Study of multiferroic materials

The present PhD work aims the research and development of materials that exhibit multiferroic properties, in particular having a significant interaction between ferromagnetism and ferroelectricity; either directly within an intrinsic single phase or by combining extrinsic materials, achieving the coupling of properties through mechanic phenomena of the respective magnetostriction and piezoelectricity. These hybrid properties will allow the cross modification of magnetic and electric polarization states by the application of cross external magnetic and/or electric fields, giving way to a vast area for scientific investigation and potential technological applications in a new generation of electronic devices, such as computer memories, signal processing, transducers, sensors, etc. Initial experimental work consisted in chemical synthesis of nano powders oxides by urea pyrolysis method: A series of ceramic bulk composites with potential multiferroic properties comprised: of LuMnO3 with La0.7Sr0.3MnO3 and BaTiO3 with La0.7Ba0.3MnO3; and a series based on the intrinsic multiferroic LuMn1-zO3 phase modified with of Manganese vacancies. The acquisition of a new magnetron RF sputtering deposition system, in the Physics Department of Aveiro University, contributed to the proposal of an analogous experimental study in multiferroic thin films and multilayer samples. Besides the operational debut of this equipment several technical upgrades were completed like: the design and construction of the heater electrical contacts; specific shutters and supports for the magnetrons and for the substrate holder and; the addition of mass flow controllers, which allowed the introduction of N2 or O2 active atmosphere in the chamber; and the addition of a second RF generator, enabling co-deposition of different targets. Base study of the deposition conditions and resulting thin films characteristics in different substrates was made from an extensive list of targets. Particular attention was given to thin film deposition of magnetic phases La1-xSrxMnO3, La1-xBaxMnO3 and Ni2+x-yMn1-xGa1+y alloy, from the respective targets: La0.7Sr0.3MnO3, La0.7Ba0.3MnO3; and NiGa with NiMn. Main structural characterization of samples was performed by conventional and high resolution X-Ray Diffraction (XRD); chemical composition was determined by Electron Dispersion Spectroscopy (EDS); magnetization measurements recur to a Vibrating Sample Magnetometer (VSM) prototype; and surface probing (SPM) using Magnetic-Force (MFM) and Piezo-Response (PFM) Microscopy. Results clearly show that the composite bulk samples (LuM+LSM and BTO+LBM) feat the intended quality objectives in terms of phase composition and purity, having spurious contents below 0.5 %. SEM images confirm compact grain packaging and size distribution around the 50 nm scale. Electric conductivity, magnetization intensity and magneto impedance spreading response are coherent with the relative amount of magnetic phase in the sample. The existence of coupling between the functional phases is confirmed by the Magnetoelectric effect measurements of the sample “78%LuM+22%LSM” reaching 300% of electric response for 1 T at 100 kHz; while in the “78%BTO+22%LBM” sample the structural transitions of the magnetic phase at ~350 K result in a inversion of ME coefficient the behavior. A functional Magneto-Resistance measurement system was assembled from the concept stage until the, development and operational status; it enabled to test samples from 77 to 350 K, under an applied magnetic field up to 1 Tesla with 360º horizontal rotation; this system was also designed to measure Hall effect and has the potential to be further upgraded. Under collaboration protocols established with national and international institutions, complementary courses and sample characterization studies were performed using Magneto-Resistance (MR), Magneto-Impedance (MZ) and Magneto-Electric (ME) measurements; Raman and X-ray Photoelectron Spectroscopy (XPS); SQUID and VSM magnetization; Scanning Electron Microscopy (SEM) and Rutherford Back Scattering (RBS); Scan Probe Microscopy (SPM) with Band Excitation Probe Spectroscopy (BEPS); Neutron Powder Diffraction (NPD) and Perturbed Angular Correlations (PAC). Additional collaboration in research projects outside the scope of multiferroic materials provided further experience in sample preparation and characterization techniques, namely VSM and XPS measurements were performed in cubane molecular complex compounds and enable to identify the oxidation state of the integrating cluster of Ru ions; also, XRD and EDS/SEM analysis of the acquired targets and substrates implied the devolution of some items not in conformity with the specifications. Direct cooperation with parallel research projects regarding multiferroic materials, enable the assess to supplementary samples, namely a preliminary series of nanopowder Y1-x-yCaxØyMn1O3 and of Eu0.8Y0.2MnO3, a series of micropowder composites of LuMnO3 with La0.625Sr0.375MnO3 and of BaTiO3 with hexagonal ferrites; mono and polycrystalline samples of Pr1-xCaxMnO3, La1-xSrxMnO3 and La1-xCaxMnO3.

