Materials Chemistry Commons^™

Exploring The Effects Of Polymer-Graphene Interactions On Bulk Composite Properties Using Finite Element Analysis, Bryant Grove

Dissertations

As a filler in high performance materials, graphene significantly enhances the mechanical properties of polymer composites. Experimental characterization of graphene composite enhancements is limited by labor-intensive processes in both synthesizing composites for different purposes and in characterizing the interactions between graphene and polymer composites that lead to these enhancements. Computational approaches such as finite element analysis (FEA) are suitable alternatives that go beyond experimental analysis. This dissertation demonstrates the utility of FEA in analyzing polymer graphene composites with an emphasis on modeling the interaction between graphene fillers and the matrix within the interphase formed between them. The accessible design framework …

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 …

The Effects Of Free Volume And Processing On The Development Of Gas Separation Membranes, Jacob Schekman

Dissertations

Structure, thermal, mechanical, gas transport, and free volume properties of thiol-ene based systems are investigated and discussed. In the pursuit of generating low energy-cost polymer membranes for gas separation, it became apparent that UV-curing of thiol-ene materials presented several routes toward achieving this goal. Network structure plays a vital role in determining the gas transport properties of membrane materials. UV photopolymerization techniques provide a means to rapidly vitrify network morphologies which can be tuned depending on choice of monomer. Thiol-ene monomers offer a broad range of precursor materials from which to choose for the design of functional membrane materials.

Chapter …

Development Of Graphene And Graphene Derivative Advanced Functional Additives: Mechanism And Application In Asphalt Formulations And Thermal Interface Management Materials, Dana Pinson

Dissertations

The overarching focus of my research is the use of graphene and graphene derivatives to enhance polymer properties. My first focus area was the prevention of oxidative degradation of asphalt through the incorporation of a graphene oxide (GO) -based nanoparticle filler to enhance oxygen barrier properties. Primary amine terminated polyisobutylene was synthesized via cationic polymerization followed by post polymerization chain end modification in a range of molecular weights and covalently grafted via the primary amine to graphene oxide aerogel (aGO) to create a polyisobutylene grafted graphene oxide (PIB-g-GO) nanoparticle. PIB-g-GO was then mixed into a substitute asphalt matrix at various …

Magnetic Interactions In Open-Shell Conjugated Polymers, Michael Steelman

Dissertations

Most materials are closed shell in which every electron participates in a bond, resulting in unremarkable magnetometry signatures and functionalities. While rare, modern technologies rely on magnetic materials in which unpaired electrons are localized to inorganic atomic centers. In recent decades, a collection of organic open-shell π-conjugated molecules have shown magnetic ordering, albeit at exceedingly low temperatures; a result of weak noncovalent intermolecular interactions limiting long range electronic exchange. Thus, practically applicable sp orbital magnetism that persists at or above room temperature remains a grand challenge for chemistry and physics. Despite the wide variety of chemical structures afforded by organic …

Designing Dynamic And Degradable Polymeric Materials With Thiol-X Chemistries, Reese Sloan

Dissertations

With plastic production poised to increase in coming years, there arises a need to develop new polymeric materials designed to combat the global pollution crisis. A commonly utilized approach in addressing this challenge is to employ a responsive functional moiety into the polymer architecture. Thiol-X reactions, a commonly utilized class of “click” reactions, have garnered broad implementation in new stimuli-responsive materials. This work specifically focuses on utilizing radical-mediated thiol-ene coupling and base-catalyzed thiol-isocyanate reactions to develop a library of ternary thiol-ene/thiourethane covalent adaptable networks (CANs) and hydrolytically labile poly(thioether ketal) thermoplastics. CANs are a class of network materials capable of …

