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The thermocouple systems used for the measurement of surface temperature in high temperature applications such as advanced aerospace propulsion systems and diesel engine systems are expected to perform in rapidly fluctuating and extremely high heat fluxes corresponding to high temperatures (in excess of 1400 K) and high speed flows. Traditionally, Pt/Pt-Rh based thin film thermocouples have been used for surface temperature measurements. However, recent studies indicated several problems associated with these thermocouples at temperatures exceeding 1000 K, some of which include poor adhesion to the substrate, rhodium oxidation and reaction with the substrate at high temperatures. Therefore, there is an impending demand for thermoelectric materials that can withstand severe environments in terms of temperature and heat fluxes. In this study, thin films of titanium carbide and tantalum carbide as well as two families of conducting perovskite oxides viz., cobaltites and manganates (La(1-x)SrxCoO3, M(1-x)Cax MnO3 where, M=La,Y) were investigated for high temperature thin film thermocouple applications as alternate candidate materials. Thin films of the carbides were deposited by r.f. sputtering while the oxide thin films were deposited using pulsed laser ablation. Sapphire (1102) was used as substrate for all the thin film depositions. All the thin films were characterized for high temperature stability in terms of phase, microstructure and chemical composition using x-ray diffraction, atomic force microscopy and electron spectroscopy for chemical analysis respectively. Electrical conductivity and seebeck coefficients were measured in-situ using a custom made device. It was observed that TiC/TaC thin film thermocouples were stable up to 1373 K in vacuum and yield high and fairly stable thermocouple output. The conducting oxides were tested in air and were found to be stable up to at least 1273 K. The manganates were stable up to 1373 K. It was observed that all the oxides studied crystallize in a single phase perovskite structure. This phase is stable up to annealing temperatures of 1373 K. The predominant electrical conduction mechanism was found to be small polaron hopping. Stable and fairly high electrical conductivities as well as seebeck coefficients accompanied with phase, structure, composition and microstructure stability indicate that these materials hold excellent promise for high temperature thin film thermocouple applications. / Master of Science

The development of molybdenum - silicon - boron (Mo-Si-B) composites having a combination of high temperature strength, creep, and oxidation residence has the potential to substantially increase the efficiency of gas turbines. The refractory nature of the αMo, Mo3Si (A15), and Mo5SiB2 (T2) phases results in good strength and creep resistance up to 1300°C. At this temperature, the formation of a borosilicate surface scale from the two intermetallic phases is able to provide oxidation resistance. However, realization of these advantages has been prevented by both a high brittle to ductile transition temperature and difficulty in forming the initial surface borosilicate to provide bulk oxidation resistance. This dissertation addresses two factors pertaining to this material system: 1) improvements to powder processing techniques, and 2) development of compositions for oxidation resistance at 1300°C. The processing of Mo-Si-B composites is strongly tied to their mechanical properties by establishing the αMo matrix, limiting impurity content, and reducing silicon supersaturation. These microstructural aspects control the brittle to ductile transition temperature which has traditionally been too high for implementation of Mo-Si-B composites. The processing here built upon the previously developed powder processing with silicon and boron nitrides which allowed for a low oxygen content and sintering of fine starting powders. Adjustments were made to the firing cycle based upon dew point measurements made during the hydrogen de-oxidation stage. Under a relatively high gas flow rate, 90% of the total water generated occurred during a ramp of 2°C /min between 450 and 800°C followed by a hold of 30 minutes. The oxidation resistance of Mo-Si-B composites was studied for a wide range of compositions. Silicon to boron atomic ratios were varied from 1 to 5 and iron, nickel, cobalt, yttria, and manganese were included as minor additions. In all these compositions, the αMo volume fraction was kept over 50% to ensure the potential toughness of the composite. For the oxidized surface glass, a silica fraction of 80 to 85% was found to be necessary for the borosilicate to have a sufficiently high viscosity and low oxygen permeability for oxidation resistance at 1300°C. For the Mo-Si-B bulk composition this corresponds to a Si/B atomic ration of 2 to 2.5. Higher viscosity compositions failed due to spallation of poorly attached, high silica scales. Lower viscosity compositions failed from continuous oxidation, either through open channels or repetitive MoO3 bubble growth and popping. Additionally, around 1% manganese was necessary for initial spreading of the borosilicate at 1300°C. In conjunction with flowing air to prevent MoO3 accumulation, oxidation weight loss rates below 0.05 mg/cm2-hr were measured. Finally, a theory is proposed here to describe the mechanisms responsible for the development of oxidation resistance. This theory involves three stages associated with: 1) generation of an initial surface borosilicate, 2) thickening of the borosilicate layer, and 3) slow parabolic oxidation controlled by the high silica surface scale.

