Engineering Commons^™

Ac Conductivity Studies Of Polyethylene-Oxide-Garnet Type Li7la3zr2o12 Hybrid Composite Solid Polymer Electrolyte For Li-Ion Battery, Parisa Bashiri

Wayne State University Dissertations

Solid electrolytes including ceramics and polymers are considered to be the ultimate substitute for organic liquid electrolytes currently used in commercialized lithium ion batteries to address the safety concerns due to Li dendrite growth and internal short circuiting. However, low ionic conductivity due to high grain boundary resistance in ceramics and semi-crystalline nature of polymers has held back the solid electrolytes from being used in Li-ion batteries. Polyethylene oxide (PEO), complexed with a Li-salt, is a well-studied polymer electrolyte showing ionic conductivity properties at room temperature. However, the coexistence of amorphous and crystalline regions at room temperature (< Tm, the melting temperature) has

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Enabling 3d Printing Technologies For Artificial Compound Eye System And Penetrating Neural Probes, Boshen Zhang

Wayne State University Dissertations

3D printing has become a useful and transformative method and has applications in many different fields, including organ printing, aerospace applications, and medical devices. With higher resolution, faster production speed, and more design flexibility, 3D printing technologies can lead to more novel devices and systems. In this research, two new techniques have been developed to enable 3D printing technologies for artificial compound eye system and penetrating glassy carbon neural electrode array.

This work focuses on developing new applications based on the SLA 3D printing process, which uses the liquid resin to create a solid 3D structure. The limitation of SLA …

Seed-Mediated Crystallization Of Charge-Transfer Complexes And Their Applications For Gas Sensing, Xuecheng Yu

Wayne State University Dissertations

The dissertation focused on controllable seed-mediated nucleaton of charge transfer complex, namely tetrathiafulvalene bromide ((TTF)Br) and Krogmann’s salts (KCP), and their applications in sensing. On gold nanoparticle (AuNP) decorated highly oriented pyrolytic graphite (HOPG) substrate, the presence of AuNP promotes the formation of charge transfer salt nanowires. The size of these nanowires, both (TTF)Br and KCP, were found to be confined by the size of AuNPs, shown by SEM and AFM characterization. On micro-disk electrodes, charge transfer salt nanowires were found to own a linear time dependency, by both SEM and in-situ optical microscopy. The micro-disk electrodes promoted higher crystallization …

Advanced Electrodes And Electrolytes For Long-Lived And High-Performance Lithium-Sulfur Batteries, Deepesh Gopalakrishnan

Wayne State University Dissertations

ABSTRACT

ADVANCED ELECTRODES AND ELECTROLYTES FOR LONG-LIVED AND HIGH-PERFORMANCE LITHIUM-SULFUR BATTERIES

by

DEEPESH GOPALAKRISHNAN

August 2020

Advisor: Dr. Leela Mohana Reddy Arava

Major: Mechanical Engineering

Degree: Doctor of Philosophy

Lithium – Sulfur (Li-S) batteries have received much attention and considered as a promising candidate for next generation energy storage devices because of their high theoretical energy density (≈2600 Wh kg‒1) and environmental friendliness. However, the uncontrollable growth of lithium dendrites in the lithium metal anode and the fatal effect of polysulfide shuttle hinder their practical applications. The formation of dendrites during repeated Li plating/stripping processes results in: reduced Li availability …

Engineering Of Gold Nanoparticles For Drug Delivery, Fangchao Liu

Wayne State University Dissertations

Due to their ease of synthesis, versatile surface chemistry, ease of imaging, and biocompatibility, gold nanoparticles (AuNPs) are employed as drug delivery devices in the treatment of respiratory problems associated with spinal cord injury (SCI). We have developed a method for the synthesis of a tripartite nanoconjugate comprised of an AuNP drug carrier chemically conjugated to a transporter protein (wheat germ agglutinin coupled to horseradish peroxidase or WGA-HRP) and to potent SCI drugs. The therapeutic efficacy and biodistribution were studied in a validated animal model. Our results show that a single administration of the nanoconjugate improved diaphragmatic activity at a …

