Materials Science and Engineering Commons^™

Development Of Multifunctional Shape Memory Polymer And Shape Memory Polymer Composites, Sesha Spandana Pulla

Theses and Dissertations--Mechanical and Aerospace Engineering

Shape memory polymers (SMPs) are an emerging class of active polymers that can be used on a wide range of reconfigurable structures and actuation devices. The present study comprehensively examines the unconstrained shape recovery abilities of an epoxy-based SMP. In doing so, epoxy based SMP is synthesized and thermo-mechanically characterized. Results show that the present SMP exhibits excellent shape recoveries under unconstraint conditions, for a range of fixing strains and temperatures. Additionally, the stress-strain behavior of the SMP is determined to be nonlinear, finite deformation at all regions. The strain energy based models have been used to capture the complicate …

Nanomechanical And Scaling Behavior Of Nanoporous Gold, Nicolas J. Briot

Theses and Dissertations--Chemical and Materials Engineering

Nanoporous metals have recently been drawn significant interest in various fields of research. Their high surface-to-volume ratio present a strong potential for applications in sensing, catalysis, micro-electromechanical systems (MEMS) and even in the medical field. However, the mechanical properties of nanoporous metals have not yet been well determined, as conducting mechanical tests was found to be challenging. Scaling relations linking the mechanical properties of porous materials to those of their dense counterparts are successfully and widely used for many porous metals. However, their applicability to nanoporous metals have recently been questioned, as estimations from the classic scaling relations were found …

Nanoindentation Of A Zinc Metal Soap Mixture For Use In A Laser Printer, George A. Nimick

Theses and Dissertations--Chemical and Materials Engineering

At the start of this project, the possible choices of metal soaps had already been narrowed to include some of the zinc soaps used in this project. These zinc soaps are mixtures of zinc stearate and zinc palmitate of varying ratios purchased from a supplier. Zinc soap was chosen as result of its common use in various industries as a lubricant and mold release, which implied potential benefits in an electrophotographic printing system. These potential benefits include, but are not limited to, a more efficient transfer from a photoconductive drum and protection of the drum from mechanical and chemical degradation. …

Fundamental Studies Of Surfactant Templated Metal Oxide Materials Synthesis And Transformation For Adsorption And Energy Applications, Saikat Das

Theses and Dissertations--Chemical and Materials Engineering

This work addresses fundamental aspects of designing templates and curing conditions for the synthesis of mesoporous metal oxide thin films. The first section addresses selection of cationic-carbohydrate surfactant mixtures to synthesize templated silica thin films for selective adsorption of simple carbohydrates based on molecular imprinting. Nuclear magnetic resonance and fluorescence spectroscopy results suggest a novel structure for mixtures of alkyl glucopyranosides or xylopyranosides with cationic (trimethylammonium) surfactants. Despite thermodynamically favorable mixing, the carbohydrate headgroups in the mixed micelle adopt an inverted configuration with their headgroups in the micelle core, and therefore are inaccessible for molecular imprinting. This orientation occurs even …

Engineered Surface Properties Of Porous Tungsten From Cryogenic Machining, Julius M. Schoop

Theses and Dissertations--Chemical and Materials Engineering

Porous tungsten is used to manufacture dispenser cathodes due to it refractory properties. Surface porosity is critical to functional performance of dispenser cathodes because it allows for an impregnated ceramic compound to migrate to the emitting surface, lowering its work function. Likewise, surface roughness is important because it is necessary to ensure uniform wetting of the molten impregnate during high temperature service. Current industry practice to achieve surface roughness and surface porosity requirements involves the use of a plastic infiltrant during machining. After machining, the infiltrant is baked and the cathode pellet is impregnated. In this context, cryogenic machining is …

Microindentation Of Bi57in26sn17 Lead-Free Alloy, Ruiting Zhao

Theses and Dissertations--Chemical and Materials Engineering

There is great need to understand the mechanical properties of lead-free alloys—an alternative of lead-based alloys—to address the environmental problems associated with the use of lead-based materials in microelectronics. In this work, the microstructures of Bi57In26Sn17 lead-free alloy were examined using Optical Microscopy and Energy Dispersive X-ray Spectroscopy analysis. The micro-indentation technique was used to study the mechanical properties of Bi57In26Sn17 lead-free alloy. The experimental results of the hardness and contact modulus were presented and discussed. Local creep during the indentation was observed from the load-displacement curves. The Vickers hardness (HV) increases with the decrease of the indentation depth, suggesting …

Synthesis, Structure, Properties And Applications Of Nanoporous Silicon And Palladium, Xu Jiang

Theses and Dissertations--Chemical and Materials Engineering

Nanoporous (np) materials with pore size below 100 nano-meters exist naturally in biological and mineral structures, and synthetic np materials have been used industrially for centuries. Np materials have attracted significant research interest in recent decades, as the development of new characterization techniques and nanotechnology allow the observation and design of np materials at a new level. This study focuses on two np materials: nanoporous silicon (np-Si) and nanoporous palladium (np-Pd).

