Polymer and Organic Materials Commons^™

Microscopic Insights On Shear Rheology Of Polyampholyte Ionomers Via Molecular Simulations, Kyle Vonscio

Williams Honors College, Honors Research Projects

Ionomers are polymers that contain a small fraction of charged groups. The ionic attraction of charged groups allows ionomers to act similarly to crosslinked polymers. Depending on the strength of electrostatic interactions and structure of the ionomers, different dynamics and rheological responses can be observed. With moderate attraction between ions, these noncovalent crosslinks can be broken when heated, allowing ionomers to flow and show the strength of a crosslinked network at low temperatures. Nonequilibrium molecular dynamics (NEMD) simulations will be performed under shear in the xy-plane and the macroscopic rheology and conformation of the polyampholyte ionomer will be determined. The …

Multifunctional Pvdf Ionogels With Magnetic Nanoparticles For Electroactive And Magnetic Actuation, Alfredo Carrillo Valverde

Chemical Engineering Undergraduate Honors Theses

The fast development of compact and multifunctional electronics has driven interest in smart materials capable of responding to multiple stimuli. Ionogels, polymers that have been swollen with ionic liquids (IL), offer several favorable electrochemical and thermal properties due to their intrinsic ion conductivity, wide electrochemical window, non-flammability, and high thermal stability. However, their poor mechanical properties (e.g., modulus and strength) limit their use in applications. In this work, multifunctional PVDF ionogel composites were made by blending magnetically responsive iron oxide nanoparticles (Fe₃O₄ MNPs) into the polymer matrix. The influence of MNP concentration (9-21 wt%) on composition, ionic …

Incorporating Recycled And Repurposed Plastic Into 100% Reclaimed Asphalt Pavement, Basant Bhatt

Graduate Theses and Dissertations (2019 - present)

The increasing awareness of sustainability in the asphalt industry has driven the use of recycled materials like reclaimed asphalt pavement (RAP) and waste plastic. This study examines the incorporation of recycled polypropylene (rPP), recycled high-density polyethylene (rHDPE), and recycled low-density polyethylene (rLDPE) at 0.3%, 0.6%, and 0.8% dosages into 100% RAP, along with the warm mix asphalt additive Evotherm® P25. Laboratory tests were conducted to evaluate the mechanical and durability performance of the modified asphalt mixtures while rutting and fatigue life were evaluated using mechanistic-empirical (ME) analysis in PerRoad software. Both plastic type and dosage had a statistically significant impact …

Modern Ir-Spectroscopic Methods For The Analysis Of Hydroxybenzene-Methanal Resin Obtained On The Basis Of 2,5-Furandion, Sherali Anvarovich Umarov, Ravshan Israilovich Ismailov Ismailov

Technical science and innovation

The chemical changes occurring during the synthesis of hydroxybenzene-methanal resins obtained on the basis of 2,5-furandion under various ratios and temperature conditions were investigated using the IR spectroscopic method. Analysis of the compositional changes in the resin during the production of the thermoreactive resin revealed that the content of hydroxyl groups (~3300–3500 cm⁻¹) decreased, while the aldehyde groups (~1700–1750 cm⁻¹) increased; moreover, the presence of ether groups (~1050–1150 cm⁻¹) indicated that the process was successful. The synthesis of resins based on thermoreactive hydroxybenzene-methanal resins was carried out at high temperatures (70°C, 80°C, 95°C). During the identification of the functional groups …

Prediction Of Glass Transition Temperature Of Polymers Using Structure-Based Models, Nicholas Wolfe

Williams Honors College, Honors Research Projects

The focus for this study is prediction of glass transition temperatures of polymers using machine learning models. The preprocessing of the data included the generation of descriptors, the scaling of the data, the principal component analysis for dimensionality reduction, and the clustering of the data. Three methods of property predictions were utilized including Linear Regression, Random Forest, and a Feedforward Neural Network. The dataset consisted of over 7000 polymers each with their respective glass transition temperatures. This study found that the Random Forest model returned the best results followed by the Feedforward Neural Network then the Linear Regression model. Each …

