THE MICROSTRUCTURES OF ZR-EXCEL ALLOY: EFFECTS OF HEAVY ION IRRADIATION, PLASTIC DEFORMATION, THERMAL TREATMENT AND IN-SITU HEATING

Zr-Excel alloy (Zr-3.5Sn-0.8Nb-0.8Mo) is a dual phase (α + β) alloy in the as-received pressure tube condition. It has been proposed to be the pressure tube candidate material for the Generation-IV CANDU-Supercritical Water Reactor (CANDU-SCWR). In this dissertation, the effects of heavy ion irradiation, deformation and heat treatment on the microstructures of the alloy were investigated to enable us to have a better understanding of the potential in-reactor performance of this alloy. In-situ heavy ion (1 MeV) irradiation was performed to study the nucleation and evolution of dislocation loops in both α- and β-Zr. Small and dense type dislocation loops form under irradiation between 80 and 450 °C. The number density tends to saturate at ~ 0.1 dpa. Compared with the α-Zr, the defect yield is much lower in β-Zr. The stabilities of the metastable phases (β-Zr and ω-Zr) and the thermal-dynamically equilibrium phase, fcc Zr(Mo, Nb)2, under irradiation were also studied at different temperatures. Chemi-STEM elemental mapping was carried out to study the elemental redistribution caused by irradiation. The stability of these phases and the elemental redistribution are strongly dependent on irradiation temperature. In-situ time-of-flight neutron diffraction tensile and compressive tests were carried out at different temperatures to monitor lattice strain evolutions of individual grain families during these tests. The β-Zr is the strengthening phase in this alloy in the as-received plate material. Load is transferred to the β-Zr after yielding of the α-Zr grains. The temperature dependence of static strain aging and the yielding sequence of the individual grain families were discussed. Strong tensile/compressive asymmetry was observed in the {0002} grain family at room temperature. The microstructures of the sample deformed at 400 °C and the samples only subjected to heat treatment at the same temperature were characterized with TEM. Concentration of β phase stabilizers in the β grain and the morphology of β grain have significant effect on the stability of β- and ω-Zr under thermal treatment. Applied stress/strain enhances the decomposition of isothermal ω phase but suppresses α precipitation inside the β grains at high temperature. An α → ω/ZrO phase transformation was observed in the thin foils of Zr-Excel alloy and pure Zr during in-situ heating at 700 °C in TEM.

Solvation Structure of Uracil in Ionic Liquids

The local solvation environment of uracil dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate has been studied using neutron diffraction techniques. At solvent:solute ratios of 3:1 and 2:1 ionic liquid:uracil, little perturbation of the ion-ion correlations compared to those of the neat ionic liquid are observed. We find that solvation of the uracil is driven predominantly by the acetate anion of the solvent. While short distance correlations exist between uracil and the imidazolium cation, the geometry of these contacts suggest that they cannot be considered as hydrogen bonds, in contrast to other studies by Araújo et al. (J. M. Araújo, A. B. Pereiro, J. N. Canongia-Lopes, L. P. Rebelo, I. M. Marrucho, J. Phys. Chem. B 2013, 117, 4109-4120). Nevertheless, this combination of interactions of the solute with both the cation and anion components of the solvents helps explain the high solubility of the nucleobase in this media. In addition, favorable uracil-uracil contacts are observed, of similar magnitude to those between cation and uracil, and are also likely to aid dissolution

Efectos de la microestructura sobre la transmisión de neutrones en materiales de interés nuclear.

