Natural gas is currently an attractive substitute for diesel fuel in the Heavy-Duty (HD) diesel transportation sector. This is primarily attributed to its cost effectiveness, but also its ability to reduce the amount of CO2 and harmful engine pollutants emitted into the atmosphere. Lean-burn dual-fuel engines substitute natural gas in place of diesel but typically suffer from high engine-out methane (CH4) emissions, particularly under low load operation. In response to this issue, this work set out to improve upon the efficiency and emissions of a lean-burn dual-fuel combustion system in an HD diesel/natural gas engine. Thermodynamic experimental engine testing was performed at various steady-state operating points in order to identify the most effective methods and technologies for improving emissions and efficiency. Low Temperature Combustion (LTC) along with several valvetrain and injection strategies were evaluated for benefits, with special attention paid to low load operating conditions. LTC was proven to be a useful method for decreasing methane emissions while simultaneously improving engine efficiency. The benefits of LTC were a function of load with the greatest advantages experienced under medium load operation. Additionally, the low load strategies tested were determined to be effective techniques for reducing methane emissions and could possibly extend the dual-fuel operating regime to lighter load conditions. Overall, no operating condition tested throughout the engine map resulted in a brake engine-out methane emissions level of less than 0.5 g/kWh at gas substitutions greater than approximately 75%. It is suggested that the limits of this particular lean-burn dual-fuel design were reached, and that it would likely require improvements to either the combustion system or exhaust after-treatment if Euro VI emissions levels for methane were to be achieved.

Graphene, a single atomic layer of graphite, has many exciting electronic and mechanical properties. On a fundamental level, the quasi-relativistic behaviour of the charge carriers in graphene arises from the honeycomb-like atomic structure. Deforming the lattice changes the lengths of the carbon-carbon bonds, breaking the hopping symmetry between carbon sites. Mathematically, elastic strain in a graphene membrane can be described by additional terms in the low-energy effective Hamiltonian, analogous to the vector potential of an external magnetic field. Hence, certain non-uniform strain geometries produce so-called `pseudo-magnetic fields', leading to a predicted zero-field quantum Hall effect. These fictitious magnetic fields are distinct from an external magnetic field in that they are only observed by charge carriers within the membrane, and have opposing polarity for electrons in the K and K' valleys, preserving time-reversal symmetry of the lattice as a whole. Deforming graphene in the non-uniform manner required to produce a homogeneous pseudo-magnetic field has proven to be a huge technological challenge, however, restricting experimental evidence to scanning tunnelling spectroscopy measurements on, for example, highly deformed nanobubbles formed by the thermal expansion of an epitaxially grown sheet on a platinum substrate. These results stimulated a large amount of interest in strain-engineering electron transport in graphene, partly due to the extreme magnitude of the observed pseudo-magnetic field, a direct consequence of the strain components strongly varying over the space of a few nanometres, but the formation of nanobubbles is a highly stochastic process which cannot be reliably reproduced. Subsequent research found a way to fabricate nanobubbles with a high degree of consistency, but the measurements were still limited to local-probe techniques due to the nanoscale size of the devices. As such, a method to reliably induce a homogeneous pseudo-magnetic field within a micron-sized membrane would be an attractive proposition, and is the basis for the work presented within this thesis. The non-uniform strain required precludes a simple bending or elongation of the substrate, hence a more local method is required. A novel nanostructure consisting of suspended gold beams surrounding a graphene membrane will deform upon cooling to cryogenic temperatures, and crucially, the actuation mechanism can be designed to produce any configuration of strain, including uniaxial strain, triaxial strain and a fan-shaped deformation, the latter two of which are predicted to create homogeneous pseudo-magnetic fields within a membrane. Strain patterns which are predicted to produce experimentally significant pseudo-magnetic fields (~1 T) may be generated with complex actuation beams that are physically achievable. Furthermore, the actuation mechanisms may be utilised as electrical contacts to the membrane, allowing its conductivity to be measured in the context of a two- or multi-terminal measurement, in conjunction with an external magnetic field. The design of the devices was developed using finite-element analysis, and the behaviour verified by low-temperature imaging of prototypes. While, after careful annealing, some conventional two-terminal suspended devices exhibited quantum Hall features at very low fields, the fabricated strain-inducing devices did not display pseudo-Landau quantisation, nor Landau quantisation, due to the difficulties of using current annealing to clean devices post-fabrication. The presented work, however, could pave the way towards observing signatures of pseudo-magnetic fields in a range of experimental measurements, as well as creating alternative strain geometries.

