Ab-initio study of hydrogen technology materials for hydrogen storage and proton conduction

This dissertation deals with two specific aspects of a potential hydrogen-based energy economy, namely the problems of energy storage and energy conversion. In order to contribute to the solution of these problems, the structural and dynamical properties of two promising materials for hydrogen storage (lithium imide/amide) and proton conduction (poly[vinyl phosphonic acid]) are modeled on an atomistic scale by means of first principles molecular dynamics simulation methods.rnrnrnIn the case of the hydrogen storage system lithium amide/imide (LiNH_2/Li_2NH), the focus was on the interplay of structural features and nuclear quantum effects. For these calculations, Path-Integral Molecular Dynamics (PIMD) simulations were used. The structures of these materials at room temperature were elucidated; in collaboration with an experimental group, a very good agreement between calculated and experimental solid-state 1H-NMR chemical shifts was observed. Specifically, the structure of Li_2NH features a disordered arrangement of the Li lattice, which was not reported in previous studies. In addition, a persistent precession of the NH bonds was observed in our simulations. We provide evidence that this precession is the consequence of a toroid-shaped effective potential, in which the protons in the material are immersed. This potential is essentially flat along the torus azimuthal angle, which might lead to important quantum delocalization effects of the protons over the torus.rnrnOn the energy conversion side, the dynamics of protons in a proton conducting polymer (poly[vinyl phosphonic acid], PVPA) was studied by means of a steered ab-initio Molecular Dynamics approach applied on a simplified polymer model. The focus was put on understanding the microscopic proton transport mechanism in polymer membranes, and on characterizing the relevance of the local environment. This covers particularly the effect of water molecules, which participate in the hydrogen bonding network in the material. The results indicate that these water molecules are essential for the effectiveness of proton conduction. A water-mediated Grotthuss mechanism is identified as the main contributor to proton conduction, which agrees with the experimentally observed decay on conductivity for the same material in the absence of water molecules.rnrnThe gain in understanding the microscopic processes and structures present in this materials can help the development of new materials with improved properties, thus contributing to the solution of problems in the implementation of fuel cells.

A multimodal tablet-based interface for designing and reviewing 3D engineering models

The ability to view and interact with 3D models has been happening for a long time. However, vision-based 3D modeling has only seen limited success in applications, as it faces many technical challenges. Hand-held mobile devices have changed the way we interact with virtual reality environments. Their high mobility and technical features, such as inertial sensors, cameras and fast processors, are especially attractive for advancing the state of the art in virtual reality systems. Also, their ubiquity and fast Internet connection open a path to distributed and collaborative development. However, such path has not been fully explored in many domains. VR systems for real world engineering contexts are still difficult to use, especially when geographically dispersed engineering teams need to collaboratively visualize and review 3D CAD models. Another challenge is the ability to rendering these environments at the required interactive rates and with high fidelity. In this document it is presented a virtual reality system mobile for visualization, navigation and reviewing large scale 3D CAD models, held under the CEDAR (Collaborative Engineering Design and Review) project. It’s focused on interaction using different navigation modes. The system uses the mobile device's inertial sensors and camera to allow users to navigate through large scale models. IT professionals, architects, civil engineers and oil industry experts were involved in a qualitative assessment of the CEDAR system, in the form of direct user interaction with the prototypes and audio-recorded interviews about the prototypes. The lessons learned are valuable and are presented on this document. Subsequently it was prepared a quantitative study on the different navigation modes to analyze the best mode to use it in a given situation.

