LOW TEMPERATURE SYNTHESIS AND CHARACTERIZATION OF SOME LOW POSITIVE AND NEGATIVE THERMAL EXPANSION MATERIALS Kathleen Madara White 151 pages Directed by Dr. Angus P. Wilkinson Low temperature non-hydrolytic sol-gel synthesis was used to explore the possibility of lowering the crystallization temperatures of some known AIVMV2O7 compounds. Crystallization temperatures for ZrP2O7 and ZrP2O7 were unaffected by the use of non-hydrolytic sol-gel methods; however, successful synthesis of these compounds broadens the range of materials that can be produced using this method and suggests the possibility of synthesizing solid solutions (or composites) including ZrP2O7 or ZrV2O7. This research presents for the first time the direct synthesis of ZrP2O7 from separate zirconium and phosphorus starting materials using mild autoclave methods. Characterization of some AIVMV2O7 compounds, using lab and high resolution synchrotron powder XRD, led to the assignment of a new symmetry for CeP2O7 and to the suggestion that the reported structure for PbP2O7 was inadequate. Studies using in situ high temperature lab and synchrotron powder XRD for PbP2O7 and CeP2O7 provided the opportunity to report their thermal properties for the first time, and to compare their behavior to that of some other AIVMV2O7. High pressure diffraction measurements on CeP2O7 provided data for the estimation of bulk moduli and suggested two possible pressure-induced phase transitions. A broad range of MIIIMVP4O14 compounds were prepared using low temperature hydrolytic sol-gel synthesis. Thermal studies revealed nearly linear trends in CTEs and lattice constants with respect to the sizes of MIIIMV cations. Some lower ionic radii compounds had CTEs comparable to that of ZrP2O7 at low temperature, suggesting a similar superstructure. Three compounds were found to exhibit temperature-induced phase transitions.

The aim of this study is to design a mixer with appropriate parts for uniform treatment of the material in household microwave ovens which can not be achieved with the turntable. The designed mixer&rsquo / s performance was tested by the help of color and surface temperature values. In the design of the mixer primarily mixing in the vertical and radial directions were sought and for this purpose blades and wings for directing the material especially in these directions were present. The rotational motion of the mixer was provided by a shaft actuated by the motor of the turntable where the motor was replaced by a speed adjustable one. Couscous macaroni beads wetted with CoCl2 solution were dried for processing in the microwave oven. The initial color values of the samples were L*= 52.0&plusmn / 0.35, a*= 8.8&plusmn / 0.21 and b*= 14.1&plusmn / 0.11 . The studied parameters were microwave power level (10%, 40%, 67% and 100% ), processing time (60,90, 120 sec), speed of rotation of the mixer (5,10,15 rpm) , location (4up, 4bt, 6up, 6bt) for the cases of with and without the mixer. v The macaroni beads were well arranged in a mixing container and then put into the microwave oven for operation. Same parameters with coloring experiments were used for the surface temperature determination. After operation the container was photographed by an IR camera. Whether the designed mixer was present or not, average a* and b* values decreased while temperature increased . All these values were significantly affected by the time and power increase. The L* value became an insignificant parameter to decide for the performance Location of the particles in the container appeared as a significant parameter affecting the a*, b* and temperature values without the mixer whereas, with the use of the mixer it became an insignificant parameter indicating uniform energy distribution. Speed of rotation of the mixer was a significant parameter for both cases. However, the color values obtained did not show the same trend with mixer which it showed without mixer. It is concluded that the designed mixer is effective in providing homogeneity of the product by providing sufficient mixing in the container hence the particles can receive about equal energy. Keywords: Microwave oven, particulate solids, mixing, mixer design, testing performance, uniform treatment

