Materials Science and Engineering Commons^™

Engineered Porous Structures For Propellants Using Additive Manufacturing, Elbert Caravaca

Dissertations

Foamed polymers are widely used today for shock absorption and packaging materials to prevent damage to their contents. Typical foamed densities vary from 0.1 g/cm³ to 0.4 g/cm³ depending on the polymeric materials used. There is a need to explore foaming densities above 0.4 g/cm³ for propellants with highly engineered surface area progression for increased combustion performance. One way to achieve this is through highly controlled and engineered graded foam structures. To further exploit this approach, additive manufacturing coupled with a tunable means to generate foamed structures is the target of this work. To generate foam structures …

Quantum And Conventional Informatics Studies Of Synthesis Energetics And Defect Formation In Nitride Crystal Epitaxy, Andrew Steven Messecar

Dissertations

Machine learning is a valuable approach for the processing and analysis of complex information. By estimating relationships from recorded data, machine learning methodologies can be effective strategies for pattern recognition, enabling investigations and technological applications based thereon. The potential for improved understanding of high-dimensional data has drawn interest towards machine learning from across the sciences, including the research and development of new and improved material systems. In the context of experimental materials research, much of the reported efforts to incorporate machine learning into conventional practice have been primarily focused on either the enhanced analysis of characterization experiment data or the …

A Generative Ai-Driven Computational Framework For Industry-Scale Discovery Of Novel Battery Materials, Joy Datta

Dissertations

The growing demand for sustainable, high-energy-density electrochemical storage has motivated the exploration of multivalent-ion batteries based on earth-abundant elements such as aluminum, calcium, magnesium, and zinc. While multivalent charge carriers offer higher theoretical energy density than lithium, their practical deployment is hindered by sluggish ion transport, strong ion-host interactions, and structural degradation of electrode materials. Identifying host materials that can reversibly accommodate multivalent ions while maintaining structural integrity remains a fundamental challenge. The dissertation develops a scalable, end-to-end computational framework that integrates density functional theory (DFT), machine learning (ML), and generative artificial intelligence (GenAI) to accelerate the discovery of next-generation …

Glass Transition Temperature Of Plga Nanoparticles And The Application In Drug Delivery, Guangliang Liu

Dissertations

The glass transition temperature (T_g) of poly(D,L-lactic-co-glycolic acid) (PLGA) nanoparticles plays a crucial role in governing molecular mobility, diffusion, and consequently, drug release kinetics. However, the interaction among residual surfactant, drug effect, nanoscale confinement, and release medium on T_g remains insufficiently characterized. This study aims to bridge this gap by correlating the thermal behavior of PLGA nanoparticles with their drug release behavior under physiologically relevant conditions.

In the present study, PLGA nanoparticles were synthesized using both nano-emulsion and surfactant-free nano-precipitation approaches. The influence of residual surfactants - poly(vinyl alcohol) (PVA) and didodecyldimethylammonium bromide (DMAB) - was systematically …

Membrane-Engineered Nanotherapeutic Platforms For Drug Delivery: Hollow Fiber Membrane Synthesis Of Lipid Nanoparticles, Biomimetic Nanocarriers, And Nanobubbles, Zhixiang Liu

Dissertations

Lipid-based nanocarriers have emerged as a cornerstone technology for RNA therapeutics, enabling effective intracellular delivery for applications ranging from vaccination to gene regulation. However, current manufacturing approaches, particularly microfluidic-based platforms, face inherent limitations in scalability, throughput, and structural tunability due to their reliance on confined channel geometries and restricted mixing architectures. Addressing these challenges requires fundamentally new strategies that decouple nanoparticle formation from traditional microscale flow constraints while maintaining precise control over physicochemical properties.

This dissertation presents a comprehensive framework for the design, engineering, and application of advanced lipid-based nanocarriers, centered on a hollow fiber membrane (HFM)—assisted nanopore-mediated assembly platform. …

Computational Design Of Nanoporous Materials For The Adsorption Of Per- And Polyfluoroalkyl Substances, Daniel D. Mottern

Dissertations

Per- and polyfluoroalkyl substances (PFAS) are a large family of chemicals that have seen wide usage due to their fluorinated carbon backbone. The presence of strong C-F bonds in the backbone lends PFAS molecules high thermal and chemical stability, as well as strong hydrophobicity and lipophobicity. This combination of properties has led to heavy use of PFAS as surfactants, non-stick coatings, and aqueous foam forming films and flame retardants. However, these properties bring their own consequences. The high chemical and thermal stability of PFAS renders them persistent, with the C-F bonds resisting naturally occurring forms of degradation. Existing forms of …