Thermal, stress, and traps effects in AlGaN/GaN HEMTs

GaN y AlN son materiales semiconductores piezoeléctricos del grupo III-V. La heterounión AlGaN/GaN presenta una elevada carga de polarización tanto piezoeléctrica como espontánea en la intercara, lo que genera en su cercanía un 2DEG de grandes concentración y movilidad. Este 2DEG produce una muy alta potencia de salida, que a su vez genera una elevada temperatura de red. Las tensiones de puerta y drenador provocan un stress piezoeléctrico inverso, que puede afectar a la carga de polarización piezoeléctrica y así influir la densidad 2DEG y las características de salida. Por tanto, la física del dispositivo es relevante para todos sus aspectos eléctricos, térmicos y mecánicos. En esta tesis se utiliza el software comercial COMSOL, basado en el método de elementos finitos (FEM), para simular el comportamiento integral electro-térmico, electro-mecánico y electro-térmico-mecánico de los HEMTs de GaN. Las partes de acoplamiento incluyen el modelo de deriva y difusión para el transporte electrónico, la conducción térmica y el efecto piezoeléctrico. Mediante simulaciones y algunas caracterizaciones experimentales de los dispositivos, hemos analizado los efectos térmicos, de deformación y de trampas. Se ha estudiado el impacto de la geometría del dispositivo en su auto-calentamiento mediante simulaciones electro-térmicas y algunas caracterizaciones eléctricas. Entre los resultados más sobresalientes, encontramos que para la misma potencia de salida la distancia entre los contactos de puerta y drenador influye en generación de calor en el canal, y así en su temperatura. El diamante posee une elevada conductividad térmica. Integrando el diamante en el dispositivo se puede dispersar el calor producido y así reducir el auto-calentamiento, al respecto de lo cual se han realizado diversas simulaciones electro-térmicas. Si la integración del diamante es en la parte superior del transistor, los factores determinantes para la capacidad disipadora son el espesor de la capa de diamante, su conductividad térmica y su distancia a la fuente de calor. Este procedimiento de disipación superior también puede reducir el impacto de la barrera térmica de intercara entre la capa adaptadora (buffer) y el substrato. La muy reducida conductividad eléctrica del diamante permite que pueda contactar directamente el metal de puerta (muy cercano a la fuente de calor), lo que resulta muy conveniente para reducir el auto-calentamiento del dispositivo con polarización pulsada. Por otra parte se simuló el dispositivo con diamante depositado en surcos atacados sobre el sustrato como caminos de disipación de calor (disipador posterior). Aquí aparece una competencia de factores que influyen en la capacidad de disipación, a saber, el surco atacado contribuye a aumentar la temperatura del dispositivo debido al pequeño tamaño del disipador, mientras que el diamante disminuiría esa temperatura gracias a su elevada conductividad térmica. Por tanto, se precisan capas de diamante relativamente gruesas para reducer ele efecto de auto-calentamiento. Se comparó la simulación de la deformación local en el borde de la puerta del lado cercano al drenador con estructuras de puerta estándar y con field plate, que podrían ser muy relevantes respecto a fallos mecánicos del dispositivo. Otras simulaciones se enfocaron al efecto de la deformación intrínseca de la capa de diamante en el comportamiento eléctrico del dispositivo. Se han comparado los resultados de las simulaciones de la deformación y las características eléctricas de salida con datos experimentales obtenidos por espectroscopía micro-Raman y medidas eléctricas, respectivamente. Los resultados muestran el stress intrínseco en la capa producido por la distribución no uniforme del 2DEG en el canal y la región de acceso. Además de aumentar la potencia de salida del dispositivo, la deformación intrínseca en la capa de diamante podría mejorar la fiabilidad del dispositivo modulando la deformación local en el borde de la puerta del lado del drenador. Finalmente, también se han simulado en este trabajo los efectos de trampas localizados en la superficie, el buffer y la barrera. Las medidas pulsadas muestran que tanto las puertas largas como las grandes separaciones entre los contactos de puerta y drenador aumentan el cociente entre la corriente pulsada frente a la corriente continua (lag ratio), es decir, disminuir el colapse de corriente (current collapse). Este efecto ha sido explicado mediante las simulaciones de los efectos de trampa de superficie. Por su parte, las referidas a trampas en el buffer se enfocaron en los efectos de atrapamiento dinámico, y su impacto en el auto-calentamiento del dispositivo. Se presenta también un modelo que describe el atrapamiento y liberación de trampas en la barrera: mientras que el atrapamiento se debe a un túnel directo del electrón desde el metal de puerta, el desatrapamiento consiste en la emisión del electrón en la banda de conducción