Controlling Degradation With Force And Light, Brad Davis

Dissertations

Stimuli-responsive polymers respond to changes in their environment by altering their physical and chemical properties. Their responsiveness allows them to be used as sensors, mechanical actuators, delivery systems, and can yield either elongated lifetimes through healing mechanisms or shortened lifetimes through triggered degradation. Still a growing field in polymer science, researchers seek to expand the capabilities of these materials by improving their specificity, range, and mechanisms of both the stimuli and the response. The work presented explores stimuli-responsive materials, focusing on mechanical and light stimuli, and how to gain control of the response by specific changes in the polymeric material. …

Doping Of Conjugated Polymers: Preparation, Characterization And Device Fabrication, Kan Tang

Dissertations

Semiconducting conjugated polymers (CPs) as emerging materials for advanced electronic applications such as sensors, OPVs, and OEFTs has become an intriguing research topic in the past decades. It opens a new avenue of “flexible” electronics, which has shown great potential in next-generation electronic devices.

However, due to the nature of CP materials and related solution processing techniques, unlike almost perfectly crystalline silicon materials, CPs in the solid-state often exhibit much lower crystallinity if it is not complete amorphous, which severely hinder the electronic property and optical property of the materials. The crystallinity of CPs in a film is often uniquely …

Synthesis And Self-Assembly Of Amphiphilic Block Copolymers For The Fabrication Of Non-Spherical Polymersomes, Tamuka Chidanguro

Dissertations

Polymersomes, also known as polymer vesicles, have gained a lot of interest over the past two decades. These hollow spherical systems are made via the self-assembly of amphiphilic block copolymers and have found use in a range of areas from drug delivery, to cellular models, to nanoreactors. Their hollow nature allows them to carry hydrophilic cargo in their inner compartment and hydrophobic cargo in their membrane. Over the last decade, increasing efforts have focused on controlling the morphology of polymersomes. Research has shown that polymersome morphology plays an important role for instance in drug delivery, where tubular or rod-like vesicles …

Data-Driven Approaches To Complex Materials: Applications To Amorphous Solids, Dil Kumar Limbu

Dissertations

While conventional approaches to materials modeling made significant contributions and advanced our understanding of materials properties in the past decades, these approaches often cannot be applied to disordered materials (e.g., glasses) for which accurate total-energy functionals or forces are either not available or it is infeasible to employ due to computational complexities associated with modeling disordered solids in the absence of translational symmetry. In this dissertation, a number of information-driven probabilistic methods were developed for the structural determination of a range of materials including disordered solids to transition metal clusters. The ground-state structures of transition-metal clusters of iron, nickel, and …

Atomic Oxygen Resistant Low Earth Orbit Stable Polymer Matrix Composites Employing Phenylphosphine Oxide Epoxy-Amines, Witold Fuchs

Dissertations

Atomic oxygen (AO) attacks polymer matrix composites (PMC’s) on the surfaces of spacecraft in low earth orbit (LEO) and threatens safe spacecraft operation and service life. Incorporating phenylphosphine oxide (PPO) groups into polymer chains offers a self-regenerating method of protection from AO but remains poorly understood. Herein, epoxies containing PPO groups were synthesized with increasing concentrations of phosphorus [P] from 0 to 8 wt % to investigate their AO resistance. Measurements confirmed the exposure of these materials to AO produces a passivation phosphate (POx) layer on the surface of the sample and the efficacy of the resultant layer was directly …

Engineering Donor-Acceptor Conjugated Polymers For High-Performance And Fast-Response Organic Electrochemical Transistors, Hanyu Jia, Zhen Huang, Peiyun Li, Song Zhang, Yunfei Wang, Jie Yu Wang, Xiaodan Gu, Ting Lei

Faculty Publications

To date, high-performance organic electrochemical transistors (OECTs) have mostly been based on polythiophene systems. Donor–acceptor (D–A) conjugated polymers are expected to be promising materials for OECTs owing to their high mobility and comparatively low crystallinity (good for ion diffusion). However, the OECT performance of D–A polymers lags far behind that of the polythiophenes. Here we synergistically engineered the backbone and side chain of a series of diketopyrrolopyrrole (DPP)-based D–A polymers and found that redox potential, molecular weight, solution processability, and film microstructures all have a severe impact on their performance. After systematic engineering, P(bgDPP-MeOT2) exhibited the best figure-of-merit (μC …

