Matching Items (25)
Filtering by
- All Subjects: chemical engineering
- All Subjects: Photovoltaic Cells
- Creators: Lin, Jerry
- Creators: Alford, Terry
Description
The use of petroleum for liquid-transportation fuels has strained the environment and caused the global crude oil reserves to diminish. Therefore, there exists a need to replace petroleum as the primary fuel derivative. Butanol is a four-carbon alcohol that can be used to effectively replace gasoline without changing the current automotive infrastructure. Additionally, butanol offers the same environmentally friendly effects as ethanol, but possess a 23% higher energy density. Clostridium acetobutylicum is an anaerobic bacterium that can ferment renewable biomass-derived sugars into butanol. However, this fermentation becomes limited by relatively low butanol concentrations (1.3% w/v), making this process uneconomical. To economically produce butanol, the in-situ product removal (ISPR) strategy is employed to the butanol fermentation. ISPR entails the removal of butanol as it is produced, effectively avoiding the toxicity limit and allowing for increased overall butanol production. This thesis explores the application of ISPR through integration of expanded-bed adsorption (EBA) with the C. acetobutylicum butanol fermentations. The goal is to enhance volumetric productivity and to develop a semi-continuous biofuel production process. The hydrophobic polymer resin adsorbent Dowex Optipore L-493 was characterized in cell-free studies to determine the impact of adsorbent mass and circulation rate on butanol loading capacity and removal rate. Additionally, the EBA column was optimized to use a superficial velocity of 9.5 cm/min and a resin fraction of 50 g/L. When EBA was applied to a fed-batch butanol fermentation performed under optimal operating conditions, a total of 25.5 g butanol was produced in 120 h, corresponding to an average yield on glucose of 18.6%. At this level, integration of EBA for in situ butanol recovered enabled the production of 33% more butanol than the control fermentation. These results are very promising for the production of butanol as a biofuel. Future work will entail the optimization of the fed-batch process for higher glucose utilization and development of a reliable butanol recovery system from the resin.
ContributorsWiehn, Michael (Author) / Nielsen, David (Thesis advisor) / Lin, Jerry (Committee member) / Lind, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2013
Description
Post-combustion carbon capture is a viable option for reducing CO2 greenhouse gas emissions, and one potentially promising technology for this route is adsorption using chemically and physically based sorbents. A number of exceptional CO2 sorbents materials have been prepared including metal organic frameworks, zeolites, and carbon based materials. One particular group of capable materials are amine based solid sorbents that has shown to possess high adsorption capacities and favorable adsorption kinetics. A key variable in the synthesis of an amine based sorbent is the support which acts as the platform for the amine modification. Aerogels, due to their high porosities and surface areas, appear to be a promising support for an amine modified CO2 sorbent. Therefore, in order to develop a commercially viable CO2 sorbent, particulate aerogels manufactured by Cabot Corporation through an economical and proprietary ambient drying process were modified with amines using a variety of functionalization methods. Two methods of physical impregnation of the amino polymer TEPA were performed in order to observe the performance as well as understand the effects of how the TEPA distribution is affected by the method of introduction. Both samples showed excellent adsorption capacities but poor cyclic stability for lack of any covalent attachment. Furthermore the method of TEPA impregnation seems to be independent on how the polymer will be distributed in the pore space of aerogel. The last two methods utilized involved covalently attaching amino silanes to the surface silanols of the aerogel. One method was performed in the liquid phase under anhydrous and hydrous conditions. The materials developed through the hydrous method have much greater adsorption capacities relative to the anhydrous sample as a result of the greater amine content present in the hydrous sample. Water is another source of silylation where additional silanes can attach and polymerize. These samples also possessed stable cyclic stability after 100 adsorption/regeneration cycles. The other method of grafting was performed in the gas phase through ALD. These samples possessed exceptionally high amine efficiencies and levels of N content without damaging the microstructure of the aerogel in contrast to the liquid phase grafted sorbents.
