Polymer and Organic Materials Commons^™

Adaption Of Catechol And Reversible Addition-Fragmentation Chain-Transfer (Raft) Chemistries For Water-Based Applications, Olabode Oyeneye

Electronic Thesis and Dissertation Repository

Incorporating the binding chemistry of catechol functionality with RAFT chemistry offers a facile and simplified approach for developing a suite of new 2D and 3D hybrid materials with tailored morphologies. Leveraging both chemistries by synthesizing catechol-end functionalized RAFT agents and catechol-containing monomeric species for RAFT (co)polymerization, this dissertation examined a new series of advanced materials that were designed for water-based applications including model flocculants, thermoresponsive hydrogels, adsorbents and underwater adhesives.

To prepare the RAFT agents, novel trithiocarbonates with several catechol end R groups (as postpolymerization anchors) were synthesized that differ in their carbonyl α-substituents (Dopa-CTAs). These materials were evaluated for …

The Processing And Polarization Reversal Dynamics Of Thin Film Poly(Vinylidene) Fluoride, Noel Mayur Dawson

Nanoscience and Microsystems ETDs

Many ferroelectric devices benefit from the ability to deposit thin ferroelectric layers. Poly(vinylidene) fluoride (PVDF) is the prototypical ferroelectric polymer, but processing of thin film ferroelectric PVDF remains a challenge due to the formation of large voids in the film during traditional thin film processing. The research described in this dissertation starts by investigating the origin of these voids. The cause of these voids is found to be caused by vapor induced phase separation (VIPS). Guided by the thermodynamics of VIPS, a process is then designed to produce void-free ferroelectric PVDF thin films on polar and non-polar substrates. The films …

Spray-Dried Cellulose Nanofibril-Reinforced Polypropylene Composites For Extrusion-Based Additive Manufacturing, Lu Wang

Electronic Theses and Dissertations

Compared to conventional manufacturing process, additive manufacturing (AM) offers free-form design, lighter and more ergonomic products, short lead time and less waste. Extrusion-based AM can be used to print thermoplastics. However, extrusion-based AM has processing challenges in printing semi-crystalline thermoplastics, for instance, polypropylene (PP). Cellulose nanofibrils (CNF) are one type of cellulose nanofibers that are produced from pulp fibers. CNF has extraordinary properties which make it an ideal candidate to reinforce polymers. Spray-dried CNF (SDCNF) is able to be incorporated into thermoplastic matrices without modifying conventional processing procedures.

The mechanical properties of 3D printed plastic parts have been considered significantly …

Characterization And Modeling Of Asphalt Concrete For Dynamic Properties And Performances, A S M A. Rahman

Civil Engineering ETDs

The recently developed mechanistic-empirical pavement design guide (MEPDG, also known as Pavement M-E design method) uses the nationally calibrated, binder viscosity-based dynamic modulus predictive model for the design and analysis of asphalt pavements. In this study, this model is assessed for its appropriateness for asphalt-aggregate mixtures typically used in New Mexico. In essence, this study investigates the predictability issue of complex modulus of New Mexico mixes. A total of 54 Superpave mixes with different aggregate gradations, air voids, and binder grades were collected from the mixing plants and from the pavement construction sites. The loose asphalt mixtures were then compacted, …

Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders

Electronic Theses and Dissertations

The purpose of this research was to investigate the use of cellulose nanofibers (CNF) compounded into an impact modified polypropylene (IMPP) matrix. A IMPP was used because it shrinks less than a PP homopolymer during FLM processing. An assessment of material properties from fused layer modeling (FLM), an additive manufacturing (AM) method, and injection molding (IM) was conducted. Results showed that material property measurements in neat PP were statistically similar between IM and FLM for density, strain at yield and flexural stiffness. Additionally, PP plus the coupling agent maleic anhydride (MA) showed statistically similar results in comparison of IM and …

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 …

Preparation Of Benzoxazine Monomers And Prepolymers From Continuous Reactor: Effects Of Molecular Architecture On Properties, Andrew S. Frazee

Dissertations

Despite the modularity in molecular design and high-performance properties of benzoxazine thermoset chemistries, there are two primary shortcomings of benzoxazine marketability. Firstly, multifunctional benzoxazines are unfavorable for processing as they are glassy solids at ambient temperature. Secondly, benzoxazine chemistries are commercially synthesized using batch reactors, which are energy intensive and require the use of environmentally unfavorable solvents.

