Polymer Science Commons^™

Convergence Of High Throughput Experimentation And Machine Learning To Rapidly Advance Application-Specific Polymer Development, Mashrafee Aryan, Daniel Struble, Felix Campbell, Saroj Upreti, S. M.Ashik Abedin, Aahil Khambawla, Jeetain Mittal, Michael S. Dimitriyev, Emily B. Pentzer, Svetlana A. Sukhishvili, Xiaodan Gu, Boran Ma

Faculty Publications

Machine learning (ML) has heavily influenced the way scientific study is done with demonstrated successes in nearly every field. However, furthering performance and explainability of ML models in increasingly complex systems and with increasingly demanding outcomes requires a significant influx of high-quality data. To that end, this Review covers some of the techniques, instrumentation, and methodologies that have shown promise for significantly accelerating the discovery of polymer materials, optimization of their properties, and elucidation of property–application relationships through high throughput (HT) experimentation, characterization, and analysis. Attention is given to not only ML, but also to hardware advancements and their synergy …

Tuning The Morphology Of Triblock Copolymers Via Homopolymer Blending, John F. Searles

Honors Theses

Morphology plays an important role in the physical properties of block copolymer (BCP) materials. Depending on the type of morphology and chemical composition of the blocks, BCPs are used in applications ranging from soft biomaterials for biomedical devices to rigid materials for ballistics protection. Due to incompatibility between comonomers and required block weight ratios to achieve targeted morphologies, it is generally necessary to use complex, time-consuming, and expensive synthetic techniques to prepare BCPs. As a result, there is increased interest in the development of new processing methods to tailor block copolymer morphology without the need for additional synthesis. The morphological …

Enabling High-Rate Thermoplastic Composite Manufacturing Through Structure-Processing-Property Relationships Of Polyphenylene Sulfide, Lina Ghanbari

Dissertations

In this dissertation, relationships between polyphenylene sulfide (PPS) chain structure and melt processing parameters are linked to thermoplastic composite (TPC) properties and mechanical performance. Deviations from linear PPS structure and the formation of branching/crosslinked moieties upon exposure to TPC manufacturing steps presents an opportunity to systematically uncover the interdependencies of melt-state thermal history on polymer rheology, crystallization, crystal structure, and translate these properties to the continuum level. This work first explores unreinforced PPS and how the formation of non-linear chain architectures yield altered rheological states when held at melt processing temperatures. These hindered chains exhibit unconventional crystallization behavior and non-uniform …

Using Afm-Ir To Study Nanoscopic Phase Behavior Of Polymer Blends And Photovoltaic Bulk Heterojunctions, Nathaniel L. Prine

Dissertations

Conjugated polymers (CPs) and polymer blends harbor the potential for high-performance organic solar cells (OSCs) due to their short energy payback time, low cost, solution processability, lightweight attributes, and flexibility. However, OSCs suffer from poor thermal stability compared to their inorganic equivalents. This study explores the thermal instability of OSCs, focusing on phase separation of the photoactive layer under heat, resulting in morphology changes and degradation of power conversion efficiency (PCE). Utilizing atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) and differential scanning calorimetry (DSC), we delve into thermal stability-morphology relationships to devise strategies to improve OSC blend durability under thermal …

Towards High-Rate Thermoplastic Composites, Chris Croshaw

Dissertations

This dissertation attempts to identify and address the problems associated with high-rate thermoplastic composites. Herein, three primary research thrusts were investigated; the first two chapters focus on the melt-state degradation mechanism of PEKK copolymers and its role on downstream crystallization and thermomechanical properties, the third chapter examines the role of graphene nanoplatelets (GNP) on the crystallization and melting behavior of PEKK 70/30, and the final chapter focused on radio frequency and induction heating of PEKK nanocomposites.