ContributorsLinneen, Nick (Author) / Lin, Jerry (Thesis advisor) / Pfeffer, Robert (Thesis advisor) / Lind, Mary (Committee member) / Rege, Kaushal (Committee member) / Nielsen, David (Committee member) / Anderson, James (Committee member) / Arizona State University (Publisher)
Created2014
Description
Pervaporation is a membrane separation technology that has had industrial application and which is the subject of ongoing research. Two major factors are important in judging the quality of a membrane: selectivity and permeation flux. Although many types of materials can be used for the separation layer, zeolites will be the material considered in this thesis. A simple mathematical model has been developed to demonstrate the inter-relationships between relative permeation flux, reduced selectivity, and the relative resistance to mass transfer of the support to the zeolite layer. The model was applied to several membranes from our laboratory and to two examples from the literature. The model offers a useful way of conceptualizing membrane performance and facilitates the comparison of different membrane performances. The model predicts the effect of different supports on zeolite supported membrane performance.
ContributorsMann, Stewart (Author) / Lin, Jerry (Thesis advisor) / Lind, Mary Laura (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2014
Description
Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H6/C3H8 separation properties of MFI zeolite membrane and CMS membrane.
MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.
CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.
CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.
CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.
CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
ContributorsMa, Xiaoli (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2015
Description
Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst.
ContributorsAnderson, Matthew Brandon (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Rege, Kaushal (Committee member) / Anderson, James (Committee member) / Rivera, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
Description
This work demonstrates a capable reverse pulse deposition methodology to influence gap fill behavior inside microvia along with a uniform deposit in the fine line patterned regions for substrate packaging applications. Interconnect circuitry in IC substrate packages comprises of stacked microvia that varies in depth from 20µm to 100µm with an aspect ratio of 0.5 to 1.5 and fine line patterns defined by photolithography. Photolithography defined pattern regions incorporate a wide variety of feature sizes including large circular pad structures with diameter of 20µm - 200µm, fine traces with varying widths of 3µm - 30µm and additional planar regions to define a IC substrate package. Electrodeposition of copper is performed to establish the desired circuit. Electrodeposition of copper in IC substrate applications holds certain unique challenges in that they require a low cost manufacturing process that enables a void-free gap fill inside the microvia along with uniform deposition of copper on exposed patterned regions. Deposition time scales to establish the desired metal thickness for such packages could range from several minutes to few hours. This work showcases a reverse pulse electrodeposition methodology that achieves void-free gap fill inside the microvia and uniform plating in FLS (Fine Lines and Spaces) regions with significantly higher deposition rates than traditional approaches. In order to achieve this capability, systematic experimental and simulation studies were performed. A strong correlation of independent parameters that govern the electrodeposition process such as bath temperature, reverse pulse plating parameters and the ratio of electrolyte concentrations is shown to the deposition kinetics and deposition uniformity in fine patterned regions and gap fill rate inside the microvia. Additionally, insight into the physics of via fill process is presented with secondary and tertiary current simulation efforts. Such efforts lead to show “smart” control of deposition rate at the top and bottom of via to avoid void formation. Finally, a parametric effect on grain size and the ensuing copper metallurgical characteristics of bulk copper is also shown to enable high reliability substrate packages for the IC packaging industry.
ContributorsGanesan, Kousik (Author) / Tasooji, Amaneh (Thesis advisor) / Manepalli, Rahul (Committee member) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2018
Description
Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation of the formation process of MOF membrane, framework defects, and two-dimensional (2D) MOFs, aiming to explore the answers for three critical questions: (1) how to obtain a continuous MOF membrane, (2) how defects form in MOF framework, and (3) how to obtain isolated 2D MOFs. To solve the first problem, the accumulated protons in the MOF synthesis solution is proposed to be the key factor preventing the continuous growth among Universitetet I Oslo-(UiO)-66 crystals. The hypothesis is verified by the growth reactivation under the addition of deprotonating agent. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium so that an oriented growth of UiO-66 film was achieved in membrane structures. To find the answer for the second problem, the defect formation mechanism in UiO-66 was investigated and the formation of missing-cluster (MC) defects is attributed to the partially-deprotonated ligands. Experimental results show the number of MC defects is sensitive to the addition of deprotonating agent, synthesis temperature, and reactant concentration. Pore size distribution allows an accurate and convenient characterization of the defects. Results show that these defects can cause significant deviations of its pore size distribution from the perfect crystal. The study of the third questions is based on the established bi-phase synthesis method, a facile synthesis method is adopted for the production of high quality 2D MOFs in large scale. Here, pyridine is used as capping reagent to prevent the interplanar hydrogen bond formation. Meanwhile, formic acid and triethylamine as modulator and deprotonating agent to balance the anisotropic growth, crystallinity, and yield in the 2D MOF synthesis. As a result, high quality 2D zinc-terephthalic acid (ZnBDC) and copper-terephthalic acid (CuBDC) with extraordinary aspect ratio samples were successfully synthesized.
