A. James Clark School of Engineering

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The collections in this community comprise faculty research works, as well as graduate theses and dissertations.

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Subject: search.filters.subject.Polymer chemistry

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    DESIGN AND PERFORMANCE EXPLORATION OF A SCALED-UP MILLIGRAM-SCALE FLAME CALORIMETER
    (2024) Cromwell Reed, Kyra; Raffan-Montoya, Fernando; Fire Protection Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Fire causes thousands of lost lives and injuries, as well as billions of dollars of property damage, each year. It is critical to understand the fire hazard associated with materials used in the built environment. One method to evaluate the flammability properties of a material is through bench- scale and milligram-scale testing with apparatus such as the Milligram-Scale Flame Calorimeter (MFC). The MFC has previously been used to test samples ranging from 30 mg – 50 mg in mass. The small samples were useful for testing materials under development or materials cost prohibitive to test at larger sizes, but presented some difficulties in testing, including in sample preparation and as inconsistency in the results of testing on inhomogeneous materials. Furthermore, the small size of the MFC caused difficulty in heater manufacturing, requiring laborious by-hand construction. The size of the MFC crucible and apparatus was increased in this work to allow testing on larger sample masses, ranging in size from 90 mg – 150 mg, and for the exploration of five alternate heater manufacturing techniques. The MFC was rebuilt with a larger heater and optimized to create the best possible test conditions for this work. Tests were conducted on five polymers: polymethyl methacrylate (PMMA), polyethylene (PE), polyvinyl chloride (PVC), and polyether ether ketone (PEEK), and on a wood-based material: oriented strand board (OSB). The tests showed general consistency when materials were tested at different sample masses and sample presentations. The results for the heat release rate and heat of combustion of the materials also aligned well with testing conducted using the previous version of the MFC apparatus. The updates to the MFC conducted in this work constitute an improvement to the versatility of the apparatus, allowing for testing on larger sample masses, but future work is needed to resolve flow and exhaust issues that caused some inconsistency in the test results and to further explore and develop alternate heater manufacturing techniques.
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    MOLD PROCESS INDUCED RESIDUAL STRESS PREDICTION USING CURE EXTENT DEPENDENT VISCOELASTIC BEHAVIOR
    (2024) Phansalkar, Sukrut Prashant; Han, Bongtae; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Epoxy molding compounds (EMC) are widely used in encapsulation of semiconductor packages. Encapsulation protects the package from physical damage or corrosion due to harsh environments. Molding processes produce residual stresses in encapsulated components. They are combined with the stresses caused by the coefficient of thermal expansion (CTE) mismatch to dictate the final warpage at room and reflow temperatures, which must be controlled for fabrication of redistribution layer (RDL) as well as yield during assembly. During molding process, EMC is continuously curing and the mechanical properties continue to evolve; more specifically, the equilibrium modulus and the relaxation modulus. The former defines behavior after complete relaxation while the latter describes the transient behavior. It is thus necessary to measure cure-dependent viscoelastic properties of EMC to be able to determine mold induced residual stresses accurately. This is the motivation for this thesis. In this thesis, a set of novel methodologies are developed and implemented to quantify a complete set of cure-dependent viscoelastic properties, including the fully cured properties. Firstly, an advanced numerical scheme has been developed to quantify cure kinetics of thermosets with both single and dual-reaction systems. Secondly, a unique methodology is proposed to measure the viscoelastic bulk modulus -K(t,T) of EMC using hydrostatic testing. The methodology is implemented with a unique test setup based on inert gas. The results of viscoelastic testing along with the shear modulus (G) and bulk modulus (K) master curves and temperature-dependent shift factors (a(T)) of fully-cured EMC are presented. Thirdly, a novel test methodology utilizing monotonic testing has been developed to measure two sets of equilibrium moduli of EMC as a function of cure extent (p). The main challenge for the measurements is that the equilibrium moduli could only be measured accurately only when the EMC has fully relaxed. The temperatures for complete relaxation typically occur above the glass transition temperature, Tg (p), where the curing rate is also high. A special measurement procedure is developed, through which the EMC moduli above Tg can be determined quickly at a near isocure state. Viscoelastic testing of partially-cured EMC is followed to determine the cure-dependent shift factors of EMC. The test durations have to be very long (several hours) and it is conducted below Tg (p) of the EMC where the reaction is slow (under diffusion-control) Finally, a numerical scheme that can utilize the measured cure-dependent viscoelastic properties is developed. It is implemented to predict the residual stress evolution of molded packages during and after molding processes.
