921 resultados para fuel cell oxide fine grain particle prepn


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Distributed Generation (DG) from alternate sources and smart grid technologies represent good solutions for the increase in energy demands. Employment of these DG assets requires solutions for the new technical challenges that are accompanied by the integration and interconnection into operational power systems. A DG infrastructure comprised of alternate energy sources in addition to conventional sources, is developed as a test bed. The test bed is operated by synchronizing, wind, photovoltaic, fuel cell, micro generator and energy storage assets, in addition to standard AC generators. Connectivity of these DG assets is tested for viability and for their operational characteristics. The control and communication layers for dynamic operations are developed to improve the connectivity of alternates to the power system. A real time application for the operation of alternate sources in microgrids is developed. Multi agent approach is utilized to improve stability and sequences of actions for black start are implemented. Experiments for control and stability issues related to dynamic operation under load conditions have been conducted and verified.

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Access control (AC) is a necessary defense against a large variety of security attacks on the resources of distributed enterprise applications. However, to be effective, AC in some application domains has to be fine-grain, support the use of application-specific factors in authorization decisions, as well as consistently and reliably enforce organization-wide authorization policies across enterprise applications. Because the existing middleware technologies do not provide a complete solution, application developers resort to embedding AC functionality in application systems. This coupling of AC functionality with application logic causes significant problems including tremendously difficult, costly and error prone development, integration, and overall ownership of application software. The way AC for application systems is engineered needs to be changed. In this dissertation, we propose an architectural approach for engineering AC mechanisms to address the above problems. First, we develop a framework for implementing the role-based access control (RBAC) model using AC mechanisms provided by CORBA Security. For those application domains where the granularity of CORBA controls and the expressiveness of RBAC model suffice, our framework addresses the stated problem. In the second and main part of our approach, we propose an architecture for an authorization service, RAD, to address the problem of controlling access to distributed application resources, when the granularity and support for complex policies by middleware AC mechanisms are inadequate. Applying this architecture, we developed a CORBA-based application authorization service (CAAS). Using CAAS, we studied the main properties of the architecture and showed how they can be substantiated by employing CORBA and Java technologies. Our approach enables a wide-ranging solution for controlling the resources of distributed enterprise applications.

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The Potengi River estuary has been affected by various anthropogenic factors over the years, as periodic dredging, industrial and domestic waste, traffic and other factors, causing various environmental disasters, including the notorious ecological accident in July 2007, which covered the municipalities of São Gonçalo do Amarante, Macaíba and Natal. Foraminifera serve as viable study tools in these environments; they are able to identify ecologically stressed environments, pointing out hydrographic changes and depositional environments in estuaries. The necessity to check the differences in environmental gradients in places anthropically impacted in Potengi River and adjacent inner shelf through species of foraminifera, and, the responses of these organisms to physical, chemical and geological factors is to provide baseline in the diagnosis of environments. The results show the dominance of opportunistic Ammonia tepida, Bolivina striatula, Quinqueloculina patagonica and Q. miletti especially in regions close to shrimp farms and Baldo Channel sewage in fine grain environments; and Q. lamarckiana indicates penetration of the saline waters in Potengi River. The occurrence of low-salinity tolerant foraminiferal species typical of mangrove environments as Trochammina inflata and T. squamata in Potengi River Channel suggest they probably could have been transported from mangrove area near the Potengi river mouth to the inner shelf regions. These findings suggest Potengi River is able to export mixohaline and mangrove organisms to inner shelf. Two distinct environments were observed, the outermost area is more influenced by marine influence and the innermost area is less influenced. Calcareous and agglutinated species dominate Potengi River, while mouth and inner shelf areas are dominated by calcareous, agglutinated and porcelaneous species, which are typical of highly saline and hydrodynamic environments and the contributive factors that controls foraminiferal distribution were balance of marine and freshwater currents, grain size, availability of CaCO3 and organic matter.