A zircônia tetragonal estabilizada por ítria (Y-TZP) têm sido utilizada na área odontológica para próteses livres de metais devido à estética associada ao alto desempenho mecânico. Porém, a presença de ambiente úmido pode causar a transformação acelerada da fase tetragonal para monoclínica e consequente falha catastrófica deste material, processo este conhecido como degradação a baixa temperatura ou envelhecimento. A cinética desta transformação é função da composição química da cerâmica e sua microestrutura. Tendo em vista que métodos químicos permitem a síntese de pós cerâmicos à base de zircônia de dimensões nanométricas, cuja microestrutura da cerâmica sinterizada é constituída por grãos submicrométricos quimicamente homogêneos, e que a presença de alumina é indicada para evitar a degradação de fases da zircônia, o objetivo deste estudo foi verificar a degradação a baixa temperatura e ambiente úmido de cerâmicas de zircônia estabilizada com 3 mol% de ítria (Y-TZP) e do compósito Y-TZP/Al2O3, proveniente de pós sintetizados pela rota de coprecipitação. A concentração de alumina na Y-TZP foi estudada na faixa de 0,05 a 20% em massa. A eficiência do processo desenvolvido foi verificada pela avaliação das características físicas dos pós obtidos (granulometria, área de superfície específica, estado de aglomeração e estrutura cristalina). As amostras cerâmicas foram prensadas, sinterizadas e avaliadas quanto à densidade aparente e microestrutura. Após a caracterização inicial das cerâmicas a degradação das amostras foi estudada in vitro em reator hidrotérmico pressurizado a 150°C. As amostras (n=4) foram submetidas à análise de difração de raios X de acordo com o tempo de envelhecimento, acompanhando a curva cinética de transformação de fase. A porcentagem de cada fase cristalina foi determinada pelo Método de Rietveld. A relação entre o tempo de envelhecimento e a concentração de fase monoclínica foi determinada pela equação de Avrami modificada por Kolmogorow (Johnson-Mehl- Avrami-Kolmogorow JMAK). Após envelhecimento a 150°C por 70 horas, todas as amostras contendo alumina apresentaram menor concentração de fase monoclínica, comparativamente à cerâmica Y-TZP, que apresentou 66,5% dessa fase. Menores porcentagens de fase monoclínica após o envelhecimento hidrotérmico foram obtidas com a adição de 10 e 20% em massa de alumina na matriz de zircônia, sendo esses valores 59,1 e 52,9%, respectivamente. Deve-se considerar, no entanto, que a diminuição da degradação total é consequência da menor porcentagem de zircônia na matriz em função da adição de alumina. Neste contexto, o efeito benéfico da adição de alumina ocorre apenas no início do envelhecimento. / The yttria tetragonal zirconia polycrystal (Y-TZP) is used in dentistry for metal free prosthesis due to esthetics associated with a high mechanical performance. However, the presence of humid environment can cause an accelerated tetragonal to monoclinic (t-m) phase transformation and consequent catastrophic failure of this material. This process is known as low temperature degradation (LTD) or aging. The kinetics of phase transformation is a function of the chemical composition of the ceramic and its microstructure. Considering that chemical methods allow the synthesis of nanometric zirconium-based ceramic powders, which microstructure of the sintered ceramic consists of submicrometric chemically homogeneous grains, and that the presence of alumina is indicated to delay the tetragonal phase degradation, the aim of this study was to verify the degradation at low temperature in humid environment of 3mol% yttria stabilized zirconia ceramics (Y-TZP) and the Y-TZP/Al2O3 composite prepared from coprecipitated powders. The addition of alumina at Y-TZP was studied in the range of 0.05 to 20wt%. The efficiency of the developed process was verified by the evaluation of the physical characteristics of the obtained powders (granulometry, specific surface area, agglomeration state and crystalline structure). The ceramic samples were pressed, sintered and submitted to apparent density and microstructure evaluation. After the initial characterization of the ceramics, the in vitro degradation of the samples was studied in a hydrothermal pressurized reactor at 150°C. The samples (n = 4) were submitted to X-ray diffraction analysis according to the aging time, followed by the determination of the kinetic curve of phase transformation. The Rietveld Method was employed to determine the percentage of each crystalline phase. The relationship between the aging time and the percentage of monoclinic phase was determined by the Johnson- Mehl-Avrami-Kolmogorow equation (JMAK). After 70 hours aging at 150°C, all the alumina-containing samples presented a lower concentration of monoclinic phase, compared to the Y-TZP ceramics, which monoclinic phase concentration was 66.5%. The lower percentages of monoclinic phase after hydrothermal aging were obtained with the addition of 10%wt and 20 wt% alumina in the zirconia matrix (59.1% and 52.9%, respectively). This behavior is due to the lower concentration of zirconia in the composite containing alumina. In this point of view beneficial effect due to alumina addition occurs in the early stage of aging.

