CoO nanoparticles embedded in three-dimensional nitrogen/sulfur co-doped carbon nanofiber networks as a bifunctional catalyst for oxygen reduction/evolution reactions

High-performance and low-cost bifunctional electrocatalysts play crucial roles in oxygen reduction and evolution reactions. Herein, a novel three-dimensional (3D) bifunctional electrocatalyst was prepared by embedding CoO nanoparticles into nitrogen and sulfur co-doped carbon nanofiber networks (denoted as CoO@N/S-CNF) through a facile approach. The carbon nanofiber networks were derived from a nanostructured biological material which provided abundant functional groups to nucleate and anchor nanoparticles while retaining its interconnected 3D porous structure. The composite possesses a high specific surface area and graphitization degree, which favors both mass transport and charge transfer for electrochemical reaction. The CoO@N/S-CNF not only exhibits highly efficient catalytic activity towards oxygen reduction reaction (ORR) in alkaline media with an onset potential of about 0.84 V, but also shows better stability and stronger resistance to methanol than Pt/C. Furthermore, it only needs an overpotential of 1.55 V to achieve a current density of 10 mA cm^-2, suggesting that it is an efficient electrocatalyst for oxygen evolution reaction (OER). The ΔE value (oxygen electrode activity parameter) of CoO@N/S-CNF is calculated to be 0.828 V, which demonstrates that the composite could be a promising bifunctional electrocatalyst for both ORR and OER.

Flash-Sintering and Characterization of La0.8Sr0.2Ga0.8Mg0.2O3-δ Electrolytes for Solid Oxide Fuel Cells

La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM), a promising electrolyte material for intermediate temperature solid oxide fuel cells, can be sintered to a fully dense state by a flash-sintering technique. In this work, LSGM is sintered by the current-limiting flash-sintering process at 690°C under an electric field of 100 V cm^-1, in comparison with up to 1400°C or even higher temperature in conventional furnace sintering. The resultant LSGM samples are investigated by scanning electron microscopy, X-ray diffraction, and electrochemical impedance spectroscopy. The SEM images exhibit well-densified microstructures while XRD results show that the perovskite structure after flash-sintering does not changed. EIS results show that the conductivity of LSGM sintered by the current-limiting flash-sintering process increases with sintering current density value. The conductivity of samples sintered at 120 mA mm^-2 reaches 0.049 σ cm^-1 at 800°C, which is approximate to the value of conventional sintered LSGM samples at 1400°C. Additionally, the flash-sintering process is interpreted by Joule heating theory. Therefore, the current-limiting flash-sintering technique is proved to be an energy-efficient and eligible approach for the densification of LSGM and other materials requiring high sintering temperature.

Radon: indicative atlas for Northern Ireland

Radon Affected Area potential in Northern Ireland was estimated using a joint mapping method. This method allows variation of radon potential both between and within geological units. The estimates are based on the results of radon measurements and geological information for more than 23,000 homes. Elevated radon potential is presented here as indicative maps based on the highest radon potential for each 1 kilometre square of the Irish grid. The full definitive detail is published as a digital dataset for geographical information systems, which can be licensed. The estimated radon potential for an individual home can be obtained through the Public Health England (PHE) UKradon website. The work was partially funded by the Northern Ireland Environment Agency and was prepared jointly by PHE and the British Geological Survey. This report replaces the 2009 review and atlas (HPA-RPD-061).

