Orientador: Edson Correa da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-09-26T17:36:33Z (GMT). No. of bitstreams: 1 Guimaraes_AndreOliveira_M.pdf: 2255240 bytes, checksum: 01c58731bfeea104f82fd18b44d26d19 (MD5) Previous issue date: 2004 / Resumo: O estudo de propriedades térmicas e espectroscópicas de materiais tem despertado o interesse não só no meio acadêmico, mas também entre diversos setores industriais. Muitas são as técnicas que possibilitam este tipo de pesquisa, porém as técnicas fototérmicas têm demonstrado extrema eficiência para uma diversidade enorme de estudos e materiais. O foco do trabalho é justamente apresentar potencialidades de algumas destas técnicas. Foi feita a descrição e caracterização de um aparato experimental que possibilita estudos de espectroscopia a partir de duas formas de detecção. Espectros de transmissão e absorção foram obtidos a partir da detecção fotopiroelétrica e fotoacústica, respectivamente, evidenciando a sensibilidade deste espectrômetro fototérmico. Um estudo sobre margarinas mostrou a sensibilidade da técnica fotopiroelétrica ao investigar o processo da quebra de emulsão para experimentos com variação¸ de temperatura. A técnica de Radiometria Infravermelho indicou que a margarina apresenta uma estrutura de camadas, tanto para a temperatura ambiente quanto para uma temperatura acima da transição de fase, e que neste caso, a concentração de gorduras é relevante. Através da configuração fotopiroelétrica de duplo sensor foi possível caracterizar termicamente um conjunto de amostras de polipropileno, carregadas com diferentes porcentagens de microesferas ocas de vidro. Obteve-se a esperada redução na condutividade do material, em função da inserção destas esferas, o que não foi possível por nenhuma outra técnica / Abstract: The study of thermal and spectroscopic properties of several sorts of materials has been increasing in interest both in the academy and in the industrial sector. There are several techniques able to develop these studies. In this thesis photothermal techniques were applied and its potentiality demonstrated. Among the photothermal techniques the photoacoustic and the photopyroelectric configurations were used as main techniques for spectroscopic purposes, allowing the obtainment of the optical spectra, from absorption and from transmission as well. The description and the characterization of a suitable apparatus for this purpose were presented. Margarine was studied showing the ability of the photopyroelectric methodology in the measurement of the thermal properties (diffusivity and effusivity) and in the detection of temperature dependent structural modifications, as melting and emulsion break as well. From frequency dependent photothermal infrared radiometry data it was possible to show that margarine presents a layered structure both for room temperature and above the transition point. Furthermore it was observed different effects for different fat content samples. Finally, we have applied for the first time the DSPPE configuration in the simultaneous determination of the thermal properties of a solid sample. Specifically, samples of a polymer composite based in the polypropylene material with hollow glass microspheres, for different proportions of microspheres were studied. It was possible to obtain the thermal conductivity of the samples from simultaneous measurement of the thermal diffusivity and effusivity. We have found a diminution in the conductivity of the samples increasing the hollow glass microspheres content, showing an increase of the thermal insulating properties of polypropylene, as expected by the composite producers / Mestrado / Física da Matéria Condensada / Mestre em Física

Over the life of nuclear fuel, inhomogeneous structures develop, negatively impacting thermal properties. New fuels are under development, but require more accurate knowledge of how the properties change to model performance and determine safe operational conditions. Measurement systems capable of small–scale, pointwise thermal property measurements and low cost are necessary to measure these properties and integrate into hot cells where electronics are likely to fail during fuel investigation. This project develops a cheaper, smaller, and easily replaceable Fluorescent Scanning Thermal Microscope (FSTM) using the blue laser and focusing circuitry from an Xbox HD-DVD player. The FSTM also incorporates novel fluorescent thermometry methods to determine thermal diffusivity. The FSTM requires minimal sample preparation, does not require access to both sides of the sample, and components can be easily swapped out if damaged, as is likely in irradiated hot cells. Using the optical head from the Xbox for sensing temperature changes, an infrared laser diode provides periodic heating to the sample, and the blue laser induces fluorescence in Rhodamine B deposited on the sample's surface. Thermal properties are fit to modulated temperature models from the literature based on the phase delay response at different modulated heating frequencies. With the FSTM method, the thermal diffusivity of a 10 cent euro coin was found to be 21±5 mm2/s. This value is compared to Laser Flash Analysis and a Thermal Conductivity Microscope (which used thermoreflectance a method), which found the thermal diffusivity to be 30.4±0.1 mm2/s and 19±3 mm2/s, respectively. The hardware and instrumentation performed as expected, but the property measurements show that the device is not yet optimized to provide accurate measurements with current heat transfer models. Future work is discussed to investigate the accuracy and necessary modeling adjustments, as well as refinements to the instrumentation.