A busca contínua por tecnologias de esterilização a baixa temperatura deve-se à necessidade de adequação dos agentes esterilizantes às características físicoquímicas dos produtos, à conveniência de maior rapidez no processamento, além dos apelos ambientais, em comparação, por exemplo, com o método de esterilização por óxido de etileno. Desta forma surgiu interesse pelo ozônio (O3), o qual pode ser considerado o mais potente germicida natural que existe, sendo capaz de eliminar microrganimos (na forma vegetativa e esporulada) com alta eficiência e rapidez, graças a sua atividade altamente oxidante. O presente trabalho teve por objetivo proceder estudos para a determinação de parâmetros para o processo de esterilização empregando ozônio, além de avaliar a eficácia do agente esterilizante em questão. O processo de esterilização foi desafiado com esporos de Geobacillus stearothermophilus ATCC 7953 o qual se caracteriza frente as mesmas com elevada resistência. A eficácia esterilizante do ozônio foi avaliada através de carreadores inoculados com 106 do esporo, introduzidos em seringas de 3 mL e tubos com diferentes comprimentos e diâmetros, simulando produtos médico hospitalares. Tais dispositivos foram submetidos a meio ciclo e ciclo completo do processo de esterilização por ozônio. A validação do processo foi comprovada através dos resultados satisfatórios para meio ciclo, obtidos com os testes efetuados. Desta forma, foi possível constatar a eficácia do processo de esterilização por ozônio. Adicionalmente, foram objeto de investigação materiais termossensíveis distintos obtidos de produtos médico-hospitalares, a fim de estudar a influência do ozônio sobre as características intrínsecas desses materiais. As amostras foram submetidas ao ciclo completo de esterilização e analisadas pelo teste de citotoxicidade in vitro e avaliação da superfície dos materiais por espectrofotometria com transformadas de Fourier com acessório de refletância atenuada (ATR-FTIR) para esclarecer eventuais efeitos do processo sobre a biocompatibilidade das mesmas. Embora os materiais estudados não demonstraram efeito citotóxico após serem submetidos à esterilização por ozônio, a superfície do derivado de polietileno (PE) demonstrou uma banda de oxidação em consequência da ação do agente esterilizante. / Ozone (O3) can be considered the most potent natural germicide against microorganisms (in vegetative and spore forms) with high efficiency and speed, because of its highly oxidizing activity. Despite this, there are a few studies describing the application of ozone as a sterilizing agent of medical devices. The aim of this paper was to describe the development and validation of a sterilization cycle applied to medical devices. The sterilization process was challenged with Geobacillus stearothermophilus ATCC 7953 spores, which have shown great resistance. The sterilizing effect of ozone was measured using carriers inoculated with 106 spores, introduced into a 3 mL syringe and lumens of tubes of different sizes and diameters simulating hospital medical products, which have undergone a half-cycle or complete cycle. The validation process was confirmed by the satisfactory results for the half cycle, which indicate an appropriate sterility assurance level. Thus, one can consider the ozone sterilization process effective for medical devices. On the other hand, there was a need to evaluate the safety of ozone sterilization in terms of medical device materials in order to clarify the influence of ozone on the intrinsic characteristics of these materials. The samples were submitted to the complete cycle of sterilization and analysis by the \"in vitro\" cytotoxicity test and evaluation of the surface of the materials using ATR-FTIR spectrometry to clarify eventual of the process on a biocompatibility. Although the materials studied did not demonstrate a cytotoxic effect after being subjected to ozone sterilization, the surface of the polyethylene (PE) derivative demonstrated an oxidation band as a consequence of the action of the sterilizing agent.

