Chemical Engineering Commons^™

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 …

Characterization Of Interlayer Laser Shock Peening During Fused Filament Fabrication Of Polylactic Acid (Pla), Fabien Denise

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

The field of additive manufacturing (AM) has gained a significant amount of popularity due to the increasing need for more sustainable manufacturing techniques and the adaptive development of complex product geometries. The problem is that AM parts routinely exhibit flaws or weaknesses that affect functionality or performance. Over the years, surface treatments have been developed to compensate certain flaws or weaknesses in manufactured products. Combining surface treatments with the modularity of additive manufacturing could lead to more adaptable and creative improvements of product functions in the future. The current work evaluates the feasibility of pursuing a new research axis in …

Measuring Of Thermal Conductivity And Heat Capacity Of Different Papers And Heat-Sealing Process Of Papers With A Polymer Layer, Amenah Khalaf

Electronic Theses and Dissertations

Packaging is an important and safe way to protect our food and other things through transportation, but the use of plastic based packaging is causing issues with plastic pollution. To replace plastic packaging with a paper-based option that has a barrier coating, good heat sealing will be needed to be a drop-in replacement. While much as been studied on the heat sealing of polymer layers, little has been reported around the heat sealing of paper that has a polymeric barrier coating.

Experiments were conducted to characterize the thermal conductivity and heat capacity of paper as a function of press pressure …

Advancing Ionomer Design To Boost Interfacial And Thin-Film Proton Conductivity Via Styrene-Calix[4]Arene-Based Ionomers, Shyambo Chatterjee, Oghenetega Allen Obewhere, Ehsan Zamani, Rajesh Keloth, Seefat Farzin, Martha D. Morton, Anandakumar Sarella, Shudipto Konika Dishari

Department of Chemical and Biomolecular Engineering: Faculty Publications

Sub-micrometer-thick ion-conducting polymer (ionomer) layers often suffer from poor ionic conductivity at the substrate/catalyst interface. The weak proton conductivity makes the electrochemical reaction at the cathode of proton-exchange-membrane fuel cells sluggish. To address this, here we report on a class of polystyrene-based ionomers having sub-nanometer-sized, sulfonated macrocyclic calix[4]arene-based pendants (PS-calix). In films with thickness comparable to that of ionomer-based binder layers, the conductivity of PS-calix film (∼41 mS/cm) is ∼13 times higher than that of the current state-of-the-art ionomer, Nafion. We observe a similar improvement in proton conductivity when PS-calix interfaces with Pt nanoparticles, demonstrating the potential of PS-calix in …

Beeswax Wraps As An Alternative To Single-Use Plastics, Sarah Skiver

Williams Honors College, Honors Research Projects

The project goal was to compare the food storage efficacy of sustainable beeswax wraps verses the single-use plastic methods of resealable plastic sandwich bags and plastic cling wrap. The goal was also to test the reusability of the beeswax wraps, as it is a key advantage of beeswax wraps that is advertised. The project purpose was to explore sustainable and eco-friendly alternatives to single use plastics, which are harmful to the environment in both their production and their disposal. Food spoilage was compared in beeswax wrap, plastic sandwich bags, and plastic cling wrap, and spoilage was also observed in a …

Demonstration Of High Detoxification Efficiency Of Glassy Polymer-Metal Hydroxide Composites Toward Chemical Warfare Agent Simulants, Peter O. Aina, Sukanta K. Mondal, Joshua Costain, Ali A. Rownaghi, Fateme Rezaei

Chemical and Biochemical Engineering Faculty Research & Creative Works

The design and development of polymeric composites that can effectively capture and destruct toxic chemicals with a fast detoxification rate is of high importance for protecting the military, first responders, and civilians. Here we report the synthesis and assessment of zirconium hydroxide (Zr (OH)4)-incorporated Ultem, Matrimid, and PIM-1 composites for detoxification of dimethyl 4-nitrophenylphosphonate (DMNP), as a type G toxic nerve agent simulant. Maintaining homogeneity, three different loadings (8, 20, 30 wt %) of Zr (OH)4 were incorporated into the polymers, and the thin films of composite materials were developed for subsequent hydrolysis tests. Our results indicated that increasing the …