The purpose of the work herein is to address these shortcomings, which include:

1.) interrelationships between molecular architectures of synthesized monofunctional benzoxazine monomers and their ambient temperature physical states (i.e. liquid or solid) using molecular dynamics simulations and experimental comparisons,

2.) continuous high-shear …

Usa Boccia Ball Ramp For Athletes With Quadriplegia, Alissa A. Koukourikos, Matthew Lee, Nathan Bernards

Mechanical Engineering

In this report, the design process in creating an assistive device for Boccia Classification 3 (BC3) players is outlined. The initial research steps, including research into the rules of the game, capabilities of the players, and existing products is documented to show where ideas for the product stemmed from. This transitions into requirements that the sponsor requested, and preliminary designs and ideas for the product. Finally, this report explains the details of the final design, which has been analyzed for safety, ease of use, and ability to function under different conditions. The processes of manufacturing and testing will also be …

Block Copolymer Nanostructures For Inorganic Oxide Nanopatterning, Krishna Pandey

MSU Graduate Theses

Self-assembled nature of block copolymer (BCP) makes them ideal for emerging technologies in nanometer scale. The micro phase separation between two or more dissimilar polymer blocks of BCP leads to uniform periodic nanostructures of different domains of dimension in the range of 5-100 nm, good for the development of emerging microelectronic and optoelectronics devices. Molecular weight and chain architecture of each blocks govern the morphology evolution; gives different structure like spherical, micelles, lamellae, cylindrical, gyroid etc. The morphology evolution of BCP nanostructure also depends on different external factors as well. In the first work of this thesis, three external factors …

Synthesis Of Graphene And Graphene-Based Composite Membrane, Yuanjun Fan

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

Vibration membrane equipped for earphone requires high performance in both mechanical properties and electronic properties. With extraordinary properties on both, graphene and graphene-based composite materials appear as a promising candidate for this application. Chemical vapor deposition (CVD) is believed to be the most convenient way to synthesize a large area (on scale of square centimeters) as well as a homogeneous thickness for the membrane. The thesis focuses on applying control variable experiment method to analyze different effects on mechanical property of the two CVD setting parameters: cooling rate, and hydrocarbon precursor. For isolating the specimens efficiently, a modified electrochemical method …

The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli

Doctoral Dissertations

Particle dispersions are ubiquitous in our daily lives ranging from food and pharmaceutical products to inks. There has been great interest in the recent years in formulation of functional inks to fabricate myriad flexible electronic devices through high-throughput roll-to-roll technologies. The formulations often contain several functional additives or rheological modifiers that can affect the microstructure, rheology and processing. Understanding the rheology of formulations is important for tuning the formulation for optimal processing. This thesis presents investigations on the rheology of particle dispersions and their impact on roll-to-roll technologies. Shear-thickening behavior is common in particle dispersions, particularly, concentrated particulate inks. We …

The Role Of Chain Configuration In Governing The Rational Design Of Polymers For Adhesion, Onyenkachi Wamuo

Doctoral Dissertations

ABSTRACT THE ROLE OF CHAIN CONFIGURATION IN GOVERNING THE RATIONAL DESIGN OF POLYMERS FOR ADHESION SEPTEMBER 2017 ONYENKACHI C. WAMUO, B.Eng., FEDERAL UNIVERSITY OF TECHNOLOGY, OWERRI (FUTO), NIGERIA M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Shaw Ling Hsu The chain configurational control of polymers used in adhesion can be utilized as a means of tuning the cohesive properties of hot melt adhesives (HMAs). The cohesive properties control the solidification, strength, setting speed. Propylene-Ethylene copolymers (PP-co-PE) and thermoplastic polyurethanes (TPUs) were studied. In the first project, the effects of sequence distribution of the two types …

Polyorganosiloxanes: Molecular Nanoparticles, Nanocomposites And Interfaces, Daniel H. Flagg