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The Potengi River estuary has been affected by various anthropogenic factors over the years, as periodic dredging, industrial and domestic waste, traffic and other factors, causing various environmental disasters, including the notorious ecological accident in July 2007, which covered the municipalities of São Gonçalo do Amarante, Macaíba and Natal. Foraminifera serve as viable study tools in these environments; they are able to identify ecologically stressed environments, pointing out hydrographic changes and depositional environments in estuaries. The necessity to check the differences in environmental gradients in places anthropically impacted in Potengi River and adjacent inner shelf through species of foraminifera, and, the responses of these organisms to physical, chemical and geological factors is to provide baseline in the diagnosis of environments. The results show the dominance of opportunistic Ammonia tepida, Bolivina striatula, Quinqueloculina patagonica and Q. miletti especially in regions close to shrimp farms and Baldo Channel sewage in fine grain environments; and Q. lamarckiana indicates penetration of the saline waters in Potengi River. The occurrence of low-salinity tolerant foraminiferal species typical of mangrove environments as Trochammina inflata and T. squamata in Potengi River Channel suggest they probably could have been transported from mangrove area near the Potengi river mouth to the inner shelf regions. These findings suggest Potengi River is able to export mixohaline and mangrove organisms to inner shelf. Two distinct environments were observed, the outermost area is more influenced by marine influence and the innermost area is less influenced. Calcareous and agglutinated species dominate Potengi River, while mouth and inner shelf areas are dominated by calcareous, agglutinated and porcelaneous species, which are typical of highly saline and hydrodynamic environments and the contributive factors that controls foraminiferal distribution were balance of marine and freshwater currents, grain size, availability of CaCO3 and organic matter.

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On the continental rise west of the Antarctic Peninsula there are nine large mounds interpreted as sediment drifts, separated by turbidity current channels. Drift 7 is 150 km long, 70 km wide and up to 700 m high and is asymmetric, with steep sides on the south-east (towards the continent) and south-west, and gentle slopes to north-west and north-east. Cores on the gentle sides of the drift show a cyclicity between brown, bioturbated, diatom-bearing mud with foraminifera and radiolarians, and grey, laminated, barren mud. Biostratigraphic evidence is consistent with a Late Quaternary age. Detailed lithostratigraphy and magnetic susceptibility data allow precise correlation over distances of tens of kilometres. On the basis of chemostratigraphy, the brown sediment is interpreted as interglacial (isotope stages 1 and 5) and the grey as glacial (stages 2-4 and 6). Sedimentation rates are 3.0-5.5 cm/ka. Cores on the steep sides of the drift recovered a condensed section with thinner cycles and hiatuses. Fine grain size, very poor sorting and the absence of a mode in the silt size range indicate deposition from suspension with only weak current activity, There is little evidence for cyclic changes in bottom current strength. Supply of sediment to the benthic nepheloid layer was by entrainment ofmud from turbidity currents, and by settling ofpelagic material (biogenic grains, IRD, sediment suspended in meltwater plumes). Cyclic changes in sediment supply include more biogenic supply in interglacials with less sea ice cover, more terrigenous supply from turbidites in glacials with ice sheets grounded to the shelf edge, and changes in IRD content.