Self-Delivery Drug Amphiphilies In Chemotherapy And Immunotherapy, Jingchao Xi

Wayne State University Dissertations

Eliminating the need for external delivery systems, self-delivery drug amphiphiles represent a simple yet effective approach designed to overcome the various biological barriers for drug delivery. The ability to program the molecular structures and the physicochemical properties, which control the interactions between the drug amphiphiles and their biological surroundings has attracted significant research interests. In this work, we constructed several amphiphilic drugs including chemotherapeutic and immunotherapeutic agents. These amphiphiles exhibited interesting interactions with their biological surroundings. Amphiphiles self-assemble into spherical micelle structures in aqueous solution. However, in the presence of complexed biological fluids, they also possess a strong affinity toward …

Force Field Optimization, Advanced Sampling, And Free Energy Methods With Gpu-Optimized Monte Carlo (Gomc) Software, Mohammad Soroush Barhaghi

Wayne State University Dissertations

In this work, to address the sampling problem for systems at high densities and low temperatures, a generalized identity exchange algorithm is developed for grand canonical Monte Carlo simulations. The algorithm, referred to as Molecular Exchange Monte Carlo (MEMC), is implemented in the GPU-Optimized Monte Carlo (GOMC) software and may be applied to multicomponent systems of arbitrary molecular topology, and provides significant enhancements in the sampling of phase space over a wide range of compositions and temperatures. Three different approaches are presented for the insertion/deletion of the large molecules, and the pros and cons of each method are discussed. Next, …

Controlling The Three-Dimensional Environment Of Catalytic Active Sites For Selective Heterogeneous Catalysis, Bingwen Wang

Wayne State University Dissertations

This thesis focuses on developing high performance heterogeneous catalytic structures for chemical and fuel production processes. This thesis work proposes to achieve enhanced catalytic performance by tuning the 3D environment of catalytically active sites. Two approaches toward development of enhanced catalytic structures are demonstrated.

The first approach involves tuning the 3D environment of active sites via the construction of the “inverted” structures, where metal core NPs are coated with a porous oxide layer. A facile, room-temperature method is utilized to synthesize the probe system, inverted Pd@TiO2 catalyst, with control over the oxide film and NPs structure. The “inverted” structures with …

Zwitterionic Polymer For Drug Delivery Applications, Yang Lu

Wayne State University Dissertations

This dissertation focuses on the applications of zwitterionic polymer materials in drug delivery. In one project, zwitterionic polymer was used to construct micelle surfactants. The zwitterionic micelles were found to have an ultralow critical micelle concentration (CMC). Potential mechanism for zwitterionic micelles achieving the ultralow CMC property has been studied. Based on the ultralow CMC feature, zwitterionic micelles were used to prepare a formulation of commercial antitumor drug docetaxel, and the resulting formulation showed excellent antitumor performance. In another project, zwitterionic polymer was used to modify protein drug insulin via conjugation reaction. Compared with current protein modification methods, such as …

Maximum Recovery Of Mechanical Energy Through Work Integration: A Work Exchange Network Synthesis Approach, Aida Amini Rankouhi

Wayne State University Dissertations

Sustainable development has become a key concern in industries, largely due to natural resource depletion, global competition, and environmental pressure. Despite the efforts for sustainability improvement, still over a half of energy consumption is wasted in manufacturing sectors, where the chemical industry is responsible for an energy efficiency lower than it should be. Many attempts have been made to recover the thermal energy using heat integration techniques. Although process work is more expensive than process heat, no efficient solution has been studied to recover mechanical energy yet. In chemical plants, many process streams need to be pressurized or depressurized in …

Drug Delivery Strategies For The Treatment Of Advanced Lung Cancer And Various Lung Metastases, Elizabeth Bielski

Wayne State University Dissertations

Lung cancer remains the leading cause of cancer-related deaths in the United States. Secondary lung tumors metastasized from other cancer sites also remains highly prevalent, in which most metastatic tumors cannot be cured with existing therapies. Chemoresistance (multi drug resistance – MDR) that develops intrinsically or acquired is one of the key factors leading to fatality in these patients. MDR develops form a variety of resistance mechanisms that can occur consecutively or concurrently, therefore, making most current treatments unsuccessful. Current therapies have known to slow tumor growth, but rarely provide a cure. Immunotherapy has seen some promise, including the use …

Fundamental Investigation Of The Electrocatalytic Activity Of Layered Mixed Metal Oxides For Low Temperature Oxygen Electrocatalysis, Ayad M. Nacy