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    MECHANICS AND THERMAL TRANSPORT MODELING IN NANOCELLULOSE AND CELLULOSE-BASED MATERIALS
    (2023) RAY, UPAMANYU; Li, Teng; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Cellulose, the abundantly available natural biopolymer, has the potential to be a next generation wonder material. The motivation behind this thesis stems from the efforts to obtain mechanical properties of two novel cellulose-based materials, which were fabricated using top-down (densified engineered wood) and bottoms-up (graphite-cellulose composite) approaches. It was observed that the mechanical properties of both the engineered wood (strength~596 MPa; toughness ~3.9 MJ/m3) and cellulose-graphite composite (strength~715 MPa; toughness ~27.7 MJ/m3) surpassed the equivalent features of other conventional structural materials (e.g., stainless steel, Al alloys etc.). However, these appealing properties are still considerably inferior to individual cellulose fibrils whose diameters are in the order of nanometers. A significant research effort needs to be initiated to effectively transfer the mechanical properties of the hierarchical cellulose fibers from the atomistic level to the continuum. To achieve that, a detailed understanding of the interplay of cellulose molecular chains that affects the properties of the bulk cellulosic material, is needed. Modeling investigations can shed light on such underlying mechanisms that ultimately dictate multiple properties (e.g., mechanics, thermal transport) of these cellulosic materials. To that end, this thesis (1) applies molecular dynamics simulations to decipher why microfibers made of aligned nanocellulose and carbon nanotubes possess excellent mechanical strength, along with understanding the role of water in fully recovering elastic wood under compression; (2) delineates an atomistically informed multi-scale, scalable, coarse grained (CG) modeling scheme to study the effect of cellulose fibers under different representative loads (shearing and opening), and to demonstrate a qualitative guideline for cellulose nanopaper design by understanding its failure mechanism; (3) utilizes the developed multi-scale CG scheme to illustrate the reason why a hybrid biodegradable straw, experimentally fabricated using both nano- and micro-fibers, exhibits higher mechanical strength than individual straws that were built using only nano or microfibers; (4) investigates the individual role of nanocellulose and boron nitride nanotubes in increasing the mechanical properties (tensile strength, stiffness) of the derived nanocellulose/boron-nitride nanotube hybrid material; (5) employs reverse molecular dynamics approach to explore how the boron nitride nanotube based fillers can improve thermal conductivity (k) of a nanocellulose derived material. In addition, this thesis also intends to educate the readers on two perspectives. The common link connecting them is the method of engineering intermolecular bonds. The first discussion presents a few novel mechanical design strategies to fabricate high-performance, cellulose-based functional materials. All these strategies are categorized under a few broad themes (interface engineering, topology engineering, structural engineering etc.). Another discussion has been included by branching out to other materials that, like nanocellulose, can also be tuned by intermolecular bonds engineering to achieve unique applications. Avenues for future work have been suggested which, hopefully, can act as a knowledge base for future researchers and help them formulate their own research ideas. This thesis extends the fundamental knowledge of nanocellulose-based polymer sciences and aims to facilitate the design of sustainable and programmable nanomaterials.
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    USE OF MILLIGRAM-SCALE FLAME CALORIMETRY FOR CHARACTERIZING FLAMMABILITY OF FABRIC SAMPLES WITH FLAME RETARDANT TREATMENTS
    (2023) Roche, Thomas William; Raffan-Montoya, Fernando; Fire Protection Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    The fire hazard associated with fabrics threatens everyone’s safety, and the current standards used to reduce those hazards are expensive and time-consuming. Fabrics are a key component in clothing, upholstery, and carpentry and are present in nearly every built environment. The inherent flammability of fabrics leads to the application of flame-retardant treatments on nearly all commercial fabric products. Recently, environmental, economic and performance concerns have driven research to develop new flame retardants across a variety of materials. The military industry in particular has focused recent research efforts on flame retardant treatments for fabrics, given the challenging environments that military uniforms must endure. Current methods for testing performance of novel flame retardants, such as the Cone Calorimeter and Microscale Combustion Calorimeter can be prohibitively expensive or only provide a limited understanding of flame-retardant action. Fabrics present additional testing challenges due to their low density and thickness, effectively reducing the amount of fuel available for testing. A novel apparatus, the Milligram-scale Flame Calorimeter (MFC), has been used to test flame retardants in polymeric materials, successfully capturing gas-phase activity and with favorable comparison to Cone Calorimeter results. This study aims to expand the use of the MFC to the testing of fabrics and flame-retardant treated fabrics. Optimization tests were run to find the optimal number of fabric layers and best method for preparing samples for use in MFC. Subsequently, cotton fabrics (untreated and treated with phosphoric acid), as well as Nylon fabrics (untreated and treated with tannic acid) were characterized with MFC, and results were compared to those from the Microscale Combustion Calorimeter and Cone Calorimeter. The MFC showed similar trends in the onset of ignition, peak heat release rate, average heat release rate, char yield, and heat of combustion for the untreated fabrics with the Cone Calorimeter and Microscale Combustion Calorimeter results. The results for the flame-retarded fabrics are inconclusive and require additional testing, though the observations of the condensed-phase and gas-phase activity for the MFC samples does provide important insights on how the mechanism for the flame retardants operate.