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An Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed to investigate the size-resolved chemical composition of single particles at an urban background site in Paris, France, as part of the MEGAPOLI winter campaign in January/February 2010. ATOFMS particle counts were scaled to match coincident Twin Differential Mobility Particle Sizer (TDMPS) data in order to generate hourly size-resolved mass concentrations for the single particle classes observed. The total scaled ATOFMS particle mass concentration in the size range 150–1067 nm was found to agree very well with the sum of concurrent High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and Multi-Angle Absorption Photometer (MAAP) mass concentration measurements of organic carbon (OC), inorganic ions and black carbon (BC) (R2 = 0.91). Clustering analysis of the ATOFMS single particle mass spectra allowed the separation of elemental carbon (EC) particles into four classes: (i) EC attributed to biomass burning (ECbiomass), (ii) EC attributed to traffic (ECtraffic), (iii) EC internally mixed with OC and ammonium sulfate (ECOCSOx), and (iv) EC internally mixed with OC and ammonium nitrate (ECOCNOx). Average hourly mass concentrations for EC-containing particles detected by the ATOFMS were found to agree reasonably well with semi-continuous quantitative thermal/optical EC and optical BC measurements (r2 = 0.61 and 0.65–0.68 respectively, n = 552). The EC particle mass assigned to fossil fuel and biomass burning sources also agreed reasonably well with BC mass fractions assigned to the same sources using seven-wavelength aethalometer data (r2 = 0.60 and 0.48, respectively, n = 568). Agreement between the ATOFMS and other instrumentation improved noticeably when a period influenced by significantly aged, internally mixed EC particles was removed from the intercomparison. 88% and 12% of EC particle mass was apportioned to fossil fuel and biomass burning respectively using the ATOFMS data compared with 85% and 15% respectively for BC estimated from the aethalometer model. On average, the mass size distribution for EC particles is bimodal; the smaller mode is attributed to locally emitted, mostly externally mixed EC particles, while the larger mode is dominated by aged, internally mixed ECOCNOx particles associated with continental transport events. Periods of continental influence were identified using the Lagrangian Particle Dispersion Model (LPDM) "FLEXPART". A consistent minimum between the two EC mass size modes was observed at approximately 400 nm for the measurement period. EC particles below this size are attributed to local emissions using chemical mixing state information and contribute 79% of the scaled ATOFMS EC particle mass, while particles above this size are attributed to continental transport events and contribute 21% of the EC particle mass. These results clearly demonstrate the potential benefit of monitoring size-resolved mass concentrations for the separation of local and continental EC emissions. Knowledge of the relative input of these emissions is essential for assessing the effectiveness of local abatement strategies.

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Hydrogen has been called the fuel of the future, and as it’s non- renewable counterparts become scarce the economic viability of hydrogen gains traction. The potential of hydrogen is marked by its high mass specific energy density and wide applicability as a fuel in fuel cell vehicles and homes. However hydrogen’s volume must be reduced via pressurization or liquefaction in order to make it more transportable and volume efficient. Currently the vast majority of industrially produced hydrogen comes from steam reforming of natural gas. This practice yields low-pressure gas which must then be compressed at considerable cost and uses fossil fuels as a feedstock leaving behind harmful CO and CO2 gases as a by-product. The second method used by industry to produce hydrogen gas is low pressure electrolysis. In comparison the electrolysis of water at low pressure can produce pure hydrogen and oxygen gas with no harmful by-products using only water as a feedstock, but it will still need to be compressed before use. Multiple theoretical works agree that high pressure electrolysis could reduce the energy losses due to product gas compression. However these works openly admit that their projected gains are purely theoretical and ignore the practical limitations and resistances of a real life high pressure system. The goal of this work is to experimentally confirm the proposed thermodynamic gains of ultra-high pressure electrolysis in alkaline solution and characterize the behavior of a real life high pressure system.

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How can applications be deployed on the cloud to achieve maximum performance? This question is challenging to address with the availability of a wide variety of cloud Virtual Machines (VMs) with different performance capabilities. The research reported in this paper addresses the above question by proposing a six step benchmarking methodology in which a user provides a set of weights that indicate how important memory, local communication, computation and storage related operations are to an application. The user can either provide a set of four abstract weights or eight fine grain weights based on the knowledge of the application. The weights along with benchmarking data collected from the cloud are used to generate a set of two rankings - one based only on the performance of the VMs and the other takes both performance and costs into account. The rankings are validated on three case study applications using two validation techniques. The case studies on a set of experimental VMs highlight that maximum performance can be achieved by the three top ranked VMs and maximum performance in a cost-effective manner is achieved by at least one of the top three ranked VMs produced by the methodology.

