Polymer Science Commons^™

A Model-Based Framework For The Smart Manufacturing Of Polymers, Santiago D. Salas Ortiz

LSU Doctoral Dissertations

It is hard to point a daily activity in which polymeric materials or plastics are not involved. The synthesis of polymers occurs by reacting small molecules together to form, under certain conditions, long molecules. In polymer synthesis, it is mandatory to assure uniformity between batches, high-quality of end-products, efficiency, minimum environmental impact, and safety. It remains as a major challenge the establishment of operational conditions capable of achieving all objectives together. In this dissertation, different model-centric strategies are combined, assessed, and tested for two polymerization systems.

The first system is the synthesis of polyacrylamide in aqueous solution using potassium persulfate …

“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 …

Using Green Emitting Ph-Responsive Nanogels To Report Environmental Changes Within Hydrogels: A Nanoprobe For Versatile Sensing, Mingning Zhu, Dongdong Lu, Shanglin Wu, Qing Lian, Wenkai Wang, L. Andrew Lyon, Weiguang Wang, Paulo Bártolo, Brian R. Saunders

Engineering Faculty Articles and Research

Remotely reporting the local environment within hydrogels using inexpensive laboratory techniques has excellent potential to improve our understanding of the nanometer-scale changes that cause macroscopic swelling or deswelling. Whilst photoluminescence (PL) spectroscopy is a popular method for such studies this approach commonly requires bespoke and time-consuming synthesis to attach fluorophores which may leave toxic residues. A promising and more versatile alternative is to use a pre-formed nanogel probe that contains a donor/acceptor pair and then “dope” that into the gel during gel assembly. Here, we introduce green-emitting methacrylic acid-based nanogel probe particles and use them to report the local environment …

Self-Assembled Nanoantenna Enhance Optical Activity And Transport In Scalable Thin Films And Interfaces, Keith Richard Berry Jr.

Graduate Theses and Dissertations

Continued population growth and the decrease of existing energy platforms demands long-term solutions for development and implementation of scalable plasmonic metamaterials for energy and agricultural applications. Self-assembled nanoantenna into random and ordered arrangements are advanced herein for optical and thermal enhancements in scalable thin film. An analytical approach to estimating the thermal dynamics of random arrangements of nanoantenna resulted in estimates within 30% across a range of geometric parameters, nanoantenna-containing media, and thermal parameters. Multimodal thermal dynamics of polymer thin films containing gold nanoparticles (AuNPs) were observed through the natural log of the dimensionless temperature driving force plotted versus time …

Nanogels And Microgels: From Model Colloids To Applications, Recent Developments, And Future Trends, Mattias Karg, Andrij Pich, Thomas Hellweg, Todd Hoare, L. Andrew Lyon, J. J. Crassous, Daisuke Suzuki, Rustam A. Gumerov, Stefanie Schneider, Igor I. Potemkin, Walter Richtering

Engineering Faculty Articles and Research

Nanogels and microgels are soft, deformable, and penetrable objects with an internal gel-like structure that is swollen by the dispersing solvent. Their softness and the potential to respond to external stimuli like temperature, pressure, pH, ionic strength, and different analytes make them interesting as soft model systems in fundamental research as well as for a broad range of applications, in particular in the field of biological applications. Recent tremendous developments in their synthesis open access to systems with complex architectures and compositions allowing for tailoring microgels with specific properties. At the same time state-of-the-art theoretical and simulation approaches offer deeper …

Biodegradable Polymeric Film For Food Packaging, Neelam Yadav, Raminder Kaur

Journal of Applied Packaging Research

Food packaging films that show post-consumer biodegradability are rarely explored by researchers. The present study was carried out to investigate the physicomechanical characteristics of ethyl cellulose (EC) based films to be used in food packaging. Ethyl cellulose was plasticized with different percentage of polyethylene glycol (PEG). The samples of standard dimensions were subjected to different testing such as soluble matter content, moisture content, oil permeability, surface morphology, mechanical testing etc. The data obtained was analysed to decide the moderate percentage of plasticizer that can be used to provide a rational explanation of a perfect quality specimen. It has been revealed …

Silver Nano Polymer Composite Membrane For Hydrogen Sulfide Sensing, Muhammad Bagus Arif

