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Under certain conditions, reactive chemicals may proceed into uncontrolled chemical reaction pathways with rapid and significant increases in temperature, pressure, and/or gas evolution. Reactive chemicals have been involved in many industrial incidents, and have harmed people, property, and the environment. Evaluation of reactive chemical hazards is critical to design and operate safer chemical plant processes. Much effort is needed for experimental techniques, mainly calorimetric analysis, to measure thermal reactivity of chemical systems. Studying all the various reaction pathways experimentally however is very expensive and time consuming. Therefore, it is essential to employ simplified screening tools and other methods to reduce the number of experiments and to identify the most energetic pathways. A systematic approach is presented for the evaluation of reactive chemical hazards. This approach is based on a combination of computational methods, correlations, and experimental thermal analysis techniques. The presented approach will help to focus the experimental work to the most hazardous reaction scenarios with a better understanding of the reactive system chemistry. Computational methods are used to predict reaction stoichiometries, thermodynamics, and kinetics, which then are used to exclude thermodynamically infeasible and non-hazardous reaction pathways. Computational methods included: (1) molecular group contribution methods, (2) computational quantum chemistry methods, and (3) correlations based on thermodynamic-energy relationships. The experimental techniques are used to evaluate the most energetic systems for more accurate thermodynamic and kinetics parameters, or to replace inadequate numerical methods. The Reactive System Screening Tool (RSST) and the Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) were employed to evaluate the reactive systems experimentally. The RSST detected exothermic behavior and measured the overall liberated energy. The APTAC simulated near-adiabatic runaway scenarios for more accurate thermodynamic and kinetic parameters. The validity of this approach was investigated through the evaluation of potentially hazardous reactive systems, including decomposition of di-tert-butyl peroxide, copolymerization of styrene-acrylonitrile, and polymerization of 1,3-butadiene.

We have carried out a theoretical and an experimental study of thermal effects arising in bulk high-Tc superconductors. The theoretical study has allowed us to predict the self-heating behaviour. We have calculated the temperature evolution. We have shown the existence of a forbidden temperature window, and we have determined the analytical expression of a threshold field (Htr2) separating the « middle» and the «high» dissipation state . From a numerical modelling of a short cylinder, we have determined the time and spatial dependance of dissipated power and temperature within the sample. We have shown that the temperature rise is the highest along the corner location where the dissipated power is maximum. We have designed and constructed a susceptometer for characterizing large bulk superconductors (f →32 mm). The susceptometer allows a small temperature gradient (< 0.1K) to be achieved in the presence of large heating rates. It allows large AC and DC fields to be applied simultaneously, and was upgraded to measure simultaneously local temperatures and magnetic inductions. We have determined the heat transfer occuring in the susceptometer chamber. Magneto-thermal measurements with this system can be carried out with a high sensitivity and are found to be in very good agreement with the theoretical predictions. This work underlines the importance of the cooling conditions that can affect the distribution of the magneto-thermal properties within the superconductor.

This thesis involves a study the fabrication and characterization of photon radiation detectors. The focus has been to develop and improve the performance of optical measurement systems, but also to reduce their cost. The work is based on the study of two types of detectors, the position sensitive detector and the thermal detector. Infrared detectors are usually subcategorized into photonic detectors and thermal detectors. In the thermal detectors, heat generated from the incident infrared radiation is converted into an electrical output by some sensitive element. The basic structure of these detectors consists of a temperature sensitive element connected to a heat sink through a thermally isolating structure. Thin membranes of Silicon and Silicon nitride have been commonly used as thermally insulation between the heat sink and the sensitive elements. However, these materials suffer from relatively high thermal conductivity, which lowers the response of the detector. The fabrication of these membranes also requires rather advanced processing techniques and equipment. SU-8 is an epoxy based photoresist, which has low thermal conductivity and requires only standard photolithography. A new application of SU-8 as a self-supported membrane in a thermal detector is presented. This application is demonstrated by the fabrication and characterization of both an infrared sensitive thermopile and a bolometer detector. The bolometer consists of nickel resistances connected in a Wheatstone bridge configuration, whereas the thermopile uses serially interconnected Ti/Ni thermocouple junctions. The position sensitive detectors include the lateral effect photodiodes and the quadrant detectors. Typical applications for these detectors are distance measurements and as centering devices. In the quadrant detectors, the active region consists of four pn-junctions separated by a narrow gap. The size of the active region in these detectors depends on the size of the light spot. In outdoor application, this spot size dependence degrades the performance of the four-quadrant detectors. In this thesis, a modified four-quadrant detector having the pn-junctions separated by a larger distance has been fabricated and characterized. By separating the pn-junctions the horizontal electric filed in the active region is removed, making the detector spot size insensitive. Linearity of the lateral effect photodiodes depends on the uniformity of the resistive layer in the active region. The introduction of mechanical stress in an LPSD results in a resistance change mainly due to resistivity changes, and this affects the linearity of the detector. Measurements and simulations, where mechanical stress is applied to LPSDs are presented, and support this conclusion.

