Asymmetric hydrogen flame in a heated micro-channel: role of Darrieus-Landau and thermal-diffusive instabilities

Present work examines numerically the asymmetric behavior of hydrogen/air flame in a micro-channel subjected to a non-uniform wall temperature distribution. A high resolution (with cell size of 25 μm × 25 μm) of two-dimensional transient Navier–Stokes simulation is conducted in the low-Mach number formulation using detailed chemistry evolving 9 chemical species and 21 elementary reactions. Firstly, effects of hydrodynamic and diffusive-thermal instabilities are studied by performing the computations for different Lewis numbers. Then, the effects of preferential diffusion of heat and mass transfer on the asymmetric behavior of the hydrogen flame are analyzed for different inlet velocities and equivalence ratios. Results show that for the flames in micro-channels, interactions between thermal diffusion and molecular diffusion play major role in evolution of a symmetric flame into an asymmetric one. Furthermore, the role of Darrieus–Landau instability found to be minor. It is also found that in symmetric flames, the Lewis number decreases behind the flame front. This is related to the curvature of flame which leads to the inclination of thermal and mass fluxes. The mass diffusion vectors point toward the walls and the thermal diffusion vectors point toward the centerline. Asymmetric flame is observed when the length of flame front is about 1.1–1.15 times of the channel width.

Particle Trajectory Computation for Accelerators and Related Technologies

This work reports an alternative method for single non-relativistic charged particle trajectory computation in 2D electrostatic or magnetostatic fields. This task is approached by analytical computation of particle trajectory, by parts, considering the constant fields within each finite element. This method has some advantages over numerical integration ones: numerical miscomputation of trajectories, and stability problems can be avoided. Among the examples presented in this paper, an interesting alternative approach for positive ion extraction from cyclotrons is shown, using strip-foils. Other particle optics devices can benefit of a method such the one proposed in this paper, as beam bending devices, spectrometers, among others. This method can be extended for particle trajectory computation in 3D domains.

IT Adoption and Usage in Non-Profit Organizations: a Cross-generational Case Study

A gulf has tended to develop between the adoption and usage of information technology by different generations, at the heart of which is different ways of experiencing and relating to the world around us. This research idea is currently being developed following data collection and feedback is sought on ways forward to enable impact. The research focuses on information technology in the form of multimedia. Multimedia meaning ‘media’ and ‘content’ that uses a combination of different content forms; or electronically integrated communication engaging all or most of the senses (e.g. graphic art, sound, animation and full-motion video presented by way of computer or other electronic means) mainly through presentational technologies. Although multimedia is not new, some organization’s particularly those in the non-profit sector do not always have the technical or financial resources to support such systems and consequently may struggle to adopt and support its usage amongst different generations. However non-profit organizations are being forced to pay more attention to the way they communicate with markets and the public due to the professionalism of communication everywhere in society. The case study used for this study is a church circuit comprising of 15 churches in the Midlands region of the United Kingdom which was selected due to the diverse age groups catered for within this type of non-profit organization. Participants in the study also had a range of skills, experiences and backgrounds which adds to the diversity of the population studied. Data gathered focused on the attitudes and opinions of the adoption and use of multimedia amongst different age groups. 395 questionnaires were distributed, comprising of 11 opinion questions and 4 demographic questions. 83% of the questionnaires were returned, representing 35% of the total circuit membership. Three people from each of the following age categories were also interviewed: 1920 – 1946 (Matures); 1947-1964 (Baby Boomers); 1965-1982 (Generation X); 1983-2004 (Net Generation). Results of the questionnaire and comments from the interviews were found not to tally with the widespread assumption that the younger generation is attracted by the use of multimedia in comparison to the older generation. The highest proportion of those who said that they gain more from a service enhanced by multimedia was from the Baby Boomers. Comments from interviews suggested that: ‘we need to embrace multimedia if we are to attract and retain the younger generation’; ‘multimedia often helps children to remain focused and clarifies the objective of the service’. However, because the younger generations’ world tends to be dominated by computer technology the questionnaire showed that they are more likely to have higher standards when it comes to the use of multimedia, such as identifying higher levels of equipment failing to work and annoying use of sounds compared to older age groups. In comparison problems experienced with multimedia for the Matures age group had the highest percentage of difficulty with the size of letters; the colour of letters and background and the sound not loud enough which is to be expected. Since every organization is unique any type of multimedia adopted and used should be specific to their needs, its stakeholders and the physical building in order to enhance that uniqueness and its needs. Giving thought to whether the type of multimedia is the best method for communicating the message to the particular audience alongside how technical and financial resources are best used can assist in accommodating different age groups that need to be catered for.