Cuando un haz policromático de neutrones pasa a través de un material, los neutrones de distintas longitudes de onda son atenuados en formas muy diferentes. Como resultado, el espectro de energía del haz de neutrones cambia cuando una muestra es colocada frente el haz. Un análisis detallado del cociente de intensidad entre los haces de transmitido e incidente puede proporcionar una gran cantidad de información acerca de la estructura cristalina y microestructura de la muestra, definidas a través de la sección eficaz total del material. Para neutrones térmicos y sub-térmicos, el ordenamiento y movimiento de los átomos a escala microscópica define en forma precisa la dependencia de esta magnitud con la energía del neutrón incidente. Así, la variación con la energía de la sección eficaz total de los sólidos debido a la estructura de los átomos para distancias entre 0,1 y 100 Å se encuentra bien establecida, y es explotada en el estudio de estructuras cristalinas y de los movimientos vibracionales y rotacionales. Como contrapartida, el efecto de la estructura mesoscópica de los materiales, esto es para dimensiones entre 0,1 y 100 µm, sobre la sección eficaz total ha sido mucho menos estudiado, a pesar de provocar cambios profundos en esta magnitud. En esta Tesis estudiamos y formalizamos la dependencia de la sección eficaz total con características microestructurales tales como la porosidad, y la distribución de tamaños y orientaciones de los granos que componen los materiales, y desarrollamos modelos teóricos a partir de las características microestructurales de muestras de interés nuclear con diferente microestructura. Estos modelos permiten describir la contribuci ón de la componente elástica coherente de la seción eficaz total sobre los espectros de transmisión de neutrones e introducen parámetros como la cantidad de cristales que conforman el material, su estructura cristalina, parámetros de red, mosaicidad, estructura de poros u orientación preferencial de granos, para describir la sección total de materiales monocristalinos o policristalinos. En todos los casos, los modelos desarrollados fueron implementados en una biblioteca basada en el lenguaje computacional MATLAB y fueron comparados con secciones eficaces totales obtenidas en experimentos de transmisión de neutrones realizados en el Departamento de Física de Neutrones del Centro Atómico Bariloche y en ISIS Facility, Reino Unido. Los novedosos modelos microestructurales propuestos describen fielmente los experimentos desarrollados sobre muestras con distinta microestructura, lo que permite el empleo de los mismos en un código de refinamiento sobre los datos experimentales. Aquí, desarrollamos herramientas computacionales que ajustan por cuadrados mínimos no lineales los modelos paramétricos representativos de cada microestructura, sobre la sección eficaz total o la transmisión experimental, para determinar parámetros microestructurales de la muestra a partir de experimentos de transmisión de neutrones con resolución en longitud de onda. Los resultados son de particular relevancia para la interpretación y el análisis cuantitativo de las imágenes realizadas por la técnica de radiografía neutrónica con resolución en energía, que ha recibido un gran impulso en años recientes.

Efectos de la microestructura sobre la transmisión de neutrones en materiales de interés nuclear.

Cuando un haz policromático de neutrones pasa a través de un material, los neutrones de distintas longitudes de onda son atenuados en formas muy diferentes. Como resultado, el espectro de energía del haz de neutrones cambia cuando una muestra es colocada frente el haz. Un análisis detallado del cociente de intensidad entre los haces de transmitido e incidente puede proporcionar una gran cantidad de información acerca de la estructura cristalina y microestructura de la muestra, definidas a través de la sección eficaz total del material. Para neutrones térmicos y sub-térmicos, el ordenamiento y movimiento de los átomos a escala microscópica define en forma precisa la dependencia de esta magnitud con la energía del neutrón incidente. Así, la variación con la energía de la sección eficaz total de los sólidos debido a la estructura de los átomos para distancias entre 0,1 y 100 Å se encuentra bien establecida, y es explotada en el estudio de estructuras cristalinas y de los movimientos vibracionales y rotacionales. Como contrapartida, el efecto de la estructura mesoscópica de los materiales, esto es para dimensiones entre 0,1 y 100 µm, sobre la sección eficaz total ha sido mucho menos estudiado, a pesar de provocar cambios profundos en esta magnitud. En esta Tesis estudiamos y formalizamos la dependencia de la sección eficaz total con características microestructurales tales como la porosidad, y la distribución de tamaños y orientaciones de los granos que componen los materiales, y desarrollamos modelos teóricos a partir de las características microestructurales de muestras de interés nuclear con diferente microestructura. Estos modelos permiten describir la contribuci ón de la componente elástica coherente de la seción eficaz total sobre los espectros de transmisión de neutrones e introducen parámetros como la cantidad de cristales que conforman el material, su estructura cristalina, parámetros de red, mosaicidad, estructura de poros u orientación preferencial de granos, para describir la sección total de materiales monocristalinos o policristalinos. En todos los casos, los modelos desarrollados fueron implementados en una biblioteca basada en el lenguaje computacional MATLAB y fueron comparados con secciones eficaces totales obtenidas en experimentos de transmisión de neutrones realizados en el Departamento de Física de Neutrones del Centro Atómico Bariloche y en ISIS Facility, Reino Unido. Los novedosos modelos microestructurales propuestos describen fielmente los experimentos desarrollados sobre muestras con distinta microestructura, lo que permite el empleo de los mismos en un código de refinamiento sobre los datos experimentales. Aquí, desarrollamos herramientas computacionales que ajustan por cuadrados mínimos no lineales los modelos paramétricos representativos de cada microestructura, sobre la sección eficaz total o la transmisión experimental, para determinar parámetros microestructurales de la muestra a partir de experimentos de transmisión de neutrones con resolución en longitud de onda. Los resultados son de particular relevancia para la interpretación y el análisis cuantitativo de las imágenes realizadas por la técnica de radiografía neutrónica con resolución en energía, que ha recibido un gran impulso en años recientes.

