal runaway safety concern, which is caused by three main reasons: mechanical, electrical, and thermal abuse. The thermal runaway is caused by the initiation of solid electrolyte interface (SEI) degradation above 80 °C on the anode surface, generating exothermic heat, and further increasing battery temperature. The SEI is a thin layer formed on anode due to electrolyte decomposition during first few charging cycles. Its degradation at low temperature generates heat inside the LIBs and triggers the thermal runaway. The thermal runaway follows SEI degradation, electrolyte reactions, polypropylene separator melting, cathode decomposition and finally leads to combustion. The thermal runaway mechanism of graphite, which is the most common and commercialized anode material of LIBs, has been studied for years. However, the thermal safety aspects of the new MXene material has not been investigated yet. </p> <p>In this thesis, we primarily used differential scanning calorimetry (DSC) and specially designed multi module calorimetry (MMC) to measure exothermic and endothermic heat generated at <a>Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> </a>anode, associated with multiple chemical reactions as the temperature increases. The <i>in-situ</i> MMC technique is employed to study the interactions and chemical reactions of all the components (separator, electrolyte, cathode and MXene anode) in the coin cell for the first time, while the <i>ex-situ</i> DSC is used to investigate the reactions happened on anode side, including electrolyte, PVDF binder, MXene, SEI and intercalated Li. Along with other <a>complementary </a>instruments and methods, the morphological, structural and compositional studies are carried out using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) surface area measurement and electrochemical measurement to support the thermal analysis. The electrochemical and thermal runaway mechanism of conventional graphitic anode is studied and used for comparison with MXene<sub> </sub>anodes.</p> <p>The Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> thermal runaway is triggered by SEI decomposition around 120 °C analogous to conventional graphite. The thermal behavior of Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> anode is highly dependent on electrode material, surface area, lithiation states, surface morphology, structure and surface-terminating functional groups on Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub>, which provides more active lithium sites for exothermic reactions with the electrolyte. Especially the terminal groups (-OH, -F, =O, etc.) from the etching process affect the lithium ion intercalation and thermal runaway mechanism. With annealing treatment, the surface-terminating functional groups are modified and can achieve less exothermic heat release. By normalizing the total heat generation by specific capacities of the anode materials, it is observed that Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> (2.68 J/mAh) generates slightly less exothermic heat than graphite (2.72 J/mAh) indicating slightly safer nature of Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> anode. The <i>in-situ</i> thermal analysis results on the Ti<sub>3</sub>C<sub>2</sub>T<sub>z</sub> half-cell exhibited less total heat generation per mass (1.56 kJ/g) compared to graphite (1.59 kJ/g) half-cell. </p><br>
15

Chemical Manufacturing in Developing Markets: Analysis and Cost Estimations

Wasiu Peter Oladipupo (8669685) 28 July 2023 (has links)
<p>Developed countries have built wealth and prosperity on the strength of their manufacturing sectors, with China’s success story of lifting 800 million people out of extreme poverty in 30 years a sterling and most recent example of how manufacturing-led industrialization can foster economic development. Sub-Saharan Africa, unfortunately, find itself today in a similar situation as China did in 1990, with over 50% of the world’s desperately poor 719 million people living in the region. But unlike China, Sub-Saharan Africa is faced with the additional challenge of overcoming poverty in a world with stricter constraints to global trade and climate change limitations to modern-day industrialization. Compounding the challenges further is the region's limited know-how and human capital — a consequence of years of underdevelopment, creating a classic chicken and egg dilemma where the lack of industrialization perpetuates the dearth of know-how and human capital, and vice versa.</p><p>Considering these challenges, we investigate how chemical manufacturing and what chemical manufacturing approaches can be leveraged to effectively drive industrialization and economic development in Sub-Saharan Africa. We propose chemicals manufacturing using prefabricated modules – which are constructed offsite in places with available human capital and transported to be assembled in places where they are needed – as a flexible and needed approach. However, Economy of Scale, which generally favors large-scale chemical manufacturing, poses as a major constraint to such modularization approach, especially given the presently small serviceable market sizes in Sub-Saharan Africa due to low purchasing power parity. We thus utilize mathematical modeling techniques to determine and establish scenarios for economic viability of the proposed approach, providing modeling frameworks and introducing measures for further studies in the process. We also provide and analyze exemplary flowsheets synthesized for a net-zero carbon emissions chemical manufacturing paradigm in the region.</p><p>This work concludes with a prefeasibility study of a chemical manufacturing project in Nigeria, as part of the author’s quest to build prefabricated modular plants across Africa. <i>Modular plants are attractive as they can be tuned to market demand of a developing market and region that needs them, putting less capital at risk.</i></p><p>This thesis is intended to be a vanguard of potential solutions to the complex challenges to industrialization in Sub-Saharan Africa. It endeavors to pave the way for addressing these issues through chemical manufacturing, offering valuable insights for sustainable progress.</p>
16