A Foundational Approach To Extrusion And Compounding, David Frankart

Williams Honors College, Honors Research Projects

With a history of nearly 200 years, polymer processing and compounding is constantly changing to fit the material science needs of the era. Exposure of undergraduate students to the technology and practices used in industry today in a lab setting would create new opportunities for experiential learning and growth. The objective was to set up a 0.75”, 25 L/D Thermo Haake single screw extruder for lab use and run trials of material in a single screw extruder to set up a basis for experiments. Trials were run of co-polyester resin through a single screw extruder with carbon fiber additives varying …

Iron-Containing Nanoparticles For The Treatment Of Chrionic Biofilm Infections In Cystic Fibrosis, Leisha M. A. Martin

Nanoscience and Microsystems ETDs

Cystic fibrosis (CF) is the most common genetic disease resulting in the morbidity and mortality of Caucasian children and adults worldwide. Due to a genetic mutation resulting in malfunction of the Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) protein, CF patients produce highly viscous mucus in their respiratory tract. This leads to impairment of the mucociliary clearance of inhaled microbes. In addition to reduced microbial clearance, anoxic environmental conditions in the lungs promote biofilm-mode growth of the pathogenic bacterial species Pseudomonas aeruginosa. Chronic infections of P. aeruginosa begin in early childhood and typically persist until respiratory failure and death result. The …

Towards Sustainable Production Of Chemicals And Fuels From The Fast Pyrolysis Of Waste Polyolefin Plastics, Ulises Gracida Alvarez

Dissertations, Master's Theses and Master's Reports

The increasing amount of plastic waste (PW) generation has become an important concern due to the leveled-off recycling rates. Therefore, governmental agencies around the world, including state governments in the United States, have proposed initiatives to minimize the amount of PW that is landfilled and encourage recycling or energy recovery. Circular economy is a strategy that attempts on reusing PW to produce new polymers while avoiding its disposal and the use of virgin material. Chemical recycling raises an interesting technology prospect due to the potential reduction of pollutant emissions and the establishment of a circular economy through the production of …

Bioluminescent Magnetic Nanoparticles As Potential Imaging Agents For Mammalian Spermatozoa, Erick Salvador Vasquez, Jean M. Feugang, Scott T. Willard, Peter L. Ryan, Keisha B. Walters

Chemical and Materials Engineering Faculty Publications

Background: Nanoparticles have emerged as key materials for developing applications in nanomedicine, nanobiotechnology, bioimaging and theranostics. Existing bioimaging technologies include bioluminescent resonance energy transfer-conjugated quantum dots (BRET-QDs). Despite the current use of BRET-QDs for bioimaging, there are strong concerns about QD nanocomposites containing cadmium which exhibits potential cellular toxicity.

Results: In this study, bioluminescent composites comprised of magnetic nanoparticles and firefly luciferase (Photinus pyralis) are examined as potential light-emitting agents for imaging, detection, and tracking mammalian spermatozoa. Characterization was carried out using infrared spectroscopy, TEM and cryo-TEM imaging, and ζ-potential measurements to demonstrate the successful preparation of these nanocomposites. Binding …

Influence Of Carbon Nanofillers On The Curing Kinetics Of Epoxy-Amine Resin, Luigi Vertuccio, Salvatore Russo, Marialuigia Raimondo, Khalid Lafdi, Liberata Guadagno

Chemical and Materials Engineering Faculty Publications

The cure kinetics of an epoxy resin based on the tetrafunctional epoxy precursor N,N′-tetraglycidyl methylene dianiline-(TGMDA) hardened with 4,4-diaminodiphenyl sulfone is investigated. The influence of carbon nanofillers (carbon nanotubes, carbon nanofibers, and graphene based nanoparticles) on the cure kinetic is studied. Kinetic analysis is performed by dynamic and isothermal differential scanning calorimetry (DSC).

