Matching Items (22)
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- All Subjects: chemical engineering
- Creators: Green, Matthew
- Member of: ASU Electronic Theses and Dissertations
Description
Water recovery from impaired sources, such as reclaimed wastewater, brackish groundwater, and ocean water, is imperative as freshwater resources are under great pressure. Complete reuse of urine wastewater is also necessary to sustain life on space exploration missions of greater than one year’s duration. Currently, the Water Recovery System (WRS) used on the National Aeronautics and Space Administration (NASA) shuttles recovers only 70% of generated wastewater.1 Current osmotic processes show high capability to increase water recovery from wastewater. However, commercial reverse osmosis (RO) membranes rapidly degrade when exposed to pretreated urine-containing wastewater. Also, non-ionic small molecules substances (i.e., urea) are very poorly rejected by commercial RO membranes.
In this study, an innovative composite membrane that integrates water-selective molecular sieve particles into a liquid-barrier chemically resistant polymer film is synthetized. This plan manipulates distinctive aspects of the two materials used to create the membranes: (1) the innate permeation and selectivity of the molecular sieves, and (2) the decay-resistant, versatile, and mechanical strength of the liquid-barrier polymer support matrix.
To synthesize the membrane, Linde Type A (LTA) zeolite particles are anchored to the porous substrate, producing a single layer of zeolite particles capable of transporting water through the membrane. Thereafter, coating the chemically resistant latex polymer filled the space between zeolites. Finally, excess polymer was etched from the surface to expose the zeolites to the feed solution. The completed membranes were tested in reverse osmosis mode with deionized water, sodium chloride, and rhodamine solutions to determine the suitability for water recovery.
The main distinguishing characteristics of the new membrane design compared with current composite membrane include: (1) the use of an impermeable polymer broadens the range of chemical resistant polymers that can be used as the polymer matrix; (2) the use of zeolite particles with specific pore size insures the high rejection of the neutral molecules since water is transported through the zeolite rather than the polymer; (3) the use of latex dispersions, environmentally friendly water based-solutions, as the polymer matrix shares the qualities of low volatile organic compound, low cost, and non- toxicity.
In this study, an innovative composite membrane that integrates water-selective molecular sieve particles into a liquid-barrier chemically resistant polymer film is synthetized. This plan manipulates distinctive aspects of the two materials used to create the membranes: (1) the innate permeation and selectivity of the molecular sieves, and (2) the decay-resistant, versatile, and mechanical strength of the liquid-barrier polymer support matrix.
To synthesize the membrane, Linde Type A (LTA) zeolite particles are anchored to the porous substrate, producing a single layer of zeolite particles capable of transporting water through the membrane. Thereafter, coating the chemically resistant latex polymer filled the space between zeolites. Finally, excess polymer was etched from the surface to expose the zeolites to the feed solution. The completed membranes were tested in reverse osmosis mode with deionized water, sodium chloride, and rhodamine solutions to determine the suitability for water recovery.
The main distinguishing characteristics of the new membrane design compared with current composite membrane include: (1) the use of an impermeable polymer broadens the range of chemical resistant polymers that can be used as the polymer matrix; (2) the use of zeolite particles with specific pore size insures the high rejection of the neutral molecules since water is transported through the zeolite rather than the polymer; (3) the use of latex dispersions, environmentally friendly water based-solutions, as the polymer matrix shares the qualities of low volatile organic compound, low cost, and non- toxicity.