Data-Driven Analysis And Atomistic Simulations Of Next-Generation Materials For Energy Conversion And Storage, Yuliang Shi

Dissertations

Metal-organic frameworks (MOFs), with their modular architectures and tunable properties, represent an especially rich domain for accelerated material design and discovery for a range of diverse applications. Within this class of multifunctional materials, two-dimensional (2D) electrically conductive MOFs (EC MOFs) are of particular interest, as their 7r-stacked layered structures combine permanent porosity with electronic conductivity, enabling potential breakthroughs in energy storage, energy conversion, and quantum sensing. But the discovery and design of new EC MOFs based on expensive experimental screening is increasingly impractical due to the infinite chemical space. Furthermore, the practical implementation of EC MOFs for specific tasks depends …

Additive Manufacturing Of Carbons From Commodity Polyolefins, Paul Smith

Dissertations

Though tremendous progress has been made engineering carbon materials across length-scales from the molecular to the macroscopic, on-demand macro-structural control of carbons is still developing. Many carbon materials like graphene, carbon nanotubes, activated carbons, and carbon fibers have powder or fiber form factors. Recent research has pioneered on-demand carbon production through additive manufacturing (AM) via 1) extrusion and post-processing of highly filled carbon slurries, or 2) printing and pyrolysis of polymeric carbon precursors such as polyimides, acrylated polyethylene glycol, and phenolics. While groundbreaking, most methods face challenges with adoption due to costly/complex materials and manufacturing processes, and large dimensional changes …

Elucidating Differences In Constitutionally Isomeric Diamine- And Bisphenol-Based Polybenzoxazine Networks, Benjamin L. G. Morasch

Dissertations

This dissertation aims to expand the fundamental understanding of diamine-based benzoxazine chemistry by examining how synthesis influences the network properties of 4,4’-ddm and phenol-based (P-ddm) benzoxazine, compared to the constitutionally isomeric bisphenol-F and aniline-based (BF-a) benzoxazine. While bisphenol-based benzoxazines such as BF-a have been studied more extensively, diamine-based benzoxazines are still relatively unexplored due to the competition with the formation of 1,3,5-hexahydrotriazine intermediates and the inconsistent thermal and mechanical properties reported in the literature. These inconsistencies stem from factors including synthetic methods, curing conditions, and degradation during polymerization that have been overlooked.

To address these issues, this dissertation is organized …

Upcycling Commodity Polymers To Advanced Materials For Energy And Environmental Sustainability, Anthony Griffin-Espinoza

Dissertations

Synthetic polymers play an essential role in nearly every aspect of our lives. Extending beyond single-use packaging, polymeric material design has progressed to attain tailorable architectures granting exceptional performance across advanced applications, including carbon-fiber reinforced polymer composites for aerospace, conductive materials for soft electronics, and drug carriers for biomedicine. While highly promising, intricately designed polymers needed to achieve excellent performance often have limited processability, complex synthetic methods, and expensive precursors. Furthermore, due to a lack of recyclability, commodity polymer waste streams result in both environmental impacts and a substantial loss of economic value. This dissertation focuses on developing robust strategies …

Understanding Crystallization Behaviors Of Polyethylene-Derived Vitrimers, Sara Valdez

Dissertations

Polyolefins (POs), particularly polyethylene (PE) and polypropylene (PP), are among the most widely utilized polymers globally, valued for their low production costs and favorable mechanical properties stemming from their semicrystalline microstructure. However, their extensive use and improper disposal have raised serious environmental and human health concerns. In response, PO-derived covalent adaptable networks (CANs) have emerged, integrating dynamic chemistries to enable recyclability and sustainable end-of-life strategies. While existing literature has largely focused on novel CAN systems, structure–property relationships, and network rearrangement in relation to thermal transitions (e.g., topological freezing temperature), the influence of network formation on crystallinity and crystallization kinetics remains …

Understanding Structure-Property Relationships Within Polyolefin-Derived Vitrimer Systems, Mikaela Sadri

Dissertations

Polyolefins are extremely ubiquitous materials due to their satisfactory material properties, ease of synthesis, and low cost. Unfortunately, their extensive use has led to a global plastic waste mismanagement problem. As such, notable efforts have recently focused on converting these commodity polymers into vitrimers, or dynamic networks, to extend their use-life and tailor their properties. However, the fundamental polymer physics of these emerging materials, remain largely underexplored, hindering their widespread implementation. To address this challenge and enable a more sustainable future, the overarching goal of my dissertation research is to understand the fundamental structure-property relationships within complex polyolefin-derived vitrimer systems. …

Colloidal Quantum Dots: A Path Toward Making Mid-Wave Infrared Sensing A Ubiquitous Technology, Mohammad Mostafa Al Mahfuz

Dissertations

Reducing the size, weight, power consumption, and cost (SWaP-C) of infrared detectors could make infrared sensing more widely accessible. In the critical mid-wavelength infrared (MWIR) spectral range of 3-5 gm, commercially available detectors are limited by the high costs associated with epitaxial growth and hybridization, as well as the need for cryogenic cooling. These factors restrict their use to defense and space applications.