Chulalongkorn University Theses and Dissertations (Chula ETD)

Optical and electrochemical sensor for H2S sensing were developed using silver nanoparticles (AgNPs) immobilized onto polyelectrolyte membranes (PEMs) as substrate. Two approach for the deposition of the silver nanoparticles namely in-situ and ex-situ were compared for their sensing efficiency. The Poly(diallyldimethylchloride) (PDADMAC) and Poly(sodium styrenesulfonate) (PSS) were used to build PEMs via layer-by-layer assembly mechanism as polycation and polyanion respectively. In situ synthesis of silver nanoparticles was achieved by dipping the PEM coated substrate in silver nitrate (AgNO₃) solution followed by sodium borohydride (NaBH₄) as reducing agent. For ex situ technique, a monolayer of pre-synthesized silver nanoparticles was deposited as …

Effects Of Micro-Features On Cell Detachment From Poly(N-Isopropylacrylamide) Coated Polydimethylsiloxane Membranes, Luke Webel

Williams Honors College, Honors Research Projects

The tested hypothesis was that features on polydimethylsiloxane (PDMS) surfaces coated with a poly(N-isopropylacrylamide)/aminopropyltriethoxysilane or pNIPAAM/APTES thin film would accelerate cell detachment than the film coated on a unfeatured surface. This project tested samples with features generated by molds, wrinkling, and sandpaper roughened substrates. Surface feature generation methods were limited to mechanical means, and characterized by microscopy and strain rates. 50/50 mixtures of 1.5 wt.% pNIPAAM/ APTES were used to coat thin films (30-40 nm) on PDMS membranes by spin-coating, and the coated membranes were thermally annealed to chemically graft pNIPAAm/APTES on the membrane and their thermo-responsive property was assessed …

Synthesis Of Polyurethane From Sustainable Sources, Jovan Jevric

Williams Honors College, Honors Research Projects

The most common method of polyurethanes involves a reaction between various petroleum-based isocyanates and a polyol along with a catalyst; all of which have a negative impact on environmental and human health. The objective of this research project is to eliminate or mitigate the risks and hazards associated with the production and degradation of polyurethane. Hexamethylene diisocyanate isocyanurates (3HDI) are one of the most common isocyanates used in the polyurethane processing industry. 3HDI contains numerous toxins, and it has a negative impact on the environment and human health¹. It has been found that there are other compounds that …

Developing A Portable Prototype To Utilize An Electrospun Colorimetric Sensor For The Detection Of Trihalomethanes In Water, Amanda Svensson

Williams Honors College, Honors Research Projects

Trihalomethane (THM) detection in water is important due to the potential health effects caused by their presence, including increased cancer risk. A cheap, quick, and portable method of identifying THM concentration at the Environmental Protection Agency limit of 80 parts per billion (ppb) will improve detection and water treatment. Electrospinning was used to make nanofiber membranes using a 2.6 wt% polypropylene solution. These membranes were utilized in the Fujiwara reaction, which creates a color change in the presence of THMs, to detect the THM bromoform in water. The color intensity of the reaction was quantified for 250 and 80 ppb …

Requalification Of Coated Fabrics Using Chemlok 2332 In Place Of Chemlok 233, Daniel Madler

Williams Honors College, Honors Research Projects

Rubber coated fabrics are an essential component in the deicing systems of the aerospace industry. Adhesives cements are applied to a fabric prior to being pressed into a rubber compound that will adhere to the fabric. The resulting fabric maintains the strength of the fabric with the added benefits of elasticity and compatibility from the rubber compound. UTC Aerospace Systems relies on these coated fabrics to create safe deicers for the aerospace industry. Chemlok 233, a now obsolete primer cement, was used extensively in the coated fabrics used by UTC. Materials testing and performance evaluation allowed for a replacement cement, …

Compression Set Improvement Of Thermoplastic Vulcanizates For High Temperature Tubing, Mitchell Valaitis

Williams Honors College, Honors Research Projects

It was hypothesized that increasing the curative level of the fluorocarbon rubber (FKM) used in manufacturing of thermoplastic vulcanizate (TPV) materials would decrease the compression set values of the TPV enough for it to be suitable as a flexible, lightweight alternative to high operating temperature thermoset rubber tubing currently being used for power steering hose. First, promising TPV formulations were identified by varying the polyamide (PA) and FKM used in a Brabender mixer. Four different types of polyamide and four different types of FKM were investigated, with two of the FKM types and one polyamide type identified as being promising. …

Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson

Williams Honors College, Honors Research Projects

Chemonic™ CCG-6 surfactant is a water-soluble poly(ethylene glycol) (PEG) conjugated alkyl glyceride emollient. This surfactant exists as a complex mixture of a glycerol cores conjugated with poly(ethylene glycol) branches (PEGylation) that were partially esterified with caprylic (C8) and capric (C10) acids. These may be esterified on one, two, or all three arms of the glyceride. The architecture of the structures in this mixture was studied using multidimensional mass spectrometry (MS). Mass spectrometry was interfaced with ultra-performance liquid chromatography (UPLC) and ion mobility (IM) separation. The mixture was separated by reversed-phase LC, oligomers of the star-branched polymer were separated according to …

The Study Of Sulfur Compounds For Oils Fingerprinting Application, Titiparn Prasantongkolmol

Chulalongkorn University Theses and Dissertations (Chula ETD)

Oil spills are one of the serious problems to marine and coastal environment worldwide. Besides the known incidents, a number of oil spills are unknown, which may come from both accident and unauthorized drainage. Moreover, the spills cause tarball to arise on the beach and the origin of tarballs are still subtle. Thus, the development of oil fingerprinting is important in order to identify the origin of oil spills and tarballs. Generally, the current standard technique is using GCxGC-TOFMS to analyze the biomarker compounds in oil such as hopane groups. However, this technique is expensive and requires long time for …

Synthesis, Functionalization, And Application Of Nanofiltration And Composite Membranes For Selective Separations, Andrew Steven Colburn

Theses and Dissertations--Chemical and Materials Engineering

Future nanofiltration (NF) membranes used for selective separations of ions and small organic molecules must maintain performance in environments where high concentrations of total dissolved solvents or foulants are present. These challenges can be addressed through the development of composite membranes, as well as the engineering of enhanced surface properties and operating conditions for existing commercial membranes.

In this work, ion transport through commercial thin film composite (TFC) polyamide NF membranes were studied in both lab-prepared salt solutions and industrial wastewater. The dependence of several variables on ion rejection was investigated, including ion radius, ion charge, ionic strength, and temperature. …

Towards The Rational Design And Application Of Polymers For Gene Therapy: Internalization And Intracellular Fate, Landon Alexander Mott

Theses and Dissertations--Chemical and Materials Engineering

Gene therapy is an approach for the treatment of acquired cancers, infectious disease, degenerative disease, and inherited genetic indications. Developments in the fields of immunotherapies and CRISPR/Cas9 genome editing are revitalizing the efforts to move gene therapy to the forefront of modern medicine. However, slow progress and poor clinical outcomes have plagued the field due to regulatory and safety concerns associated with the flagship delivery vector, the recombinant virus. Immunogenicity and poor transduction in certain cell types severely limits the utility of viruses as a delivery agent of nucleic acids. As a result, significant efforts are being made to develop …

Development Of Novel Temperature Responsive Polymeric Sorbents And Their Applications In Water Remediation, Shuo Tang

Theses and Dissertations--Chemical and Materials Engineering

Water remediation utilizing sorption has found strong interest due to its inexpensiveness, universal nature and ease of operation. In particular, thermo-responsive sorbents consisting of N-isopropylacrylamide (NIPAAm) offer significant potential as “smart” and advanced materials to remove multiple aqueous pollutants. NIPAAm exhibits excellent thermo-responsiveness, which senses the external temperature variation and changes its swelling and sorption behaviors in a sharp and rapid manner. At the beginning of this work, an extensive review of literature has been compiled to provide a summary of NIPAAm-based thermo-responsive sorbents in water/wastewater remediation applications.