mediante túnel asistido por fonones. El modelo también simula la corriente de puerta, debida a la emisión electrónica dependiente de la temperatura y el campo eléctrico. Además, también se ilustra la corriente de drenador dependiente de la temperatura y el campo eléctrico. ABSTRACT GaN and AlN are group III-V piezoelectric semiconductor materials. The AlGaN/GaN heterojunction presents large piezoelectric and spontaneous polarization charge at the interface, leading to high 2DEG density close to the interface. A high power output would be obtained due to the high 2DEG density and mobility, which leads to elevated lattice temperature. The gate and drain biases induce converse piezoelectric stress that can influence the piezoelectric polarization charge and further influence the 2DEG density and output characteristics. Therefore, the device physics is relevant to all the electrical, thermal, and mechanical aspects. In this dissertation, by using the commercial finite-element-method (FEM) software COMSOL, we achieved the GaN HEMTs simulation with electro-thermal, electro-mechanical, and electro-thermo-mechanical full coupling. The coupling parts include the drift-diffusion model for the electron transport, the thermal conduction, and the piezoelectric effect. By simulations and some experimental characterizations, we have studied the device thermal, stress, and traps effects described in the following. The device geometry impact on the self-heating was studied by electro-thermal simulations and electrical characterizations. Among the obtained interesting results, we found that, for same power output, the distance between the gate and drain contact can influence distribution of the heat generation in the channel and thus influence the channel temperature. Diamond possesses high thermal conductivity. Integrated diamond with the device can spread the generated heat and thus potentially reduce the device self-heating effect. Electro-thermal simulations on this topic were performed. For the diamond integration on top of the device (top-side heat spreading), the determinant factors for the heat spreading ability are the diamond thickness, its thermal conductivity, and its distance to the heat source. The top-side heat spreading can also reduce the impact of thermal boundary resistance between the buffer and the substrate on the device thermal behavior. The very low electrical conductivity of diamond allows that it can directly contact the gate metal (which is very close to the heat source), being quite convenient to reduce the self-heating for the device under pulsed bias. Also, the diamond coated in vias etched in the substrate as heat spreading path (back-side heat spreading) was simulated. A competing mechanism influences the heat spreading ability, i.e., the etched vias would increase the device temperature due to the reduced heat sink while the coated diamond would decrease the device temperature due to its higher thermal conductivity. Therefore, relative thick coated diamond is needed in order to reduce the self-heating effect. The simulated local stress at the gate edge of the drain side for the device with standard and field plate gate structure were compared, which would be relevant to the device mechanical failure. Other stress simulations focused on the intrinsic stress in the diamond capping layer impact on the device electrical behaviors. The simulated stress and electrical output characteristics were compared to experimental data obtained by micro-Raman spectroscopy and electrical characterization, respectively. Results showed that the intrinsic stress in the capping layer caused the non-uniform distribution of 2DEG in the channel and the access region. Besides the enhancement of the device power output, intrinsic stress in the capping layer can potentially improve the device reliability by modulating the local stress at the gate edge of the drain side. Finally, the surface, buffer, and barrier traps effects were simulated in this work. Pulsed measurements showed that long gates and distances between gate and drain contact can increase the gate lag ratio (decrease the current collapse). This was explained by simulations on the surface traps effect. The simulations on buffer traps effects focused on illustrating the dynamic trapping/detrapping in the buffer and the self-heating impact on the device transient drain current. A model was presented to describe the trapping and detrapping in the barrier. The trapping was the electron direct tunneling from the gate metal while the detrapping was the electron emission into the conduction band described by phonon-assisted tunneling. The reverse gate current was simulated based on this model, whose mechanism can be attributed to the temperature and electric field dependent electron emission in the barrier. Furthermore, the mechanism of the device bias via the self-heating and electric field impact on the electron emission and the transient drain current were also illustrated.