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    Magnetic nanoparticle inks for syringe printable inductors
    (2023) Fedderwitz, Rebecca; Kofinas, Peter; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Direct Ink Writing (DIW) additive manufacturing (AM) has the transformative potential to construct complex shapes and devices with a single apparatus by exchanging the printable material at the print head. Iron cobalt (FeCo), permalloy (Ni80Fe20), and iron (II,III) oxide (Fe2O3·FeO) nanoparticles with varying magnetic properties were incorporated in resins to explore the influence of particle loading on printability and inductor device performance. It was generally found that increasing particle loading increased ink viscosity, with a loading maximum approaching 29 – 42 vol% depending on the particle type and resin mixtures due to differences in particle shape and size and resin viscosity. With more magnetic content, composites had higher magnetic permeability and inductance. Syringe printable, colloidal, aqueous magnetic inks were made using both stabilized iron oxide and MnZn doped ferrite nanoparticles with added free polymers. MnZn doped ferrite inks are printed into toroids, sintered to improve magnetic permeability and mechanical robustness, and constructed into an inductor device. Inductors with high magnetic permalloy nanoparticle content were also syringe printed into toroids and hand-wound to demonstrate their viability in fabricating three-dimensional inductors. The effect of particle size on stability and printability was observed. The research presented in this thesis investigates various methods for formulating magnetic nanoparticle inks and evaluates the contributions of particle stabilization, free polymer content, solvent composition, and particle loading on the rheological behavior required for syringe printing. Material properties and device performances were characterized using methods such as zeta potential and settling studies to observe particle functionalization and stability, rheology to study viscoelastic flow behavior, and vector network analysis to measure inductance and device efficiency to showcase the viability of this technique to manufacture passive electronic devices.
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    Simulation of polymeric drop dynamics: Effect of photopolymerization, impact velocity, and multi-material coalescence
    (2023) Sivasankar, Vishal Sankar; Das, Siddhartha; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Over the past couple of decades, additive manufacturing has emerged as one of the most promising manufacturing tools and has rightfully garnered the attention of researchers across various fields ranging from biochemistry and medicine to energy and infrastructure. Especially, direct-ink-writing methods (e.g., inkjet printing, aerosol jet printing, or AJ printing, etc.) have been widely studied because of their ability to print highly complex geometries with finer resolution. In order to design a more efficient droplet-based direct ink writing system, it is essential to understand the deposition process and the post-deposition dynamics of the drop. The post-deposition drop dynamics dictate the spreading radius of the drop and hence the print resolution. Such an understanding is even more critical when there are multiple drops interacting with each other, given the fact that such interactions determine the presence/absence of surface defects in addition to determining the print resolution. Moreover, to have a holistic understanding of the post-deposition process, it is essential to further account for the droplet solidification mechanisms (for example, through effects such as in-situ curing) that might interplay with multiple drop dynamics events (such as drop spreading, drop coalescence, drop impact, etc.). In this dissertation, computation fluid dynamics (CFD) frameworks have been developed to investigate the facets dictating the post-deposition dynamics of one (or several) solidifying polymer drops, with these dynamics show-casing the different post-deposition events that are intrinsic to the droplet-based additive manufacturing processes. First, we considered a situation where the polymeric drop undergoes simultaneous spreading and photopolymerization, with the timescales of the spreading and photopolymerization events being τ? and τ? respectively. The findings from this work confirmed the significant impact of the ratio of timescales (τ? and τ?) on the thermo-fluidic-solutal dynamics of the polymeric drops. Moreover, the evolution of the curing front showed distinct behaviors as a function of the timescale ratio.Subsequently, the effect of the interaction of multiple polymeric drops during the post-deposition event, as seen in the typical printing process, was investigated. Specifically, we studied the effect of drop impact on the coalescence dynamics of two polymeric drops of identical and different sizes. The study revealed the presence of two distinct stages of coalescence. The early-stage coalescence was found to be enhanced with an increase in the impact velocity; however, the late-stage coalescence behavior remained unaffected by the impact velocity. Further, the coalescence dynamics of polymeric drops of different materials, as witnessed in multi-jet printing, was probed. This study shed light on the mechanisms that drive the mixing process at different stages of drop coalescence. Finally, we evaluated the effects of the in-situ photopolymerization on the coalescence dynamics of multiple polymeric drops deposited on a substrate. Here too the comparative values of the drop dynamics timescale and the photopolymerization became important. Our results show three-distinct regimes characterizing the bridge growth which was further validated through physics-based theoretical scaling. This study would provide key insights into the direct-ink writing process and would aid in designing parameters for polymer-based additive manufacturing and product repair.
