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.

Formação do pensamento científico durante o processo de alfabetização científica no ensino de teorias atômicas e elementos químicos

Acompanha: Sequências didáticas para o ensino de teorias atômicas e elementos químicos

Relatório de estágio de qualificação profissional

Relatório EPE - Relatório de estágio em Educação Pré-Escolar: O presente relatório de estágio de qualificação profissional tem como objetivo relatar as dificuldades e conquistas pelas quais a mestranda passou durante a prática pedagógica supervisionada no pré-escolar, no decorrer do Mestrado em Educação Pré-Escolar e Ensino do 1ºCiclo do Ensino Básico, na Escola Superior de Educação do Porto. Este relatório descreve algumas das atividades desenvolvidas, as estratégias de formação e desenvolvimento profissional às quais a mestranda fez recurso, bem como os diversos modelos curriculares onde se apoiou para criar o seu próprio modelo. A mestranda desenvolveu ainda as relações jardim-de-infância- família bem como as relações com a equipa educativa.

Relatório de estágio de qualificação profissional

Relatório EPE - Relatório de estágio em Educação Pré-Escolar: O presente relatório de estágio de qualificação profissional, elaborado no âmbito da formação da mestranda em Educação Pré-Escolar, visa a descrição e reflexão da ação educativa desenvolvida ao longo deste processo formativo, explanando, também, as competências profissionais e pessoais construídas pela mesma. Este perspetiva a mobilização de pressupostos teóricos e legais que fundamentaram a prática pedagógica da mestranda, com recurso a estratégias que visam uma educação inclusiva e equitativa, atendendo às características das crianças, encaradas como co-construtoras das suas aprendizagens. Com base numa visão socioconstrutivista, são apresentadas as perspetivas pedagógicas que se propuseram a dar resposta às necessidades e interesses evidenciados, tendo em consideração a capacidade de pensar e agir no contexto educativo em que foi desenvolvido o estágio. Assim, revelou-se fundamental o recurso ao método de investigação-ação, em que o educador é investigador da sua ação, sendo um profissional crítico e reflexivo, que está aberto à mudança. Este relatório pretende dar a conhecer as técnicas e estratégias utilizadas para alcançar os objetivos e desafios propostos todos os dias, tendo em vista a melhoria da praxis educativa desenvolvida pela mestranda, conforme os dados observados, recolhidos e analisados. Procurase, também, expressar as suas aprendizagens, pensar sobre as mesmas e como estas influenciaram a prática profissional. O educador de infância deve manter uma postura atenta em relação ao grupo de crianças com quem exerce a sua profissionalidade, intervindo de forma adequada e ponderada e, assim, desenvolvendo competências pessoais e profissionais. Considerando os princípios apresentados no perfil geral de desempenho profissional do educador de infância, este deve realizar formação ao longo da vida e avaliar constantemente a sua ação e adaptá-la, conduzindo a uma flexibilidade na tomada de decisões.

Estrutura e processo de formação das formas culturais: o caso do cante alentejano

Qualquer sistema de práticas individualizado que se distinga aos olhos dos seus praticantes é caracterizável pela forma que assume e pelo seu conjunto de atributos. A essa forma corresponde uma moldura analítica que encontra o seu equivalente real nos actores e no modo como formulam discursos sobre as suas práticas, do qual emerge um conjunto de normas. Por conseguinte, a forma tanto é uma construção metodológica externa para a descrição do sistema e das suas condições de existência como uma realidade dinâmica, produtora de identidades culturais. Pretendemos substituir uma noção imprecisa de “forma cultural” por um conceito estruturado, definindo-a como sistema de referência que os membros de uma cultura partilham e que define e regula as produções e reproduções culturais e que comporta um elemento estruturante, um sistema normativo e uma dinâmica social. O caminho para essa conceptualização implica a aplicação do conceito a um objecto empírico, operação que realizamos ao analisar o Cante Alentejano – conjunto de maneiras de cantar observadas do Alentejo – enquanto forma cultural; Abstract: Any system of practices that can be individualized and distinguished by its practitioners can be characterized through the form it assumes and the set of its attributes. Such form corresponds to an analytical framework that has its equivalent in the real actors world and in the ways they formulate utterances about their practices, from which emerges a set of rules. Therefore, the form is both an external methodological construction needed for the system’s description and a dynamic “emic” reality that produces cultural identities. We intend to replace an inaccurate notion of "cultural form" by a structured concept. We will define it as the reference system that the members of a given culture share and that guides and regulates the cultural processes of production and reproductions of the system. The concept comprises a structural element, a normative system, and a social dynamic. The path to this conceptualization implies applying the concept to an empirical object, operation that will be held by analyzing Cante Alentejano – a set of ways of singing from Alentejo – as a cultural form.

