L’objectif de cette thèse est d’aboutir à une meilleure compréhension des mécanismes de ségrégation du bore aux joints de grains austénitiques (γGB) et de leur effet sur la décomposition de l’austénite. En effet, l’addition de très faibles quantités de bore comme élément d’alliage permet d’augmenter de manière remarquable la résistance mécanique des aciers à très haute résistance. Cet effet est lié à l’état du bore aux γGBs qui décale la cinétique de décomposition de l’austénite.Tout d’abord, la distribution du bore dans la microstructure a été identifiée de manière très précise à l’aide des analyses de la même zone par Nano-SIMS et par MEB. De plus, le couplage de la sonde atomique tomographique et du Nano-SIMS a apporté une meilleure quantification de l’état du bore dans la microstructure. Ces études ont été réalisées après différents traitements thermiques qui ont été conçus spécifiquement pour étudier séparément chaque mécanisme. L’ensemble de ces résultats permet d’écarter la contribution de la ségrégation hors équilibre et confirme la présence d’un équilibre local entre les γGBs et la solution solide dans leurs voisinages. Par conséquent, le niveau de ségrégation du bore aux γGBs est contrôlé par l’état de précipitation des borures qui définit la concentration du bore en solution solide.Par ailleurs, des mesures de DRX in situ et de dilatomètrie ont été effectuées afin de suivre les cinétiques de formation de la bainite. Les résultats montrent que la cinétique de formation de la bainite est retardée en augmentant la quantité de bore ségrégé, par contre l’augmentation de la taille de grain austénitique l’accélère. / The aim of this thesis is to lead to a better understanding of the mechanisms of boron segregation at austenite grain boundaries (γGB) and its effect on the austenite decomposition. Indeed, the small quantity of boron as alloying element remarkably improves the mechanical resistance of the advanced high strength steels. This effect is related to the boron state at γGBs, which delays the kinetics of austenite decomposition.The boron distribution in the microstructure was precisely identified thanks to the analyses of the same field by using correlative nano-SIMS and SEM. In addition, the coupling of APT and nano-SIMS provided a better quantification of the boron state in the microstructure. These studies were performed after different heat treatments, which were specifically designed to study separately each mechanism. The results excludes the contribution of non-equilibrium segregation mechanism on boron segregation at γGBs and confirm the local equilibrium between the γGBs and the solid solution at the γGBs vicinity. Consequently, the level of boron segregation at γGBs is controlled by boride precipitation, which controls the concentration of boron in solid solution.Measurements of in situ XRD and the dilatometry were performed in order to follow the kinetics of bainite formation. The specific heat treatments were applied before bainite formation in order to study the effect of boron segregated amount at γGBs and the austenite grain size. These results show that the kinetics of bainitic transformation is delayed by the increase of boron segregated amount. Whereas, the increasing of austenite grain size accelerates the kinetics of bainitic transformation.

As pentoses são subprodutos de vários rejeitos agrícolas tais como palha de arroz, palha e sabugo de milho, casca de aveia, bagaço da cana-de-açúcar, caroço de algodão, resíduos de madeira e outros, de onde se pode obter, por digestão com ácido forte, o furfural, e dele, por hidrogenação, o álcool furfurílico (FFA). A polimerização do FFA conduzindo a um produto inerte, resistente a corrosão, que tem sido utilizado principalmente como revestimento de mesas e bancadas de laboratório e de tanques industriais, é um produto negro que apresenta estrutura fortemente intercruzada. Porém, seu relativo alto custo tem constituído uma barreira para que suas aplicações se popularizem. Com o aproveitamento de resíduos industriais da produção de etanol, óleo de arroz, algodão, milho, e da indústria madeireira, espera-se a redução de seu custo de produção e, consequentemente, a ampliação de seu campo de aplicações principalmente por tratar-se de um polímero natural não derivado do petróleo. Por outro lado, o país enfrenta sérias dificuldades no campo habitacional, uma delas sendo o elevado custo dos materiais de construção. Viabilizando-se o emprego de madeiras de reflorestamento para emprego em construção civil e industrial, por exemplo, aumentando sua resistência ao ataque de fungos e de insetos, a propagação da chama e a variação dimensional, proporciona-se um número maior de moradias sem, contudo, promover o desmatamento de reservas de madeiras nobres. Neste trabalho tem-se como objetivos a obtenção de compósitos de madeira e polímero que apresentem vantagens sobre a madeira de reflorestamento sem tratamento, e o estudo de um meio de fixar o bom usando o álcool furfurílico para que as propriedades de ambos sejam combinadas e melhoradas. Impregnou-se duas espécies de coníferas muito