Solid oxide fuel cells with graded electrodes consisting of multiple composite layers yield generally lower polarization resistances than single layer composite electrodes. Optimization of the performance of solid oxide fuel cells with graded electrode composition and/or microstructure requires an evaluation of both the three phase boundary length per unit volume and the effective diffusion coefficient in order to provide insight into how these properties vary over the design space. A numerical methodology for studying the three phase boundary length and effective diffusivity in composite electrode layers with controlled properties is developed. A three dimensional solid model of a sintered composite electrode is generated for which the mean particle diameter, composition, and total porosity may be specified as independent variables. The total three phase boundary length for the modeled electrode is calculated and tomographic methods are used to estimate the fraction of this length over which the electrochemical reactions can theoretically occur. Furthermore, the open porosity of the modeled electrode is identified and the effective diffusion coefficient is extracted from the solution of the concentration of the diffusing species within the open porosity. Selected example electrode models are used to illustrate the application of the methods developed, and the resulting connected three phase boundary length and diffusion coefficients are compared. A significant result is the need for thickness-specific effective diffusivity to be determined, rather than the general volume averaged property, for electrodes with porosity between the upper and lower percolation thresholds. As the demand for current increases, more of the connected three phase boundaries become active, and therefore a greater fraction of the electrode layer is utilized for a given geometry, resulting in a higher apparent effective diffusivity compared to the same electrode geometry operating at a lower current. The methods developed in this work may be used within a macroscopic electrode performance model to investigate optimal designs for solid oxide fuel cell electrodes with stepwise graded composition and/or microstructure.

This study investigates the turbulent mixing characteristics of Peng-hu Channel, South China Sea along 21¢XN and the Kuroshio region by using CTD/LADCP and MicroRider. Dissipation rate of turbulent kinetic energy or thermal variances is estimated primarily by the Thorpe overturn method, and is compared with the microstructure turbulence from direct measurement as well as those estimated from the parameterization method based on shear and strain spectra. Our results indicate that there are different turbulent characteristics and dynamic mechanisms at these three regions. Because of its funnel-shaped topography and strong semi-diurnal tides in the Peng-hu Channel, the turbulent mixing and eddy diffusivity reach a maximum value at the narrowest part of Peng-hu Channel near its sea bottom and show a clear tidal variation. In the main stream of Kuroshio where the current speed is faster than 0.8 m/s, turbulent mixing is not particularly stronger than non-main stream zone. In the Kuroshio frontal zone between the Kuroshio and the coastal waters off east Taiwan coast, strong turbulent mixing in the surface layer can be detected. Island wake which is formed when Kuroshio runs into the Lan-yu Island is a transient feature. Strong mixing in the upper 100 m accompanied with upwelling and vortices were observed during one event. The topography along the latitude of 21¢XN is rugged and rough in the Luzon Strait which consists of several ridges and seamounts. Due to its complicated topography and generation of strong semi-diurnal internal tides, eddy diffusivity as high as 10^(-2)m^2/s was measured in the bottom layer of the Luzon Strait.

Uranium-Molybdenum (U-Mo) alloys are of interest to the nuclear engineering community for their potential use as reactor fuel. The addition of molybdenum serves to stabilize the gamma phase of uranium, as well as increasing the melting point of the fuel. Thermal properties of U-Mo alloys have not been fully characterized, especially within the area of partial phase decomposition of the gamma phase of the alloy. Additional data was acquired through this research to expand the characterization data set for U-Mo alloys. The U-Mo alloys used for this research were acquired from the Idaho National Laboratory and consisted of three alloys of nominal 7, 10, and 13 percent molybdenum by weight. The sample pins were formed by vacuum induction melt casting. Once the three sample pins were fabricated and sent to the Fuel Cycle and Materials Laboratory at Texas A&M University, the pins were homogenized and sectioned for heat treatment. Several heat treatments were performed on the samples to induce varying degrees of phase decomposition, and the samples were subsequently sectioned for phase verification and thermal analysis. An Electron Probe Microanalyzer with wavelength dispersive spectroscopy was used to observe the phases in the samples as well as to characterize each phase. The density of each sample was determined using Archimedes method. Finally, a light flash analyzer was used to determine thermal diffusivity of the samples up to 300 degrees C as well as to estimate the thermal conductivity. For U-10Mo, thermal diffusivity increased with increasing phase decomposition from gamma to alpha +U2Mo while U-7Mo saw a flattening of the thermal diffusivity curve with increased phase decomposition.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1962. / Bibliography: leaves 93-95.