Correlating The Macrostructural Variations Of An Ion Gel With Its Carbon Dioxide Sorption Capacity, Tung Nguyen,, Mona Bavarian, Siamak Nejati

Department of Chemical and Biomolecular Engineering: Faculty Publications

We report on a direct correlation between the macroscale structural variations and the gas sorption capacities of an ion gel. Here, we chose 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([Emim][TF₂N]) and poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) as the ionic liquid and host polymer, respectively. The CO₂ sorption in the thin films of the IL-polymer was measured using the gravimetric method. The results of our experiment showed that the trend in CO₂ uptake of these mixtures was nonlinearly correlated with the content of IL. Here, we highlight that the variations in the molecular structure of the polymers were the main reason behind …

Improving Electrical Properties Of Polypropylene/Gnp Composites Using Compatibilizer And Solvent-Assisted Melt Blending, Yazan Al Jawhari

Undergraduate Student Research Internships Conference

Over the past few years, polymer products have become essential to our lives. Many people may think that polymers are simply plastics, however, that is just the tip of the iceberg. Polymer products are used in food, sport, medical, and technological industries. There have been numerous applications in all these areas, but in the technological industry, electronic devices, in particular, are affected by electrostatic discharge (ESD) generated by friction during handling, packaging, or transportation. This requires the use of antistatic packaging, a special package that has low electrical resistivity in order to avoid electron accumulation.

This study is an attempt …

Functional Bottlebrush Polymer Additives For Thin Films And Coatings, Travis S. Laws

Doctoral Dissertations

Bottlebrush polymers are a class of highly branched polymers consisting of polymeric side chains that are densely grafted to a linear backbone. Their highly branched architecture results in surface enrichment across a broad range of materials. The goal of my research has been centered around the design of functional bottlebrush polymers and their use as surface active additives in blend films and coatings.

In the first chapter, we examine the segregation behavior of polystyrene bottlebrushes that are blended with linear polystyrene. We systematically vary the lengths of the bottlebrush backbone (Nb), side-chain (Nsc), and the linear matrix (Nm) in order …

Sustainable Polylactic Acid Foam Development Through Solid-State Processing, Philip Onffroy

Honors Theses

Plastics play a vital role in global materials industries, but they contribute to environmental and ecological toxicity effects that accelerate climate change. One important category of plastic material is polymer foams, which have widespread applications in insulation, packaging, and storage. Current bio-based plastic foams that originate from natural, non-petroleum feedstocks are potential solutions but do not yet have adequate properties to supplant petrochemical-based plastic foams. This project aims to generate, test, and analyze bio-based polylactic acid (PLA) polymer foams developed through methods involving solid-state processing such as solid-state shear pulverization (SSSP) and cryogenic milling. SSSP has previously been shown to …

Mimicking The Namib Desert Beetle With Hydrophilic And Hydrophobic Surfaces, Tyler Bracewell

Williams Honors College, Honors Research Projects

The Namib Desert beetle, Stenocara gracilipes, condenses fog that rolls in off the west coast of Namibia to provide itself with the water it needs for the day. By lifting its abdomen into the air to collect the water vapor, it condenses on hydrophilic bumps that are about 500μm in diameter and are spaced apart about 500-1500μm. Once the water reaches a critical size, the droplet rolls off the hydrophilic bump and onto the flat hydrophobic surface of the elytra. Since the beetle is angled with its abdomen in the air, the water rolls down to its mouth. A …

Amine-Functionalized Interpenetrating Polymer Networks For Co2 Capture, James Wills