populares, uma no Brasil e outra no Japão, com álcool furfurílico em combinação com compostos de boro e testou-se algumas de suas propriedades. Espécies de Coníferas \"Japanese cedar\' (Cryptomena japonica D. Don.) - o sugi, e (Pinus caribaea var. hondurensis) - pinus - foram impregnadas com álcool furfurílico (FFA) pelo processo vácuo-encharcamento seguido da cura do FFA sob aquecimento. Compostos de boro: ácido bórico, borato de amônia e biborato de amônia foram adicionados a solução de impregnação. Espécies impregnadas foram submetidas aos testes de eficiência anti-inchamento, resistência aos térmitas, resistência aos microrganismos, resistência a inflamabilidade e resistência as intempéries. Ao lado destes testes, os resíduos das soluções submetidas aos ciclos de lixiviação de acordo com as normas padrões JIS 9201 (1992) foram analisados através de cromatografia iônica com o objetivo de estudar métodos de fixação do boro na madeira. Os resultados mostraram que a resina de FFA confere a madeira alta estabilidade dimensional. Resultados semelhantes são obtidos quando FFA é combinada com compostos de boro. A mobilidade do bom mostrou diferentes comportamentos em comparação com o tratamento com o ácido bórico, embora o boro ainda seja Iixiviável. A madeira tratada com FFA combinada com compostos de boro apresentou grande resistência a ataques de térmitas e à deterioração biológica quando não submetida a lixiviação. Quando lixiviadas a resistência biológica diminui consideravelmente mas ainda assim é maior que a da madeira sem tratamento ou da tratada somente com ácido bórico. O tratamento mostrou que a combinação aumentou a resistência da madeira contra a queima sem chama. A queima produz pouca fumaça e cinzas. As combinações de tratamento não se mostraram eficazes para fixar a cor durante a exposição as condições climáticas / Pentosans are by-products of many agricultural crops such as rice, com and oat husks, comcobs, sugar cane bagasse, cotton seeds, wood wastes, etc. By digesting these by-products with strong acid furfural can be produced, which, in its turn, can be transformed into furfuryl alcohol through hydrogenation. Polymerization of furfuryl alcohol transforms it into an inert corrosion-resistant product that is used as a coating material for laboratory tables, workbenches and industrial tanks. Its relatively high cost, however, has so far been an obstacle to its widespread application. By taking advantage of industrial waste from ethanol distilleries and from the rice, cotton, com oil and wood industries, it is expected to reduce the cost of furfuryl alcohol production and, thus, to increase its applications. This becomes an increasingly relevant objective when one considers the future scarcity of petroleum. Brazil is also beset by a variety of housing-related problems, one of which is the high cost of construction materials. Increasing the resistance of reforested wood against termite and fungi attacks and enhancing its fireproof and anti-swelling characteristics will enable the country to increase housing and preclude further deforestation of hardwood forests. Present work discusses the work involved in developing a wood-polymer composite with particular characteristics for improving the dimensional stability of wood, increasing its resistance against termite and fungi attacks, decreasing its flammability and enhancing its weathering resistance, for proposing the utilization of furfuryl alcohol as boron fixation agent. Two species of very popular softwoods, one of them in Brazil, pine and the other in Japan, sugi were impregnated with poli-FFA. Sapwood blocks of Japanese cedar (Cryptomeria japonica D. Don.) and Caribbean pitch pine (Pinus caribaea varohondurensis) were impregnated with furfuryl alcohol (FFA) by a vacuum-impregnation process followed by curing of FFA under heating. Boron compounds: boric acid, ammonium borate and ammonium biborate were mixed in the impregnation solution. Impregnated specimens were submitted to an anti-swelling efficiency (ASE) test, exposed to attack by termites and microorganisms, and subjected to a flame resistance and natural weathering test. Boron leachability was determined, along with ten cycles of weathering, according to JIS 9201 (1992), by ion chromatography (IC). Results indicated that FFA imparted high dimensional stability to wood when mixed with boron compounds. Boron mobility showed differentiated behavior in comparison to treatment with boric acid alone, although boron was still leachable. Wood specimens treated with a FFA-boron compound combination were quite resistant to termite attacks and to biological deterioration when they were not submitted to leaching cycles. When were submitted to leaching cycles, their biological resistance decreased significantly; however, it was still higher than in untreated wood or in wood treated only with boric acid. The treatment proved to be effective as a glowing retardan1.The combustion yields small amount of smoke and ash. Treatments did not prove efficiency to avoid the color changes in outdoor exposure