Preparation of Excitation Sources to Portable X-Ray Spectrometer by Recovering 241am from Radioactive Lightning Conductor

With the prohibition of the use of radioactive lightning conductor in Brazil, this material passed to be collected and stored as radioactive waste in the waste deposits of The Brazilian National Nuclear Energy Commission (CNEN). The majority of these lightning conductor used as radioactive source 241Am with activity varying of 1 the 5 mCi. In this work are presented preliminary studies by recovering of 241Am through the electroplating technique, in order to posterior use as sources to portable X-rays fluorescence spectrometer. The 241Am sources have been removed from lightning conductor and dissolved in acid solution. The solution presented an activity of 0,6 Ci L-1. Small amounts of this solution were added to some electrolytes and tested in order to evaluate optimum electrolyte for deposition of 241Am. It was studied as electrolytes: HNO3 (0,2 mol L-1), NH4Cl (5,0 mol L-1) and a mixture of KCN and K2CO3 (in the rate of 2,0 g of each per liter). Yields of up to 90% were obtained applied a current density of 50 mA cm-2.

Evaluating New Matrix Pooled Testing Methods for Detecting HIV Treatment Failure with and without Covariate Information

Thesis (Master's)--University of Washington, 2016-08

Self-Assembled InAs/GaAs Quantum Dot Solar Cells

Our work focuses on experimental and theoretical studies aimed at establishing a fundamental understanding of the principal electrical and optical processes governing the operation of quantum dot solar cells (QDSC) and their feasibility for the realization of intermediate band solar cell (IBSC). Uniform performance QD solar cells with high conversion efficiency have been fabricated using carefully calibrated process recipes as the basis of all reliable experimental characterization. The origin for the enhancement of the short circuit current density (Jsc) in QD solar cells was carefully investigated. External quantum efficiency (EQE) measurements were performed as a measure of the below bandgap distribution of transition states. In this work, we found that the incorporation of self-assembled quantum dots (QDs) interrupts the lattice periodicity and introduce a greatly broadened tailing density of states extending from the bandedge towards mid-gap. A below-bandgap density of states (DOS) model with an extended Urbach tail has been developed. In particular, the below-bandgap photocurrent generation has been attributed to transitions via confined energy states and background continuum tailing states. Photoluminescence measurement is used to measure the energy level of the lowest available state and the coupling effect between QD states and background tailing states because it results from a non-equilibrium process. A basic I-V measurement reveals a degradation of the open circuit voltage (Voc) of QD solar cells, which is related to a one sub-bandgap photon absorption process followed by a direct collection of the generated carriers by the external circuit. We have proposed a modified Shockley-Queisser (SQ) model that predicts the degradation of Voc compared with a reference bulk device. Whenever an energy state within the forbidden gap can facilitate additional absorption, it can facilitate recombination as well. If the recombination is non-radiative, it is detrimental to solar cell performance. We have also investigated the QD trapping effects as deep level energy states. Without an efficient carrier extraction pathway, the QDs can indeed function as mobile carriers traps. Since hole energy levels are mostly connected with hole collection under room temperature, the trapping effect is more severe for electrons. We have tried to electron-dope the QDs to exert a repulsive Coulomb force to help improve the carrier collection efficiency. We have experimentally observed a 30% improvement of Jsc for 4e/dot devices compared with 0e/dot devices. Electron-doping helps with better carrier collection efficiency, however, we have also measured a smaller transition probability from valance band to QD states as a direct manifestation of the Pauli Exclusion Principle. The non-linear performance is of particular interest. With the availability of laser with on-resonance and off-resonance excitation energy, we have explored the photocurrent enhancement by a sequential two-photon absorption (2PA) process via the intermediate states. For the first time, we are able to distinguish the nonlinearity effect by 1PA and 2PA process. The observed 2PA current under off-resonant and on-resonant excitation comes from a two-step transition via the tailing states instead of the QD states. However, given the existence of an extended Urbach tail and the small number of photons available for the intermediate states to conduction band transition, the experimental results suggest that with the current material system, the intensity requirement for an observable enhancement of photocurrent via a 2PA process is much higher than what is available from concentrated sun light. In order to realize the IBSC model, a matching transition strength needs to be achieved between valance band to QD states and QD states to conduction band. However, we have experimentally shown that only a negligible amount of signal can be observed at cryogenic temperature via the transition from QD states to conduction band under a broadband IR source excitation. Based on the understanding we have achieved, we found that the existence of the extended tailing density of states together with the large mismatch of the transition strength from VB to QD and from QD to CB, has systematically put into question the feasibility of the IBSC model with QDs.