Silicon (Si), because of its high capacity to store lithium (Li), is increasingly becoming an attractive candidate as anode material for Li ion batteries (LIB). One significant problem with …

Evaporation-Induced Formation Of Well-Ordered Surface Patterns On Polymer Films, Wei Sun

Theses and Dissertations--Chemical and Materials Engineering

Various techniques of fabricating surface patterns of small scales have been widely studied due to the potential applications of surface patterns in a variety of areas. It is a challenge to fabricate well-ordered surface area efficiently and economically. Evaporation-induced surface patterning is a promising approach to fabricate well-ordered surface patterns over a large area at low cost. In this study, the evaporation-induced surface patterns with controllable geometrical characteristics have been constructed. The dewetting kinetics on deformable substrate is also investigated.

Using simple templates to control the geometry and the evaporation behavior of a droplet of volatile solvent, various gradient surface …

Interfacial Polymerization For Colorimetric Labeling Of Protein Expression In Cells, Jacob L. Lilly, Phillip R. Sheldon, Liv J. Hoversten, Gabriela Romero, Vivek Balasubramaniam, Brad J. Berron

Chemical and Materials Engineering Faculty Publications

Determining the location of rare proteins in cells typically requires the use of on-sample amplification. Antibody based recognition and enzymatic amplification is used to produce large amounts of visible label at the site of protein expression, but these techniques suffer from the presence of nonspecific reactivity in the biological sample and from poor spatial control over the label. Polymerization based amplification is a recently developed alternative means of creating an on-sample amplification for fluorescence applications, while not suffering from endogenous labels or loss of signal localization. This manuscript builds upon polymerization based amplification by developing a stable, archivable, and colorimetric …

Field-Limited Migration Of Li-Ions In Li-Ion Battery, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

The migration of Li-ions in lithium-ion battery cannot be simply described by Fick's second law; the interactions among ionic migration, field, and stress need to be taken into account when analyzing the migration of Li-ions. Using the theory of thermal activation process, the flux for ionic migration under concurrent action of electric field and mechanical stress is found to be a nonlinear function of the gradient of electric potential and the gradient of stress. Electric field can either accelerate or retard the growth of the lithiation layer, depending on polarity of the field.

The Stochastic Dynamics Of Tethered Microcantilevers In A Viscous Fluid, Brian A. Robbins, Milad Radiom, William A. Ducker, John Y. Walz, Mark R. Paul

Chemical and Materials Engineering Faculty Publications

We explore and quantify the coupled dynamics of a pair of micron scale cantilevers immersed in a viscous fluid that are also directly tethered to one another at their tips by a spring force. The spring force, for example, could represent the molecular stiffness or elasticity of a biomolecule or material tethered between the cantilevers. We use deterministic numerical simulations with the fluctuation-dissipation theorem to compute the stochastic dynamics of the cantilever pair for the conditions of experiment when driven only by Brownian motion. We validate our approach by comparing directly with experimental measurements in the absence of the tether …

Liquid Metal Electrodes For Rechargeable Batteries, Rutooj Deshpande, Juchuan Li, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Patents

An electrode for a lithium ion battery includes a liquid metal having a melting point that is below the operating temperature of the battery, which transforms from a liquid to a solid during lithiation, and wherein the liquid metal transforms from a solid to a liquid during delithiation.