Initially, we developed a novel approach to synthesize and characterize NIPAAm copolymeric …

Functionalization Of Iron Oxide Nanoparticles And The Impact On Surface Reactive Oxygen Species Generation For Potential Biomedical And Environmental Applications, Trang Mai

Theses and Dissertations--Chemical and Materials Engineering

Iron oxide nanoparticles (IONPs) have been widely studied for a variety of applications, from biomedical applications (e.g., cell separation, drug delivery, contrast agent for magnetic resonance imaging and magnetically mediated energy delivery for cancer treatment) to environmental remediations (e.g., heavy metal removal and organic pollutants degradation). It has been demonstrated that IONPs can induce the production of reactive oxygen species (ROS) via Fenton/Haber-Weiss reactions which has been shown to be one of the key underlying mechanisms of nanoparticles toxicity. This inherent toxicity of nanoparticles has been shown to enhance the efficacy of traditional cancer therapies such as chemotherapy and radiation. …

Synthesis, Characterization And Applications Of Reduced Graphene Oxide And Composite Membranes For Selective Separations And Removal Of Organic Contaminants, Ashish Aher

Theses and Dissertations--Chemical and Materials Engineering

Among the next generation materials being investigated for membrane development, partially reduced Graphene Oxide (rGO) has received increasing attention from the membrane community. rGO-based nanofiltration membranes have shown promising results in applications such as partial desalination, organic contaminant removal, gas-phase separations, and separations from solvent media. rGO offers a unique platform compared to common polymeric membranes since it can be used for separation applications in both aqueous and organic solvent media. An rGO-based platform could also be utilized to synthesize reactive membranes, giving rGO membranes the additional capability of reactively removing organic contaminants. This research focuses on the synthesis of …

The Fabrication And Characterization Of Metal Oxide Nanoparticles Employed In Environmental Toxicity And Polymeric Nanocomposite Applications, Matthew Logan Hancock

Theses and Dissertations--Chemical and Materials Engineering

Ceria (cerium oxide) nanomaterials, or nanoceria, have commercial catalysis and energy storage applications. The cerium atoms on the surface of nanoceria can store or release oxygen, cycling between Ce³⁺ and Ce⁴⁺, and can therefore act as a therapeutic to relieve oxidative stress within living systems. Nanoceria dissolution is present in acidic environments in vivo. In order to accurately define the fate of nanoceria in vivo, nanoceria dissolution or stabilization is observed in vitro using acidic aqueous environments.

Nanoceria stabilization is a known problem even during its synthesis; in fact, a carboxylic acid, citric acid, is …

Production Of Bio-Jet Fuel From Palm Fatty Acid Distillate Over Bi-Functional Copd/Hzsm-12 Catalysts, Jarujit Chaowichitra

Chulalongkorn University Theses and Dissertations (Chula ETD)

Jet fuel is one of the major products from a petroleum refinery, its combustion emissions contribute to global warming. Therefore, bio-jet fuel is introduced to solve this problem. Palm fatty acid distillate (PFAD) is an interesting feedstock for bio-jet fuel production via three reactions including deoxygenation, hydrocracking, and isomerization. In this study, the monometallic (Co and Pd) and bimetallic (CoPd and NiPd) supported on HZSM-12 zeolite with various metal loadings and bimetallic CoPd with various zeolite supports (HZSM-12, HZSM-5, and HY) were investigated in a continuous flow trickle bed reactor. The presence of bimetallic CoPd on HZSM-12 zeolite support enhanced …

Removal Of Trace Olefins From Aromatics With Modified Usy Zeolite And Clays, Sirawit Lertprapaporn

Chulalongkorn University Theses and Dissertations (Chula ETD)

Naphtha reforming is an important raw material for aromatic hydrocarbon products in petrochemical processes. However, aromatic hydrocarbon streams obtained from refinery contain unavoidable trace amounts of olefins as an impurity. The trace olefins must be removed because these undesirable olefins are harmful to the following separation processes. Alkylation reaction has been used to remove olefins with acid catalysts. In this study, clays and zeolites were screened for further modification in order to enhance the catalytic activity of olefins removal. The catalytic activity testing was studied in a batch reactor at 195 ℃ for 6 h under 12 barg. USY was …

Combined Life Cycle Analysis And Material Flow Analysis As A Tool For End Of Life Options Of Used Lubricating Oils, Komsan Toeipomthong

Chulalongkorn University Theses and Dissertations (Chula ETD)

Used lubricating oils are one of the most significant material flows in the economy. After being used, they are typically contaminated with, e.g., heavy metals, which could harm the environments if they are treated improperly. The used oils should be properly treated by reprocessing or recycling which the recyled products can be used to subsitute the production the new product, as a result a net reduction of the environemental impacts. This study aimed to investigate the waste flow and then evaluate the environmental impacts of waste management options using the Material Flow Analysis (MFA, STAN v.2.6.801) and Life Cycle Assessment …

