<p> A new paradigm in biomedical engineering calls for biologically active implants that are absorbed by the body over time. One popular application for this concept is in the engineering of endovascular stents that are delivered concurrently with balloon angioplasty. These devices enable the injured vessels to remain patent during healing, but are not needed for more than a few months after the procedure. Early studies of iron- and magnesium-based stents have concluded that magnesium is a potentially suitable base material for such a device; alloys can achieve acceptable mechanical properties and do not seem to harm the artery during degradation.</p><p> Research done up to the onset of research contained in this dissertation, for the most part, failed to define realistic physiological corrosion mechanisms, and failed to correlate degradation rates between <i>in vitro</i> and <i>in vivo</i> environments. Six previously published works form the basis of this dissertation. The topics of these papers include (1) a method by which tensile testing may be applied to evaluate biomaterial degradation; (2) a suite of approaches that can be used to screen candidate absorbable magnesium biomaterials; (3) <i>in vivo-in vitro</i> environmental correlations based on mechanical behavior; (4) a similar correlation on the basis of penetration rate; (5) a mid-to-late stage physiological corrosion mechanism for magnesium in an arterial environment; and (6) the identification of corrosion products in degradable magnesium using transmission electron microscopy.</p>

<p> The objective of this research was to characterize the seawater transport and its effect on the transverse tensile strength of a carbon/vinylester composite. The moisture contents of neat vinylester and unidirectional carbon/vinylester composite panels immersed in seawater were monitored until saturation. A model for moisture up-take was developed based on superposition of Fickian diffusion, and Darcy&rsquo;s law for capillary transport of water. Both the predicted and measured saturation times increased with increasing panel size, however the diffusion model predicts much longer times while the capillary model predicts shorter time than observed experimentally. It was also found that the saturation moisture content decreased with increasing panel size. Testing of macroscopic and miniature composite transverse tensile specimens, and SEM failure inspection revealed more fiber/matrix debonding in the seawater saturated composite than the dry composite, consistent with a slightly reduced transverse tensile strength. </p>

<p> The tensile strength of the fiber/matrix interface was determined through the development of an innovative test procedure. A miniature tensile coupon with a through-thickness oriented, embedded single fiber was designed. Tensile testing was conducted in a scanning electron microscope (SEM) while the failure process could be observed. Finite element stress analysis was conducted to determine the state of stress at the fiber/matrix interface in the tensile loaded specimen, and the strength of the interface. Test specimens consisting of dry E-glass/epoxy and dry and seawater saturated carbon/vinylester 510A were prepared and tested. The load at the onset of debonding was combined with the radial stress distribution near the free surface of the specimen to reduce the interfacial tensile strength (&sigma;<i>_i</i>). For glass/epoxy, &sigma;<i>_i</i> was 36.7&#129;&plusmn;8.8 MPa. For the dry and seawater saturated carbon/vinylester specimens the tensile strengths of the interface were 23.0&#129;&plusmn;6.6 and 25.2&#129;&plusmn;4.1 MPa, respectively. The difference is not significant.</p>

<p> For galvanized or galvannealed steels to be commercially successful, they must exhibit several attributes: (i) easy and inexpensive processing in the hot mill, cold mill and on the coating line, (ii) high strength with good formability and spot weldability, and (iii) good corrosion resistance. At the beginning of this thesis, compositions with a common base but containing various additions of V or Nb with or without high N were designed and subjected to Gleeble simulations of different galvanizing(GI), galvannealing(GA) and supercooling processing. The results revealed the phase balance was strongly influenced by the different microalloying additions, while the strengths of each phase were somewhat less affected. Our research revealed that the amount of austenite formed during intercritical annealing can be strongly influenced by the annealing temperature and the pre-annealing conditions of the hot band (coiling temperature) and cold band (% cold reduction). In the late part of this thesis, the base composition was a low carbon steel which would exhibit good spot weldability. To this steel were added two levels of Cr and Mo for strengthening the ferrite and increasing the hardenability of intercritically formed austenite. Also, these steels were produced with and without the addition of vanadium in an effort to further increase the strength. Since earlier studies revealed a relationship between the nature of the starting cold rolled microstructure and the response to CGL processing, the variables of hot band coiling temperature and level of cold reduction prior to annealing were also studied. Finally, in an effort to increase strength and ductility of both the final sheet (general formability) and the sheared edges of cold punched holes (local formability), a new thermal path was developed that replaced the conventional GI ferrite-martensite microstructure with a new ferrite-martensite-tempered martensite and retained austenite microstructure. The new microstructure exhibited a somewhat lower strength but much high general and local formabilities. In this thesis, both the physical and mechanical metallurgy of these steels and processes will be discussed. This research has shown that simple compositions and processes can result in DP steels with so-called Generation III properties. </p>

