No description available.

No description available.

No description available.

El reformado de gas natural con vapor de agua es el proceso industrial más extendido para la producción de gas de síntesis (H_2+ CO) y subsecuentes productos. El reformado de metano con dióxido de carbono, o reformado seco, se considera una alternativa conveniente para el aprovechamiento de yacimien-tos de gas natural con alto contenido de CO_2 y la obtención de gas de síntesis con una relación CO/H_2 1 más adecuada para algunos procesos de síntesis. Desde el punto de vista de la materia prima la importancia del proceso está ampliamente justificada en Argentina por la existencia de yacimientos de gas natural con alta proporción de CO_2 particularmente en la cuenca neuquina. El principal inconveniente para la implemen-tación industrial del proceso de reformado de CH_4 con CO2 es la disponibilidad de catalizadores comerciales resistente_s a la desactivación por formación de depósitos de carbono. Este fenómeno adquiere mayor importancia con relación al reforma-do con vapor en razón de la mayor proporción de C y menor presencia de O. A esta causa de pérdida de actividad se suma la debida a la sinterización del metal como consecuencia de las altas temperaturas de trabajo. Por estas razones existe un permanente interés en el desarrollo de nuevos catalizadores y en la introducción de modificaciones al proceso que le permi-tan obtener conversiones elevadas con razonable estabilidad. A nivel laboratorio se han logrado catalizadores basados en el uso de metales nobles (Pt, Rh) soportados en materiales como ZrO_2 o MgO que satisfacen dichas exigencias. En nuestro laboratorio los estudios se han centrado en la utilización de Pd como metal activo empleando como material soporte a-Al_2O_3 comercial. Esta elección se ha basado en el menor costo del Pd respecto a Pt y Rh pero fundamentalmente a que su acti-vidad para la activación de CH_4 a > 600 C es mayor que la de Ni, Rh o Pt. En este trabajo de tesis queda claramente demostrado que catalizadores Pd/(@1 %)/a-Al2-O-3 son muy activos para la reacción de reformado seco a > 600 oC, pero se desactivan rapidamente por la acumulación de depósitos carbonosos. El agregado de Ce (0,3 - 2,5 %) inhibe este pro-ceso lográndose un catalizador de alta actividad y estabilidad. La interacción Ce-Pd presente en dichos catalizadores ha sido motivo de estudio empleándose para tal finalidad técnicas de caracterización como microscopía electrónica de transmisión (TEM), microscopía electrónica de alta resolución (HRTEM), espectroscopía infrarroja (FTIR), difracción de rayos X (XRD) y espectroscopía fotoelectrónica de rayos X (XPS), las que fueron aplicadas a muestras nuevas y usadas en reacción. Los estudios de FTIR de CO adsorbido no mostraron cambios de consideración por el efecto del agregado del Ce a cataliza-dores de Pd de baja dispersión (< 20 %). Los resultados de XRD y de HRTEM indicarían que el CeOx forma pequeños cristales en contacto con las partículas de Pd. Por otra parte, el análisis de los espectrosXPS para las regiones del Ce 3d y Pd 3d, dan cuenta de que el Ce se encuentra mayormente como Ce+3 y de una elevada energía de ligadura para la señal del Pd 3d5/2 (335,3 eV), evidenciando una clara interacción Pd-Ce. Los resultados obtenidos en su conjunto avalan el mecanismo de acción promotora del CeOx para la eliminación de C evitando la desactivación. También se investigó el proceso de formación de nanofibras de carbón (NFC) en la reacción de reformado de CH_4 con CO_2 a 650 oC sobre Pd/(@1 %)/a-Al_2O_3. El material nanocarbonoso obtenido, caracterizado por microscopía electrónica de alta resolución (HRTEM), mostró la formación de NFC de estructuras bien definidas de entre 8 y 18 nm de diámetro. Una fracción de estas fibras presenta ramificaciones. Los resultados de la caracterización indican que, la fibra crece desprendiendo a la partícula metálica del sustrato. El tipo de fibra obtenido se vincula a la forma de la partícula que la genera y el creci-miento de la fibra se origina a partir de la formación de capas grafíticas sobre la partícula metálica. En la búsqueda de optimizar el empleo del Pd e investigar el efecto del tamaño de partícula en la reacción de reformado, se prepararon catali-zadores con un contenido