Neutron powder diffraction study of Ba3ZnRu2-xIrxO9 (x=0, 1, 2) with 6H-type perovskite structure

The triple perovskites Ba3ZnRu2-xIrxO9 with x = 0, 1, and 2 are insulating compounds in which Ru(Ir) cations form a dimer state. Polycrystalline samples of these materials were studied using neutron powder diffraction (NPD) at 10 and 295 K. No structural transition nor evidence of long range magnetic order was observed within the investigated temperature range. The results from structural refinements of the NPD data and its polyhedral analysis are presented, and discussed as a function of Ru/Ir content. (C) 2015 Elsevier Masson SAS. All rights reserved.

High pressure in situ diffraction studies of metal–hydrogen systems

“Hybrid” hydrogen storage, where hydrogen is stored in both the solid material and as a high pressure gas in the void volume of the tank can improve overall system efficiency by up to 50% compared to either compressed hydrogen or solid materials alone. Thermodynamically, high equilibrium hydrogen pressures in metal–hydrogen systems correspond to low enthalpies of hydrogen absorption–desorption. This decreases the calorimetric effects of the hydride formation–decomposition processes which can assist in achieving high rates of heat exchange during hydrogen loading—removing the bottleneck in achieving low charging times and improving overall hydrogen storage efficiency of large hydrogen stores. Two systems with hydrogenation enthalpies close to −20 kJ/mol H2 were studied to investigate the hydrogenation mechanism and kinetics: CeNi5–D2 and ZrFe2−xAlx (x = 0.02; 0.04; 0.20)–D2. The structure of the intermetallics and their hydrides were studied by in situ neutron powder diffraction at pressures up to 1000 bar and complementary X-ray diffraction. The deuteration of the hexagonal CeNi5 intermetallic resulted in CeNi5D6.3 with a volume expansion of 30.1%. Deuterium absorption filled three different types of interstices, Ce2Ni2 and Ni4 tetrahedra, and Ce2Ni3 half-octahedra and was accompanied by a valence change for Ce. Significant hysteresis was observed between deuterium absorption and desorption which profoundly decreased on a second absorption cycle. For the Al-modified Laves-type C15 ZrFe2−xAlx intermetallics, deuteration showed very fast kinetics of H/D exchange and resulted in a volume increase of the FCC unit cells of 23.5% for ZrFe1.98Al0.02D2.9(1). Deuterium content, hysteresis of H/D uptake and release, unit cell expansion and stability of the hydrides systematically change with the amount of Al content. In the deuteride D atoms exclusively occupy the Zr2(Fe,Al)2 tetrahedra. Observed interatomic distances are Zr–D = 1.98–2.11; (Fe, Al)–D = 1.70–1.75A˚ . Hydrogenation slightly increases the magnetic moment of the Fe atoms in ZrFe1.98Al0.02 and ZrFe1.96Al0.04 from 1.9 �B at room temperature for the alloy to 2.2 �B for its deuteride.

Study of crystal structure and phase transition studies in perovskite-type oxides using powder-diffraction techniques and symmetry-mode analysis.

251 p.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([C(n)mim][PF6], n=4, 6, and 8)

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases-leading to local mesoscopic inhomogeneity-with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

Physical properties and neutron texture measuerments of deep-sea carbonates of DSDP Holes 62-463 and 62-465A

In weakly indurated, nannofossil-rich, deep-sea carbonates compressional wave velocity is up to twice as fast parallel to bedding than normal to it. It has been suggested that this anisotropy is due to alignment of calcite c-axes perpendicular to the shields of coccoliths and shield deposition parallel to bedding. This hypothesis was tested by measuring the preferred orientation (fabric) of calcite c-axes in acoustic anisotropic, calcareous DSDP sediment samples by X-ray goniometry, and it was found that the maximum c-axis concentrations are by far too low to explain the anisotropies. The X-ray method is subject to a number of uncertainties due to preparatory and technical shortcomings in weakly indurated rocks. The most serious weaknesses are: sample preparation, volume of measured sample (fraction of a mm3), beam defocusing and background intensity corrections, combination of incomplete pole figures, and necessity of recalculation of the c-axis orientations from other crystallographic directions. Goniometry using thermal neutrons overcomes most of these difficulties, but it is time consuming. We test the interferences made about velocity anisotropy by X-ray studies about the concentration of c-axes in deep-sea carbonates by employing neutron texture goniometry to eight DSDP samples comprising mostly nannofossil material. Fabric and sonic velocity were determined directly on the core specimens, thus from the same rock volume and requiring no preparation. The c-axis orientation is obtained directly from the [0006] calcite diffraction peak without corrections. The fabrics are clearly defined, but weak (1.1 to 1.86 times uniform) with the maximum about normal to bedding. They have crudely orthorhombic symmetry, but are not axisymmetric around the bedding normal. The observed c-axis intensities, although higher than determined by the X-ray method on other samples, are by far too low to explain the observed acoustic anisotropies.

