Materials Science and Engineering Commons^™

Modular Composite Sandwich Structures For Thermal And Structural Retrofitting Of Existing Buildings, Marc Al Ghazal

Masters Theses

Around 40% of global energy consumption and 30% of worldwide carbon dioxide (CO2) emissions are attributed to buildings. Most of this consumption is dedicated to ensuring thermal comfort. The goal of this research was to develop and field validate retrofit solutions to improve the energy efficiency of buildings. Exterior cladding panels were designed and tested to ensure adequate thermal and structural performance. Sandwich panels (glass fibers reinforced polymer (GFRP) skins and polymeric foam cores) were fabricated using the vacuum assisted resin transfer molding (VARTM) process. Extruded polystyrene (XPS) and polyurethane (PU) foams were compared as core materials through a series …

Evaluation Of Biomass As Bio-Additive In 3d Printing, Shuyang Zhang

Doctoral Dissertations

The petrol-based polymer has been widely applied in current daily life. The end-of-life of polymeric products has drawn environmental concerns. One of the solutions to such issues is to use bio-renewable materials to replace or reduce the use of petrol-based materials. Lignocellulosic materials are one of the potential candidates. Along with the features of 3D printing and the unique properties of biomass, 3D-printed biomass-based materials could be promising in preparing sustainable alternatives.

In this dissertation, lignin and other biomass were applied to various 3D printing techniques for sustainable composites. Stereolithography (SLA) was first used, and the kraft softwood lignin was …

Comparative Analysis On Low Cost Continuous Carbon Fiber Polypropylene Composite Using Compression Molding And Automated Tape Placement, Benjamin U. Schwartz

Masters Theses

Carbon fiber reinforced plastics (CFRP) are widely used throughout the aerospace industry where a weight reduction remains the highest priority with less emphasis on cost. Textile grade carbon fiber (TCF) and other low cost carbon fiber (LCCF) alternatives have recently emerged for use in the automotive market where emissions regulations have pushed automotive manufacturers and research institutions to look for cost effective light weight materials. Fiber reinforced thermoplastics provide an effective solution that align with automotive design including low cost, high processing rates, high impact toughness, unlimited shelf life, and recyclability.

TCF and Zoltek_PX35 fibers are two LCCF aimed at …

Optimized 3d-Printing Of Carbon Fiber-Reinforced Polyether-Ether-Ketone (Cfr-Peek) For Use In Overmolded Lattice Composite, Ryan C. Ogle

Masters Theses

Current orthopedic implants are overwhelmingly composed from metallic materials. These implants show superior mechanical properties, but this can additionally result in stress shielding due to a modulus mismatch between the bone tissue and implanted device. Polymeric implants reduce this stress shielding effect but have much lower mechanical properties, limiting their use. Polylactic acid (PLA) is a widely used biodegradable thermoplastic polymer, however, its use has been limited by the polymer’s mechanical properties and rapid loss of strength during degradation in vivo. Polyether-ether-ketone (PEEK) is another common biocompatible polymer , with chemical and mechanical properties which make it a popular alternative …

Functional Bottlebrush Polymer Additives For Thin Films And Coatings, Travis S. Laws

Doctoral Dissertations

Bottlebrush polymers are a class of highly branched polymers consisting of polymeric side chains that are densely grafted to a linear backbone. Their highly branched architecture results in surface enrichment across a broad range of materials. The goal of my research has been centered around the design of functional bottlebrush polymers and their use as surface active additives in blend films and coatings.

In the first chapter, we examine the segregation behavior of polystyrene bottlebrushes that are blended with linear polystyrene. We systematically vary the lengths of the bottlebrush backbone (Nb), side-chain (Nsc), and the linear matrix (Nm) in order …

How Dynamic Bond Results In The Unique Viscoelastic Behavior Of The Associating Polymers, Sirui Ge

Doctoral Dissertations

Associating polymer is a special kind of polymer possessing transient reversible bonds in addition to the conventional covalent bonds. The reversible bonds provide unique dynamics and fascinating viscoelastic properties, resulting in attractive applications for these polymers, such as self-healing and shape memory materials. Despite many years of studies, the understanding of dynamics of polymers with reversible bonds, especially on molecular level, is still in the rudimentary stage, preventing the rational design of the potential novel functional materials based on associating polymers. In this dissertation, we provide a detailed and quantitative understanding of the dynamics and viscoelastic properties of associating polymers. …

