Experiments of directional solidification in a Hele-Shaw cell, 240 mm x 245 mm x 1 mm, were carried out to study the effects of convective flows and the evolution of structure in the "mushy layer", consisting of fluid and crystallites. Three different concentrations of ammonium chloride (NH₄Cl) solution, 26%, 27% and 28%, with a constant bottom cooling temperature ranging from 5°C to -20°C were used as an analogue model for metallic alloy systems. The experimental design included techniques using Peltier heat pumps along with PID feedback control for temperature regulation. A shadowgraphic visualization method made possible the simultaneous observation of the evolution of convection in the liquid region and the phenomena of chimney formation within the mushy layer. More than one hundred runs were carried out. Temperature information and simultaneously acquired digital images were recorded automatically. The time evolution of the solidification process was traced by image processing technique from the digital images. Results show that the phenomenon of intermittent plumes frequently occurs. The number of plumes near the liquid-mush interface decreases from a larger number in the beginning to about the same number of high plumes in the liquid region or chimneys in the mush. The number of chimneys is more static than that of plumes due to the relatively low speed of solidification or dissolution. The mush consists of three different layers. A thin layer of generally upward oriented crystal forms rapidly in the beginning, followed by a second layer aggregate gradually covering it. Finally a third layer of dendritic crystals dominates the top of the growing mush. Preliminary experiments in a Hele-Shaw cell inclined at 21 degrees caused the mush structures to develop differently than in the normal geometry. The significant differences include the dendritic crystal form, the lacunae of the mush, the shape of the chimneys, and the porosity changes of the structures. Directions for future research are suggested.

<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>The effect of surfaces on the electron transport at reduced scales is attracting continuous interest due to its broad impact on both the understanding of materials properties and their application for nanoelectronics. The size dependence of for conductor?s electrical resistivity ? due to electron surface scattering is most commonly described within the framework of Fuchs and Sondheimer (FS) and their various extensions, which uses a phenomenological scattering parameter p to define the probability of electrons being elastically (i.e. specularly) scattered by the surface without causing an increase of ? at reduced size. However, a basic understanding of what surface chemistry and structure parameters determine the specularity p is still lacking. In addition, the assumption of a spherical Fermi surface in the FS model is too simple for transition metals to give accurate account of the actual surface scattering effect. The goal of this study is to develop an understanding of the physics governing electron surface/interface scattering in transition metals and to study the significance of their Fermi surface shape on surface scattering. The advancement of the scientific knowledge in electron surface and interface scattering of transition metals can provide insights into how to design high-conductivity nanowires that will facilitate the viable development of advanced integrated circuits, thermoelectric power generation and spintronics. Sequential in situ and ex situ transport measurements as a function of surface chemistry demonstrate that electron surface/interface scattering can be engineered by surface doping, causing a decrease in the ?. For instance, the ? of 9.3-nm-thick epitaxial and polycrystalline Cu is reduced by 11-13% when coated with 0.75 nm Ni. This is due to electron surface scattering which exhibits a specularity p = 0.7 for the Cu-vacuum interface that transitions to completely diffuse (p = 0) when exposed to air. In contrast, Ni-coated surfaces exhibit partial specularity with p = 0.3 in vacuum and p = 0.15 in air, as Cu2O formation is suppressed, leading to a smaller surface potential perturbation and a lower density of localized surface states, yielding less diffuse electron scattering. The localized surface density of states (LDOS) at the Fermi level N(Ef) as a primary parameter determining the surface scattering specularity is further confirmed by a different surface dopant. In particular, the measured sheet resistance of 9-25-nm-thick epitaxial Cu(001) layers increases when coated with dTi = 0.1-4.0 monolayers (ML) of Ti, but decreases again during exposure to 37 Pa of O2. The corresponding changes in ? are a function of dCu and dTi and are due to a transition from partially specular electron scattering at the Cu surface to completely diffuse scattering at the Cu-Ti interface, and the recovery of surface specularity as the Ti is oxidized. X-ray reflectivity and photoelectron spectroscopy indicate the formation of a 0.47?0.03 nm thick Cu2O surface layer on top of the TiO2-Cu2O during air exposure, while density functional calculations of TiOx cap layers as a function of x = 0-2 and dTi = 0.25-1.0 ML show a reduction of N(Ef) by up to a factor of four. This reduction is proposed to be the key cause for the recovery of surface specularity and results in electron confinement and channeling in the Cu layer upon Ti oxidation. Transport measurements at 293 and 77 K confirm the electron channeling and demonstrate the potential for high-conductivity metal nanowires by quantifying the surface specularity parameter p = 0.67?0.05, 0.00?0.05, and 0.35?0.05 at the Cu-vacuum, Cu-Ti, and Cu-TiO2 interfaces. In order to determine the effect of the Fermi surface shape on the size effect, experimental and simulation results are combined to study how the resistivity changes with film thickness dw on monocrystalline W layers with different surface orientation, W(001) and W(110). As the first step of the experiments, the growth of epitaxial W(001) layers on MgO(001) substrates by ultra-high vacuum magnetron sputtering is studied, in order to obtain an alternative W layer orientation in addition to the well-known growth of epitaxial W(011) on Al2O3 substrates. X-ray diffraction ?-2? scans, ?-rocking curves, and pole figures show that 5-400 nm thick W(001) layers grown at Ts = 900 ?C are monocrystalline with a relaxed lattice constant of 3.167?0.001 nm, as determined from high resolution reciprocal space mapping. The magnitude of the residual in-plane compressive strain decreases from -1.2?0.1% to 0.1?0.1% with increasing dw. This is attributed to the glide of threading dislocations which increases the average misfit dislocation length, causing relaxation of the stress associated with differential thermal contraction. X-ray reflectivity measurements indicate smooth surfaces with a root-mean-square surface roughness ?1.0 nm and a roughness exponent of 0.38 for dw below 20 nm. Secondly, the effect of surface roughness on surface scattering is investigated to ensure its contribution to the resistivity size effect is properly included when comparing W films grown on different substrates. In fact it is found the ? of in situ annealed 4-20 nm thick epitaxial W(001) layers grown on MgO(001) samples show weaker dw dependence than that of unannealed samples in vacuum and air at both 295 and 77 K although completely diffuse surface scattering are present on both sets of films. No significant change in the structural quality of the samples after annealing is observed for d ? 20 nm. While a combination of X-ray reflectivity and Atomic Force Microscope study on surface morphology shows flatter surface mounds after annealing. Consequently, in situ annealing treatment is carried out on both epitaxial W(110) and W(001) from dw =4-320 nm to obtain surface with comparable rms roughness and lateral correlation length. Thus the ? increase due to the surface roughness is estimated in similar degree for the two types of films. Finally, a transport model for thin films with anisotropic Fermi surfaces is presented, which includes the effect of electron surface scattering. Simulations done using the calculated W Fermi surface show the resistivity ? to be 1.15-2.23 and 1.21-3.14 times larger than that of bulk W for (011) and (001) oriented thin films, respectively at a layer thickness d = 37.5- 3.75 nm, indicating an orientation dependent surface scattering effect on ?. The resistivity of epitaxial W(110) increases from 5.77?0.03 to 13.24?0.24 ??-cm as d decreases from 320 to 5.7 nm, but increases stronger for epitaxial W(001) from ? = 5.77?0.03 to 24.42?0.58 ??-cm for d = 320 and 4.5 nm. This orientation dependence is quantified with a different effective mean free path lambda(110) = 18.5?0.3 nm vs lambda(001) = 33?0.4 nm at 295 K by fitting using ? vs t with the Fuchs-Sondheimer (FS) model for spherical Fermi surfaces since their surface scattering is found completely diffuse by sequential in situ and ex situ electron transport measurements. Similarly, the ? from simulation can be fitted to obtain another set of lambda(110) and lambda(001) . The ratio lambda(110)/lambda(001) = 0.57?0.01 from simulations, in good agreement with 0.56?0.01 from experiment. The orientation dependent size effect is the result of (1) the projected Fermi surface area along the surface normal and (2) the rate of electrons approaching the surfaces due to the anisotropic electron Fermi velocity distribution along different directions.