Oxidation-Resistant, Solution-Processed Plasmonic Ni Nanochain-SioX (X < 2) Selective Solar Thermal Absorbers, Xiaobai Yu, Xiaoxin Wang, Qinglin Zhang, Juchuan Li, Jifeng Liu

Chemical and Materials Engineering Faculty Publications

Metal oxidation at high temperatures has long been a challenge in cermet solar thermal absorbers, which impedes the development of atmospherically stable, high-temperature, high-performance concentrated solar power (CSP) systems. In this work, we demonstrate solution-processed Ni nanochain-SiO_x (x < 2) and Ni nanochain-SiO₂ selective solar thermal absorbers that exhibit a strong anti-oxidation behavior up to 600 °C in air. The thermal stability is far superior to previously reported Ni nanoparticle-Al₂O₃ selective solar thermal absorbers, which readily oxidize at 450 °C. The SiO_x (x < 2) and SiO₂ matrices are derived from hydrogen silsesquioxane and tetraethyl orthosilicate precursors, respectively, which comprise Si-O cage-like …

A Non-Destructive Method For Measuring The Mechanical Properties Of Ultrathin Films Prepared By Atomic Layer Deposition, Qinglin Zhang, Xingcheng Xiao, Yang-Tse Cheng, Mark W. Verbrugge

Chemical and Materials Engineering Faculty Publications

The mechanical properties of ultrathin films synthesized by atomic layer deposition (ALD) are critical for the liability of their coated devices. However, it has been a challenge to reliably measure critical properties of ALD films due to the influence from the substrate. In this work, we use the laser acoustic wave (LAW) technique, a non-destructive method, to measure the elastic properties of ultrathin Al₂O₃ films by ALD. The measured properties are consistent with previous work using other approaches. The LAW method can be easily applied to measure the mechanical properties of various ALD thin films for multiple …

A Low Temperature Nonlinear Optical Rotational Anisotropy Spectrometer For The Determination Of Crystallographic And Electronic Symmetries, Darius H. Torchinsky, Hao Chu, Tongfei Qi, Gang Cao, David Hsieh

Center for Advanced Materials Faculty Publications

Nonlinear optical generation from a crystalline material can reveal the symmetries of both its lattice structure and underlying ordered electronic phases and can therefore be exploited as a complementary technique to diffraction based scattering probes. Although this technique has been successfully used to study the lattice and magnetic structures of systems such as semiconductor surfaces, multiferroic crystals, magnetic thin films, and multilayers, challenging technical requirements have prevented its application to the plethora of complex electronic phases found in strongly correlated electron systems. These requirements include an ability to probe small bulk single crystals at the μm length scale, a need …

Transparent Conducting Oxides: A Δ-Doped Superlattice Approach, Valentino R. Cooper, Sung S. Ambrose Seo, Suyoun Lee, Jun Sung Kim, Woo Seok Choi, Satoshi Okamoto, Ho Nyung Lee

Physics and Astronomy Faculty Publications

Metallic states appearing at interfaces between dissimilar insulating oxides exhibit intriguing phenomena such as superconductivity and magnetism. Despite tremendous progress in understanding their origins, very little is known about how to control the conduction pathways and the distribution of charge carriers. Using optical spectroscopic measurements and density-functional theory (DFT) simulations, we examine the effect of SrTiO3 (STO) spacer layer thickness on the optical transparency and carrier distribution in La δ-doped STO superlattices. We experimentally observe that these metallic superlattices remain highly transparent to visible light; a direct consequence of the appropriately large gap between the O 2p and Ti 3d …

Correlation Between Microstructure And Thermionic Electron Emission From Os-Ru Thin Films On Dispenser Cathodes, Phillip D. Swartzentruber, Thomas John Balk, Michael P. Effgen

Chemical and Materials Engineering Faculty Publications

Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large {10-11} Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposed …

Biomechanical Properties Of Hemlocks: A Novel Approach To Evaluating Physical Barriers Of The Plant-Insect Interface And Resistance To A Phloem-Feeding Herbivore, Paul Ayayee, Fuqian Yang, Lynne K. Rieske

Entomology Faculty Publications

Micromechanical properties that help mediate herbivore access may be particularly important when considering herbivorous insects that feed with piercing-sucking stylets. We used microindentation to quantify the micromechanical properties of hemlock, Tsuga spp., to quantify the hardness of the feeding site of the invasive hemlock woolly adelgid, Adelges tsugae. We measured hardness of the hemlock leaf cushion, the stylet insertion point of the adelgid, across four seasons in a 1 y period for four hemlock species growing in a common garden, including eastern, western, mountain, and northern Japanese hemlocks. Leaf cushion hardness was highest in the fall and winter and …

Co2 Recycling Using Microalgae For The Production Of Fuels, Michael H. Wilson, John Groppo, Andrew Placido, S. Graham, S. A. Morton Iii, Eduardo Santillan-Jimenez, Aubrey Shea, Mark Crocker, Czarena Crofcheck, Rodney Andrews