The melt-state degradation mechanism was identified using a combination of x-ray photoelectron spectroscopy (XPS), molecular dynamics (MD), and quantum mechanics (QM) simulations. Melt-state degradation …

Machine Learning Prediction Of Glass Transition Temperature Of Conjugated Polymers From Chemical Structure, Amirhadi Alesadi, Zhiqiang Cao, Zhaofan Li, Song Zhang, Haoyu Zhao, Xiaodan Gu, Wenjie Xia

Faculty Publications

Predicting the glass transition temperature (T_g) is of critical importance as it governs the thermomechanical performance of conjugated polymers (CPs). Here, we report a predictive modeling framework to predict T_g of CPs through the integration of machine learning (ML), molecular dynamics (MD) simulations, and experiments. With 154 T_g data collected, an ML model is developed by taking simplified “geometry” of six chemical building blocks as molecular features, where side-chain fraction, isolated rings, fused rings, and bridged rings features are identified as the dominant ones for T_g. MD simulations further unravel the fundamental roles …

Receptor-Doped Organic Transistors: Transducing Anion Binding From Mixed Ionic-Electronic Transport, Anthony Benasco

Dissertations

Organic semiconductors based on π-conjugated polymers show remarkable properties such as high tolerance to structural defects, low processing temperature requirements, biocompatibility, ease of fabrication, and tunable properties. Conjugated polymers integrated into device arrays can exhibit collective properties sensitive to minor perturbations in the surrounding media. However, these devices rely on serendipitous sensitivity to the analyte of interest, and strategies for specific detection remain a considerable change. There remains a compelling, global need for technologies to monitor phosphate due to its prevalence in agricultural runoff, leading to fish kills and economic decline for commercial and recreational fisheries. The strong hydration energies …

Layered Epoxide-Amine/Boron Nitride/Graphene Nanocomposites For Enhanced Multifunctional Shielding, Alyssa J. Necaise

Honors Theses

The development of high-power electromagnetic wave sources in the modern era has the ability to interfere with aircraft electronics and cause localized heating – necessitating advanced materials for electromagnetic interference (EMI) and thermal shielding. Multifunctional nanoparticles dispersed within polymer matrices can combat these issues; however, the best way to combine thermally and electrically conductive species to maximize electromagnetic interference shielding and thermal shielding is undetermined. Multifunctional layered epoxide/amine nanocomposites were prepared from tetra and octafunctional epoxide monomers (TGDDM and SU-8), 4,4-DDS tetrafunctional amine curative, and 1 wt.% hexagonal boron nitride nanoplatelets and/or 1 wt.% graphene nanoplatelets to form monolayer and …

Development Of Upconverting Films Containing Singlet Sink, Blake Mckay

Honors Theses

Upconversion is the conversion of light from a longer wavelength to a shorter wavelength. This technique has a wide range of applications in solar technology, bioimaging, drug delivery, and many other fields.¹ In this study, a three-part upconverting system was developed including a component termed singlet sink in order to increase upconversion efficiency. The components of this system included Palladium (II) Octaethylporphrin (PdOEP), pyrenebutanol, and 9-phenyl-10-(p-tolylethynyl)-anthracene (PTEA). A procedure was developed in order to create and process films containing these three materials dispersed in a poly(methyl methacrylate) (PMMA) matrix. Upconversion was analyzed in both solution and the …

Investigating The Effect Of Polymer Hydrogels On The Antimicrobial Properties Of Activated Carbon Through The Utilization Of Bacterial, Viral, And Parasitic Microorganisms, Zoe Gunter

Honors Theses

Activated carbon (AC) has long been utilized in biomedical applications due to its innate antimicrobial characteristics. However, little is understood about the mechanism of action that allows AC to prohibit the propagation of different pathogen species. To further ascertain these characteristics and how they affect the propagation of pathogens, procedures were designed with bacterial, viral, and parasitic agents which were utilized in conjunction with varying concentrations of polymer hydrogels to examine the antimicrobial efficacy of AC. The studies performed for this thesis were conducted employing coconut-based AC and Noveon^® AA-1 Polycarbophil USP or Carbopol^® 974P NF hydrogels which, …

Approaching Disorder-Tolerant Semiconducting Polymers, Xinwen Yan, Miao Xiong, Xin Yu Deng, Kai Kai Liu, Jia Tong Li, Xue Qing Wang, Song Zhang, Nathaniel Prine, Zhuoqiong Zhang, Wanying Huang, Yishan Wang, Jie Yu Wang, Xiaodan Gu, Shu Kong So, Jia Zhu, Ting Lei

Faculty Publications

Doping has been widely used to control the charge carrier concentration in organic semiconductors. However, in conjugated polymers, n-doping is often limited by the tradeoff between doping efficiency and charge carrier mobilities, since dopants often randomly distribute within polymers, leading to significant structural and energetic disorder. Here, we screen a large number of polymer building block combinations and explore the possibility of designing n-type conjugated polymers with good tolerance to dopant-induced disorder. We show that a carefully designed conjugated polymer with a single dominant planar backbone conformation, high torsional barrier at each dihedral angle, and zigzag backbone curvature is highly …

Epoxy Curing: Paramount Or Trivial? A Cure Path Dependent Inquiry, Jared Bates

Dissertations

The presented research delves into epoxy network formation corroborating reactant concentration profiles and physical property development throughout cure, providing an experimental basis for burgeoning molecular dynamics and coarse-grained simulation methodologies. Herein, three primary subjects were investigated: the first two examine neat and toughened epoxide/amine network formation with respect to various cure profiles aimed at altering reaction pathways, the final chapter intends to augment traditionally utilized activation energy (E_a) methodologies.