Ordering induced by chemical, thermal and mechanical constraints at solid interfaces

We know that classical thermodynamics even out of equilibrium always leads to stable situation which means degradation and consequently d sorder. Many experimental evidences in different fields show that gradation and order (symmetry breaking) during time and space evolution may appear when maintaining the system far from equilibrium. Order through fluctuations, stochastic processes which occur around critical points and dissipative structures are the fundamental background of the Prigogine-Glansdorff and Nicolis theory. The thermodynamics of macroscopic fluctuations to stochastic approach as well as the kinetic deterministic laws allow a better understanding of the peculiar fascinating behavior of organized matter. The reason for the occurence of this situation is directly related to intrinsic non linearities of the different mechanisms responsible for the evolution of the system. Moreover, when dealing with interfaces separating two immiscible phases (liquid - gas, liquid -liquid, liquid - solid, solid - solid), the situation is rather more complicated. Indeed coupling terms playing the major role in the conditions of instability arise from the peculiar singular static and dynamic properties of the surface and of its vicinity. In other words, the non linearities are not only intrinsic to classical steps involving feedbacks, but they may be imbedded with the non-autonomous character of the surface properties. In order to illustrate our goal we discuss three examples of ordering in far from equilibrium conditions: i) formation of chemical structures during the oxidation of metals and alloys; ii) formation of mechanical structures during the oxidation of metals iii) formation of patterns at a solid-liquid moving interface due to supercooling condition in a melt of alloy. © 1984, Walter de Gruyter. All rights reserved.

Fluctuations in and out of equilibrium: Thermalization, quantum measurements and Coulomb disorder

This purely theoretical thesis covers aspects of two contemporary research fields: the non-equilibrium dynamics in quantum systems and the electronic properties of three-dimensional topological insulators. In the first part we investigate the non-equilibrium dynamics in closed quantum systems. Thanks to recent technologies, especially from the field of ultracold quantum gases, it is possible to realize such systems in the laboratory. The focus is on the influence of hydrodynamic slow modes on the thermalization process. Generic systems in equilibrium, either classical or quantum, in equilibrium are described by thermodynamics. This is characterized by an ensemble of maximal entropy, but constrained by macroscopically conserved quantities. We will show that these conservation laws slow down thermalization and the final equilibrium state can be approached only algebraically in time. When the conservation laws are violated thermalization takes place exponential in time. In a different study we calculate probability distributions of projective quantum measurements. Newly developed quantum microscopes provide the opportunity to realize new measurement protocols which go far beyond the conventional measurements of correlation functions. The second part of this thesis is dedicated to a new class of materials known as three-dimensional topological insulators. Also here new experimental techniques have made it possible to fabricate these materials to a high enough quality that their topological nature is revealed. However, their transport properties are not fully understood yet. Motivated by unusual experimental results in the optical conductivity we have investigated the formation and thermal destruction of spatially localized electron- and hole-doped regions. These are caused by charged impurities which are introduced into the material in order to make the bulk insulating. Our theoretical results are in agreement with the experiment and can explain the results semi-quantitatively. Furthermore, we study emergent lengthscales in the bulk as well as close to the conducting surface.

Oceans of energy? The non-linear trajectory of the emerging wave energy technology

