Iron-cobalt (FeCo) and its various alloys have many applications where soft magnetic materials are needed, especially in high temperature applications. Recent research has looked into the nanocrystallization of amorphous alloys of FeCo and very briefly into the oxidation of FeCo nanoparticles and bulk materials. Attempts will be made to more carefully investigate the oxidation of FeCo and its alloys utilizing nanoparticles, and thin films with (100), (110), and (211) texture to observe the kinetics of oxidation. Thin film epitaxial relationships between the substrate and thin films have been determined, and this will be extended to the oxide and thin film. The role of alloying has been discussed, especially in the context of oxidation of FeCo. The composition of the oxide at different oxidizing temperatures is also proposed. FeCo-based nanoparticles have been analyzed to understand their change in magnetization and oxide phase as a function of temperature. The oxide thickness has been measured at various temperatures, along with the observation of a voided core. This research has been coupled with thin film work to show that the core gets richer in cobalt as oxidation progresses, with Fe acting as the mobile species. Oxygen may diffuse early in the oxidation, but only until a certain oxide thickness has been established. The oxidation kinetics seen in the nanoparticles is slower than that seen in thin films, and it has currently been analyzed to follow a logarithmic rate law at lower temperatures. To understand the formation of faceted nanoparticles, nucleation and growth has been modeled for both BCC and FCC systems showing the surface energy ratios necessary to produce different faceting of nanoparticles. It has been shown that the critical nuclei are the same as the growth shapes. To extend the basic science research into the applications field, thin film work on CoCrPt has been performed to achieve out-of-plane anisotropy in thicker films for use in a portable AGFM. While this has been achieved, further study is necessary to improve the remnant magnetization and make it more comparable to SmCo, which is the current standard. The magnetic properties have been measured as a function of temperature and film thickness to begin understanding the system better to produce the desired thin film properties for a biomedical sensor.

<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>

The mechanical properties of the extracellular matrix are dynamic and change during biological processes such as disease progression and wound healing. Most synthetic (or man-made) tissue scaffolds have static properties. Therefore it is necessary to replate cells in order to determine the effects that different matrix mechanical properties have on cells, and virtually impossible to study the effects of a dynamically changing modulus on cell growth. There have been several scaffolds recently developed with tunable mechanical properties, but few exhibit any reversibility which is important for simulating repeated wounding and healing cycles. In this work, we develop a gelatin based hydrogel with azodianiline (ADA) as a secondary crosslinking unit. Upon irradiation with 365 nm light the gel softens as the ADA undergoes a photoisomerization. These changes can be reversed upon exposure to visible light. With applications in mechanobiology in mind, contraction at the cellular scale was measured, as well as the macroscopic changes in the shear elastic modulus and compressive modulus in response to exposure to UV and visible light.

Environmental microorganisms are implicated as the causative agents in a significant portion of healthcare associated infections (HAI) and antimicrobial resistant infections (AMR), which result in increased costs and suffering around the world. Furthermore, common environmental microorganisms participate in microbiological degradation of materials and the bio-fouling of various systems. This also results in a tremendous amount of damage in many different materials and many different sectors. The focus of this dissertation was the development of an additive that could be easily added to common materials to make them self-disinfecting and to protect them from microbial damage. The ultimate goal was to develop an additive that could be added using standard techniques and without adversely affecting the final material. Cuprous iodide (CuI) was determined to be an ideal starting material for the development of improved antimicrobial materials because of its neutral appearance and high antimicrobial activity as compared to other silver and copper materials. It was found that the antimicrobial efficacy of CuI could be amplified if prepared as a small particle and especially in the presence of vinylpyrrolidone polymers. A comminution process was then developed to produce these small particles. By using select copolymers, various CuI small particles formulation were developed to be compatible with a variety of different matrices. The efficacy of these CuI containing matrices was dependent on the compatibility of the CuI formulation with the matrix. A variety of applications were demonstrated with good antimicrobial efficacy where the particles were easily added to the finished material with minimal or no change in appearance.

<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.