In dynamic experiments, the activation energy was computed using an advanced isoconversional method while under isothermal conditions, the Kamal’s model of diffusion control was applied to simulate the systems throughout the curing process. The isothermal analysis shows that the introduction of the diluent decreases, …

Minimizing Sheet Resistance Of Organic Photovoltaic Cell Top Contact Electrode Layer: Silver Nanowire Concentration Vs. Conductive Polymer Doping Concentration, Caitlyn Cook

Materials Engineering

The top contact electrode layers of nine organic photovoltaic cells were prepared with two varying factors: three Silver nanowire (AgNW) densities deposited on a conductive polymer doped with three concentrations. Silver’s low sheet resistance of 20-Ω/sq is hypothesized to lower the sheet resistance of the anode layer and thus enhance the overall efficiency of the cell. Four-point probe measurements indicated that increasing AgNW density in the top contact electrode layer of an organic photovoltaic cell significantly reduces sheet resistance from 52.2k-Ω/sq to 18.0 Ω/sq. Although an increase in doping concentration of the conductive polymer reduced sheet resistance in low AgNW …

Optimization Of Graphene-Based Materials Outperforming Host Epoxy Matrices, Liberata Guadagno, Marialuigia Raimondo, Luigi Vertuccio, Marco Mauro, Gaetano Guerra, Khalid Lafdi, Biagio De Vivo, Patrizia Lamberti, Giovanni Spinelli, Vincenzo Tucci

Chemical and Materials Engineering Faculty Publications

The degree of graphite exfoliation and edge-carboxylated layers can be controlled and balanced to design lightweight materials characterized by both low electrical percolation thresholds (EPT) and improved mechanical properties. So far, this challenging task has been undoubtedly very hard to achieve.

The results presented in this paper highlight the effect of exfoliation degree and the role of edge-carboxylated graphite layers to give self-assembled structures embedded in the polymeric matrix. Graphene layers inside the matrix may serve as building blocks of complex systems that could outperform the host matrix. Improvements in electrical percolation and mechanical performance have been obtained by a …

Computational Multiscale Modeling And Characterization Of Piezoresistivity In Fuzzy Fiber Reinforced Polymer Composites, Xiang Ren, Josh Burton, Gary D. Seidel, Khalid Lafdi

Chemical and Materials Engineering Faculty Publications

In this paper, the piezoresistive response (i.e. the change of resistance under the application of strain) of polymer composites reinforced by a novel material known as fuzzy fibers is characterized by using single tow piezoresistive fragmentation tests and modeled by using a 3D computational multiscale model based on the finite element analysis. In the characterization work, the fuzzy fiber tow is embedded in a dog-bone specimen infused by epoxy, with resistance and displacement measured simultaneously to obtain its piezoresistive response. An approximately linear and stable piezoresistive response is observed within the fuzzy fiber tow region yielding gauge factors on average …

Characterization Of Dimethyl Sulfoxide-Treated Wool And Enhancement Of Reactive Wool Dyeing In Non-Aqueous Medium, Luyi Chen, Bijia Wang, Jiangang Chen, Xinhui Ruan, Yiqi Yang

Department of Textiles, Merchandising and Fashion Design: Faculty Publications

Wool pretreated with dimethyl sulfoxide (DMSO) was characterized and its dyeing behavior in non-aqueous green solvents was investigated. Reactive dyeing of wool in deep shades is challenging because the mandatory alkaline aftertreatment to match the fastness of mordant dyes inevitably causes damage to wool keratin. The current study showed that the colorfastness-integrity dilemma could be solved by replacing water with organic solvents as the dyeing medium. Covalent fixation is predominantly favored in solvent dyeing so that excellent colorfastness is achievable at any given shade without alkali aftertreatment. Compared with aqueous dyeing, solvent dyeing was found to give 30% higher covalent …

