Engineering Commons^™

The Development Of An Advanced Biorefinery To Produce Cellulosic Sugars And Bionanomaterials, Carlaile Fernanda De Oliveira Nogueira

Electronic Theses and Dissertations

Market trends show growing interest in cellulose nanomaterials due to their low environmental impact. However, current nanocellulose isolation technologies face technoeconomic and life cycle limitations. Previous research has shown that enzymatic treatments effectively reduce the energy input for mechanical nanocellulose isolation. Simultaneously, there is potential to improve the viability of cellulosic ethanol facilities by coproducing nanocelluloses as high-value product obtained from agricultural feedstock. Here, our goal was to study the mass balance of enzymatic-mechanical processes that coproduces cellulosic sugars and nanocelluloses, evaluating the technical feasibility of converting lignified and non-lignified materials.

First, we have determined a feasible 50:50 mass ratio …

Advances In Cellulose Nanomaterial-Based Foams For Environmental Applications, Md Musfiqur Rahman

Electronic Theses and Dissertations

The use of metal-oxide nanoparticles adsorbents is limited to fixed-bed columns in industrial-scale water treatment applications. This limitation is commonly attributed to the tendency of nanoparticles to aggregate, the use of non-sustainable and inefficient polymeric resins as supporting materials, or a lack of adsorption capacity. Foams and aerogels derived from cellulose nanomaterials have unique characteristics, such as high porosity and low density, which enables their use in a variety of environmental applications, including water treatment. However, the overall use of cellulose nanomaterial-based foams in various environmental sectors is limited due to the high cost of production associated with time- and …

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 …

Development Of Lignin-Based Copolymers And Polymer Blends, David Chem

Graduate Theses and Dissertations

Increasing industrial interest in reducing fossil fuels in virgin polymer production and incorporating bio-based polymeric materials has led researchers to explore the potential of utilizing plant-based polymers such as lignin. Chapter 1 of this thesis presents a comprehensive overview of copolymerization and blending techniques for lignin and synthetic polymers, emphasizing different types of modifications and copolymerization techniques as well as key parameters such as temperature, reaction time, pH level, and solution compositions. These valorization methods are directed towards the development of high-value lignin-based materials with properties well-suited for various commercial applications. Chapter 2 offers a fundamental exploration into the amination …

Investigating The Rheological Behavior Of A Simple Yield Stress Fluid Under Shear Flows, Francesco Accetta

Theses

Many soft materials display unique and complex rheological behavior characterized by a transition from a solid-like to a fluid-like state upon the application of a force that exceeds the threshold to flow, known as the yield stress. Yield stress fluids are found in a wide range of commonly encountered materials including microgels, emulsions, and foams, and have been widely studied by rheologists over the last several decades. Carbopol is a popular polymeric microgel system as it displays simple, non-thixotropic rheological behavior and is typically seen as an ideal yield stress fluid. Previous research has demonstrated the reproducible behavior of shear …

Elucidating Self-Assembly Of Semiconducting Polymers In The Presence Of A Low Molecular Weight Gelator, Madhubhashini Lakdusinghe

Theses and Dissertations

Semiconducting polymers with a conjugated backbone are important for energy storage, conversion, and biomedical field applications. The self-assembly process of these polymers in solutions depends on the polymer concentration and quality of the solvent. The electrical properties of thin films obtained from the solution phase depend on the self-assembled process. Thin films of conjugated polymer gels with percolating networks of self-assembled structures display improved electrical conductivities. In this dissertation, we studied the impact of the secondary gel matrix formed by a low molecular weight gelator, on the self-assembly of conjugated polymers, the preservation of assembled structures in dried gel films …

