Avaliação das condições de precipitação do azul da Prússia sobre pó de grafite visando o desenvolvimento de eletrodos de pasta de carbono para a quantificação de nitrito

An amperometric FIA method for nitrite quantification based on nitrite electroreduction and employing a carbon paste electrode (CPE) chemically modified with iron hexacyanoferrate (HCF) as an amperometric detector was developed. The influence of experimental conditions on the preparation of the electrode materials was evaluated and the materials obtained in each study were used for the development of modified electrodes. The electrochemical sensors were prepared by a fast, simple, and inexpensive procedure, and the long-term performance of the electrodes were quite satisfactory as the stability was maintained over one year. HCF was an effective redox mediator for nitrite electroreduction in acidic media, allowing nitrite detection at +0.2 V vs. Ag/AgClsat, which is a potential free of possible interfering species that are normally present in food and water samples. The electrochemical cell used in the FIA system was similar to a batch injection analysis cell, enabling recirculation of the carrier solution. This is an attractive feature because it allows the use of a high flow rate (6 mL min-1) leading to high sensitivity and analysis speed, while keeping reagent consumption low. The proposed method had a detection limit of 9 μmol L-1 and was successfully employed for nitrite quantification in spiked water and sausage samples. The obtained results were in good agreement with those provided by the spectrophotometric official method. At a 95 % confidence level it was not observed statistical differences neither in nitrite content nor in the precision provided by both methods. The experimental conditions for the synthesis of HCF were optimized and the best electrode material was prepared by mixing FeCl3, K4[Fe(CN)6] and carbon powder subjected to an acid and thermal treatment (400 ºC), followed by ultrasonic agitation at 4 °C. This material was used to construct an electrode with improved analytical performance to reduce nitrite, which presented greater stability compared to HCF film electrodeposited on the EPC, showing that the preparation procedure of the electrode material is an effective strategy for the development of HCF modified electrodes.

Efeitos da internacionalização no desvio da estrutura de capital alvo e na velocidade de ajuste

This dissertation investigates the effects of internationalization in two gaps related to the capital structure that have not been discussed by the Brazilian literature yet. To this, were developed two independent sections. The first examined what the effects of internationalization on the deviation from the target capital structure. The second examined what the effects of internationalization on speed of adjustment (SOA) of the capital structure. It used data from Brazil, multinational and domestic companies, from 2006 to 2014. The results of the first analysis indicate that internationalization helps reduce the difference between the target and the current debt. That is, to the extent that the level of internationalization increases; whether only export or a combination of export, assets and employees abroad, the gap between the current structure and the target structure decreases. This reduction is given as a function of internationalization as a consequence of the upstream effect of the upstream-downstream hypothesis. Thus, as the Market Timing theory, it can be seen as an opportunity for adjustment of the capital structure, and with the reduction of deviation, there is also a reduction in the cost of capital of the firm. The result of the second analysis indicates that internationalization is able to significantly increase the speed adjustment, ensuring for the multinational a faster adjustment of its capital structure. Exports increase the SOA in 9 to 23%. And when also kept active assets and employees abroad the increase is 8 to 20%. In terms of time, while domestic company takes more than three years to reduce half of the deviation that has, while multinacional companies take on average one and a half year to reduce the same proportion of the deviation. The validity of the upstream-downstream hypothesis for the effect of internationalization in SOA was confirmed by comparing the results for US companies. Thus, the phenomenon of internationalization increases SOA when companies are from less stable markets, such as Brazil; and it has a less significcative effect when companies are derived from more stable markets, because they already have a high speed of adjustmennt. In addition, the adequacy analysis of the estimators also showed the model pooled OLS (Ordinary Least Squares) presents the highest quality in predicting the SOA than the system GMM (Generalized Method of Moments). For future studies it is suggested to analyze the effect of international event, by itself, and to validate the hypothesis using samples of different markets and the use of other estimators.

O PLANEJAMENTO DA COMUNICAÇÃO ON-LINE: Como a velocidade no fluxo da informação altera a forma de planejar

O advento da internet causou uma revolução na forma como a sociedade se relaciona. A consolidação das mídias sociais na ambiência digital acentuou o poder das mudanças e forçou a comunicação a rever paradigmas. O imediatismo e a velocidade com que a informação se propaga num processo simétrico de mão dupla – emissor e receptor – mudou a forma de trabalhar, pensar e planejar. O presente trabalho traz uma pesquisa com profissionais de comunicação e analisa como o fator prazo tem impactado no processo do planejamento de longo prazo – tradicionalmente anual – das ações voltadas para o ambiente digital. A pesquisa baseou-se em amplo referencial teórico das áreas de comunicação, marketing, redes e mídias sociais, tecnologia, administração, além de institutos de pesquisas e empresas. A fim de descrever as experiências vividas pelos profissionais, empreendemos ainda uma pesquisa qualitativa com entrevistas em profundidade, com amostra não probabilística, com foco nas disciplinas de marketing e propaganda e relações públicas. Os resultados apontam para um aprendizado ainda sendo conquistado, dia após dia, a partir de tentativas e erros, onde a preocupação dos profissionais fica dividida entre o prazo de antecedência com que é feito um planejamento e a obrigatoriedade de sua revisão contínua.