Review of greenhouse gas emissions from the storage and land application of farm dairy effluent

The amounts of farm dairy effluent stored in ponds and irrigated to land have steadily increased with the steady growth of New Zealand's dairy industry. About 80% of dairy farms now operate with effluent storage ponds allowing deferred irrigation. These storage and irrigation practices cause emissions of greenhouse gases (GHG) and ammonia. The current knowledge of the processes causing these emissions and the amounts emitted is reviewed here. Methane emissions from ponds are the largest contributor to the total GHG emissions from effluent in managed manure systems in New Zealand. Nitrous oxide emissions from anaerobic ponds are negligible, while ammonia emissions vary widely between different studies, probably because they depend strongly on pH and manure composition. The second-largest contribution to GHG emissions from farm dairy effluent comes from nitrous oxide emissions from land application. Ammonia emissions from land application of effluent in New Zealand were found to be less than those reported elsewhere from the application of slurries. Recent studies have suggested that New Zealand's current GHG inventory method to estimate methane emissions from effluent ponds should be revised. The increasing importance of emissions from ponds, while being a challenge for the inventory, also provides an opportunity to achieve mitigation of emissions due to the confined location of where these emissions occur. © 2015 © 2015 The Royal Society of New Zealand.

MICROSCALE DIELECTRIC ANTI-REFLECTION COATINGS FOR PHOTOVOLTAICS

In order to power our planet for the next century, clean energy technologies need to be developed and deployed. Photovoltaic solar cells, which convert sunlight into electricity, are a clear option; however, they currently supply 0.1% of the US electricity due to the relatively high cost per Watt of generation. Thus, our goal is to create more power from a photovoltaic device, while simultaneously reducing its price. To accomplish this goal, we are creating new high efficiency anti-reflection coatings that allow more of the incident sunlight to be converted to electricity, using simple and inexpensive coating techniques that enable reduced manufacturing costs. Traditional anti-reflection coatings (consisting of thin layers of non-absorbing materials) rely on the destructive interference of the reflected light, causing more light to enter the device and subsequently get absorbed. While these coatings are used on nearly all commercial cells, they are wavelength dependent and are deposited using expensive processes that require elevated temperatures, which increase production cost and can be detrimental to some temperature sensitive solar cell materials. We are developing two new classes of anti-reflection coatings (ARCs) based on textured dielectric materials: (i) a transparent, flexible paper technology that relies on optical scattering and reduced refractive index contrast between the air and semiconductor and (ii) silicon dioxide (SiO2) nanosphere arrays that rely on collective optical resonances. Both techniques improve solar cell absorption and ultimately yield high efficiency, low cost devices. For the transparent paper-based ARCs, we have recently shown that they improve solar cell efficiencies for all angles of incident illumination reducing the need for costly tracking of the sun’s position. For a GaAs solar cell, we achieved a 24% improvement in the power conversion efficiency using this simple coating. Because the transparent paper is made from an earth abundant material (wood pulp) using an easy, inexpensive and scalable process, this type of ARC is an excellent candidate for future solar technologies. The coatings based on arrays of dielectric nanospheres also show excellent potential for inexpensive, high efficiency solar cells. The fabrication process is based on a Meyer rod rolling technique, which can be performed at room-temperature and applied to mass production, yielding a scalable and inexpensive manufacturing process. The deposited monolayer of SiO2 nanospheres, having a diameter of 500 nm on a bare Si wafer, leads to a significant increase in light absorption and a higher expected current density based on initial simulations, on the order of 15-20%. With application on a Si solar cell containing a traditional anti-reflection coating (Si3N4 thin-film), an additional increase in the spectral current density is observed, 5% beyond what a typical commercial device would achieve. Due to the coupling between the spheres originated from Whispering Gallery Modes (WGMs) inside each nanosphere, the incident light is strongly coupled into the high-index absorbing material, leading to increased light absorption. Furthermore, the SiO2 nanospheres scatter and diffract light in such a way that both the optical and electrical properties of the device have little dependence on incident angle, eliminating the need for solar tracking. Because the layer can be made with an easy, inexpensive, and scalable process, this anti-reflection coating is also an excellent candidate for replacing conventional technologies relying on complicated and expensive processes.