Doctoral Dissertations

Five research projects described. First, a reproducible, lab-scale synthesis of MQ silicone copolymers is presented. MQ copolymers are commercially important materials that have been ignored by the academic community. One possible reason for this is the difficulty of controlling and reproducing the preparative copolymerizations that have been reported. A reproducible method for lab-scale preparation was developed that controls molecular weight by splitting the copolymerization into the discrete steps of sol growth from silicate precursor and end-capping by trimethylsiloxy groups. Characterization of MQ products implicates that they are composed of highly condensed, polycyclic structures. The MQ copolymers prepared in the first …

Synthesis And Structure-Property Relationships Of Polymeric Membranes For Small Molecule Transport, Haomiao Yuan

Doctoral Dissertations

One key challenge for alkaline anion exchange membrane fuel cells is the lack of alkaline stable polycations. The synthesis of random, crosslinked and block copolymers based on the cobaltocenium phenylene norbornene (NPC) monomer is described. The polymers were synthesized from ring-opening metathesis polymerization (ROMP) of the NPC monomer showed excellent thermo-alkaline and thermo-oxidative stability. Random copolymers, crosslinked networks and amphiphilic diblock copolymers were prepared by copolymerizing NPC with different hydrophobic monomers: norbornene for random copolymers, dicyclopentadiene for crosslinked networks and a norbornene dibenzyl ether monomer for amphiphilic diblock copolymers. Mechanical robust membranes were prepared from all these copolymers. Polymers with …

Solution-Based Assembly Of Conjugated Polymers Into Nanofibers For Organic Electronics, Daniel E. Acevedo Cartagena

Doctoral Dissertations

Solution-based crystallization of conjugated polymers offers a scalable and attractive route to develop hierarchical structures for electronic devices. The introduction of well-defined nucleation sites into metastable solutions provides a way to regulate the crystallization behavior, and therefore the morphology of the material. A crystallization method for generating metastable solutions of poly(3-hexylthiophene) (P3HT) was established. These metastable solutions allow P3HT to selectively crystallize into nanofibers (NFs) on graphene-coated surfaces. It was found that the crystallization kinetics is faster with increasing P3HT molecular weight and concentration. Through in situ atomic force microscopy, it was confirmed that NFs grow vertically in a face-on …

Guiding The Self-Assembly Of Block Copolymers In 2d And 3d With Minimal Patterning, Jaewon Choi

Doctoral Dissertations

Directed self-assembly (DSA) of block copolymers (BCPs) based on topographic patterns is one of the most promising strategies for overcoming resolution limitations in the current lithographic process and fabricating the next generation data storage devices. While the DSA of BCPs with deep topographic patterning has been extensively studied both experimentally and theoretically over the past two decades, less attention has been paid to the development of the DSA process using minimal topographic patterning. This dissertation focuses on understanding the effect of minimal topographic patterning on guiding the self-assembly of BCPs in 2D and 3D. We demonstrate that minimal trench patterns …

Note On The Rate And Energy Efficiency Limits For Additive Manufacturing, Timothy Gutowski, Sheng Jiang, Daniel Cooper, Gero Corman, Michael Hausmann, Jan-Anders Manson, Timo Schudeleit, Konrad Wegener, Matias Sabelle, Jorge Ramos-Grez, Dusan P. Sekulic

Mechanical Engineering Faculty Publications

We review the process rates and energy intensities of various additive processing technologies and focus on recent progress in improving these metrics for laser powder bed fusion processing of metals, and filament and pellet extrusion processing of polymers and composites. Over the last decade, observed progress in raw build rates has been quite substantial, with laser metal processes improving by about 1 order of magnitude, and polymer extrusion processes by more than 2 orders of magnitude. We develop simple heat transfer models that explain these improvements, point to other possible strategies for improvement, and highlight rate limits. We observe a …

Hybrid Polymer Electrolyte For Lithium-Oxygen Battery Application, Amir Chamaani

FIU Electronic Theses and Dissertations

The transition from fossil fuels to renewable resources has created more demand for energy storage devices. Lithium-oxygen (Li-O₂) batteries have attracted much attention due to their high theoretical energy densities. They, however, are still in their infancy and several fundamental challenges remain to be addressed. Advanced analytical techniques have revealed that all components of a Li-O₂ battery undergo undesirable degradation during discharge/charge cycling, contributing to reduced cyclability. Despite many attempts to minimize the anode and cathode degradation, the electrolyte remains as the leading cause for rapid capacity fading and poor cyclability in Li-O₂ batteries. In this …