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Face à la diminution des ressources énergétiques et à l’augmentation de la pollution des énergies fossiles, de très nombreuses recherches sont actuellement menées pour produire de l’énergie propre et durable et pour réduire l’utilisation des sources d’énergies fossiles caractérisées par leur production intrinsèque des gaz à effet de serre. La pile à combustible à membrane échangeuse de protons (PEMFC) est une technologie qui prend de plus en plus d’ampleur pour produire l’énergie qui s’inscrit dans un contexte de développement durable. La PEMFC est un dispositif électrochimique qui fonctionne selon le principe inverse de l’électrolyse de l’eau. Elle convertit l’énergie de la réaction chimique entre l’hydrogène et l’oxygène (ou l’air) en puissance électrique, chaleur et eau; son seul rejet dans l’atmosphère est de la vapeur d’eau. Une pile de type PEMFC est constituée d’un empilement Électrode-Membrane-Électrode (EME) où la membrane consiste en un électrolyte polymère solide séparant les deux électrodes (l’anode et la cathode). Cet ensemble est intégré entre deux plaques bipolaires (BP) qui permettent de collecter le courant électrique et de distribuer les gaz grâce à des chemins de circulation gravés sur chacune de ses deux faces. La plupart des recherches focalisent sur la PEMFC afin d’améliorer ses performances électriques et sa durabilité et aussi de réduire son coût de production. Ces recherches portent sur le développement et la caractérisation des divers éléments de ce type de pile; y compris les éléments les plus coûteux et les plus massifs, tels que les plaques bipolaires. La conception de ces plaques doit tenir compte de plusieurs paramètres : elles doivent posséder une bonne perméabilité aux gaz et doivent combiner les propriétés de résistance mécanique, de stabilité chimique et thermique ainsi qu’une conductivité électrique élevée. Elles doivent aussi permettre d’évacuer adéquatement la chaleur générée dans le cœur de la cellule. Les plaques bipolaires métalliques sont pénalisées par leur faible résistance à la corrosion et celles en graphite sont fragiles et leur coût de fabrication est élevé (dû aux phases d’usinage des canaux de cheminement des gaz). C’est pourquoi de nombreuses recherches sont orientées vers le développement d’un nouveau concept de plaques bipolaires. La voie la plus prometteuse est de remplacer les matériaux métalliques et le graphite par des composites à matrice polymère. Les plaques bipolaires composites apparaissent attrayantes en raison de leur facilité de mise en œuvre et leur faible coût de production mais nécessitent une amélioration de leurs propriétés électriques et mécaniques, d’où l’objectif principal de cette thèse dans laquelle on propose: i) un matériau nanocomposite développé par extrusion bi-vis qui est à base de polymères chargés d’additifs solides conducteurs, incluant des nanotubes de carbone. ii) fabriquer un prototype de plaque bipolaire à partir de ces matériaux en utilisant le procédé de compression à chaud avec un refroidissement contrôlé. Dans ce projet, deux polymères thermoplastiques ont été utilisés, le polyfluorure de vinylidène (PVDF) et le polyéthylène téréphtalate (PET). Les charges électriquement conductrices sélectionnées sont: le noir de carbone, le graphite et les nanotubes de carbones. La combinaison de ces charges conductrices a été aussi étudiée visant à obtenir des formulations optimisées. La conductivité électrique à travers l’épaisseur des échantillons développés ainsi que leurs propriétés mécaniques ont été soigneusement caractérisées. Les résultats ont montré que non seulement la combinaison entre les charges conductrices influence les propriétés électriques et mécaniques des prototypes développés, mais aussi la distribution de ces charges (qui de son côté dépend de leur nature, leur taille et leurs propriétés de surface), avait aidé à améliorer les propriétés visées. Il a été observé que le traitement de surface des nanotubes de carbone avait aidé à l’amélioration de la conductivité électrique et la résistance mécanique des prototypes. Le taux de cristallinité généré durant le procédé de moulage par compression des prototypes de plaques bipolaires ainsi que la cinétique de cristallisation jouent un rôle important pour l’optimisation des propriétés électriques et mécaniques visées.