Lanthanide oxide and phosphate nanoparticles for thermometry and bimodal imaging

Nesta tese relatam-se estudos de fotoluminescência de nanopartículas de óxidos e fosfatos dopados com iões trivalentes de lantanídeos, respectivamente, nanobastonetes de (Gd,Eu)2O3 e (Gd,Yb,Er)2O3 e nanocristais de (Gd,Yb,Tb)PO4, demonstrando-se também aplicações destes materiais em revestimentos inteligentes, sensores de temperatura e bioimagem. Estuda-se a transferência de energia entre os sítios de Eu3+ C2 e S6 dos nanobastonetes Gd2O3. A contribuição dos mecanismos de transferência de energia entre sítios para o tempo de subida 5D0(C2) é descartada a favor da relaxação directa 5D1(C2) 5D0(C2) (i.e., transferência de energia entre níveis). O maior tempo de decaimento do nível 5D0(C2) nos nanobastonetes, relativamente ao valor medido para o mesmo material na forma de microcristais, é atribuído, quer à existência de espaços livres entre nanobastonetes próximos (factor de enchimento ou fracção volúmica), quer à variação do índice de refracção efectivo do meio em torno dos iões Eu3+. A dispersão de nanobastonetes de (Gd,Eu)2O3 em três resinas epoxi comerciais através da cura por UV permite obter nanocompósitos epoxi- (Gd,Eu)2O3. Relatam-se estudos cinéticos e das propriedades térmicas e de fotoluminescência destes nanocompósitos. Estes, preservam as típicas propriedades de emissão do Eu3+, mostrando o potencial do método de cura por UV para obter revistimentos inteligentes e fotoactivos. Considera-se um avanço significativo a realização de uma nanoplataforma óptica, incorporando aquecedor e termómetro e capaz de medir uma ampla gama de temperaturas (300-2000 K) à escala nano, baseada em nanobastonetes de (Gd,Yb,Er)2O3 (termómetros) cuja superfície se encontra revestida com nanopartículas de ouro. A temperature local é calculada usando, quer a distribuição de Boltzmann (300-1050 K) do rácio de intensidades da conversão ascendente 2H11=2!4I15=2/4S3=2!4I15=2, quer a lei de Planck (1200-2000 K) para uma emissão de luz branca atribuída à radiação do corpo negro. Finalmente, estudam-se as propriedades de fotoluminescência correspondentes às conversões ascendente e descendente de energia em nanocristais de (Gd,Yb,Tb)PO4 sintetizados por via hidrotérmica. A relaxividade (ressonância magnética) do 1H destes materiais são investigadas, tendo em vista possíveis aplicações em imagem bimodal (luminescência e ressonância magnética nuclear).

Finite Element Analysis (FEA) applied to heat transfer optimization process of pultrusion die systems

The aim of this study is to optimize the heat flow through the pultrusion die assembly system on the manufacturing process of a specific glass-fiber reinforced polymer (GFRP) pultrusion profile. The control of heat flow and its distribution through whole die assembly system is of vital importance in optimizing the actual GFRP pultrusion process. Through mathematical modeling of heating-die process, by means of Finite Element Analysis (FEA) program, an optimum heater selection, die position and temperature control was achieved. The thermal environment within the die was critically modeled relative not only to the applied heat sources, but also to the conductive and convective losses, as well as the thermal contribution arising from the exothermic reaction of resin matrix as it cures or polymerizes from the liquid to solid condition. Numerical simulation was validated with basis on thermographic measurements carried out on key points along the die during pultrusion process.