The Cosolvent And Association Effect On Polymer Behaviors, Xiangyu Zhang

Theses and Dissertations

The blending or mixing is extensively utilized in diverse processes of polymers to bring about advantageous properties, but the behavior becomes intriguing when associations are involved and multi-solvents are used. Explanations based on chemistry-specific arguments are less than satisfactory in abstracting essential features, and lack the general applicability across various systems. So, this work focuses on capturing the physical force governing the phenomenon of interest by using a generic model. Highly non-trivial behaviors of polymers are often observed in multi-solvent solutions. It is known that polymers swell and dissolve in good solvents, while they tend to collapse and aggregate in …

Designing Bioinspired Materials With Tunable Structures And Properties From Natural And Synthetic Polymers, Anandavalli Varadarajan

Theses and Dissertations

Biological systems are composed of complex materials which are responsible for performing various functions, such as providing structural support, mobility, functional adaptation to the environment, damage repair, and self-healing. These complex materials display excellent mechanical properties and can rapidly adapt to external stimuli. Thus, nature inspires in terms of source materials, functions, and designs to develop new-generation structural and functional materials. Polymers (natural or synthetic) are excellent sources of developing materials to mimic the functions of soft segments in biological systems. This dissertation focuses on synthesizing and characterizing two different materials with tunable structures and properties: complexes from natural polysaccharides …

Activated Carbon Synthesis From Lignin-Rich Byproduct Streams Of Biorefineries, Chengjun Wu

All Dissertations

Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, it is necessary to add value to the “ligno-” components (up to 30% by mass) of the biomass. Instead of just burning it for heat and electricity generation, direct conversion of lignin carbon into a product provides a complementary path to carbon capture, promoting a more environmentally conscious approach. However, the utilization of these lignin-rich byproduct streams, which are separated from the biofuels production, for industrial products can be challenging. The use of specific …

Improving Lignin Recovery From Paper Mill And Biorefinery Waste Streams Via Liquid-Phase Splitting, Carter Fitzgerald

All Dissertations

Lignin is an abundant biopolymer with significant promise due to its aromaticity. It has been targeted as a replacement for a number of petroleum-based products including adhesives, coatings, polyurethane foams, activated carbon, and carbon fibers. However, commercially available bulk lignins are too polydisperse, and contain too many residual metals from the pulping process that are detrimental to the properties of the final product.

The Sequential Liquid-lignin Recovery and Purification (SLRP) process was developed by Michael Lake and John Blackburn, in collaboration with Clemson, with the intention of creating a continuous method for recovering lignin from paper-mill black liquors. Thies and …

Carbon Fibers From Athabasca Oil-Sand Asphaltenes, Blake Reardon

All Theses

Carbon fibers possess ultra-high specific strength and modulus. Therefore, the material is popular in aerospace, automotive, and sports industries. Approximately 95% of all carbon fibers are spun from a high-cost precursor, polyacrylonitrile (PAN). There is a need for a cheaper grade of carbon fiber for low-cost applications because about half of carbon fiber cost is associated with precursor cost. A promising alternative to the high-cost PAN precursor is petroleum-based asphaltene. Asphaltenes are highly aromatic and have a high carbon content but lack the purity of the PAN precursor. Processes like the molten- sodium desulfurization upgrading have been used to harvest …

Characterization Of Mechanically Recycled Polylactic Acid (Pla) Filament For 3d-Printing By Evaluating Mechanical, Thermal, And Chemical Properties And Process Performance, Mahsa Shabani Samghabady

All Theses

Polylactic acid (PLA) is a biopolymer made from renewable resources such as sugar and corn. PLA filament is a popular material used in Fused Deposition Modeling (FDM) 3D-printing. While this material has many advantages, all the failed parts, support structures, rafts, nozzle tests, and the many prototype iterations during the 3D-printing process contribute to the plastic pollution and release of greenhouse gases. Although PLA is biodegradable, it can take years to degrade in landfills. Instead of throwing away PLA waste and buying new filaments, PLA can be recycled. Amongst the different recycling technologies, mechanical recycling is the most environmentally friendly. …