Wayne State University Dissertations

Li–O2 (Li–air) batteries are among the most promising energy storage technologies due to their high theoretical specific capacity and energy density. Key challenges with this technology include high overpotential losses associated with catalyzing the electrochemical reactions (i.e., oxygen reduction and evolution reactions) at the cathode of the battery. One way to address this challenge is to incorporate an active electrocatalyst, such as first-order Ruddlesden-Popper series of layered oxides. We show that the composition of the A-site in first-order Ruddlesden-Popper series of layered oxides (A2BO4) has a significant effect in the electrochemical activity of Li-O2 cathodes. Among the oxides composed of …

Computational Modeling Of High-Performance Nickel-Metal Hydride Battery Materials, Diana Felicia Wong

Wayne State University Dissertations

With 10 million hybrid electric vehicles on the road worldwide powered primarily by nickel-metal hydride (NiMH) batteries, research into this battery chemistry will improve the hybrid vehicle driving experience, extending electric-only driving ranges while reducing emissions and using less gasoline. The transfer, storage and transport of protons and electrons depend strongly on the structural and electrical features of the active material, including multiple phases, defects, and structural and compositional disorder. The contributions of such subtle defects and the difference with the bulk structure can be difficult to discern experimentally. Ab initio calculations such as the ones based on density functional …

Bio-Inspired Synthesis Of Nanostructured Materials On Substrates For Environmental And Energy Applications, Xinghua Meng Meng

Wayne State University Dissertations

It is still a challenging task to develop simple methods for facile synthesis of functional nanostructures on substrates under mild conditions without using expensive instruments. We have successfully developed a bio-inspired method using simple diaphragm-assisted system to synthesize functional nanostructures on various substrates under mild conditions. We have systematically studied the effects of experimental parameters on the formation of nanostructures under controlled conditions. The fundamental mechanism involved has been systematically studied and revealed. By growing the unique networks of nanostructures on a piece of substrate, a double-rough surface, with structures at both nanoscale and microscale, has been achieved, showing interesting …

New Chemistry For The Growth Of First-Row Transition Metal Films By Atomic Layer Deposition, Joseph Peter Klesko

Wayne State University Dissertations

Thin films containing first-row transition metals are widely used in microelectronic, photovoltaic, catalytic, and surface-coating applications. In particular, metallic films are essential for interconnects and seed, barrier, and capping layers in integrated circuitry. Traditional vapor deposition methods for film growth include PVD, CVD, or the use of plasma. However, these techniques lack the requisite precision for film growth at the nanoscale, and thus, are increasingly inadequate for many current and future applications. By contrast, ALD is the favored approach for depositing films with absolute surface conformality and thickness control on 3D architectures and in high aspect ratio features. However, the …

Engineering Gold Nanoparticles And Their Use To Control Nucleation, Pedram Jahanian

Wayne State University Dissertations

This study focuses on fabrication of hybrid nanostructures using gold nanoparticles (AuNP) as seeds and partially oxidized potassium tetracyanoplatinate, known as Krogmann’s salt (KCP), and later this method will be employed to manufacture a prototype sensor for detecting different vapors. Nanocrystals are synthesized using electrochemical method with the aim to have more control over the size and shape of the charge transfer salt based on the seed mediated nucleation method. AuNP seeds are prepared on highly ordered pyrolytic graphite (HOPG) substrate by the electrocrystallization method. An aqueous solution of 0.05 to 1 mM Hydrogen tetrachloroaurate (HAuCl4) with 0.1 mM (Potassium …

Force Field Development With Gomc A Fast New Monte Carlo Molecular Simulation Code, Jason Richard Mick

Wayne State University Dissertations

In this work GOMC (GPU Optimized Monte Carlo) a new fast, flexible, and free molecular Monte Carlo code for the simulation atomistic chemical systems is presented. The results of a large Lennard-Jonesium simulation in the Gibbs ensemble is presented. Force fields developed using the code are also presented. To fit the models a quantitative fitting process is outlined using a scoring function and heat maps. The presented n-6 force fields include force fields for noble gases and branched alkanes. These force fields are shown to be the most accurate LJ or n-6 force fields to date for these compounds, capable …

Life Cycle Based Sustainability Assessment And Decision Making For Industrial Systems, Hao Song

Wayne State University Dissertations

Increasing concern with the environmental impact resulted from human activities has led to a rising interest in sustainable development that will not only meet the needs of current development but also protect the natural environment without compromising the needs of future generations. This leads to the necessity of a systems approach to decision-making in which economic, environmental and social factors are integrated together to ensure the triple bottom lines of sustainability. Although current studies provide a variety of different methodologies to address sustainability assessment and decision-making, the increasing size and complexity of industrial systems results in the necessity to develop …