X-Ray Diffraction Study of Boron Produced by Pyrolysis of Boron Tribromide

The goal of this research was to determine the composition of boron deposits produced by pyrolysis of boron tribromide, and to use the results to (a) determine the experimental conditions (reaction temperature, etc.) necessary to produce alpha-rhombohedral boron and (b) guide the development/refinement of the pyrolysis experiments such that large, high purity crystals of alpha-rhombohedral boron can be produced with consistency. Developing a method for producing large, high purity alpha-rhombohedral boron crystals is of interest because such crystals could potentially be used to achieve an alpha-rhombohedral boron based neutron detector design (a solid-state detector) that could serve as an alternative to existing neutron detector technologies. The supply of neutron detectors in the United States has been hampered for a number of years due to the current shortage of helium-3 (a gas used in many existing neutron detector technologies); the development of alternative neutron detector technology such as an alpha-rhombohedral boron based detector would help provide a more sustainable supply of neutron detectors in this country. In addition, the prospect/concept of an alpha-rhombohedral boron based neutron detector is attractive because it offers the possibility of achieving a design that is smaller, longer life, less power consuming, and potentially more sensitive than existing neutron detectors. The main difficulty associated with creating an alpha-rhombohedral boron based neutron detector is that producing large, high purity crystals of alpha-rhombohedral boron is extremely challenging. Past researchers have successfully made alpha-rhombohedral boron via a number of methods, but no one has developed a method for consistently producing large, high purity crystals. Alpha-rhombohedral boron is difficult to make because it is only stable at temperatures below around 1100-1200 °C, its formation is very sensitive to impurities, and the conditions necessary for its formation are not fully understood or agreed upon in the literature. In this research, the method of pyrolysis of boron tribromide (hydrogen reduction of boron tribromide) was used to deposit boron on a tantalum filament. The goal was to refine this method, or potentially use it in combination with a second method (amorphous boron crystallization), to the point where it is possible to grow large, high purity alpha-rhombohedral boron crystals with consistency. A pyrolysis apparatus was designed and built, and a number of trials were run to determine the conditions (reaction temperature, etc.) necessary for alpha-rhombohedral boron production. This work was focused on the x-ray diffraction analysis of the boron deposits; x-ray diffraction was performed on a number of samples to determine the types of boron (and other compounds) formed in each trial and to guide the choices of test conditions for subsequent trials. It was found that at low reaction temperatures (in the range of around 830-950 °C), amorphous boron was the primary form of boron produced. Reaction temperatures in the range of around 950-1000 °C yielded various combinations of crystalline boron and amorphous boron. In the first trial performed at a temperature of 950 °C, a mix of amorphous boron and alpha-rhombohedral boron was formed. Using a scanning electron microscope, it was possible to see small alpha-rhombohedral boron crystals (on the order of ~1 micron in size) embedded in the surface of the deposit. In subsequent trials carried out at reaction temperatures in the range of 950 °C – 1000 °C, it was found that various combinations of alpha-rhombohedral boron, beta-rhombohedral boron, and amorphous boron were produced; the results tended to be unpredictable (alpha-rhombohedral boron was not produced in every trial), and the factors leading to success/failure were difficult to pinpoint. These results illustrate how sensitive of a process producing alpha-rhombohedral boron can be, and indicate that further improvements to the test apparatus and test conditions (for example, higher purity/cleanliness) may be necessary to optimize the boron deposition. Although alpha-rhombohedral boron crystals of large size were not achieved, this research was successful in (a) developing a pyrolysis apparatus and test procedure that can serve as a platform for future testing, (b) determining reaction temperatures at which alpha-rhombohedral boron can form, and (c) developing a consistent process for analyzing the boron deposits and determining their composition. Further experimentation is necessary to achieve a pyrolysis apparatus and test procedure that can yield large alpha-rhombohedral boron crystals with consistency.

Estimating total cross sections from neutron-nucleus collisions using a simple functional form

Total cross sections for neutron scattering from nuclei, with energies ranging from 10 to 600 MeV and from many nuclei spanning the mass range 6Li to 238U, have been analyzed using a simple, three-parameter, functional form. The calculated cross sections are compared with results obtained by using microscopic (g-folding) optical potentials as well as with experimental data. The functional form reproduces those total cross sections very well. When allowance is made for Ramsauer-like effects in the scattering, the parameters of the functional form required vary smoothly with energy and target mass. They too can be represented by functions of energy and mass.