<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.

Recently, a new technology termed the controllable photochromic has emerged within the field of chromogenic technology. This technology represents a novel approach to the control of solar heat gain and adjustable transmission by utilizing a combination of chromogenic and radiation sensitive technologies. By harnessing solar energy for coloration, these systems represent a low-energy approach to controllable transmission glazings when compared to other chromogenic technologies available today. The zero external power required to reduce the glazing transmission and to maintain that state will provide opportunities for applications where today's chromogenic technologies are not well suited. One emphasis of this work was the rationalization of a general framework through which present and future controllable photochromic systems can be discussed. This framework discusses the roles and properties of the system components, necessary and desired for the function of the system, including a radiation sensitive electrode, a chromogenic electrode, and an electrolyte. The framework was also examined through a detailed case study of a system involving an anatase TiO₂ radiation sensitive electrode and a WO₃ chromogenic electrode. While this study involved a particular implementation of the technology, it exposed a great many attributes of this system including kinetics, wavelength sensitivity, influence of construction parameters, sensitivity to non-uniform incident radiation, and control over the photochromic response. While the general framework is useful for discussion of the principles involved in device operation, the detailed mechanisms occurring in a particular implementation will generally be more complex. Through careful study of the example system described in this thesis, the primary mechanisms occurring in the device were identified, and a model is proposed which is consistent with the observed findings. The source of degradation occurring due to prolonged cycling in the devices was studied through investigation of changes occurring in individual device components. While only one implementation of the technology was studied in detail in this investigation, three configurations were discussed in terms of the general framework. These systems exhibit an impressive array of desirable properties; however, it is clear that there is still much to be done to bring the technology to full fruition.

Pollucite (CsAlSi₂O₆) is a refractory phase within the Cs₂O-Al₂O₃-SiO₂. It melts at >1900°C and also has a reported thermal expansion value of 15 x 10⁻⁷/°C. These qualities make it suitable for study as a high temperature structural ceramic. Amorphous powders were synthesized by a novel sol-gel process in the Cs₂O-Al₂O₃-SiO₂ system. Gels were produced from tetraethoxysilane (TEOS), Aluminum chelate, and Cs-acetate. Powders were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), chemical, differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The glass transition and crystallization temperatures were determined to be 945°C and 1026°C, respectively, for the amorphous powders. Pollucite and mullite phases were observed by XRD of bulk glass-ceramics. A density of 3.02 gm/cm³ was observed for the hot pressed material. Dielectric constants in the frequency range 1kHz-1MHz were found to be in the range of 5.23 to 5.78 for the as hot pressed and heat treated samples. Thermal expansion coefficients were also determined.