Brain Inspired Organic Electronic Devices And Systems For Adaptive Signal Processing, Memory, And Learning., Subhadeep Koner

Doctoral Dissertations

A new class of electronic device has emerged which bear the potential for low powered brain like adaptive signal processing, memory, and learning. It is a non-linear resistor with memory coined as memristor. A memristor is a two-terminal electrical device which simultaneously changes its resistance (processing information) and store the resistance state pertaining to the applied power (memory). Therefore, it can collocate memory and processing much like our brain synapse which can save time and energy for information processing. Leveraging stored memory, it can thereby help future engineered systems to learn autonomously from past experiences. There has been a growing …

Polynorbornenes For Advanced Applications And Processes, Xinyi Wang

Doctoral Dissertations

Polynorbornenes have dramatically different properties and various applications depending on their chemical structures. The modular nature of norbornene-based systems provides a facile route toward synthesizing diverse polymeric materials, thus making them ideal materials for systematic structure-property investigations. Herein, their application as gas separation membranes and the correlation between their gas-transport properties and polymer structures will be investigated. Though many valuable correlations between gas-permeability and polynorbornene structure have been studied previously, many of these efforts have focused heavily on designing materials with various chemical structures to achieve high permeabilities. In contrast, the influence of molecular structure on: a) polynorbornene chain packing …

Cmos Compatible Carbonization Of Polymer For Elctrochemical Sensors, Mohammad Aminul Haque

Doctoral Dissertations

Carbon-based electrodes that are integrable with CMOS readout electrodes possess great potential in a wide range of cutting-edge applications. The primary scientific contribution is the development of a processing sequence which can be implemented on CMOS chips to fabricate pyrolyzed carbon microelectrodes from 3D printed polymer microstructures to develop lab-on-CMOS monolithic electrochemical sensor systems. Specifically, optimized processing conditions to convert 3D printed polymer micro- and nano-structures to carbonized electrodes have been explored in order to obtain sensing electrodes for lab-on- CMOS electrochemical systems. Processing conditions have been identified, including a sequel of oxidative and inert atmosphere anneals to form pyrolyzed …

Oligodimethylsiloxanes With Charged Chain Ends: Synthesis, Characterization, And Properties, Tianyu Li

Doctoral Dissertations

Charged polymers have been intensively studied because of their scientific and industrial importance. In certain cases, a single charged group in the chain end can alter the structure and properties of a polymer dramatically. On the other hand, oligomers, which are different from both discrete small molecules and higher molecular weight polymers, have become an emergent class of materials. There are several charged chain-end functionalized oligomers reported, but this area has been largely unexplored. The work described in this dissertation is aimed at using well-characterized end-group functionalized oligodimethylsiloxane (oDMS) as model materials to understand the effects of charged end groups …

Chiral Mesogen-Free Liquid Crystalline Polyethers With Sulfonylated Side Chains And Patchy Brush Nanoparticles, Caleb A. Bohannon

Doctoral Dissertations

Ferroelectric liquid crystalline polymers (LCPs) hold promise for various applications driven by low electric fields, e.g., electrocaloric materials, because of the higher molecular motion in the liquid crystalline (LC) state. However, traditional chiral smectic C (SmC*) LCPs exhibit small spontaneous polarizations due to the bulky aromatic mesogens and weak polar groups. This dissertation research is focused on the design of mesogen-free sulfonylated LCPs with a goal of seeking the ferroelectric SmC* phase. Such LCPs are expected to exhibit high polarizations owing to the sulfonyl’s large dipole moment. A series of poly(oxypropylene)s (POPs), with chirality being introduced into either the backbone …

Chemistry And Functionality Of Plant Waxes: Applications Toward Postharvest Coatings, Francisco Miguel Angel Leyva Gutierrez

Doctoral Dissertations

The cuticle of all higher-plants is covered in lipidic layers of amorphous and crystalline waxes. The chemical composition and structure of cuticular waxes impart numerous functional properties to the surfaces of plants. Moreover, plant waxes are valuable industrial products with myriad applications; the postharvest coating of agricultural commodities for preservation serves as a salient example. There is an unfulfilled need in the agricultural sector for alternative wax materials to reduce reliance on imported waxes of botanical origin. Plant waxes are inherently complex mixtures composed of n-alkanes, as well as aliphatic alcohols, aldehydes, fatty acids, ketones, esters, and derivatives thereof. …