Experimental and numerical analyses were both adopted in the thesis. First, the BGA with three different solder ball components and pads, were investigated and their strength was affected by drop tests and thermal cycling test. Then the concept of numerical simulation to do the follow-up analysis was adopted. the relationships of stress, strain, and creep strain energy density were found. The lead-free solder ball has better resistance to the drop test with lower silver content; on the contrary, it has better properties due to thermal cycling tests with higher silver content. In the drop test, the failure of solder ball were found obviously in the packages that near four corner of the test board, and concentrated in the diagonal screw holes. The failure of solder ball was distributed over the peripheral of the package in the middle cross section of test board. Comparing the different position of 15 packages due to drop test, the amount of failed solder balls showed that the package positions U3, U8, U13 was obviously fractured, and the situation of fracture was relatively slight in the positions of U1, U5, U6, U7, U9, U10, U11, U15. In the fatigue life prediction of thermal cycling test, the simplified model of package in 45¢X direction was mostly close to the experimental data. After the except ion of the solder ball with failure mode A1, the major failure mode in drop test was mode B3. But the mode C was the majority of thermal cycling test. The structure and intensity of SMD play an important role on above experiments; the better choice of SMD can reduce the rate of failure mode A1, and improve the accuracy of the experiment.

Titanium nitride coatings have been widely applied and studied as high temperature diffusion barrier for silicon devices in microelectronics, wear resistant coatings in turbine blade materials, and materials for future high temperature nuclear reactors. In order to enhance the material property, superlattices is one of artificially engineered protective coatings, such as AlN/TiN and TaN/TiN multilayered films. Epitaxial cubic multilayer films, TaN/TiN and AlN/TiN nanolayers were grown on Si(001) by Pulsed Laser Deposition (PLD) with various nanolayer thicknesses and number of interfaces. Microstructural studies include X-ray diffraction (XRD), transmission electron microscopy (TEM), and high resolution TEM with ion-irradiation experiments. Electrical, mechanical and thermal property studies were conducted for the interface and size effects on the nanolayers by using nanoindentation and Transient Thermo-Reflectance (TTR) methods. The microstructural and hardness study on TaN/TiN films with ion irradiation (12 keV and 50 keV He ) suggest no obvious microstructural or mechanical behavior change due to ion irradiation. In addition, titanium nitride that serves as effective diffusion barrier to prevent the inter-diffusion between the nuclear fuel and the cladding material was studied in order to enhance the lifetime of the fuels and the reliability of the fuel claddings. The TiN has good adhesion with the stainless steel and higher hardness than that of bulk TiN on the stainless steel. Thermal conductivity test demonstrates that thin TiN film has compatible thermal conductivity as the MA957 and HT-9 bars. The size effect on electrical resistivity is dominant in both of the epitaxial cubic and the polycrystalline TiN thin films in the thickness ranged from ~60 nm down to ~35nm. In the TaN/TiN multilayer, the grain scattering effect on resistivity is dominant rather than interface influence on the resistivity with comparing epitaxial cubic phase and polycrystalline phase. The microstructure and hardness studies of the AlN/TiN multilayer films with He implantation present that the suppression of amorphization in AlN layers and the reduction of radiation-induced softening were achieved in all nanolayer films. Radiation tolerance was found to be size dependent and the layer thickness leading to the highest radiation tolerance was around 10 nm. In addition, the embedded epitaxial cubic AlN with cladding TiN nanolayers showed higher effective thermal conductivity than that of AlN single layer as well as the embedded polycrystalline AlN in the thickness ranged from 10 nm down to 2 nm. It confirms a suppressed size effect, which reduces the amount of decrease in through-plane thermal conductivity.

Chromium martensitic hot-work tool steel (AISI H13) is commonly used as die material in hot forming techniques such as die casting, hot rolling, extrusion and hot forging. They are developed to endure the severe conditions by high mechanical properties attained by a complex microstructure. Even though the hot-work tool steel has been improved over the years by alloying and heat treatment, damages still occur. Thermal fatigue is believed to be one of the most common failure mechanisms in hot forming tools. In this thesis tools used in hot forging and die casting were examined to determine damage, material response, thermal fatigue crack initiation and propagation. Different chromium martensitic hot-work tool steels, heat treated at four different austenitizing temperatures were experimentally tested in thermal fatigue and isothermal fatigue. The materials were then evaluated using X-ray line broadening analysis and transmission electron microscopy to explore the relation between fatigue softening and the change in microstructure. The high temperature fatigue softening was also simulated using an elasto-plastic, non-linear kinematic and isotropic model. The model was implemented in a numerical simulation to support the integration of die design, tool steel properties and its use. It was found that the dominant damage mechanisms in the investigated tools were thermal fatigue and that tool material experiences a three stage softening at high temperature loading. The primary stage was concluded to be influenced by the dislocation density and the second stage by the temper resistance i.e. carbide morphology. The microstructural changes during the softening stages were also connected to the non-linear kinematic and isotropic model. The general aim of this thesis is to increase the knowledge of the chromium martensitic hot-work tool steel damage, performance and microstructure.