Mecanismos de neurotoxicidade induzidos pela Dopamina e pela 6–OH-dopamina num modelo celular humano: efeito da presença de extratos de algas com elevada capacidade antioxidante

O aumento da esperança média de vida tem elevado a prevalência de doenças neurodegenerativas, como é o caso da doença de Parkinson. Nos últimos anos a procura de novas soluções terapêuticas, assim como a minimização dos efeitos dos tratamentos atualmente utilizados tem promovido a procura de novas soluções. Deste modo, o objetivo deste trabalho consistiu no estudo dos mecanismos moleculares de neurotoxicidade induzidos pela dopamina (DA) e 6-hidroxidopamina (6-OHDA) num modelo celular do neuroblastoma humano (SH-SY5Y), bem como na avaliação do potencial neuroprotetor de extratos de algas com elevada capacidade antioxidante. O efeito neurotóxico da DA e 6-OHDA, assim como o efeito protetor dos extratos das algas com maior atividade antioxidante (Sargassum muticum, Saccorhiza polyschides, Padina pavonica, Codium tomentosum, Ulva compressa) foi avaliado através da viabilidade celular das células SH-SY5Y utilizando o método de MTT. De modo a compreender os efeitos induzidos na viabilidade celular pela DA e 6-OHDA procedeu-se ao estudo da atividade da caspase-3, alterações do potencial mitocondrial e quantificação de H2O2. Os resultados demonstraram um claro efeito dependente da concentração da DA (30-3000μM) e 6-OHDA (10-1000μM) na viabilidade celular das células SH-SY5Y, bem como do tempo de exposição (6-48h). No que diz respeito a prevenção do efeito neurotóxico da DA (1000μM (56,41±5,05% de células viáveis); 24h) e 6-OHDA (100μM (66,76±3,24% de células viáveis);24h) pelos extratos das algas (1mg/mL; 24h) verificou-se que os extratos que apresentaram um efeito preventivo mais marcado pertencem as algas Sargassum muticum (82,37±6,41% de células viáveis e 115,8±8,53% de células viáveis, após tratamento com DA e 6-OHDA, respetivamente), Saccorhiza polyschides (89,26±8,62% de células viáveis e 106,51±4,26% de células viáveis, após tratamento com DA e 6-OHDA, respetivamente) e Codium tomentosum (81,28±3,68% de células viáveis e 103,17±7,25% de células viáveis, após tratamento com DA e 6-OHDA, respetivamente). A morte celular induzida pela DA e pela 6-OHDA foi acompanhada pelo aumento da atividade da caspase-3 quando comparado com o controlo (DA - 66,46±1,49fluorescência (u.a)/mg de proteína/minuto; 6-OHDA - 22,56±1,71fluorescência (u.a)/mg de proteína/minuto; controlo – 4,8 ±0,48fluorescência (u.a)/mg de proteína/minuto), pela presença de elevadas quantidades de peróxido de hidrogénio (H2O2) (363,81±28,58 % do controlo e 214,26 ± 8,46 % do controlo, após tratamento com DA e 6-OHDA, respetivamente) e pela despolarização da membrana mitocondrial (162,3±2,34 % do controlo e 144,7±2,87 % do controlo, após tratamento com DA e 6-OHDA, respetivamente). Por sua vez, durante o tratamento com extratos das algas (1mg/mL) na presença de DA e 6-OHDA verificou-se uma inibição da atividade da caspase-3 induzida pelas algas Sargassum muticum (2,53±2,49fluorescência (u.a)/mg de proteína/minuto e 4,52±1,36 fluorescência (u.a)/mg de proteína/minuto, após tratamento com DA e 6-OHDA, respetivamente), Saccorhiza polyschides (4,71±0,70fluorescência (u.a.)/mg de proteína/minuto e 2,73±1,11 fluorescência (u.a.)/mg de proteína/minuto, após tratamento com DA e 6-OHDA, respetivamente) e Codium tomentosum (17,05±1,72fluorescência (u.a.)/mg de proteína/minuto e 2,58±1,77fluorescência (u.a)/mg de proteína/minuto, após tratamento com DA e 6-OHDA, respetivamente). De igual modo verificou-se uma diminuição da produção de H2O2 pelas células SH-SY5Y na presença dos extratos das algas Sargassum muticum (132,58 ± 10,68% controlo), Saccorhiza polyschides (150,54 ± 23,54% controlo) e Codium tomentosum (54,074 ± 6,66% do controlo), quando expostas a 6-OHDA, contudo não se verificou o mesmo efeito na presença de DA. Relativamente ao potencial mitocondrial observou-se uma inibição da despolarização mitocondrial induzida pela DA e 6-OHDA nas células SH-SY5Y pela presença dos extratos das algas Sargassum muticum (135,7±2,97% controlo e 49,3±1,17% controlo, após tratamento com DA e 6-OHDA, respetivamente), Saccorhiza polyschides (126,7±5,46% controlo e 94,3±1,70% controlo, após tratamento com DA e 6-OHDA, respetivamente). Os resultados obtidos demonstraram o potencial citoprotetor dos extratos de algas sobre efeitos neurotóxicos induzidos pela DA e 6-OHDA no modelo celular SH-SY5Y. O efeito protetor é mediado pela diminuição da condição de stress oxidativo, com redução da produção de H2O2, diminuição da atividade da caspase-3 e prevenção da alteração do potencial mitocondrial induzido pela DA e 6-OHDA. Conclui-se que os extratos de algas produzem moléculas bioativas com elevado potencial antioxidante, podendo ser uma fonte promissora de novos compostos neuroprotetores com aplicação terapêutica para doenças neurodegenerativas como a doença de Parkinson.