ContributorsShan, Bohan (Author) / Mu, Bin (Thesis advisor) / Forzani, Erica (Committee member) / Dai, Lenore (Committee member) / Lin, Jerry (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2019
Description
In order to meet climate targets, the solar photovoltaic industry must increase photovoltaic (PV) deployment and cost competitiveness over its business-as-usual trajectory. This requires more efficient PV modules that use less expensive materials, and longer operational lifetime. The work presented here approaches this challenge with a novel metallization method for solar PV and electronic devices.
This document outlines work completed to this end. Chapter 1 introduces the areas for cost reductions and improvements in efficiency to drive down the cost per watt of solar modules. Next, in Chapter 2, conventional and advanced metallization methods are reviewed, and our proposed solution of dispense printed reactive inks is introduced. Chapter 3 details a proof of concept study for reactive silver ink as front metallization for solar cells. Furthermore, Chapter 3 details characterization of the optical and electrical properties of reactive silver ink metallization, which is important to understanding the origins of problems related to metallization, enabling approaches to minimize power losses in full devices. Chapter 4 describes adhesion and specific contact resistance of reactive ink metallizations on silicon heterojunction solar cells. Chapter 5 compares performance of silicon heterojunction solar cells with front grids formed from reactive ink metallization and conventional, commercially available metallization. Performance and degradation throughout 1000 h of accelerated environmental exposure are described before detailing an isolated corrosion experiment for different silver-based metallizations. Finally, Chapter 6 summarizes the main contributions of this work.
The major goal of this project is to evaluate potential of a new metallization technique –high-precision dispense printing of reactive inks–to become a high efficiency replacement for solar cell metallization through optical and electrical characterization, evaluation of durability and reliability, and commercialization research. Although this work primarily describes the application of reactive silver inks as front-metallization for silicon heterojunction solar cells, the work presented here provides a framework for evaluation of reactive inks as metallization for various solar cell architectures and electronic devices.
This document outlines work completed to this end. Chapter 1 introduces the areas for cost reductions and improvements in efficiency to drive down the cost per watt of solar modules. Next, in Chapter 2, conventional and advanced metallization methods are reviewed, and our proposed solution of dispense printed reactive inks is introduced. Chapter 3 details a proof of concept study for reactive silver ink as front metallization for solar cells. Furthermore, Chapter 3 details characterization of the optical and electrical properties of reactive silver ink metallization, which is important to understanding the origins of problems related to metallization, enabling approaches to minimize power losses in full devices. Chapter 4 describes adhesion and specific contact resistance of reactive ink metallizations on silicon heterojunction solar cells. Chapter 5 compares performance of silicon heterojunction solar cells with front grids formed from reactive ink metallization and conventional, commercially available metallization. Performance and degradation throughout 1000 h of accelerated environmental exposure are described before detailing an isolated corrosion experiment for different silver-based metallizations. Finally, Chapter 6 summarizes the main contributions of this work.
The major goal of this project is to evaluate potential of a new metallization technique –high-precision dispense printing of reactive inks–to become a high efficiency replacement for solar cell metallization through optical and electrical characterization, evaluation of durability and reliability, and commercialization research. Although this work primarily describes the application of reactive silver inks as front-metallization for silicon heterojunction solar cells, the work presented here provides a framework for evaluation of reactive inks as metallization for various solar cell architectures and electronic devices.