inferior al 0,5%, empleando el méto-do de recarga con etapas de lavado intermedio para evitar la formación de grandes partículas. Las muestras fueron caracte-rizadas por espectroscopia FTIR, quimisorción de H_2 y XPS. Los resultados de la caracterización por FTIR y quimisorción evidencian una mayor dispersión metálica y los espectros de XPS indican la existencia de partículas de paladio de pequeño tamaño que permanecen en estado Pd+x, aun después de ser expuestas a tratamientos severos de reducción (700 C; 1 hora). Los ensayos de actividad mostraron que estos catali-zadores exhiben una baja actividad inicial seguida de una activación progresiva en 24 horas de reacción que correlacio-na con el aumento del tamaño de partícula por sinterizado y la disminución de la fracción de Pd+x. La formación de partículas de Pd donde predominan estructuras superficiales que favo-recen la adsorción de CO en formas múltiplemente coordina-das, resultaría ser necesaria para lograr actividad catalítica en la reacción de interés. El análisis por XPS de catalizadores Pd(<0,5%)/a-Al_2O_3 activados mostró la formación de una fase de carburo de Pd. El agregado de Ce a estos cataliza-dores de bajo contenido metálico permitió un notable incre-mento de la actividad (la conversión de CH_4 aumento del 11 al 51 % bajo similares condiciones operativas). Por otra parte los espectros FTIR de CO adsorbido fueron modificados por el agregado de Ce indicando la existencia de una interacción Ce-Pd no observada en los catalizadores CeOx-Pd/(@1%)/a-Al_2O_3. Este comportamiento sugiere que el Ce agregado a catalizadores de Pd de alta dispersión interviene en la formación de los sitios activos para la reacción de reformado. / The steam reforming of natural gas is a well-known process for the production of synthesis gas (H_2 + CO) and its derived products. CH_4 reforming with CO_2 (dry reforming) is considered a convenient alternative for the utilization of natural gas wells with a high CO_2 content to obtain a CO/H_2 1, which is an adequate ratio for certain syn-thesis processes. From the point of view of natural resour-ces this process is important for Argentina taking into account the existence of numerous natural gas fields with high CO_2 content mainly in Neuquen. The key limiting condition for the use of CH_4 reforming with CO2 is the lack of commercial catalysts that are capable of resisting the deactivation caused by the formation of carbonaceous deposits. This is a major problem due to the higher C con-tent and lower O content in the feed mixture, as compared to steam reforming. Another reason for catalyst deactiva-tion is the occurrence of a sintering process, which results from the high operating temperature. For these reasons there is a permanent interest in the development of new catalysts and to introduce process modifications in order to obtain high levels of conversion with adequate stability. At laboratory level catalysts based on noble metals (Pt, Rh) supported on ZrO_2 or OMg that avoid the mentioned problems have been obtained. In our laboratory we have focused the attention on the employment of Pd as the active metal using commercial a-Al_2O_3 as a support material. This choice was based on the lower cost of Pd compared with Pt and Rh, but mainly on the knowledge that Pd activity for CH4 activation at > 600 oC is higher than Ni, Rh or Pt activity. In this thesis it was clearly shown that Pd/(@1%)/a-Al_2O_3 catalysts are very active for dry reforming at > 600 oC, although they deactivate rapidly due to carbon deposits. However, it is clearly demons-trated that Ce (0,3 - 2,5 %) addition inhibits this pro-cess leading to an active and stable catalyst. Ce-Pd inte-raction in the mentioned catalyst was studied by using several characterization techniques, such as transmission electron microscopy (TEM), high resolution electron micros-copy (HRTEM), infrared spectroscopy (FTIR) and X-ray pho-toelectron spectroscopy (XPS) applied on fresh and used samples. The FTIR study of adsorbed CO did not reflect an effect of Ce addition on catalysts of low metal dispersion (<20 %), while the XRD and HRTEM results suggested that CeOx forms small crystallites in contact with the Pd particles. On the other hand, the XPS spectra of the Ce3d and Pd3d regions showed the