Temporally And Spatially Resolved Plasma Spectroscopy In Pulsed Laser Deposition Of Ultra-Thin Boron Nitride Films, Nicholas R. Glavin, Christopher Muratore, Michael L. Jespersen, Jianjun Hu, Timothy S. Fisher, Andrey A. Voevodin

Chemical and Materials Engineering Faculty Publications

Physical vapor deposition (PVD) has recently been investigated as a viable, alternative growth technique for two-dimensional materials with multiple benefits over other vapor deposition synthesis methods. The high kinetic energies and chemical reactivities of the condensing species formed from PVD processes can facilitate growth over large areas and at reduced substrate temperatures. In this study, chemistry, kinetic energies, time of flight data, and spatial distributions within a PVD plasma plume ablated from aboron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated. Time resolved spectroscopy and wavelength specific imaging were used to identify and …

The Future Of Carbon-Based Scaffolds In Foot And Ankle Surgery, Jarema S. Czarnecki, Khalid Lafdi, Panagiotis A. Tsonis

Chemical and Materials Engineering Faculty Publications

Autologous grafts have been the gold standard in tissue replacement and the most accurate means of recapitulating both the biological and mechanical properties of tissue. However, autologous grafts have had complications and drawbacks. Skin grafting, a prime example of an autologous tissue graft, has been limited by the size of graft, availability, and secondary donor site morbidity. Use of cadaveric tissues circumvents several limitations of autologous grafts; however, sterilization processes used to reduce the risk of disease transmission potentially weaken tissues and eliminate living cells and some growth factors from scaffolds, making them suboptimal tissue replacements. Chemical cross-linkage of tissue …

Effects Of Disorder State And Interfacial Layer On Thermal Transport In Copper/Diamond System, Vikas Sinha, Jaime J. Gengler, Christopher Muratore, Jonathan E. Spowart

Chemical and Materials Engineering Faculty Publications

The characterization of Cu/diamond interface thermal conductance (h_c) along with an improved understanding of factors affecting it are becoming increasingly important, as Cu-diamond composites are being considered for electronic packaging applications. In this study, ∼90 nm thick Cu layers weredeposited on synthetic and natural single crystal diamond substrates. In several specimens, a Ti-interface layer of thickness ≤3.5 nm was sputtered between the diamond substrate and the Cu top layer. The h_c across Cu/diamond interfaces for specimens with and without a Ti-interface layer was determined usingtime-domain thermoreflectance. The h_c is ∼2× higher for similar interfacial layers on …

Effect Of Nanofiber Morphology On Pvdf Air Filter Performance, Andrew W. Marton

Williams Honors College, Honors Research Projects

Poly(vinylidene fluoride) (PVDF) can be formed into small nanofibers by electrospinning that are useful for a variety of applications. Air filters produced with PVDF are known to capture ionic particles with high efficiency. Existing studies have focused on the effects of electrospinning conditions on nanofiber morphology. In this study fibers were generated with varying morphologies. Air filters were then made from each sample and then characterized by TSI. Air filters were found to have increased resistances relative to their capture efficiencies according to particle diameter. Capture efficiencies did not correlate strongly with particle diameter, and the presence of beads in …

Growth And Properties Of Carbon Microcoils And Nanocoils, Muneaki Hikita, Robyn Bradford, Khalid Lafdi

Chemical and Materials Engineering Faculty Publications

Various types of coiled carbon filaments have been synthesized using chemical vapor deposition and other methods. These carbon filaments exhibit unique electrical and mechanical properties due to their versatile shapes and structures. To form coiled shapes, different types of catalyst compositions and reactive gases have been explored. Generally, coiled carbon filaments are classified by coil diameter and shape (e.g., microcoil and nanocoil). In this review, coiled carbon filaments are classified into three growth mechanism categories:

(1) bidirectional double helical growth;

(2) bidirectional twisted growth; and

(3) tip single helical or twisted growth.