Low-Molecular-Weight Fucoidan Induces Endothelial Cell Migration via the PI3K/AKT Pathway and Modulates the Transcription of Genes Involved in Angiogenesis

Low-molecular-weight fucoidan (LMWF) is a sulfated polysaccharide extracted from brown seaweed that presents antithrombotic and pro-angiogenic properties. However, its mechanism of action is not well-characterized. Here, we studied the effects of LMWF on cell signaling and whole genome expression in human umbilical vein endothelial cells and endothelial colony forming cells. We observed that LMWF and vascular endothelial growth factor had synergistic effects on cell signaling, and more interestingly that LMWF by itself, in the absence of other growth factors, was able to trigger the activation of the PI3K/AKT pathway, which plays a crucial role in angiogenesis and vasculogenesis. We also observed that the effects of LMWF on cell migration were PI3K/AKT-dependent and that LMWF modulated the expression of genes involved at different levels of the neovessel formation process, such as cell migration and cytoskeleton organization, cell mobilization and homing. This provides a better understanding of LMWF's mechanism of action and confirms that it could be an interesting therapeutic approach for vascular repair.

Relatório de Estágio

O presente Relatório de Estágio tem como objetivo descrever e refletir sobre a Prática de Ensino Supervisionada, no âmbito da unidade curricular de Integração Curricular: Prática Educativa e Relatório de Estágio, inserida no plano de estudos do Mestrado em Ensino do 1.º e 2.º Ciclo do Ensino Básico. A prática desenvolvida reflete o resultado de um percurso de formação desde a Licenciatura em Educação Básica até ao Mestrado, num permanente exercício crítico, reflexivo e investigativo, onde se procurou mobilizar e articular saberes científicos, didáticos e pedagógicos. Assim, descreve-se e reflete-se sobre vivências e experiências desenvolvidas ao longo da prática educativa, atendendo a um quadro teórico e legal e uma análise do contexto e das práticas, que potenciaram o encadeamento e o amadurecimento dos saberes profissionais em estreita relação com os saberes experienciados. No desenvolvimento da prática pedagógica, a metodologia de investigação-ação norteou a conduta do formando ao traduzir-se numa espiral cíclica de observação, planificação, ação e reflexão, cuja dinâmica permite a construção de conhecimentos sólidos que sustentam o desenvolvimento da profissionalidade docente. Neste processo formativo, o formando atribuiu uma especial importância aos momentos de reflexão partilhada com os Professores envolvidos nesta formação, bem como o par pedagógico que permitiram a partilha de saberes e de experiências com reflexos na transformação e melhoramento das práticas. No final deste percurso, consciente do empenho e da determinação aplicados ao longo do percurso formativo, o mestrando evidencia a importância de um ensino com significado e globalizante para o estudante, e que possa dar sentido à expressão “assas para poder voar”.