Comprendre l’interaction entre la douleur et le système moteur : une étude novatrice combinant la stimulation magnétique transcrânienne et l’électroencéphalographie

Résumé : L’interaction entre la douleur et le système moteur est bien connue en clinique et en réadaptation. Il est sans surprise que la douleur est un phénomène considérablement invalidant, affectant la qualité de vie de ceux et celles qui en souffrent. Toutefois, les bases neurophysiologiques qui sous-tendent cette interaction demeurent, encore aujourd’hui, mal comprises. Le but de la présente étude était de mieux comprendre les mécanismes corticaux impliqués dans l’interaction entre la douleur et le système moteur. Pour ce faire, une douleur expérimentale a été induite à l’aide d’une crème à base de capsaïcine au niveau de l’avant-bras gauche des participants. L'effet de la douleur sur la force des projections corticospinales ainsi que sur l’activité cérébrale a été mesuré à l’aide de la stimulation magnétique transcrânienne (TMS) et de l’électroencéphalographie (EEG), respectivement. L’analyse des données EEG a permis de révéler qu'en présence de douleur aiguë, il y a une augmentation de l’activité cérébrale au niveau du cuneus central (fréquence têta), du cortex dorsolatéral préfrontal gauche (fréquence alpha) ainsi que du cuneus gauche et de l'insula droite (toutes deux fréquence bêta), lorsque comparée à la condition initiale (sans douleur). Également, les analyses démontrent une augmentation de l'activité du cortex moteur primaire droit en présence de douleur, mais seulement chez les participants qui présentaient simultanément une diminution de leur force de projections corticales (mesurée avec la TMS t=4,45, p<0,05). Ces participants ont également montré une plus grande connectivité entre M1 et le cuneus que les participants dont la douleur n’a pas affecté la force des projections corticospinales (t=3,58, p<0,05). Ces résultats suggèrent qu’une douleur expérimentale induit, chez certains individus, une altération au niveau des forces de projections corticomotrices. Les connexions entre M1 et le cuneus seraient possiblement impliquées dans la survenue de ces changements corticomoteurs.