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Authentication plays an important role in how we interact with computers, mobile devices, the web, etc. The idea of authentication is to uniquely identify a user before granting access to system privileges. For example, in recent years more corporate information and applications have been accessible via the Internet and Intranet. Many employees are working from remote locations and need access to secure corporate files. During this time, it is possible for malicious or unauthorized users to gain access to the system. For this reason, it is logical to have some mechanism in place to detect whether the logged-in user is the same user in control of the user's session. Therefore, highly secure authentication methods must be used. We posit that each of us is unique in our use of computer systems. It is this uniqueness that is leveraged to "continuously authenticate users" while they use web software. To monitor user behavior, n-gram models are used to capture user interactions with web-based software. This statistical language model essentially captures sequences and sub-sequences of user actions, their orderings, and temporal relationships that make them unique by providing a model of how each user typically behaves. Users are then continuously monitored during software operations. Large deviations from "normal behavior" can possibly indicate malicious or unintended behavior. This approach is implemented in a system called Intruder Detector (ID) that models user actions as embodied in web logs generated in response to a user's actions. User identification through web logs is cost-effective and non-intrusive. We perform experiments on a large fielded system with web logs of approximately 4000 users. For these experiments, we use two classification techniques; binary and multi-class classification. We evaluate model-specific differences of user behavior based on coarse-grain (i.e., role) and fine-grain (i.e., individual) analysis. A specific set of metrics are used to provide valuable insight into how each model performs. Intruder Detector achieves accurate results when identifying legitimate users and user types. This tool is also able to detect outliers in role-based user behavior with optimal performance. In addition to web applications, this continuous monitoring technique can be used with other user-based systems such as mobile devices and the analysis of network traffic.

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La determinación en tiempo real de los estados críticos de operación de la pila de combustible de membrana intercambio protónico (siglas en ingles, PEM) es uno de los principales retos para los sistemas de control de pilas de combustible PEM. En este trabajo, se presenta el desarrollo e implementación de un método no invasivo de bajo coste basado en técnicas de decisión borrosa que permite estimar los estados críticos de operación de la pila de combustible PEM. La estimación se realiza mediante perturbaciones al estado de operación de la pila y el análisis posterior de la evolución temporal del voltaje generado por la pila. La implementación de esta técnica de estimulación-percepción de estado de la pila de combustible para la detección de estados críticos constituye una novedad y un paso hacia el control autónomo en óptimas condiciones de la operación de las pilas de combustible PEM.

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In this work, was studied the formation of a composite of the refractory metal niobium with copper, through the process of high-energy milling and liquid phase sintering. The HEM can be used to synthesize composite powders with high homogeneity and fine size particle distribution. It may also produce the solid solubility in immiscible systems such as Nb-Cu, or extend the solubility of systems with limited solubility. Therefore, in the immiscible system Cu-Nb, the high-energy milling was successfully used to obtain the composite powder particles. Initially, the formation of composite particles during the HEM and the effect of preparation technique on the microstructure of the material was evaluated. Four loads of Nb and Cu powders containing 20%wt Cu were synthesized by MAE in a planetary type ball mill under different periods of grinding. The influence of grinding time on the metal particles is evaluated during the process by the withdrawal of samples at intermediate times of milling. After compaction under different forces, the samples were sintered in a vacuum furnace. The liquid phase sintering of these samples prepared by HEM produced a homogeneous and fine grained. The composite particles forming the sintered samples are the addition of a hard phase (Nb) with a high melting point, and a ductile phase (Cu) with low melting point and high thermal and electrical conductivities. Based on these properties, the Nb-Cu system is a potential material for many applications, such as electrical contacts, welding electrodes, coils for generating high magnetic fields, heat sinks and microwave absorbers, which are coupled to electronic devices. The characterization techniques used in this study, were laser granulometry, used to evaluate the homogeneity and particle size, and the X-ray diffraction, in the phase identification and to analyze the crystalline structure of the powders during milling. The morphology and dispersion of the phases in the composite powder particles, as well the microstructures of the sintered samples, were observed by scanning electron microscopy (SEM). Subsequently, the sintered samples are evaluated for density and densification. And finally, they were characterized by techniques of measuring the electrical conductivity and microhardness, whose properties are analyzed as a function of the parameters for obtaining the composite