Design Of Functional Dendrimer Nanocarriers And Their Formulations In Propellant-Based Inhalers For Pulmonary Drug Delivery, Lin Yang

Wayne State University Dissertations

This Dissertation focuses on addressing two of the major challenges in developing pressurized metered dose inhalers for pulmonary drug / gene delivery to and through the lungs. First challenge is to design biocompatible moieties for the steric stabilization of suspension formulations in HFO-based propellants. Using a combination of tools including ab initio calculation, molecular dynamics simulation and high pressure tensiometry, potential fluorocarbon-philic moieties were systematically screened. Surfactants with those chemistries as tail fragments were studied at the HFO|H2O interface for their ability to lower the interfacial tension at HFO|H2O interface. Selected surfactants were further optimized for surfactant balance by altering …

Development Of Silicon-Based Anodes And In-Situ Characterization Techniques For Lithium Ion Batteries, Jinho Yang

Wayne State University Dissertations

Development of lithium ion batteries (LIBs) with higher capacity has been booming worldwide, as growing concerns about environmental issues and increasing petroleum costs. The demands for the LIBs include high energy and power densities, and better cyclic stability in order to meet a wide range of applications, such as portable devices and electric vehicles. Silicon has recently been explored as a promising anode material due to its low discharge potential (<0.4 V) and high specific capacity (4200 mAh g^-1). The capacity of silicon potentially exceeds more than 10 times of the conventional graphite anode (372 mAh g^-1). However, the silicon anode experiences huge volume …

Biofuels Production Via Catalytic Hydrocracking Of Ddgs Corn Oil And Hydrothermal Decarboxylation Of Oleic Acid Over Transition Metal Carbides Supported On Al-Sba-15, Basem A. Al Alwan

Wayne State University Dissertations

The purpose of this research is to minimize the gap between the production of biofuels and the production of petroleum-based fuels by developing catalysts that can utilize renewable non-food based feedstocks (waste vegetable oils, algal oil, brown grease, etc.) and have great performance under low operation conditions. In particular, green diesel has become an attractive biofuel due to its superior properties that are quite similar to petroleum diesel. Therefore, no modifications are required to existing infrastructures. Three distinct experimental phases have been identified in order to achieve the objective of this work as follow:

First, the hydrocracking of distillers dried …

Advanced Optimization Techniques For Monte Carlo Simulation On Graphics Processing Units, Eyad Hailat

Wayne State University Dissertations

The objective of this work is to design and implement a self-adaptive parallel GPU optimized Monte Carlo algorithm for the simulation of adsorption in porous materials. We focus on Nvidia's GPUs and CUDA's Fermi architecture specifically. The resulting package supports the different ensemble methods for the Monte Carlo simulation, which will allow for the simulation of multi-component adsorption in porous solids. Such an algorithm will have broad applications to the development of novel porous materials for the sequestration of CO2 and the filtration of toxic industrial chemicals.

The primary objective of this work is the release of a massively parallel …

How Atomic Level Interactions Drive Membrane Fusion: Insights From Molecular Dynamics Simulations, Navendu Bhatnagar

Wayne State University Dissertations

This project is focused on identifying the role of key players in the membrane fusion process at the atomic level with the use of molecular dynamics simulations. Membrane fusion of apposed bilayers is one of the most fundamental and frequently occurring biological phenomena in living organisms. It is an essential step in several cellular processes such as neuronal exocytosis, sperm fusion with oocytes and intracellular fusion of organelles to name a few. Membrane fusion is a frequent process in a living organism but is still not fully understood at the atomic level in terms of the role of various factors …

Polymeric Nanocarriers And Their Oral Inhalation Formulations For The Regional Delivery Of Nucleic Acids To The Lungs, Denise Santos Conti

Wayne State University Dissertations

Gene therapy has attracted attention in the fields of medicine, pharmacy, and bionanotechnology due to the potential for treating a large number of medically relevant diseases. Oral inhalation (OI) is a promising route for the administration of therapeutics, including small molecules and biomacromolecules, such as nucleotides, peptides, and proteins, to (locally) and through (systemically) the lungs. The use of OI is especially attractive for the delivery of nucleic acids as it provides a direct and non-invasive route for targeting the lungs. Pressurized metered-dose inhalers (pMDIs), are the most commonly used OI in treatment of lung diseases and are thus promising …