This paper addresses the construction and structuring of a technological niche – i.e. a protected space where promising but still underperforming technologies are stabilized and articulated with societal needs – and discusses the processes that influence niche development and may enable niche breakout. In theoretical terms the paper is grounded on the multi-level approach to sustainability transitions, and particularly on the niche literature. But it also attempts to address the limitations of this literature in what concerns the spatial dimension of niche development. It is argued that technological niches can transcend the narrow territorial boundaries to which they are often confined, and encompass communities and actions that span several spatial levels, without losing some territorial embeddedness. It is further proposed that these features shape the niche trajectory and, therefore, need to be explicitly considered by the niche theoretical framework. To address this problem the paper builds on and extends the socio-cognitive perspective to technology development, introducing a further dimension – space – which broadens the concept of technological niche and permits to better capture the complexity of niche behaviour. This extended framework is applied to the case of an emerging renewable energy technology – wave energy - which exhibits a particularly slow and non-linear development trajectory. The empirical analysis starts by examining how an “overall niche space” in wave energy was spatially constructed over time. Then it investigates in greater detail the niche development processes that took place in Portugal, a country that was among the pioneers in the field, and whose actors have been, from very early stages, engaged in the activities conducted at various spatial levels. Through this combined analysis, the paper seeks to understand whether and how niche development is shaped by processes taking place at different spatial levels. More specifically it investigates the interplay between territorial and relational elements in niche development, and how these different dynamics influence the performance of the niche processes and impact on the overall niche trajectory. The results confirm the niche multi-spatial dynamics, showing that it is shaped by the interplay between a niche relational space constructed by actors’ actions and interactions on/across levels, and the territorial effects introduced by these actors’ embeddedness in particular geographical and institutional settings. They contribute to a more precise understanding of the processes that can accelerate or slow down the trajectory of a technological niche. In addition, the results shed some light into the niche activities conducted in/originating from a specific territorial setting - Portugal - offering some insights into the behaviour of key actors and its implications for the positioning of the country in the emerging field, which can be relevant for the formulation of strategies and policies for this area.

ENABLING HARDWARE TECHNOLOGIES FOR AUTONOMY IN TINY ROBOTS: CONTROL, INTEGRATION, ACTUATION

The last two decades have seen many exciting examples of tiny robots from a few cm3 to less than one cm3. Although individually limited, a large group of these robots has the potential to work cooperatively and accomplish complex tasks. Two examples from nature that exhibit this type of cooperation are ant and bee colonies. They have the potential to assist in applications like search and rescue, military scouting, infrastructure and equipment monitoring, nano-manufacture, and possibly medicine. Most of these applications require the high level of autonomy that has been demonstrated by large robotic platforms, such as the iRobot and Honda ASIMO. However, when robot size shrinks down, current approaches to achieve the necessary functions are no longer valid. This work focused on challenges associated with the electronics and fabrication. We addressed three major technical hurdles inherent to current approaches: 1) difficulty of compact integration; 2) need for real-time and power-efficient computations; 3) unavailability of commercial tiny actuators and motion mechanisms. The aim of this work was to provide enabling hardware technologies to achieve autonomy in tiny robots. We proposed a decentralized application-specific integrated circuit (ASIC) where each component is responsible for its own operation and autonomy to the greatest extent possible. The ASIC consists of electronics modules for the fundamental functions required to fulfill the desired autonomy: actuation, control, power supply, and sensing. The actuators and mechanisms could potentially be post-fabricated on the ASIC directly. This design makes for a modular architecture. The following components were shown to work in physical implementations or simulations: 1) a tunable motion controller for ultralow frequency actuation; 2) a nonvolatile memory and programming circuit to achieve automatic and one-time programming; 3) a high-voltage circuit with the highest reported breakdown voltage in standard 0.5 μm CMOS; 4) thermal actuators fabricated using CMOS compatible process; 5) a low-power mixed-signal computational architecture for robotic dynamics simulator; 6) a frequency-boost technique to achieve low jitter in ring oscillators. These contributions will be generally enabling for other systems with strict size and power constraints such as wireless sensor nodes.