Análise da eficiência de contratos de serviços de elevada especificidade terceirizados pela petrobras

The definition of the boundaries of the firms is subject that has occupied the organizational theorists long ago, being the seminal work of Coase (1937) indicated as the trigger for one theoretical evolution, with emphasis on governance structures, which led to a modern theory of incomplete contracts. The Transaction Cost Economics (TCE) and Agency Theory arise within this evolution, being widely used in studies related to the theme. Empirically, data envelopment analysis (DEA) has established itself as a suitable tool for analysis of efficiency. Although TCE argues that specific assets must be internalized, recent studies outside the mainstream of theory show that, often, firms may decide, for various reasons, hire them on the market. Researches on transaction costs face with the unavailability of information and methodological difficulties in measuring their critical variables. There`s still the need for further methodological deepening. The theoretical framework includes classic works of TCE and Agency Theory, but also more recent works, outside the mainstream of TCE, which warn about the existence of strategies in use of specific assets that aren`t necessarily aligned with the classical ideas of TCE. The Brazilian oil industry is the focus of this thesis, that aimed to evaluate the efficiency of contracts involving high specificity service outsourced by Petrobras. In order to this, we made the categorization of outsourced services in terms of specificity, as well the description of services with higher specificity. Then, we verified the existence of relationship between the specificity of services and a number of variables, being found divergent results than those that are preached by the mainstream of TCE. Then, we designed a DEA model to analyze the efficiency in the use of onshore drilling rigs, identified among the services of highest specificity. The next step was the application of the model to evaluate the performance of drilling rigs contracts. Finally, we verified the existence of relationship between the efficiency of contracts and a number of variables, being found, again, results not consistent with the theory mainstream. Regarding to analyze of efficiency of drilling rigs contracts, the model developed is compatible with what is found in academic productions in efficiency of drilling rigs. The results on efficiency show a wide range of scores, with efficiencies ranging from 31.79% to 100%, being low the sample efficiency average. There is consonance between the model results and the practices adopted by Petrobras. The results strengthen the DEA as an important tool in studies of efficiency with possibility to use for analysis other types of contracts. In terms of theoretical findings, the results reinforce the arguments that there are situations in which the strategies of the organizations, in terms of use of assets and services of high specificity, do not necessarily follow what is recommended by the mainstream of TCE

Qual a contribuição das características antropométricas na velocidade de corrida de curta distância ?

v. 19, n. 2, abr./jun. 2016.