Next, their synthesis methods and hypothetical growth mechanisms …

Slow Release Of Ions From Internalized Silver Nanoparticles Modifies The Epidermal Growth Factor Signaling Response, Kristen K. Comfort, Elizabeth I. Maurer, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

Due to their distinctive physiochemical properties, including a robust antibacterial activity and plasmonic capability, hundreds of consumer and medical products contain colloidal silver nanoparticles (AgNPs). However, even at sub-toxic dosages, AgNPs are able to disrupt cell functionality, through a yet unknown mechanism. Moreover, internalized AgNPs have the potential to prolong this disruption, even after the removal of excess particles. In the present study, we evaluated the impact, mechanism of action, and continual effects of 50 nm AgNP exposure on epidermal growth factor (EGF) signal transduction within a human keratinocyte (HaCaT) cell line. After AgNP expose, EGF signaling was initially obstructed …

Photo-Sensitivity Of Large Area Physical Vapor Deposited Mono And Bilayer Mos2, Baoming Wang, Christopher Muratore, Andrey A. Voevodin, M. Amanul Haque

Chemical and Materials Engineering Faculty Publications

We present photosensitivity in large area physical vapour deposited mono and bi-layer MoS2 films. Photo-voltaic effect was observed in single layer MoS2 without any apparent rectifying junctions, making device fabrication straightforward. For bi-layers, no such effect was present, suggesting strong size effect in light-matter interaction. The photo-voltaic effect was observed to highly direction dependent in the film plane, which suggests that the oblique deposition configuration plays a key role in developing the rectifying potential gradient. To the best of our knowledge, this is the first report of any large area and transfer free MoS2 photo device with performance comparable to …

Influence Of Nanofiller Morphology On The Viscoelastic Properties Of Cnf/Epoxy Resins, Liberata Guadagno, Marialuigia Raimondo, Khalid Lafdi, Annalisa Fierro, Salvatore Rosolia, Maria Rossella Nobile

Chemical and Materials Engineering Faculty Publications

In this paper we discuss the viscoelastic properties of CNF/Epoxy-Amine Resins for structural applications. The use of reactive diluent inside the unfilled and nanofilled epoxy mixture as proven to be of benefit to strongly decrease the viscosity.

Continuous Ultra-Thin Mos2 Films Grown By Low-Temperature Physical Vapor Deposition, Christopher Muratore, Jianjun Hu, Baoming Wang, M. Amanul Haque, John E. Bultman, Michael L. Jespersen, Michael E. Mcconney, R. D. Naguy

Chemical and Materials Engineering Faculty Publications

Uniform growth of pristine two dimensional (2D) materials over large areas at lower temperatures without sacrifice of their unique physical properties is a critical pre-requisite for seamless integration of next-generation van der Waals heterostructures into functional devices. This Letter describes a vapor phasegrowth technique for precisely controlled synthesis of continuous, uniform molecular layers of MoS2 on silicon dioxide and highly oriented pyrolitic graphite substrates of over several square centimeters at 350 °C. Synthesis of few-layer MoS2 in this ultra-high vacuum physical vapor deposition process yieldsmaterials with key optical and electronic properties identical to exfoliated layers. The films are composed of …

Optical Properties Of Carbon Microcoils, Muneaki Hikita, Li Cao, Khalid Lafdi

Chemical and Materials Engineering Faculty Publications

Carbon microcoils (CMCs) have emerged as versatile material artifacts for a variety of applications due to their helical and spiral structures. Embedded in matrix, CMCs have already been demonstrated for their potential tactile/proximity sensor application. In this study, CMCs were prepared using a conventional chemical vapor deposition method, and then were functionalized with octadecylamine.