Processing Of Preceramic Polymers For Direct-Ink Writing, James W. Kemp

Doctoral Dissertations

Preceramic polymers are organosilicon polymers that, when pyrolyzed to above 1000°C, convert from a polymer to an amorphous ceramic. These polymers have been used for fiber spinning, polymer infiltration, and casting of materials but have recently gained interest for use as the feedstock material for additive manufacturing techniques. This work explores preceramic polymers being used for direct-ink writing (an additive manufacturing method) and many of the issues that occur with the polymers during curing and pyrolysis.

The first chapter of this dissertation provides a review of preceramic polymers, while the second and third chapters focus on the development of inks …

Structural Stability Of Thermosets During Material Extrusion Additive Manufacturing, Stian K. Romberg

Doctoral Dissertations

Over the past decade, the scale of polymer additive manufacturing has been revolutionized with machines that print massive thermoplastic parts with greater geometric complexity than can be achieved by traditional manufacturing methods. However, the heat required to print thermoplastics consumes energy and induces thermal gradients that can reduce manufacturing flexibility and final mechanical properties. With the ability to be extruded at room temperature and excellent compatibility with fibers and fillers, thermoset resins show promise to decrease the energy consumption, expand the manufacturing flexibility, and broaden the material palette offered by large-scale polymer additive manufacturing. However, structural instability in the uncured …

Interfaces And Dynamics In Polymeric 3d Printing And Crystalline Polymer Blends, Stevenson C. Perryman

Doctoral Dissertations

This dissertation presents experimental work that provide a foundation to rationally improve fused filament fabrication (FFF) and immiscible blend compatibilization. Objects generated from additive manufacturing processes, such as FFF, have intrinsic structural weaknesses which include two project specific examples: structural anisotropy and irreversible thermal strain. Due to low adhesion between individual print layers that results in macroscopic defects, the mechanical strength of printed objects when force is applied perpendicular to the build orientation is drastically reduced. In the first dissertation chapter, we present a protocol to produce interlayer covalent bonds by depositing multi-amine additives between individual layers of a print …

Interfacial Bonding Between Thermoset And Thermoplastic Polyurethane Reinforced Textile Grade Carbon Fiber: Structure Property Relationships, Surbhi Subhash Kore

Doctoral Dissertations

The research work focused on examining the interfacial adhesion of unsized, epoxy, and urethane-sized textile grade carbon fiber (TCF) reinforced in different classes of polyurethane (PU) thermoplastic (TPU) and thermoset (TSU) polyurethane (PU) through the structure-property relationship. The Carbon Fiber Technology Facility (CFTF) at Oak Ridge National Laboratory (ORNL) has produced TCF to reduce the cost of commercial-grade carbon fiber. The first part of the research examined the fundamental relationships between (a) soft segment thermoplastic polyurethane (S-TPU), (b) hard segment thermoplastic polyurethane (H-TPU), (c) thermoset polyurethane (TSU) and TCF reinforcement’s molecular behavior at the interface using the surface and thermal …

Characterization Techniques And Cation Exchange Membrane For Non-Aqueous Redox Flow Battery, Kun Lou

Doctoral Dissertations

The motivation of this work comes from one of the major problems of emerging non-aqueous flow battery (NAFB) that a separator or membrane which facilitates conductivity and blocks redox species crossover does not exist. Although many aspects of principles can be mirrored from mature fuel cell and aqueous flow battery, it is found that some well-defined membrane properties in aqueous systems such as swelling, transport and interactions are different in non-aqueous solvents to some extent. However, the approach of this work does follow the way perfluorosulfonate ion exchange membrane (PFSA) facilitated development of fuel cell and aqueous flow battery in …

3d Printing Of Hybrid Architectures Via Core-Shell Material Extrusion Additive Manufacturing, Robert Cody Pack

