Sharp leading edges required for hypersonic vehicles improve the maneuverability as well as reduce aerodynamic drag. However, due to the sharp design, increased surface temperatures require materials that can withstand these extreme conditions. Ultra-high temperature ceramics are a material group being considered for the leading-edge material, specifically ZrB₂/SiC (ZBS) which has a high thermal shock resistance, melting temperature, and thermal conductivity. Studies done by Tan et. al. has shown that adding samarium (Sm) as a dopant to ZBS has an emittance of 0.9 at 1600^oC and develop oxide scales that have excellent ablation performance. However, it remained unknown how the Sm doped oxide scale formed as well as how the emittance and ablation performance are affected by the microstructure. This study investigates the oxide scale development of 3 mol% doped Sm-ZBS billets as well as how differences in microstructure affect the emittance and ablation performance. Samples were prepared via chemical infiltration of samarium nitrate into spray-dried powders of 80 vol.% ZrB₂/20 vol.% SiC; powders were then pressed into billets and pressureless sintered. Samples cut and polished from these billets were then oxidized for 10, 60, or 300 s, respectively, using an oxyacetylene torch. X-ray diffraction was used to determine the sequence of oxidation of Sm-ZBS, beginning with the formation of ZrO₂ and Sm₂O₃. The final oxide scale was determined to be c₁-Sm_0.2Zr_0.8O_1.9, with a melting temperature exceeding 2500^oC. SEM and EDS were also used to investigate the microstructural formation that occurs from the bursting of convection cells. Samples with different microstructures revealed similar topographical microstructures post-ablation due to the sequence of the oxide formation. However, samples with rougher surfaces and higher porosities had a higher concentration of trapped glass in the cross-sectional oxide scale. It was also found that due to differences in heating the sample during emittance testing compared to ablation testing, the oxide developed was identical for all the samples. It was also found that variances in microstructure had no effect on the spectral emittance of Sm-ZBS at ultra-high temperatures. The fabrication of c₁-Sm_0.2Zr_0.8O_1.9 (SZO) as a bulk billet was also investigated to use as a thermal barrier coating (TBC) in replacement of Sm-ZBS.

<p>Hypersonic flight causes ultra-high surface temperatures which are most intense on sharp leading edges. One way of reducing the surface temperature is to apply a high emittance ceramic (HEC) on the leading edge, increasing the radiation component of heat transfer. An ideal HEC must have a high emittance, while also possessing a strong ablation resistance. From a scientific standpoint, it would be helpful if emittance could be tailored at different wavelengths. For example, materials with tailorable emittance could be used to improve the efficiency of engines, thermo-photo voltaic cells, and other applications. The approach used to create a ceramic with tailorable emittance was to use two different rare-earth elements, adding them to an ultra-high temperature ceramic (UHTC) in small quantities. The samarium element was added to increase the emittance of the UHTC over a large wavelength range (visible to near infrared wavelengths, consistent with the temperature range expected for hypersonic flight), and the erbium element was added to decrease the emittance at specific wavelength ranges. The goal of this study was to create an UHTC with tailorable emittance while maintaining the required ablation resistance. Therefore, ZBS billets with five different Sm to Er ratios and with a nominal total amount of 3 mol.% dopant incorporated were prepared by sintering in vacuum to 2000 °C. The ablation resistance was evaluated by using an oxyacetylene torch and observing at exposure times of 60 s and 300 s, whereas the emittance was evaluated at the Air Force Research Lab facilities via a laser heating testing. The results for the ablation testing showed that ZrB₂-SiC (ZBS) billets co-doped with Sm and Er formed a beneficial <i>c₁</i>-(Sm/Er)_0.2Zr_0.8O_1.9 oxide scale as the majority phase, which is more thermally stable than the <i>m</i>-ZrO₂ oxide scale typically formed in oxidized ZBS systems, resulting in a more adherent oxide scale to the unreacted material. The crystalline oxide scale and the amorphous phase were formed by a convection cell mechanism where the <i>c₁</i>-(Sm/Er)_0.2Zr_0.8O_1.9 crystalline islands precipitate, grow, and coalesce. Moreover, differences in surface temperatures between ZBS samples with different dopant ratios suggest differences in spectral absorptance/emittance between each of the five compositions evaluated. Despite that the emittance profiles with varying Sm:Er molar ratios were similar because <i>m</i>-ZrO₂ was formed as the major oxide phase, the emittance study showed that the erbium oxide influences the emittance profile, as can be noted by the maximum and minimum emittance peaks. Furthermore, results showed that the emittance varies as a function of dopant(s) molar ratios and temperature at shorter wavelength ranges. These changes in the emittance are caused by the different Sm and Er concentration on the surface. Future work should be focused on producing the beneficial <i>c₁</i>-(Sm/Er)_0.2Zr_0.9O_1.8phase directly from the manufacturing process, and therefore, maximize the effect of varying the Sm:Er molar ratios to tailor the emittance. Nonetheless, this study represents the first generation and reported emittance data of UHTC doping ZBS systems with both Sm and Er elements. </p>