Neste trabalho de mestrado são descritos o projeto, a montagem e os testes de funcionamento de uma câmara porta amostra para medidas elétricas de quatro pontas de prova dc. A estrutura da câmara porta amostra é em material cerâmico, que garante a estabilidade física e química do sistema, prolongando sua vida útil e melhorando a qualidade das análises realizadas. Este sistema permite a realização de medidas elétricas de diferentes materiais desde a temperatura ambiente até ~1500 °C em ampla faixa de pressões parciais de oxigênio. A funcionalidade da câmara porta amostras foi avaliada por meio da comparação de medidas da dependência da resistividade elétrica com a temperatura de amostras de zircônia estabilizada com ítria. Visando à aferição e a aplicação deste sistema de medidas elétricas, foram fabricados e caracterizados compósitos à base de zircônia estabilizada com ítria e nitreto de titânio, obtidos pela técnica de sinterização por plasma pulsado (\"spark plasma sintering\", SPS). As propriedades gerais destes compósitos foram investigadas por meio de análises térmicas, difratometria de raios X (DRX) e medidas elétricas de quatro pontas de prova dc, usando o sistema construído. As análises das amostras dos compósitos à base de zircônia e TiN mostraram que a técnica SPS produz amostras densas, sem reação entre as fases ou degradação do TiN por oxidação. As amostras com adição de TiN apresentaram comportamento metálico da resistividade elétrica, evidenciando a percolação do nitreto na matriz de zircônia para frações volumétricas ≤ 27 vol.%. Medidas de resistividade elétrica combinadas com análises térmicas e de DRX foram usadas para monitorar a oxidação do TiN nos compósitos em altas temperaturas. As amostras produzidas apresentam propriedades promissoras para aplicações de alta temperatura que requeiram elevada condutividade elétrica. / This study describes the design, construction, and tests of a sample holder for four-probe dc electrical measurements. The structural parts of the sample holder are built using ceramic material (alumina) that ensures physical and chemical stability, prolonging its use and the quality of experiments. The sample holder allows electrical measurements from room temperature up to ~1500 °C in a wide range of oxygen partial pressures. The functionality of the constructed sample holder was assessed by comparing measurements of the temperature dependence of the electrical resistivity of yttria-stabilized zirconia samples. To further explore the capabilities of the measuring apparatus, samples of high-temperature composites based on yttria-stabilized zirconia and titanium nitride were prepared by spark plasma sintering (SPS). The general properties of these composites were investigated by thermal analysis, X-rays diffraction (XRD), and four-probe dc electrical measurements. The study of the composites showed that SPS resulted in dense samples with no detected reaction between phases and free from TiN oxidation. Samples with TiN addition displayed metallic behavior of the electrical resistivity, evidencing that the nitride attained the percolation threshold in the oxide matrix at volume fractions ≤ 27 vol.%. Electrical measurements combined with thermal analysis and XRD were used to monitor the oxidation of TiN at high temperature. The studied composites show good properties indicating that it is a promising material for high temperature applications that require high electrical conductivity.