ContributorsKhosravi, Afsaneh Khosravi (Author) / Lind, Mary Laura (Thesis advisor) / Dai, Lenore (Committee member) / Green, Matthew (Committee member) / Lin, Jerry (Committee member) / Seo, Don (Committee member) / Arizona State University (Publisher)
Created2016
Description
A comprehensive and systematic investigation on the diffusion and phase behaviors of nanoparticles and macromolecules in two component liquid-liquid systems via Molecule Dynamic (MD) simulations is presented in this dissertation.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
ContributorsGao, Wei (Author) / Dai, Lenore (Thesis advisor) / Jiao, Yang (Committee member) / Liu, Yongming (Committee member) / Green, Matthew (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2017
Description
The engineering of microbial cell factories capable of synthesizing industrially relevant chemical building blocks is an attractive alternative to conventional petrochemical-based production methods. This work focuses on the novel and enhanced biosynthesis of phenol, catechol, and muconic acid (MA). Although the complete biosynthesis from glucose has been previously demonstrated for all three compounds, established production routes suffer from notable inherent limitations. Here, multiple pathways to the same three products were engineered, each incorporating unique enzyme chemistries and/or stemming from different endogenous precursors. In the case of phenol, two novel pathways were constructed and comparatively evaluated, with titers reaching as high as 377 ± 14 mg/L at a glucose yield of 35.7 ± 0.8 mg/g. In the case of catechol, three novel pathways were engineered with titers reaching 100 ± 2 mg/L. Finally, in the case of MA, four novel pathways were engineered with maximal titers reaching 819 ± 44 mg/L at a glucose yield of 40.9 ± 2.2 mg/g. Furthermore, the unique flexibility with respect to engineering multiple pathways to the same product arises in part because these compounds are common intermediates in aromatic degradation pathways. Expanding on the novel pathway engineering efforts, a synthetic ‘metabolic funnel’ was subsequently constructed for phenol and MA, wherein multiple pathways were expressed in parallel to maximize carbon flux toward the final product. Using this novel ‘funneling’ strategy, maximal phenol and MA titers exceeding 0.5 and 3 g/L, respectively, were achieved, representing the highest achievable production metrics products reported to date.
ContributorsThompson, Brian (Author) / Nielsen, David R (Thesis advisor) / Nannenga, Brent (Committee member) / Green, Matthew (Committee member) / Wang, Xuan (Committee member) / Moon, Tae Seok (Committee member) / Arizona State University (Publisher)
Created2017
Description
This is a two-part thesis assessing the long-term reliability of photovoltaic modules.
Part 1: Manufacturing dependent reliability - Adapting FMECA for quality control in PV module manufacturing
This part is aimed at introducing a statistical tool in quality assessments in PV module manufacturing. Developed jointly by ASU-PRL and Clean Energy Associates, this work adapts the Failure Mode Effect and Criticality Analysis (FMECA, IEC 60812) to quantify the impact of failure modes observed at the time of manufacturing. The method was developed through analysis of nearly 9000 modules at the pre-shipment evaluation stage in module manufacturing facilities across south east Asia. Numerous projects were analyzed to generate RPN (Risk Priority Number) scores for projects. In this manner, it was possibly to quantitatively assess the risk being carried the project at the time of shipment of modules. The objective of this work was to develop a benchmarking system that would allow for accurate quantitative estimations of risk mitigation and project bankability.
Part 2: Climate dependent reliability - Activation energy determination for climate specific degradation modes
This work attempts to model the parameter (Isc or Rs) degradation rate of modules as a function of the climatic parameters (i.e. temperature, relative humidity and ultraviolet radiation) at the site. The objective of this work was to look beyond the power degradation rate and model based on the performance parameter directly affected by the degradation mode under investigation (encapsulant browning or IMS degradation of solder bonds). Different physical models were tested and validated through comparing the activation energy obtained for each degradation mode. It was concluded that, for the degradation of the solder bonds within the module, the Pecks equation (function of temperature and relative humidity) modelled with Rs increase was the best fit; the activation energy ranging from 0.4 – 0.7 eV based on the climate type. For encapsulant browning, the Modified Arrhenius equation (function of temperature and UV) seemed to be the best fit presently, yielding an activation energy of 0.3 eV. The work was concluded by suggesting possible modifications to the models based on degradation pathways unaccounted for in the present work.