Elemental Anisotropic Growth and Atomic-Scale Structure of Shape-Controlled Octahedral Pt–Ni–Co Alloy Nanocatalysts

Multimetallic shape-controlled nanoparticles offer great opportunities to tune the activity, selectivity, and stability of electrocatalytic surface reactions. However, in many cases, our synthetic control over particle size, composition, and shape is limited requiring trial and error. Deeper atomic-scale insight in the particle formation process would enable more rational syntheses. Here we exemplify this using a family of trimetallic PtNiCo nanooctahedra obtained via a low-temperature, surfactant-free solvothermal synthesis. We analyze the competition between Ni and Co precursors under coreduction “one-step” conditions when the Ni reduction rates prevailed. To tune the Co reduction rate and final content, we develop a “two-step” route and track the evolution of the composition and morphology of the particles at the atomic scale. To achieve this, scanning transmission electron microscopy and energy dispersive X-ray elemental mapping techniques are used. We provide evidence of a heterogeneous element distribution caused by element-specific anisotropic growth and create octahedral nanoparticles with tailored atomic composition like Pt1.5M, PtM, and PtM1.5 (M = Ni + Co). These trimetallic electrocatalysts have been tested toward the oxygen reduction reaction (ORR), showing a greatly enhanced mass activity related to commercial Pt/C and less activity loss than binary PtNi and PtCo after 4000 potential cycles.

Playgrounds: Safe designs and infrastructures for our children… an urgent matter in Costa Rica

The purpose of this article is to offer the design and infrastructure parameters necessary to have safe playgrounds since they represent a unique opportunity to foster an integral development, particularly in children.  In these public places, children learn to resolve conflicts to continue playing, having fun, and developing.  These recreational areas then become learning places that foster the formation process and provide great social, emotional, physical, cognitive, intellectual, and spiritual benefits.  However, such benefits are diminished by the lack of interest of the communities and the adult population to optimize playground conditions and by unscrupulous developers, who design playgrounds in inappropriate places putting the population at risk.  Therefore, the following must be taken seriously into consideration before, during, and after the construction of a playground: design, construction, materials, equipment, components and the procedures to meet the necessary safety requirements and the objective for which they were created, that being an area designed, equipped, and located exclusively for playing that facilitates the integral development of the population.  Consequently, it is urgent for Costa Rica to enact clear regulations that guarantee the construction, design, and use of playgrounds that do not put the population’s health at risk, prevent accidents, and guarantee the inalienable rights of each Costa Rican.

A psicologia e o psicólogo do esporte : uma formação necessária

Dissertação (mestrado)—Universidade de Brasília, Instituto de Psicologia, Programa de Pós-graduação em Processos de Desenvolvimento Humano e Saúde, 2016.

Tertúlia Literária Dialógica : contribuições para a formação omnilateral de estudantes, na educação profissional do Instituto Federal de Brasília – Campus Taguatinga Centro, Programa Mulheres Mil - 2012

Dissertação apresentada para obtenção a grau de Mestre na área de Educação Social e Intervenção Comunitária

Incidence of debris discs around FGK stars in the solar neighbourhood

Context. Debris discs are a consequence of the planet formation process and constitute the fingerprints of planetesimal systems. Their counterparts in the solar system are the asteroid and Edgeworth-Kuiper belts. Aims. The aim of this paper is to provide robust numbers for the incidence of debris discs around FGK stars in the solar neighbourhood. Methods. The full sample of 177 FGK stars with d ≤ 20 pc proposed for the DUst around NEarby Stars (DUNES) survey is presented. Herschel/PACS observations at 100 and 160 μm were obtained, and were complemented in some cases with data at 70 μm and at 250, 350, and 500 μm SPIRE photometry. The 123 objects observed by the DUNES collaboration were presented in a previous paper. The remaining 54 stars, shared with the Disc Emission via a Bias-free Reconnaissance in IR and Sub-mm (DEBRIS) consortium and observed by them, and the combined full sample are studied in this paper. The incidence of debris discs per spectral type is analysed and put into context together with other parameters of the sample, like metallicity, rotation and activity, and age. Results. The subsample of 105 stars with d ≤ 15 pc containing 23 F, 33 G, and 49 K stars is complete for F stars, almost complete for G stars, and contains a substantial number of K stars from which we draw solid conclusions on objects of this spectral type. The incidence rates of debris discs per spectral type are 0.26^+0.21_-0.14 (6 objects with excesses out of 23 F stars), 0.21^+0.17_-0.11 (7 out of 33 G stars), and 0.20^+0.14_-0.09 (10 out of 49 K stars); the fraction for all three spectral types together is 0.22^+0.08_-0.07 (23 out of 105 stars). The uncertainties correspond to a 95% confidence level. The medians of the upper limits of L_dust/L_∗ for each spectral type are 7.8 × 10^-7 (F), 1.4 × 10^-6 (G), and 2.2 × 10^-6 (K); the lowest values are around 4.0 × 10^-7. The incidence of debris discs is similar for active (young) and inactive (old) stars. The fractional luminosity tends to drop with increasing age, as expected from collisional erosion of the debris belts.