Williams Honors College, Honors Research Projects

The research performed looked to advance the studies of vacuum swing absorption of Carbon Dioxide to help combat global climate change issues. The focus of the project was to create an anime-polymer sorbent that will weakly absorb and desorb CO2. The sorbent must be durable and be able to withstand multiple uses. The creation of a porous polymer matrix aided in the amines' ability to absorb CO2. Created samples underwent several qualitative and quantitative tests to determine their usefulness as an industrial sorbent. Infrared spectroscopy was used to study the effectiveness of the amine sorbents. Studying the changes in the …

Wetting Transition On 3d-Printed Surfaces, Isabelle Moryan

Williams Honors College, Honors Research Projects

Taking the previous research conducted, this project aims to further the study and research of the wettability of surfaces. Surface features and types are important factors to their wettability. The geometric properties of a surface can make it more hydrophobic and hydrophilic. Extreme cases of hydrophobic and hydrophilic surfaces lead to water repulsion or water absorption, even under extreme conditions. The goal of this project is to gain further insight on how fabricated 3D-printed featured surfaces and examine the wetting transition on these surfaces. In particular, cylindrical pillars will be studied with varied pillar spacing, height and diameter. In addition, …

Sealant Injectivity Through Void Space Conduits To Assess Remediation Of Well Cement Failure, Mohammed Alkhamis, Abdulmohsin Imqam

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

The primary cement of oil and gas wells is prone to fail under downhole conditions. Thus, a remedial operation must be conducted to restore the wellbore integrity and provides zonal isolation. Many types of materials are currently used and/or have the potential to be employed in wellbore integrity applications, including, but not limited to, conventional Portland cement, microfine and ultrafine cement, thermoset materials, and thermoplastic materials. In this study, several types of materials were selected for evaluation: (1) conventional Portland cement, which is the most widely used in remedial operations in the petroleum industry, (2) polymer resin, which is one …

Stretching The Applications Of Biomass: Development Of Lignin Based Thermoplastic Elastomers And Composite Materials, Anthony Stephen Bova

Doctoral Dissertations

Bio-based plastics and composites have seen increased industry adoption in recent years due to growing demand for materials with a low carbon footprint. The use of lignin as a feedstock for polymers has seen growing interest as the concept of an integrated cellulosic biorefinery gains traction and advances the need to use all components of separated biomass for value-added applications. Historically, use of lignin in thermoplastic and elastomeric copolymers and blends has been bottlenecked by the inability to introduce lignin content above 30 weight percent due to difficulties with interfacial adhesion of lignin with other soft segments. Efforts to overcome …

Enhancement Of Electrospun Nanofiber Properties Via Automated Track Post-Draw Processing, David Anthony Brennan

Theses and Dissertations

Electrospinning is an alternative manufacturing method, capable of producing fibers with nanoscale diameters from a wide range of different polymers in a process which is relatively simple and inexpensive in comparison to other forms of nanofiber production. This has made electrospinning the subject a great deal of research as a method of producing nanofibers for various high-performance applications. However, electrospun nanofiber tensile strength is weak in comparison to conventional fibers of the same material, preventing widespread use and marketization. This disparity in mechanical strength is attributed to poor polymer chain alignment in individual fibers, caused by the absence of a …

An Investigation Of Cross-Links On Crystallization And Degradation In A Novel, Photocross-Linkable Poly (Lactic Acid) System, Nicholas Baksh

USF Tampa Graduate Theses and Dissertations

Polymeric molecular structure consists of repeating units bonded together. Mechanicalproperties can be altered without affecting chemical makeup by altering the number of these units. Small molecules can be introduced and/or polymers can be modified to form bonds between molecular chains. Cross-linking, as this is called, also introduces mechanical variation with minimal effects on chemical composition. Lastly, polymer chains reorient themselves in response to intermolecular forces. This temperature dependent response is known as crystallization. Although chemistry is unaltered, mechanical properties can depend highly on the percent of the sample that is crystallized.