A multimodal tablet-based interface for designing and reviewing 3D engineering models

The ability to view and interact with 3D models has been happening for a long time. However, vision-based 3D modeling has only seen limited success in applications, as it faces many technical challenges. Hand-held mobile devices have changed the way we interact with virtual reality environments. Their high mobility and technical features, such as inertial sensors, cameras and fast processors, are especially attractive for advancing the state of the art in virtual reality systems. Also, their ubiquity and fast Internet connection open a path to distributed and collaborative development. However, such path has not been fully explored in many domains. VR systems for real world engineering contexts are still difficult to use, especially when geographically dispersed engineering teams need to collaboratively visualize and review 3D CAD models. Another challenge is the ability to rendering these environments at the required interactive rates and with high fidelity. In this document it is presented a virtual reality system mobile for visualization, navigation and reviewing large scale 3D CAD models, held under the CEDAR (Collaborative Engineering Design and Review) project. It’s focused on interaction using different navigation modes. The system uses the mobile device's inertial sensors and camera to allow users to navigate through large scale models. IT professionals, architects, civil engineers and oil industry experts were involved in a qualitative assessment of the CEDAR system, in the form of direct user interaction with the prototypes and audio-recorded interviews about the prototypes. The lessons learned are valuable and are presented on this document. Subsequently it was prepared a quantitative study on the different navigation modes to analyze the best mode to use it in a given situation.

Interactions at the head-tape interface of a linear tape system

Many of the recent improvements in the capacity of data cartridge systems have been achieved through the use of narrower tracks, higher linear densities and continuous servo tracking with multi-channel heads. These changes have produced new tribological problems at the head/tape interface. It is crucial that the tribology of such systems is understood and this will continue since increasing storage capacities and faster transfer rates are constantly being sought. Chemical changes in the surface of single and dual layer MP tape have been correlated to signal performance. An accelerated tape tester, consisting of a custom made cycler ("loop tester"), was used to ascertain if results could be produced that were representative of a real tape drive system. A second set of experiments used a modified tape drive (Georgens cycler), which allowed the effects of the tape transport system on the tape surface to be studied. To isolate any effects on the tape surface due to the head/tape interface, read/write heads were not fitted to the cycler. Two further sets of experiments were conducted which included a head in the tape path. This allowed the effects of the head/tape interface on the physical and chemical properties of the head and tape surfaces to be investigated. It was during the final set of experiments that the effect on the head/tape interface, of an energised MR element, was investigated. The effect of operating each cycler at extreme relative humidity and temperature was investigated through the use of an environmental chamber. Extensive use was made of surface specific analytical techniques such as XPS, AFM, AES, and SEM to study the physical and chemical changes that occur at the head/tape interface. Results showed that cycling improved the signal performance of all the tapes tested. The data cartridge drive belt had an effect on the chemical properties of the tape surface on which it was in contact. Also binder degradation occurred for each tape and appeared to be greater at higher humidity. Lubricant was generally seen to migrate to the tape surface with cycling. Any surface changes likely to affect signal output occurred at the head surface rather than the tape.