O aço 10B06 é utilizado na produção de fio máquina para trefilação. Por ser produzido em aciaria elétrica, o teor de nitrogênio desse aço tende a ser elevado, o que pode causar o fenômeno de envelhecimento, resultando em aumento de resistência e queda de ductilidade. Reduzir o teor de nitrogênio livre é uma forma de minimizar esse efeito, o que é realizado pela adição de boro. Dessa forma, o presente trabalho teve como objetivo estudar o efeito do boro no aço 10B06. Foram utilizadas amostras de fio máquina, diâmetro 5,50mm, e arame trefilado com teores de boro variando de 55 a 112ppm. Os dois principais fatores que influenciam a microestrutura e propriedades mecânicas do material são a composição química e o processo produtivo. Por esse motivo, inicialmente foi avaliada a etapa de resfriamento durante a laminação do fio máquina, por meio de uma análise termográfica. Foi encontrada a temperatura de 767ºC no início do resfriamento do material, valor próximo de Ac1, limite inferior do intervalo intercrítico. Esse fato favorece o enriquecimento da austenita em carbono, facilitando a formação de martensita e/ou austenita retida. Os resultados da análise metalográfica com Nital revelaram microestrutura composta de aproximadamente 88% de ferrita e 12% de perlita. Já o reagente Le Pera identificou ilhas de martensita e/ou austenita retida (MA), o que foi comprovado por análises de microscopia eletrônica de varredura. Os resultados de microdureza mostraram uma tendência de queda com o aumento do teor de boro. As medições de nanodureza confirmaram a presença do microconstituinte MA. A ferrita apresentou dureza na faixa de 280 - 320 HV, enquanto o MA ficou no intervalo de 349 - 424 HV. Comparando-se o limite de resistência obtido no fio máquina com menor teor de boro (55ppm - 434MPa) com o de maior (112ppm - 394MPa), observasse uma redução de 40MPa para um acréscimo de 57ppm de boro, confirmando o efeito esperado para esse elemento pela formação de BN. Utilizando os dados da curva tensão versus deformação foram obtidos os coeficientes de encruamento dos fios máquina, que apresentaram uma tendência de crescimento com o teor de boro, sendo que o material com 101ppm de boro mostrou o melhor valor para aplicação em processos de conformação. As análises fractográficas revelaram que os mecanismos de fratura presentes em todos os materiais foram a formação e coalescimento de microvidades. Considerando-se todas as análises realizadas nesse trabalho foi possível evidenciar o efeito do boro na redução do efeito do envelhecimento provocado pelo nitrogênio. Entre os testes realizados, os que apresentaram as melhores relações B/N foram os de teores 109 e 112ppm de boro. Essas relações estão próximas do valor máximo indicado de 0,8. / The 10B06 steel grade is applied to the production of wire rod for drawing. The steel is produced in an Electric Arc Furnace and this process can lead to higher nitrogen levels that cause strain aging resulting in an increase of the strength and ductility loss. The reduction of free nitrogen content through boron addition is one way to minimize this effect that can be done through boron addition. In this way, the present work aims to study boron effect on 10B06 steel. It was used wire rod, diameter 5,50mm and a cold-drawn wire rod with chemical composition from 55 to 112ppm of boron. The main factors that influence the microstructure and mechanical properties of the material are the chemical composition and the productive process. For this reason, initially, the cooling treatment was analyzed using thermography and it was found at the beginning of the cooling process a temperature of 767oC in the material, close to Ac1, lower limit of the intercritical interval. This temperature can facilitate the enrichment of carbon in the austenite, making easier martensite and/or retained austenite formation. The metallographic analysis with Nital etchant showed a microstructure composed of about 88% ferrite and 12% perlite, and Le Pera etchant identified martensite and/or retained austenite (MA), what was confirmed by scanning electron microscope analysis. Furthermore, nanohardness measurements confirmed the presence of the microconstituent MA, as ferrite presented hardness from 280 to 320 HV and MA from 349 to 424 HV. Microhardess results decreased with increasing boron content. A decrease of 40MPa in the tensile strength was observed between the wire rod with boron content of 55ppm (434MPa) and the one with 112ppm (394MPa), in agreement with the expected effect of the BN formation. It was possible to obtain hardening coefficient of the wire rod using the data of the stress versus strain curve, which increased with boron content, and the material with 101ppm of boron showed the best value for forming application. Fractographic analysis revealed that the fracture mechanisms in all the materials were the development and coalescing of microcavity. Considering all the analysis of this study it was possible to confirm boron\'s effect to reduce strain aging caused by nitrogen. Materials with 109 and 112ppm of boron presented the best B/N ratio, with values close to the maximum indicated, 0,8.