STUDY OF STRUCTURE-PROPERTY-PERFORMANCE OF THE POLYMER ELECTROLYTE MEMBRANE FUEL CELLS (PEMFCS)

Chenzhao Li (14141316) 23 November 2022 (has links)
<p>  </p> <p>With the surge of interest in the electrification of transportation driven by global climate change, the need for powertrains using non-carbon energy sources has become more urgent than ever. The fuel cell electric vehicles (FCEVs) using polymer electrolyte membrane fuel cells (PEMFCs) have many advantages over the internal combustion engine (ICE) and other renewable energy vehicles such as high efficiency, zero-emission, fast fueling, unique power, and energy scalability (without heavy penalty from the increased mass). After three decades of intensive development, there are only several thousand FCEVs on the road, in contrast to the millions of battery electric vehicles (BEV) in use today. The biggest challenge of the widespread implantation of the PEMFCs is the cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited using a rotating disc electrode (RDE) is rarely realized in the membrane electrode assembly (MEA), which is the core of PEMFC, due to the difference on the electrolyte(ionomer)/catalyst interfaces. Much of my Ph. D research effort is concentrated on how to reduce the Pt usage and improve the stability of catalyst to reduce the operation cost of fuel cells. Several approaches were practiced improving the performance of MEA in a fuel cell, such as optimizing the ink formulation and MEA fabrication method, enhancing proton conductivity of carbon support for catalysts, engineering the ionomer and catalyst interface via surface functionalization. Such studies unraveled the relationship between property, structure, and performance of MEA, and significantly improved the performance of MEA. Further, to reduce the cost of fuel cell operation, approaches that is to improve the stability of catalysts either in reducing Oswald ripening or limiting surface migration were practiced on developing novel catalysts. Such as doping anion into Pt and Ni alloy crystal structure, introducing PANI on catalyst surface. These approaches significantly improve the stability of catalyst and MEA. Finally, same as platinum group metal (PGM) catalysts, PGM-free catalysts as well as their MEAs were studied. A novel method of PGM-free MEA fabrication was developed which significantly reduced the thickness of catalyst layer, thus greatly reduced the mass transfer resistance. Also, a highly stable and active PGM-free catalyst was developed and can be considered as a strong competitor to replace the traditional PGM catalysts in MEA.</p>
17

<b>Batch and Continuous Low-Pressure Hydrothermal Processing Methods for Polystyrene Conversion to Oils</b>

Clayton C Gentilcore (20430524) 17 December 2024 (has links)
<p dir="ltr">Annual rates for global polystyrene (PS) waste accumulation have reached 28 million tons, yet recycling rates remain around 1%. Conventional waste treatment methods have proven largely ineffective in reducing PS waste accumulation. As PS waste degrades, it generates microplastics and releases harmful chemicals that impact human health and ecosystems. This study developed batch and continuous low-pressure hydrothermal processing (LP-HTP) methods to convert PS into oils. In the batch LP-HTP study, the effects of temperature, time, and water loading on oil yield and composition were evaluated. The process converted PS to 96-99% oils with minimal char formation (1-2%) while requiring no catalyst, outperforming traditional pyrolysis. The LP-HTP methods also require lower energy inputs and pressures than supercritical water liquefaction. Co-processing PS with polyolefins resulted in oil yields of 87% and higher aromatic contents compared to polyolefin-only oils. Mono-aromatic (C<sub>6</sub>-C<sub>9</sub>) yields were limited by reversible reactions with poly-aromatics (C<sub>10</sub>-C<sub>24+</sub>). Efficient continuous LP-HTP methods were then developed, achieving 95-99% oil yields at 0.2-1.2 kg/hr under atmospheric pressure. The oil contained styrene monomers, dimers, and trimers with a total yield of 88.5% at 391°C. A detailed kinetic model was constructed, with intrinsic parameters estimated from continuous conversion data to enable process optimization and scale-up. These LP-HTP methods show potential for reducing environmental impacts and achieving up to 4.7 times higher energy recovery than incineration. The resulting hydrocarbons, if separated into pure monomers, can be used as chemical feedstocks, supporting a circular hydrocarbon economy that incentivizes plastic waste conversion.</p>
18