ContributorsJeffries, April M (Author) / Bertoni, Mariana I (Thesis advisor) / Saive, Rebecca (Committee member) / Holman, Zachary (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2019
Description
Global photovoltaic (PV) module installation in 2018 is estimated to exceed 100 GW, and crystalline Si (c-Si) solar cell-based modules have a share more than 90% of the global PV market. To reduce the social cost of PV electricity, further developments in reliability of solar panels are expected. These will lead to realize longer module lifetime and reduced levelized cost of energy. As many as 86 failure modes are observed in PV modules [1] and series resistance increase is one of the major durability issues of all. Series resistance constitutes emitter sheet resistance, metal-semiconductor contact resistance, and resistance across the metal-solder ribbon. Solder bond degradation at the cell interconnect is one of the primary causes for increase in series resistance, which is also considered to be an invisible defect [1]. Combination of intermetallic compounds (IMC) formation during soldering and their growth due to solid state diffusion over its lifetime result in formation of weak interfaces between the solar cell and the interconnect. Thermal cycling under regular operating conditions induce thermo-mechanical fatigue over these weak interfaces resulting in contact reduction or loss. Contact reduction or loss leads to increase in series resistance which further manifests into power and fill factor loss. The degree of intermixing of metallic interfaces and contact loss depends on climatic conditions as temperature and humidity (moisture ingression into the PV module laminate) play a vital role in reaction kinetics of these layers. Modules from Arizona and Florida served as a good sample set to analyze the effects of hot and humid climatic conditions respectively. The results obtained in the current thesis quantifies the thickness of IMC formation from SEM-EDS profiles, where similar modules obtained from different climatic conditions were compared. The results indicate the thickness of the IMC and detachment degree to be growing with age and operating temperatures of the module. This can be seen in CuxSny IMC which is thicker in the case of Arizona module. The results obtained from FL
ii
aged modules also show that humidity accelerates the formation of IMC as they showed thicker AgxSny layer and weak interconnect-contact interfaces as compared to Arizona modules. It is also shown that climatic conditions have different effects on rate at which CuxSny and AgxSny intermetallic compounds are formed.
ii
aged modules also show that humidity accelerates the formation of IMC as they showed thicker AgxSny layer and weak interconnect-contact interfaces as compared to Arizona modules. It is also shown that climatic conditions have different effects on rate at which CuxSny and AgxSny intermetallic compounds are formed.
ContributorsBuddha, Viswa Sai Pavan (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Alford, Terry (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Arizona State University (Publisher)
Created2018
Description
Lithium-ion batteries are the predominant source of electrical energy storage for most portable electronics applications, including hybrid/electric vehicles, laptops, and cellular phones. However, these batteries pose safety concerns due to their flammability and tendency to violently ignite upon short circuiting or failing. Solid electrolytes are a current research development aimed at reducing the flammability and reactivity of lithium batteries. The compound Li7La3Zr2O12, or LLZO, exhibits satisfactory ionic conductivity in the cubic phase, which is normally synthesized via doping with Al. It has recently been discovered that synthesizing nanostructured LLZO can stabilize the cubic phase without the need for doping. Here nanostructured LLZO was formed using templating on various cellulosic fibers, including cotton fibers, printer paper, filter paper, and nanocellulose fibrils followed by calcination at 700-800 °C. The effect of templating material, calcination temperature, calcination time, and heating ramp rate on LLZO phase and morphology was thoroughly investigated. Templating was determined to be an effective method for controlling the LLZO size and morphology, and most templating experiments resulted in LLZO fibers or ligaments similar in size and morphology to the original template material. A systematic study on the various experimental parameters was performed, concluding that low calcination time and low ramp rate favored smaller ligament formation. Further, it was verified that cubic phase stabilization occurred for LLZO with ligaments of less than 1 micron on average without the use of doping. This research provides more information regarding the size dependence on cubic LLZO stabilization that has not been previously investigated in detail.
ContributorsGordon, Zachary Daniel (Author) / Chan, Candace K. (Thesis director) / Lin, Jerry (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05