Materials Science and Engineering Commons^™

A Mechanical Model For Stress Relaxation Of Polylactic Acid/Thermoplastic Polyurethane Blends, Yi-Sheng Jhao, Hao Ouyang, Chien-Chao Huang, Fuqian Yang, Sanboh Lee

Chemical and Materials Engineering Faculty Publications

Polylactic acid (PLA) is considered a promising biodegradable polymer alternative. Due to its high brittleness, composite materials made by melt blending thermoplastic polyurethane (TPU) with PLA can enhance the toughness of PLA. To understand the forced aging caused by stress relaxation in polymer materials, this study explains the stress relaxation experiments of PLA/TPU blends with different mass ratios under applied strain through mechanical model simulations. The Kelvin representation of the standard linear solid model (SLSM) is used to analyze the stress relaxation data of TPU/PLA blends, successfully explaining that the Young’s moduli (E1 and E2) of springs decrease with increasing …

Shorting At Long Duration: Impact Of Extended Discharge Capacity On Battery Solid Electrolytes, Ryan C. Hill, Amanda S. Peretti, Leo J. Small, Erik D. Spoerke, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Publications

Long-duration energy storage (LDES) is critical to a stable, resilient, and decarbonized electric grid. While batteries are emerging as important LDES devices, extended, high-power discharges necessary for cost-competitive LDES present new materials challenges. Focusing on a new generation of low-temperature molten sodium batteries, we explore here unique phenomena related to long-duration discharge through a well-known solid electrolyte, NaSICON. Specifically, molten sodium symmetric cells at 110 ° C were cycled at 0.1 A cm−2 for 1–23 h discharges. Longer discharges led to unstable overpotentials, reduced resistances, and decreased electrolyte strength, caused by massive sodium penetration not observed in shorter duration discharges. …

Local Strain Quantification Of A Porous Carbon Fiber Network Material, Robert N Quammen, Paul F. Rottmann

Chemical and Materials Engineering Faculty Publications

While porous materials’ wide range of attractive functional properties have led to their development for a variety of applications, their intrinsically stochastic microstructures prevent straightforward approaches to predicting their mechanical behavior. This is attributed to the mechanisms that govern the macroscale behavior of these materials operating on multiple microstructure-specific length scales spanning several orders of magnitude. The goal of this work was to experimentally observe these operative deformation mechanisms to better improve the development of mechanism-informed models that more accurately predict the behavior of these materials. In this study compression tests were conducted on a porous carbon fiber network material. …

The Janssen Effect And The Chini Ordinary Differential Equation, Adam Rogers, George Dyck, Jitendra Paliwal, Kurt Hildebrand, Michael D. Montross, Aaron P. Turner

Chemical and Materials Engineering Faculty Publications

The Janssen effect describes the increase in pressure with depth in granular materials. However, the original Janssen formulation treats the density as constant. In this work, we examine parametric density models that depend on both pressure and moisture content and allow for temperature dependence to be easily included. We focus on physically-motivated empirical models that are built on power-law terms. These power-law terms correspond to thermodynamic equations of state, such as the ideal gas law, and polytropic processes. When coupled with the Janssen ordinary differential equation (ODE), these power-law models have the form of a Chini ODE. We study the …

Protocol For Modeling And Simulating Lithiation-Induced Stress In Largely Deformed Spherical Nanoparticles Using Comsol, Yong Li, Yungpeng Guo, Yunhao Wu, Yin Rao, Kai Zhang, Dashun Liu, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Here, we present a finite element method-based scheme for solving coupled par- tial differential equations (PDEs) for the analysis of lithiation-induced stress in largely deformed spherical nanoparticles via the PDE module in COMSOL. We describe steps for software installation and setting PDEs, initial/boundary condi- tions, and mesh parameters. We then detail procedures for dividing the mesh and analyzing lithium trapping during electrochemical cycling. This protocol can also be extended to analyze a wide range of problems involving diffusion-induced stress. For complete details on the use and execution of this protocol, please refer to Li et al.