Development Of Non-Viral Nano-Carriers For Gene Delivery And Covid-19 Vaccines, Zhongyu Li

Dissertations

Gene therapy is one of the most promising medical fields with the potential to effectively advance the treatment of difficult diseases by producing therapeutic proteins or repairing defective gene sequences. However, gene therapy presents severe challenges in delivery including renal clearance, phagocytosis, enzymatic degradation, protein absorption, and cellular internalization barriers, which have been barriers for translation into the clinic. Naked nucleic acids, with their intrinsic negative charge, electrostatically repulse the anionic cell membrane, preventing cellular uptake. Also, they are considered foreign genetic material when introduced into the body and are rapidly cleared by the reticuloendothelial system or degraded by nucleases, …

The Biological Activity Of Dual-Responsive Glycopolymers For Intracellular Codelivery Of Antigen And Lipophilic Adjuvant, Micaela Shields

Honors Theses

Subunit vaccines present themselves as an attractive alternative to traditional approaches to vaccines, which utilizes whole organisms to trigger an immune response. While these traditional approaches have proven themselves reliable within the history of vaccinations, they generally deliver subpar robust cellular-mediated immunity and pose many safety risks. Composed of proteins and /or peptides, subunit vaccines are safer and more precise alternatives to traditional approaches. However, the pharmacokinetic properties of the macromolecules that make up these vaccines hinder the subunit vaccine’s level of immunogenicity [d1] Examples of this hindrance include but are not limited to aggregation at the injection site and …

Effects Of Fibril Morphology And Interfacial Interactions On The Behavior Of Polymer-Grafted Cellulose Nanofibril Reinforced Thermoplastic Composites, Peter V. Kelly

Electronic Theses and Dissertations

Mechanically refined cellulose nanofibrils (CNFs) promise to be a high-volume, sustainable, nanoscale reinforcement for thermoplastic composites. They are currently held back by poor interfacial interactions with composite matrices, energy intensive drying, and drying induced fibril aggregation. In this dissertation, we explored how a grafting-through polymerization scheme modified the surface of CNFs with a wide variety of commodity polymers and overcame many of these technical challenges.

The first phase of the research was concerned with characterizing the unique morphology of these CNFs as a function of refinement energy. This characterization was employed to understand how the materials’ morphologies affected their interfacial …

The Influence Of Heat And Mass Transfer On The Setting Rate Of Adhesives Between Porous Substrates, Mubarak Mohammed Khlewee

Electronic Theses and Dissertations

The dynamic penetration of fluid into a porous media where other changes are occurring such as temperature or concentration is of interest to a number of situations. However, little experimental and theoretical analysis of this situation is found in the literature where most of the previously published works have studied the penetration with constant physical properties, where there is no change of the fluid as it enters the pores. This situation is important in the setting of adhesives in porous medium such as in the setting of hot melt and water-based adhesives in the production of paper based packaging. The …

Lignin Copolymer Property Prediction Using Machine Learning, Collin Larsen

Chemical Engineering Undergraduate Honors Theses

Lignin, an abundant biopolymer, is a waste byproduct of the paper and pulp industry. Despite its renewable nature and potential applicability in various products, such as plastics and composites, the development of lignin-based materials has been impeded by the cumbersome, Edisonian process of trial and error. This research proposes a novel approach to forecasting the properties of lignin-based copolymers by utilizing a recurrent neural network (RNN) based on the Keras models previously created by Tao et al. Example units of modified lignin were synthesized via esterification and amination functional group modifications. To increase the efficiency and accuracy of the prediction …

Characterization Of Lignin And Cellulose Biopolymers Structure – Function Relationships, Zachariah Pittman

