Chemical Engineering Commons^™

Harnessing Nanocellulose For Sustainable Carbon Capture: Synthesis, Processing, And Performance Evaluation, Jerred C. Wassgren

Doctoral Dissertations

Scientists and governments have recognized the need for environmental remediation, most notably with the adoption of the Paris Agreement in 2016. One of the major concerns is the production of greenhouse gases (GHGs). The major GHG is carbon dioxide (CO₂) in which humans emit over 36 gigatons yearly. Atmospheric CO₂ is responsible for 60% of the heat retained by the earth – resulting in rising temperatures, melting ice caps, and increasing ocean acidification. Therefore, a major goal of the Paris Agreement was to reduce GHG emissions as well as the capture of CO₂ from the atmosphere. …

Experimental Investigation Of The Vortex-Induced Vibration Response Of A Flexibly-Mounted Rigid Cylinder In The Shear-Thinning And Inertial-Viscoelastic Flow Regimes, Pieter Boersma

Doctoral Dissertations

Flexible or flexibly-mounted structures with bluff cross-sections in flow can shed vortices at frequencies that increase with increasing flow velocity. When this shedding frequency is equal to the structure's natural frequency, the structure can oscillate. This is called vortex-induced vibrations (VIV). VIV is present in multiple fluid-structure interaction (FSI) systems which can be found in industrial, medical, and engineering applications. These oscillations can be desirable or undesirable, so understanding the physics behind this phenomenon is important. This work seeks to investigate experimentally the VIV response in the inertial-viscoelastic regime where fluid inertia and elasticity influence the system. The subcritical Newtonian …

Optimizing Channel Formation In Peg Maleimide Hydrogels, Bakthavachalam Kannadasan

Masters Theses

Blood vessels including the arteries, veins, and capillaries are a critical and indispensable component of various organisms. Some studies estimate that if all the blood vessels present in our body are arranged in line, they would amount to a total length of approximately 60,000 miles. This distance is enough to circle the world two and a half times! In addition to being all pervasive, blood vessels perform certain key functions such as delivery of oxygen and nutrients to various tissues in the body. They also assist in the spread of diseases such as cancer. Therefore, it is important to study …

Electrostatic Effects On Lipid Bilayer Physicochemal Properties And Vesicle Adhesion, Oscar Zabala-Ferrera

Doctoral Dissertations

Lipids are an integral part of cells, being the principal component of the cell membrane, and contributing to the function and regulation of biological processes. Lipid nanoparticles mimicking a cell’s endosomes or exosomes are of particular interest within the pharmaceutical industry for their ability to deliver cargo such as RNA into target cells. The delivery process faces a multitude of challenges, so a rational design approach for vesicles that considers a lipid’s physicochemical contribution to the membrane is desired. To that end, this thesis explores the creation of large area biomembranes along with the development of electromechanical and optical characterization …

Machine Learning Modeling Of Polymer Coating Formulations: Benchmark Of Feature Representation Schemes, Nelson I. Evbarunegbe

Masters Theses

Polymer coatings offer a wide range of benefits across various industries, playing a crucial role in product protection and extension of shelf life. However, formulating them can be a non-trivial task given the multitude of variables and factors involved in the production process, rendering it a complex, high-dimensional problem. To tackle this problem, machine learning (ML) has emerged as a promising tool, showing considerable potential in enhancing various polymer and chemistry-based applications, particularly those dealing with high dimensional complexities.

Our research aims to develop a physics-guided ML approach to facilitate the formulations of polymer coatings. As the first step, this …

Polyesters Derived From Biobased 1,5-Pentanediol For Coatings, Adhesives, And Biodegradable Plastics, Lei Zheng

Doctoral Dissertations

Biomass-derived polymers are drawing increased attention from researchers due to unique performance attributes, potential for biodegradability, new low-cost feedstocks, and improved sustainability. Biobased feedstocks are employed in both major applications of polymers thermosets and thermoplastics. For thermoset coatings and adhesives, biobased resins such as biobased alkyds, epoxy resins, benzoxazine resins, starch derivatives, and proteins from plants and animals, are promising candidates to replace petroleum-derived counterparts. Thermoplastics such as polyethylene are mainly produced from fossil resources, generally have poor degradability and are difficult to effectively recycle. Currently, in the United States, less than 10% plastics are recycled, and more than 70% …