A SuperCritical Water-cooled Nuclear Reactor (SCWR) is a Generation IV concept currently being developed worldwide. Unique to this reactor type is the use of light-water coolant above its critical point. The current research presents a thermal-hydraulic analysis of a single fuel channel within a Pressure Tube (PT) - type SCWR with a single-reheat cycle. Since this reactor is in its early design phase many fuel-channel components are being investigated in various combinations. Analysis inputs are: steam cycle, Axial Heat Flux Profile (AHFP), fuel-bundle geometry, and thermophysical properties of reactor coolant, fuel sheath and fuel. Uniform and non-uniform AHFPs for average channel power were applied to a variety of alternative fuels (mixed oxide, thorium dioxide, uranium dicarbide, uranium nitride and uranium carbide) enclosed in an Inconel-600 43-element bundle. The results depict bulk-fluid, outer-sheath and fuel-centreline temperature profiles together with the Heat Transfer Coefficient (HTC) profiles along the heated length of fuel channel. The objective is to identify the best options in terms of fuel, sheath material and AHFPS in which the outer-sheath and fuel-centreline temperatures will be below the accepted temperature limits of 850°C and 1850°C respectively. The 43-element Inconel-600 fuel bundle is suitable for SCWR use as the sheath-temperature design limit of 850°C was maintained for all analyzed cases at average channel power. Thoria, UC2, UN and UC fuels for all AHFPs are acceptable since the maximum fuel-centreline temperature does not exceed the industry accepted limit of 1850°C. Conversely, the fuel-centreline temperature limit was exceeded for MOX at all AHFPs, and UO2 for both cosine and downstream-skewed cosine AHFPs. Therefore, fuel-bundle modifications are required for UO2 and MOX to be feasible nuclear fuels for SCWRs. / UOIT

The thermal history of the Earth, from planetary accretion and core differentiation up to the present time, is of paramount importance for understanding our planet. The thermal evolution of the core and the mantle dictate the generation of the Earth's internal magnetic field and its evolution through time. In this dissertation, I study scenarios for the thermal and magnetic evolution of the Earth, using numerical simulations for mantle convection and implementing recent geochemical models for the mantle and core. The conditions for which a magnetic field can be generated in the Earth's core are studied using parameterized models for energy and entropy. The model devised in this project couples the results of the numerical simulations with the parameterized models for the core, to produce a global thermal and magnetic history, with feed-back between events happening in the mantle and the core.<p> The dissertation presents an analysis of the scenarios that can be constructed from implementing new constraints into the thermal models for the mantle and core and emphasizes the most relevant scenarios which can be applied to the Earth's evolution, consistent with physical parameters, and geochemical and magnetic constraints known to date. In addition, I discuss the relevance of some of the scenarios which appear incompatible with the Earth's evolution, but are reminiscent of the evolution of other terrestrial bodies.<p> The results of this work show that the most successful scenarios for the thermal and magnetic evolution require the presence of small amounts of core internal heating in the form of radioactive potassium, or a slightly increased concentration of radioactive elements at the base of the mantle, due to isolated, if the base of the mantle is less mobile and acts as a thermal insulator between the core and the overlying convective mantle primordial reservoirs. Successful scenarios are also obtained if the base of the mantle is less mobile and acts as a thermal insulator between the core and the overlying convective mantle. If the base of the mantle is less mobile and acts as a thermal insulator between the core and the overlying convective mantle.

Surface temperature and heat flux measurements were made in a single cylinder SI engine piston when uncoated and with two different surface coatings: a metal TBC and YSZ. A new thermocouple was developed to accurately measure surface temperatures. The engine was operated in a standard full load mode and a knock promoting mode featuring heated intake air and advanced spark timing. Cylinder pressures were measured to quantify knock. It was found that average heat flux into the piston substrate was 33 % higher with the metal TBC and unchanged with the YSZ relative to the uncoated surface. The increase with the metal TBC was attributed to its surface roughness. However, the metal TBC and YSZ reduced peak heat flux by 69 and 77 %, respectively. Both the metal TBC and YSZ reduced knock compared to the uncoated surface. After testing, the metal TBC was undamaged and the YSZ was slightly chipped.