Spontaneous Alignment Of Myotubes Through Myogenic Progenitor Cell Migration, Lauren E. Mehanna, Adrianna R. Osborne, Charlotte A. Peterson, Brad J. Berron

Chemical and Materials Engineering Faculty Publications

In large-volume muscle injuries, widespread damage to muscle fibers and the surrounding connective tissue prevents myogenic progenitor cells (MPCs) from initiating repair. There is a clinical need to rapidly fabricate large muscle tissue constructs for integration at the site of large volume muscle injuries. Most strategies for myotube alignment require microfabricated structures or prolonged orientation times. We utilize the MPC’s natural propensity to close gaps across an injury site to guide alignment on collagen I. When MPCs are exposed to an open boundary free of cells, they migrate unidirectionally into the cell-free region and align perpendicular to the original boundary …

Inhibited Surface Diffusion In Nanoporous Multi-Principal Element Alloy Thin Films Prepared By Vacuum Thermal Dealloying, Tibra Das Gupta, Thomas John Balk

Chemical and Materials Engineering Faculty Publications

Nanoporous structures with 3D interconnected networks are traditionally made by dealloy- ing a binary precursor. Certain approaches for fabricating these materials have been applied to refrac- tory multi-principal element alloys (RMPEAs), which can be suitable candidates for high-temperature applications. In this study, nanoporous refractory multi-principal element alloys (np-RMPEAs) were fabricated from magnesium-based thin films (VMoNbTaMg) that had been prepared by magnetron sputtering. Vacuum thermal dealloying (VTD), which involves sublimation of a higher vapor pres- sure element, is a novel technique for synthesizing nanoporous refractory elements that are prone to oxidation. When VMoNbTaMg was heated under vacuum, a nanoporous structure was …

The Roles Of Carbonaceous Wastes For Catalysis, Energy, And Environmental Remediation, Chi Huey Ng, Mohd Aizzan Mistoh, Siow Hwa Teo, Andrea Galassi, Hin Taufiq-Yap, Nancy Julius Siambun, Jurry Foo, Coswald Stephen Sipaut, Jeffrey Seay, Jidon Janaun

Chemical and Materials Engineering Faculty Publications

This article reviews recent studies about various generations of the carbon materials for their applications in energy and environmental remediation. The synthesis routes of the carbon materials including the condition parameters, interaction of precursors, dopants and carbon materials, as well as their physical/chemical properties are explicated first. Then, the application and mechanism of metal-free/metal-doped/non-metal-doped carbon materials are discussed in detail. Lastly, this review is ended with a summary and invigorating perspectives on the challenges and future directions at the forefront of the catalysis platform to take a step further for real application.

Investigating The Structure And Performance Of Electrodes Made By Dry And Wet Slurry Processes, Kubra Uzun, Bhamiti Sharma, Bradley R. Frieberg, Ming Wang, Jiazhi Hu, Anita Li, Xiaosong Huang, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Publications

Performance, cost, and safety are vital factors in producing and handling lithium-ion batteries. Using a dry process reduces the cost and environmental impact of producing large-scale lithium-ion battery electrodes significantly as solvents are eliminated. Thus, in this study, solvent-free dry electrostatic spray deposition (ESD) and conventional slurry processes were compared to uncover the influence of the manufacturing process on thick LiNi 0.8Mn0.1Co 0.1O 2 (NMC 811) positive electrodes. More pressure during calendering was found necessary for the dry-made (dry) electrodes to have the same porosity, leading to more cracks within the NMC particles and better adhesion. At slower discharge rates, …

Sustainable Additive Manufacturing Of Polysulfone Membranes For Liquid Separations, Brian Leonard, Harrison Loh, David Lu, Ebuka A. Ogbuoji, Isabel Escobar, Konstantinos Sierros, Oishi Sanyal

UK CARES Faculty Publications

Membranes serve as important components for modern manufacturing and purification processes but are conventionally associated with excessive solvent usage. Here, for the first time, a procedure for fabricating large area polysulfone membranes is demonstrated via the combination of direct ink writing (DIW) with non-solvent induced phase inversion (NIPS). The superior control and precision of this process allows for complete utilization of the polymer dope solution during membrane fabrication, thus enabling a significant reduction in material usage. Compared to doctor blade fabrication, a 63% reduction in dope solution volume was achieved using the DIW technique for fabricating similarly sized membranes. Cross …