Part 1: Manufacturing dependent reliability - Adapting FMECA for quality control in PV module manufacturing
This part is aimed at introducing a statistical tool in quality assessments in PV module manufacturing. Developed jointly by ASU-PRL and Clean Energy Associates, this work adapts the Failure Mode Effect and Criticality Analysis (FMECA, IEC 60812) to quantify the impact of failure modes observed at the time of manufacturing. The method was developed through analysis of nearly 9000 modules at the pre-shipment evaluation stage in module manufacturing facilities across south east Asia. Numerous projects were analyzed to generate RPN (Risk Priority Number) scores for projects. In this manner, it was possibly to quantitatively assess the risk being carried the project at the time of shipment of modules. The objective of this work was to develop a benchmarking system that would allow for accurate quantitative estimations of risk mitigation and project bankability.
Part 2: Climate dependent reliability - Activation energy determination for climate specific degradation modes
This work attempts to model the parameter (Isc or Rs) degradation rate of modules as a function of the climatic parameters (i.e. temperature, relative humidity and ultraviolet radiation) at the site. The objective of this work was to look beyond the power degradation rate and model based on the performance parameter directly affected by the degradation mode under investigation (encapsulant browning or IMS degradation of solder bonds). Different physical models were tested and validated through comparing the activation energy obtained for each degradation mode. It was concluded that, for the degradation of the solder bonds within the module, the Pecks equation (function of temperature and relative humidity) modelled with Rs increase was the best fit; the activation energy ranging from 0.4 – 0.7 eV based on the climate type. For encapsulant browning, the Modified Arrhenius equation (function of temperature and UV) seemed to be the best fit presently, yielding an activation energy of 0.3 eV. The work was concluded by suggesting possible modifications to the models based on degradation pathways unaccounted for in the present work.
ContributorsPore, Shantanu (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Green, Matthew (Thesis advisor) / Srinivasan, Devrajan (Committee member) / Arizona State University (Publisher)
Created2017
Description
There are limited analyses of the properties of segmented ionenes on the influence of the type, structure, content of soft/hard segments, and type of counterions through direct comparisons, which are needed for a diverse set of applications. This dissertation research focuses on resolving the gaps in the structure-property-function relationship of segmented ionenes. First, the synthesis of novel segmented ionenes using step-growth polymerization via the Menshutkin reaction of ditertiary amines and alkyl dihalides was performed with PEG soft segment with three different content of soft/hard segments, 25, 50, and 75 wt%, and two different hard segments, linear aliphatic and heterocyclic aliphatic hard segments. The content of the soft segment influenced the degree of phase separation and ionic aggregation which affected the thermomechanical properties of segmented ionenes. In addition, the crystallization of the soft segment influenced the mechanical properties of the ionenes. Second, the effect of the type of the soft segment was investigated by analyzing the novel PTMO-based segmented ionenes possessing three different content of soft/hard segments, as well as two different hard segments. The heterocyclic aliphatic hard segment provided a better degree of phase separation compared to the linear aliphatic hard segment irrespective of the type of soft segment, PEG, or PTMO. Moreover, the type and content of hard segments not only affected the thermal and mechanical properties but also the morphology of the segmented ionenes significantly that even inducing an ordered morphology. Third, the counter-anion metathesis was performed with PEG- and PTMO-based segmented ionenes possessing two structurally different hard segments to investigate the effect of the type of counter-anions with a direct comparison of the type of soft and hard segments. The type of counterion significantly influenced the thermomechanical properties of the segmented ionenes, and the degree of phase separation of different types of counter-anions was dependent on the type of soft and hard segments. The results of this dissertation provide fundamental insights into the correlations between each factor that influences the properties of the segmented ionenes and enable the design of segmented ionenes for a diverse range of applications.