Practical Adhesion Measurements In Organic Coatings; Advancing Understanding And Mechanical Methods Development, Diana Gottschalk

Dissertations

“Adhesion” can be considered either a mechanical or chemical phenomenon. The mechanical interpretation describes the difficulty of separating surfaces and is useful for quantifying performance within applications that depend on bulk and interfacial properties. Chemical adhesion describes interfacial resistance to chemical attack and does not depend on bulk properties. Predicting chemical failure through mechanical measurement is confounded by the influence of bulk properties. However, the prospect is attractive because of the robust tolerance for sample geometries, allowing experiments to resemble an end-use system. The present work's primary goal was to elevate mechanical methods to provide a detailed interfacial characterization of …

An Atomistic Study Of The Effects On Mechanical Properties And Bonding Interactions Of Carbon Nanofillers In Nylon 6 Nanocomposites, Michael Roth

Dissertations

Polymers have potential for a wide range of applications. The effectiveness of polymers can be further enhanced through the addition of nanofillers that improve thermal, mechanical, and electrical properties of the polymer. Carbon based nanofillers such as carbon nanotube (CNT), graphene, and carbon nanofibre (CNF) are of particular interest due to their high properties and high aspect ratios. However, limited understanding of the governing interactions of these nanofillers with polymers limits the effectiveness of the final nanocomposite.

The first facet of this dissertation focuses on determining the dominating interactions between pristine CNT and graphene with nylon 6 monomer and the …

Engineering Multifunctional And Morphologically Diverse Polymer Brush Surfaces, Cassandra M. Reese

Dissertations

The combination of surface-initiated polymerization (SIP) and post-polymerization (PPM) serves as a powerful approach to fabricate complex, multifunctional polymer films, which can be precisely tuned for desired surface engineering applications. Careful manipulation of PPM parameters such as reaction conditions, the tethered brush parameters, and the physical properties of the unbound post-modifier greatly influence the depth of penetration of the post-modifier and the polymer brush compositional heterogeneity. This dissertation focuses on engineering polymer brush surfaces with multifunctional chemistries and tunable morphologies by investigating the PPM parameters that dictate the distribution of post-modifiers on grafted polymer brush surfaces.

The first chapter of …

Thermosetting Polymers Via Azide Alkyne Cycloaddition, Richard H. Cooke Iii

Dissertations

This dissertation exploits properties inherent to azide-alkyne cycloaddition and applies practical solutions to difficult problems. Chapter II addresses structure-property relationships in glassy azido-alkyne matrices by varying the identity of the central linkage within tetrapropargyl bis-aniline-type crosslinkers, and by the addition or omission of Cu(I) catalyst. This systematic study showed that an ether or methylene linkage yielded lower melting tetrapropargyl crosslinkers that were soluble in, and produced homogeneous, networks when cured with, a standard azido resin, di(3-azido-2-hydroxypropyl) ether of bisphenol-A; in contrast, a sulfone linkage yielded a relatively insoluble crosslinker and poorly dispersed, heterogeneous networks when reacted with the same …

Photoelectrochemical Studies On Non-Noble Metal Based Catalysts Towards Tandem Solar Water Splitting, Arun Siddarth Sridhar

Dissertations

Photoelectrochemical (PEC) water splitting makes direct use of solar energy incident on semiconductor photoelectrodes, and it is a convenient, economic option to produce high purity hydrogen at low temperatures. The use of multiple light absorbers can increase overall solar energy utilization and provide a solution to the trade-off between overall band gap and band edge positioning of photoelectrodes specific to solar water oxidation and water reduction. The study of non-noble metal based catalysts for hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) are essential for economic practical commercialization of photo-electrolyzers. This dissertation focuses on the use of a variety …

Understanding The Coating-Substrate Interface Changes And Degradation Caused By Environmental Acclimation With Water And Electrolytes, Russell Vick