User interface design support for the development of knowledge-based systems

The present scarcity of operational knowledge-based systems (KBS) has been attributed, in part, to an inadequate consideration shown to user interface design during development. From a human factors perspective the problem has stemmed from an overall lack of user-centred design principles. Consequently the integration of human factors principles and techniques is seen as a necessary and important precursor to ensuring the implementation of KBS which are useful to, and usable by, the end-users for whom they are intended. Focussing upon KBS work taking place within commercial and industrial environments, this research set out to assess both the extent to which human factors support was presently being utilised within development, and the future path for human factors integration. The assessment consisted of interviews conducted with a number of commercial and industrial organisations involved in KBS development; and a set of three detailed case studies of individual KBS projects. Two of the studies were carried out within a collaborative Alvey project, involving the Interdisciplinary Higher Degrees Scheme (IHD) at the University of Aston in Birmingham, BIS Applied Systems Ltd (BIS), and the British Steel Corporation. This project, which had provided the initial basis and funding for the research, was concerned with the application of KBS to the design of commercial data processing (DP) systems. The third study stemmed from involvement on a KBS project being carried out by the Technology Division of the Trustees Saving Bank Group plc. The preliminary research highlighted poor human factors integration. In particular, there was a lack of early consideration of end-user requirements definition and user-centred evaluation. Instead concentration was given to the construction of the knowledge base and prototype evaluation with the expert(s). In response to this identified problem, a set of methods was developed that was aimed at encouraging developers to consider user interface requirements early on in a project. These methods were then applied in the two further projects, and their uptake within the overall development process was monitored. Experience from the two studies demonstrated that early consideration of user interface requirements was both feasible, and instructive for guiding future development work. In particular, it was shown a user interface prototype could be used as a basis for capturing requirements at the functional (task) level, and at the interface dialogue level. Extrapolating from this experience, a KBS life-cycle model is proposed which incorporates user interface design (and within that, user evaluation) as a largely parallel, rather than subsequent, activity to knowledge base construction. Further to this, there is a discussion of several key elements which can be seen as inhibiting the integration of human factors within KBS development. These elements stem from characteristics of present KBS development practice; from constraints within the commercial and industrial development environments; and from the state of existing human factors support.

Systematic Molecular Phenotyping: A Path Toward Precision Emergency Medicine?

Precision medicine is an emerging approach to disease treatment and prevention that considers variability in patient genes, environment, and lifestyle. However, little has been written about how such research impacts emergency care. Recent advances in analytical techniques have made it possible to characterize patients in a more comprehensive and sophisticated fashion at the molecular level, promising highly individualized diagnosis and treatment. Among these techniques are various systematic molecular phenotyping analyses (e.g., genomics, transcriptomics, proteomics, and metabolomics). Although a number of emergency physicians use such techniques in their research, widespread discussion of these approaches has been lacking in the emergency care literature and many emergency physicians may be unfamiliar with them. In this article, we briefly review the underpinnings of such studies, note how they already impact acute care, discuss areas in which they might soon be applied, and identify challenges in translation to the emergency department (ED). While such techniques hold much promise, it is unclear whether the obstacles to translating their findings to the ED will be overcome in the near future. Such obstacles include validation, cost, turnaround time, user interface, decision support, standardization, and adoption by end-users.

User Interface Abstraction for enabling TV set based Inclusive Access to the Information Society

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Quantificação de fluxos de mercúrio gasoso na interface solo/atmosfera utilizando câmara de fluxo dinâmica: aplicação na bacia do Rio Negro

Gaseous mercury sampling conditions were optimized and a dynamic flux chamber was used to measure the air/surface exchange of mercury in some areas of the Negro river basin with different vegetal coverings. At the two forest sites (flooding and non-flooding), low mercury fluxes were observed: maximum of 3 pmol m-2 h-1 - day and minimum of -1 pmol m-2 h-1 - night. At the deforested site, the mercury fluxes were higher and always positive: maximum of 26 pmol m-2 h-1 - day and 17 pmol m-2 h-1 - night. Our results showed that deforestation could be responsible for significantly increasing soil Hg emissions, mainly because of the high soil temperatures reached at deforested sites.

Production and body composition traits of broilers in relation to breast weight evaluated by path analysis

Breast weight has great economic importance in poultry industry, and may be associated with other variables. This work aimed to estimate phenotypic correlations between performance (live body weight at 7 and 28 days, and at slaughter, and depth of the breast muscle measured by ultrasonography), carcass (eviscerated body weight and leg weight) and body composition (heart, liver and abdominal fat weight) traits in a broiler line, and quantify the direct and indirect influence of these traits on breast weight. Path analysis was used by expanding the matrix of partial correlation in coefficients which give the direct influence of one trait on another, regardless the effect of the other traits. The simultaneous maintenance of live body weight at slaughter and eviscerated body weight in the matrix of correlations might be harmful for statistical analysis involving systems of normal equations, like path analysis, due to the observed multicollinearity. The live body weight at slaughter and the depth of the breast muscle as measured by ultrasonography directly affected breast weight and were identified as the most responsible factors for the magnitude of the correlation coefficients obtained between the studied traits and breast weight. Individual pre-selection for these traits could favor an increased breast weight in the future reproducer candidates of this line if the broilers' environmental conditions and housing are maintained, since the live body weight at slaughter and the depth of breast muscle measured by ultrasonography were directly related to breast weight.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