Polymer Based Energy Storage And Thermal Management On Textile Devices, Wesley A. Viola

Doctoral Dissertations

Humans developed textiles to manage thermal energy transfer with the environment and support homeostasis in a wide range of climates. With the anticipation of wearable technologies to transform healthcare via early, pre-symptomatic detection of illness, there is now a demand for electrical energy storage to support such on-body devices. Finding energy materials to merge seamlessly with textiles is basic requirement to ensure widespread adoption of wearable health monitors. Here we use a vapor deposition process to conformally coat ordinary fabrics with the doped conjugated polymer poly(3,4 ethylenedioxythiophene) (PEDOT-Cl), a soft material which possesses electronic and redox capabilities. We demonstrate PEDOT-Cl …

Assembly Of Polymer Colloids At Fluid Interfaces Through External Fields And Nanoscale Surface Topography, Samuel Trevenen

Doctoral Dissertations

The superposition of dipolar repulsion and capillary attraction energies between colloidal particles pinned at fluid interfaces dictates their microstructural organization and therefore the macroscopic interfacial material properties of particle-stabilized emulsions and 2D monolayer materials. While isotropic, spherical, particles have been extensively utilized, expanding the possible applications and material property tunability via anisotropic particles has been a challenge due to the propensity of particles to form disordered aggregates at the interface. My thesis presents the synthesis of anisotropic polymer ellipsoids and the development and use of experimental tools to study their interfacial behavior to reveal how dipolar and capillary interactions can …

Phosphorus-Containing Zeolites For Biofuel Production, Jason Gulbinski

Doctoral Dissertations

Fossil fuel consumption increases 2% a year due to transportation fuels and specialty chemicals for plastics and synthetic fibers such as p-xylene, a monomer of polyethylene terephthalate. p-Xylene demand was over 50 million tons in 2021 and will increase by 5% a year through 2026. Therefore, sustainable p-xylene production is desired. p-Xylene is produced renewably through Diels-Alder cycloaddition of biomassderived 2,5-dimethylfuran (DMF) with ethylene from bio-ethanol and dehydration over an acid catalyst. Industrial aluminosilicate zeolite catalysts achieve a selectivity of 75%, with loss to side products and coking. A new class of catalysts, phosphoric acid-containing aluminum-free zeolites, P-zeosils, like dealuminated …

Effect Of Chemical Identity And Morphology On Amphiphilic-Zwitterionic Block Copolymer Membranes, Ria Ghosh

Doctoral Dissertations

Amphiphilic block copolymers have gained a broad research interest attributed to their self-assembly properties over a range of pH, temperature, and ionic strength. Polyzwitterions have attracted special attention due to their hydrophilicity, charge sensitivity and coulombic attraction of the opposite charges over a range of environments making them a popular material of study in the field of stimuli responsive systems, for example in self-healing hydrogels, and water transport membranes. Combining the stimuli responsiveness and higher hydrophilicity of zwitterionic polymers with self-assembly behavior of amphiphilic block copolymers created an interest to study the effect of composition and identity of the zwitterionic …

Supplementary Code For "Chain Trajectories, Domain Shapes And Terminal Boundaries In Block Copolymers", Benjamin R. Greenvall, Michael S. Dimitriyev, Gregory M. Grason

Data and Datasets

Supplementary code used for the publication "Chain trajectories, domain shapes and terminal boundaries in block copolymers" by Benjamin R. Greenvall, Michael S. Dimitriyev, and Gregory M. Grason. Includes code for extracting and analyzing polar order and chain trajectories from self-consistent field calculations of block copolymers.