Avaliação e Otimização Energética das Fornalhas da Fábrica de Aromáticos

O consumo energético verificado nas refinarias petrolíferas é muito elevado, sendo as fornalhas os equipamentos que mais contribuem para esse consumo. Neste estudo foi efetuada uma avaliação e otimização energética às fornalhas da Fábrica de Aromáticos da Refinaria de Matosinhos. Numa primeira fase foi efetuado um levantamento exaustivo de dados de todas as correntes de entrada e saída dos equipamentos para posteriormente efetuar os balanços de massa e energia a cada uma das fornalhas. Os dados relativos ao levantamento compreenderam dois períodos de funcionamento distintos da unidade fabril, o período de funcionamento normal e o período relativo ao arranque. O período de funcionamento normal foi relativo ao ano de 2012 entre os meses de janeiro a setembro, por sua vez o período de arranque foi de dezembro de 2012 a março de 2013. Na segunda fase foram realizados os balanços de massa e energia quantificando todas as correntes de entrada e saída das fornalhas em termos mássicos e energéticos permitindo o cálculo do rendimento térmico das fornalhas para avaliar a sua performance. A avaliação energética permitiu concluir que existe um consumo maior de energia proveniente da combustão do Fuel Gás do que do Fuel Óleo, tanto no período de funcionamento normal como no arranque. As fornalhas H0101, H0301 e a H0471 possuem os consumos mais elevados, sendo responsáveis por mais de 70% do consumo da Fábrica de Aromáticos. Na terceira fase foram enunciadas duas medidas para a otimização energética das três fornalhas mais consumidoras de energia, a limpeza mensal e o uso exclusivo de Fuel Gás como combustível. As poupanças energéticas obtidas para uma limpeza mensal foram de 0,3% na fornalha H0101, 0,7% na fornalha H0301 e uma poupança de 0,9 % na fornalha H0471. Para o uso exclusivo de Fuel Gás obteve-se uma poupança de 0,9% na fornalha H0101 e uma poupança de 1,3% nas fornalhas H0301 e H0471. A análise económica efetuada à sugestão de alteração do combustível mostra que os custos de operação sofrerão um aumento anual de 621 679 €. Apesar do aumento dos custos, a redução na emissão de 24% de dióxido de carbono, poderá justificar este aumento na despesa.

Estudo de uma bomba de calor de expansão direta assistida por energia solar para a preparação de AQS

Este estudo consiste na caracterização da eficiência energética de uma bomba de calor de expansão direta que utiliza a energia solar como fonte térmica. De uma forma geral, teve-se a obrigação de procurar cada vez mais recursos renováveis e neste sentido a bomba de calor de expansão direta tem um papel importante no aquecimento de águas quentes sanitárias (AQS). Como ponto de partida, foi realizada uma descrição detalhada sobre todos os equipamentos da bomba de calor e elaborado um desenho técnico que identifica todos os componentes. No laboratório (casa inteligente) realizaram-se vários ensaios a fim de interpretar com rigor os resultados obtidos do desempenho da bomba de calor (COP) e do fator médio de desempenho sazonal (SPF). No início, realizaram-se ensaios para determinar as perdas estáticas do sistema termodinâmico, de seguida foram elaborados ensaios segundo a norma EN 16147 e por fim, ensaios de acordo com o perfil de utilização de AQS definido. No estudo experimental do COP, obteve-se uma elevada eficiência energética com um valor médio de 4,12. O COP aumenta para valores médios de 5 quando a temperatura de água no termoacumulador desce para 35ºC. Verificou-se que durante o período diurno o COP aumenta aproximadamente de 10% relativamente ao período noturno. A potência elétrica é mais elevada (450W) quando a água no termoacumulador está perto da temperatura desejável (55ºC), originando um esforço maior da bomba de calor. No estudo experimental do SPF, verificou-se que nos ensaios segundo a norma EN16147 os valores obtidos variaram entre 1,39 e 1,50 (Classe “B”). No estudo realizado de acordo com o perfil de utilização de AQS definido pelo utilizador, o SPF é superior em 12% relativamente ao obtido segundo os ensaios realizados de acordo a norma EN16147. Verificou-se que o aumento da temperatura do ar exterior implica um aumento do SPF (cerca de 2% a 5%), enquanto a energia solar não influência nos resultados.