Colloidal quantum dots present a promising material for overcoming these challenges, with wafer-scale monolithic integration and Auger suppression being the key material capabilities to minimize the sensor's SWaP-C. Infrared sensors based on colloidal quantum dots have been …

Data-Driven Decision Making For Quality Control In Foundry Applications, Ronit Shetty

Dissertations

In the transformative landscape of Industry 4.0, advanced quality control in manufacturing demands innovative methods for processing and analyzing datasets. This dissertation presents a comprehensive study on leveraging high volume data and machine learning to enhance decision making in the foundry industry. The research explores three crucial challenges in the foundry industry: predicting surface roughness, monitoring refractory coating thicknesses, and comparing feature extraction techniques for surface quality classification. The findings underscore the transformative potential of integrating advanced feature engineering techniques and machine learning into manufacturing quality control.

The first of the three challenges introduces a framework that integrates digital images …

First-Principles Study Of Ferroelectric Properties And Co2 Reduction Reaction Capabilities In Two-Dimensional Monolayers And Heterostructures, Mo Li

Dissertations

Two-dimensional (2D) materials hold significant potential for CO₂ reduction reactions (CO₂RR) due to their high surface-to-volume ratio. However, achieving high selectivity for desired products and overcoming limitations posed by scaling relationships remain challenging. Recent studies suggest that ferroelectric (FE) materials with switchable out-of-plane polarization (OOP) can effectively tune the adsorption behavior, thermodynamics, and kinetics of CO₂RR, offering promising solutions to these challenges. Using density functional theory (DFT) and the Berry phase approach, this work expands the family of 2D ferroelectrics by theoretically identifying Y₂CO₂, Y₂CS₂, and Sc …

Determination Of Electrochemical Parameters For Predicting Reaction Mechanism And Algorithmic Approaches To Pain Assessment, Huize Xue

Dissertations

This dissertation introduces novel advancements in electrochemical kinetics and pain assessment, structured into two main parts. The first part focuses on the comprehensive analysis of the kinetic and mechanistic aspects of electrochemical reactions, utilizing a combination of experimental techniques and simulation methods. A new software tool, Envismetrics, was developed using Python to facilitate the analysis of complex electrochemical data, including cyclic voltammetry (CV), chronoamperometry (CA), and hydrodynamic voltammetry (HDV). The software was rigorously tested and validated with well-characterized redox systems such as the ferricyanide/ferrocyanide couple, dimethylamine borane (DMAB), and Per- and Polyfluoroalkyl Substances (PFAS). It was successfully used to determine …

Gas-Generating Reactive Materials: Design, Evaluation And Effect Of Morphology On Their Ignition And Combustion, Purvam Mehulkumar Gandhi

Dissertations

This work investigates optimizing gas-generating reactive materials, focusing on particle morphology's effect on ignition and combustion behavior. Metal-based gas-generating energetic materials (EMs) are promising alternatives to replace traditional CHNO compounds. Design of advanced metal-based EMs requires consistent ways of evaluating how their characteristics affect their ignition and combustion. Many relevant evaluation approaches exist; however, the results may be difficult to compare directly across different studies. Commonly, experimentalists ignite metal-based EMs in enclosed chambers and report pressures, P. However, direct comparison of these pressures is hindered by variations in the chamber volume, V, and the EM mass, m. To standardize the …

Decomposition Of Diisopropyl Methylphosphonate (Dimp) Exposed To Elevated Temperatures And Combustion Products Of Reactive Materials, Elif Irem Senyurt

Dissertations

The safe and efficient destruction of chemical weapon agents (CWAs) stockpiles remains a critical global challenge. Understanding the thermophysical properties, decomposition mechanisms, and interactions of CWAs with their environment is crucial for developing effective strategies to mitigate their threats. Diisopropyl methylphosphonate (DIMP) and Dimethyl methylphosphonate are commonly used nerve agent surrogates. This dissertation focuses on DIMP and DMMP, investigates their properties and behavior under conditions relevant to prompt defeat scenarios.