Polymer-Based Microfluidic Device For On-Chip Counter-Diffusive Crystallization And In Situ X-Ray Crystallography At Room Temperature, Sarthak Saha, Can Özden, Alfred Samkutty, Silvia Russi, Aina Cohen, Margaret M. Stratton, Sarah L. Perry

Chemical Engineering Faculty Publication Series

Proteins are long chains of amino acid residues that perform a myriad of functions in living organisms, including enzymatic reactions, signalling, and maintaining structural integrity. Protein function is determined directly by the protein structure. X-ray crystallography is the primary technique for determining the 3D structure of proteins, and facilitates understanding the effects of protein structure on function. The first step towards structure determination is crystallizing the protein of interest. We have developed a centrifugally-actuated microfluidic device that incorporates the fluid handling and metering necessary for protein crystallization. Liquid handling takes advantage of surface forces to control fluid flow and enable …

Synthesis And Assembly Of Polymer Materials At Interfaces, Xiaoshuang Wei

Doctoral Dissertations

The overarching goal of the thesis is to understand growth and assembly of polymer materials at interfaces. Chapter 2 and Chapter 3 study simultaneous polymer growth and assembly at fluid interfaces, where in-situ photopolymerization and vapor phase deposition were utilized to grow polymers, respectively. Chapter 4 leverages capillary condensation to pattern polymer growth at solid substrates. Chapter 1 provides background information on polymer materials at interfaces, and vapor phase deposition method (initiated chemical vapor deposition, iCVD) to grow polymers. This chapter also reviews polymer thin film wetting, and colloidal assemblies at interfaces. In Chapter 2, we demonstrate the preparation …

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian

Doctoral Dissertations

The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context …

Chromatographic Dynamic Chemisorption, Shreya Thakkar

Masters Theses

Reaction rates of catalytic cycles over supported metal catalysts are normalized by the exposed metal atoms on the catalyst surface, reported as site time yields which provide a rigorous standard to compare distinct metal surfaces. Defined as the fraction of exposed metal surface atoms to the total number of metal atoms, it is important to measure the dispersion of supported metal catalysts to report standardized rates for kinetic investigations. Multiple characterization techniques such as electron microscopy, spectroscopy and chemisorption are exploited for catalyst dispersion measurements. While effective, electron microscopy and spectroscopy are not readily accessible due to cost and maintenance …

Modeling Chain Packing In Complex Phases Of Self-Assembled Block Copolymers, Anugu Abhiram Reddy

Doctoral Dissertations

Block copolymer (BCP) melts undergo microphase seperation and form ordered soft matter crystals with varying domain shapes and symmetries. We study the con- nection between diblock copolymer molecular designs and thermodynamic selection of ordered crystals by modeling features of variable sub-domain geometry filled with individual blocks within non-canonical sphere-like and network phases that together with layered, cylindrical and canonical spherical phases forms “natural forms” of self- assembled amphiphilic soft matter at large. First, we present a model to revise our understanding of optimal Frank-Kasper sphere-like morphologies by advancing the- ory to account for varying domain volumes. We then develop generic …

New Isomeric Silicones: Synthesis, Compositions And Surface Properties, Yan Cong

Doctoral Dissertations

This dissertation presents research performed in the field of silicone polymer science, which refers to polymers with alternating silicon-oxygen backbones. Three research topics will be explored. The first topic involves the synthesis of trimethylsiloxysilsesquioxane (MT) copolymers with vinyl and hydride functionalities as reactive liquid silicone precursors. The second topic describes titration of dimethylsiloxy (D) composition into trimethylsiloxysilsesquioxane (MT) copolymers for the purpose of controlling the mechanical properties and thermal stabilities of the material. The last topic explores the modification of hydrophobic silicone surfaces with oxygen plasma to form silica-like, hydrophilic surfaces and the behaviors of hydrophobic recovery. The first chapter …

Computational Rational Design Of Electrocatalysts For Electrochemical Ammonia And Hydrogen Synthesis, Akash Jain

Doctoral Dissertations

The electrochemical hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR) offer fossil-fuel-free routes for hydrogen and ammonia synthesis, respectively. However, currently, both processes lack suitable electrocatalysts for practical applications. Thus, this dissertation focuses on the computational rational design of HER and NRR electrocatalysts. HER is most efficiently catalyzed by platinum (Pt), which is expensive. To reduce the catalyst cost, we investigate core-shell nanoparticles of inexpensive tungsten-carbide (WC) and Pt (WC@Pt). Using first-principles density functional theory (DFT) calculations, we compare the suitability of two WC phases, α-WC and β-WC as support materials for Pt overlayers. We dope WC with titanium …

Development Of Crosslinking Technologies For Waterborne & Powder Coatings, Mengfei Huang