All Dissertations

Biomass is vital to ongoing efforts to secure a sustainable future. While many of our efforts focus on finding alternative forms of energy, biomass among them, only biomass has the potential to serve as a sustainable materials feedstock. However, biomass is heterogenous, complicating the upgrading processes needed to manufacture commodity and performance products. For example, plant biomass consists largely of cellulose, a crystalline polysaccharide, and lignin, a highly stable polyaromatic. The specific properties of cellulose and lignin depend greatly on the plant, harvesting conditions, and isolation procedures. Thus, accurate and reliable determination of the fundamental properties of biomass is crucial …

Elucidating The Mechanical And Transport Properties Of Lignin-Based Hydrogel Composites, Nicholas Gregorich

All Dissertations

The use of lignin in the fabrication of soft composites has become an emerging area of research in polymer science and polymer chemistry. These lignin-based materials present numerous benefits, notably, a reduction in the use of petroleum-based precursor, improved structural benefits to otherwise soft host polymers, as well as the inherent antimicrobial and antioxidant properties of lignin, making it suitable for biomaterials. Herein, we present two chemical reaction pathways of incorporating lignin that was fractionated and cleaned using the Aqueous Lignin Purification with Hot Agents (ALPHA) process into poly(vinyl alcohol) (PVA) hydrogel composites for aqueous-based separations. By leveraging the ALPHA …

Chloramine Devulcanization Of Waste Rubber., Patrick Kroeger

Electronic Theses and Dissertations

The disposal of waste rubber, particularly tire rubber, continues to pose a challenge in the 21st century. As a result, most end-of-life tires (ELTs) are either dumped in landfills or burned as tire-derived fuel. Chloramine devulcanization may offer a viable solution to this problem. Chloramine devulcanization is a low-temperature, low-pressure, process that selectively breaks sulfur crosslinks while preserving the polymer backbone. Chloramine devulcanization enables the recovery of chloramine recovered carbon black (CrCB) and devulcanized rubber (CdR) as separate products. Initial analysis of CdR revealed that it was formable and malleable, suggesting that crosslinking was absent. Spectroscopy showed that CdR contained …

Bridging The Gap Between Phase Behavior And Processing For Renewable And Refinable Carbonaceous Precursors, Graham Tindall

All Dissertations

As a category of materials, engineered carbons, specifically carbon fibers, are first-in-class for properties such as modulus, specific strength, and thermal resilience; however, the inability to directly process atomic carbon necessitates the development and optimization of carbonaceous precursors. Because the structure and properties of carbon are highly dependent on the precursors and requisite processing, numerous materials have been investigated as feedstocks for large-scale production. Although cellulose and rayon were among the first investigated, polyacrylonitrile (PAN) is the current hegemon of carbon fiber precursors. PAN feeds 90% of this market, but it is neither inexpensive nor renewable. Because a significant fraction …

Poly(Ether Imide)S: Synthesis And Properties, Rachel Price

Honors College Theses

The synthesis of strong polymers is crucial to the creation of heat-resistant, durable, and mechanically useful plastics that we use every day. Poly(ether imide)s are used in applications such as food service, aerospace, automotive, and many more. This thesis will discuss the synthesis and properties of these plastics to help express a larger understanding of these polymers.

Effect Of Process Parameters On The Mechanical Properties Of Carbon Fiber Epoxy Composites By Wet Compression Molding, Saboora Ayatollahi

Electronic Thesis and Dissertation Repository

In recent years, due to growing environmental concerns, composite materials have emerged as a promising lightweight alternative for metals in structural applications in automobiles. Among composite manufacturing processes, Wet Compression Molding (WCM) is a new method of producing Carbon Fiber Reinforced Polymer (CFRP) components. For similar processes like RTM, operating conditions are always one of the factors that impact the mechanical performance of CFRP parts. Thus, this thesis aimed to investigate the effects of operating conditions, including resin temperature, mold temperature, resin set time, gap closure speed, and mold curing time on the mechanical property of the composite parts. In …

An Experimental Study On The Mechanical Properties And Chemical Composition Of Lcd 3d Printed Specimens, Sebastian Gomez