presence of Ce+3 species and a high binding energy for the Pd peak (335,3 eV) suggesting a Ce-Pd interaction. These results support a redox process as the promotion mechanism of Ce for the elimination of C deposition. The formation of carbon nanofibers (CNF) over Pd/(@1%)/a-Al_2O_3 catalysts during CH_4 reforming with CO2 at 650 oC was also investigated. The carbonaceous material, which was characterized by high resolution elec-tron microscopy (HRTEM), showed the formation of carbon nanofibers with a diameter between 8 and 18 nanometers. A fraction of the fibers presents branches. It was also observed that the fibers grow separating the metal parti-cles from the support, that they retain the particles shape and that the formation of graphitic layers on the particles surface initiates the fibers growth process. In order to optimize the use of Pd and to investigate the effect of particle size on the reforming reaction, cata-lysts with a metal loading < 0,5 % were prepared by using a recharging procedure with intermediate washing steps to avoid the formation of large particles. The samples were characterized by FTIR spectroscppy, H_2 chemisorption and XPS. The FTIR results give evidence of high metal dis-persion and the XPS spectra reveal the presence of small Pd particles that remain on a Pd+x state despite a one-hour hydrogen pretreatment at 700 oC. The catalytic acti-vity tests showed that these catalysts exhibit a low ini-tial activity followed by a continuous activation during 24 hours, which is related with a particle size grow and the diminution of the fraction of Pd+x. The formation of Pd particles with a surface structure that favors the adsorption of multiple coordinated CO seems to be ne-cessary to obtain a good catalytic activity. The XPS ana-lysis of activated Pd(<0,5%)/a-Al_2O_3 catalysts showed the presence of a Pd carbide phase. The addition of Ce to these catalysts of low metal loading produced a marked increase inactivity (the CH4 conversion increased from 11 % to 51 % under similar operating conditions). On the other hand, the FTIR spectra of adsorbed CO was modified by Ce addition indicating the presence of a Ce-Pd interac-tion that was not observed on the CeOx-Pd(@1%)/a-Al_2O_3 catalysts. This behavior suggests that Ce added to high dispersion catalysts participates in the formation of the active sites for the reforming reaction.

En los últimos años, las técnicas de modelado y simulación a escala cuántica han alcanzado logros inimaginables gracias a los avances tecnológicos y como respuesta a la necesidad de correlacionar un sistema de partículas interactuantes con comportamientos observados experimentalmente. Los actuales métodos ab-initio conducen a una mayor diversidad y exactitud de resultados predictivos aunque son computacionalmente más costosos. En la presente tesis doctoral, se propuso como objetivo estudiar la hidrogenación de aceites comestibles sobre catalizadores metálicos modelo usando métodos de primeros principios y empleando un modelo periódico para representar mejor al sistema; todo motivado a partir del interés suscitado por la hidrogenación catalítica de los ácidos grasos para obtener productos 0% trans con el fin de mejorar la selectividad y especificidad de los catalizadores empleados. En particular se ha utilizado al 1,3-butadieno (13BD) como modelo de un ácido graso, por ser el alqueno más simple con dos dobles enlaces conjugados, y a superficies bimetálicas multilaminares de Pd-Ni, como catalizadores. Estas superficies resultan ser modelos de catalizadores modificados a los de Pd y Ni puros, conocidos por sus actividades catalíticas en el estudio de la hidrogenación parcial, así como por sus desventajas asociadas al alto costo y/o limitada actividad en la formación de isómeros cis. La incorporación de pequeñas cantidades de otro metal de transición, como por ejemplo Pd en una superficie de Ni, mejora la actividad y la selectividad hacia los isómeros butenos. Las superficies evaluadas PdnNim(111), donde n corresponde al número de capas de Pd (n = 0 - 4) depositadas sobre m capas de Ni (n + m = 4), fueron caracterizadas mediante sus propiedades estructurales, electrónicas y magnéticas. A partir de una correcta descripción de las mismas se seleccionaron dos de ellas: PdNi3(111) y