No presente trabalho, foi realizado um estudo sobre a influência da adição do boro em um aço C-Mn, nas transformações de fases por resfriamento contínuo, através da técnica dilatométrica. Para este estudo, utilizou-se dois aços de composição química semelhante: o aço 10B22 com 30 ppm de boro e o aço sem boro é o E1522, equivalente. Foram traçadas as curvas de CCT dos dois aços, onde analisou-se o efeito de temperabilidade do boro através das curvas de resfriamento. Os materiais foram ensaiados em um dilatômetro de resfriamento rápido, utilizando corpos de prova cilíndricos, resfriados por injeção de ar e hélio. Os resultados gráficos dos processos de resfriamento foram comparados com análises metalográficas ótica estruturais e quantitativas e também por medidas de dureza. Detalhes microestruturais, tais como, contagem de fases formadas em função das taxas de resfriamento, tamanho de grão, distribuição de inclusões e precipitados, foram extraídos, através de um sistema de análise de imagens. Complementando o trabalho, foi realizado uma completa documentação fotográfica das microestruturas, com uma indicação final do tratamento térmico mais adequado aos aços C-Mn microligados ao boro. / This work presents a study about the influence of boron on phase transformation by continuous cooling in a C-Mn steel using the dilatometric technique. For this study two close chemical composition steels were applied: a 10B2 steel with 30 ppm of boron and a E1522 steel without boron. For both steels the CCT curves were obtained, where the effect of boron on hardenability was analysed throughout continuous cooling curves. Both materials were testedcin a high speed quenching dilatometer, using cilindricals samples quenched by helium blow on their surfaces. The graphics results of cooling processes were compared with microstructural and quantitative optical metallographic analysis and hardness measurements. Microstructural features as such phases fraction as a function of cooling rates, grain size, and distributions of inclusions and precipitates were obtained through an image analysis system. In addition, complete microstructural photography documentation was carried out where it was possible to indicate the best heat treatment to boron microalloyed C-Mn steels.