Letter and envelope addressed to S.D. Woodruff from the office of T.B. Stewart and Co. of New York

Letter and envelope addressed to S.D. Woodruff from the office of T.B. Stewart and Co. of New York, Manufacturers of Mantles, Marble and Wood Mantels. The letter states that the heater and grates have been shipped, July 14, 1876.

Fliesslochformen und Gewindefurchen in dünne Bleche und Rohre aus Kupfer und Kupferlegierungen

This thesis in Thermal Flow Drilling and Flowtap in thin metal sheet and pipes of copper and copper alloys had as objectives to know the comportment of copper and copper alloys sheet metal during the Thermal Flow Drill processes with normal tools, to know the best Speed and Feed machine data for the best bushing quality, to known the best Speed for Form Tapping processes and to know the best bush long in pure copper pipes for water solar interchange equipment. Thermal Flow Drilling (TFD) and Form Tapping (FT) is one of the research lines of the Institute of Production and Logistics (IPL) at University of Kassel. At December 1995, a work meeting of IPL, Santa Catarina University, Brazil, Buenos Aires University, Argentine, Tarapacá University (UTA), Chile members and the CEO of Flowdrill B.V. was held in Brazil. The group decided that the Manufacturing Laboratory (ML) of UTA would work with pure copper and brass alloys sheet metal and pure copper pipes in order to develop a water interchange solar heater. The Flowdrill BV Company sent tools to Tarapacá University in 1996. In 1999 IPL and the ML carried out an ALECHILE research project promoted by the DAAD and CONICyT in copper sheet metal and copper pipes and sheet metal a-brass alloys. The normal tools are lobed, conical tungsten carbide tool. When rotated at high speed and pressed with high axial force into sheet metal or thin walled tube generated heat softens the metal and allows the drill to feed forward produce a hole and simultaneously form a bushing from the displacement material. In the market exist many features but in this thesis is used short and longs normal tools of TFD. For reach the objectives it was takes as references four qualities of the frayed end bushing, where the best one is the quality class I. It was used pure copper and a-brass alloys sheet metals, with different thickness. It was used different TFD drills diameter for four thread type, from M-5 to M10. Similar to the Aluminium sheet metals studies it was used the predrilling processes with HSS drills around 30% of the TFD diameter (1,5 – 3,0 mm D). In the next step is used only 2,0 mm thick metal sheet, and 9,2 mm TFD diameter for M-10 thread. For the case of pure commercial copper pipes is used for ¾” inch diameter and 12, 8 mm (3/8”) TFD drill for holes for 3/8” pipes and different normal HSS drills for predrilling processes. The chemical sheet metal characteristics were takes as reference for the material behaviour. The Chilean pure copper have 99,35% of Cu and 0,163% of Zinc and the Chilean a-brass alloys have 75,6% of Cu and 24,0% of Zinc. It is used two German a-brass alloys; Nº1 have 61,6% of Cu, 36,03 % of Zinc and 2,2% of Pb and the German a-brass alloys Nº2 have 63,1% of Cu, 36,7% of Zinc and 0% of Pb. The equipments used were a HAAS CNC milling machine centre, a Kistler dynamometer, PC Pentium II, Acquisition card, TESTPOINT and XAct software, 3D measurement machine, micro hardness, universal test machine, and metallographic microscope. During the test is obtained the feed force and momentum curves that shows the material behaviour with TFD processes. In general it is take three phases. It was possible obtain the best machining data for the different sheet of copper and a-brass alloys thick of Chilean materials and bush quality class I. In the case of a-brass alloys, the chemical components and the TFD processes temperature have big influence. The temperature reach to 400º Celsius during the TFD processes and the a-brass alloys have some percents of Zinc the bush quality is class I. But when the a-brass alloys have some percents of Lead who have 200º C melting point is not possible to obtain a bush, because the Lead gasify and the metallographic net broke. During the TFD processes the recrystallization structures occur around the Copper and a-brass alloy bush, who gives more hardness in these zones. When the threads were produce with Form Tapping processes with Flowtap tools, this hardness amount gives a high limit load of the thread when hey are tested in a special support that was developed for it. For eliminated the predrilling processes with normal HSS drills it was developed a compound tool. With this new tool it was possible obtain the best machining data for quality class I bush. For the copper pipes it is made bush without predrilling and the quality class IV was obtained. When it is was used predrilling processes, quality classes I bush were obtained. Then with different HSS drill diameter were obtained different long bush, where were soldering with four types soldering materials between pipes with 3/8” in a big one as ¾”. Those soldering unions were tested by traction test and all the 3/8” pipes broken, and the soldering zone doesn’t have any problem. Finally were developed different solar water interchange heaters and tested. As conclusions, the present Thesis shows that the Thermal Flow Drilling in thinner metal sheets of cooper and cooper alloys needs a predrilling process for frayed end quality class I bushings, similar to thinner sheets of aluminium bushes. The compound tool developed could obtain quality class I bushings and excludes predrilling processes. The bush recrystalization, product of the friction between the tool and the material, the hardness grows and it is advantageous for the Form Tapping. The methodology developed for commercial copper pipes permits to built water solar interchange heaters.