<p> Formation of a high density of Mn-Ni-Si nanoscale precipitates in irradiated reactor pressure vessel steels could lead to severe, unexpected embrittlement, which may limit the lifetimes of our nation&rsquo;s light water reactors. While the existence of these precipitates was hypothesized over 20 years ago, they are currently not included in embrittlement prediction models used by the Nuclear Regulatory Commission. This work aims to investigate the mechanisms and variables that control Mn-Ni-Si precipitate (MNSP) formation as well as correlate their formation with hardening and embrittlement. </p><p> A series of RPV model steels with systematic variations in Cu and Ni contents, two variables that have been shown to have a dominant effect on hardening, were irradiated in a series of test reactor and power reactor surveillance irradiations. Atom probe tomography (APT) measurements show that large volume fractions (f_v) of MNSPs form in all the steels irradiated at high fluence, even those containing no added Cu, which were previously believed to have low sensitivity to embrittlement. It is demonstrated that while Cu enhances the rate of MNSP formation, it does not appear to significantly alter their saturation f_v or composition. The high fluence MNSPs have compositions consistent with known intermetallic phases in the Mn-Ni-Si system and have f_v very near those predicted by equilibrium thermodynamic models. In addition, X-ray diffraction experiments by collaborators shows that these precipitates also have the expected crystal structure of the predicted Mn-Ni-Si phases. </p><p> Post irradiation annealing experiments are used to measure the hardness recovery at various temperatures as well as to determine if the large f_v of MNSPs that form under high fluence neutron irradiation are thermodynamically stable phases or non-equilibrium solute clusters, enhanced or induced by irradiation, respectively. Notably, while post irradiation annealing of a Cu-free, high Ni steel at 425&deg;C results in dissolution of most precipitates, a few larger MNSPs appear to remain stable and may begin to coarsen after long times. A cluster dynamics model rationalizes the dissolution and reduction in precipitate number density, since most are less than the critical radius at the annealing temperature and decomposed matrix composition. The stability of larger precipitates suggests that they are an equilibrium phase, consistent with thermodynamic models. </p><p> Charged particle irradiations using Fe³⁺ ions are also used to investigate the precipitates which form under irradiation. Two steels irradiated to a dose of 0.2 dpa using both neutrons and ions show precipitates with very similar compositions. The ion irradiation shows a smaller f_v, likely due to the much higher dose rate, which has been previously shown to delay precipitation to higher fluences. While the precipitates in the ion irradiated condition are slightly deficient in Mn and enriched in Ni and Si compared to neutron irradiated condition, the overall similarities between the two conditions suggest that ion irradiations can be a very useful tool to study the susceptibility of a given steel to irradiation embrittlement. </p><p> Finally, the large f_v of MNSPs that are shown to form in all steels, including those low in Cu, at high fluence, even those without added Cu, result in large amounts of hardening and embrittlement. A preliminary embrittlement prediction model, which incorporates MNSPs at high fluence, is presented, along with results from a recent test reactor irradiation to fluences representative of extended lifetimes. This model shows very good agreement with the data.</p>

<p>Among the existing corrosion control methods, surfactant inhibitors have widely been used for corrosion inhibition of pipelines in water-oil-steel pipe (WOS) environments. This dissertation includes a systemic review of the causes of pipeline corrosion in WOS environments containing carbon dioxide (CO2), general corrosion control using surfactant inhibitors and associated concerns, and commonly used classes of surfactants and their properties, various processes and phenomena that affect overall surfactant performance. This dissertation also provides a review of experimental evaluation techniques and various developed models (semi-empirical model, mechanistic model, and multiphysics model) in evaluation of surfactant inhibition efficiency. An integrated corrosion inhibition (ICI) model is proposed, developed, and validated based on the current understanding of the inhibition of CO2 corrosion in WOS environments using surfactants. The developed ICI model for the modeling and prediction of corrosion inhibition efficiency of mixed surfactant inhibitors is a multiphysics model, based on the fundamentals from many areas of corrosion science, electrochemistry, metallurgical engineering, and chemical and analytical engineering, etc., and the integration of several submodels, including a water-oil surfactant distribution submodel, the aqueous cmc prediction submodel, and the modified Langmuir adsorption (MLA)/ modified quantitative structure activity relation (MQSAR) submodel. Software is developed based on the ICI model and the use of computational and programming resources. The phenomena and processes integrated into the ICI model include surfactant partitioning between oil and water, micellization and precipitation, adsorption/desorption at surfaces and interfaces, surfactant-solvent interactions, surfactant-counterion pairing, lateral interactions between surfactant molecules, and fluid flow. These phenomena are incorporated into three main processes and associated modeling: partitioning between oil and water, micellization/precipitation, and effective adsorption on metal substrate and water/oil interface. The framework of multiphysics ICI model is intended to serve as a basic framework in the understanding of mixed surfactant inhibitor performance with a focus on the application in salt-containing WOS environments. Beyond this, other potential applications may be extended to the design of surfactants, selection of optimal surfactants for specific applications, experimental validation of developed models, simulation of conceivable processes and phenomena, and the integration into more comprehensive lifetime prediction models in which all the surfactant efficiency-affecting factors may be evaluated.