Cross-linking is known to enhance the mechanical properties of …

Surface Driven Flows : Liquid Bridges, Drops And Marangoni Propulsion, Samrat Sur

Doctoral Dissertations

Molecules sitting at a free liquid surface against vacuum or gas have weaker binding than molecules in the bulk. The missing (negative) binding energy can therefore be viewed as a positive energy added to the surface itself. Since a larger area of the surface contains larger surface energy, external forces must perform positive work against internal surface forces to increase the total area of the surface. Mathematically, the internal surface forces are represented by surface tension, defined as the normal force per unit of length. One common manifestation of surface tension is the difference in pressure it causes across a …

Catalysts For Polymer Membrane Fuel Cells, William E. Mustain, Bryan Pivovar

Faculty Publications

No abstract provided.

Effects Of Crosslinking Conditions On Biofouling Of Polymer Substrates With A Hydrogel Layer, Laura Davila

Williams Honors College, Honors Research Projects

The introduction of a hydrogel coating to a surface has been looked at for different benefits. Certain hydrogels offer antifouling properties that are beneficial to different applications like medical components. Previous attempts (2) (3)have been done to introduce a hydrogel surface to plastic substrates. One of them is to use grafting brushes which works properly but it is not sufficient since the layer is too thin and therefore can be damaged. The second method have a bulkier coating without crosslinking. Opposite to grafting brushes this method has too thick of a layer. Additionally, there is no crosslink therefore the coating …

Methods For Film Coating Electrospun Fibers, Kristopher Dejean

Williams Honors College, Honors Research Projects

Electrospinning uses high voltages to form polymer nanofiber membranes. These membranes have potential for use in filtration, tissue engineering, drug delivery, and catalysis. The nonwoven fiber mat is malleable but has a low tensile strength compared to a solid film of the same polymer. Joining the fibers with a thin film is desired to balance the strength and flexibility. Three methods of producing a film on fiber membrane were tested. The techniques are spraying then melting, spin coating, and dip coating. Electrospinning setup conditions, solvent ratios, damage to fibers, and spin coating speeds were determined. Research was abruptly stopped and …

Filtration Apparatus Design For Oil-Water Separation Using Membranes And Sponges, Alec Jerger

Williams Honors College, Honors Research Projects

It can be difficult to separate water and oil emulsions through traditional filtration. Therefore, investigations of filtering using thermo-responsive (TR) polymers, in this case poly(vinyl methyl ether) (PVME), was conducted. It’s hypothesized that below its lower critical solution temperature (LCST), PVME has an affinity for water while oil substances do not. Above the LCST the opposite will be true. To verify this hypothesis, iterations of filtration designs were created to provide optimum control over the parameters to measure flow. The final optimized experimental apparatus was a Chromaflex glass column which was air tight and controlled all parameters besides fluid flow. …

A Comparison Of Fiber Mat Thickness Measurement Techniques Using Laser Interferometry And Water Displacement, Ryan Seabeck

Williams Honors College, Honors Research Projects

Polymer fiber mats may often be very thin which leads to complications in measuring thickness. The thickness of fiber mats, however, is crucial in understanding their behavior. Thickness affects how well the mat works as a filter as well as the pressure drop across the mat, and herein lies the need for accurate measurement techniques. Currently two of the available techniques for measuring mat thickness are by laser interferometry[1] and by buoyancy force when submerged in water[2]. Instead of measuring the buoyancy force in this experiment, an enclosure intended to measure the thickness via water displacement was …

Self-Assembled Metal Nanoparticle/Polymer Nanocomposites As Nanoreactors For One-Pot Reactions, Andrew Harrison

Theses and Dissertations

Polymer nanoreactors incorporating gold nanoparticle catalysts were self-assembled via Flash Nanoprecipitation. The incorporated gold nanoparticles maintained catalytic activity, which was evaluated using reduction of 4-nitrophenol with sodium borohydride as a model reaction. The diffusion coefficient for 4-nitrophenol was determined by NMR and used to calculate the second Damköhler number, which indicated that the systems were not diffusion limited. Despite similar diffusion coefficients, catalytic performance was strongly affected by the co-precipitant. For example, the apparent reaction rate per surface area using castor oil was over 8-fold greater than polystyrene. Thus, we measured the partition coefficient of 4-nitrophenol between water and castor …