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    Radiation-Induced Modification of Aramid Fibers: Optimizing Crosslinking Reactions and Indirect Grafting of Nanocellulose for Body Armor Applications
    (2022) Gonzalez Lopez, Lorelis; Al-Sheikhly, Mohamad; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    The goal of this dissertation was to design, synthesize, and analyze novel aramid fibers by covalently grafting nanocellulose through electron beam irradiation. These nanocellulose functionalized fibers showed enhanced strength and larger surface areas, which improves their performance and applicability in fiber-reinforced composites. Unmodified aramid fibers have smooth and chemically inert surfaces, which results in poor adhesion to many types of resins. Nanocellulose was chosen as the ideal filler to functionalize the fibers due to its reactive surface and high strength-to-weight ratio. Aramid fibers were further modified by radiation-induced crosslinking reactions as a means to avoid scission of the polymeric backbone and to further increase the fiber strength.An indirect radiation-induced grafting approach was used for synthesizing these novel nanocellulose-grafted aramid fibers while avoiding the irradiation of nanocellulose. The fibers were irradiated using the e-beam linear accelerator (LINAC) at the Medical Industrial Radiation Facility (MIRF) at the National Institute of Standards and Technology (NIST). After the irradiation, the fibers were kept in an inert atmosphere and then mixed with a nanocellulose solution for grafting. The grafted fibers were evaluated by gravimetric analysis, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) spectroscopy. The mechanical properties of the synthesized fibers were studied by single fiber tensile tests. Aramid fibers were also irradiated at the MIRF in the presence of acetylene gas and triacrylate solution as a means to induce crosslinking reactions. These fibers were irradiated at both low doses and high dose rates at room temperature. A mechanism for the crosslinking of aramid fibers was proposed in this dissertation. Mechanical testing of the fibers after crosslinking showed an increase in the strength of the fibers of up to 15%. Ultra-high molecular weight polyethylene (UHMWPE) fibers were also studied, but due to an issue of entanglement of the fibers during the grafting process, their mechanical properties could not be analyzed. Future work will focus on using a better set up to avoid entanglement of these fibers. To complete the study of the radiation effects on polymers, this thesis explored the radiation-induced degradation of aromatic polyester-based resins. The composition of the resins studied included phenyl groups and epoxies, which complicate radiation-induced grafting and crosslinking reactions. Unlike aramid and polyethylene fibers, polyester-based resins have a C-O-C bond that is susceptible to degradation. The resins were irradiated at high doses in the presence of oxygen. The scission of the polymeric backbone of the polymers was studied using Electron Paramagnetic Resonance (EPR) analysis. EPR showed the formation of alkoxyl radicals and C-centered radicals as the primary intermediate products of the C-O-C scissions. The degradation mechanisms of the resins in the presence of different solvents were proposed. Changes in the Tg of the polymers after irradiation, as an indication of degradation, were studied by Dynamic Mechanical Analysis (DMA). The results obtained from this work show that irradiation of these resins results in continuous free radical-chain reactions that lead to the formation of recyclable oligomers.
