The research presented in this thesis represents an effort to characterize the properties of ultra-high molecular weight polyethylene (UHMWPE). As a composite of polymers, the properties of UHMWPE are time-dependent. It is desired by research sponsors to know the properties of the material at high strain rates, in order to simulate the use of these materials in computer models. Properties believed to be significant which are investigated in this research are the tensile properties of lamina and laminates, and the interlaminar shear properties of laminates. The efficacy of using time-temperature superposition to shift tensile properties of the composite is investigated, and a novel apparent shear strength test is proposed and demonstrated. The effects of processing the material at various temperatures and pressures are also investigated. / Master of Science

The research presented herein is an effort to support computational modeling of ultra-high molecular weight polyethylene (UHMWPE) composites. An effort is made to characterize the composites and their constituents. UHMWPE, as a polymer, is time and temperature dependent. Using time-temperature superposition (tTSP), the constituent properties are studied as a function of strain rate. Properties that are believed to be significant are fiber tensile properties as a function of strain rate, as well as the through-thickness shear behavior of composite laminates. Obtaining fiber properties proved to be a challenge. The high strength and low surface energy of the fibers makes gripping specimens difficult. Several different methods of fixturing and gripping are investigated, eventually leading to a combination of friction and adhesion approaches where a fiber was wrapped on an adhesive coated cardboard mandrel and then gripped in the test fixture. Fiber strength is estimated using tTSP to equivalent strain rates approaching 10^6 sec^-1. Punch-shear testing of UHMWPE laminates is conducted at quasi-static strain rates and the dependence of the results on thickness and test geometry is investigated. / Master of Science

The mechanical property of polymeric materials changes over time, especially when they are subjected to long-term loading scenarios. To predict the time-dependent viscoelastic behaviors of epoxy-based adhesive materials, it is imperative that reliable accelerated tests be developed to determine their long-term performances under different exposed environments. A neat epoxy resin system and a commercial structural adhesive system for bonding aluminum substrates are investigated. A series of moisture diffusion tests have been performed for more than three months in order to understand the influence of the absorbed moisture on creep behavior. The material properties, such as elastic modulus and glass transition temperature, are also studied under different environmental conditions. The time-temperature superposition method produces a master curve allowing the long-term creep compliance to be estimated. The physics-based Coupling model is found to fit well the long-term creep master curve. The equivalence of the temperature and moisture effect on the creep compliance of the epoxy adhesives is also addressed. Finally, a methodology for predicting the long-term creep behavior of epoxy adhesives is proposed.

The mechanical property of polymeric materials changes over time, especially when they are subjected to long-term loading scenarios. To predict the time-dependent viscoelastic behaviors of epoxy-based adhesive materials, it is imperative that reliable accelerated tests be developed to determine their long-term performances under different exposed environments. A neat epoxy resin system and a commercial structural adhesive system for bonding aluminum substrates are investigated. A series of moisture diffusion tests have been performed for more than three months in order to understand the influence of the absorbed moisture on creep behavior. The material properties, such as elastic modulus and glass transition temperature, are also studied under different environmental conditions. The time-temperature superposition method produces a master curve allowing the long-term creep compliance to be estimated. The physics-based Coupling model is found to fit well the long-term creep master curve. The equivalence of the temperature and moisture effect on the creep compliance of the epoxy adhesives is also addressed. Finally, a methodology for predicting the long-term creep behavior of epoxy adhesives is proposed.