Green Diesel Production Via Catalytic Hydrogenation/Decarboxylation Of Triglycerides And Fatty Acids Of Vegetable Oil And Brown Grease, Elvan Sari

Wayne State University Dissertations

Increase in the petroleum prices, projected increases in the world’s energy demand and environmental awareness have shifted the research interest to the alternative fuel technologies. In particular, green diesel, vegetable oil/animal fat/waste oil and grease derived hydrocarbons in diesel boiling range, has become an attractive alternative to biodiesel— a mixture of fatty acid methyl esters, particularly due to its superior fuel properties that are similar to petroleum diesel. Hence, green diesel can be used as a drop-in fuel in the current diesel engines. The current technology for production of green diesel– hydrodeoxygenation of triglycerides and fatty acids over conventional hydrotreating …

Bioreducible Polymer Nanosystems For Gene Delivery, Yi Zou

Wayne State University Dissertations

This dissertation describes the research of bioreducible polymers for gene delivery. A series of bioreducible poly(amido amine)s (PAAs) were synthesized. They complex with DNA forming polyplex nanoparticles and layer-by-layer (LbL) thin films as gene delivery vectors. Atomic force microscope (AFM), especially in situ real time AFM, provides a microscopic view of DNA release dynamics. It is shown that the depolymerization of bioreducible polymer triggers DNA release via disulfide-thiol exchange reaction. The AFM images revealed a three-stage pathway beginning with a morphological change from metastable nanostructures into the more favorable toroid structure. Then toroids interact with each other by aggregation and …

Engineering Nanoparticle And Nanoring Patterns For The Study Of Molecular Crystallization Under Nanoconfinement, Sunxi Wang

Wayne State University Dissertations

This dissertation focuses on generating the inorganic nanoparticle/organic nanorod hybrid nanostructures by the strategy of nanoparticle induced molecular crystallization developed by us and the new electrochemical method. We synthesize the gold nanoparticles with different sizes and functional groups and then fabricate the nanohybrids with fatty acid nanorods by spin coating method. Atomic force microscope monitors the topography of the hybrid nanostructures to help understand the underlying mechanism of the crystallization process. This successful self-assembled method could be used to fabricate nanohybrids based on seed-mediated nucleation. Also the novel "nano-flasks" have been generated by particle lithography method, which could be served …

New Precursors And Chemistry For The Growth Of Transition Metal Films By Atomic Layer Deposition, Thomas Joseph Knisley

Wayne State University Dissertations

The advancing complexity of advanced microelectronic devices is placing rigorous demands on currently used PVD and CVD deposition techniques. The ALD deposition method is proposed to meet the film thickness and conformality constraints needed by the semiconductor industry in future manufacturing processes. Unfortunately, there is a limited number of chemical precursors available that have high thermal stability, reactivity, and vapor pressure suitable for ALD film growth to occur. These properties collectively contribute to the lack of suitable transition metal precursors available for use in ALD. In this thesis, we report the discovery of a series of novel transition metal diazadienate …

Polymeric Nanocarriers For The Regional And Systemic Delivery Of Therapeutics To And Through The Lungs, Balaji Bharatwaj

Wayne State University Dissertations

The lungs are considered as one of the fastest portals of entry to the bloodstream and oral inhalation (OI) has long been accepted as the preferred mode of administration of therapeutics to the respiratory tract. However, despite its advantages, the lungs have been largely underutilized to target ailments not only of systemic relevance but also several other grave conditions including lung cancer and tuberculosis. Polymeric nanocarriers (PNCs) have several advantages over other drug delivery vehicles including sustained release of moieties, ease of cellular internalization and improved targeting, and hence hold the promise to greatly augment the potential of OI therapies. …

Sustainable Design Of Complex Industrial And Energy Systems Under Uncertainty, Zheng Liu

Wayne State University Dissertations

Depletion of natural resources, environmental pressure, economic globalization, etc., demand seriously industrial organizations to ensure that their manufacturing be sustainable. On the other hand, the efforts of pursing sustainability also give raise to potential opportunities for improvements and collaborations among various types of industries.

Owing to inherent complexity and uncertainty, however, sustainability problems of industrial and energy systems are always very difficult to deal with, which has made industrial practice mostly experience based. For existing research efforts on the study of industrial sustainability, although systems approaches have been applied in dealing with the challenge of system complexity, most of them …