<p> In this study, the performance of a Gold-Copper alloy has been examined in order to explore the possibility of its use as a cathode catalyst in a Proton Exchange Membrane (PEM) Fuel Cell. The performance of Oxygen Reduction Reaction (ORR), which occurs at the cathode, is evaluated using the Density Function Theory (DFT) computational code, SeqQuest. A surface segregation study is performed to identify a low energy surface of the catalyst. A binding site analysis of various intermediate molecules that occur during the ORR process is performed. The intermediate reactions of the ORR are simulated on the surface. Using the binding energies and energy barriers, the pathway that the Gold-Copper alloy prefers to follow is determined. The alloy is found to be a promising catalyst as it prefers to take the four electron pathway. An estimation of the Current Density has been made, and the effect the operating temperature has on it is observed.</p>

<p> In this work, beneficial effects of tensile mean strain on fatigue behavior and microstructure of superelastic NiTi (i.e. Nitinol) are studied. Most applications, such as endovascular stents made with NiTi, are subjected to a combination of constant and cyclic loading; thus, understanding the fatigue behavior of NiTi undergoing mean strain loading is necessary. Cyclic strain-controlled fatigue tests are designed to investigate the effects of tensile mean strain on fatigue of superelastic NiTi. Experimental observations show that combinations of large tensile mean strains and small strain amplitudes improve the fatigue life of superelastic NiTi. This behavior arises from reversible, stress-induced phase transformations. The phase transformations cause &ldquo;stress plateaus&rdquo; or strain ranges with no change in stress value. Scanning electron microscopy (SEM) of the fracture surfaces of specimens revealed generally short crack growth. Electron backscatter diffraction (EBSD) found the amount of residual martensite to be about ~8%, regardless of loading conditions.</p>

<p> Carbon-fiber composites are increasingly employed in the Aerospace and Automotive industries owing to their lightweight and excellent mechanical properties. However, this class of material, when subjected to out-of-plane loads, is often susceptible to an internal damage in the form of delamination that can severely reduce its load bearing capacity. Several toughening methods including the implementation of thermoplastic materials are used to increase the damage tolerance of the polymer-matrix composites. In particular, non-woven thermoplastic veils, when used as interleaving materials between the plies in a composite structure, is extremely efficient at improving the interlaminar (delamination) fracture toughness and impact-resistance of composites. In addition, the toughening of the polymer matrix, if not adversely affecting the manufacturing process, can result in an increase in the toughness-related properties of composite laminates such as the resistance to micro-cracking under thermal-cycling conditions. </p><p> In this study, the effects of matrix toughening and interleaving of the composite with non-woven Polyamide (PA) veils on the Interlaminar Fracture Toughness (ILFT) of Carbon-fiber/Benzoxazine composites are investigated. Formulated Benzoxazine (BZ) resins in non-toughened and toughened variants along with several non-woven PA veils with different melt temperatures are used to manufacture composite laminates through the Vacuum Assisted Resin Transfer Molding (VARTM) process. The ILFT of composites is measured by obtaining the resistance to crack propagation in the interlayer under tensile forces (Mode-I ILFT) or shear forces (Mode-II ILFT). The critical strain energy release rate (Gc) recorded during interlaminar fracture gives a measure of the ILFT of a composite. </p><p> The laminates interleaved with the PA veils show an increase of nearly 50% for the Mode-I crack initiation (GIc initiation), regardless of the melt temperature of the PA veils. The Mode-I crack propagation (GIc propagation) of the laminate increases by using the PA veils with melt temperatures lower than the cure temperature of the BZ resin. </p><p> In the Mode-II ILFT (GIIc) tests, the laminates interleaved with the PA veils show a significant impact on the GIIc values, as increases of nearly 170% are observed. A strong correlation between PA melt temperatures and the GIIc values is noted. The greatest GIIc values are noted when the melt temperature of the PA veil is greater than the cure temperature of the BZ resin. </p><p> The matrix toughness plays a significant role in affecting the GIc values. The laminates manufactured with the toughened BZ resin result in the greatest increase in the GIc values. In contrary, the use of the toughened BZ resin does not result in an improvement in the GIIc values.</p>