From medicine to aerospace, innovation in multiple fields will not occur without addressing current questions that still exist in polymer behavior and manipulation. This dissertation represents the research carried out over the course of three separate experiments using rheometry as the key technique to explore the behavior of polymer composites. In all three studies, polymer composites were investigated for changes to their known physical properties caused through the addition of a filler or functionalization. Chapter Two examines the possibility of enhancing poly(4-methyl-1-pentene) through the use of soluble carbon nanotubes. In this series of experiments, carbon nanotubes were covalently functionalized using reductive alkylation with a dodecyl group to render them easily soluble in the same organic solvents as low molecular weight poly(4-methyl-1-pentene). The polymer and the functionalized nanotubes were dissolved together in carbon tetrachloride then the solvent is removed leaving the functionalized nanotubes uniformly dispersed in the polymer matrix. The composites were then compression molded and the changes to the physical properties were explored. The functionalized nanotube filler generally acted to plasticize the samples producing transparent but colored polymers. The samples had a lower modulus and glass transition which was the opposite found by Clayton et al. using sonicated pristine carbon nanotubes. Polyurethanes have a growing significance in the biomedical field, and we explore the possibility fine tuning the properties of a polyurethane for such uses in Chapter Three. Here, self healing Polycarbonate polyurethanes (PCU) were synthesized with two different soft segments, Nippollan 964 and T-5652, and characterized with dielectric analysis (DEA), differential scanning calorimetry (DSC) and rheometry. The extra methyl group acted to produce a crystalline-like ordered hard segment that caused the 964 PCU to become Arrhenius in the glass transition region where the 5652 PCU had followed WLF behavior. Results showed the pendent methyl group acted to impart a crystalline-like character to the 964 PCU making it a candidate for applications that would be suited to a stiffer polymer. In Chapter Four we explore the possibility of increasing the wearability and comfort of contact lenses through increased hydration. The hydrogels 2-hydroxyethylmethacrylate (HEMA) and glycidyl methacrylate (GMA) solutions were created in three concentrations; neat, 50/50 and 60/40. Into these samples [Cu2({μ2-CO2}R)4(axial)2] (Cu(II) 4-hydroxybenzoic acid (MHBC) were dissolved 0.05% by weight. The samples were then polymerized via UV polymerization and compression molded. The experiments performed included penetration resistance , water absorption, micro hardness and glass transition. Addition of the MHBC acted to increase the water uptake of the samples but also reduced their ability to withstand mechanical penetration. With further study into crosslinking of the polymers, the MHBC could show promise in increasing hydration for commercial use.

Resilin is an almost perfect elastic protein found in many insects. It can be stretched up to 300% of its resting length and is not affected by creep or stress relaxation. While much is known about the static mechanical properties of resilin, it is most often used dynamically by insects. Unfortunately, the dynamic mechanical properties of resilin over the biologically relevant frequency range are unknown. Here, nearly pure samples of resilin were obtained from the dragonfly, Libellua luctuosa, and dynamic mechanical analysis was performed with a combination of time-temperature and time-concentration superposition to push resilin through its glass transition. The tensile properties for resilin were found over five different ethanol concentrations (65, 70, 82, 86 and 90% by volume in water) between temperatures of -5°C and 60°C, allowing for the quantification of resilin's dynamic mechanical properties over the entire master curve. The glass transition frequency of resilin in water at 22°C was found to be 106.3 Hz. The rubber storage modulus was 1.6 MPa, increasing to 30 MPa in the glassy state. At 50 Hz and 35% strain over 98% of the elastic strain energy can returned each cycle, decreasing to 81% at the highest frequencies used by insects (13 kHz). However, despite its remarkable ability to store and return energy, the resilin tendon in dragonflies does not act to improve the energetic efficiency of flight or as a power amplifying spring. Rather, it likely functions to passively control and stabilize the trailing edge of each wing during flight. / Master of Science

