Engineering Commons^™

Formulation Optimization Effects On Mechanical And Rheological Properties Of Filled Polysiloxanes, Kevin Mcnay

Electronic Theses & Dissertations

Polysiloxanes are a class of high-performance polymeric materials that are used in a wide variety of applications, including O-rings, gaskets, sealants, coatings, and adhesives. These materials have high temperature resistances as well as flexibility at low temperatures. This is due to the bond between the oxygen and silicon atom, a bond that requires a high dissociation energy to break. However, their elastomers, which can be obtained by crosslinking linear precursors using various crosslinkers, generally exhibit low strength and have poor mechanical properties unless reinforced. Therefore, fillers, additives, UV-stabilizers, and anti-oxidants are often incorporated in order to improve the resulting properties. …

An Investigation Of The Chemistry, Thermodynamics And Catalytic Activity Of Molybdenum Carbides, Shanti Kiran Nayak

Chemical and Biological Engineering ETDs

These studies investigate the chemistry and stability of molybdenum carbides as an electrocatalyst. Due to their unique electronic properties, molybdenum carbides are purposed as electrocatalysts for reaction systems such as hydrogen evolution reaction, bifunctional water splitting and CO oxidation.

In this study, various synthesis processes were utilized to produce different types of molybdenum carbide with varying properties of particle size, surface area and excess carbon. The samples characterized by XRD accompanied by Whole Profile Fitting, Electron Microscopy, Gas Adsorption (surface area) and XPS.

These synthesis processes were refined using fundamental thermodynamic analyses. These analyses highlight regions of stability of different …

A Kinetic And Thermodynamic Model Of Ethylene Dichloride Pyrolysis., Travis J Czechorski

Electronic Theses and Dissertations

Ethylene dichloride (EDC) is a precursor for the production of vinyl chloride (VCM) which is subsequently polymerized to form polyvinyl chloride (PVC). To convert EDC to VCM, EDC undergoes a pyrolysis process in the absence of oxygen at temperatures exceeding 500C. However, process yields are limited by the uncontrolled production of side-products that can degrade the quality of PVC and poison the reactor. Thus, tight process controls and costly separations guided by heuristics and plant operator experience are used to optimize EDC pyrolysis. To improve the process, I have programed a kinetic model of EDC pyrolysis based upon estimations of …

Controlling Selectivities In Heterogeneously Catalyzed Aldol Reactions, Koushik Ponnuru

Doctoral Dissertations

Aldol condensation is an important C-C bond formation reaction in chemical synthesis that finds versatile applications in bulk and fine chemical industries and has the potential for upgrading of biomass to fuels. However, aldol reactions pose a challenge for controlling the product selectivity by forming a mixture of desired and undesired self, cross, and poly-condensation products. Furthermore, a side reaction, the fission of aldol products resulting in an olefin and a carboxylic acid, has garnered attention recently as a route to isobutene from acetone. While a high level of selectivity control is achievable by homogeneous catalysis, selective solid catalysts, which …

Hydrodynamics Of Liquid-Solid And Three-Phase Inverse Circulating Fluidized Beds, Tian Nan

Electronic Thesis and Dissertation Repository

The hydrodynamics of inverse liquid-solid circulating fluidized bed (ILSCFB) is experimentally studied in a 5.4 m tall and 0.076 m ID column. 5 types of low density particles are investigated with different particle terminal velocities.

Solids holdup distribution is found to be uniform in a wide range of superficial liquid velocities and over 10 solid circulation rates. Average solids hold is not sensitive to particle properties. Clustering phenomenon is found to be significant affecting the slip velocity in the ILSCFB. And the cluster phenomenon is directly related to particle R_­eynolds number (R_et). Particles with little …

A Study Of Protein And Peptide-Directed Nanoparticle Synthesis For Catalytic Materials, Abdollah Mosleh

Graduate Theses and Dissertations

Nanoparticles have received much attentions due to their unique properties that makes them suitable candidates for a broad range of applications. As the size of particles decreases, their surface area-to-volume ratio would increase which is the main cause of much attention. In addition to the size, their morphologies and compositions may also play important roles for defining unique properties. Nanoparticle synthesis include both bottom-up and top-down strategies. To control the process of inorganic nanoparticles synthesis one could follow the bottom-up approach to have atom-level control over their compositions, morphologies, phases, and sizes which is the subject of this work. Due …

