Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Análise da qualidade das águas, Ribeira Brava

O planeamento e gestão dos recursos hídricos é nos dias de hoje uma tarefa complicada, mas interessante e necessária, tendo em vista a satisfação de cada vez mais exigentes padrões de vida das populações e da qualidade do ambiente. Para que sejam possíveis escolhas e decisões judiciosas sobre a melhor forma de utilizar a água disponível, a sua gestão deve ser enformada por leis, actuações administrativas e disposições económico-financeiras, as quais determinam a necessidade da existência de sistemas institucionais competentes para as implementar. Sob o paradigma da sustentabilidade no contexto dos recursos hídricos, procedeu-se a uma avaliação do estado qualitativo das águas superficiais e subterrâneas do concelho da Ribeira Brava, quer a nível da distribuição de águas quer a nível das águas residuais. Inicialmente, caracterizou-se a região hidrográfica em estudo quanto aos aspetos geográficos, demográficos, socioeconómicos, bem como uma perspetiva quanto à caracterização hidrológica e geomorfológica da bacia hidrográfica a ser monitorizada. Posteriormente, apresentou-se, sob um manto teórico, o funcionamento de todo o sistema de abastecimento de água desde a captação até à sua devolução à natureza, passando pelas ETA, redes de distribuição e ETAR, passando a descrever-se a realidade em termos de infraestruturas existentes no concelho da Ribeira Brava. De seguida, procedeu-se à análise paramétrica temporal nas ETA e ETAR do concelho, cruzando esses dados com a legislação em vigor. Como etapa final, retratam-se as principais ilações quanto à monitorização efetuada, quer a nível de águas de distribuição, quer a nível das águas residuais, bem como se contribui com algumas recomendações, tendo em conta a manutenção e melhoria quantitativa e qualitativa da água no concelho da Ribeira Brava.

El Infante don Fadrique y la estela del arte suabo en el Reino de Castilla en la segunda mitad del siglo XIII

Esta investigación pretende someter a análisis los intercambios arquitectónicos y artísticos que se establecieron entre el Reino de Castilla e Italia en el siglo XIII, centrando la atención en la denostada figura del infante Fadrique de Castilla. Don Fadrique de Castilla fue el segundogénito de Fernando III y Beatriz de Suabia, para quien sus progenitores habían previsto la herencia materna del ducado de Suabia. Con el fin de reclamar el legado de su madre Fadrique emprendió su viaje hacia la corte imperial de Federico II, llegando a la ciudad de Foggia en el mes de abril de 1240. Su permanencia junto al emperador se prolongó hasta el mes de junio de 1245, momento en el cual, el infante decidió abandonar la corte del emperador sin previo aviso para pasar a Milán, principal enemigo del bando gibelino y, después, regresar a Castilla. Una vez en Castilla, Fadrique participó junto a su padre y sus hermanos, Alfonso y Enrique, en la conquista de Sevilla. En el repartimiento recibió amplios territorios en el norte de la ciudad, decidiendo establecer su residencia en el área del actual Convento de Santa Clara. En el interior de este recinto erigió una torre exenta conocida como Torre de don Fadrique que, según la inscripción ubicada sobre la puerta, se construyó en el año 1252. El modelo arquitectónico al que se ajusta es ajeno a la arquitectura civil castellana del siglo XIII, sin embargo podemos hallar correspondencias con una estructura muy difundida en Italia: la torre nobiliaria. Esta analogía fue el punto de partida para el estudio de las relaciones artísticas entre ambos países configurándose en nuestra investigación un corpus heterogéneo y complejo de obras de arte que engloban la mencionada torre, la Capilla Real hispalense y las tallas marianas vinculadas a ella, el ajuar funerario de Beatriz de Suabia o las Cantigas de Santa María...

Boas práticas de produção nas granjas de ovos comerciais.

2016

Amostragem em ensaios com frangos de corte considerando variáveis de abate.

2016

Petrofac International Limited: el mercadeo interno, una estrategia efectiva en el manejo de personal

Como futuros administrados es importante recordar que nuestra función no será únicamente crear una empresa y generar constantemente ingresos. Esto es una de tantas tareas que tiene una persona que se encamina por crear o ser parte de una empresa, sea grande o pequeña siempre existirán variables que con los años se han convertido más y más indispensables en los procesos de este recorrido. El tema principal de nuestro estudio de caso es entender el concepto del endomarketing o como muchos lo conocen marketing interno; en pocas palabras es algo que por años se ha visto su efectividad en la productividad y satisfacción de los empleados. Google es una de las multinacionales más grandes del mundo, que el ultimo reconocimiento fue por parte de uno de los ranking más influyentes “The World’s Billionaries” ocupando como el CEO de la compañía Larry Page el puesto #12 , que por años ha sabido invertir en su recurso más importante que son sus empleados. En una entrevista con la revista Fortune, Larry exclama que “es importante que la empresa sea una familia, que las personas sientan que son parte de la empresa, y que la empresa es como una familia para ellos. Cuando se trata a las personas de esa manera, se obtiene una mejor productividad”. Con este pequeño ejemplo e idea de cómo una de las marcas más influyentes en el mundo ha fortalecido su mejor recurso por años el cual le ha remunerado con el éxito que tiene hoy en día. Entonces es como el mercadeo interno o endomarketing siendo uno de los conceptos tratados en el mercadeo en general hoy en día, logrando meterse como un modelo de negocio en la mayoría de empresas que existen hoy. Este es uno de los motivos que nos motivó para desarrollar este estudio de caso que verán a continuación, el cual se basa en la investigación y análisis de variables que comprenden a la empresa Petrofac, y si bien ha sabido implementar el concepto en sus procesos diarios. El estudio de caso describe como a través de los años ha sabido implementar con éxito la herramienta de evaluación y análisis del mercado interno a los empleados que constituyen hoy en día Petrofac International Limited. Abarcaremos primero con los objetivos del estudio, seguido del inicio y crecimiento de la empresa en los últimos años, en que países tiene presencia y cuáles son sus proyectos más importantes hoy en día. El estudio de caso será implementado por un tipo de investigación descriptiva, que con la recopilación de suficiente información tanto cuantitativa como cualitativa nos ira fortaleciendo la hipótesis principal, usaremos datos estadísticos que serán recopilados de encuestas, entrevistas y focus group. Al final con el análisis y a las conclusiones que lleguemos se busca demostrar el impacto positivo que ha tenido los empleados de diferentes países y de diferentes culturas que poco a poco han influenciado a la empresa para alcanzar el éxito que ha logrado hasta ahora, y de la misma forma como la empresa ha influenciado en cada una de las vidas de estas personas sin importar el lugar en el que estén laborando, siempre la empresa busca que se sientan parte de ella. Como resultados generales, se obtienen argumentos que sustentan que la implementación del mercadeo interno le permite a la empresa generar ventajas competitivas y dinámicas, que son desarrolladas internamente para un futuro reflejarlas ante los clientes externos. El estudio permitió concluir que el mercadeo interno debe ser una estrategia de comunicación dentro de una empresa convirtiéndose de primera necesidad para la compañía, pues los beneficios que genera son cada vez más necesarios para cada área que abarca el negocio.