Electric Reaction Towers Re-thinking Endothermic Processes for a Net-Zero Future

Edwin Andres Rodriguez Gil (14071050) 28 July 2024 (has links)
<p dir="ltr">The chemical industry faces unprecedented pressure to reduce its carbon footprint while meeting growing global demand. As a major contributor to greenhouse gas emissions, accounting for approximately 7% of global carbon release, the sector plays a crucial role in achieving net-zero goals. This challenge is further compounded by projections suggesting that demand for chemicals could increase up to four-fold by 2050, and by the sector's role in producing several raw materials for other industries.</p><p dir="ltr">Within this context, endothermic reactors are of particular concern. The production of ethylene, propylene, and hydrogen alone accounts for around 3.6% of global CO2 emissions, representing over half of the chemical industry's total release. This situation underscores the need for alternatives in reactor design and operation.</p><p dir="ltr">To address these challenges, we introduce novel decarbonized process schemes and unit operations. The research centers around the development of Electric Reaction Towers (ERTs), a novel reactor configuration designed to ensure consistent product composition despite intense process fluctuations, such as those associated with Variable Renewable Energy (VRE). This is achieved by creating Custom Non-linear Heat Profiles (CNHPs) that maintain the key dimensionless groups of the system under dynamic conditions.</p><p dir="ltr">We present the concept of ERTs, explore their key principles, and the intuition behind their design. Additionally, we introduce Modular Reaction Towers (MRTs), which retain the benefits of handling fluctuations while addressing the investment and logistical challenges of adopting electric reactors.</p><p dir="ltr">The research employs a combination of Dimensional Analysis, Process Simulations, and Computational Fluid Dynamics (CFD) to evaluate these novel designs. Using ethylene production as a case study, we demonstrate that ERTs can enhance output by up to 4.2 times compared to state-of-the-art industrial designs.</p><p dir="ltr">The study further explores several additional concepts: Intermediate Cooling Zones (ICZs) and their potential to optimize complex reaction systems; the application of MRTs in the decentralized production of liquid hydrocarbons from shale gas to reduce flaring; and TurboQuenching, a novel approach to rapidly cool reaction products without a cooling agent while co-producing power. Finally, we discuss the broader implications of these innovations for the chemical industry's transition to more sustainable and efficient production methods.</p><p dir="ltr">By fundamentally re-thinking reactor design, this research contributes to the development of more efficient and sustainable production methods in the chemical industry, supporting the transition to a Net-Zero future.</p><p><br></p>
19

Reduced Degradation of CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> Solar Cells by Graphene Encapsulation

Kyle Reiter (6639662) 14 May 2019 (has links)
<div> <div> <div> <p>Organic-inorganic halide perovskite solar cells have increased efficiencies substantially (from 3% to > 22%), within a few years. However, these solar cells degrade very rapidly due to humidity and no longer are capable of converting photons into electrons. Methylammonium Lead Triiodide (CH3NH3PbI3 or MAPbI3) is the most common type of halide perovskite solar cell and is the crystal studied in this thesis. Graphene is an effective encapsulation method of MAPbI3 perovskite to reduce degradation, while also being advantageous because of its excellent optical and conductive properties. Using a PMMA transfer method graphene was chemical vapor depostion (CVD) grown graphene was transferred onto MAPbI3 and reduced the MAPbI3 degradation rate by over 400%. The PMMA transfer method in this study is scalable for roll-to- roll manufacturing with fewer cracks, impurites, and folds improving upon dry transfer methods. To characterize degradation a fluorescent microscope was used to capture photoluminescence data at initial creation of the samples up to 528 hours of 80% humidity exposure. Atomic force microscopy was used to characterize topographical changes during degradation. The study proves that CVD graphene is an effective encapsulation method for reducing degradation of MAPbI3 due to humidity and retained 95.3% of its initial PL intensity after 384 hours of 80% humidity exposure. Furthermore, after 216 hours of 80% humidity exposure CVD graphene encapsulated MAPbI3 retained 80.2% of its initial number of peaks, and only saw a 35.1% increase in surface height. Comparatively, pristine MAPbI3 only retained 16% of its initial number of peaks and saw a 159% increase in surface height. </p> </div> </div> </div>
20