Pd3Ni(111), sobre las cuales se adsorbieron el 13BD, los intermediarios y los productos de reacción. Mediante el análisis de las geometrías, las energías de adsorción y las densidades de estados se pudieron identificar las geometrías más estables que fueron empleadas en el posterior análisis de la reacción. La hidrogenación parcial del 13BD se evaluó de acuerdo al mecanismo de Horiuti-Polanyi. El proceso resultó ser exotérmico en la superficie modelo de PdNi3(111) con barreras de activación más bajas y endotérmico en la de Pd3Ni(111). Sobre la superficie PdNi3(111) se obtuvieron como productos de la reacción exclusivamente butenos, con cierta selectividad hacia el isómero 2-buteno. El trans-2- buteno es el isómero geométrico más esperable del 2-buteno, debido a la geometría de adsorción más estable del 13BD. Al evaluar la isomerización del trans al cis-2-buteno y la formación del cis-2-buteno, a partir de la hidrogenación del dieno adsorbido en el modo apropiado para esta geometría, se descubrió que el cis-2-buteno sólo se formaría a partir de la hidrogenación del 13BD adsorbido en el sitio de igual geometría. Mediante la extrapolación de los resultados obtenidos en esta tesis sería de esperar que un catalizador con las características del modelo PdNi3(111) mejore la actividad y aumente la selectividad de los productos hacia los isómeros cis al hidrogenar aceites comestibles. / In recent years, modeling techniques and scale quantum simulation have reached unimaginable achievements through technological progress and as response to the need to correlate a system of interacting particles with experimentally observed behaviour. Current ab-initio methods lead to greater diversity and accuracy of predictable results, but are computationally expensive. This thesis mainly studies hydrogenation of edible oils on model metallic catalysts using first principle methods and a periodic model to better represent the system, all motivated from the interest generated by fatty acid catalyst hydrogenation to obtain 0% trans products in order to improve selectivity and specificity of the catalysts employed. In particular, 1,3-butadiene (13BD) has been used as a fatty acid model since it is the simplest alkene with two conjugated double bonds, and the two bi-metallic Pd-Ni surfaces multilayers have been used as catalysts. These surfaces are modified catalysts models of Pd and Ni, known for their catalytic activity in the study of the partial hydrogenation catalysts, but presenting some disadvantages associated with high cost and/or limited activity in the formation of cis isomers. The incorporation of small amounts of other transition metal such as Pd in a surface of Ni greatly improves the activity and selectivity towards butenes isomers. The evaluated PdnNim(111) surfaces, where n is the number of Pd layers (n = 0- 4) deposited on m Ni layers (n + m = 4), were characterized by studying their structural, electronic and magnetic properties. From a correct description of these surfaces, two of them PdNi3(111) and Pd3Ni(111) were selected to adsorb 13BD, intermediaries and reaction products. Analyzing geometries, adsorption energies and densities of states the most stable geometries could be identified and later employed in the subsequent analysis of the reaction. Partial hydrogenation of 13BD was evaluated according to Horiuti-Polanyi mechanism. It was found that the process was exothermic on PdNi3(111) surface model with lower barriers and endothermic on Pd3Ni(111). On PdNi3(111) surface, butenes are the exclusive reaction products, with some selectivity to 2-butene isomer. The trans-2- butene is the most expected geometric isomer of 2-butene, due to the geometry of the most stable adsorption mode of 13BD. Evaluating the isomerization reaction from trans to cis-2-butene and the cis-2-butene formation, from diene hydrogenation adsorbed in the appropriate mode for this geometry, it was found that the cis-2-butene is formed only from the 13BD hydrogenation adsorbed on the mode with the same geometry. By extrapolation of the results obtained in this thesis would be expected that a catalyst with the characteristics of the PdNi3(111) model enhance the activity and increase the selectivity of the products to the cis isomers by hydrogenating edible oils.