Polymeric Impulsive Actuation Mechanisms: Development, Characterization, And Modeling, Yongjin Kim

Doctoral Dissertations

Recent advances in the field of biomedical and life-sciences are increasingly demanding more life-like actuation with higher degrees of freedom in motion at small scales. Many researchers have developed various solutions to satisfy these emerging requirements. In many cases, new solutions are made possible with the development of novel polymeric actuators. Advances in polymeric actuation not only addressed problems concerning low degree of freedom in motion, large system size, and bio-incompatibility associated with conventional actuators, but also led to the discovery of novel applications, which were previously unattainable with conventional engineered systems. This dissertation focuses on developing novel actuation mechanisms …

Progress Toward Durable Icephobic Materials, Matthew J. Coady

Electronic Thesis and Dissertation Repository

Ice accumulation is a major engineering challenge in many fields including aerospace, power generation, transportation, and infrastructure. A variety of solutions are being researched to address this challenge. Perhaps the most promising method of combating ice accumulation is by applying coatings with low values of interfacial ice adhesion strength, τ_ice. Icephobic materials are those with ice adhesion below 100 kPa, and it has been shown that passive delamination can occur on surfaces with τ_ice below 20 kPa. While various low adhesion surfaces have been prepared, durability concerns pervade applications where surfaces experience repeated icing or freeze-thaw cycles, …

Production Optimization Of Ring-Banded Spherulitic Crystals Of Poly (3-Butylthiophene-2,5-Diyl) Using Controlled Solution Evaporation, Frederick Paul Henderson Iii

Materials Engineering

Conductive polymers can carry a charge due to the presence of excess electrons along the carbon backbone. By growing these polymers into crystals, the usual insulative isotropic matrix that polymers form will be replaced with anisotropic regions where conduction is possible parallel to the crystal lattice growth direction. In previous research, while growing sphere shaped crystals it was observed that a few would exhibit rings that formed parallel to the circumference of the sphere. In this project, the conditions to produce this ring structure were examined by looking at two polymer solutions (with carbon disulfide or dichlorobenzene as solvent) and …

A Review Of Field Oil-Production Response Of Injection-Well Gel Treatments, Munqith Aldhaheri, Mingzhen Wei, Na Zhang, Baojun Bai

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

As life-span extenders, bulk gels have been widely applied to rejuvenate oil production from uneconomic producers in mature oil fields by improving the sweep efficiency of improved-oil-recovery (IOR)/enhanced-oil-recovery (EOR) floods. This paper presents a comprehensive review of the responses of injection-well gel treatments implemented between 1985 and 2014. The survey includes 61 field projects compiled from SPE papers and US Department of Energy reports. Seven parameters related to the oil-production response were evaluated according to the reservoir lithology, formation type, and recovery process, using univariate analysis and stacked histograms. The interquartile-range (IQR) method was used to detect the underperforming and …

Chemical Stability And Performance Influence Of Choice Substituents And Core Conjugation Of Organic Semiconductors, Jack Ly

Doctoral Dissertations

Realizing organic based active materials for electronic devices, such as thin film transistors and photovoltaics, has been long sought after. Advancement in the field driven by chemists, engineers, and physicists alike have bolstered organic based semiconductor performance levels to rival those of traditional inorganic amorphous silicon-based devices. Within the field of organic semiconductors (OSC), two categories of active materials may be generalized: (1) polymer and (2) small molecule semiconductors. Each class of OSC inherently have their own advantages and disadvantages. Polymer semiconductors (PSC) allow a wide range in tunability via choice monomers and side chain engineering to illicit desirable energy …

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 …