Large-Size AlGaN/GaN HEMT Large-Signal Electrothermal Characterization and Modeling for Wireless Digital Communications

The rapid growth in high data rate communication systems has introduced new high spectral efficient modulation techniques and standards such as LTE-A (long term evolution-advanced) for 4G (4th generation) systems. These techniques have provided a broader bandwidth but introduced high peak-to-average power ratio (PAR) problem at the high power amplifier (HPA) level of the communication system base transceiver station (BTS). To avoid spectral spreading due to high PAR, stringent requirement on linearity is needed which brings the HPA to operate at large back-off power at the expense of power efficiency. Consequently, high power devices are fundamental in HPAs for high linearity and efficiency. Recent development in wide bandgap power devices, in particular AlGaN/GaN HEMT, has offered higher power level with superior linearity-efficiency trade-off in microwaves communication. For cost-effective HPA design to production cycle, rigorous computer aided design (CAD) AlGaN/GaN HEMT models are essential to reflect real response with increasing power level and channel temperature. Therefore, large-size AlGaN/GaN HEMT large-signal electrothermal modeling procedure is proposed. The HEMT structure analysis, characterization, data processing, model extraction and model implementation phases have been covered in this thesis including trapping and self-heating dispersion accounting for nonlinear drain current collapse. The small-signal model is extracted using the 22-element modeling procedure developed in our department. The intrinsic large-signal model is deeply investigated in conjunction with linearity prediction. The accuracy of the nonlinear drain current has been enhanced through several issues such as trapping and self-heating characterization. Also, the HEMT structure thermal profile has been investigated and corresponding thermal resistance has been extracted through thermal simulation and chuck-controlled temperature pulsed I(V) and static DC measurements. Higher-order equivalent thermal model is extracted and implemented in the HEMT large-signal model to accurately estimate instantaneous channel temperature. Moreover, trapping and self-heating transients has been characterized through transient measurements. The obtained time constants are represented by equivalent sub-circuits and integrated in the nonlinear drain current implementation to account for complex communication signals dynamic prediction. The obtained verification of this table-based large-size large-signal electrothermal model implementation has illustrated high accuracy in terms of output power, gain, efficiency and nonlinearity prediction with respect to standard large-signal test signals.

Caracterización de los pacientes con hemorragia de vías digestivas altas no varicosa atendidos en el Hospital Universitario de la Samaritana, Cundinamarca