Doctoral Dissertations

Waterborne coatings and powder coatings are fast-growing sectors of the world coating market due to their environmentally friendliness as they have low or zero volatile organic compounds (VOCs) emission. However, compared with solventborne coatings, significant limitations need to be overcome to enable their broad applications. My dissertation will discuss several novel crosslinking strategies for waterborne and powder coating that could enable curing on-demand at ambient conditions, with facile polymerization and easy processing, and ultimately, exhibit a high degree of crosslinking and excellent performance that is comparable to solventborne coatings. We introduced and demonstrated the anionic polymerization mechanism and the high …

Anaerobic Digestion: Awareness, Implementation, And Simulation, Kieran Tay, Nicholas Sbalbi, Michael Forozis, Flo Sabatini

Student Showcase

Anaerobic digestion (AD) is the process in which organic matter is fermented in an oxygen-deprived environment to produce renewable biogas. Our project is multi-faceted, with the overall goal of raising public awareness of AD as a transitional energy source. To that end, our group has named itself Undergraduates Raising Awareness for Anaerobic Digestion (URAAD). We are approaching this goal on three fronts, including (i) a website, (ii) a physical lab-scale digester, and (iii) a computer simulation of anaerobic digestion.

The first component, the website, was developed with the aim of serving as a resource for the public. It includes educational …

Metabolic Modeling Of Cystic Fibrosis Airway Microbiota From Patient Samples, Arsh Vyas

Masters Theses

Cystic Fibrosis (CF) is a genetic disorder, found with higher prevalence in the Caucasian population, affecting > 30,000 individuals in the United States and > 70,000 worldwide. Due to the astoundingly high rate of mortality among CF patients being attributed to respiratory failure brought on by chronic bacterial infections and subsequent airway inflammation, there has been a lot of focus on systematically analyzing CF lung airway communities. While it is observed traditionally that Pseudomonas aeruginosa is the most threatening and persistent CF colonizer due to high antibiotic resistance, recent studies have elicited the roles of other pathogens and it has been widely …

Synthesis Of Functionalized Acrylic Nanoparticles As A Precursor To Bifunctional Colloids, Guinevere E. Tillinghast

Masters Theses

Water-borne coatings have increased in popularity due to the recent environmental regulations being placed on coating formulation. The most readily available coatings without volatile organic compounds are thermoplastic polymer dispersions that rely on interdiffusion to form a film. These dispersions are reliant on toxic crosslinking chemistries to achieve adequate coating mechanical properties, but still have significantly inferior properties when compared with current thermosetting industrial coatings that contain volatile organic compounds. As a result, waterborne coatings made with conventional emulsion polymers cannot be considered for high-performance coatings. Polyurethane dispersions have been developed that can meet these demands, but require several lengthy …

Spatiotemporal Metabolic Modeling Of Pseudomonas Aeruginosa Biofilm Expansion, Robert Sourk

Masters Theses

Spatiotemporal metabolic modeling of microbial metabolism is a step closer to achieving higher dimensionalities in numerical studies (in silico) of biofilm maturation. Dynamic Flux Balance Analysis (DFBA) is an advanced modeling technique because this method incorporates Genome Scale Metabolic Modeling (GSMM) to compute the biomass growth rate and metabolite fluxes. Biofilm thickness is pertinent because this variable of biofilm maturation can be measured in a laboratory (in vitro). Pseudomonas aeruginosa (P. aeruginosa) is the model bacterium used in this computational model based on previous research conducted by Dr. Michael Henson, available GSMMs, and the societal significance of patients suffering from …

Effect Of Phase Composition Of Tungsten Carbide On Its Catalytic Activity For Toluene Hydrogenation, Aditya Rane

Masters Theses

Commercially important hydrogenation reactions make use of precious noble metal catalysts which are becoming increasingly scarce, and the search for capable alternative catalysts prevails. Transition metal carbides of group IV-VI metals show similar catalytic behavior to platinum and are $103/kg lower in price than the precious metal catalysts. Tungsten carbide, studied in this work, can form in different stoichiometries and phase compositions depending upon synthesis methods. Synthesis of high surface area tungsten carbide with control over its phase composition remains a challenge currently. In this work, the novel isothermal synthesis method of tungsten carbide (WC, W2C) in a CH4/H2 carburization …