Honors Theses

While it is well known that polymeric coatings are used to protect metals from corrosion, efficient and reliable protocols for quantifying and estimating protective coatings’ lifetimes have yet to match real-time results in rate or in detected mechanisms of material failure. Alkoxysilane pretreatments are widely utilized for substrate preparation and improved coating system performance by changing the metal substrate surface morphology to improve adhesion at the coating-substrate interface by creating a foundation and excluding water from the system. Three pretreatments used were 3-aminopropyltriethoxy silane (APS), tetraethylortho silicate (TEOS), N-[3-(trimethoxysilyl)propyl]ethylenediamine (DAS). They were investigated to improve the understanding of the relationships …

Polymer Nanocomposites Containing High Aspect Ratio Particulates: Innovation In Co-Extruded Multilayer Barrier Films, Kevin Meyers

Dissertations

Delaminated montmorillonite (MMT) clay/ maleic anhydride grafted LLDPE nanocomposite multilayer films with alternating layers of LDPE were produced through multilayer co-extrusion. The MMT concentration within the nanocomposite layers was increased through annealing the films in the melt due to a mismatch in interdiffusion rates of the polymer layers. Analysis of the nanocomposite layers upon annealing revealed that the platelets impinged upon one another resulting in significant improvement in oxygen barrier in the multilayer system, exceeding the results of bulk nanocomposites.

Model analysis demonstrated that increasing the nanoplatelet aspect ratio or initial concentration in the filled layers would lead to even …

Barrier Properties Of Polymer Nanocomposites With Graphene Oxide And Its Derivatives: Mechanism And Applications In Anticorrosive Coatings, Yidan Guan

Dissertations

Metallic devices made from steel or aluminum are subjected to deterioration by environmental contaminants over time. As one of the corrosion control methods, organic coatings show many advantages due to their low cost, versatility, decoration aesthetics and effective protections. Corrosion protection theories and failure modes of organic coatings are still not fully understood due to complicated interactions in the coating-metal-environment system, however, it is widely agreed that the barrier nature of polymeric materials towards aggressive species, such as oxygen, water, electrolyte, plays a key role. Improved barrier property of polymer nanocomposites (PNCs) with two-dimensional (2D) carbon filler, graphene and graphene …

Cellulose Reinforced Thermoplastic Composites By In-Situ Ring-Opening Polymerization, Shahab Kashani Rahimi

Dissertations

Over the past two decades, the increasing concern about the negative environmental impacts of synthetic materials has led to rising interests in utilizing renewable natural resources to develop polymer materials with comparable properties and performance to their synthetic counterparts. One of the major fields of interest is polymer composites where the replacement of synthetic fibers with bio renewable natural fibers is of great potential. However, the processing difficulties, in terms of fiber dispersion and thermal stability have limited the application of cellulosic fibers to polymers with low processing temperatures which are mostly hydrophobic polymers. As a result, the true reinforcing …

Anodic Nanocatalysts For Formic Acid Fuel Cells: An Electrochemical Study, Tamanna F. Shanta Mcfarland

Dissertations

Direct formic acid fuel cells (DFAFCs) have been reported as a prominent source of alternative green energy and solution to imminent energy crisis for the last two decades. The challenge to commercialize DFAFCs is primarily the utilization of cost effective, high performance and durable anodic catalyst for formic acid oxidation (FAO). Consequently, this dissertation addresses the extensive electrochemical study of a number of nanomaterials towards the potential use as electrocatalysts for FAO. Morphology and elemental analyses of the prepared nanomaterials were obtained using electron microscopy techniques.