Thesis advisor: James P. Morken / This dissertation will present four main projects focused on stereoselective construction of borylated compounds as well as their applications in asymmetric syntheses. The first two projects describe the development of a catalytic conjunctive cross-coupling reaction. By merging three simple starting materials, an organolithium reagent, an organoboronate, and an organic electrophile, a synthetically valuable secondary boronate is furnished by the conjunctive cross-coupling in an efficient and enantioselective fashion. Next, this strategy is expanded to synthesize severely hindered tertiary boronates, a synthetic challenging but powerful building block to access a variety of quaternary stereocenters. The third project presents a platinum-catalyzed enantioselective diboration of alkenyl boronates to furnish a broad range of 1,1,2-tris(boronates) products. A deborylative alkylation of the 1,1,2-tris(boronates) leads to a variety of internal vicinal bis(boronates) with high diastereoselectivity. In the final chapter, a general and practical synthesis of alkenyl boronates via the boron-Wittig reaction is disclosed. Utilizing readily accessible geminal bis(boronates) and aldehydes, a broad range of disubstituted and trisubstituted alkenyl boronates are afforded with good yield and stereoselectivity. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis (MTech (Agriculture)--Cape Peninsula University of Technology, 2018. / Choumollier (narrow-stem kale) (Brassica oleracea, L.) has been progressively used in recent years as a supplementary forage harvest in many countries with a temperate climate. Boron (B) and calcium (Ca) are the two most important elements for supporting plant structure and function of plasma membranes. Boron nutrition is vital for obtaining high quality yields in vegetables. The main objective of this study was to evaluate the extent to which boric acid concentration can affect growth parameters (plant height, leaf numbers, chlorophyll levels, and leaf size) of Brassica olereacea var. acephala at different stages of growth and development. Treatment comprised of four concentrations of boron (0.3 mg/kg, 0.4 mg/kg, 0.5 mg/kg and 0.6 mg/kg). Yield and physiological growth responses were measured during the course of the study to ascertain effectiveness and influence of boron treatments on the test crops. Leaves of B. oleracea were harvested at weekly intervals (W1, W2, W3, W4 and W5) after each treatment regimen for approximate basic mineral analysis and composition. Soil pH did not vary much among the various orchard blocks tested, regardless of soil depth. Exchangeable cations Na+ and K+ levels did not vary significantly, but Ca2+ and Mg2+ levels fluctuated considerably among orchards analyzed. The Control Orchard exhibited a higher P content than the other orchards. Ca, Mg, Cu and B levels did not vary significantly among the orchards, but Na, Fe and Zn levels were markedly raised in the Orchard treated with 0.3 mg/kg boron) relative to the Control Orchard. Chlorophyll fluorescence was significantly dependent on the treatment dose of boron as compared to control. Chlorophyll fluorescence also increased significantly with the growth period, i.e., the duration following the initial treatment at all doses of boron. Boron at all did not significantly affect leaf count, leaf length and plant height. The work may add to the body of knowledge on the influence of boron on the physiological performance, mineral contents and proximate composition of leaves of the species. Furthermore, the findings may have important applications in achieving high quality yields in vegetable crops.

Les traceurs à base de bore (δ11B et B/Ca) dans les carbonates ont reçu une attention considérable au cours des dernières décennies dans le domaine des géosciences de par leur potentiel à recalculer le pH. Cette thèse explore les frontières des applications de ces traceurs à la paléocéanographie et à la biogéochimie. A cause de la montée des teneurs en CO2 d’origine anthropique, il est devenu extrêmement important de comprendre comment les systèmes de la Terre répondront dans le futur. Les organismes marins sont aussi impactés par le réchauffement et l’acidification des océans, c’est pourquoi il est essentiel d’identifier les espèces résilientes et de comprendre les mécanismes sous-jacents à leur acclimatation. Les objectifs de cette thèse sont de répondre à certaines questions fondamentales, comment le CO2 atmosphérique a évolué au cours des transitions climatiques majeures du Néogène? Comment le dégazage ou l’absorption de carbone ont-ils évolué dans l’Est équatorial Pacifique au cours des derniers 6.5 Ma? Les changements de source et puits de carbones peuvent-ils moduler le CO2 atmosphérique passé et expliquer les transitions climatiques? Et pour les organismes marins, comment les mécanismes permettant la biominéralisation sont-ils impactés par l’augmentation des températures et l’acidification des océans dans les coraux tropicaux ? / Boron-based proxies (δ11B and B/Ca) in carbonates have gained considerable attention in the geosciences over the last several decades, given their potential to constrain pH. This thesis explores frontier applications of these proxies to paleoceanography and biogeochemistry. Due to rising anthropogenic CO2 levels, it is becoming increasingly important to understand how Earth’s systems will respond in the future.Marine organisms are also impacted by the warming and acidification of the ocean, therefore it is essential to identify resilient species and understand the underlying mechanisms of acclimatization.The objectives of this thesis are to answer several fundamental questions, for instance, how has atmospheric CO2 changed during major climate transitions over the Neogene? How did degassing or absorption of carbon evolve in the East equatorial Pacific during the last 6.5 Ma? Can changes of sources and sinks modulate past atmospheric CO2 and explain past climate transitions? And for marine organisms, how are the mechanisms allowing biomineralization impacted by increased temperature and the acidification of the ocean in tropical corals?