Efeito da ligadura de reposicionamento do perónio em basquetebolistas adultos com instabilidade crónica da tibiotársica

Introdução: A instabilidade crónica da tibiotársica apresenta uma elevada incidência e prevalência nos basquetebolistas, pelo que é fundamental aprofundar as estratégias existentes para a redução das limitações funcionais e mecânicas decorrentes desta condição. Objetivo: comparar o efeito da ligadura de reposicionamento do perónio segundo Mulligan com o de uma ligadura placebo imediatamente após a sua aplicação e após o teste de corrida (Yo-Yo IRT). Metodologia: Estudo cruzado de amostras emparelhadas. Participantes: 16 basquetebolistas adultos (10 homens, 6 mulheres) com instabilidade crónica da tibiotársica com idade média de 21,50 ± 2,76 anos. Procedimentos de avaliação e intervenção: Avaliação do controlo postural estático (teste de apoio unipodal com os olhos fechados numa plataforma de forças durante 15 segundos), performance funcional (hop test em 8 e hop test lateral) e controlo neuromuscular (tempo de latência do músculo longo peronial durante o movimento de inversão repentina) em duas sessões: Mulligan e Placebo. Resultados: Em ambos Hop tests não houve um efeito significativo para o fator ligadura (p>0,17) mas houve para o fator tempo (p<0,03). No tempo de latência do músculo longo peronial, houve um efeito significativo para o fator tempo (p=0,042) e interação significativa entre os dois fatores (p=0,028). Em relação ao controlo postural, nas variáveis de deslocamento do CoP em x e y, área de deslocamento do CoP, velocidade de deslocamento do CoP, e comprimento total do CoP não houve nenhum efeito significativo (p≥0,10). Conclusão: Não há diferenças no controlo postural estático nem na performance funcional de basquetebolistas com instabilidade crónica da tibiotársica entre a ligadura de reposicionamento do perónio de Mulligan e uma ligadura placebo. Contudo, a ligadura de Mulligan parece reduzir o tempo de latência do longo peronial após a corrida quando comparada com uma ligadura placebo.

Oclusão percutânea do apêndice auricular esquerdo e estrutura auricular: efeito na função mecânica e endócrina auricular

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Área de especialização: Intervenção Cardiovascular.

Neuromuscular adaptations in football athletes with prior history of hamstring strain injury

Background: Hamstring strain injuries (HSI) are one of the most common injuries in a wide variety of running-sports, resulting in a considerable loss of competition and training time. One of the most problematic consequences regarding HSI is the recurrence rate and its non-decrease over the past decades, despite increasing evidence. Recent studies also found several maladaptations post-HSI probably due to neuromuscular inhibition and it has been proposed that these adaptations post-injury may contribute as risk factors for the injury-reinjury cycle and high recurrence rates. Furthermore it has been recently proposed not to disregard the inter-relationship between these adaptations and risk-factors post-injury in order to better understand the mechanisms of this complex injury. Objective: To determine, analyze and correlate neuromuscular adaptations in amateur football players with prior history of HSI per comparison to uninjured athletes in similar conditions. Methodology: Every participant was subjected to isokinetic concentric (60 and 240deg.sec) and eccentric (30 and 120deg.sec¯¹) testing, and peak torque, angle of peak torque and hamstrings to quadriceps (H:Q) conventional ratios were measured, myoelectrical activity of Bicep Femoris (BF) and Medial Hamstrings (MH) were also measured during isokinetic eccentric testing at both velocities and muscle activation percentages were calculated at 30, 50 and 100ms after onset of contraction. Furthermore active and passive knee extension, knee joint position sense (JPS) test, triple-hop distance (THD) test and core stability (flexors and extensors endurance, right and left side bridge test) were used and correlated. Results: Seventeen players have participated in this study: 10 athletes with prior history of HSI, composing the Hamstring injury group (HG) and 7 athletes without prior severe injuries as control group (CG). We found statistical significant differences between HG injured and uninjured sides in the BF myoelectrical activity at almost all times in both velocities and between HG injured and CG non-dominant sides at 100ms in eccentric 120deg.sec¯¹ velocity (p<.05). We found no differences in MH activity. Regarding proprioception we found differences between the HG injured and uninjured sides (p=.027). We found no differences in the rest of used tests. However, significant correlation between myoelectrical activation at 100ms in 120deg.sec¯¹ testing and JPS with initial position at 90º (r-.372; p=0.031) was found, as well as between isokinetic H:Q ratio at 240deg.sec and THD score (r=-.345; p=.045). Conclusion: We found significant differences that support previous research regarding neuromuscular adaptations and BF inhibition post-HSI. Moreover, to our knowledge, this was the first study that found correlation between these adaptations, and may open a door to new perspectives and future studies.