Electronic Theses and Dissertations

Additive manufacturing technologies have been enhanced throughout the years yet have surprised the manufacturing industry due to their high-end surface finish and dimensional accuracy. Different experiments have been done to identify a specific phenomenon known in the vat-polymerization field. Distortion and dimensional inaccuracy tend to affect the overall properties of the process, either physical or chemical. This approach allows the understanding of how the physical properties have been affected and how to study the chemical properties to avoid this type of phenomenon. The chemical reaction between polymer and UV light has been studied and experimented with to the point that …

Running Shoe Pedometer, Benjamin Kasper

Williams Honors College, Honors Research Projects

Running shoe pedometer aims to solve the issue of worn out running shoes. It can be difficult to know just how many miles you have run in your shoes and when a new pair is needed. Running in old shoes and worn out shoes is heavily linked to injury. My proposed project is a device that is powered by the compressive forces on the shoes soles that counts the number of steps the wearer takes using a microcontroller. Then, when the shoe reaches milestone that indicate it has been used 75% 90% and 100% of its expected life, it will …

Defining The Proper Operating Time For The Septa Extractor, Abigail Jones

Williams Honors College, Honors Research Projects

Anionic polymerizations are a common type of reaction used to produce synthetic rubber. During these reactions, it is necessary to charge initiators, modifiers, and other substances, through pressurized containers that are sealed with rubber septa. These septa prevent oxygen and moisture from entering the pressurized container, and the reactor, though they need to be cleaned before use to remove other impurities. Currently a glass Soxhlet Extractor is used to remove such impurities, and though effective, it has a limited capacity, so it has to run frequently. This limitation led to the commissioning of the Septa Extractor, which is an automated …

Anti-Freeze Double Network Hydrogels, William Gross

Williams Honors College, Honors Research Projects

Three polyethylene glycol (PEG) based crosslinkers with repeat unit nominal weights of 62.1, 200, and 400 g/mol in agar/PAM double network (DN) hydrogels were used to study the effect of different crosslinkers on thermal and mechanical properties. Using the one-pot synthesis method, hydrogels with the PEG crosslinkers or methylene-bis-acrylamide (MBAA) were made via sol-gel transition for formation of agar network, and photopolymerization of the PAM network using Irgacure 2959 as photo initiator. Tensile and compression tests were performed on as prepared, swollen, and swollen & cooled specimens of each hydrogel. Freezing time and thermal imaging were performed in -20 °C …

Utilizing Computer-Aided Molecular Design With Azido-Ester Plasticizers, Justin Ebert

Williams Honors College, Honors Research Projects

The goal of this project was to utilize Computer-Aided Molecular Design (CAMD) using the Signature molecular descriptor to inversely design optimized azido-ester plasticizers. Azido-ester plasticizers are used to modify the mechanical properties of propellant and explosive formulations. With the assistance of quantitative structure-property relationships, QSPRs, and two types of constraint equations, these new, novel plasticizers have the potential to possess optimal physical and chemical properties. Properties investigated in this work were decomposition temperature, heat of formation, glass transition temperature, and molecular weight. These properties were chosen for their importance when formulating propellants or explosives. After the filters were applied to …

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 …

Mechanisms Of Emulsion Destabilization: An Investigation Of Surfactant, Stabilizer, And Detergent Based Formulations Using Diffusing Wave Spectroscopy, Jordan N. Nowaczyk

Theses and Dissertations

Conventional approaches for studying emulsions, such as microscopy and macroscopic phase tracking, present challenges when it comes to establishing detailed mechanistic descriptions of the impact of emulsifier and stabilizer additives. Additionally, while a combination of sizing methods and macroscopic phase tracking can provide insights into droplet size changes and concentration, the use of multiple measurements can be cumbersome and error-prone. It is the focus of this work, to present a new method for studying water in oil (W/O) emulsions that involves using diffusing wave spectroscopy (DWS) to examine the impact of three different surface stabilizing additives at varying concentrations. By …