There is a well-known connection between the structure and dynamics that is present in molecular and colloidal systems. Using this connection as a guide we are able to design interparticle potentials that optimizes the diffusivity of a single particle. While structure-dynamic correlations provide the insight that diffusion could be enhanced, the effect of this enhancement on the dynamics of neighboring particles is more difficult to quantify. A novel method for calculating position-dependent dynamics is introduced that can be easily implemented into existing simulation protocols. The computational requirements are very low compared to existing methods and this technique can also be applied to a wide variety of systems, including experiments where particle trajectories can be determined. Using this method, the position-dependent diffusivity of solvent particles in the vicinity of a tracer particle can be measured. This information allows for determination of the microscopic changes that take place as a result of the optimization discussed above. To study the effect of a non-continuum solvent, we design a system that eliminates inhomogeneous structuring near an interface. Hydrodynamic theory can predict the position-dependent diffusivity of a sphere in continuum solvent. Comparing these systems not only highlights the difference in position-dependent dynamics for continuum and non-continuum solvents, but is a starting point to study what happens to dynamics when structure is reintroduced. This allows us to answer many other questions about the relationships between structure and dynamics. While these connections have been studied extensively for average properties, they have not been explored for their position-dependent counterparts. For bulk fluids, the insertion probability and two-body excess entropy has proven useful for predicting average dynamic properties. We develop expressions for the position-dependent versions of both of these quantities. We show that when using the appropriate reference state the position-dependent diffusivity can be qualitatively related to the insertion probability. / text

Distillers’ spent grain (DSG) is a by-product of ethanol production and used for swine feed supplement due to its nutrient composition. Lowering the moisture content of DSG using superheated steam (SS) drying can be more energy efficient compared to hot air drying. One objective was to investigate parameters associated with SS drying on DSG including maximum condensation, condensation time, and restoration time. Increasing SS temperature from 120 to 180 °C and SS velocity from 1.0 to 1.4 m/s resulted in a 97% and 67% decrease in maximum condensation, respectively. Another objective was to determine the effect of SS temperature, velocity, and pellet orientation on effective moisture diffusivity of DSG pellets. The diffusion model was based on finite cylinder geometry accounting for volumetric shrinkage. The diffusivity coefficient was determined to be 1.56 × 10-8 m2/s. A significant effect of pellet orientation on moisture diffusivity was found during the constant drying-rate period. / October 2015

Solid oxide fuel cells with graded electrodes consisting of multiple composite layers yield generally lower polarization resistances than single layer composite electrodes. Optimization of the performance of solid oxide fuel cells with graded electrode composition and/or microstructure requires an evaluation of both the three phase boundary length per unit volume and the effective diffusion coefficient in order to provide insight into how these properties vary over the design space. A numerical methodology for studying the three phase boundary length and effective diffusivity in composite electrode layers with controlled properties is developed. A three dimensional solid model of a sintered composite electrode is generated for which the mean particle diameter, composition, and total porosity may be specified as independent variables. The total three phase boundary length for the modeled electrode is calculated and tomographic methods are used to estimate the fraction of this length over which the electrochemical reactions can theoretically occur. Furthermore, the open porosity of the modeled electrode is identified and the effective diffusion coefficient is extracted from the solution of the concentration of the diffusing species within the open porosity. Selected example electrode models are used to illustrate the application of the methods developed, and the resulting connected three phase boundary length and diffusion coefficients are compared. A significant result is the need for thickness-specific effective diffusivity to be determined, rather than the general volume averaged property, for electrodes with porosity between the upper and lower percolation thresholds. As the demand for current increases, more of the connected three phase boundaries become active, and therefore a greater fraction of the electrode layer is utilized for a given geometry, resulting in a higher apparent effective diffusivity compared to the same electrode geometry operating at a lower current. The methods developed in this work may be used within a macroscopic electrode performance model to investigate optimal designs for solid oxide fuel cell electrodes with stepwise graded composition and/or microstructure.

This work explored the viability of two solid adsorbents, limestone and cement powder, for use in a flow-through packed-bed column for HCl and HF gas neutralization following refrigerant destruction. Neutralization tests performed at 408 K using 5% HCl in N2 and 5% HF in N2, showed that limestone had a significantly higher adsorption capacity for both HF & HCl, future tests therefore utilized limestone only. The results showed that ~49% of the fed HCl and between 7.8% - 16.2% of the fed HF gases were adsorbed by 0.007 kg of limestone for a 6.67×10-6 m3/s (STP) flow rate over 30 – 180 minutes. Applying the shrinking core model, effective diffusivities (De) of HCl & HF into the limestone particles were 1.5×10-9 & 2.2×10-9 m2/s respectively. Under these conditions, complete particle conversion times were 227 hours for HCl–limestone and 154 hours for HF–limestone. Estimating De values at plasma-reactor temperatures gave 5.61x10-9 m2/s & 8.24x10-9 m2/s for HCl–limestone and HF–limestone respectively. Correspondingly, particle consumption times were reduced to 61 and 41 hours for HCl–limestone and HF–limestone. Considering the conversion times for the 1 mm particle sizes, shorter conversion times would require micron-scale particle sizes, suitable for entrained flow but not for a packed-bed arrangement.