Design And Cost Analysis Of Acrylic Acid Plant, Adam Ferrier

Chemical Engineering Undergraduate Honors Theses

The purpose of this project was to model and design a plant to produce 75,000 tons per year of acrylic acid. Using the design in section B.9 of Richard Turton’s Analysis, Synthesis, and Design of Chemical Processes as a starting point, a plant was designed based around the partial oxidation of propylene to acrylic acid. The final plant design produces about 86,000 tons per year of acrylic acid. Using an interest rate of 10%, the plant has a discounted cash flow rate of return of 32% over 2 years of startup and 10 years of operation. Attached is an executive …

Modeling Of Electrochemical Processes At The Magnesium Anode During Struvite Formation, Tobias Dwyer

Chemical Engineering Undergraduate Honors Theses

This study analyzes the current transients observed during the electrochemical formation of struvite from a solution of ammonium phosphate using a pure magnesium and magnesium alloy electrode. Through converting the chronoamperometric data to chronocoulometric data and fitting the data to various models, the driving mechanisms for struvite nucleation were elucidated. While the pure magnesium anode is controlled by only instantaneous nucleation at the electrode, the AZ31 alloy is nucleation controlled at short times and Cottrell diffusion controlled at long times.

Nanowire Based Adsorbents/Catalysts For Co2 Capture And Utilization., Apolo Nambo

Electronic Theses and Dissertations

Even today, the major energy source is fossil fuels, which release CO₂, a greenhouse gas that contributes to global warming. CO₂ capture, storage (CCS) and/or utilization (CCU) technologies are two routes to mitigate this problem. Sorbents are being investigated in either temperature swing or pressure swing absorption approaches for carbon capture from flue gases. Solid sorbent based technology is a promising one but suffers from slow kinetics, low capacity and need for high temperatures. Thus, new sorbent materials that can have good CO₂ sorption capacity, recyclability are sought. Similarly, one of the utilization approaches for CO …

Synthesis, Characterization, And Evaluation Of Metal Complexes With Cancer Selective Anti-Proliferative Effects And Hydrogen Evolution Catalytic Properties., Nicholas Vishnosky

Electronic Theses and Dissertations

Bis-thiosemicarbazones (BTSC) and their metal chelates have properties that are useful in several different scientific fields. These systems have already received attention in major fields of biology and engineering. Hydrogen evolution reaction (HER) catalysts need to be cheap and operate under minimal overpotentials with a long lifetime. The treatment of cancer requires, novel agents that have potent cytotoxic activity against cancer cells while displaying minimal side effects. In this dissertation the modular synthesis of these bis-thiosemicarbazone systems is utilized to regulate the redox chemistry for employment in the desired sector of chemistry. The ligand and metal chelates synthesized were characterized …

Development Of A Ws2 Catalyst For Hydrogen Evolution And Improvement Via Platinum Nanoparticle Decoration, Alexander O'Brien

Chemical Engineering Undergraduate Honors Theses

In response to a growing global need to improve utilization of green energy, the concept of renewable energy storage via electrolytic hydrogen production has gained popularity in recent years. However, the prohibitive expense of the bulk platinum catalysts currently used for the hydrogen evolution reaction prevents such a concept from being widely adoptable. This research focuses on a possible alternative catalyst, nanolayer WS₂, which is capable of promoting the hydrogen evolution reaction while maintaining economic viability. Bulk WS₂ was prepared in semiconducting, nanolayer form through liquid phase exfoliation. Prepared catalyst inks consisting of this material demonstrated successful …

Effect Of Thiols For Nitrogen Reduction To Ammonia, Zakary R. Ford

Chemical Engineering Undergraduate Honors Theses

Ammonia is an important chemical used for fertilizers and also a potential carbon-free hydrogen storage medium. The Haber-Bosch process is the main production process, which requires large energy- and capital-input. Therefore, it is crucial to develop an alternate scalable synthesis that provides a less energy intensive and more economical route for synthetic ammonia production. In this paper, a 1Fe1Ni film was functionalized with C₃OH and C₆OH for the electrochemical synthesis of ammonia. This work will provide some insight into how thiol ligands can increase the selectivity of the catalyst for nitrogen reduction reaction and can be …