Interfacial Tension and Phase Behavior of Oil/Aqueous Systems with Applications to Enhanced Oil Recovery

Jaeyub Chung (9511022) 16 December 2020 (has links)
Chemical enhanced oil recovery (cEOR) aims to increase the oil recovery of mature oil fields, using aqueous solutions of surfactants and polymers, to mobilize trapped oil and maintain production. The interfacial tensions (IFTs) between the injected aqueous solution, the oil droplets in reservoirs, and other possible phases formed (e.g., a “middle phase” microemulsion) are important for designing and assessing a chemical formulation. Ultralow IFTs, less than 10<sup>-2</sup> mN·m<sup>-1</sup>, are needed to increase the capillary number and help mobilize trapped oil droplets. Despite this fact, phase behavior tests have received more attention than IFTs for designing and evaluating surfactant formulations that result in high oil recovery efficiencies, because incorporating reliable IFTs into such evaluation process is avoided due to difficulties in obtaining reliable values. Hence, the main thrusts of this dissertation are to: (a) develop robust IFT measurement protocols for obtaining reliable IFTs regardless of the complexity of water and oil phase constituents and (b) improve the existing surfactant polymer formulation evaluation and screening processes by successfully incorporating the IFT as one of the critical parameters.<br>First, two robust tensiometry protocols using the known emerging bubble method (EBM) and the spinning bubble method (SBM) were demonstrated, for determining accurately equilibrium surface tensions (ESTs) and equilibrium IFTs (EIFTs). The protocols are used for measuring the dynamic surface tensions (DSTs), determining the steady state values, and establishing the stability of the steady state values by applying small surface area perturbations by monitoring the ST or IFT relaxation behavior. The perturbations were applied by abruptly expanding or compressing surface areas by changing the bubble sizes with an automated dispenser for the EBM, and by altering the rotation frequency of the spinning tube for the SBM. Such robust tension measurement protocols were applied for Triton X-100 aqueous solutions at a fixed concentration above its critical micelle concentration (CMC). The EST value of the model solution was 31.5 ± 0.1 mN·m<sup>-1</sup> with the EBM and 30.8 ± 0.2 mN·m<sup>-1</sup> with the SBM. These protocols provide robust criteria for establishing the EST values.<br>Second, the EIFTs of a commercial single chain anionic surfactant solution in a synthetic brine against a crude oil from an active reservoir were determined with the new protocol described earlier. The commercial surfactant used here has an oligopropoxy group between a hydrophobic chain and a sulfate head group. The synthetic brine has 9,700 ppm of total dissolved salts, which are a mixture of sodium chloride (NaCl), potassium chloride (KCl), manganese (II) chloride tetrahydrate (MnCl<sub>2</sub>·4H<sub>2</sub>O), magnesium (II) chloride hexahydrate (MgCl<sub>2</sub>·6H<sub>2</sub>O), barium chloride dihydrate (BaCl<sub>2</sub>·2H<sub>2</sub>O), sodium sulfate decahydrate (Na<sub>2</sub>SO<sub>4</sub>·10H<sub>2</sub>O), sodium bicarbonate (NaHCO<sub>3</sub>), and calcium chloride dihydrate (CaCl<sub>2</sub>·2H<sub>2</sub>O). The DSTs curves of the surfactant concentrations from 0.1 ppm to 10,000 ppm by weight had a simple adsorption/desorption equilibrium at air/water surface with surfactant diffusion from bulk aqueous phase. Such a mechanism was also observed from the tension relaxation behavior after area perturbations for the oil/water interfaces while DIFT measurements. The CMC of the commercial surfactant was determined to be 12 ppm in water and 1 ppm in the synthetic brine used. From the initial tension reduction curves from DST and DIFT measurements, the equilibrium timescales were shorter with brine than with water, because the adsorbed surfactant on the oil/water interfaces were partitioned into oil phases. For both DST and DIFT results suggest that the adsorbed surfactant layer at interfaces were typical adsorbed soluble monolayers.<br>Third, the phase and rheological behavior of a commercial anionic surfactant in water and in brine are important for large scale applications. A phase map of the surfactant at 25 °C at full range of surfactant concentration was obtained. The supramolecular structures of the various phases were characterized by dynamic light scattering (DLS), cryogenic transmission electron microscopy (cryo-TEM), conductimetry, densitometry, and x-ray scattering. The identified phases evolved as the surfactant concentration was increased; they were a micellar solution phase, a hexagonal liquid crystalline phase, and a lamellar liquid crystalline phase. In addition, the characterization results provided detailed information about supramolecular structure parameters such as micellar sizes and their aggregation numbers, and liquid crystal spacings. The phase and rheological behavior trends identified here were of great importance because the trend was similar to that of single chain monoisomeric surfactant. Thus, this study provides a potential universality of phase behavior trends of surfactant-water systems despite of the multicomponent nature of surfactants.