The thermophysical properties of DIMP and DMMP were experimentally characterized, including vapor-liquid surface tension (3-60 °C) and viscosities of neat and aqueous solutions. Results revealed significant non-ideal behavior in aqueous …

Influence Of Glycopolymer Structure On Amphiphilic, Hybrid, Linear Branched Block Copolymer Properties For Use In Biomedical Applications, Kevin Green

Dissertations

The focus of this dissertation is evaluating and adding fundamental knowledge regarding the structure-property relations of glycopolymers used in the design of hybrid block copolymers (HBC) that are cable of self-assembling into delivery vehicles for biomedical applications. A shift to the utilization of natural materials in the design and fabrication of drug-delivery vehicles has garnered significant attention. Understanding the effects of linear glycopolymers content and composition on the resulting HBCs properties can provide valuable insight into how these materials may be tailored for use in targeted biological applications.

The first chapter introduces current literature on the need for improvement in …

Electrified Membrane For Water Treatment And Resource Recovery: Advancing Multiscale Strategies In Gas-Involving Reactions, Jianan Gao

Dissertations

Multifunctional, modular, and scalable water treatment technologies that operate without chemical additives are crucial for addressing global water pollution challenges. While traditional membrane-based separation processes are crucial for ensuring clean water supplies, they primarily focus on pollutant removal rather than on the upcycling of pollutants into valuable resources. Electrified membrane filtration presents a robust alternative, utilizing minimal or no chemical additives and harnessing electrical power to directly reduce contaminants or produce reactive oxidants or reductants on-site.

This dissertation is dedicated to the development of innovative electrochemically reactive membranes designed to address three major challenges: (1) the engineering of electrocatalysts with …

Development And Structural Origin Of Stretchable Semiconducting Polymers And Composites, Yunfei Wang

Dissertations

Stretchable semiconductors are pivotal in advancing wearable and implantable electronics, with those boasting both high stretchability and self-healing capabilities being especially significant for a myriad of wearable applications. In this dissertation, we developed an extremely soft, highly stretchable, and self-healing elastomer based on H-bonding crosslinked amide-functionalized polyisobutylene (PIB-amide). When blended with a high-performance conjugated diketopyrrolopyrrole (DPP-T) polymer, the composite exhibits unprecedented stretchability, exceptionally low elastic modulus, and an innate ability to self-heal at room temperature.

The morphology of conjugated polymer/elastomer semiconducting composites have significant impacts on electrical and mechanical properties Further investigations focused on manipulating the phase separation size in …

Poly(Thioether) Thermosets With Gated Photodegradation, Surabhi Jha

Dissertations

Photodegradable polymer networks are attractive due to the precise spatiotemporal control and large-area applicability of light. Chemical linkages that enable these polymer networks to be photo-responsive, also hinder their applicability in ambient light. Photostable and photodegradable networks have recently been reported to overcome this challenge by combining other stimuli with light for degradation. We report the design of a network that responds to a simultaneous, dual stimulus for photodegradation. We design poly(thioether acetal) networks with benzylidene acetal moieties that are known to undergo β-scission in the presence of free thiols. By blocking these free thiols with a thermally labile protecting …

Printed Graphite Electrodes For Fast-Charging Lithium-Ion Batteries, Guanyi Wang

Dissertations

The rapid growth of the electric vehicle (EV) market has demanded lithium-ion batteries (LIBs) with high energy density and fast charging capability. However, charging energy-dense LIBs with thick graphite electrodes at high current densities is typically facing challenges and leading to adverse performance, such as low energy density, short cycle life, rapid temperature rises and safety issues. The root cause is the onset of Li plating. During fast charging application, the sluggish lithium ions accumulated at the surface of graphite due to kinetic limitation and formed Li plating, especially when lithiated to a high state of charge (SOC). It has …

Interaction Of Particles With Plasma And Shock Produced By Pulsed Spark Discharge, Shomik Mukhopadhyay

Dissertations

Interactions of powders with high-temperature plasma and shockwaves occur in diverse scenarios, such as nuclear blasts, accidental industrial dust explosions, solid propellant combustion in explosive charges and when removing contaminants from surfaces. Electrostatic Discharge (ESD), known for generating shock and plasma, is a promising lab-scale technique for simulating these interactions. Studies with ESD involved placing powders near a spark-producing gap between electrodes and observing mechanical and chemical processes like particle motion and ignition. A limited range of spark conditions and material properties have been tested, which facilitated the development and validation of preliminary computational models describing this system. Significant gaps …