Experimental Investigations On The Instantaneous Flow Structure In Circulating Fluidized Beds, Xiaoyang Wei

Electronic Thesis and Dissertation Repository

Knowing the instantaneous flow structure is of great importance for the understanding of gas-particle interaction and for the prediction of reactor performances. In this thesis, a systematic and comprehensive study has been conducted on the instantaneous flow structure in a narrow rectangular riser (19 mm in thickness, 114 mm in width and 7.6 m in height), in a cylindrical riser (76 mm in diameter, 10.2 m in height) and in a cylindrical downer (50 mm in diameter, 4.9 m in height). A wider range of operating conditions has been achieved in risers and downer with superficial gas velocity from 3.0 …

Natural Gas Conversion Into Value Added Chemicals Using Solid Acid Catalysts, Swarom Ravindra Kanitkar

LSU Doctoral Dissertations

Direct, non-oxidative conversion of natural gas to value-added chemicals has been identified as one of the grand challenges of the 21^st century. Circumventing indirect and costly reforming steps is highly sought after and solid acids can play an important role in that.

The direct conversion of methane to higher hydrocarbons and hydrogen can be catalyzed using “superacids” at < 450 °C. Reported superacid catalysts in solid, liquid, and gas phase included sulfated zirconia (SZ), HF-SbF₅, FSO₃H-SbF₅, and HBr-AlBr₃. Liquid and gas phase superacids presented difficulties in separation while the solid ones provided low yields. Here, we report a new class of Br-based solid superacids, AlBr_x/H-ZSM-5 (“ABZ-5”, …

Theoretical Investigation Of The Ring Opening Of Cyclohexane On Ir(111) And Pt(111), Kushal Ghale

LSU Master's Theses

Diesel engines have higher fuel efficiency and can burn cleaner than gasoline engines. To enhance quality of diesel fuels as measured by the cetane number (CN), the removal of aromatic compounds is necessary. A potentially highly efficient approach would be to convert aromatics to saturated cycloparaffin, followed by selective ring opening to linear or branched alkanes, to increase the CN. Here the focus of the project is to study the mechanism of metal-catalyzed ring opening (RO) of cyclohexane (denoted CHA, or c-C₆H₁₂) through theoretical and computational modeling. CHA, a simplest cycloparaffin, is used as probe molecule …

Quantitative Probing Of Vacancies And Ions Dynamics In Electroactive Oxide Materials, Jiaxin Zhu

Doctoral Dissertations

Oxygen vacancy and ion dynamics in functional oxides are critical factors influencing electrical conductivity and electrochemical activity of oxides assemblies. The recent advancements in deposition and fabrication of oxide heterostructured films with atomic-level precision has led to discovery of intriguing physical properties and new artificial materials. While still under debate, researchers most often attribute these observed behaviors to unique oxygen vacancy distributions in the substrate near heterointerfaces. In electroactive oxides devices such as solid oxide cells (SOCs), oxygen vacancy and ion transport at the triple-phase boundary determines the performance of the device. This complex process motivates numerous remaining questions regarding …

Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli

Doctoral Dissertations

The advent of nanoporous materials such as zeolites and nanoporous membranes has provided cost-effective solutions to some of the most pressing problems of the 20^th century such as the conversion of crude oil into fuels and valuable chemicals. Hierarchical zeolites and mesoporous inorganic membranes are showing great promise in addressing new problems such as the conversion of biomass into value-added chemicals and development of energy-efficient separation processes. The synthesis and fundamental aspects of molecular transport in these new materials with hierarchical porosities need to be better understood in order to rationally develop them for these desired applications. Pore narrowing …

The Investigation Of Surface Barrier During Molecular Transport In Hierarchical Zeolites, Xiaoduo Qi