Doctoral Dissertations

Biological materials often employ hybrid architectures, such as the core-shell motif present in porcupine quills and plant stems, to achieve unique properties and performance. Drawing inspiration from these natural materials, a new method to fabricate lightweight and stiff core-shell architected filaments is reported. Specifically, a core-shell printhead conducive to printing highly loaded fiber-filled inks, as well as a new low-density syntactic foam ink, are utilized to 3D-print core-shell architectures consisting of a syntactic epoxy foam core surrounded by a stiff carbon fiber-reinforced epoxy composite shell. Effective printing of test specimens and structures with controlled geometry, composition, and architecture is demonstrated …

Spin Effects Of Excited States In Organic Semiconductors And Hybrid Perovskites For Optoelectronics And Spintronics, Miaosheng Wang

Doctoral Dissertations

Organic semiconductors and organic-inorganic hybrid perovskites have demonstrated versatile functionalities for optoelectronic and spintronic applications. Research in this dissertation focuses on the spin effects of excited states in emerging organic semiconductor and hybrid perovskite systems to understand the fundamental working principle. The investigation on the spin effects in excited states can provide insightful guidance for the development of the next-generation organic and hybrid perovskite optoelectronics and spintronics.

In organic semiconductors, the excited states, namely, excitons can be characterized by the total spin angular momentum S=S_e+S_h of the constituent electron and hole, which determines the …

Stretching The Applications Of Biomass: Development Of Lignin Based Thermoplastic Elastomers And Composite Materials, Anthony Stephen Bova

Doctoral Dissertations

Bio-based plastics and composites have seen increased industry adoption in recent years due to growing demand for materials with a low carbon footprint. The use of lignin as a feedstock for polymers has seen growing interest as the concept of an integrated cellulosic biorefinery gains traction and advances the need to use all components of separated biomass for value-added applications. Historically, use of lignin in thermoplastic and elastomeric copolymers and blends has been bottlenecked by the inability to introduce lignin content above 30 weight percent due to difficulties with interfacial adhesion of lignin with other soft segments. Efforts to overcome …

Engineered Carbon Materials With Nano-Graphitic Domains Derived From Lignin, Valerie Garcia Negron

Doctoral Dissertations

This work focuses on establishing a comprehensive understanding of lignin-derived materials as a function of carbonization with the goal of identifying processing-structure-property-performance relationships. A combination of modeling, statistical, and empirical materials characterization techniques are applied to lignin materials varying in feedstock source, extraction method, and processing conditions. The first part of this study evaluates the structure of carbon composite materials, possessing both crystalline and amorphous domains, using scattering techniques. One approach performs atomistic simulations of a proposed structure, from which the analogous scattering pattern can be obtained for validation. An alternative approach based on a hierarchical decomposition of the radial …

Discontinuous Recycled And Repurposed Carbon Fiber Reinforced Thermoplastic Organosheet Composites, Philip R. Barnett

Doctoral Dissertations

There is a significant need for low cost, high volume composites in the automotive industry to aid in vehicle lightweighting and safety. The current state-of-the-art severely compromises the mechanical properties of composites to achieve cost and cycle time goals. In this dissertation, a novel composite format, termed discontinuous carbon fiber organosheets, using recycled and repurposed carbon fibers in a thermoplastic matrix is developed and studied. Unlike traditional composites, the long fiber length and rapid processing time yield mechanical properties and cycle times competitive with automotive metals.

Several studies were performed to characterize this new material format. First, samples were manufactured …

Processing-Structure-Performance Relationships In Fused Filament Fabricated Fiber Reinforced Abs For Material Qualification, William Howard Ferrell

Doctoral Dissertations

This dissertation uses the processing-structure-performance relationships to elucidate future needs in qualification of materials manufactured by fused filament fabrication and also introduces a previously unused testing method for the determination of fracture toughness in these materials. Fused filament fabrication (FFF) is an additive manufacturing technique that utilizes the layering of deposited molten plastic in two dimensional shapes to create three dimensional objects. This technique has gained traction over the past two decades as a disruptive manufacturing technology that promises many benefits. In order for FFF to truly be a staple in manufacturing spaces across the world for the production of …

Development Of High-Performing Polydimethylsiloxane-Based Membranes For Carbon Dioxide Separation, Tao Hong

Doctoral Dissertations

Membrane separation is highlighted as one of the most promising approaches to mitigate the excessive CO₂ [carbon dioxide] emission, due to its significant reduction of energy cost compared with many conventional separation techniques. Unfortunately, the separation performance of current membranes does not meet the practical CO₂/N₂ [nitrogen] separation requirements. And due to the huge volume of industrial flue gas, membranes with exceptionally high permeability are needed for practical reasons.