Superfícies funcionais dependem do controle das características das superfícies de um material para obter-se um desempenho funcional desejado. Essas superfícies têm importância em diversas áreas na engenharia, como: eletrônica, ótica, energia e tribologia. No campo da tribologia, uma aplicação é em virabrequins. A funcionalização da superfície adiciona micro cavidades que diminuem o atrito e aumentam as forças de sustentação do virabrequim. Para isso, essas cavidades possuem uma geometria específica, uma microrampa. Devido a essa forma especial, a fabricação dessas microrampas é complexa, já tendo sido alcançada empregando a metodologia de texturização com rebolos padronizados. Essa metodologia consiste na inscrição de padrões geométricos no rebolo durante a dressagem, posteriormente transferidos para a peça. Como a indústria moderna utiliza rebolos de CBN de ligante vitrificado para a retificação de virabrequins, a metodologia de texturização supracitada deve ser aplicável a esse ferramental. Esse trabalho descreve o desenvolvimento de uma unidade de dressagem capaz de inscrever padrões geométricos em rebolos de CBN vitrificados, sendo seu projeto baseado em análise modal. O trabalho apresenta as restrições de projeto, conceitos de solução, simulações dinâmicas e modelagem do processo de texturização. Para maximizar a resposta dinâmica, a unidade foi projetada para operar próxima de sua frequência natural. A unidade projetada é capaz de inscrever padrões geométricos no rebolo utilizando um disco dressador rotativo, e as texturas das peças produzidas com esse rebolo padronizado apresentam boa precisão geométrica para a aplicação em virabrequins. / Engineered surfaces rely on the control of the surface characteristics of a material to achieve a desired functional performance. These functional surfaces are important in several areas of engineering, such as: electronics, optics, energy and tribology. On tribology field, an application is in crankshafts. The surface functionalization is achieved by adding micro-cavities that reduce friction and increase crankshaft lift forces. These cavities have a specific geometry, called microramp. Due to this special geometry, manufacturing microramps is a complex process, having been achieved using the methodology of texturizing via grinding. This methodology consists in the inscription of geometric patterns in the grinding wheel during the dressing operation, later transferred to the piece. As the modern industry uses vitrified CBN grinding wheels for crankshaft grinding, the texturing methodology should be applicable to this tool. This work describes the development of a dressing unit capable of inscribing geometric patterns in vitrified CBN grinding wheels, having its design based on modal analysis. The work presents the design constraints, solution concepts, dynamic simulations and modeling of the texturing process. To maximize dynamic response, the unit is designed to operate near its natural frequency. The designed unit can inscribe geometric patterns on the grinding wheel using a rotating dressing disc, and the textures of the parts produced have good geometric precision for crankshaft applications.

No presente trabalho foram produzidas duas ligas policristalinas de Fe-Ga e Fe-Ga-B para estudar a influência do boro nas propriedades piezomagnéticas da liga Fe-Ga. As propriedades piezomagnéticas foram obtidas a partir de medidas de magnetostricção (λ) em função de campo magnético (H) pelo coeficiente d33 = dλ/dH e medidas de indução magnética (B) em função da tensão compressiva aplicada (σ) pelo coeficiente d*33 = dB/dσ. A composição escolhida foi com 18,6% de Ga para ambas as ligas, que é a composição que possui o maior valor de magnetostricção na liga binária. A análise da microestrutura indicou a presença das fases Fe(Ga)-α (A2) e Fe3Ga (D03) para ambas as ligas e da fase Fe2B para a liga ternária. A presença da fase Fe2B causou o refinamento dos grãos e consequentemente um pequeno aumento do campo coercitivo da liga Fe-Ga-B se comparada à liga Fe-Ga e, além disto, aumentou o campo de saturação. Consequentemente os coeficientes piezomagnéticos da liga com boro foram duas vezes menores que da liga Fe-Ga. A igualdade d33* = d33 não é satisfeita para a liga Fe-Ga nem para a Fe-Ga-B, significando que os experimentos não foram realizados em condições estritamente reversíveis. Atribui-se esta irreversibilidade à alta velocidade de carregamento usada nos experimentos de B vs σ. No entanto, a dependência dos coeficientes piezomagnéticos do campo magnético e da tensão compressiva aplicada da liga Fe-Ga-B é bem menor