Neat and toughened epoxide/amine slurries were monitored in-situ throughout cure via near infrared (NIR) spectroscopy and rheological techniques. Functional group conversion and moduli development were related with specific attention …

Noise And Detectivity Limits In Organic Shortwave Infrared Photodiodes With Low Disorder, Zhenghui Wu, Ning Li, Naresh Eedugurala, Jason D. Azoulay, Dong Seok Leem, Tse Nga Ng

Faculty Publications

© 2020, The Author(s). To achieve high detectivity in infrared detectors, it is critical to reduce the device noise. However, for non-crystalline semiconductors, an essential framework is missing to understand and predict the effects of disorder on the dark current. This report presents experimental and modeling studies on the noise current in exemplar organic bulk heterojunction photodiodes, with 10 donor–acceptor combinations spanning wavelength between 800 and 1600 nm. A significant reduction of the noise and higher detectivity were found in devices using non-fullerene acceptors (NFAs) in comparison to those using fullerene derivatives. The low noise in NFA blends was attributed …

Bulk Properties Correlated To The Hydrogen Bond Organization In Dendrimers, Hyperbranched Polymers, And Linear Polymers, Beibei Chen

Dissertations

Although a lot of research was conducted on dendritic polymers, our understanding of their structure-property is still limited. Our previous study, which focused on a family of dendritic polymers based on 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) as a monomer, discovered unique hydrogen bond organizations contributed by their dendritic structures. However, the influence of the H-bond organization on bulk properties has yet to be understood. The goal of this dissertation is to elucidate the correlation between the H-bond organization with the dielectric and volumetric properties of bis-MPA based dendritic polymers, with an emphasis on developing a fundamental understanding of to what extent …

Investigating The Effect Of Hydrophilic Block Length On The Co-Assembly Behavior Of Amphiphilic Triblock Copolymers, Alexandra M. Garrett

Honors Theses

Polymer vesicles and micelles have been of interest in the scientific community for the past few decades due to potential biomedical applications in areas such as drug delivery, nanoreactors, and biosensing. Polymer vesicles and micelles are formed through the self-assembly of amphiphilic block copolymers. The objective of this project is to gain a better understanding of the influence of hydrophilic block copolymer length and composition in controlling the resulting morphologies from the co-assembly of triblock copolymers. First, a hydrophobic block composed of poly(methyl acrylate) was synthesized using reversible addition-fragmentation chain-transfer (RAFT) polymerization mediated by a difunctional chain-transfer agent. The block …

The Effect Of Precursor Design And Processing On The Semi-Crystalline Morphologies Of Polyacrylonitrile-Based Carbon Fiber, Katelyn Cordell

Dissertations

Basic research to control the morphology of polyacrylonitrile (PAN)-based carbon fiber is crucial for next generation composites as it determines their mechanical properties and final use. Poor molecular design of PAN-based precursors and fiber processing causes morphological defects and mechanical limitations.^1,2 This research focused on utilizing the controlled polymerization technique, reversible addition-fragmentation chain transfer (RAFT), of novel acrylamide comonomers to afford well-defined precursors with precisely controlled molecular design. This controlled RAFT technique improved the overall precursor graphitic structure as evident by the increased extent of stabilization and reduced activation energy as compared to precursors prepared by traditional free radical …

“Polysoaps” Via Raft Copolymerization To Form Well-Defined Micelles For Water Remediation And Targeted Drug Delivery Applications, Phillip Pickett

Dissertations

Amphiphilic copolymers have become increasingly important for environmental and biological applications due to their behavioral characteristics in aqueous solution. For example, structurally-tailored statistical amphiphilic copolymers or “polysoaps” can self-assemble into micelles or other architectures in water at various concentrations. Polysoaps may be differentiated from small molecule surfactant micelles in their capability to self-assemble into unimolecular associates (unimolecular micelles) with no dependence on concentration. Such micelles offer enormous potential for dispersion of hydrophobic species in water at high dilution. Importantly, each polymer chain forms its own micelle and upon dilution, these micelles remain intact and capable of dispersing hydrocarbon material in …