<br>Fourth, the EIFTs of the pre-equilibrated mixtures of surfactant, brine, and oil were determined and compared to the EIFTs prior to pre-equilibration, in order to systematically identify the most relevant IFT for oil recovery. The EIFT between surfactant solutions and oil without any pre-equilibration prior to tension measurements is defined as the un-pre-equilibrated EIFT (EIFT<sub>up</sub>). The EIFT between oil and water phases after the pre-equilibration of surfactant, brine, and oil is defined as pre-equilibrated EIFT (EIFT<sub>p</sub>). The EIFT<sub>p</sub>’s were generally higher than EIFT<sub>up</sub>’s. In addition, the effects of three mixing methods and the water-to-oil volume ratio (WOR) on the EIFT<sub>p</sub> were evaluated. Out of three mixing methods, (A) mild mixing, (B) magnetic stirring, and (C) shaking vigorously by hand, method C produced mixtures which are the closest to the equilibrium state. The mixtures produced by method C had the largest decrease of the surfactant concentration during pre-equilibration due to the surfactant partitioning into oil phases. Moreover, the WOR affects the EIFT<sub>p</sub> significantly due to the preferential partitioning of surfactant components into oil phases. More specifically, the WOR and the EIFT<sub>p</sub> were found to be inversely correlated, because the amount of partitioned surfactant increased as the oil volume fraction increased. The EIFT<sub>p</sub>’s were different from the EIFT<sub>up</sub>’s at the same total surfactant concentrations in the aqueous layer evidently because of preferential partitioning of the various surfactant components.<br>Finally, the effect of surfactant losses due to adsorption into the rock surface on the pre-equilibrated EIFT (EIFT<sub>p</sub>) were evaluated to improve surfactant formulation protocols. Here, five types of EIFTs were identified, along with robust protocols for determining them. These are: (I) the un-pre-equilibrated equilibrium IFT (EIFT<sub>up</sub>); (II) the un-pre-equilibrated EIFTs in the presence of rock (EIFT<sub>up,rock</sub>); (III) the pre-equilibrated EIFTs (EIFT<sub>p</sub>) in the presence of oil; (IV) the pre-equilibrated EIFT in the presence of rock and oil (EIFT<sub>p,rock</sub>); and (V) the effluent EIFT (EIFT<sub>eff</sub>). The EIFT<sub>up</sub> is the EIFT of the aqueous surfactant/brine solution against an oil drop without any pre-equilibration. The EIFT<sub>up,rock</sub> is the EIFT between an oil drop and the surfactant solution after pre-equilibration with a rock sample to account for adsorption losses. The EIFT<sub>p</sub> is the EIFT between the pre-equilibrated water and the oil phases from surfactant/brine/oil mixtures. The EIFT<sub>p,rock</sub> is the EIFT between the pre-equilibrated water and the oil phases from surfactant/brine/oil/rock mixtures. The EIFT<sub>eff</sub> is the EIFT from an effluent sample mixture of a laboratory-scale core flood test. Among the five types of EIFTs, the EIFT<sub>p,rock</sub> was found to be the most important for the highest oil recovery performance in core flood tests, because it captures the most important surfactant partition processes, the partitioning to the oil phase and the partitioning by adsorption on the rock surface. Among three surfactant formulations tested with core flood experiments, the one with the lowest EIFT<sub>p,rock</sub> (~0.01 mN·m<sup>-1</sup>) had the highest oil recovery ratio (78%), and the one with the highest EIFT<sub>p,rock</sub> (~0.2 mN·m<sup>-1</sup>) had the lowest oil recovery ratio (55%). The other EIFTs correlated less with the oil recovery performance. Identifying surfactant formulations that have low or ultralow EIFTs, especially ultralow EIFT<sub>p,rock</sub>’s, are critical for screening formulations appropriate for core flood tests and target field applications, and for predicting oil recovery performance. These works are a significant contribution for improving (a) the surfactant formulation evaluation protocols, and (b) the utilization of reliable IFTs and phase behavior test protocols for oil recovery and many other surfactant and colloid sciences applications.<br>

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