Doctoral Dissertations

Hierarchical zeolites with micropore lengths on the order of nanometers have been synthesized with the aim of reducing mass transfer limitation. However, due to large external surface to volume ratios, the mass transport in these materials can be hindered by a secondary rate limitation step imposed on the external surface of the zeolites. This has led to the general phenomenon referred to as “surface barriers”, which cause the enhancement in mass transport being far lower than expected. In order to fully unlock the potential of hierarchical zeolites, it is imperative to fundamentally understand the molecular transport in these new types …

Improving The Delivered Specific Impulse Of Composite Rocket Propellant Through Alteration Of Chemical Composition: Methodology And Parameters For Characterization Of Propellant And Validation Of Simulation Software Common To The Amateur Rocketry Community, Isaac O'Brien, Austin Ryan

Williams Honors College, Honors Research Projects

In this study, two solid composite rocket propellants were designed utilizing ProPEP, a rocket propellant formulation software common in the amateur and hobby rocketry communities. The two propellants were designed to optimize specific impulse relative to a literature propellant designed by 1020 Research Labs. The literature propellant was also tested in order to validate the design of experiment as well as the mixing and testing procedures. All three propellants, which includes the literature propellant RCS-P, and the two novel propellants AKR-P1 and AKR-P2 were characterized with static tests. The results of the static tests provide data on propellant performance and …

Compression Set Improvement Of Thermoplastic Vulcanizates For High Temperature Tubing, Mitchell Valaitis

Williams Honors College, Honors Research Projects

It was hypothesized that increasing the curative level of the fluorocarbon rubber (FKM) used in manufacturing of thermoplastic vulcanizate (TPV) materials would decrease the compression set values of the TPV enough for it to be suitable as a flexible, lightweight alternative to high operating temperature thermoset rubber tubing currently being used for power steering hose. First, promising TPV formulations were identified by varying the polyamide (PA) and FKM used in a Brabender mixer. Four different types of polyamide and four different types of FKM were investigated, with two of the FKM types and one polyamide type identified as being promising. …

Functionalization Of Iron Oxide Nanoparticles And The Impact On Surface Reactive Oxygen Species Generation For Potential Biomedical And Environmental Applications, Trang Mai

Theses and Dissertations--Chemical and Materials Engineering

Iron oxide nanoparticles (IONPs) have been widely studied for a variety of applications, from biomedical applications (e.g., cell separation, drug delivery, contrast agent for magnetic resonance imaging and magnetically mediated energy delivery for cancer treatment) to environmental remediations (e.g., heavy metal removal and organic pollutants degradation). It has been demonstrated that IONPs can induce the production of reactive oxygen species (ROS) via Fenton/Haber-Weiss reactions which has been shown to be one of the key underlying mechanisms of nanoparticles toxicity. This inherent toxicity of nanoparticles has been shown to enhance the efficacy of traditional cancer therapies such as chemotherapy and radiation. …

Impact Of Conformational Change, Solvation Environment, And Post-Translational Modification On Desulfurization Enzyme 2'-Hydroxybiphenyl-2-Sulfinate Desulfinase (Dszb) Stability And Activity, Landon C. Mills

Theses and Dissertations--Chemical and Materials Engineering

Naturally occurring enzymatic pathways enable highly specific, rapid thiophenic sulfur cleavage occurring at ambient temperature and pressure, which may be harnessed for the desulfurization of petroleum-based fuel. One pathway found in bacteria is a four-step catabolic pathway (the 4S pathway) converting dibenzothiophene (DBT), a common crude oil contaminant, into 2-hydroxybiphenyl (HBP) without disrupting the carbon-carbon bonds. 2’-Hydroxybiphenyl-2-sulfinate desulfinase (DszB), the rate-limiting enzyme in the enzyme cascade, is capable of selectively cleaving carbon-sulfur bonds. Accordingly, understanding the molecular mechanisms of DszB activity may enable development of the cascade as industrial biotechnology. Based on crystallographic evidence, we hypothesized that DszB …