Effect Of Admixtures On Rapid Hardening, Self-Consolidating Concrete, Haley Johnson

Theses and Dissertations--Civil Engineering

Self-consolidating, rapid-hardening concrete is a sought-after product in the market now, however the effects of admixtures on fresh and hardened concrete rheology are still uncertain. This study aims to create a self-consolidating concrete (SCC) using calcium sulfoaluminate (CSA) cement for its rapid-hardening properties, and tests two set time retarders and two viscosity-modifying admixtures (VMAs) to determine how they affect the properties of concrete. The properties studied in this thesis are workability, viscosity, set times, air content, compressive strength, and freeze-thaw resistance of self-consolidating concrete. It was found that tartaric acid creates a very workable SCC with consistent results regardless of …

The Characterization And Nanomechanical Properties Of Microstructurally Complex Systems, Kerry Ann Baker

Theses and Dissertations--Chemical and Materials Engineering

Since the dawn of civilization, the use of metals has played an integral role in the evolution of human society. Over the years, and with the introduction of new engineering and science, we have learned how to combine metals to create new metallic systems. We have expanded our understanding of dealloying and chemical reactions, and, in doing so, we created nanoporous metals. Our use of metals has evolved from basic alloys such as bronze and steel to more complex alloys such as multi-principal element alloys. Nanoporous gold is an advanced metallic system that can be created through the dealloying process. …

Advancing Combinatorial Screening Of Refractory High Entropy Alloys Through Intrinsic Ductility Assessment Via Thin Film Fragmentation Testing, Taohid Bin Nur Tuhser

Theses and Dissertations--Chemical and Materials Engineering

High Entropy Alloys (HEAs), also known as Multiprincipal Element Alloys (MPEAs), represent a paradigm shift in alloy design. Unlike traditional practices that limit compositions to the edges of phase diagrams, HEAs exploit equiatomic mixing of five or more elements at the center of phase diagrams to maximize configurational entropy. This unconventional approach exponentially expands the spectrum of potential alloy compositions, rendering conventional experimental methods inadequate for exploring this extensive compositional space.

In response to these challenges, the scientific community has shown a growing interest in high-throughput techniques, encompassing both computational and experimental domains. Particularly, Refractory High Entropy Alloys (RHEAs) have …

Microstructural Investigation Of The Influence Of Geometry On The Mechanical Reliability Of Additively Manufactured Metals, Tracy Connor Varney

Theses and Dissertations--Chemical and Materials Engineering

The adoption of additive manufacturing across a wide range of fields is ever-increasing, allowing for solutions that were previously impossible to achieve. This dissertation demonstrates the wide range of macro- and micro- characterization techniques used to investigate several precipitation strengthened AM alloy systems. While AM allows for nearly unlimited design freedom, this brings along its own issues as the interplay between scan strategy and part geometry is less well known. In this work, a novel thin-wall dogbone geometry was utilized to study one type of complex geometry observed in a large portion of AM focused designs. The mechanical behavior of …

Optoelectrical Properties And Photostability Of Cspbbr3 Quantum Dots: Effects Of Dopants And Ligands, Md Shad Bin Salam

Theses and Dissertations--Chemical and Materials Engineering

Metal halide perovskite QDs have a great potential for displays and lighting because of their exceptional optoelectronic characteristics associated with quantum confinement effect. However, the stability in the environment during the applications of halide perovskite QDs remains a significant challenge, impeding their practicality and lowering their commercial scalability. High-temperature methods are well-established for producing doped perovskite QDs, the influence of room-temperature synthesis on thermal, size-dependent optical properties, and long-term stability remains inadequately understood. Also, there is a demand for strategies to increase the absorption of light, reduce trap states, and modify the energy levels of perovskite QDs.