Nanostructured catalysts for the development of the hydrogen economy

La catalyse joue un rôle essentiel dans de nombreuses applications industrielles telles que les industries pétrochimique et biochimique, ainsi que dans la production de polymères et pour la protection de l’environnement. La conception et la fabrication de catalyseurs efficaces et rentables est une étape importante pour résoudre un certain nombre de problèmes des nouvelles technologies de conversion chimique et de stockage de l’énergie. L’objectif de cette thèse est le développement de voies de synthèse efficaces et simples pour fabriquer des catalyseurs performants à base de métaux non nobles et d’examiner les aspects fondamentaux concernant la relation entre structure/composition et performance catalytique, notamment dans des processus liés à la production et au stockage de l’hydrogène. Dans un premier temps, une série d’oxydes métalliques mixtes (Cu/CeO2, CuFe/CeO2, CuCo/CeO2, CuFe2O4, NiFe2O4) nanostructurés et poreux ont été synthétisés grâce à une méthode améliorée de nanocasting. Les matériaux Cu/CeO2 obtenus, dont la composition et la structure poreuse peuvent être contrôlées, ont ensuite été testés pour l’oxydation préférentielle du CO dans un flux d’hydrogène dans le but d’obtenir un combustible hydrogène de haute pureté. Les catalyseurs synthétisés présentent une activité et une sélectivité élevées lors de l’oxydation sélective du CO en CO2. Concernant la question du stockage d’hydrogène, une voie de synthèse a été trouvée pour le composét mixte CuO-NiO, démontrant une excellente performance catalytique comparable aux catalyseurs à base de métaux nobles pour la production d’hydrogène à partir de l’ammoniaborane (aussi appelé borazane). L’activité catalytique du catalyseur étudié dans cette réaction est fortement influencée par la nature des précurseurs métalliques, la composition et la température de traitement thermique utilisées pour la préparation du catalyseur. Enfin, des catalyseurs de Cu-Ni supportés sur silice colloïdale ou sur des particules de carbone, ayant une composition et une taille variable, ont été synthétisés par un simple procédé d’imprégnation. Les catalyseurs supportés sur carbone sont stables et très actifs à la fois dans l’hydrolyse du borazane et la décomposition de l’hydrazine aqueuse pour la production d’hydrogène. Il a été démontré qu’un catalyseur optimal peut être obtenu par le contrôle de l’effet bi-métallique, l’interaction métal-support, et la taille des particules de métal.

Characterization of Non-linear Polymer Properties to Predict Process Induced Warpage and Residual Stress of Electronic Packages

Nonlinear thermo-mechanical properties of advanced polymers are crucial to accurate prediction of the process induced warpage and residual stress of electronics packages. The Fiber Bragg grating (FBG) sensor based method is advanced and implemented to determine temperature and time dependent nonlinear properties. The FBG sensor is embedded in the center of the cylindrical specimen, which deforms together with the specimen. The strains of the specimen at different loading conditions are monitored by the FBG sensor. Two main sources of the warpage are considered: curing induced warpage and coefficient of thermal expansion (CTE) mismatch induced warpage. The effective chemical shrinkage and the equilibrium modulus are needed for the curing induced warpage prediction. Considering various polymeric materials used in microelectronic packages, unique curing setups and procedures are developed for elastomers (extremely low modulus, medium viscosity, room temperature curing), underfill materials (medium modulus, low viscosity, high temperature curing), and epoxy molding compound (EMC: high modulus, high viscosity, high temperature pressure curing), most notably, (1) zero-constraint mold for elastomers; (2) a two-stage curing procedure for underfill materials and (3) an air-cylinder based novel setup for EMC. For the CTE mismatch induced warpage, the temperature dependent CTE and the comprehensive viscoelastic properties are measured. The cured cylindrical specimen with a FBG sensor embedded in the center is further used for viscoelastic property measurements. A uni-axial compressive loading is applied to the specimen to measure the time dependent Young’s modulus. The test is repeated from room temperature to the reflow temperature to capture the time-temperature dependent Young’s modulus. A separate high pressure system is developed for the bulk modulus measurement. The time temperature dependent bulk modulus is measured at the same temperatures as the Young’s modulus. The master curve of the Young’s modulus and bulk modulus of the EMC is created and a single set of the shift factors is determined from the time temperature superposition. The supplementary experiments are conducted to verify the validity of the assumptions associated with the linear viscoelasticity. The measured time-temperature dependent properties are further verified by a shadow moiré and Twyman/Green test.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