Sensibilidade à mudança de trajetória de deformação no aço TWIP980

Resultante dos avanços tecnológicos, conseguiu-se obter um aço que elimina o paradigma de se aliar alta ductilidade e resistência mecânica. Assim foi desenvolvido durante a última década o aço TWIP, deformação induzida por maclação, tendo como principal mecanismo de deformação a maclação. Este presente trabalho teve como principal objetivo caraterizar o aço TWIP980 em três temáticas diferentes: química, mecânica e microestrutura. Na primeira temática, a química, esta teve como objetivo encontrar a designação do aço TWIP em estudo. Sendo apenas conhecida a direção de laminação, RD, e a empresa que forneceu as chapas, a POSCO, o objetivo era obter a sua designação. Através da comparação das curvas de tração encontradas para o material em estudo, e conjuntamente, com as diversas curvas de tração de vários aços TWIP da empresa POSCO, realizou-se a comparação. Visto ter-se ficado reduzido a dois possíveis aços TWIP, foi através de uma análise à composição química, EDS - Espectroscopia da energia dispersa por raios-X, que se concluiu que o aço em estudo era o TWIP980. Na caraterização mecânica, e através de ensaios de tração, foram estudadas propriedades como: o módulo de elasticidade, tensão limite elástico, ductilidade, anisotropia, coeficiente de encruamento e Poisson. Estas propriedades foram estudas para três mudanças na trajetória de deformação e quatro pré-deformações em estudo. Assim estudou-se a alteração de trajetória para os ângulos a 0º, 45º e 90º em relação a RD, para as deformações de engenharia de 0%, 10%, 20% e 30%. Por último, na análise à microestrutura, esta teve como objetivo obter valores para o tamanho de grão e de macla bem como as suas orientações cristalográficas. Também a densidade de deslocações e maclação para cada uma das 4 pré-deformações esteve em estudo. Estes parâmetros foram obtidos através de microscopia ótica, eletrónica de varrimento, MEV e eletrónica de transmissão, MET.

Avaliação da deformação em lajes bidirecionais de concreto armado

A avaliação da deformação excessiva para peças fletidas de concreto armado é abordada pela norma em vigor. O texto conclusivo do projeto de revisão de 2001 adota para o cálculo de deformações em vigas, a inércia equivalente, que leva em consideração a contribuição do concreto não fissurado e entre as fissuras, que implica na consideração do aumento da rigidez da peça. Já para o caso das lajes bidirecionais de concreto armado, não é apresentada nenhuma formulação de inércia equivalente. O cálculo de flechas com inércia do estádio I fornece resultados contra a segurança nos casos de laje onde o momento de fissuração é ultrapassado em serviço e portanto a laje está fissurada. Já o cálculo com inércia do estádio II fornece resultados com flechas excessivas pois não considera a parte íntegra da peça e sua contribuição para o aumento da rigidez. Neste trabalho são apresentadas considerações para o cálculo do estado limite de deformação excessiva para as lajes bidirecionais. Como exemplo foram obtidas as flechas variando de 0,5 m para as dimensões 4x4 até 8x8 m adotando a inércia equivalente e considerando o momento de serviço para a definição do estádio a considerar no cálculo da flecha.

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.

Adubação de sistemas: antecipação de adubação nitrogenada para a cultura do milho em integração lavoura-pecuária

Traditionally in no-tillage systems, fertilization is done to the catch crop. In general nutrient cycling in crop systems has not been treated as an important tool in the process of nutrient supplying for plants. The type and the condition in which vegetable residuesis decomposed can affect the efficiency of nutrient cycling.This study assessed the effect of anticipated nitrogen fertilization in crop-livestock systems on cultivated cornproduction, rate ofnutrient release from plant residue, and theN-minerallevels of soil. The study was carried out in the city Abelardo Luz (SC) in a Clayey Oxisol. The experimental design was a randomized block design with three replications. The treatments were arranged in a 2 x 2 factorial arrangement. The first factor was N Fertilization Time: in the N-Pasture level, nitrogen (200 kg ha-1 N) and N-Grains level, no nitrogen was applied. The second factor was the Grazing Height, characterized by two sward heights of oat at 15 cm (Low Height Pasture) and at 30 cm (High Height Pasture). Corn hybrid ‘Máximus’ was sowed in 10thOctober, 31 days after the removal of animals. In the twelve resulting plots from the combination of treatments on pasture phase (N Fertilization Time x Grazing Height) rates of N-fertilizer (0, 100, 200 e 300 Kg ha-1 of N) as urea were allocated in the split plot.We conclude that anticipated N fertilization of winter cover crop pasture to provide high-quality forage and carry-over N to the subsequent corn crop and may eventually replace side drees nitrogen fertilization on corn and can improve overall N fertilizer efficiency use in integrated crop-livestock systems.The rate of K release from plant residues is very fast, releasing large quantities in the first days after plant desiccation.Despite of considerably high nitrogen dose used in both the pasture and at the grain crop it was not observed nitrate leaching risks during the study period.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.