ContributorsLee, Jae Sang (Author) / Green, Matthew (Thesis advisor) / Long, Timothy (Committee member) / Holloway, Julianne (Committee member) / Jin, Kailong (Committee member) / Seo, Soyoung (Committee member) / Arizona State University (Publisher)
Created2023
Description
Drug delivery has made a significant contribution to cancer immunotherapy and can have a tremendous impact on modulating immunometabolism, thereby affecting cancer outcomes. Notably, the science of delivery of cancer vaccines and immunotherapeutics, modulating immune cell functions has inspired development of several successful companies and clinical products. For example, cancer vaccines require activation of dendritic cells (DCs) and tumour associated Mɸs (TAMs) through modulation of their energy metabolism (e.g., glycolysis, glutaminolysis, Krebs cycle). Similar to activated immune cells, cancer cells also upregulate glucose and glutamine transporters for proliferation and survival. Cancer cells having accelerated energy metabolism, which has been exploited as a target for various therapeutic studies. In the first strategy, an immunometabolism strategy based on sustained release of succinate from biomaterials, which incorporate succinate in the backbone of the polymer was developed. This study demonstrates that succinate-based polymeric microparticles act as alarmins by modulating the immunometabolism of DCs and Mɸs to generate robust pro-inflammatory responses for melanoma treatment in immunocompetent young as well as aging mice. In the second strategy, a biomaterial-based strategy was developed to deliver metabolites one-step downstream of the node where the glycolytic pathway is inhibited, to specifically rescue DCs from glycolysis inhibition. The study successfully demonstrated for the first time that the glycolysis of DCs can be rescued both in vitro and in vivo using a biomaterial strategy of delivering metabolites downstream of the inhibitory node. Overall, it is believed that advanced drug delivery strategies will play an important role in marrying the fields of immunometabolism and immunotherapy to generate translatable anti-cancer treatments.
ContributorsInamdar, Sahil (Author) / Acharya, Abhinav P (Thesis advisor) / Rege, Kaushal (Committee member) / Green, Matthew (Committee member) / Curtis, Marion (Committee member) / Seetharam, Mahesh (Committee member) / Arizona State University (Publisher)
Created2022
Description
Membrane based technology is one of the principal methods currently in widespread use to address the global water shortage. Pervaporation desalination is a membrane technology for water purification currently under investigation as a method for processing reverse osmosis concentrates or for stand-alone applications. Concentration polarization is a potential problem in any membrane separation. In desalination concentration polarization can lead to reduced water flux, increased propensity for membrane scaling, and decreased quality of the product water. Quantifying concentration polarization is important because reducing concentration polarization requires increased capital and operating costs in the form of feed spacers and high feed flow velocities. The prevalent methods for quantifying concentration polarization are based on the steady state thin film boundary layer theory. Baker’s method, previously used for pervaporation volatile organic compound separations but not desalination, was successfully applied to data from five previously published pervaporation desalination studies. Further investigation suggests that Baker’s method may not have wide applicability in desalination. Instead, the limitations of the steady state assumption were exposed. Additionally, preliminary results of nanophotonic enhancement of pervaporation membranes were found to produce significant flux enhancement. A novel theory on the mitigation of concentration polarization by the photothermal effect was discussed.
ContributorsMann, Stewart, Ph.D (Author) / Lind, Mary Laura (Thesis advisor) / Walker, Shane (Committee member) / Green, Matthew (Committee member) / Forzani, Erica (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2019
Description
Managing water resources has become one of the most pressing concerns of scientists both in academia and industry. The reverse osmosis (RO) water treatment process is a well-researched technology among the pressure driven processes to produce potable water. RO is an energy intensive process and often RO membranes are susceptible to fouling and scaling that drives up operational cost and hinder the efficiency. To increase the performance of RO membranes the feed water is pretreated to remove pollutants before desalination. This work aims to fabricate pretreatment membranes to prevent the effects of fouling and scaling by introducing hydrophilic character to membrane. This work explores electrospinning, a cost-effective and scalable technique, to blend two polymers into a nonwoven membrane comprised of fibers ~100 nm - 10 µm in diameter.