Chemical And Physical Modification Of Thiol-Ene And Epoxy-Amine Networks For Advanced Control Of Gas Transport And Flame Retardant Behavior, Vivek Vasagar

Dissertations

Crosslinked polymers are widely used due to its several advantages not limited to high mechanical strength combined with the easy processability. Despite of its popular usage, the fundamental understanding of polymer structure affecting the desired properties is still lacking. This PhD thesis is in two parts, the first part is devoted to the design and developing a basic understanding of structure and chemical composition dependencies of gas transport, whereas in the second part a fundamental relationship between structure to the fire-retardant properties is established.

Membrane based gas separation technique has attracted interest of selective removal of carbon dioxide gas from …

Bioinspired Glycopolymers: Models To Investigate The Effect Of Saccharide Structure And Concentration On Amyloid Beta Aggregation, Pradipta Kumar Das

Dissertations

Aggregation and subsequent deposition of amyloid-β (Aβ) peptide on neuronal cell membranes have been implicated as a cause of Alzheimer’s disease. Gangliosides in their clustered form seed and promote the Aβ aggregation process. However, the effects of the structure and the concentration of ganglioside saccharides on Aβ aggregation are not well understood. We investigated how the specific structure of saccharides (β-D-galactose and β-D-glucose) affect the aggregation pathways, kinetics, and the aggregated structures of Aβ via in vitro experiments. The effects of the local concentration of saccharides on the Aβ aggregation were also investigated.

To mimic the multivalent effect of the …

Biocompatible, Responsive Polysoaps Via Raft Copolymerization For The Delivery Of Model Cancer Therapeutics, Mason Dearborn

Honors Theses

Many chemotherapeutic drugs are small, hydrophobic molecules that require water-soluble, biocompatible nanocarriers for enhanced vascular circulation. Existing polymeric carriers either conjugate the drug along a copolymer backbone or sequester drugs within a protected interior domain to be delivered to specific sites in the body. Such therapeutic systems must overcome a myriad of hurdles, beginning with complex, multi-step syntheses, followed by other inherent barriers that limit the efficiency of drug delivery at the targeted site. This work aims to circumvent a number of these issues using biocompatible, stimuli-responsive polysoaps that are capable of unimeric micelle formation, hydrophobic drug delivery, and triggered …

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 …

Comparison Study Between Post-Fermentation Stillage And Pre-Fermentation Mash Utilizing Acidification And Steam Explosion Techniques For Cellulose Saccharification, Daniel Mckee

Master's Theses

Pre-fermentation mash fiber and post-distillation stillage fiber were examined and compared using a variety of preparatory techniques to determine the better source for cellulose fiber saccharification. Once screened, dried, and diluted to a 10% solution, mash fiber and stillage fiber were exposed to increasing temperatures for steam explosion techniques as well as increasing acidification techniques. Both underwent enzymatic saccharification to convert the exposed cellulose to glucose and other sugars. Once the optimum steam explosion technique parameters and acidification parameters were determined to be 2.5% sulfuric acid at 127.8°C for 1 hour, a comparison of the saccharification of pre-fermentation mash fiber …

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 …

Polyisobutylene Telechelic Prepolymers By In Situ End-Quenching And Post-Polymerization Modifications, Bin Yang

Dissertations

This volume focuses on the development of telechelic polyisobutylene (PIB) prepolymers by combining end-capping of living carbocationic polymerization of isobutylene (IB) with suitable reactants and post-polymerization modifications. Alkylation kinetics of PIB tert-chloride with alkoxybenzenes using either TiCl₄ or AlCl₃ were investigated. Quantitative para-position end-capped products were only achieved if the alkoxybenzene/AlCl₃ molar ratio was greater than unity; while no such molar ratio is required for TiCl₄, but the alkylation rate was slower than AlCl₃ under the same conditions. Photopolymerization kinetics analysis of PIB triphenol tri(meth)acrylates with low and high M_ns, …