Les industries productrices de matériaux, que ce soit dans le domaine des polymères ou celui des métaux, conçoivent de nouveaux matériaux pour répondre à des fonctions spécifiques définies par leurs clients. Elles s'appuient sur les progrès spectaculaires des dernières années dans le domaine de la modélisation des procédés et de la prédiction des propriétés d'emploi. Cependant, des efforts importants restent encore à faire dans la compréhension des relations entre une microstructure et ses propriétés de mise en forme et de tenue en service pour développer et inventer les matériaux de demain. Pour mieux comprendre les relations entre microstructures et propriétés mécaniques, les modèles basés sur une démarche micromécanique par changement d'échelles sont très utiles par leur caractère prédictif étendu. Comment représenter au mieux cette microstructure ? Quel est le rôle de la topologie, c'est-à-dire de la morphologie et l'arrangement spatial des constituants ? Quel est le rôle du comportement propre de chaque constituant sur la réponse du matériau ? Ces questions sont au centre de mes activités de recherche. Ma contribution porte plus particulièrement sur le développement de modèles micromécaniques par changement d'échelles dans deux domaines ouverts : le couplage entre des mécanismes instantanés et dépendants du temps tels que l'élasticité et la viscoplasticité et la prise en compte de la topologie dans les matériaux hétérogènes à fort contraste mécanique.<br /><br />Dans le cas d'un fort contraste mécanique, l'arrangement des phases joue un rôle du premier ordre sur les propriétés mécaniques. Il induit en particulier que seule une fraction des phases, appelée fraction effective, est active mécaniquement. Cela amène à définir des «phases mécaniques» qui (i) ne sont pas forcément définies par une homogénéité chimique ou physique et (ii) peuvent évoluer avec les conditions de chargements. On parle alors de « motif morphologique évolutif ». Le modèle autocohérent appliqué au motif morphologique de l'inclusion enrobée a été appliqué avec succès aux semi-solides où inclusion et enrobage sont tous deux composés de liquide et de solide. Il a été implanté dans un code d'éléments finis afin de simuler la mise en forme d'alliages métalliques à l'état semi-solide et en particulier le thixoforgeage en collaboration avec ASCOMETAL CREAS.<br /><br />En ce qui concerne le couplage entre des déformations élastiques instantanés et des déformations viscoplastiques dépendants du temps, un modèle de transition d'échelle, dit modèle à champs translatés, est proposé en s'inspirant de l'approximation autocohérente. Il fournit une description élastique-viscoplastique des interactions entre hétérogénéités efficace et simple à mettre en œuvre numériquement. Cet outil de transition d'échelle a été appliqué à l'étude du comportement élastique-viscoplastique d'aciers polycristallins présentant différentes microstructures en collaboration avec ARCELOR. Les lois décrivant le comportement du monocristal fondées sur la théorie de la plasticité cristalline, prenant en compte les mécanismes de déformation par glissement cristallographique et éventuellement par maclage, ont été adaptées et enrichies aux types de comportement étudiés : dépendants de la vitesse de déformation, de la température, sous sollicitations monotones ou cycliques, après vieillissement de type Bake Hardening.<br /><br />La démarche de modélisation proposée jusqu'alors décrit l'activité plastique à l'aide de variables internes homogènes à l'échelle du grain. Or la plasticité apparaît selon des événements spatio-temporels discrets. Un nouveau projet de recherche est proposé pour lever cette hypothèse de « microhomogénéité » en représentant l'activité plastique par une distribution spatiale mais périodique de « particules » de déformation. Cette approche cherche à prendre en compte l'auto-organisation spatiale de la microstructure dans les calculs de champs dans le but de rendre compte naturellement des effets de taille en plasticité.

This thesis is an investigation on water reuse in the fresh-cut fruits and vegetable industry. Fresh water is used intensively in washing, cutting/peeling processes and disinfecting fruits and vegetables, as a result washwater with heavy solids is generated. Effective removal of solids is needed to allow for water reuse. Thus dissolved air flotation (DAF) and centrifuge with coagulation and flocculation process were explored for solid removal capabilities; some settling analysis was also conducted. Bench scale studies show DAF and centrifuge produce waters of similar quality (Turbidity). DAF is able to produce waters with higher UV transmittance and can work better with membrane filtration and UV disinfection. While centrifuge showed higher reduction in pathogen levels, it can be cost effective and compact in design. Membrane filtration feasibility showed that high quality waters (low turbidity) can be produced, but were unable to remove pathogens. Collimated beam results show UV disinfection can further be used to completely eliminate pathogens and allow for water reuse. This allows the processors to reduce their water foot-print, increase sustainability of their operations, and meet the increasing demand for fresh-cut fruits and vegetables.

No description available.

An alternative approach to energy integrating systems is photon counting which provides higher dose efficiency through efficient noise rejection and optimal energy weighting, and, moreover, is not susceptible to memory artifacts such as image lag and ghosting. The first large-area photon counting imager was Charpak's Nobel Prize winning invention of the gas-filled multiwire proportional chamber (MWPC), which revolutionized the field of radiation detection in 1968. In most applications, however, the use of a solid detection medium is preferable because solid densities are about three orders-of-magnitude greater than gas, and thus, they can yield much smaller detector dimensions with unsurpassed spatial and temporal resolution. Thus far, crystalline Cadmium Zinc Telluride is the only room-temperature solid-state detector that meets the requirements for photon counting imaging. However, the material is grown in small ingots and production costs are high for large-area imaging applications. The problem is that disordered (or non-crystalline) solids, which are easier and less expensive to develop over large-area than single crystalline solids, have been ruled out as viable photon counting detectors because of their poor temporal resolution, or more specifically, extremely low carrier mobilities and transit-time-limited photoresponse. To circumvent the problem of poor charge transport in disordered solids with a conventional planar detector structure, we propose unipolar charge sensing by establishing a strong near-field effect using an electrostatic shield within the material. We introduce the concept of time-differential photoresponse in unipolar solids and show that their temporal resolution can be improved substantially to reach the intrinsic physical limit set by spatial dispersion. Inspired by Charpak's MWPC and its variants, and for the first time, we have implemented an electrostatic shield inside evaporated amorphous selenium (a-Se) using the proposed lithography-based microstrip solid-state detector (MSSD). The fabricated devices are characterized with optical, x-ray, and gamma-ray impulse-like excitations. Using optical time-of-flight (TOF) measurements, we show for the first time a unipolar Gaussian TOF transient from the new MSSD structure, instead of a rectangular response with a Gaussian-integral at the tail which is a typical response of a conventional planar device. The measured optical and x-ray TOF results verify the time-differential property of the electrostatic shield and the practicality of the dispersion-limited photoresponse. Furthermore, we use single gamma-ray photon excitations to probe detector's temporal resolution in pulse mode for photon counting. For the MSSD, we show a depth-independent signal for photon absorption across the bulk and a reduction in signal risetime by a factor of 350, comparing performance limiting factors being hole-dispersion for the MSSD and electron-transit-time for the conventional planar device. The time-differential response obtained from the proposed unipolar detector structure enables disordered photoconductive films to become viable candidates for large-area photon counting applications.