Polymeric adhesives play an increasingly critical role in today's engineering designs. When used, adhesively bonded components reduce or eliminate the need for bolted or welded connections. In many cases, this can reduce stress concentrations and weight. With energy dissipating adhesives, noise and vibration reduction are possible, as is the use of unique or complicated designs that could not otherwise be constructed. Adhesive properties however, can vary greatly with time, temperature, and environmental exposure conditions such as moisture. It is therefore critical, to understand the behavior of adhesives over the range of conditions that a bonded component might experience. In this work, the behavior of a urethane-based adhesive was characterized and long-term durability predictions were developed as a result of the data collected. The popular T-peel sample geometry has been used extensively in this study to explore the mechanics of a bonded system and the resulting impact on adhesive durability. The T-peel specimens used, consist of two aluminum sheets or adherends bonded together, with tabs bent back in the shape of a "T" for gripping in a universal load frame. Unlike some other test geometries, T-peel samples are often made with relatively thin adherends that may experience significant plastic deformation during testing. This extraneous energy dissipation greatly complicates the analysis to extract meaningful fracture properties of the adhesive. During testing, the load required to propagate a crack in the adhesive layer is measured at fixed displacement rates. The total system energy can then be partitioned into the energy dissipated within the adhesive (fracture energy), and the energy dissipated through plastic work in bending of the adherends. By performing these tests at different temperatures and rates, the calculated fracture energies span a wide range of possible material behavior. Using the principles of Time Temperature Superposition (TTS), the collected data can be shifted to different times or temperatures. This behavior is well understood in polymer physics, and is made possible with material specific "shift factors". By using the principles of TTS, data collected in in a relatively short experimental window, can be used to accurately predict the behavior of the adhesive in years or even decades. In this work, nearly 200 T-peel samples were tested in four different studies. A preliminary set of unaged specimens was used to develop testing and data analysis methodologies. A second set of unaged samples was tested over a wide range of temperatures and rates, in addition to a third group, subjected to constant moisture and cyclically varying temperature. The final set of specimens, was exposed to 20 separate isothermal aging conditions. The experimental data showed that the 400+ cycles, were insufficient to statistically distinguish these samples from their unaged counterparts. Additionally, samples aged for up to 2000 hours in a dry environment, or 500 hours in a wet environment, showed no reduction in fracture energies in comparison with unaged samples. Specimens aged for more than 500 hours however, were observed to have a significant decrease in fracture energy values. Strong correlations between the thickness of the adhesive layer and estimated fracture energy values were found in this study. As adhesive thickness varied substantially due to manufacturing differences in the specimens tested, new analysis techniques were developed to deal with the variations in adhesive thickness. A MATLAB code based on the ICPeel program, was written to provide a spatial variation of parameters such as adhesive thickness, peel load, and fracture energy. This provided additional insights into the behavior of these T-peel coupons, and prompted the investigation of the Universal Peel Diagram concept. While this diagram was not found to be applicable to the adhesive tested in this study, the analysis indicated that T-peel coupons could be multivalued. That is, a single measured load value does not always describe an adhesive's fracture energy (as is widely believed). Depending on the sample's geometry and material properties, several measured loads could cause debonding. This has potentially far reaching implications on the selection of appropriate T-peel test geometries, as a single measured load is often assumed to correlate to an adhesive's true fracture energy. In this work, both aged and unaged T-peel specimens were tested and the basis of the Universal Peel Diagram investigated. Given sufficient exposure times to moisture, elevated temperatures were found to significantly reduce the amount of energy dissipated in the urethane-based adhesive. Additionally, the Universal Peel Diagram indicated that for some systems, the load required for debond is in fact, multivalued. Therefore, care should be taken when designing a T-peel test configuration to avoid the multivalued regions. / Master of Science / Polymeric adhesives play an increasingly critical role in today's engineering designs. When used, adhesively bonded components reduce or eliminate the need for bolted or welded connections, reducing their weight in the process. With adhesives, noise and vibration reduction are possible, as is the use of unique or complicated designs that could not otherwise be constructed. Adhesive properties, however, can vary greatly with time, temperature, and other environmental exposure conditions such as moisture. It is therefore critical to understand the behavior of adhesives over the range of conditions that a bonded component might experience. In this work, the behavior of a urethane-based adhesive was characterized in order to develop long-term durability predictions. Numerous test methods have been developed to characterize the behavior of adhesively bonded joints. In this work, T-peel specimens were used consisting of two aluminum sheets (the adherends), bonded together with tabs bent back in the shape of a "T" for gripping in a universal load frame. During testing, the load required to propagate a crack in the adhesive layer is measured. An outcome of this measurement and subsequent data analysis is the fracture energy—a measure of the effectiveness of the adhesive in transferring loads. If we perform these tests at different temperatures and loading rates, we can determine fracture energy values which span a wide range of possible material behavior. Using principles from basic polymer physics, the collected data can be shifted to different times or temperatures enabling us to accurately predict the behavior of the adhesive over years or even decades. In this work, nearly 200 T-peel samples were tested in four different studies. A preliminary set of unaged specimens was used to develop testing and data analysis methodologies. Unaged and cyclically (temperature) aged samples were tested over a wide range of temperatures and rates. The fourth set of specimens was subjected to 20 separate isothermal aging conditions and also tested at different temperatures and rates. The experimental data showed that the 400+ temperature cycles were insufficient to damage these samples significantly. Additionally, samples aged for up to 2000 hours in a dry environment, or 500 hours in a wet environment showed no reduction in performance in comparison with unaged samples. Specimens aged for more than 500 hours in a wet environment however, demonstrated a significant decreases in fracture energy values. Strong correlations between the thickness of the adhesive layer and estimated fracture energy values were found in this study, and new analysis techniques were developed to analyze the effect of these thickness variations on the joint performance.