FLOW REGIME DRIVEN THERMAL ENHANCEMENT IN INTERNALLY-GROOVED TUBES

Internally-grooved refrigeration tubes maximize tube-side evaporative heat transfer rates and have been identified as a most promising technology for integration into compact cold plates. Unfortunately, the absence of phenomenological insights and physical models hinders the extrapolation of grooved-tube performance to new applications. The success of regime-based heat transfer correlations for smooth tubes has motivated the current effort to explore the relationship between flow regimes and enhanced heat transfer in internally-grooved tubes. In this thesis, a detailed analysis of smooth and internally-grooved tube data reveals that performance improvement in internally-grooved tubes at low-to-intermediate mass flux is a result of early flow regime transition. Based on this analysis, a new flow regime map and corresponding heat transfer coefficient correlation, which account for the increased wetted angle, turbulence, and Gregorig effects unique to internally-grooved tubes, were developed. A two-phase test facility was designed and fabricated to validate the newly-developed flow regime map and regime-based heat transfer coefficient correlation. As part of this setup, a non-intrusive optical technique was developed to study the dynamic nature of two-phase flows. It was found that different flow regimes result in unique temporally varying film thickness profiles. Using these profiles, quantitative flow regime identification measures were developed, including the ability to explain and quantify the more subtle transitions that exist between dominant flow regimes. Flow regime data, based on the newly-developed method, and heat transfer coefficient data, using infrared thermography, were collected for two-phase HFE-7100 flow in horizontal 2.62mm - 8.84mm diameter smooth and internally-grooved tubes with mass fluxes from 25-300 kg/m²s, heat fluxes from 4-56 kW/m², and vapor qualities approaching 1. In total, over 6500 combined data points for the adiabatic and diabatic smooth and internally-grooved tubes were acquired. Based on results from the experiments and a reinterpretation of data from independent researchers, it was established that heat transfer enhancement in internally-grooved tubes at low-to-intermediate mass flux is primarily due to early flow regime transition to Annular flow. The regime-based heat transfer coefficient outperformed empirical correlations from the literature, with mean and absolute deviations of 4.0% and 32% for the full range of data collected.

Defining a management strategy for the azorean natural thermal resources : valuing criteria identification

Dissertação de Mestrado, Gestão de Empresas (MBA), 23 de Maio de 2016, Universidade dos Açores.

A III-V channel field effect transistor for non-classical CMOS: process optimisation for improved gate stack function

This thesis describes a collection of studies into the electrical response of a III-V MOS stack comprising metal/GaGdO/GaAs layers as a function of fabrication process variables and the findings of those studies. As a result of this work, areas of improvement in the gate process module of a III-V heterostructure MOSFET were identified. Compared to traditional bulk silicon MOSFET design, one featuring a III-V channel heterostructure with a high-dielectric-constant oxide as the gate insulator provides numerous benefits, for example: the insulator can be made thicker for the same capacitance, the operating voltage can be made lower for the same current output, and improved output characteristics can be achieved without reducing the channel length further. It is known that transistors composed of III-V materials are most susceptible to damage induced by radiation and plasma processing. These devices utilise sub-10 nm gate dielectric films, which are prone to contamination, degradation and damage. Therefore, throughout the course of this work, process damage and contamination issues, as well as various techniques to mitigate or prevent those have been investigated through comparative studies of III-V MOS capacitors and transistors comprising various forms of metal gates, various thicknesses of GaGdO dielectric, and a number of GaAs-based semiconductor layer structures. Transistors which were fabricated before this work commenced, showed problems with threshold voltage control. Specifically, MOSFETs designed for normally-off (VTH > 0) operation exhibited below-zero threshold voltages. With the results obtained during this work, it was possible to gain an understanding of why the transistor threshold voltage shifts as the gate length decreases and of what pulls the threshold voltage downwards preventing normally-off device operation. Two main culprits for the negative VTH shift were found. The first was radiation damage induced by the gate metal deposition process, which can be prevented by slowing down the deposition rate. The second was the layer of gold added on top of platinum in the gate metal stack which reduces the effective work function of the whole gate due to its electronegativity properties. Since the device was designed for a platinum-only gate, this could explain the below zero VTH. This could be prevented either by using a platinum-only gate, or by matching the layer structure design and the actual gate metal used for the future devices. Post-metallisation thermal anneal was shown to mitigate both these effects. However, if post-metallisation annealing is used, care should be taken to ensure it is performed before the ohmic contacts are formed as the thermal treatment was shown to degrade the source/drain contacts. In addition, the programme of studies this thesis describes, also found that if the gate contact is deposited before the source/drain contacts, it causes a shift in threshold voltage towards negative values as the gate length decreases, because the ohmic contact anneal process affects the properties of the underlying material differently depending on whether it is covered with the gate metal or not. In terms of surface contamination; this work found that it causes device-to-device parameter variation, and a plasma clean is therefore essential. This work also demonstrated that the parasitic capacitances in the system, namely the contact periphery dependent gate-ohmic capacitance, plays a significant role in the total gate capacitance. This is true to such an extent that reducing the distance between the gate and the source/drain ohmic contacts in the device would help with shifting the threshold voltages closely towards the designed values. The findings made available by the collection of experiments performed for this work have two major applications. Firstly, these findings provide useful data in the study of the possible phenomena taking place inside the metal/GaGdO/GaAs layers and interfaces as the result of chemical processes applied to it. In addition, these findings allow recommendations as to how to best approach fabrication of devices utilising these layers.