A rotary drum collector holding the mat was used to simultaneously collect the electrospun hydrophobic poly(vinyl chloride) (PVC) and hydrophilic poly(vinyl alcohol) (PVA) fibers from two separate solutions. The hydrophilicity of the resulting membrane was tuned by controlling the relative deposition rate of PVA onto the co-spun mat. Fiber diameter and morphologies were characterized by scanning electron microscopy, and Fourier-transform infrared spectroscopy and Confocal fluorescence microscopy further confirmed the presence of both polymers. Moreover, a rigorous analysis to map the PVA/PVC concentration was established to accurately report the relative concentrations of the two polymers on the co-spun mat. After electrospinning, the PVA in the co-spun mats were cross-linked with poly(ethylene glycol) diacid to impart mechanical strength and tune the porosity.
EDS analysis revealed inconsistencies in the mass deposition of both polymers suggesting an improvement in the current experimental design to establish a meaningful relationship between PVA concentration and hydrophilicity. However, tensile test revealed that co-spun mats with high mass flow ratios of PVA possessed high mechanical strength showing a significant improvement in the Young’s Modulus. Furthermore, the co-spun mats were challenged with filtration experiments expecting a positive correlation of flux with PVA concentration. But it was found that with increased concentration, crosslinked PVA constricted PVC fibers minimizing the pores causing a lower flux and a dense membrane structure suitable for filtration.
A rotary drum collector holding the mat was used to simultaneously collect the electrospun hydrophobic poly(vinyl chloride) (PVC) and hydrophilic poly(vinyl alcohol) (PVA) fibers from two separate solutions. The hydrophilicity of the resulting membrane was tuned by controlling the relative deposition rate of PVA onto the co-spun mat. Fiber diameter and morphologies were characterized by scanning electron microscopy, and Fourier-transform infrared spectroscopy and Confocal fluorescence microscopy further confirmed the presence of both polymers. Moreover, a rigorous analysis to map the PVA/PVC concentration was established to accurately report the relative concentrations of the two polymers on the co-spun mat. After electrospinning, the PVA in the co-spun mats were cross-linked with poly(ethylene glycol) diacid to impart mechanical strength and tune the porosity.
EDS analysis revealed inconsistencies in the mass deposition of both polymers suggesting an improvement in the current experimental design to establish a meaningful relationship between PVA concentration and hydrophilicity. However, tensile test revealed that co-spun mats with high mass flow ratios of PVA possessed high mechanical strength showing a significant improvement in the Young’s Modulus. Furthermore, the co-spun mats were challenged with filtration experiments expecting a positive correlation of flux with PVA concentration. But it was found that with increased concentration, crosslinked PVA constricted PVC fibers minimizing the pores causing a lower flux and a dense membrane structure suitable for filtration.
ContributorsMithaiwala, Husain (Author) / Green, Matthew (Thesis advisor) / Dai, Lenore (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2020
Description
As experiencing hot months and thermal stresses is becoming more common, chemically protective fabrics must adapt and provide protections while reducing the heat stress to the body. These concerns affect first responders, warfighters, and workers regularly surrounded by hazardous chemical agents. While adapting traditional garments with cooling devices provides one route to mitigate this issue, these cooling methods add bulk, are time limited, and may not be applicable in locations without logistical support. Here I take inspiration from nature to guide the development of smart fabrics that have high breathability, but self-seal on exposure to target chemical(s), providing a better balance between cooling and protection.
Natural barrier materials were explored as a guide, focusing specifically on prickly pear cacti. These cacti have a natural waxy barrier that provides protection from dehydration and physically changes shape to modify surface wettability and water vapor transport. The results of this study provided a basis for a shape changing polymer to be used to respond directly to hazardous chemicals, swelling to contain the agent.
To create a stimuli responsive material, a novel superabsorbent polymer was synthesized, based on acrylamide chemistry. The polymer was tested for swelling properties in a wide range of organic liquids and found to highly swell in moderately polar organic liquids. To help predict swelling in untested liquids, the swelling of multiple test liquids were compared with their thermodynamic properties to observe trends. As the smart fabric needs to remain breathable to allow evaporative cooling, while retaining functionality when soaked with sweat, absorption of water, as well as that of an absorbing liquid in the presence of water were tested.