This thesis is concerned with applications of modern solid-state NMR spectroscopy. Investigations of three quite different types are undertaken, each of which attempt to advance knowledge in the fields of chemistry and NMR. The goal of each project is to obtain insight into the effects of chemical environment, in particular bonding, on the NMR observables. Carbon-13 and nitrogen-15 solid-state nuclear magnetic resonance has been used to study solid samples containing the dicyanoaurate(I) anion, [Au(CN)2]-, with n-butylammonium, potassium, and thallium counterions. Differences in Au-Tl metallophilic bonding are shown to cause a difference in the isotropic cyanide carbon-13 chemical shift of up to 15.7 ppm, while differences in Au-Au aurophilic bonding are found to be responsible for a change of up to 5.9 ppm. Disordered polymeric gold(I) monocyanide was also investigated, and a range of 7+-2% to 25+-5% of the AuCN chains are found to be "slipped" instead of aligned with the neighbouring chains at the metal position. An investigation of the chemical shift tensors of the 13C-labelled carbons in solid samples of Ph13C≡13CPh and (η2-Ph13C≡13CPh)Pt(PPh3)2·(C6H6) has also been carried out. Coordination of diphenylacetylene to platinum causes a change in the 13C chemical shift tensor orientation and a net increase in the isotropic chemical shift. The carbon chemical shift tensors in the platinum complex bear a striking similarity to those of the alkenyl-carbons in trans-Ph(H)C=C(H)Ph, and a theoretical discussion of these observations is presented. Each of the fundamental NMR interaction tensors (σ, J, D and V) may be decomposed into isotropic, symmetric, and antisymmetric components. Observations of all theoretically allowed components other than the antisymmetric portion of J (Janti) have previously been published. Andrew and Farnell's theory (Mol. Phys. 15, 157 (1968)) for the effects of Janti on NMR spectra has been extended to powdered samples, and methods for analyzing the resultant line shapes have been determined. Finally, the first reported experimental attempts to measure Janti are presented, and experimental proof that no elements of Janti(119Sn,119Sn) in hexa(p-tolyl)ditin are larger than 2900 Hz is given.

This thesis describes procedures and theory for a family of one-sided ultrasonic methods for determining third order elastic constants (TOEC) using sets of angle-beam wedges mounted on one side of a specimen. The methods are based on the well-known acoustoelastic effect, which is the change of wave speed with applied loads and is a consequence of the mechanical nonlinearity of a material. Increases in material nonlinearity have been correlated to the progression of damage, indicating that tracking changes in TOECs may provide a practical means of monitoring damage accumulation at the microstructural level prior to formation of macroscopic defects. Ultrasonic methods are one of the only ways to measure TOECs, and most prior techniques have utilized wave propagation paths parallel and perpendicular to the loading directions. A few additional ultrasonic techniques reported in the literature have employed oblique paths but with immersion coupling. These reported techniques are generally unsuitable for field implementation. The one-sided contact approach described here is applicable for in situ measurements of TOECs and thus lays the foundation for tracking of TOECs with damage. Theory is reviewed and further developed for calculating predicted velocity changes, and thus time shifts, as a function of uniaxial tensile loading for longitudinal, shear vertical, and shear horizontal waves in the context of angle-beam transducers mounted on the surface of the specimen. A comparison is made to published results where possible. The inverse problem of determining the three TOECs of an isotropic material from three measurements employing three different angle beam configurations is comprehensively analyzed. Four configurations providing well-posed solutions are identified and examined. A detailed sensitivity analysis is carried out to identify the best mounting configuration, wave mode combinations, refracted angles and geometry requirements for recovering the three TOECs. Two transducer mounting configurations are considered: (1) attached (glued-on) transducers potentially suitable for in situ monitoring, and (2) floating (oil-coupled) transducers potentially suitable for single measurements. Limited experimental results are presented for the attached case using two longitudinal measurements and one shear vertical measurement. The floating case experiments utilized three of the four well-posed solutions, and measurements were made on several aluminum alloys and low carbon steel. Key experimental issues are identified and discussed for both transducer mounting configurations.

Thesis (Ph.D.)--McMaster University (Canada), 1993. / Source: Dissertation Abstracts International, Volume: 55-06, Section: B, page: 2345. Adviser: G. C. Weatherly.

Thesis (M.Sc.)(Hons) -- University of Western Sydney, 2005. / "A thesis presented to the University of Western Sydney in fulfilment of the requirements for the degree of Master of Science (Honours) Physics" Bibliography: leaves 101-108.