Neste trabalho de mestrado são descritos o projeto, a montagem e os testes de funcionamento de uma câmara porta amostra para medidas elétricas de quatro pontas de prova dc. A estrutura da câmara porta amostra é em material cerâmico, que garante a estabilidade física e química do sistema, prolongando sua vida útil e melhorando a qualidade das análises realizadas. Este sistema permite a realização de medidas elétricas de diferentes materiais desde a temperatura ambiente até ~1500 °C em ampla faixa de pressões parciais de oxigênio. A funcionalidade da câmara porta amostras foi avaliada por meio da comparação de medidas da dependência da resistividade elétrica com a temperatura de amostras de zircônia estabilizada com ítria. Visando à aferição e a aplicação deste sistema de medidas elétricas, foram fabricados e caracterizados compósitos à base de zircônia estabilizada com ítria e nitreto de titânio, obtidos pela técnica de sinterização por plasma pulsado (\"spark plasma sintering\", SPS). As propriedades gerais destes compósitos foram investigadas por meio de análises térmicas, difratometria de raios X (DRX) e medidas elétricas de quatro pontas de prova dc, usando o sistema construído. As análises das amostras dos compósitos à base de zircônia e TiN mostraram que a técnica SPS produz amostras densas, sem reação entre as fases ou degradação do TiN por oxidação. As amostras com adição de TiN apresentaram comportamento metálico da resistividade elétrica, evidenciando a percolação do nitreto na matriz de zircônia para frações volumétricas ≤ 27 vol.%. Medidas de resistividade elétrica combinadas com análises térmicas e de DRX foram usadas para monitorar a oxidação do TiN nos compósitos em altas temperaturas. As amostras produzidas apresentam propriedades promissoras para aplicações de alta temperatura que requeiram elevada condutividade elétrica. / This study describes the design, construction, and tests of a sample holder for four-probe dc electrical measurements. The structural parts of the sample holder are built using ceramic material (alumina) that ensures physical and chemical stability, prolonging its use and the quality of experiments. The sample holder allows electrical measurements from room temperature up to ~1500 °C in a wide range of oxygen partial pressures. The functionality of the constructed sample holder was assessed by comparing measurements of the temperature dependence of the electrical resistivity of yttria-stabilized zirconia samples. To further explore the capabilities of the measuring apparatus, samples of high-temperature composites based on yttria-stabilized zirconia and titanium nitride were prepared by spark plasma sintering (SPS). The general properties of these composites were investigated by thermal analysis, X-rays diffraction (XRD), and four-probe dc electrical measurements. The study of the composites showed that SPS resulted in dense samples with no detected reaction between phases and free from TiN oxidation. Samples with TiN addition displayed metallic behavior of the electrical resistivity, evidencing that the nitride attained the percolation threshold in the oxide matrix at volume fractions ≤ 27 vol.%. Electrical measurements combined with thermal analysis and XRD were used to monitor the oxidation of TiN at high temperature. The studied composites show good properties indicating that it is a promising material for high temperature applications that require high electrical conductivity.

Further crosslinking of the fluorinated polyimide was examined to separate the cure reactions from degradation and to determine the optimum post curing conditions. Glass transition/melting temperatures were ascertained using DSC, while weight loss during curing and Td were determined using TGA. Furthermore, the mechanical properties were measured using an Instron to relate to the thermal properties to find the optimum curing conditions. The polyimide resin exhibited the best post-curing conditions for further crosslinking for 8 hours at 410 degress C based on Tg, thermal stability, and mechanical properties. Blister temperatures, resulting from rapid heating, were obtained by monitoring changes in transverse thickness expansion using two different techniques. Both techniques employed showed similar blister temperatures in relation to the amount of absorbed moisture, regardless of sample size. The polyimide resin exhibited blister temperatures ranging from 225 - 362 degrees C, with 1.7 - 3.0 wt% absorbed moisture, and the polyimide composite had blister temperatures from 246 - 294 degrees C with 0.5 - 1.5 wt% moisture. Weight loss of the fluorinated polyimide and its corresponding polyimide carbon fiber composite under elevated temperature was examined. Weight loss as a function of exposure temperature and time was measured using TGA and by pre- and post-weighing of specimens treated in an oven. Both techniques showed similar weight loss trends as a function of time and temperature, but TGA showed much greater weight loss due to greater surface area to volume (i.e., small sample size). The neat polyimide resin and carbon fiber composite exhibited negligible weight loss at temperatures below 430 degrees C for exposure times up to 20 minutes. Transition-metal carbides were initially synthesized by carbothermal reduction of transition-metal halides and polymer precursor mixtures, at temperatures that range from 900 to 1500 degrees C in an argon atmosphere. TaC was synthesized from TaBr5, as a model carbide for this process. Significant (> 40 vol%) amounts of TaC were formed at reaction temperatures as low as 900 degrees C for one hour, with greater times and temperatures leading to > 90 vol% yield. Universality of method was also proven by using other various transition-metal halide salts (NbBr5, WCl4, and WCl6) with the polyimide.