A range of titanium dioxide (titania) samples provided by Huntsman Pigments and Additives were investigated for their suitability for use in various optoelectronic devices, specifically dye-sensitized solar cells (DSSCs). Five of the titania samples are 1-20 micrometre size spherical 3D porous beads made up of titania nanoparticles and a further six samples are porous titania nanoparticle clusters of no specific shape, all of which possess high surface areas from 85 to 276 m2g-1. The samples were compared to commercially available nanocrystalline TiO2 powders and paste. All of the samples were initially assessed for suitability in DSSC devices by investigating various properties such as crystal phase, particle size, band gap, morphology and N719 dye adsorption, both as a powder sample and as a sintered film, employing techniques such as powder x-ray diffraction, UV/Vis spectroscopy and scanning electron microscopy. Different methods of formulating the samples into pastes for application to a substrate were attempted and electrochemical properties of a selection of films were also compared. The more promising titania samples were formulated into dye-sensitized solar cells and cell efficiencies calculated. DSSC devices were also fabricated with low temperature (125oC) sintering of the titania layer to assess the suitability of the samples for use in devices with flexible substrates. Initial devices incorporating the Huntsman TiO2 samples provided low efficiencies (< 0.1%). The samples were then modified with pre-sintering treatment prior to paste formulation to optimize crystallinity, particle size, porosity and surface area. The modified titania bead samples showed great promise in low temperature sintered devices, providing device efficiencies of 2.8%, more than double that of those incorporating the standard P25 TiO2 (1.3%). After sample modification a superior solar cell performance (3.2%) was also observed in 510oC sintered devices when compared to the standard P25 TiO2 devices (2.9%), with higher photocurrent and open circuit voltage than devices fabricated from commercially optimized TiO2 paste. Devices were also fabricated using pre-sensitized titania in an attempt to reduce device manufacturing time. The modified samples again showed good performance, providing working devices with efficiencies comparable to the equivalent pre-sensitized P25 devices.