Engineering Of Earth-Abundant Electrochemical Catalysts, Dylan D. Rodene

Theses and Dissertations

Alternative energy research into hydrogen production via water electrolysis addresses environmental and sustainability concerns associated with fossil fuel use. Renewable-powered electrolyzers are foreseen to produce hydrogen if energy and cost requirements are achieved. Electrocatalysts reduce the energy requirements of operating electrolyzers by lowering the reaction kinetics at the electrodes. Platinum group metals (PGMs) tend to be utilized as electrocatalysts but are not readily available and are expensive. Ni_1-xMo_x alloys, as low-cost and earth-abundant transition metal nanoparticles (NPs), are emerging as promising electrocatalyst candidates to replace expensive PGM catalysts in alkaline media. Pure-phase cubic and hexagonal Ni_{1-x …}

Reduction Of Nox Emissions In A Single Cylinder Diesel Engine Using Sncr With In-Cylinder Injection Of Aqueous Urea, Anthony Timpanaro

UNF Graduate Theses and Dissertations

The subject of this study is the effect of in-cylinder selective non-catalytic reduction (SNCR) of NO_x emissions in diesel exhaust gas by means of direct injection of aqueous urea ((NH₂)₂CO) into the combustion chamber. A single cylinder diesel test engine was modified to accept an electronically controlled secondary common rail injection system to deliver the aqueous urea directly into the cylinder during engine operation.

Direct in-cylinder injection was chosen in order to ensure precise delivery of the reducing agent without the risk of any premature reactions taking place. Unlike direct in-cylinder injection of neat water, …

Towards Sustainable Production Of Chemicals And Fuels From The Fast Pyrolysis Of Waste Polyolefin Plastics, Ulises Gracida Alvarez

Dissertations, Master's Theses and Master's Reports

The increasing amount of plastic waste (PW) generation has become an important concern due to the leveled-off recycling rates. Therefore, governmental agencies around the world, including state governments in the United States, have proposed initiatives to minimize the amount of PW that is landfilled and encourage recycling or energy recovery. Circular economy is a strategy that attempts on reusing PW to produce new polymers while avoiding its disposal and the use of virgin material. Chemical recycling raises an interesting technology prospect due to the potential reduction of pollutant emissions and the establishment of a circular economy through the production of …

Intensification Of Gas Absorption In A Downward Flow Microbubble Bioreactor, Manizheh Ansari

Dissertations and Theses

Bioreactors are of interest for value-upgrading of stranded or waste industrial gases, such as CO, CH₄, or syngas. Process economics requires reduction of reactor cost and size while maintaining high production rate via rapid delivery of gas feedstock to the liquid phase which in turn requires a high volumetric mass transfer rate (). One strategy to achieve this goal is to increase interfacial area density, a, to >3000 m² m^-3, while minimizing use of energy. Here we show a novel reactor column design that uses a micro-jet array to break feedstock at ambient pressure …

Elucidation Of The Catalytic Partial Oxidation Of Methane Utilizing The One-Of-A-Kind Catalytic Shock Tube Technique, Robyn E. Smith

Dissertations and Theses

The mechanism for the catalytic partial oxidation of methane has been debated in scientific literature for over 20 years. This is a seemingly simple reaction producing CO, CO₂, H₂ and H₂O through either partial oxidation followed by complete oxidation or complete oxidation followed by reforming steps. What is happening when the reaction is allowed to occur in an environment absent of transport limitations, absent of temperature gradients and temperature changes, absent of boundary layers must be understood and, until now, has yet to be achieved in one experimental technique.

A novel method using a one …

Mechanism Study Of Shale Gas Conversion Via Chemical Looping And Heterocatalytic Processes, Lei Bai

Graduate Theses, Dissertations, and Problem Reports

The shale gas revolution has significantly changed the energy landscape in US. The technical-feasible, energy-effective schemes for shale gas combustion and utilization, especially from remote resources, have attracted increasing interest due to expensive transportation/distribution cost. In this research, for the first time, chemical looping combustion (CLC) of methane with inherent CO₂ capture, oxidative coupling of methane (OCM) and dehydro-aromatization (DHA) of ethane are systematically studied as promising alternatives at O₂-rich, O₂-lean and non-oxidative conditions, respectively.

Chemical looping combustion is bridging clean fuel combustion in energy production with inherent CO₂ capture. CLC utilized an oxygen …