In this study, …

Thermal Alteration Of The Mineralogy Of Calcium Sulfoaluminate Cements: Implications For The Performance Of Rapid Repair Materials, Jillian Cavellier

Theses and Dissertations--Earth and Environmental Sciences

Calcium sulfoaluminate (CSA) was developed in part to lessen the environmental impact of cementitious materials compared to traditional Portland cements. CSA was first put into production in the 1970s and has been undergoing various performance testing to investigate its durability. Yet to be evaluated is CSA’s response to a rapid, high temperature event. In this study, X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectrometry and scanning electron microscope imaging were used to analyze alterations in the mineralogy due to such an event. As found in previous studies, after ~125°C, ettringite has been completely dehydrated. Ettringite decomposes into bassanite and calcium …

Mechanochemical Synthesis Of Halide Perovskite Microcrystals, Xuan Huang

Theses and Dissertations--Mechanical and Aerospace Engineering

Halide perovskites have emerged as a promising class of materials for various optoelectronic applications, including light-emitting diodes (LEDs), solar cells, photodetectors, and lasers, owing to their exceptional photophysical properties and ease of synthesis. Lead-based halide perovskites, despite their success, raise concerns regarding environmental toxicity, necessitating the exploration of lead-free alternatives. This thesis explores the synthesis and characterization of lead-free halide perovskites, focusing on tin-based variants, using a mechanochemical approach, which eliminates the use of toxic solvents and offers a sustainable synthesis route.

By employing a solventless mechanochemical method, lead-free tin-based halide perovskite microcrystals were successfully synthesized. This approach not only …

Development Of Synthetically Accessible Glycolated Polythiophenes For High-Performance Organic Electrochemical Transistors, Bowen Ding, Vianna N. Le, Hang Yu, Guanchen Wu, Adam V. Marsh, Edgar Gutiérrez-Fernández, Nicolás Ramos, Martina Rimmele, Jaime Martín, Jenny Nelson, Alexandra F. Paterson, Martin Heeney

Chemical and Materials Engineering Faculty Publications

Four glycolated polythiophene-based organic mixed ionic-electronic conductors (OMIECs), PE2gTT, PE2gT, PT2gTT, and PT2gT are prepared by atom-efficient direct arylation polymerization, avoiding the need for toxic organometallic pre- cursors. PE2gT, PT2gTT, and PT2gT are operable in p-type accumulation mode organic electrochemical transistors (OECTs), with PT2gT displaying the best device performance with a μC* product figure-of-merit of 290 F cm−1 V−1 s−1 . A record volumetric capacitance among p-type glycolated polythiophene OMIECs of 313 F cm−3 is observed for PE2gT, ascribed to the high proportion- ality of polar components in its materials design. The good OECT performance of PE2gT with μC* = …

The Integrated Behavioral Model Of Mental Health Help Seeking (Ibm-Hs): A Health Services Utilization Theory Of Planned Behavior For Accessing Care, Joseph H. Hammer, David L. Vogel, Patrick R. Grzanka, Nayeon Kim, Brian T. Keum, Claire Adams, Sarah A. Wilson

Chemical and Materials Engineering Faculty Publications

This article introduces the integrated behavioral model of mental health help seeking (IBM-HS), a theoretical model for understanding the constructs (e.g., systemic, predisposing, and enabling factors; mental health literacy; illness perceptions; perceived need; stigma; shame; perceived benefits, motivation) that influence people’s decision making around seeking professional mental health care and their ultimate access to formal treatment. The IBM-HS is a help-seeking-specific adaptation of the empirically supported integrated behavioral model and integrative model, which are themselves evolutions of the theory of planned behavior and theory of reasoned action. The IBM-HS posits that help-seeking determinants (e.g., structural forces; cultural influences; past help-seeking …

Solvent-Free Manufacturing Of Lithium-Ion Battery Electrodes Via Cold Plasma, Zhiming Liang, Tianyi Li, Holden Chi, Joseph Ziegelbauer, Kai Sun, Ming Wang, Wei Zhang, Tuo Liu, Yang-Tse Cheng, Zonghai Chen, Xiaohong Gayden, Chunmei Ban