A substantial raise in recuperator effectiveness has been established in the past by improving the fabricating and joining configurations regarding the manufacturing of compact recuperators. Further advancement of state-of-the-art recuperators requires providing for increased temperatures and pressures. 1bis can only be achieved by incorporating high temperature materials into the recuperator design. Although many high temperature materials have been identified in past research, less of these can be utilized in new concepts due to difficulties regarding fabricating and joining. However recently, in an independent study, a tungsten-copper alloy was identified through detailed material selection methods as a suitable material for high temperature applications. The validity of tungsten-copper regarding fabricating and joining, to establish a leak tight structure still needs to be demonstrated. The aim of the study is to carry out a comprehensive review of existing recuperator technologies and design methodologies as well as to investigate the manufacturability of tungsten-copper for use in a recuperator design of limited size. More specifically, the objectives entail the following: (1) The comprehensive review of existing recuperator technologies and recuperator design methodologies, (2) The design and fabrication of a recuperator of limited size using tungsten-copper as a heat transfer material and (3) The determination of the feasibility of fabrication of the design and the applicability of the selected W -eu alloy in the design. The fabrication technique that is presented in the design entailed the use of 2.Irm tungsten carbide drill bits to machine the correct recuperator profile, while the recuperator unit was joined by utilizing a mechanical fastening system. Although diffusion bonding was initially identified as the ideal joining technique for the recuperator of this research, restrictions and limitations relating to the use of diffusion bonding has lead to the identification of a fastening system as the technique used. Evaluation of the fabricated recuperator revealed that several factors were outside the initially specified values, inter alia the flatness tolerance of recuperator plate geometries and machined slots precision. These factors contributed to a leaJdng recuperator structure when tested. The most likely contributing factors for the latter relate to non-conforming tolerances achieved in the fabricated design, residual stresses induced by the machining process as well as design issues relating to the recuperator plate geometries. The design and fabrication of a recuperator of limited size using tungsten-copper as a heat transfer material, requires re-evaluation. Similar work will ensure a design of a high quality when provision is made for advanced surface fmishing of machined parts (notably the recuperator plate geometries), slight modifications to the design as well as stress relieving of machined components for the purpose of eliminating any residual stresses thatJnight be present. / Thesis (M.Ing. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2009.

A substantial raise in recuperator effectiveness has been established in the past by improving the fabricating and joining configurations regarding the manufacturing of compact recuperators. Further advancement of state-of-the-art recuperators requires providing for increased temperatures and pressures. 1bis can only be achieved by incorporating high temperature materials into the recuperator design. Although many high temperature materials have been identified in past research, less of these can be utilized in new concepts due to difficulties regarding fabricating and joining. However recently, in an independent study, a tungsten-copper alloy was identified through detailed material selection methods as a suitable material for high temperature applications. The validity of tungsten-copper regarding fabricating and joining, to establish a leak tight structure still needs to be demonstrated. The aim of the study is to carry out a comprehensive review of existing recuperator technologies and design methodologies as well as to investigate the manufacturability of tungsten-copper for use in a recuperator design of limited size. More specifically, the objectives entail the following: (1) The comprehensive review of existing recuperator technologies and recuperator design methodologies, (2) The design and fabrication of a recuperator of limited size using tungsten-copper as a heat transfer material and (3) The determination of the feasibility of fabrication of the design and the applicability of the selected W -eu alloy in the design. The fabrication technique that is presented in the design entailed the use of 2.Irm tungsten carbide drill bits to machine the correct recuperator profile, while the recuperator unit was joined by utilizing a mechanical fastening system. Although diffusion bonding was initially identified as the ideal joining technique for the recuperator of this research, restrictions and limitations relating to the use of diffusion bonding has lead to the identification of a fastening system as the technique used. Evaluation of the fabricated recuperator revealed that several factors were outside the initially specified values, inter alia the flatness tolerance of recuperator plate geometries and machined slots precision. These factors contributed to a leaJdng recuperator structure when tested. The most likely contributing factors for the latter relate to non-conforming tolerances achieved in the fabricated design, residual stresses induced by the machining process as well as design issues relating to the recuperator plate geometries. The design and fabrication of a recuperator of limited size using tungsten-copper as a heat transfer material, requires re-evaluation. Similar work will ensure a design of a high quality when provision is made for advanced surface fmishing of machined parts (notably the recuperator plate geometries), slight modifications to the design as well as stress relieving of machined components for the purpose of eliminating any residual stresses thatJnight be present. / Thesis (M.Ing. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2009.