Metabolic Modeling Of Bacterial Co-Cultures For Co-To-Butyrate Conversion In Bubble Column Bioreactors, Naresh Kandlapalli

Masters Theses

One of the most promising routes to renewable liquid fuels and chemicals is the fermentation of waste carbon by specialized microbes. Commercial development of gas fermentation technology is underway but many fundamental research problems must be addressed to further advance the technology towards economic competitiveness. This thesis addresses the important problem of developing integrated metabolic and transport models that predict gas fermentation performance in industrially relevant bubble column reactors. The computational models describe the conversion of CO-rich waste streams including synthesis gas to the platform chemical butyrate. The proposed modeling approach involves combining genome-scale reconstructions of bacterial species metabolism with …

Synthesis Of Hybrid Inorganic-Organic Microparticles, Shreyas Joshi

Masters Theses

The self-assembly of isotropic and anisotropic colloidal particles into higher-ordered structures has been of great interest recently due to the promise of creating metamaterials with novel macroscopic properties. The physicochemical properties of these metamaterials can be tailored to achieve composites with tunable functionalities. The formation of these metamaterials can be used as a pathway to emulating advanced biological systems. In particular, synthetically mimicking the surface of a moth’s eye, which consists of arrays of ellipsoidal protuberances, can be used as a strategy for fabricating antireflective coatings.

To enable this technology, it is necessary to design a synthesis scheme that produces …

Free Radical Polymerization Of Novel Copolymer; Ethylene-Co-Diethyl Methylene Malonate Copolymers, Sydney Foster

Masters Theses

Ethylene copolymers are widely used as packaging materials, adhesives and specialty polymers for well-regarded cost savings, durability, chemical resistance, and hot melt character. This work examines the use of diester monomers known as malonates to determine the plausibility of utilizing an uncommon monomer class for producing novel ethylene copolymers. Ethylene is copolymerized with diethyl methylene malonate—a simple malonate representative of more complex and highly modified malonate monomers and macromers—to produce ethylene-co-diethyl methylene malonate in a range of molecular weights. Ethylene-co-diethyl methylene malonate is analyzed to determine physical properties such as glass transition temperature, chain length and monomer incorporation. Successful copolymerization …

Advanced Materials Design Using Application-Based Processing Techniques, Daniel S. Camarda

Doctoral Dissertations

This dissertation pertains to generating advanced materials using application-based processing techniques. First, billets consisting of PTFE sintering powders are evaluated using Thermomechancal Analysis. It was found that both shape change and volume change are associated with enthalpic and entropic recoil, respectively. These phenomena, due to melting and stored energy during the powder compaction process, were found to be molecular weight dependent. Additionally, kinetics of the recovery and sintering process were found to be slower in blended specimens than pure samples. Next, the creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer …

Spectroscopic Investigations Of Zeolite-Catalyzed Carbenium Ion Chemistry, Eric David Hernandez

Doctoral Dissertations

The catalytic conversion of methanol to olefins on zeolites is an industrially important process, yet the mechanistic details remain unresolved. Enylic cations (unsaturated carbenium ions) are active intermediates in the production of olefins and aromatics. However, these long-lived species are also precursors to carbonaceous deposits, the accumulation of which is responsible for catalyst deactivation. The aim of this work is to develop a mechanistic understanding that will ultimately allow steering the surface chemistry toward active intermediates. An in situ spectroscopic approach is applied to determine the nature of the relevant surface species and to track their transformations. The UV–vis and …

Understanding Complex Coacervation Of Low Charge Density Copolymers And Latexes, Nicholas Bryant

Masters Theses

Many coatings only need to either be durable or fast drying, usually sacrificing long term stability in favor of quick setting, or vice versa. One coating type that cannot afford to sacrifice either performance feature is traffic paint. These paints are made up of a weak polycation, an anionic latex, and a volatile base which evaporates upon application. The high pH in the initial formulation deprotonates the polycation, rendering it charge neutral. However, upon evaporation, the resulting drop in pH allows for the electrostatic complexation between the polycation and the latex. The electrostatic interactions used in these formulations parallels that …