Chemical and Materials Engineering Faculty Publications

Slurry casting has been used to fabricate lithium-ion battery electrodes for decades, which involves toxic and expensive organic solvents followed by high-cost vacuum drying and electrode calendering. This work presents a new manufacturing method using a nonthermal plasma to create inter- particle binding without using any polymeric binding materials, enabling solvent-free manufacturing electrodes with any electrochemistry of choice. The cold-plasma-coating technique enables fabricating electrodes with thickness (>200 lm), high mass loading (>30 mg cm^-2), high peel strength, and the ability to print lithium-ion batteries in an arbitrary geometry. This crosscutting, chemistry agnostic, platform technology would increase energy density, …

Calculation Of Elastic Constants Of Bulk Metallic Glasses From Indentation Tests, Zhitong Xu, Ming Liu, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

One of the challenges in the applications of instrumented indentation is to simultaneously measure elastic modulus and Poisson’s ratio of homogeneous, isotropic materials. This work proposes empirical equations for simultaneous calculation of elastic modulus and Poisson’s ratio of bulk metallic glasses (BMGs) from the ratio of the short diagonal length to the long diagonal length and the area of the Knoop imprint. The parameters pre- sented in the empirical equations are determined first by Knoop microhardness tests of 24 BMGs, whose elastic moduli and Poisson’s ratios are measured by resonant ultrasound spectroscopy. These empirical equations are further validated by the …

“Zero” Porosity High Loading Nmc622 Positive Electrodes For Li-Ion Batteries, Haidar Y. Alolaywi, Kubra Uzun, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Publications

LiNi0.6 Mn0.2Co0.2 O 2 (NMC622) is a widely used positive electrode material for lithium-ion batteries, including electric vehicles. In this work, we investigated the effects of porosity, ranging from “zero” to the typical 35%, on the electrochemical behavior of high- loading NMC622 electrodes. Although it is well known that the energy density of the electrode increases with increasing areal capacity and decreasing porosity, NMC-positive electrodes with exceedingly low porosity (e.g., near zero) and high loading (e.g., 4 mAh cm−2 ) have not been investigated. Here, we report an intriguing observation that the “zero porosity” NMC electrode can have higher capacity …

Machine-Learning-Assisted Design Of Deep Eutectic Solvents Based On Uncovered Hydrogen Bond Patterns, Usman Lame Abbas, Yuxuan Zhang, Joseph Tapia, Md Selim, Jin Chen, Jian Shi, Qing Shao

Markey Cancer Center Faculty Publications

Non-ionic deep eutectic solvents (DESs) are non-ionic designer solvents with various applications in catalysis, extraction, carbon capture, and pharmaceuticals. However, discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation. The search for DES relies heavily on intuition or trial-and-error processes, leading to low success rates or missed opportuni- ties. Recognizing that hydrogen bonds (HBs) play a central role in DES formation, we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning (ML) models to discover new DES systems. We first analyze the …

Thermomechanical Process Simulation And Quantification Of Nanoscale Precipitation Influencing Ductility And Strength During Alloy Processing, Alyssa Stubbers

Theses and Dissertations--Chemical and Materials Engineering

Experimental process simulation and quantification of microstructure development during processing are challenging due to limitations with machinery temperature capability, inadequate resolution and sampling volume of currently available characterization techniques, and difficulty characterizing material microstructures as close to processing-relevant conditions as possible. This dissertation addresses how process simulation can be performed using Gleeble thermomechanical technologies and how microstructure development during these processing simulations can be quantified both in-situ and ex-situ.

The first portion of this dissertation demonstrates how Gleeble technologies can be applied to simulate complex material processing conditions in order to produce process-property profiles that can be used to inform …

Faceting Of Tungsten Via Environmental Control Of Temperature, Pressure And Chemistry, And Evolution Of Thermionic Cathode Materials, Huanhuan Bai

Theses and Dissertations--Chemical and Materials Engineering

Scandate cathode presents a great potential of being used as electron emitters in vacuum electron device due to its excellent emission performance. However, it is burdened by several issues, including poor emission uniformity, inadequate reproducibility, and limited lifetime, which have impeded its further industrial application. Therefore, extensive efforts and studies need to be conducted to obtain a more comprehensive understanding of scandate cathode.