<p> Thin films (~100 nm) have been prepared of the prototypical spin-crossover complex Fe(phen)₂(NCS)₂ (phen = 1,10-phenanthroline). Initial attempts to prepare these films by direct vapor deposition yielded films of a different material. Through extensive FT-IR, Raman, UV-Vis, and x-ray photoelectron spectroscopy it is shown that these as-deposited films are the ferroin-based tris complex [Fe(phen)₃](SCN)₂. Structural characterization by AFM and powder XRD reveals them to be smooth and amorphous. When heated, the [Fe(phen)₃](SCN)₂ films are converted first to Fe(phen)₂(SCN)₂ and then to a third species postulated to be Fe(phen)(NCS)₂ which is likely a one-dimensional coordination polymer. On the other hand, deposition from Fe(phen)₂(NCS)₂ onto heated substrates produces a mixture of these three materials. The identity of the Fe(phen)₂(NCS)₂ films is proved by additional spectroscopic, structural, and magnetic characterization. Magnetometry reveals them to remain spin-crossover active albeit with a more gradual and incomplete spin-transition than the bulk material. The films are found to be granular in nature and deep crevices were observed at the grain boundaries. Within the optical microscope, the coloring of the grains is seen to be dependent upon sample orientation. Powder XRD indicates texturing of crystalline domains where the crystallographic c-axis is parallel to the surface normal. This represents a new process for production of Fe(phen)₂(NCS)₂ films.</p><p> With the aim of realizing the potential for spin-crossover materials to modulate electrical conduction and vise versa, electrical characterization has been performed as a function of temperature on vertical junction devices incorporating the prepared Fe(phen)₂(NCS)₂ films. In order to prevent penetration of the top electrode through the cracks and crevices in the organometallic layer, a multiple sequential deposition and annealing process was developed to produce films with a continuous surface topography. A small change in the weak electrical conductivity of these devices appears at the spin transition temperature, demonstrating for the first time in this important material a coupling of the electrical conductivity and magnetic spin state. Here, the HS state has a higher electrical conductivity. Incorporation of LiF interfacial layers between the Fe(phen)₂(NCS)₂ and the metal electrodes improves conduction slightly but tunneling still appears to be the current-limiting mechanism. Electrical measurements were also performed on devices made with the related complex [Fe(phen)₃](SCN)₂. Such films were much more conductive&mdash;as good as other typical organic semiconductor materials. All together, this work establishes the potential for this family of complexes to be incorporated into thin-film based electrical devices whose operation is based on the spin-crossover effect or otherwise.</p>

Use of electroless nickel plating for self-regulating low temperature induction heating of tumors (hyperthermia) was investigated. The desired magnetic properties for the material were: (1) a Curie temperature, T(C), in the range of about 52-62°C, (2) high induced power above T(C), and (3) an abrupt drop in induced power at the Curie temperature. An amorphous ferromagnetic material would provide the highest corrosion resistance and superior magnetic properties, while cylindrical geometry is necessary for clinical considerations and for maximum heating. Electroless Ni-P containing near 11-12 atomic percent phosphorus (Curie temperature 45-60°C) was plated to thicknesses exceeding three skin depths (calculated for nickel) onto 1 mm diameter wires. Power produced by the plated wires was low and no sharp drop in power was seen in the range of 20-80°C. High internal stress, which decreases magnetic permeability, and thus reduces power, can be reduced by annealing at 150°C. The lack of a sharp temperature drop was attributed to inherent inhomogeneity in the plating, determined by x-ray microanalysis. Stainless steel tubes filled with amorphous high permeability material heated well in a magnetic field, while no heating was obtained using the same amount of amorphous material packed into plastic tubing or using empty stainless steel tubing. The heat produced per unit length by the composite implants was greater than that produced by solid 1 mm diameter NiSi, but less than that estimated for stranded NiSi implants, which are comprised of optimum diameter strands to maximize eddy current heating. Electroless Ni-P alone cannot be used to provide high power implants, but it or other biocompatible conductive coatings could possibly be used on the outside of a flexible implant filled with high permeability material. This would allow the possibility of producing a flexible, biocompatible device which is thermally self-regulating and produces high induced power. It also opens up the possibility of using induction heating and radiotherapy sequentially or simultaneously if the radiation sources could be loaded with the high permeability material.

Novel unidirectional crystallization was tested in glasses of the Bi-Sr-Ca-Cu-O system to produce highly oriented microstructures. Some evidence of liquid-liquid phase separations on cooling melts of Bi₂Sr₂Ca₁Cu₂Oₓ and Pb₀ͺ₃₂Bi₁ͺ₆₈Sr₁ͺ₇₅Ca₂Cu₃Oₓ is found for the first time from Differential Thermal Analysis (DTA), X-ray Diffraction (XRD), and Transmission Electron Microscope (TEM). This made it difficult to produce highly oriented microstructures through the present route because one of the phases in the phase separated structure is likely close to "R"-phase composition and lead to copious nucleation of "R"-phase on heating. This also resulted in sequential crystallization of the current liquids, first to "R"-phase and then to the Bi₂Sr₂Ca₁Cu₂Oₓ phase. Theoretical modelling was performed to understand general questions in the present route. The model suggests that a liquid with high interfacial energy is a good candidate for the present route to produce highly oriented microstructures. The model was tested in lithium diborate glass and showed a highly oriented microstructure. Thus, unidirectional crystallization is generally an attractive processing option for a liquid free of phase separation.