In this thesis, power system transients are considered as an opportunity for development of on-line diagnostics of power components and specifically the insulation systems of power transformers and bushings. A new technique for on-line dielectric response measurement of power transformer bushings is proposed which utilizes natural transients in the power system, such as lightning and switching surges, as stimuli. Laboratory investigations are done on implementation of the proposed technique. Measurement considerations, data acquisition and processing involved in achievement of reasonable accuracy in the Dielectric Response (DR) are presented. Capability of the technique in tracking of the degradation signatures such as moisture content in the insulation has been evaluated and it has shown a good level of accuracy by being compared to the Frequency Domain Spectroscopy (FDS).  The proposed technique is tested on the service-aged 150 kV bushings and feasibility of the technique for monitoring of dielectric properties of power transformer bushings has been assessed; the results are promising for the technique to be used in the real application.  Partial Discharges (PD) behavior under transients has been also studied for different materials in this project. PD behavior of different defects, at different insulation condition, responding to the overvoltage transients in form of superimposed impulses on ac voltages was investigated and it was perceived how their distinctive response and the interpretation of  that, can be useful for their identification. Besides the conventional materials, surface ac PD properties of modified paper with silica and zinc oxide nanoparticles under the superimposed impulses have been assessed in this project. Proper type and optimum concentration level of nanoparticles in the paper are the factors that lead to the improvement of PD behavior in the modified paper under overvoltage transients. / <p>QC 20160525</p>

Neste trabalho foram produzidos eletrocatalisadores Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C e PdAuIr/C a partir do método de redução por borohidreto para oxidação eletroquímica de metanol, etanol e etilenoglicol. No método de redução por borohidreto, adiciona-se de uma só vez uma solução alcalina contendo borohidreto de sódio a uma mistura contendo água/2-propanol, precursores metálicos e o suporte de carbono Vulcan XC72. Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios-X (EDX), difração de raios-X (DRX), microscopia eletrônica de transmissão (MET) e voltametria cíclica. A oxidação eletroquímica do metanol, etanol e etilenoglicol foi estudada por cronoamperometria utilizando a técnica do eletrodo de camada fina porosa. O estudo do mecanismo de oxidação eletroquímica do etanol foi estudado por meio da técnica de espectroscopia no infravermelho com transformada de Fourier (FTIR) in situ. Os melhores eletrocatalisadores foram testados em células alcalinas unitárias alimentadas diretamente por metanol, etanol e etilenoglicol. Estudos preliminares mostraram que a composição atômica adequada para preparar catalisadores ternários é igual a 50:45:05. De acordo com os experimentos eletroquímicos em meio básico, o eletrocatalisador PdAuPt/C (50:45:05) apresentou a maior atividade para oxidação eletroquímica de metanol, enquanto que, nas mesmas condições, o PdAuIr/C foi mais ativo para oxidação do etanol e o PdAuBi/C mais ativo para a oxidação do etilenoglicol. Estes resultados indicam que a adição de ouro na composição dos eletrocatalisadores contribui para uma maior atividade catalítica dos mesmos. Os resultados de FTIR mostraram que o mecanismo da oxidação do etanol se processa de modo indireto, ou seja, a ligação CC não é rompida, formando acetato. / In this study Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C and PdAuIr/C electrocatalysts were prepared by the sodium borohydride reduction method for the electrochemical oxidation of methanol, ethanol and ethylene glycol. This methodology consists in mix an alkaline solution of sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. The electrocatalysts were characterized by energy dispersive X-ray (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry. The electrochemical oxidation of the alcohols was studied by chronoamperometry using a thin porous coating technique. The mechanism of ethanol electro-oxidation was studied by Fourier Transformed Infrared (FTIR) in situ. The most effective electrocatalysts were tested in alkaline single cells directly fed with methanol, ethanol or etylene glycol. Preliminary studies showed that the most suitable atomic composition for preparing the ternary catalysts is 50:45:05. Electrochemical data in alkaline medium show that the electrocatalyst PdAuPt/C (50:45:05) showed the better activity for methanol electrooxidation, while PdAuIr/C was the most active for ethanol oxidation and PdAuBi/C (50:45:05) was the most effective for ethylene glycol oxidation in alkaline medium. These results show that the addition of gold in the composition of electrocatalysts increases their catalytic activities. The spectroelectrochemical FTIR in situ data permitted to conclude that C-C bond is not broken and the acetate is formed.