Currently, the separation mechanism of most polymeric membranes is based on size-sieving. However, this method is not sufficient for CO₂/N₂ separations due to the …

Modulation Of Cell Behaviors On Photo-Crosslinked Polymer Networks And Polymer Spherulites, Jinbo Dou

Doctoral Dissertations

This dissertation presents novel biodegradable and photo-crosslinkable poly(-caprolactone) acrylates (PCLAs) to achieve polymer networks with controllable surface chemistry, stiffness, and topographical features, as well as crystallization-induced PCL, poly(3-hydroxybutyrate) (PHB) and poly(L-lactic acid) (PLLA) surfaces for investigating cell-material interactions. Chapter I reviews the recent progress of injectable polymeric biomaterials in the last decade for various tissue engineering applications. Chapter II investigates the variation of thermal and mechanical properties of PCL triacrylate (PCLTA) networks with different crosslinking time, and further studies the smooth muscle cell (SMC) responses to these networks. Chapter III studies the SMC responses to hydrolyzed PCLTA/methoxyl polyethylene glycol monoacrylate …

Effect Of Crosslinking On Carbon Nanotube Materials Through Chemical Treatment And Irradiation, Xinyi Lu

Doctoral Dissertations

Carbon nanotubes (CNTs) exhibit a variety of exceptional properties, especially their ultrahigh tensile strength on the order of 100GPa show promise for constituting the next-generation carbon fiber. However, challenges remain to translate these properties into useful technology, primarily due to the sliding of the tubes past one another under tensile loading. The work presented in this dissertation is focused on enhancing the interaction between the CNTs and their bundles in a macro-assembly, in order to improve the tensile properties of the material.

Applying inter-tube crosslinks has been predicted to significantly enhance the stress transfer between the CNT components. We developed …

Renewable And Abundant Battery Components, Jordan T. Sutton, Daniel San Roman, Austin Thomas, Daniel Kitsmiller, Alec Affolter

Chancellor’s Honors Program Projects

No abstract provided.

All Acrylic Based Thermoplastic Elastomers: Design And Synthesis For Improved Mechanical Performance, Wei Lu

Doctoral Dissertations

Thermoplastic elastomers (TPEs) have been widely studied because of their recyclability, good processability, low production cost and distinct performance. Compared to the widely-used styrenic TPEs, acrylate based TPEs have potential advantages including exceptional chemical, heat, oxygen and UV resistance, optical transparence, and oil resistance. However, their high entanglement molecular weight lead to “disappointing” mechanical performance as compared to styrenic TPEs. The work described in this dissertation is aimed at employing various approaches to develop the all acrylic based thermoplastic elastomers with improved mechanical performance.

The first part of this work focuses on the introduction of acrylic polymers with high glass …

End-Capping Star-Like Polycaprolactone With Different Functional Groups And The Interaction With Smooth Muscle Cells, Qingya Zeng

Masters Theses

Polycaprolactone (PCL) is a PDA-approved biodegradable polymer with excellent biocompatibility and flexibility. My work has been designed to find out how different functional end groups in star-like PCL samples affect the surface properties (such as hydrophilicity, morphology) and bulk properties (such as thermal, mechanical, rheological properties, and crystallization), and consequently the behavior and functions of primary rat aortic smooth muscle cells (SMCs).

I focused on the synthesis of PCL with different functional groups and their characterizations. In chapter 2, PCL samples with four or six hydroxyl end groups were synthesized with different molecular weights ranging from 8,000 to 30,000 g/mol …

Structure And Properties Of Cnt Yarns And Cnt/Cnf Reinforced Pan-Based Carbon Fibers, Nitilaksha Phalaxayya Hiremath

Doctoral Dissertations

There is continuing effort to enhance the strength and modulus of carbon fibers by various combinations of materials and processing. Carbon fibers are produced from various precursors, and the strength of the CFs are directly related to the type of precursor used to make them. Carbon Nanotubes (CNTs) have received a great deal of attention due to their unique structure and properties. Major focus of this research is on the evaluation of processing, structure and properties of CNT based yarns and composite fibers.

High strength and low cost carbon fibers (CFs) are needed for today’s applicatio ns. A low cost …