Development Of Starch-Polyvinyl Alcohol (Pva) Biodegradable Film: Effect Of Cross-Linking Agent And Antimicrobials On Film Characteristics, Aniket Satish More, Chandani Sen, Madhusweta Das

Journal of Applied Packaging Research

To satisfy the need of developing eco-friendly flexible antimicrobial packaging film with minimum use of synthetic chemical ingredients, the present study examined the efficacy of citric acid (CA) as cross-linking agent and essential oils (EOs), viz., cinnamon essential oil (CEO) and oregano essential oil (OEO) as natural antimicrobials in corn starch-polyvinyl alcohol (CS-PVA) film. Compared to film prepared from filmogenic solution (FS) containing 75 kg CS+8.75 kg PVA+24.6 kg glycerol per m³ FS, film additionally containing CA at 0.07 kg/kg CS indicated 95% higher ultimate tensile strength (UTS) and 27% lower water vapor permeability (WVP). Film developed with incorporation …

Effects Of Lignin As A Stabilizer Or Antioxidant In Polyolefins, Afsana S. Kabir

Electronic Thesis and Dissertation Repository

Lignin, a major component of biomass, is an attractive alternative to hindered phenol-based antioxidants for polymers due to its renewable nature and naturally occurring hindered phenolic structure. In this study, for the first time, lignin de-polymerization was explored as a promising approach to improve the reactivity of the lignin-based antioxidants for polymers (polyethylene, PE and polypropylene, PP). A proprietary hydrolytic de-polymerization process was utilized to increase the antioxidant activity of two types of technical lignin: kraft lignin, KL (a by-product from the pulp and paper industry) and hydrolysis lignin, HL (a by-product from the pre-treatment processes in cellulosic ethanol plants). …

Additive Manufacturing Process Of 3d Polyaniline Transducers Via Direct Ink Writing, Frederick Benjamin Holness

Electronic Thesis and Dissertation Repository

Electroactive polymers exhibit a change in properties, typically size or shape, in response to electrical stimuli. One class of electroactive polymer of particular interest are the conjugated polymers, whose conjugated backbone structure imparts electrical conductivity. However, this structure imposes processing limitations restricting their form to 2D structures. To overcome this, we develop specially formulated polyaniline- based blends via counter-ion induced thermal doping for the fabrication of 3D conductive structures via direct ink writing. This approach employs multi-material extrusion for the production of structures with passive and active features, rapid device fabrication, and improved design freedom. A model of the thermal …

Structure-Force Field Generator For Molecular Dynamics Simulations, Carlos M. Patiño, Lorena Alzate, Alejandro Strachan

The Summer Undergraduate Research Fellowship (SURF) Symposium

Atomistic and molecular simulations have become an important research field due to the progress made in computer performance and the necessity of new and improved materials. Despite this, first principle simulations of large molecules are still not possible because the high computational time and resources required. Other methods, such as molecular dynamics, allow the simplification of calculations by defining energy terms to describe multiple atom interactions without compromising accuracy significantly. A group of these energy terms is called a force field, and each force field has its own descriptions and parameters. The objective of this project was to develop a …

Usage Of Fomblin Y To Improve Water Repellence Of Surface Coatings, Shawn Pj Kirby, Jeffrey Alston, Andrew Guenthner

STAR Program Research Presentations

Fluoro-Decyl POSS (FDP) has shown strong potential as a water repellant surface coating. Additionally, Fomblin is a solvent believed to have the ability to control the crystallization of POSS compounds on surfaces. Controlling the crystallization is key to improving water repelling abilities of surfaces. Thus, dip coating FDP and Fomblin onto surfaces is being investigated for water repulsion, mechanical stability, and deposition feasibility. Relative water repelling abilities of different coatings were determined by measuring contact angle of surfaces with water. Coatings with and without POSS and Fomblin were compared. It was shown that the surfaces treated with both POSS and …

Usage Of Fomblin Y To Improve Water Repellence Of Surface Coatings, Shawn Pj Kirby, Jeffrey Alston, Andrew Guenthner