La hemorragia de vías digestivas altas (HVDA) es una emergencia frecuente. La etiología más común es la úlcera péptica. La restauración del volumen intravascular y la presión arterial son la prioridad del manejo. La endoscopia (EGD) debe realizarse luego de la reanimación inicial y lograda la estabilización hemodinámica, tratar la lesión subyacente mediante hemostasia. Se realiza un estudio en un hospital de referencia de tercer nivel, Cundinamarca, Colombia Materiales y métodos: Estudio descriptivo retrospectivo, datos obtenidos de la historia clínica electrónica de pacientes adultos que consultaron por urgencias en el Hospital Universitario de la Samaritana (HUS) por HVDA, diagnosticada por hematemesis, melenas, hematoquezia y/o anemia; a quienes se les realizó EGD durante abril del 2010 - abril del 2011. Resultados: Se atendieron 385 pacientes en el período de estudio, 100 fueron excluidos debido a hemorragia secundaria a várices esofágicas, historia incompleta y hemorragia digestiva baja, para un total de 285 pacientes analizados. El 69.1% eran mayores de 60 años. El 73.3% presentaba hipertensión arterial, el 55.1% reportaba ingesta de Anti-inflamatorios no esteroideos (AINES) y Aspirina (ASA). El 19.6% reportaba episodios de sangrado previos y 17.9% presentó inestabilidad hemodinámica. Sesenta y tres pacientes (22,1%) requirieron hemostasia endoscópica, treinta y dos (11.2%) presentaron resangrado. La mortalidad reportada fue del 13.1%, del cual 55.3% correspondía a hombres. Discusión: La mayoría de la población atendida en el HUS por HVDA son adultos mayores de 60 años. La úlcera péptica, continúa siendo el diagnóstico más frecuente asociado al uso de AINES y ASA.

Análisis económico de las vacunas 10-valente y 13-valente contra neumococo: revisión sistemática

Introducción: Las vacunas clásicamente han representado un método económico y eficaz para el control y prevención de múltiples enfermedades infecciosas. En los últimos años se han introducido nuevas vacunas contra neumococo a precios elevados, y los diferentes análisis económicos a nivel mundial de estas vacunas no muestran tendencias. El objetivo de este trabajo era resumir la evidencia existente a través de los diferentes estudios económicos evaluando las dos vacunas de segunda generación contra neumococo en la población a riesgo. Metodología: En este trabajo se realizo una revisión sistemática de la literatura en 8 bases de datos localizadas en diferentes partes del mundo y también que tuvieran literatura gris. Los artículos fueron inicialmente evaluados acorde a su titulo y resumen, posteriormente los elegidos se analizaron en su totalidad. Resultados: Se encontraron 404 artículos, de los cuales 20 fueron incluidos en el análisis final. Se encontró que la mayoría de los estudios se realizaron en áreas donde la enfermedad tiene una carga baja, como es Norte América y Europa, mientras que en los lugares del mundo donde la carga es mas alta, se realizaron pocos estudios. De igual manera se observo que la mayoría de los estudios mostraron por los menos ser costo efectivos respecto a la no vacunación, y en su totalidad las dos vacunas de segunda generación mostraron costo efectividad respecto a la vacunación con PCV-7. Los resultados de los estudios son muy heterogéneos, hasta dentro del mismo país, señalando la necesidad de guías para la conducción de este tipo de estudios. De igual manera, la mayoría de los estudios fueron financiados por farmacéuticas, mientras en un numero muy reducido por entes gubernamentales. Conclusiones: La mayoría de los estudios económicos sobre las vacunas de segunda generación contra neumococo han sido realizados en países con un alto índice de desarrollo económico y patrocinados por farmacéuticas. Dado que la mayoría de la carga de la enfermedad se encuentran en regiones con un menor nivel de desarrollo económico se deberían realizar mas en estas zonas. De igual manera, al ser la vacunación un asunto de salud publica y con un importante impacto económico los gobiernos deberían estar mas involucrados en los mismos.

La pelota no se mancha: Un estudio histórico sobre el desarrollo y la política en FIFA

Esta investigación se centra en la Fédération Internationale de Football Association (FIFA) como organización política. Intenta responder dos interrogantes primordiales: 1) ¿cómo la FIFA ha constituido el poder que tiene actualmente y, así, hacerse del monopolio indiscutido del fútbol? Y 2) ¿cómo ha cambiado en el tiempo la política interna de FIFA y su vínculo con la política internacional? Para lograr esto, se realiza un estudio histórico, basado principalmente en documentos, que intenta caracterizar y analizar los cambios de la organización en el tiempo. Se enfatizan las últimas dos presidencias de FIFA, de João Havelange y Joseph Blatter, como casos de estudio.

Tortoises.

Se pretende enseñar a los niños el ciclo de vida de las tortugas y la forma en que interactúan con su entorno, sus hábitos, su estilo de vida y las amenazas a los que se enfrenta por la actuación de los hombres al modificar las condiciones ambientales. La obra contiene un mapa de distribución del hábitat de la tortuga, glosario y bibliografía.