Center for Applied Energy Research Faculty and Staff Publications

CO₂ capture and recycle using microalgae was demonstrated at a coal-fired power plant (Duke Energy’s East Bend Station, Kentucky). Using an in-house designed closed loop, vertical tube photobioreactor, Scenedesmus acutus was cultured using flue gas as the CO₂ source. Algae productivity of 39 g/(m² day) in June–July was achieved at significant scale (18,000 L), while average daily productivity slightly in excess of 10 g/(m² day) was demonstrated in the month of December. A protocol for low-cost algae harvesting and dewatering was developed, and the conversion of algal lipids—extracted from the harvested biomass—to diesel-range hydrocarbons via catalytic …

Porous Nanocomposites With Integrated Internal Domains: Application To Separation Membranes, Wenle Li, John Y. Walz

Chemical and Materials Engineering Faculty Publications

Asymmetric membranes with layered structure have made significant achievements due to their balanced properties and multi-functionalities that come from a combination of multiple layers. However, issues such as delamination and substructure resistance are generated by the intrinsic layered structure. Here, we present a strategy to integrate the traditional layered structure into an asymmetric but continuous porous network. Through infiltrations of microparticles and nanoparticles to targeted regions, active domains are created inside the porous scaffold versus having them applied externally. The fabricated internal active domains are highly adjustable in terms of its dimensions, pore size, and materials. We demonstrate that it …

Tunneling Into The Mott Insulator Sr2Iro4, John A. Nichols, Noah Bray-Ali, Armin Ansary, Gang Cao, Kwok-Wai Ng

Center for Advanced Materials Faculty Publications

We studied the single-layered iridate Sr₂IrO₄ with a scanning tunneling microscope. The finite low temperature conductance enables the electronic structure of this antiferromagnetic Mott insulator to be measured by tunneling spectroscopy. We imaged the topography of freshly cleaved surfaces and measured differential tunneling conductance at cryogenic temperatures. We found the Mott gap in the tunneling density of states to be 2Δ=615 meV. Within the Mott gap, additional shoulders are observed which are interpreted as inelastic loss features due to magnons.

Compounds And Methods For Reducing Oxidative Stress, Thomas Dziubla, J. Zach Hilt, Dipti Biswal, David B. Cochran, Paritosh Wattamwar

Chemical and Materials Engineering Faculty Patents

Antioxidant polymeric compounds are provided that comprise a plurality of monomeric portions, where each monomeric portion includes an antioxidant molecule interposed between at least two acrylate molecules, and where at least one acrylate molecule of each monomeric portion is linked by a diamine molecule to an acrylate molecule of an adjacent monomeric portion to thereby form the polymer. Methods of synthesizing polymeric compounds and methods of using the antioxidant polymeric compounds to reduce oxidative stress are also provided.

Development Of Cementitious Materials For Adhesion Type Applications Comprising Calcium Sulfoaluminate (Csa) Cement And Latex Polymer, Joshua V. Brien

Theses and Dissertations--Civil Engineering

The objective of this research was to develop high performing polymer modified calcium sulfoaluminate (CSA) cement materials for use in applications requiring superior adhesion characteristics. Little information is available describing interactions of CSA cement containing minor phase tri-calcium aluminate (C₃A) with commonly used admixtures. Given the scarcity of information, a basic approach for developing cementitious materials was followed. The basic approach consisted of four tasks: cement design, admixture design, polymer design and testing developed materials. The iterative, time consuming process is necessary for understanding the influence of specific constituent components on overall system behavior. Results from the cement …

Precise Control Of Carbon Nanotube Membrane Structure For Enzyme Mimetic Catalysis, Nicholas W. Linck

Theses and Dissertations--Chemical and Materials Engineering

The ability to fabricate a charge-driven water pump is a crucial step toward mimicking the catalytic ability of natural enzyme systems. The first step towards making this water pump a reality is the ability to make a carbon nanotube (CNT) membrane with uniform, 0.8 nm pore diameter. Proposed in this work is a method for synthesizing these carbon nanotubes via VPI-5 zeolite templated, transition metal catalyzed pyrolysis. Using a membrane composed of these CNTs, it is possible to get water molecules to flow single file at a high flow rate, and to orient them in such a way that would …

Shape Memory Behavior Of Single And Polycrystalline Nickel Rich Nickel Titanium Alloys, Irfan Kaya