Low grade heat (LGH) sources, here defined as below 80ºC, are one group of abundant energy sources that are under-utilised in the production of electricity. Industrial waste heat provides a convenient source of concentrated LGH, while solar ponds and geothermal resources are examples of sustainable sources of this energy. For a number of years RMIT has had two ongoing, parallel heat engine research projects aimed at the conversion of LGH into electricity. The Thermosyphon Rankine Engine (TSR) is a heat engine that uses water under considerable vacuum. The other research stream uses a hydrocarbon based working fluid in a heat engine employing the Trilateral Flash Cycle (TFC). The TSR Mk V was designed and built as a low cost heat engine for the conversion of LGH into electricity. Its main design advantages are its cost and the employment of only one moving part. Using the data gained from the experimental rig, deviations from the expected results (those derived theoretically) were explored to gain insight for further development. The results from the TSR rig were well below those expected from the design specifications. Although the experimental apparatus was able to process the required heat energy, the efficiency of conversion fell well below the expected 3% and was approximately 0.2%. The inefficiency was explained by a number of contributing factors, the major being form drag upon the rotor that contributed around 2/3 of the losses. Although this was the major cause of the power loss, other factors such as the interference with the rotor by the condensate on its return path contributed to the overall poor performance of the TSR Mk V. The RMIT TFC project came about from exploration of the available academic literature on the subject of LGH conversion. Early work by researchers into applying Carnot's theory to finite heat sources led them to explore the merits of sensible heat transfer combined with a cycle that passes a liquid (instead of a gas) though an expander. The results showed that it was theoretically possible to extract and convert more energy from a heat source of this type using this method than using any other alternative. This previous research was targeted at heat sources above 80ºC and so exploration of the theoretical and empirical results for sources below this temperature was needed. Computer models and an experimental rig using isopentane (with a 28ºC boiling point at atmospheric pressure) were produced to assess the outcomes of employing low temperature heat sources using a TFC. The experimental results from the TFC research proved promising with the efficiency of conversion ranging from 0.8% to 2.4%. Although s uch figures seem poor in isolation, it should be noted that the 2.4% efficiency represents an achievement of 47% of the theoretical ideal conversion efficiency in a rig that uses mainly off-the-shelf components. It also confirms that the TFC shows promise when applied to heat sources less than 80ºC.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 114-120).

The work presented in this thesis detail the measurement of the thermal expansion coefficient of three magnetic spin materials. Thermal expansion coefficient values were measured by capacitive dilatometry in several key low (T < 250 K) temperature regions specific to each material. This thesis is separated into several key parts. The first part establishes the theory behind observing phase transitions through the thermal expansion coefficient. Beginning with the classical definitions of the specific heat, compressibility and thermal expansion coefficient, the three properties are related using a property known as the Grüneisen parameter. To first order, the parameter allows phase transitions to be observed by the thermal expansion coefficient. The second part introduces capacitive dilatometry; a technique used to measure the thermal expansion coefficient. Three capacitive dilatometer devices are presented in this section. The silver compact dilatometer, the fused quartz dilatometer and the copper dilatometer. Each device discusses merits and weaknesses to their designs. Particular focus is made on the fused quartz dilatometer which was built during the duration of this thesis. The third part presents research on three magnetic spin materials; LiHoF4, Tb2Ti2O7 and Ba3NbFe3Si2O14. These materials are studied individually focusing on specific aspects. LiHoF4, a candidate material for the transverse field Ising model, provides insight to quantum phase transitions. Thermal expansion coefficient and magnetostriction along the c-axis for T ≈ 1.3-1.8 K and transverse field Ht ≈ 0-4 T were measured extracting critical points for a Ht-T phase diagram. Existing thermal expansion coefficient measurements had evidence of possible re-entrant behaviour. With a high density of low transverse field critical points it was established that LiHoF4 showed no evidence of re-entrant behaviour. The highly debated material Tb2Ti2O7 has a rich, controversial low temperature behaviour. Originally believed to be a spin liquid, specific heat results propose a scenario involving a sample composition dependent ordered state. Still under considerably attention, thermal expansion coefficient measurements were performed for T < 1 K. The results are interpreted to either fit into the proposed scenario or provide evidence for an alternate scenario. The material Ba3NbFe3Si2O14 exhibits a magnetoelectric multiferroic phase below TN ≈ 27 K; a phase where magnetic and electric order simultaneously exist. The formation of this phase is believed to have a similar structural shift observed in hexagonal perovskite multiferroic materials. The ferroelectric ordering in those materials are brought about through a centrosymmetric to non-centrosymmetric structural shift. The thermal expansion and thermal expansion coefficient coefficient along the a and c axis are measured for T > TN searching for a displacive structural phase transition.