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Carbon-supported Pt–Sn catalysts commonly contain Pt–Sn alloy and/or Pt–Sn bimetallic systems (Sn oxides). Nevertheless, the origin of the promotion effect due to the presence of Sn in the Pt–Sn/C catalyst towards ethanol oxidation in acid media is still under debate and some contradictions. Herein, a series of Ptx–Sny/C catalysts with different atomic ratios are synthesized by a deposition process using formic acid as the reducing agent. Catalysts structure and chemical compositions are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and their relationship with catalytic behavior towards ethanol electro-oxidation was established. Geometric structural changes are producing by highest Sn content (Pt1–Sn1/C) promoted the interaction of Pt and Sn forming a solid solution of Pt–Sn alloy phase, whereas, the intermediate and lowest Sn content (Pt2–Sn1/C and Pt3–Sn1/C, respectively) promoted the electronic structure modifications of Pt by Sn addition without the formation of a solid solution. The amount of Sn added affects the physical and chemical characteristics of the bimetallic catalysts as well as reducing the amount of Pt in the catalyst composition and maintaining the electrocatalytic activities at the anode. However, the influence of the Sn oxidation state in Pt–Sn/C catalysts surfaces and the alloy formation between Pt and Sn as well as with the atomic ratio on their catalytic activity towards ethanol oxidation appears minimal. Similar methodologies applied for synthesis of Ptx–Sny/C catalysts with a small change show differences with the results obtained, thus highlighting the importance of the conditions of the preparation method.

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The development and optimization of electrocatalysts for application in fuel cell systems have been the focus of a variety of studies where core–shell structures have been considered as a promising alternative among the materials studied. We synthesized core–shell nanoparticles of Sn x @Pt y and Rh x @Pt y (Sn@Pt, Sn@Pt2, Sn@Pt3, Rh@Pt, Rh@Pt2, and Rh@Pt3) through a reduction methodology using sodium borohydride. These nanoparticles were electrochemically characterized by cyclic voltammetry and further analyzed by cyclic voltammetry studying their catalytic activity toward glycerol electro-oxidation; chronoamperometry and potentiostatic polarization experiments were also carried out. The physical characterization was carried out by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The onset potential for glycerol oxidation was shifted in 130 and 120 mV on the Sn@Pt3/C and Rh@Pt3/C catalysts, respectively, compared to commercial Pt/C, while the stationary pseudo-current density, taken at 600 mV, increased 2-fold and 5-fold for these catalysts related to Pt/C, respectively. Thus, the catalysts synthesized by the developed methodology have enhanced catalytic activity toward the electro-oxidation of glycerol, representing an interesting alternative for fuel cell systems.

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Carbon-supported Pt x –Rh y –Sn z catalysts (x:y:z = 3:1:4, 6:2:4, 9:3:4) are prepared by Pt, Rh, and Sn precursors reduction in different addition order. The materials are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and are evaluated for the electrooxidation of ethanol in acidic media by cyclic voltammetry, chronoamperometry, and anode potentiostatic polarization. The influence of both the order in which the precursors are added and the composition of metals in the catalysts on the electrocatalytic activity and physico-chemical characteristics of Pt x –Rh y –Sn z /C catalysts is evaluated. Oxidized Rh species prevail on the surface of catalysts synthesized by simultaneous co-precipitation, thus demonstrating the influence of synthesis method on the oxidation state of catalysts. Furthermore, high amounts of Sn in composites synthesized by co-precipitation result in very active catalysts at low potentials (bifunctional effect), while medium Sn load is needed for sequentially deposited catalysts when the electronic effect is most important (high potentials), since more exposed Pt and Rh sites are needed on the catalyst surface to alcohol oxidation. The Pt3–Rh1–Sn4/C catalyst prepared by co-precipitation is the most active at potentials lower than 0.55 V (related to bifunctional effect), while the Pt6–Rh2–Sn4/C catalyst, prepared by sequential precipitation (first Rh and, after drying, Pt + Sn), is the most active above 0.55 V.