Theses and Dissertations--Mechanical and Aerospace Engineering

NiTi is the most commonly used shape memory alloy (SMA) and has been widely used for bio-medical, electrical and mechanical applications. Nickel rich NiTi shape memory alloys are coming into prominence due to their distinct superelasticity and shape memory properties as compared to near equi-atomic NiTi shape memory alloys. Besides, their lower density and higher work output than steels makes these alloys an excellent candidate for aerospace and automotive industry. Shape memory properties and phase transformation behavior of high Ni-rich Ni₅₄Ti₄₆ (at.%) polycrystals and Ni-rich Ni₅₁Ti₄₉ (at.%) single-crystals are determined. Their properties are sensitive …

Precipitation, Orientation And Composition Effects On The Shape Memory Properties Of High Strength Nitihfpd Alloys, Emre Acar

Theses and Dissertations--Mechanical and Aerospace Engineering

NiTiHf high temperature shape memory alloys are attractive due to their high operating temperatures (>100 ^oC) and acceptable transformation strain compared to NiTi. However, NiTiHf has limitations due to their lack of ductility and low strength, resulting in poor shape memory properties. In this study, Pd has been added to NiTiHf alloys in an attempt to improve their shape memory behavior. A combined approach of quaternary alloying and precipitation strengthening was used.

The characterization of a Ni_45.3Ti_29.7Hf₂₀Pd₅ (at. %) polycrystalline alloy was performed in compression after selected aging treatments. Transmission electron …

Effects Of Sodium Hydroxide Pretreatment On Structural Components Of Biomass, Alicia A. Modenbach, Sue E. Nokes

Biosystems and Agricultural Engineering Faculty Publications

Pretreatment is a unit operation in the conversion of biomass to valuable products that utilizes various combinations of conditions, including chemicals, heat, pressure, and time, to reduce the recalcitrance of lignocellulose. Many such pretreatments have been developed over the years, as the operating conditions can be adapted so that lignocellulose is modified in ways unique to each pretreatment. By tailoring pretreatment conditions to achieve these modifications, the types of final products produced can be controlled. The purpose of this review is to provide a consolidated source of information for sodium hydroxide effects on lignocellulose. The structural characteristics of lignocellulose and …

Structure And Catalytic Properties Of Ultra-Small Ceria Nanoparticles, Xing Huang

Theses and Dissertations--Chemical and Materials Engineering

Cerium dioxide (ceria) is an excellent catalytic material due to its ability to both facilitate oxidation/reduction reactions as well as store/release oxygen as an oxygen buffer. The traditional approach to assess and improve ceria's catalytic behavior focuses on how efficiently O-vacancies can be generated and/or annihilated within the material, and how to extend established understandings of "bulk" ceria to further explain the greatly enhanced catalytic behavior of ultra-small ceria nanoparticles (uCNPs) with sizes less than 10 nm. Here, using density functional theory (DFT) calculations, we reexamine the atomic and electronic structures of uCNPs, especially their surface configurations. A unique picture …

Influence Of Ferrite Phase In Alite-Calcium Sulfoaluminate Cements, Tristana Y. Duvallet

Theses and Dissertations--Chemical and Materials Engineering

Since the energy crisis in 1970’s, research on low energy cements with low CO₂-emissions has been increasing. Numerous solutions have been investigated, and the goal of this original research is to create a viable hybrid cement with the components of both Ordinary Portland cement (OPC) and calcium sulfoaluminate cement (CSAC), by forming a material that contains both alite and calcium sulfoaluminate clinker phases. Furthermore, this research focuses on keeping the cost of this material reasonable by reducing aluminum requirements through its substitution with iron. The aim of this work would produce a cement that can use large amounts …

The Development And Biocompatibility Of Low Temperature Co-Fired Ceramic (Ltcc) For Microfluidic And Biosensor Applications, Jin Luo

Theses and Dissertations--Chemical and Materials Engineering

Low temperature co-fired ceramic (LTCC) electronic packaging materials are applied for their electrical and mechanical properties, high reliability, chemical stability and ease of fabrication. Three dimensional features can also be prepared allowing integration of microfluidic channels and cavities inside LTCC modules. Mechanical, optical, electrical, microfluidic functions have been realized in single LTCC modules. For these reasons LTCC is attractive for biomedical microfluidics and Lab-on-a-Chip systems. However, commercial LTCC systems, optimized for microelectrics applications, have unknown cytocompatibility, and are not compatible with common surface functionalization chemistries.

The first goal of this work is to develop biocompatible LTCC materials for biomedical applications. …