This thesis provides new evidence which contributes to a clearer understanding of the mixing history of the lunar soil, the interactions of cosmic rays with the lunar surface and any temporal and spatial variations in cosmic ray intensity at the lunar surface. The bombardment of the lunar surface by cosmic rays produces secondary neutrons which are thermalised by the lunar soil. These thermal neutrons are captured by trace elements with large neutron capture cross sections such as cadmium, gadolinium and samarium. Measurements by thermal ionisation mass spectrometry of the changes in the isotopic abundances of cadmium, gadolinium and samarium due to neutron capture are presented in this thesis. Evidence is also presented of the first observations of mass fractionation in cadmium in lunar soils.Changes have been observed in samples from the Apollo 14, 16 and 17 missions. In 114 [superscript 114]Cd/[superscript 113]Cd changes of 0.3% to 0.5% have been observed in lunar samples 60501,105, 65701,23 and 72161,73, of 0.4% and 0.8% in [superscript 158]Gd/[superscript 157]Gd in samples 14163,848 and 60501,105 and of 0.8%, 1.2% and 0.06% in [superscript 150]Sm/[superscript 149]Sm in samples 14163,848 and 60501,105 and 74220,125 respectively. This is the first time that neutron capture has been detected in cadmium. Mass fractionation effects of 0.30%, 0.53% and 0.54% per mass unit have been observed in lunar samples 60501,105, 65701,23 and 72161,73, the first cadmium mass fractionation observed in lunar soils. The cause of elemental mass fractionation on the Moon is not yet understood. These new data from cadmium, a volatile element with a large mass range from [superscript 106]Cd to [superscript 116]Cd is a valuable contribution to the debate.Thermal neutrons are captured preferentially at resonance energies of 0.03 eV by [superscript 155]Gd and [superscript 157]Gd, at 0.09 ++ / eV by [superscript 149]Sm and at 0.178 eV by [superscript 113]Cd. A comparison of the changes in [superscript 114]Cd/[superscript 113]Cd, [superscript 156]Gd/[superscript 155]Gd, [superscript 158]Gd/[superscript 157] and [superscript 15O]Sm/[superscript149]Sm due to neutron capture can therefore indicate the relative energies of the neutrons.Previous work has compared changes in [superscript 158]Gd/[superscript 157]Gd and [superscript 150]Sm/[superscript 149]Sm, this work extends the comparison with the new measurements of the changes in 114 [superscript 114]Cd/[superscript 113]Cd, This thesis shows that the intensity of the thermal neutrons peaks at a higher energy than the <0.1 eV assumed by Lingenfelter et al. (1972). The capture rate for gadolinium calculated by Lingenfelter, has been shown to be too high, this thesis shows that if a modified energy spectrum is considered, biased towards higher energies, it will bring the calculated neutron capture rate by gadolinium closer to the measured rates.The concentrations of cadmium, gadolinium and samarium in nine lunar samples have been measured for the first time by high precision isotope dilution mass spectrometry. Cadmium in 10017,341, 14310,615, 15041,188, 15059,240, 60501,105, 65701,23, 72161,73 and 74220,125 is 10.0_+0.2, 1.51_+0.02, 32.8+_0.6, 34.9+_0.3, 112+_2, 68.3_+0.8, 57.0+_0.6 and 300+_7 ppb respectively. Gadolinium concentrations of 21+_7 ppm in 14163,848, 3.26+_0.05 and 5.8_+0.3 ppm in 60501,105, and 8.1+_0.2 and 8.6+_0.1 ppm in 74220,125 are presented. Samarium concentrations of 24.3_+0.4 and 29.8_+0.5 ppm were found in 14163,848, 2.68+_0.04 and 14+2 ppm in 60501,105, and 6.3+_0.1 and 6.8+_0.1 ppm in 74220,125.The concentrations of cadmium, gadolinium and samarium in the seven geochemical reference materials BCR-1, BHVO-1, BIR-1, DNC1, MAG-1, PCC-1 and W-2 are also presented, some measured for the first ++ / time by isotope dilution mass spectrometry.