Thermally Rearranging Polyimide Networks For High-Temperature Applications, William Guzman

Dissertations

High-performance polymers can retain functional properties when exposed to long-term or short-term durations of harsh conditions, such as mechanical action, at elevated temperatures (>177 °C). A mixture of intramolecular and intermolecular forces of and between polymer chains provide excellent property retention at elevated temperatures. Specifically, the highly aromatic nature of high-performance polymer backbones provides outstanding thermal stability, which is typically attributed to π-π stacking. However, the interrelationship between thermal stability and high aromaticity creates a challenging structure-processing relationship paradigm, which causes poor polymer processability in most high-performance polymers. Herein, it was demonstrated that rationally designing a crosslinking phenylethynyl imide …

Sustainable Diamond-Like Carbon Fabricated Gravure Cylinders For Printing Fine Lines Of Electrodes And Graphic Structures, Chandramohan Seetharamiah Srinivasaraju

Dissertations

The main objective of this work is to evaluate the potential of Diamond-Like Carbon (DLC) as an alternative to chrome for use on gravure cylinders. DLC coatings consist of carbon atoms, arranged into a diamond-like structure that closely resembles that of natural diamond. In contrast to chrome, DLC is environmentally friendly. The focus of the study is to determine the viability of DLC as a substitute material for chrome to be used on gravure cylinders by determining key material properties and evaluating printing performance.

In the first research paper, four DLC variants (Standard DLC, A-DLC, S-DLC, and Organic Silica) and …

Data-Driven 2d Materials Discovery For Next-Generation Electronics, Zeyu Zhang

Dissertations

The development of material discovery and design has lasted centuries in human history. After the concept of modern chemistry and material science was established, the strategy of material discovery relies on the experiments. Such a strategy becomes expensive and time-consuming with the increasing number of materials nowadays. Therefore, a novel strategy that is faster and more comprehensive is urgently needed. In this dissertation, an experiment-guided material discovery strategy is developed and explained using metal-organic frameworks (MOFs) as instances. The advent of 7r-stacked layered MOFs, which offer electrical conductivity on top of permanent porosity and high surface area, opened up new …

Cu/Bnx Catalysts For Electrocatalytic Reduction Of Nitrogen And Nitrate Waste, Siming Huo

Dissertations

Ammonia (NH₃) is one of the most important chemicals to the whole human society. The invention of the Haber-Bosch process enabled the industrial production of NH₃. However, owing to the high capital costs of the centralized plant and the equipment and the negative environmental impact, it is no longer suitable for today's needs of human development. As a result, there is an urgent need to investigate sustainable approaches for ammonia production. Among those reported studies, nitrogen reduction (NRR) and nitrate reduction reaction (NO₃RR) are considered applicable in the future. However, after decades of studying …

Influence Of Material Properties On Granules Prepared By Dry Co-Rotating Twin Screw Extrusion And Counterrotating Batch Mixing, Afstathios Steve Pafiakis

Dissertations

Recently, the pharmaceutical industry has shown interest in continuous granulating technology because of the flexibility it offers as an option that bypasses the costly scale-up process associated with batch manufacturing. However, the granulation mechanism(s) using twin screw co-rotating hot melt extrusion (HME) has not been fully explored, and it is not yet well understood. This leads to costly experiments during development and process reliability problem in commercial manufacturing. The main objective of this dissertation is to increase the mechanistic understanding of the twin screw granulation process of systems containing an active pharmaceutical ingredient (API) and a polymer excipient. This is …

The Influence Of Diamine Curing Additives On The Network Architecture Of Phthalonitrile Thermosetting Polymers, Tyler J. Richardson

Dissertations

Phthalonitrile monomers undergo diamine-promoted polymerization by a complex reaction mechanism involving two competitive cure pathways, forming two primary network architectures: linear polyisoindoline chains and branched triazine crosslinks. The influence of the diamine curing additive on the polymerization pathway, and the influence of the resulting network architectures on cured network properties, have not been adequately explored within the phthalonitrile field. Two structurally different diamine curing additives, bis[4-(3-aminophenoxy)phenyl] sulfone (mBAPS) and 1,3-phenylenebis((4-(4-aminophenoxy)phenyl)methanone) (AEK-134), were studied for the polymerization of resorcinol phenylphosphate phthalonitrile (RPPhPN), where the influence of diamine structure and concentration on the polymerization behavior, network architecture, and bulk thermal and thermomechanical …