After a general introduction and overall review of this dissertation (Chapter I), studies of …

Synthesis Of A Thermally Reversible Cross-Linked System Using Electrophilic Cleavage/Functionalization Of Poly(Isobutylene-Co-Isoprene), Savannah H. Steadman

Honors Theses

Multifunctional polyisobutylenes (PIBs) are of great academic and commercial interest. Current methods to create these materials currently utilize prohibitively expensive synthetic strategies. Recently, Storey et al. reported a novel method for the synthesis of multifunctional PIB which is more commercially viable than the current methods. For this research, the material produced via this technique was utilized to create a thermally reversible crosslinked system using Diels-Alder chemistry. To achieve this, a bromide-functional polyisobutylene obtained via electrophilic cleavage and functionalization of butyl rubber was split into two portions and further functionalized. The first portion of the bromide-functional PIB was reacted with furfuryl …

An Investigation Of The Use Of Cerium And Polyhedral Oligomeric Silsesquioxanes For The Protection Of Polymeric Epoxy Compounds In The Low Earth Orbit Environment, Jessica Miriam Piness

Dissertations

Low Earth orbit presents many hazards for composites including atomic oxygen, UV radiation, thermal cycling, micrometeoroids, and high energy protons. Atomic oxygen and vacuum ultraviolet radiation are of concern for space-bound polymeric materials as they degrade the polymers used as matrices for carbon fiber composites, which are used in satellites and space vehicles due to their high strength to weight ratios. Epoxy-amine thermosets comprise a common class of matrix due to processability and good thermal attributes. Polyhedral oligomeric silsesquioxanes (POSS) have shown the ability to reduce erosion in polyimides, polyurethanes, and other polymers when exposed to atomic oxygen. The POSS …

Influence Of Multiwall Carbon Nanotubes On Corrosion Performance And Water Hydrogen Bonding Of Epoxy-Amine Thin Films, Greg William Curtzwiler

Dissertations

This dissertation research sought to provide a fundamental basis of understanding to commence the systematic investigation of developing economically viable fully formulated epoxy-amine coating systems containing multiwall carbon nanotubes (MWCNT). Namely, a facile and rapid method for multiwall carbon nanotube surface modification and molecular structure interpretation was developed to assist in designing MWCNT-polymer interactions and achieving high levels of dispersion. Additionally, a rapid and quantitative method was developed to investigate the dispersibility potential of MWCNTs possessing a given surface modification in combination with a dispersion protocol which can further be utilized as a quality control metric in commercial applications. It …

Bioinspired Design Of Wetting And Anti-Wetting Surfaces Via Thiol-Ene Photopolymerization, Li Xiong

Dissertations

Surface wettability is known to have a profound influence in both academic study and industrial application of materials. Superhydrophobic surfaces, with a static contact angle higher than 150° and a contact angle hysteresis lower than 10°, have received continued attention for their broad applications, such as self-cleaning, antifogging and frosting, and drag reduction. The continuous development of materials and approaches that used to create superhydrophobic surfaces has led to further exploration of coatings with other desirable properties such as superamphiphobicity, mechanical robustness and thermal stability.

In this work, coatings with super wetting and super anti-wetting properties were designed and fabricated …

Effect Of Chain Rigidity On Network Architecture And Deformation Behavior Of Glassy Polymer Networks, Kyler Reser Knowles

Dissertations

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Electrogenerated Chemiluminescence Study Of Semiconductor Nanoparticles Towards Sensitive Detection Of Biomolecules, Yiliyasi Wusimanjiang

Dissertations

The main focus of this dissertation is to unfold the fundamental aspects of electrogenerated chemiluminescence (ECL) generation from semiconductor nanoparticles (also known as quantum dots or QDs) within different ECL systems. The ECL and photo-physical interactions between the CdTe QDs (λ_emission= ~760 nm) and the CdSe QDs (λ_emission= ~550 nm), as well as the effects of carbon nanotubes on ECL of QDs were separately investigated. Optimum experimental conditions for peptide bond formation on an electrode surface through EDC (1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide hydrochloride)/NHS (N-Hydroxysulfosuccinimide) coupling were also revealed using cyclic voltammetry technique. Based on the information …

Correlation Of Polymer Performance And Hansen Solubility Parameters, Daniel Jobse Mania

Master's Theses

Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it is a fast-growing product that not only is creating its own space, but is beginning to supplant existing technology.

The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC).

Polymer architecture was also determined to be extremely important, but …