Um relato de vida, um caminho institucional: juventude, medicalização e sofrimentos sociais

Apresenta-se uma história de vida com o intuito de traçar uma análise das manifestações particulares de uma trajetória individual em diálogo com os elementos presentes na vida de jovens de grupos populares. Foca-se na discussão dos equipamentos sociais na produção de sentidos, lugares e sofrimentos em algumas vidas, ocasionando processos em que "doenças" e medicalização são geradas a partir de problemas sociais. Com base nos pressupostos da pesquisa etnográfica, acompanhou-se a trajetória de uma jovem, por quatro anos, em sua passagem por serviços sociais de atenção à infância e à juventude, assim como de saúde mental. Considera-se que as políticas sociais devem intervir com jovens sob uma compreensão ampliada dos problemas sociais, sendo que o campo da atenção em saúde mental, em conexão com a esfera social, deve cuidar das situações de sofrimento sem que haja a homogeneização das necessidades, traduzindo-se numa iatrogenia e na medicalização do social.

Motor Nerve-Conduction Studies in Obstetric Brachial Plexopathy for a Selection of Patients with a Poor Outcome

Background: The criteria and timing for nerve surgery in infants with obstetric brachial plexopathy remain controversial. Our aim was to develop a new method for early prognostic assessment to assist this decision process. Methods: Fifty-four patients with unilateral obstetric brachial plexopathy who were ten to sixty days old underwent bilateral motor-nerve-conduction studies of the axillary, musculocutaneous, proximal radial, distal radial, median, and ulnar nerves. The ratio between the amplitude of the compound muscle action potential of the affected limb and that of the healthy side was called the axonal viability index. The patients were followed and classified in three groups according to the clinical outcome. We analyzed the receiver operating characteristic curve of each index to define the best cutoff point to detect patients with a poor recovery. Results: The best cutoff points on the axonal viability index for each nerve (and its sensitivity and specificity) were <10% (88% and 89%, respectively) for the axillary nerve, 0% (88% and 73%) for the musculocutaneous nerve, <20% (82% and 97%) for the proximal radial nerve, <50% (82% and 97%) for the distal radial nerve, and <50% (59% and 97%) for the ulnar nerve. The indices from the proximal radial, distal radial, and ulnar nerves had better specificities compared with the most frequently used clinical criterion: absence of biceps function at three months of age. Conclusions: The axonal viability index yields an earlier and more specific prognostic estimation of obstetric brachial plexopathy than does the clinical criterion of biceps function, and we believe it may be useful in determining surgical indications in these patients.

Ultrastructure of the Interface between Periodontal Tissues and Titanium Mini-Implants

Objective: To describe the ultrastructure of the interface between periodontal tissues and titanium mini-implants in rat mandibles. Materials and Methods: A titanium mini-implant was placed between the buccal roots of the mandibular first molar of 24 adult rats. After 21, 30, 45, 60, 90, and 120 days of implantation, the mandibular portion was removed and fixed in cacodylate-buffered 2% glutaraldehyde + 2.5% formaldehyde. The material was decalcified and processed for scanning and transmission electron microscopy. Results: Ultrastructural analysis revealed a thin cementum-like layer at longer times after implantation at the areas in which the periodontal ligament was in contact with the implant. Conclusions: The alveolar bone and the periodontal ligament reorganized their constituents around the implant, and a thin cementum-like layer was formed at longer times after implantation at the areas in which the periodontal ligament was in contact with the implant. (Angle Orthod. 2010;80:459-435.)