STAR Program Research Presentations

Fluoro-Decyl POSS (FDP) has shown strong potential as a water repellant surface coating. Additionally, Fomblin is a solvent believed to have the ability to control the crystallization of POSS compounds on surfaces. Controlling the crystallization is key to improving water repelling abilities of surfaces. Thus, dip coating FDP and Fomblin onto surfaces is being investigated for water repulsion, mechanical stability, and deposition feasibility. First, temperature dependence of solubility of Fluoro-Decyl POSS in Fomblin was tested using Dynamic Light Scattering. Relative water repelling abilities of different coatings were determined by measuring contact angle of surfaces with water. Coatings with and without …

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 …

Comparative Solubility Of Poss Compounds In Fomblin Y, Shawn Pj Kirby, Jeffrey Alston, Andrew Guenthner

STAR Program Research Presentations

Fluoro-Decyl POSS (FDP) has shown strong potential as a water repellant surface coating. Additionally, Fomblin is a solvent believed to have the ability to control the crystallization of POSS compounds on surfaces. Controlling the crystallization is key to improving water repelling abilities of surfaces. Thus, dip coating FDP and Fomblin onto surfaces is being investigated for water repulsion, mechanical stability, and deposition feasibility. However, in order for this to be successful, POSS must be soluble in Fomblin. Temperature dependence of solubility of Fluoro-Hexyl, Fluoro-Octyl, Fluoro-Decyl POSS in Fomblin was tested using Dynamic Light Scattering. The values were compared, and it …

Membranes For Food And Bioproduct Processing, Alexandru Marius Avram

Graduate Theses and Dissertations

Modified membranes for process intensification in biomass hydrolysis

Production of biofuels and chemicals from lignocellulosic biomass is one of the leading candidates for replacement of petroleum based fuels and chemicals. However, conversion of lignocellulosic biomass into fuels and chemicals is not cost effective compared to the production of fuels and chemicals from crude oil reserves. Some novel and economically feasible approaches involve the use of ionic liquids as solvents or co-solvents, since these show improved solvation capability of cellulose over simple aqueous systems. Membranes offer unique opportunities for process intensification which involves fractionation of the resulting biomass hydrolysate leading to …

Molecular Dynamics Modeling And Simulation Of Bitumen Chemical Aging, Farshad Fallah

Department of Civil and Environmental Engineering: Dissertations, Theses, and Student Research

Chemical aging of asphalt binder leads to significant changes in its mechanical and rheological properties, resulting in poor pavement behavior and distress. Various laboratory methods have been used to simulate asphalt aging during the service life of the pavement. However, controversy exists regarding the capability of these methods to predict field aging, as various factors interact with the pavement during service and the mechanism behind aging is not fully understood. The two main outcomes of chemical aging are oxidation of asphalt molecules, and change in asphalt SARA (saturate, aromatic, resin, and asphaltene) fractions. Reaction of oxygen with asphalt components forms …

Synthesis, Characterization And Application Of Block Copolymer And Nanoparticle Composites, Yue Gai

Doctoral Dissertations

The “bottom-up” fabrication of functional hybrid material can be achieved by using directed self-assembly of functional nanoparticles (NP) and block copolymers (BCP) as templates. The versatile nanostructures of BCP provide possibilities to precisely control NPs spatial distribution and the resulting hybrid materials exhibit enhanced electrical, mechanical and optical functionalities. Three main topics related to BCP/NP composites are discussed in this dissertation: I) the spatial distribution of large NP in linear BCP; II) the morphology control of BCP templates with new architectures; and III) the magneto-optical properties of hybrid material using magnetic NPs. For well-ordered BCP/NP composite, the ratio of NP …

Characterization Of Electronic And Ionic Transport In Soft And Hard Functional Materials, Lawrence A. Renna

Doctoral Dissertations

Control over concurrent transport of multiple carrier types is desired in both soft and hard materials. For both types of materials, I demonstrate ways to characterize and execute governance over both electronic and ionic transport, and apply these concepts in the fabrication of devices with applications in conducting composites, photovoltaics, electrochemical energy storage, and memristors. In soft materials, such as polymers, the topology of the binary polymer mesoscale morphology has major implications on the charge/ion transport. Traditional approaches to co-continuous structures involve either using blends of polymers or diblock copolymers. In polymer blends, the structures are kinetically trapped and …