Upon photoexcitation, the functionalized CMCs exhibited photoluminescence in the visible region, which has never been found before. Similar to carbon based nanoparticles, the photoluminescence of CMCs was attributed to electron-hole radiative recombination after surface passivation. The results suggested that this kind of fluorescent functionalized CMCs might …

Domain Engineering Of Physical Vapor Deposited Two-Dimensional Materials, Tarek Alam, Baoming Wang, Raghu Pulavarthy, M. Amanul Haque, Christopher Muratore, Nicholas R. Glavin, Ajit K. Roy, Andrey A. Voevodin

Chemical and Materials Engineering Faculty Publications

Physical vapor deposited two-dimensional (2D) materials span larger areas compared to exfoliated flakes, but suffer from very small grain or domain sizes. In this letter, we fabricate freestanding molybdenum disulfide (MoS2) and amorphous boron nitride (BN) specimens to expose both surfaces. We performed in situ heating in a transmission electron microscope to observe the domain restructuring in real time. The freestanding MoS2 specimens showed up to 100× increase in domain size, while the amorphous BN transformed in to polycrystalline hexagonal BN (h-BN) at temperatures around 600 °C much lower than the 850–1000 °C range cited in the literature.

Less Is More: Long-Term In Vitro Exposure To Low Levels Of Silver Nanoparticles Provides New Insights For Nanomaterial Evaluation, Kristen K. Comfort, Laura K. Braydich-Stolle, Elizabeth I. Maurer, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

In view of the vast number of new nanomaterials (NMs) that require testing and the constraints associated with animal models, the majority of studies to elucidate nanotoxicological effects have occurred in vitro, with limited correlation and applicability to in vivo systems and realistic, occupational exposure scenarios.

In this study, we developed and implemented a chronic in vitromodel coupled with lower, regulatory dosages in order to provide a more realistic assessment of NM-dependent consequences and illuminate the implications of long-term NM exposure. When keratinocytes were exposed to 50 nm silver nanoparticles (Ag-NPs), we determined that chronically dosed cells operated …

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

Theses and Dissertations--Civil Engineering

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

Electrospinning Applications Air Filtration And Superhydrophobic Materials, Negar Ghochaghi, Adetoun Taiwo

Graduate Research Posters

Electrospinning is a widely applicable technique that generates non-woven fibers in the micro and nano range. In this project two of its applications are highlighted namely filtration media and enhancement of wettability. The first project demonstrates that electrospinning can be used to produce new fiber filtration media with controlled microstructure. The bimodal and unimodal orthogonal and random filters were made and characterized against their filtration efficiency and pressure drop. Figure of Merit (FOM) was also calculated and discussed. It is shown that the FOM increases when the electrospun fibers are arranged into alternating layers of aligned course and fine fibers. …

Physiological Fluid Specific Agglomeration Patterns Diminish Gold Nanorod Photothermal Characteristics, Kristen K. Comfort, Jared W. Speltz, Bradley M. Stacy, Larry R. Dosser, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

Investigations into the use of gold nanorods (Au-NRs) for biological applications are growing exponentially due to their distinctive physicochemical properties, which make them advantageous over other nanomaterials. Au-NRs are particularly renowned for their plasmonic characteristics, which generate a robust photothermal response when stimulated with light at a wavelength matching their surface plasmon resonance. Numerous reports have explored this nanophotonic phenomenon for temperature driven therapies; however, to date there is a significant knowledge gap pertaining to the kinetic heating profile of Au-NRs within a controlled physiological setting. In the present study, the impact of environmental composition on Au-NR behavior and degree …

The Biological Impact Of Concurrent Exposure To Metallic Nanoparticles And A Static Magnetic Field, Kristen K. Comfort, Elizabeth I. Maurer, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

The rapid advancement of technology has led to an exponential increase of both nanomaterial and magnetic field utilization in applications spanning a variety of sectors. While extensive work has focused on the impact of these two variables on biological systems independently, the existence of any synergistic effects following concurrent exposure has yet to be investigated. This study sought to ascertain the induced alterations to the stress and proliferation responses of the human adult low calcium, high temperature keratinocyte (HaCaT) cell line by the application of a static magnetic field (approximately 0.5 or 30 mT) in conjunction with either gold or …