Tertúlia Literária Dialógica : contribuições para a formação omnilateral de estudantes, na educação profissional do Instituto Federal de Brasília – Campus Taguatinga Centro, Programa Mulheres Mil - 2012

Dissertação apresentada para obtenção a grau de Mestre na área de Educação Social e Intervenção Comunitária

Improving Bangla ocr output through correction algorithms

Bangla OCR (Optical Character Recognition) is a long deserving software for Bengali community all over the world. Numerous e efforts suggest that due to the inherent complex nature of Bangla alphabet and its word formation process development of high fidelity OCR producing a reasonably acceptable output still remains a challenge. One possible way of improvement is by using post processing of OCR’s output; algorithms such as Edit Distance and the use of n-grams statistical information have been used to rectify misspelled words in language processing. This work presents the first known approach to use these algorithms to replace misrecognized words produced by Bangla OCR. The assessment is made on a set of fifty documents written in Bangla script and uses a dictionary of 541,167 words. The proposed correction model can correct several words lowering the recognition error rate by 2.87% and 3.18% for the character based n- gram and edit distance algorithms respectively. The developed system suggests a list of 5 (five) alternatives for a misspelled word. It is found that in 33.82% cases, the correct word is the topmost suggestion of 5 words list for n-gram algorithm while using Edit distance algorithm the first word in the suggestion properly matches 36.31% of the cases. This work will ignite rooms of thoughts for possible improvements in character recognition endeavour.

Study of Bone Biomineralization in 2D and 3D Cultures of a Human Osteosarcoma Cell Line As Osteoblast-like Model

This PhD project focuses on the study of the early stages of bone biomineralization in 2D and 3D cultures of osteoblast-like SaOS-2 osteosarcoma cells, exposed to an osteogenic cocktail. The efficacy of osteogenic treatment was assessed on 2D cell cultures after 7 days. A large calcium minerals production, an overexpression of osteogenic markers and of alkaline phosphatase activity occurred in treated samples. TEM microscopy and cryo-XANES micro-spectroscopy were performed for localizing and characterizing Ca-depositions. These techniques revealed a different localization and chemical composition of Ca-minerals over time and after treatment. Nevertheless, the Mito stress test showed in treated samples a significant increase in maximal respiration levels associated to an upregulation of mitochondrial biogenesis indicative of an ongoing differentiation process. The 3D cell cultures were realized using two different hydrogels: a commercial collagen type I and a mixture of agarose and lactose-modified chitosan (CTL). Both biomaterials showed good biocompatibility with SaOS-2 cells. The gene expression analysis of SaOS-2 cells on collagen scaffolds indicated an osteogenic commitment after treatment. and Alizarin red staining highlighted the presence of Ca-spots in the differentiated samples. In addition, the intracellular magnesium quantification, and the X-ray microscopy on mineral depositions, suggested the incorporation of Mg during the early stages of bone formation process., SaOS-2 cells treated with osteogenic cocktail produced Ca mineral deposits also on CTL/agarose scaffolds, as confirmed by alizarin red staining. Further studies are underway to evaluate the differentiation also at the genetic level. Thanks to the combination of conventional laboratory methods and synchrotron-based techniques, it has been demonstrated that SaOS-2 is a suitable model for the study of biomineralization in vitro. These results have contributed to a deeper knowledge of biomineralization process in osteosarcoma cells and could provide new evidences about a therapeutic strategy acting on the reversibility of tumorigenicity by osteogenic induction.