For high-resolution X-ray imaging scintillator applications, we have prepared and optically characterized divalent samarium doped fluorochlorozirconate (FCZ:Sm2+) glasses and glass-ceramics. Sm2+ doped FCZ glasses were obtained by adding a reducing agent, NaBH4 into the initial melt to convert some of the Sm3+ to Sm2+. However, the Sm2+ concentration at most was estimated to be only approximately 0.003 %. The as-prepared glass samples were further heat treated to obtain glass-ceramics; the nucleation and growth of BaCl2 nanocrystals were confirmed by powdered X-ray diffraction (XRD) experiments. Depending on the heat treatment conditions (temperature and time), the average nanocrystal size varies from 8 to 170 nm, and the sample contains BaCl2 nanocrystals with the orthorhombic and/or hexagonal structure. The optical absorption spectra for our glass-ceramic samples suggested the substitution of Sm2+ ions into the BaCl2 lattice site. The FCZ:Sm2+ glass-ceramics samples showed strong fluorescence in the red region of spectrum (approximately 8 times that of an as-prepared glass), and the transparency can be very high (transmittance > 80 % for samples with thickness about 0.5 mm) and can be equivalent to that of an as-prepared glass . These two results promise potential as a high-resolution X-ray scintillator due to the emission wavelength range and high transparency. Extensive studies of photoluminescence (PL) spectra at low temperatures (12 -- 200 K) for FCZ:Sm2+ glass-ceramics suggested useful indicators of the crystal structure and average size of embedded BaCl2 nanocrystals. A detailed analysis of the optical spectra has lead to the identification of the origin of the emission peaks and the location of Sm ions at specific crystallographic sites. X-ray induced luminescence (XL) studies have suggested a strong dependence of the fluorescence intensity on the concentration of Sm2+ ions. In addition, for more efficient fluorescence, a sample should be heat treated in a hydrogen containing atmosphere (e.g. H2 + Ar gas), and the heat treatment conditions should be such that the nanocrystals grow in the hexagonal structure.

Microbeam Radiation Therapy (MRT) is an experimental form of radiation treatment which has the potential to improve the treatment of many types of cancer. In MRT, the radiation is applied as a grid by passing the collimated X-ray beam from a synchrotron through a microplane collimator, which is a stack of parallel plates of two materials with dramatically different X-ray transparencies. The peak-to-valley dose ratio (PVDR) is the difference between the dose in the microbeams and the dose delivered between the beams. It is the PVDR that is of biological importance in MRT. Therefore a dosimeter for MRT requires a combination of a large dynamic range for dose response into the kilo-Gray regime, and high spatial resolution on the micron scale. This project characterizes fluorophosphate glasses doped with trivalent samarium ions as a potential valency conversion dosimeter for MRT using the conversion of Sm3+→Sm2+ to measure the delivered dose. Samples irradiated at the Canadian Light Source synchrotron showed X-ray induced conversion that could be optically characterized by changes in the photoluminescence emission spectra to obtain irradiation dose. The conversion efficiency depends almost linearly on the irradiation dose up to 150 Gy and saturates at doses exceeding 1500 Gy. The conversion shows a strong correlation with an observed increase in absorbance of the glass in the range of 200-750 nm. The absorbance increases with X-ray dose and is related to the formation of phosphorous-oxygen hole centers (POHC) and POn electron centers. The presence of these defects within the irradiated glass was determined by examination of the induced optical absorbance and electron paramagnetic resonance (EPR) spectra. The formation of these hole centers along with the conversion of Sm3+→Sm2+ under X-ray irradiation suggests that the X-rays cause the formation of electron-hole pairs in the glass. The electrons are then primarily captured by the Sm3+ ions, becoming Sm2+ ions, with some of the electrons being captured by POn electron centers. The holes are captured by the POHCs. This process can be represented chemically as Sm3+ + e-→ Sm2+ and PO + h+→POHC. The stability of the Sm conversion under illumination was examined using photoluminescence spectra and the stability of the X-ray induced defects was examined via the induced optical absorbance and EPR spectra.