Modulação da resposta imune no local do tumor é um mecanismo crítico envolvido com evasão dos tumores. Sinais de PD-1 e PD-L1/PD-L2 podem estar envolvidos com o escape tumoral. Entretanto, pouco se sabe a respeito destas moléculas no desenvolvimento de carcinoma de células escamosas. No presente estudo, nós investigamos a expressão de PD-1 sobre células T das lesões e linfonodos de carcinomas de células escamosas. A carcinogênese de pele foi induzida quimicamente com DMBA/PMA em camundongos. A caracterização da expressão de PD-1, PD-L1 e PD-L2 na lesão e linfonodos foram analisados por citometria de fluxo. A produção IL-10, IL-12, TGF- e IFN- foi determinada por ELISA. Camundongos tratados com DMBA/PMA apresentaram maior taxa de papilomas e progressão para carcinoma de células escamosas. Nós encontramos também que células T CD4+PD-1+ migraram para o local do tumor e que maior nível de CD4+PD-1+, CD8+PD-1+, CD14+PD-1+ e CD4+PD-L1+ foram detectados nos linfonodos quando comparados com o grupo controle. Além disso, as produções de IL-12, IFN- e TGF-, mas não IL-10, foram altamente detectadas nas lesões comparada com do grupo controle. Estes dados indicam que a expressão de PD-1 está regulada positivamente sobre linfócitos infiltrados nos tumores e linfonodos. Este fato e os altos níveis de TGF- e IL-10 podem contribuir para supressão da resposta imune antitumor. / Modulation of immune response in tumor site is a critical mechanism involved with tumor evasion. PD-1 and PD-L1/PD-L2 signals could be involved in tumor escape. However, little is known about the role of these molecules in squamous cell carcinoma development. In the present study, we investigated the expression of PD-1 on T cells from squamous cell carcinoma lesions and lymph nodes. Skin carcinogenesis was chemically induced with DMBA/PMA in mice. Characterization of PD-1, PD-L1 and PD-L2 expression in the lesion and lymph nodes were analysed by flow cytometry. IL-10, IL-12, TGF- and IFN- production was determined by ELISA. DMBA/PMA-treated mice showed higher rate of papillomas and progression to squamous cell carcinoma. We also found that CD4+PD-1+ T cells migrated to the tumor site and that higher level of CD4+PD-1+, CD8+PD-1+, CD14+PD-1+ and CD4+PD-L1+ were detected in the lymph nodes when compared with the control group. Besides, IL-12, IFN- and TGF-, but not IL-10, productions were higher detected in the lesions compared with the control group. These data indicate that PD-1 expression is up-regulated on tumor infiltrating lymphocytes and lymph nodes. This fact and high levels of TGF- and IL-10 may contribute to suppression of anti-tumor immune response.

No description available.

The work is motivated by the goal of linking reality and model, and to see if there is an opportunity to develop an inexpensive educational tool for training in cyber-physical systems. This project has investigated the possibilities to build a cheap inverted pendulum with controller and connect this with the modeling language Acumen. Acumen models is used for comparison with the actual prototype. To solve these problems has a 3D printer been used to create hardware, Arduino UNO for control and Raspberry Pi for enable communication with Acumen over WLAN. The result was a cheap inverted pendulum, which can be built for a cost around 750 SEK. Graphs created in Acumen and from data collected from sensors can be analyzed. With a model of the inverted pendulum system, the results show that Acumen can be used in the development of cyber-physical systems. There are differences between model and reality but also similarities. / Arbetet motiveras av målet att knyta samman verklighet och modell, samt att se om det finns möjlighet att utveckla ett billigt utbildningsverktyg för utbildning i cyberfysiska system. Detta projekt har undersökt möjligheter att bygga en billig inverterad pendel med regulator samt koppla samman denna med modelleringsspråket Acumen. I Acumen skapa en modell av systemet och jämföra den med en fysisk prototyp. För att lösa dessa problem har en 3D skrivare använts för att skapa hårdvara. Arduino UNO för styrning och Raspberry Pi för att möjligöra kommunikation med Acumen över WLAN. Resultatet blev en billig inverterad pendel, som kan byggas för en kostnad runt 750 kr. Grafer från Acumen, och från data samlad från sensorer kan analyseras. Med en modell av en inverterad pendel visar resultaten att Acumen kan användas i utveckling av cyberfysiska system. Skillnader finns mellan modell och verklighet men även likheter.