High-Throughput Assessment Of A Novel, Thiol-Acrylate Hydrogel For Tumor Spheroid Synthesis In A Microfluidic Device, Nathan Daniel Kersker

LSU Master's Theses

The extracellular environment plays an important role in regulating cell behavior. The mechanical, structural, and compositional properties of the extracellular matrix can determine the fate of the growing cells. Standard two-dimensional culturing in a flask fails to represent a native cellular environment. To create the native environment suitable for cells, hydrogels were previously studied. One of the most extensively studied synthetic hydrogels was a poly(ethylene glycol diacrylate) (PEGDA) hydrogel. However, the need for UV polymerization may introduce unwanted changes in cell morphology and viability. The hydrogel being proposed was a form of a thiol-acrylate hydrogel that can eliminate this problem …

Controlled Nanomorphology Of Hybrid Organic/Inorganic Multi-Component Composites Through Cooperative Non-Covalent Interactions, Lingyao Meng

Shared Knowledge Conference

Hybrid organic–inorganic nanocomposite polymers, with inorganic nanoparticles embedded in organic matrix have emerged as a special category of multifunctional materials. With rational materials design, these hybrids can show the synergistic effect of the properties from both phases. Homogenous dispersion and orderly arrangement of the organic and inorganic components are key in their functionalities. By controlling the interface and corresponding interfacial interactions between the organic and inorganic entities, we have developed a logical approach to form stable and controlled hybrid nanofiber structures. We demonstrate the formation of hybrid polymer/quantum dots (or iron oxide nanoparticles) nanocomposites through non-covalent interactions (hydrogen bonding, ionic …

Thin-Film Block Copolymers (Bcps) Self-Assembly As Versatile Patterning Scheme For Functional Nanomaterials, Le Zhang

LSU Master's Theses

Nanopattern generation is required for building various structural entities in every production process that involves nanostructures. Advancing nanopatterning technologies play an important role in developing and broadening the current nanopatterning technologies to meet up with the ever-demanding requirements in the realm of smaller feature sizes, smoother line-edge roughness (LER) and facile pattern transfer in pursuit of faster computer processors, better electrocatalysts and more compact and intelligent sensors, etc. Conventionally, patterning needs are heavily relied on photolithography, a technique that dominate chip-making industry for more than 50 years. However conventional photolithography is bounded by inherent resolution limits and difficult to be …

Electrochemical Hydrogenation Of Acetone To Produce Isopropanol Using A Polymer Electrolyte Membrane Reactor, Chen Li, Ashanti M. Sallee, Xiaoyu Zhang, Sandeep Kumar

Civil & Environmental Engineering Faculty Publications

Electrochemical hydrogenation (ECH) of acetone is a relatively new method to produce isopropanol. It provides an alternative way of upgrading bio-fuels with less energy consumption and chemical waste as compared to conventional methods. In this paper, Polymer Electrolyte Membrane Fuel Cell (PEMFC) hardware was used as an electrochemical reactor to hydrogenate acetone to produce isopropanol and diisopropyl ether as a byproduct. High current efficiency (59.7%) and selectivity (>90%) were achieved, while ECH was carried out in mild conditions (65 degrees C and atmospheric pressure). Various operating parameters were evaluated to determine their effects on the yield of acetone and …

Interface Model Of Pem Fuel Cell Membrane Steady-Dtate Behavior, Russell L. Edwards, Ayodeji Demuren

Mechanical & Aerospace Engineering Faculty Publications

Modeling works which simulate the proton-exchange membrane fuel cell with the computational fluid dynamics approach involve the simultaneous solution of multiple, interconnected physics equations for fluid flows, heat transport, electrochemical reactions, and both protonic and electronic conduction. Modeling efforts vary by how they treat the physics within and adjacent to the membrane-electrode assembly (MEA). Certain approaches treat the MEA not as part of the computational domain, but rather an interface connecting the anode and cathode computational domains. These approaches may lack the ability to consistently model catalyst layer losses and MEA ohmic resistance. This work presents an upgraded interface formulation …