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    Processing and structural characterization toward all-cellulose nanocomposites
    (2021) Henderson, Doug A; Briber, Robert M; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Cellulose is the most abundant biopolymer on the planet and is used in a variety of industry sectors including paper, coatings, medicine, and food. A deep understanding of cellulose is important for its development as an alternative polymer to those based on petroleum. This work focuses on two cellulose systems. The first of these, cellulose nanofibers, are the basic structural elements of naturally-occurring cellulosic materials; they exhibit excellent mechanical characteristics due to high crystallinity and a dense network of hydrogen bonding. These fibers can be separated from bulk cellulose via a TEMPO oxidation reaction followed by mechanical homogenization into a suspension in water. In this work, the production of these fibers is investigated by monitoring the change in structure of cellulose as a function of TEMPO reaction time and mechanical homogenization using small angle neutron scattering, atomic force microscopy, and optical microscopy. The second cellulose system is a molecular solution of cellulose formed using a binary solvent mixture consisting of ionic liquid and an aprotic solvent. Cellulose is difficult dissolve due to a dense hydrogen bonding network, and ionic liquids have been shown to be an effective alternative to more hazardous and energy-intensive dissolution methods for cellulose currently used in industry. The phase behavior of these solutions has been investigated using small angle neutron scattering as a function of temperature. The process of regenerating cellulose from these solutions is also investigated, as dense gels of cellulose and ionic liquid were produced with a unique multiscale ordered structure. The ultimate goal of this work is to combine cellulose nanofibers and molecular cellulose solutions in order to create all-cellulose nanocomposite films. These films are characterized using tensile testing, atomic force microscopy, and water uptake measurements in order to understand the interaction between cellulose nanofibers and molecular cellulose solutions, water resistance and tunability of mechanical properties.
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    Development of a Comprehensive Pyrolysis Model for Flexible Polyurethane Foam
    (2021) Saar, William; Stoliarov, Stanislav; Fire Protection Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Flexible polyurethane foams (FPUFs) are polymeric materials which have widespread use and present a large fire risk in modern society. Accurate prediction of their fire behavior is valuable for assessing the risk they pose in any fire scenario they are involved in. Several models have been developed to predict FPUF thermal decomposition at the milligram scale. However, none of these models are able to predict pyrolysis and combustion of gram-sized or kilogram-sized FPUF samples. In this work, a combination of experiments and modeling was used to develop a complete pyrolysis model for a standard FPUF foam. Inverse modeling of thermogravimetric analysis, differential scanning calorimetry, microscale combustion calorimetry, and Controlled Atmosphere Pyrolysis Apparatus II experiments was conducted to obtain a comprehensive list of decomposition reaction kinetics, thermodynamic and transport properties that define the pyrolysis and flaming combustion of this material.
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    ATOMISTIC AND THEORETICAL DESCRIPTION OF LIQUID FLOWS IN POLYELECTROLYTE-BRUSH-GRAFTED NANOCHANNELS
    (2021) Sachar, Harnoor Singh; Das, Siddhartha; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Polyelectrolyte (PE) chains grafted in close proximity stretch out to form a “brush”-like configuration. Such PE brushes can represent a special class of nanomaterials that are capable of exhibiting stimuli-responsive behavior. They can be manipulated as needed by changing the environmental conditions like pH, solvent quality, salt concentration, temperature, etc. This responsiveness renders them very useful for a plethora of applications such as lubrication, emulsion stabilization, current rectification, nanofluidic energy conversion, drug delivery, oil recovery, etc. Therefore, gaining fundamental insights into PE brush systems is of utmost importance for both industrial as well as academic research. In this dissertation, we make use of theoretical and computational tools to improve our understanding of planar PE brushes and then use this understanding to probe flows in PE brush-grafted nanochannels. We begin our quest by conducting all-atom Molecular Dynamics (MD) simulations to probe the microstructure of planar PE brushes with an unprecedented atomistic resolution. This allows us to not only investigate the properties of the PE chains but also the local structure and arrangement of the counterions and water molecules trapped within the brushes. Next, we use our atomistic model to probe the effects of variation in charge density on the microstructure of weak polyionic brushes. Such a variation in the charge density is typically enforced by a change in the surrounding pH and is a characteristic behavior of pH-responsive (annealed) PE brushes. Furthermore, we go on to develop the most exhaustive theoretical model for pH-responsive PE brushes known as the augmented Strong Stretching Theory (SST). Our model is an improvement over the existing state-of-the-art as it considers the effects of the excluded volume interactions and an expanded form of the mass action law. We further improve this model by including several non-Poisson Boltzmann effects, especially relevant at high salt concentrations. This improved model is in excellent agreement with the results of our all-atom MD simulations. Next, we use our augmented SST to model pressure-driven transport in backbone-charged PE brush-grafted nanochannels. Our results are an improvement over previous electrokinetic studies that did not consider a thermodynamically self-consistent description of the brushes. Finally, we conduct all-atom MD simulations to probe the pressure-driven transport of water in PE brush-grafted nanochannels using an all-atom framework. The nanoscale energy conversion characteristics obtained from our simulations are in reasonable agreement with the predictions of our continuum framework and lie within the range of values reported by a prior experimental study.