Micron sized particles of the developed polymer were deposited on a plastic mesh with pore size and open area similar to common clothing fabric to establish the proof of concept of using a breathable barrier to provide chemical protection. The polymer coated mesh showed minimal additional resistance to water vapor transport, relative to the mesh alone, but blocked more than 99% of a xylene aerosol from penetrating the barrier.
Natural barrier materials were explored as a guide, focusing specifically on prickly pear cacti. These cacti have a natural waxy barrier that provides protection from dehydration and physically changes shape to modify surface wettability and water vapor transport. The results of this study provided a basis for a shape changing polymer to be used to respond directly to hazardous chemicals, swelling to contain the agent.
To create a stimuli responsive material, a novel superabsorbent polymer was synthesized, based on acrylamide chemistry. The polymer was tested for swelling properties in a wide range of organic liquids and found to highly swell in moderately polar organic liquids. To help predict swelling in untested liquids, the swelling of multiple test liquids were compared with their thermodynamic properties to observe trends. As the smart fabric needs to remain breathable to allow evaporative cooling, while retaining functionality when soaked with sweat, absorption of water, as well as that of an absorbing liquid in the presence of water were tested.
Micron sized particles of the developed polymer were deposited on a plastic mesh with pore size and open area similar to common clothing fabric to establish the proof of concept of using a breathable barrier to provide chemical protection. The polymer coated mesh showed minimal additional resistance to water vapor transport, relative to the mesh alone, but blocked more than 99% of a xylene aerosol from penetrating the barrier.
ContributorsManning, Kenneth (Author) / Rykaczewski, Konrad (Thesis advisor) / Burgin, Timothy (Committee member) / Emady, Heather (Committee member) / Green, Matthew (Committee member) / Thomas, Marylaura (Committee member) / Arizona State University (Publisher)
Created2020
Description
Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals used for a wide variety of products and industrial processes, including being an essential class of chemicals in the fabrication of semiconductors. Proven concerns related to bioaccumulation and toxicity across multiple species have resulted in health advisory and regulatory initiatives for PFAS in drinking and wastewaters. Among impacted users of PFAS, the semiconductor industry is in urgent need of technologies to remove PFAS from water. Specifically, they prefer technologies capable of mineralizing PFAS into inorganic fluoride (F-). The goal of this thesis is to compare the effectiveness of photo- versus electrocatalytic treatment in benchtop reactor systems PFAS in industrial wastewater before selecting one technology to investigate comprehensively. First, a model wastewater was developed based upon semiconductor samples to represent water matrices near where PFAS are used and the aggregate Fab effluent, which were then used in batch catalytic experiments. Second, batch experiments with homogenous photocatalysis (UV/SO32-) were found to be more energy-intensive than heterogeneous catalysis using boron-doped diamond (BDD) electrodes, and the latter approach was then studied in-depth.
During electrocatalysis, longer chain PFAS (C8; PFOA & PFOS) were observed to degrade faster than C6 and C4 PFAS. This study is the first to report near-complete defluorination of not only C8- and C6- PFAS, but also C4-PFAS, in model wastewaters using BDD electrocatalysis, and the first to report such degradation in real Fab wastewater effluents. Based upon differences in PFAS degradation rates observed in single-solute systems containing only C4 PFAS versus multi-solute systems including C4, C6, and C8 PFAS, it was concluded that the surfactant properties of the longer-chain PFAS created surface films on the BDD electrode surface which synergistically enhanced removal of shorter-chain PFAS. The results from batch experiments that serve as the basis of this thesis will be used to assess the chemical byproducts and their associated bioaccumulation and toxicity. This thesis was aimed at developing an efficient method for the degradation of perfluoroalkyl substances from industrial process waters at realistic concentrations.
ContributorsNienhauser, Alec Brockway (Author) / Westerhoff, Paul (Thesis advisor) / Garcia-Segura, Sergi (Committee member) / Thomas, Marylaura (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2021