A new adhesive bonding method is introduced for microlamination architectures, for producing low-temperature microchannel arrays in a wide variety of metals. Sheet metal embossing and chemical etching processes have been used to produce sealing bosses and flow features, resulting in approximately 50% fewer laminae over traditional methods. These lamina designs are enabled by reduced bonding pressures required for the new method. An assembly process using adhesive dispense and cure is outlined to produce leak-free devices. Feasible fill ratios were determined to be 1.1 in general and 1.25 around fluid headers, largely due to gaps between faying surfaces caused by surface roughness. Bond strength investigation reveals robustness to surface conditions and a bond strength of 5.5-8.5 MPa using a 3X safety factor. Dimensional characterization reveals a two sigma (95%) post-bonded channel height tolerance under 10% (9.6%) after bonding. Patterning tolerance and surface roughness of the faying laminae were found to have a significant influence on the final postbonded channel height. Leakage and burst pressure testing on several samples has established confidence that adhesive bonding can produce leak-free joints. Operating pressures up to 413 kPa have been satisfied, equating to tensile pressure on bond joints of 1.9 MPa. Higher operating pressures can be accommodated by increasing the bond area of devices. A two-fluid counterflow microchannel heat exchanger has been redesigned, fabricated and tested to demonstrate feasibility of the new method. Results show greater effectiveness and higher heat transfer rates, suggesting a smaller device than the original heat exchanger. A maximum effectiveness of 82.5% was achieved with good agreement between theoretical and experimental values. Although thermal performance was improved, higher pressure drops were noted. Pressure drops were predicted with a maximum error of 16% between theoretical and experimental values. Much of the pressure drop was found to be in the device manifolds, which can be improved in subsequent designs. Fluid flow simulation results show a 45-65X reduction in fluid leakage velocity past sealing bosses, thereby mitigating adhesive erosion concerns. Theoretical models indicate that the worst-case adhesive erosion rate is 1/12th the rate of aluminum and 1/7th the rate of stainless steel, implying satisfactory reliability in high fluid velocity applications. Economic comparison indicates an 83% reduction in material cost and 71% reduction in assembly cost with the new adhesive bonding process, when compared to diffusion bonding for the recuperator investigated in this study. Adhesive compatibility with common refrigerants is reviewed through literature references, with no adverse compatibility issues noted. The findings of this research suggest a fairly quick path to commercialization for the new bonding method. Future studies required to pursue commercialization are liquid and gas permeability evaluations, and long term strength and performance testing of adhesives in targeted applications. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Mar. 26, 2012 - Mar. 26, 2013

This work evaluates two SiGe BiCMOS technology platforms as candidates for implementing extreme environment capable circuitry, with an emphasis on applications requiring high sensitivity and low noise. In Chapter 1, applications requiring extreme environment sensing circuitry are briefly reviewed and the motivation for undertaking this study is outlined. A case is then presented for the use of SiGe BiCMOS technology to meet this need, documenting the benefits of operating SiGe HBTs at cryogenic temperatures. Chapter 1 concludes with a brief description of device radiation effects in bipolar and CMOS devices, and a basic overview of noise in semiconductor devices and electronic components. Chapter 2 further elaborates on a specific application requiring low-noise circuitry capable of operating at cryogenic temperatures and proposes a number of variants of band-gap reference circuits for use in said system. Detailed simulation and theoretical analysis of the proposed circuits are presented and compared with measurements, validating the techniques used in the proposed designs and emphasizing the need for further understanding of device level low-temperature noise phenomena. Chapter 3 evaluates the feasibility of using a SiGe BiCMOS process, whose response to ionizing radiation was previously uncharacterized, for use in unshielded electronic systems needed for exploration of deep space planets or moons, specifically targeting Europa mission requirements. Measured total ionizing dose (TID) responses for both CMOS and bipolar SiGe devices are presented and compared to similar technologies. The mechanisms responsible for device degradation are outlined, and an explanation of unexpected results is proposed. Finally, Chapter 4 summarizes the work presented and understanding provided by this thesis, concluding by outlining future research needed to build upon this study and fully realize SiGe based extreme environment capable precision electronic systems.