Resilin is a cuticular protein found in a variety of insects. It can stretch up to 300% of its natural length without any creep or relaxation. Further, it operates across a wide frequency range from 5 Hz in locomotion to 13 kHz in sound production. Both the protein sequence and composition of natural resilin as well as the dynamic mechanical properties vary substantially across species. This suggests that mechanical properties may be evolutionarily tuned for specific functions within an insect. Here, samples of resilin obtained from the tibia-tarsal joint of the cockroach, Periplaneta americana, were tested using a custom built dynamic mechanical analyzer. The material properties in compression are obtained from the rubbery to glassy domain with time-temperature superposition (-2C to 55C) and time-concentration superposition (0 % to 93% ethanol by volume in water). At low frequency the storage modulus was found to be 1.5 MPa increasing to about 5 MPa in the transition zone. The glass transition frequency at 23C in complete hydration was found to be 200 kHz. The data shows that cockroach resilin is less resilient than dragonfly resilin at low frequencies, returning about 79% of the elastic strain energy at 25 Hz compared to 97% for dragonfly resilin. However, at the glass transition (200 kHz) the material returns about 47% of the elastic strain energy compared to 30% in dragonfly (2MHz ). The resilin pad in cockroach is a composite structure, acting as a compressive spring to passively extend the tibia-tarsal joint during cockroach locomotion. Its mechanical properties are more similar to the composite locust pre-alar arm than to the pure resilin dragonfly tendon, suggesting that macroscopic structural influences may be as important as molecular sequence differences in setting properties. / Master of Science

This thesis presents the results of testing and modeling conducted to characterize the performance of 3M™ VHB™ structural glazing tape in both shear and tension. Creep rupture testing results provided the failure time at a given static load and temperature, and ramp-to-fail testing results provided the ultimate load resistance at a given rate of strain and temperature. Parallel testing was conducted on three structural silicone sealants to compare performance. Using the time temperature superposition principle, master curves of VHB tape storage and loss moduli in shear and tension were developed with data from a dynamic mechanical analyzer (DMA). The thermal shift factors obtained from these constitutive tests were successfully applied to the creep rupture and ramp-to-fail data collected at 23°C, 40°C, and 60°C (73°F, 104°F, and 140°F), resulting in master curves of ramp-to-fail strength and creep rupture durability in shear and tension. A simple linear damage accumulation model was then proposed to examine the accumulation of wind damage if VHB tape is used to attach curtain wall glazing panels to building facades. The purpose of the model was to investigate the magnitude of damage resulting from the accumulation of sustained wind speeds that are less than the peak design wind speed. The model used the equation derived from tensile creep rupture testing, extrapolated into the range of stresses that would typically be generated by wind loading. This equation was applied to each individual entry in the data files of several real wind speed histories, and the fractions of life used at each entry were combined into a total percentage of life used. Although the model did not provide evidence that the established design procedure is unsafe, it suggested that the accumulation of damage from wind speeds below the peak wind speed could cause a VHB tape mode of failure that merits examination along with the more traditional peak wind speed design procedure currently recommended by the vendor. / Master of Science

The high strain rate fiber direction tensile response of Ultra High Molecular Weight Polyethylene (UHMWPE) composites is of interest in applications where impact damage may occur. This response varies substantially with strain rate. However, physical testing of these composites is difficult at strain rates above 10^-1/s. A Monte Carlo simulation of composite tensile strength is constructed to estimate the tensile behavior of these composites. Load redistribution in the vicinity of fiber breaks varies according to fiber and matrix properties, which are in turn strain rate dependent. The distribution of fiber strengths is obtained from single fiber tests at strain rates ranging from 10^-4/s to 10^-1/s and shifted using the time-Temperature Superposition Principle (tTSP) to strain rates of 10^-4/s to 10^6/s. Other fiber properties are obtained from the same tests, but are assumed to be deterministic. Matrix properties are also assumed to be deterministic and are obtained from mechanical testing of neat matrix material samples. Simulation results are compared to experimental data for unidirectional lamina at strain rates up to 10^-1/s. Above 10^-1/s, simulation results are compared to experimental data shifted using tTSP. Similarly, through-thickness shear response of UHMWPE composites is of interest to support computational modeling of impact damage. In this study, punch shear testing of UHMWPE composites is conducted to determine shear properties. Two test fixtures, one allowing, and one preventing backplane curvature are used in conjunction with finite element modeling to investigate the stress state under punch shear loading and the resulting shear strength of the composite. / Ph. D.