W particles, as the base material, play a fundamental role in scandate cathode. Most recent experimental research has reported that the highly faceted crystallography of W grains contributes to the properties of scandate cathode. In order to …

Experimental Characterization And Quantification Of Deformation Behavior In A Porous Carbon Fiber Network, Robert N Quammen

Theses and Dissertations--Chemical and Materials Engineering

Due to their wide range of attractive functional properties (such as low thermal conductivity and low density) porous materials are utilized in a variety of applications. In order to characterize these properties and others, the intrinsically heterogeneous microstructures of these materials need to be taken into account. These microstructures result in interactions across multiple length scales spanning several orders of magnitude. This makes the creation of robust computational models and straight-forward predictions of mechanical properties difficult for porous materials. With this in mind, this dissertation aims to provide experimental mechanical and deformation information spanning the length scales of interest for …

Novel Precursors For Carbon Fiber Prepared By Direct Carbonization, Leah Noble

Theses and Dissertations--Chemical and Materials Engineering

For decades carbon fiber-based composites have been most heavily employed in lightweight, structural applications where low density and high strength are necessary, most notably within the aerospace industry. However, the advancement of carbon fiber into a wider array of industries has largely been limited by the high financial and energetic costs associated with its manufacture. Moreover, with an increasing societal emphasis on sustainability, there is an ever-growing desire for low-energy carbon fiber production pathways. One such pathway is the conversion of precursor fiber to carbon fiber by direct carbonization, wherein the energy-intensive, pre-carbonization stabilization step is omitted from the carbonization …

Single-Atom Catalysts For Electrochemical Energy Conversion: Copper Single-Atom Catalyst For Oxygen Reduction Reaction And Quantification Of Site Density By Co Stripping Voltammetry, Dawatage Perera

Theses and Dissertations--Chemistry

Fuel cells are considered a promising technology for achieving cleaner and more sustainable energy production and utilization. However, one of the current major challenges is the economic viability associated with the extensive use of Pt group metal (PGM) catalysts, particularly on the cathode side. Therefore, non-PGM single-atom catalysts (SACs) have received considerable attention as alternatives for PGM catalysts in the oxygen reduction reaction (ORR), which occurs at the cathode of the fuel cell. Among various SAC structures, the non-PGM/nitrogen-doped carbon-based structure (M-N-C) stands out for its excellent ORR performance.

Chapter 2 illustrates the use of copper metal in place of …

Molecular Control Of Triplet-Pair Spin Polarization And Its Optoelectronic Magnetic Resonance Probes, Obadiah G. Reid, Justin C. Johnson, Joel D. Eaves, Niels H. Damrauer, John E. Anthony

Chemical and Materials Engineering Faculty Publications

Preparing and manipulating pure magnetic states in molecular systems are the key initial requirements for harnessing the power of synthetic chemistry to drive practical quantum sensing and computing technologies. One route for achieving the requisite higher spin states in organic systems exploits the phenomenon of singlet fission, which produces pairs of triplet excited states from initially photoexcited singlets in molecular assemblies with multiple chromophores. The resulting spin states are characterized by total spin (quintet, triplet, or singlet) and its projection onto a specified molecular or magnetic field axis. These excited states are typically highly polarized but exhibit an impure spin …

Design And Characterization Of A Novel Eef2k Degrader With Potent Therapeutic Efficacy Against Triple-Negative Breast Cancer, Changxin Zhong, Rongfeng Zhu, Ting Jiang, Sheng Tian, Xiaobao Zhao, Xiaoya Wan, Shilong Jiang, Zonglin Chen, Rong Gong, Linhao He, Jin-Ming Yang, Na Ye, Yan Cheng

Markey Cancer Center Faculty Publications

Dysregulated eEF2K expression is implicated in the pathogenesis of many human cancers, including triple-negative breast cancer (TNBC), making it a plausible therapeutic target. However, specific eEF2K inhibitors with potent anti-cancer activity have not been available so far. Targeted protein degradation has emerged as a new strategy for drug discovery. In this study, a novel small molecule chemical is designed and synthesized, named as compound C1, which shows potent activity in degrading eEF2K. C1 selectively binds to F8, L10, R144, C146, E229, and Y236 of the eEF2K protein and promotes its proteasomal degradation by increasing the interaction between eEF2K and the …