The expansion ratio (defined as the ratio of the expanded thickness to the original thickness) of intumescent coatings is the most important quantity that determines their fire protection performance. This thesis explores two possible methods of predicting intumescent coating expansion: an analytical method, and a detailed numerical simulation method using Smoothed Particle Hydrodynamics (SPH).The analytical method is based on a cell-model and predicts bubble growth due to pressure increase in viscous liquid with constant viscosity. It has been extended to non-uniform temperature field and temperature-dependent viscosity of intumescent melt. Accuracy of this extended analytical method is assessed by comparison against the cone calorimeter and furnace fire tests on intumescent coating protected steel plates with different intumescent coating thicknesses, steel plate thicknesses, and heating conditions. The extended analytical method is then used to investigate how intumescent coating expansion and intumescent coating effective thermal conductivity are affected by changing the coating thickness, the steel thickness and the fire condition (including smouldering fire). The main conclusion is that the expansion ratio decreases as the rate of heating increases. Therefore, the intumescent coating properties obtained from the Standard fire exposure may be safely used for slower realistic fires, but would produce unsafe results for faster fires. The second method explores the potential of a meshless numerical simulation: Smoothed Particle Hydrodynamics (SPH). SPH modelling of intumescent coating expansion has been implemented using the SPHysics FORTRAN open-source code as a platform. To check the validity of this modelling method, the modelling results are compared against theoretical solutions for surface tension (Young-Laplace theorem), and available numerical and analytical solutions for bubble expansion. A new algorithm for representing the mass transfer of gas into the bubble using SPH particle insertion and particle shifting scheme is presented to simulate the bubble expansion process. Close agreement with an analytical solution for the initial bubble expansion rate computed by SPH is obtained. Whilst this research has demonstrated the potential of using SPH to numerically simulate intumescent coating expansion, it has also revealed significant challenges that should be overcome to make SPH a feasible method to simulate intumescent coating expansion. The main challenges include:• Simulating gas-polymer flows when expansion is occurring where there are vastly different properties of these two fluids with a density ratio of about 1000. This high density ratio may easily cause numerical pressure noise, especially at the liquid-gas interface.• Extremely high computational cost necessary to achieve sufficient accuracy by using a large number of particles (higher resolution), especially for the multi-phase SPH program, and very small time step for the lighter fluid (air). • The behaviour of intumescent coatings involves expansion ratios on the order of 10-100 with thousands of bubbles which grow, merge and burst. Based on the results of this exploratory research, future improvements are outlined to further develop the SPH simulation method.

This dissertation presents new solutions for turbine engines in need of wireless temperature sensors at temperatures up to 1300oC. Two important goals have been achieved in this dissertation. First, a novel method for precisely characterizing the dielectric properties of high temperature ceramic materials at high temperatures is presented for microwave frequencies. This technique is based on a high-quality (Q)-factor dielectrically-loaded cavity resonator, which allows for accurate characterization of both dielectric constant and loss tangent of the material. The dielectric properties of Silicon Carbonitride (SiCN) and Silicoboron Carbonitride (SiBCN) ceramics, developed at UCF Advanced Materials Processing and Analysis Center (AMPC) are characterized from 25 to 1300oC. It is observed that the dielectric constant and loss tangent of SiCN and SiBCN materials increase monotonously with temperature. This temperature dependency provides the valuable basis for development of wireless passive temperature sensors for high-temperature applications. Second, wireless temperature sensors are designed based on the aforementioned hightemperature ceramic materials. The dielectric constant of high-temperature ceramics increases monotonically with temperature and as a result changes the resonant frequency of the resonator. Therefore, the temperature can be extracted by measuring the change of the resonant frequency of the resonator. In order for the resonator to operate wirelessly, antennas need to be included in the design. Three different types of sensors, corresponding to different antenna configurations, are designed and the prototypes are fabricated and tested. All of the sensors successfully perform at temperatures over 1000oC. These wireless passive sensor designs will significantly benefit turbine engines in need of sensors operating at harsh environments