Nanostructured Morphologies In Glassy Polymer Networks, Brian Greenhoe

Dissertations

The body of this work describes a novel approach for the dispersion of multi-walled carbon nanotubes in a high T_g epoxy prepolymer matrix using a twin screw high-shear continuous reactor. The method demonstrated improves on previous dispersion methods in several ways. It offers increased efficiency through excellent heat transfer, while being solvent-less, scale-able, and tailorable to drive dispersion states to judiciously chosen dispersion states. Furthermore, it was shown that dispersion state and agglomerate morphology can be directed, in several ways, through processing conditions and also by controlling the matrix viscosity profile through cure. Broadband dielectric spectroscopy, optical hot-stage microscopy, …

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 …

Hybrid Aryl-Ether-Ketone And Hyperbranched Epoxy Networks, John Misasi

Dissertations

In this dissertation, relationships between chemical structures, cure kinetics and network architectures are correlated to bulk mechanical properties for novel, hybrid epoxy-amine networks. The work is split into two primary sections: the first is the synthesis and characterization of multifunctional glassy networks based on aryl-ether-ketone diamine curatives, while the second is based on the synthesis and characterization of hyperbranched epoxy polymers and their resulting networks.

Three aryl-ether-ketone (AEK) diamines of increasing molecular weights were synthesized and used to cure 4,4’-tetraglycidylether of diaminodiphenylmethane (TGDDM); the resulting networks were compared to 4,4’-diaminodiphenyl sulfone cured TGDDM. Architectural differences were created by varying cure …

High Temperature Proton Exchange Membranes With Enhanced Proton Conductivities At Low Humidity And High Temperature Based On Polymer Blends And Block Copolymers Of Poly(1,3-Cyclohexadiene) And Poly(Ethylene Glycol), Shawn Deng, Mohammad K. Hassan, Amol Nalawade, Kelly A. Perry, Karren L. More, Kenneth A. Mauritz, Marshall T. Mcdonnell, David J. Keffer, Jimmy W. Mays

Faculty Publications

Hot (at 120 °C) and dry (20% relative humidity) operating conditions benefit fuel cell designs based on proton exchange membranes (PEMs) and hydrogen due to simplified system design and increasing tolerance to fuel impurities. Presented are preparation, partial characterization, and multi-scale modeling of such PEMs based on cross-linked, sulfonated poly(1,3-cyclohexadiene) (xsPCHD) blends and block copolymers with poly(ethylene glycol) (PEG). These low cost materials have proton conductivities 18 times that of current industry standard Nafion at hot, dry operating conditions. Among the membranes studied, the blend xsPCHD-PEG PEM displayed the highest proton conductivity, which exhibits a morphology with higher connectivity of …

Hydrocarbon-Based Fuel Cell Membranes: Sulfonated Crosslinked Poly(1,3-Cyclohexadiene) Membranes For High Temperature Polymer Electrolyte Fuel Cells, Suxiang Deng, Mohammad K. Hassan, Kenneth A. Mauritz, Jimmy W. Mays

Faculty Publications

High temperature fuel cell membranes based on poly(1,3-cyclohexadiene) were prepared by a Polymerization-Crosslinking-Sulfonation (PCS) approach, and a broad range of membrane compositions were achieved using various sulfonating reagents and reaction conditions. Membranes were characterized for their proton conductivity and thermal degradation behavior. Some of the membranes showed up to a 68% increase in proton conductivity as compared to Nafion under the same conditions (100% relative humidity and 120 °C). Thermogravimetric analysis revealed that these membranes are thermally stable up to 200 °C. High proton conductivity and thermal stability, combined with much lower cost as compared to Nafion®, make these materials …

Morphology And Magnetic Properties Of Sulfonated Poly[Styrene-(Ethylene/Butylene)-Styrene]/Iron Oxide Composites, Sateesh K. Peddini, Huy N. Pham, Leonard Spinu, James L. Weston, David E. Nikles, Kenneth A. Mauritz

Faculty Publications

α-Fe₂O₃ structures were initiated in the sulfonated polystyrene block domains of poly[styrene–(ethylene/butylene)–styrene] (SEBS) block copolymers via a domain-targeted in-situ chemical precipitation method. The crystal structure of these particles was determined using wide-angle X-ray diffraction and selected area electron diffraction using a transmission electron microscope (TEM). TEM revealed that for less sulfonated SEBS (10 mole%), nanoparticles were aggregated with aggregate size range of 100–150 nm whereas for high sulfonation (16 and 20 mole% sSEBS) there were needle-like structures with length and width of 200–250 nm and 50 nm, respectively. Dynamic mechanical analyses suggest that initial iron oxide nanoparticle …