<p> The next generation of rechargeable batteries must have significantly improved gravimetric and volumetric energy densities while maintaining a long cycle life and a low risk of catastrophic failure. Replacing the conventional graphite anode in a lithium ion battery with lithium foil increases the theoretical energy density of the battery by more than 40%. Furthermore, there is significant interest within the scientific community on new cathode chemistries, like sulfur and air, that presume the use of a lithium metal anode to achieve theoretical energy densities as high as 5217 W&dot;h/kg. However, lithium metal is highly unstable toward traditional liquid electrolytes like ethylene carbonate and dimethyl carbonate. The solid electrolyte interphase that forms between lithium metal and these liquid electrolytes is brittle which causes a highly irregular current distribution at the anode, resulting in the formation of lithium metal protrusions. Ionic current concentrates at these protrusions leading to the formation of lithium dendrites that propagate through the electrolyte as the battery is charged, causing it to fail by short-circuit. The rapid release of energy during this short-circuit event can result in catastrophic cell failure. </p><p> Polymer electrolytes are promising alternatives to traditional liquid electrolytes because they form a stable, elastomeric interface with lithium metal. Additionally, polymer electrolytes are significantly less flammable than their liquid electrolyte counterparts. The prototypical polymer electrolyte is poly(ethylene oxide). Unfortunately, when lithium anodes are used with a poly(ethylene oxide) electrolyte, lithium dendrites still form and cause premature battery failure. Theoretically, an electrolyte with a shear modulus twice that of lithium metal could eliminate the formation of lithium dendrites entirely. While a shear modulus of this magnitude is difficult to achieve with polymer electrolytes, we can greatly enhance the modulus of our electrolytes by covalently bonding the rubbery poly(ethylene oxide) to a glassy polystyrene chain. The block copolymer phase separates into a lamellar morphology yielding co-continuous nanoscale domains of poly(ethylene oxide), for ionic conduction, and polystyrene, for mechanical rigidity. On the macroscale, the electrolyte membrane is a tough free-standing film, while on the nanoscale, ions are transported through the liquid-like poly(ethylene oxide) domains. </p><p> Little is known about the formation of lithium dendrites from stiff polymer electrolyte membranes given the experimental challenges associated with imaging lithium metal. The objective of this dissertation is to strengthen our understanding of the influence of the electrolyte modulus on the formation and growth of lithium dendrites from lithium metal anodes. This understanding will help us design electrolytes that have the potential to more fully suppress the formation of dendrites yielding high energy density batteries that operate safely and have a long cycle life. </p><p> Synchrotron hard X-ray microtomography was used to non-destructively image the interior of lithium-polymer-lithium symmetric cells cycled to various stages of life. These experiments showed that in the early stages of lithium dendrite development, the bulk of the dendritic structure was inside of the lithium electrode. Furthermore, impurity particles were found at the base of the lithium dendrites. The portion of the lithium dendrite protruding into the electrolyte increased as the cell approached the end of life. This imaging technique allowed for the first glimpse at the portion of lithium dendrites that resides inside of the lithium electrode. </p><p> After finding a robust technique to study the formation and growth of lithium dendrites, a series of experiments were performed to elucidate the influence of the electrolyte&rsquo;s modulus on the formation of lithium dendrites. Typically, electrochemical cells using a polystyrene &ndash; block&not; &ndash; poly(ethylene oxide) copolymer electrolyte are operated at 90 &deg;C which is above the melting point of poly(ethylene oxide) and below the glass transition temperature of polystyrene. In these experiments, the formation of dendrites in cells operated at temperatures ranging from 90 &deg;C to 120 &deg;C were compared. The glass transition temperature of polystyrene (107 &deg;C) is included in this range resulting in a large change in electrolyte modulus over a relatively small temperature window. The X-ray microtomography experiments showed that as the polymer electrolyte shifted from a glassy state to a rubbery state, the portion of the lithium dendrite buried inside of the lithium metal electrode decreased. These images coupled with electrochemical characterization and rheological measurements shed light on the factors that influence dendrite growth through electrolytes with viscoelastic mechanical properties. (Abstract shortened by ProQuest.)</p>