For high-resolution X-ray imaging scintillator applications, we have prepared and optically characterized divalent samarium doped fluorochlorozirconate (FCZ:Sm2+) glasses and glass-ceramics. Sm2+ doped FCZ glasses were obtained by adding a reducing agent, NaBH4 into the initial melt to convert some of the Sm3+ to Sm2+. However, the Sm2+ concentration at most was estimated to be only approximately 0.003 %. The as-prepared glass samples were further heat treated to obtain glass-ceramics; the nucleation and growth of BaCl2 nanocrystals were confirmed by powdered X-ray diffraction (XRD) experiments. Depending on the heat treatment conditions (temperature and time), the average nanocrystal size varies from 8 to 170 nm, and the sample contains BaCl2 nanocrystals with the orthorhombic and/or hexagonal structure. The optical absorption spectra for our glass-ceramic samples suggested the substitution of Sm2+ ions into the BaCl2 lattice site. The FCZ:Sm2+ glass-ceramics samples showed strong fluorescence in the red region of spectrum (approximately 8 times that of an as-prepared glass), and the transparency can be very high (transmittance > 80 % for samples with thickness about 0.5 mm) and can be equivalent to that of an as-prepared glass . These two results promise potential as a high-resolution X-ray scintillator due to the emission wavelength range and high transparency. Extensive studies of photoluminescence (PL) spectra at low temperatures (12 -- 200 K) for FCZ:Sm2+ glass-ceramics suggested useful indicators of the crystal structure and average size of embedded BaCl2 nanocrystals. A detailed analysis of the optical spectra has lead to the identification of the origin of the emission peaks and the location of Sm ions at specific crystallographic sites. X-ray induced luminescence (XL) studies have suggested a strong dependence of the fluorescence intensity on the concentration of Sm2+ ions. In addition, for more efficient fluorescence, a sample should be heat treated in a hydrogen containing atmosphere (e.g. H2 + Ar gas), and the heat treatment conditions should be such that the nanocrystals grow in the hexagonal structure.

Surface Biological Modification and Cellular Interactions of Magnetic Spinel Nanoparticles Eva Liang-Huang Heintz 191 Pages Directed by Dr. Z. John Zhang The interest in magnetic nanoparticles is multi-dimensional. Fundamentally, it is important to be able to control their magnetic properties and to correlate to specific applications. In biology, magnetic nanoparticles offer promising potential as magnetic carriers or chaperones for magnetic localization and manipulation of therapeutic reagents. The synthesis of superparamagnetic CoFe2-xSmxO4 nanoparticles and the tunability of their magnetic properties by size and composition variations are discussed. An increase in size of CoSm0.19Fe1.81O4 nanoparticles produced an increase in blocking temperature and saturation magnetization, but a non-linear coercitivity response was observed with change in size. By varying the composition, the saturation magnetization of CoFe2-xSmxO4 decreased dramatically while the coercitivity increased when compared to native cobalt spinel ferrite (CoFe2O4) nanoparticles. These results demonstrate how the magnetic properties of cobalt spinel ferrite nanoparticles can be tailored to specific applications. Surface modifications of cobalt spinel ferrite nanoparticles facilitated the conjugation of oligonucleotides. Using a transfection reagent, CoFe2O4 ??igonucleotide conjugates were delivered into mammalian cells. Post transfection, synchronized movement of cells in response to an external magnetic field was observed. This demonstrated the possibility of magnetic manipulation and localization of therapeutic reagents coupled to CoFe2O4 magnetic nanoparticles. Results from this thesis demonstrate the potential role of magnetic spinel nanoparticles in cell biology and will facilitate the progress towards in vivo testing.

Proefschrift--Amsterdam. / Summary in Dutch. Includes bibliographical references.

Thesis (Ph. D.)--Florida State University, 2004. / Advisor: Dr. William G. Moulton, Florida State University, College of Arts and Sciences, Dept. of Physics. Title and description from dissertation home page (viewed June 15, 2004). Includes bibliographical references.

Thesis (M.S. in Mechanical Engineering)--Naval Postgraduate School, June 1069. / Thesis Advisor(s): Marto, P. J. "June 1969." Description based on title screen as viewed on June 2, 2010. DTIC Descriptor(s): (Research Reactors, Reactor Reactivity), Reactor Cores, Fuel Burn Up, Fission Product Poisoning, Polyethylene Plastics, Perturbation Theory, Computer Programs, Theses. Author(s) subject terms: Perturbation, Polyethylene, Fermi Age, Extrapolation, Neutron Temperature, Samarium. Includes bibliographical references (p. 88). Also available in print.