Heat dissipation from carbon nano-electronics

The incorporation of graphitic compounds such as carbon nanotubes (CNTs) and graphene into nano-electronic device packaging holds much promise for waste heat management given their high thermal conductivities. However, as these graphitic materials must be used in together with other semiconductor/insulator materials, it is not known how thermal transport is affected by the interaction. Using different simulation techniques, in this thesis, we evaluate the thermal transport properties - thermal boundary conductance (TBC) and thermal conductivity - of CNTs and single-layer graphene in contact with an amorphous SiO2 (a-SiO2) substrate. First, the theoretical methodologies and concepts used in our simulations are presented. In particular, two concepts are described in detail as they are necessary for the understanding of the subsequent chapters. The first is the linear response Green-Kubo (GK) theory of thermal boundary conductance (TBC), which we develop in this thesis, and the second is the spectral energy density method, which we use to directly compute the phonon lifetimes and thermal transport coefficients. After we set the conceptual foundations, the TBC of the CNT-SiO2 interface is computed using non- equilibrium molecular dynamics (MD) simulations and the new Green-Kubo method that we have developed. Its dependence on temperature, the strength of the interaction with the substrate, and tube diameter are evaluated. To gain further insight into the phonon dynamics in supported CNTs, the scattering rates are computed using the spectral energy density (SED) method. With this method, we are able to distinguish the different scattering mechanisms (boundary and CNT-substrate phonon-phonon) and rates. The phonon lifetimes in supported CNTs are found to be reduced by contact with the substrate and we use that lifetime reduction to determine the change in CNT thermal conductivity. Next, we examine thermal transport in graphene supported on SiO2. The phonon contribution to the TBC of the graphene-SiO2 interface is computed from MD simulations and found to agree well with experimentally measured values. We derive the theory of remote phonon scattering of graphene electrons and compute the heat transfer coefficient dependence on doping level and temperature. The thermal boundary conductance from remote phonon scattering is found to be an order of magnitude smaller than that of the phonon contribution. The in-plane thermal conductivity of supported graphene is calculated from MD simulations. The experimentally measured order of magnitude reduction in thermal conductivity is reproduced in our simulations. We show that this reduction is due to the damping of the flexural (ZA) modes. By varying the interaction between graphene and the substrate, the ZA modes hybridize with the substrate Rayleigh modes and the dispersion of the hybridized modes is found to linearize in the strong coupling limit, leading to an increased thermal conductance in the composite structure.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Architectural-Physical Co-Design of 3D CPUs with Micro-Fluidic Cooling

The performance, energy efficiency and cost improvements due to traditional technology scaling have begun to slow down and present diminishing returns. Underlying reasons for this trend include fundamental physical limits of transistor scaling, the growing significance of quantum effects as transistors shrink, and a growing mismatch between transistors and interconnects regarding size, speed and power. Continued Moore's Law scaling will not come from technology scaling alone, and must involve improvements to design tools and development of new disruptive technologies such as 3D integration. 3D integration presents potential improvements to interconnect power and delay by translating the routing problem into a third dimension, and facilitates transistor density scaling independent of technology node. Furthermore, 3D IC technology opens up a new architectural design space of heterogeneously-integrated high-bandwidth CPUs. Vertical integration promises to provide the CPU architectures of the future by integrating high performance processors with on-chip high-bandwidth memory systems and highly connected network-on-chip structures. Such techniques can overcome the well-known CPU performance bottlenecks referred to as memory and communication wall. However the promising improvements to performance and energy efficiency offered by 3D CPUs does not come without cost, both in the financial investments to develop the technology, and the increased complexity of design. Two main limitations to 3D IC technology have been heat removal and TSV reliability. Transistor stacking creates increases in power density, current density and thermal resistance in air cooled packages. Furthermore the technology introduces vertical through silicon vias (TSVs) that create new points of failure in the chip and require development of new BEOL technologies. Although these issues can be controlled to some extent using thermal-reliability aware physical and architectural 3D design techniques, high performance embedded cooling schemes, such as micro-fluidic (MF) cooling, are fundamentally necessary to unlock the true potential of 3D ICs. A new paradigm is being put forth which integrates the computational, electrical, physical, thermal and reliability views of a system. The unification of these diverse aspects of integrated circuits is called Co-Design. Independent design and optimization of each aspect leads to sub-optimal designs due to a lack of understanding of cross-domain interactions and their impacts on the feasibility region of the architectural design space. Co-Design enables optimization across layers with a multi-domain view and thus unlocks new high-performance and energy efficient configurations. Although the co-design paradigm is becoming increasingly necessary in all fields of IC design, it is even more critical in 3D ICs where, as we show, the inter-layer coupling and higher degree of connectivity between components exacerbates the interdependence between architectural parameters, physical design parameters and the multitude of metrics of interest to the designer (i.e. power, performance, temperature and reliability). In this dissertation we present a framework for multi-domain co-simulation and co-optimization of 3D CPU architectures with both air and MF cooling solutions. Finally we propose an approach for design space exploration and modeling within the new Co-Design paradigm, and discuss the possible avenues for improvement of this work in the future.