que da liga Fe-Ga e os valores obtidos de ~ 4 nm/A são suficientemente adequados para muitas aplicações. / In this work were maked two polycrystalline alloys of Fe-Ga e Fe-Ga-B for to study the influence of borun in the piezomagnetc properties of the Fe-Ga alloys. The piezomagnetc properties were obteined from magnetostrictive measuments (λ) in function of magnetic field (H) by the coefficient d33 = dλ/dH and magnetic induction measuments (B) in function of compressive stress applied (σ) by the coefficient d*33 = dB/dσ. The chosen composition were 18.6% of Ga to both alloys, which is the composition for the largest magnetostriction to the binary alloy. The microstructural analysis indicated the presence of the phases Fe(Ga)-α and Fe3Ga (D03) for the both alloys and Fe2B phases to the ternary alloy. The presence of the Fe2B caused the refinament of the grains and consequently a small increase in the coercive field of the Fe-Ga alloy and, in addition, increased the saturation field. Consequently, the piezomagnetic coefficients of the boron alloys were twice as low as that of the Fe-Ga alloy. The equality d33* = d33 was not satisfied for the Fe-Ga and to Fe-Ga-B meaning that the experiments were not performed under strictly reversible conditions. This irreversibility was attributed to the high loading speed used in the experiments of B vs σ. However, the dependence of the piezomagnetic coefficients of the magnetic field and the applied compressive stress of the Fe-Ga-B alloy is much lower than that of the Fe-Ga alloy and the values obtained from ~ 4nm/A are sufficiently suitable for many applications.

Neste trabalho, foi avaliada a reatividade de compostos orgânicos contendo boro frente a reações catalisadas por enzimas. Diferentes exemplos de álcoois secundários quirais contendo boro foram acetilados enantiosseletivamente pela lipase de Candida antarctica (CALB). Todas as reações ocorreram com excelente enantiosseletividade (E >200) e ambos os produtos acetilados, bem como os álcoois remanescentes foram obtidos com alto excesso enantiomérico (ee >99%). Além da resolução cinética enzimática, foi avaliado também o processo de resolução cinética dinâmica quimio-enzimática, empregando complexos de rutênio como agentes de racemização. Após estabelecer as condições adequadas para a reação, foi possível obter o produto acetilado de configuração-(R) com 83% de conversão, mantendo a enantiosseletividade observada na reação de resolução cinética enzimática. Como extensão ao trabalho realizado com os álcoois contendo boro, foi estudada a resolução cinética de aminas primárias quirais contendo boro. Foram avaliadas diversas condições reacionais para alcançar a máxima resolução cinética destas aminas via acilação enantiosseletiva catalisada pela lipase CALB. Excelente enantiosseletividade (E >200) e altos excessos enantioméricos (até >99%) foram obtidos utilizando acetato de etila tanto como reagente doador de acila como solvente da reação. Adicionalmente, foi investigada a reação de biorredução de cetonas pró-quirais contendo boro. Os melhores resultados foram obtidos com as enzimas álcool desidrogenases (ADHs) purificadas dos microorganismos Rhodococcus ruber e Lactobacillus brevis. A ADH de R. ruber (ADH-A) promoveu a biorredução das cetonas aos respectivos álcoois de configuração-(R) com excelente enantiosseletividade (ee >99%), enquanto a ADH de L. brevis (ADH-LB) catalisou a redução de alguns exemplos de cetonas aos respectivos álcoois de configuração-(S), também com excelente enantiosseletividade. / In this work, was evaluated the reactivity of boron-containing organic compounds in enzyme-catalyzed reactions. Different examples of boron-containing chiral secondary alcohols were resolved by enantioselective acetylation mediated by lipase from Candida. antarctica (CALB). All reactions showed excellent enantioselectivities (E >200) and both remaining substrates and acetylated product were obtained in high enantiomeric excesses (up to >99%). Besides the enzymatic kinetic resolution, the chemoenzymatic dynamic kinetic resolution was also evaluated, using ruthenium complexes as racemization agents. After establishing the best conditions, the acetylated (R)-product was obtained with 83% conversion, maintaining the high enantioselectivity observed in the enzymatic kinetic resolution. As an expansion of work with boron-containing alcohols, the kinetic resolution of boron-containing chiral amines was studied. Several reaction conditions were studied to achieve the kinetic resolution of boron-containing amines via enantioselective acylation mediated by CAL-B. Excellent enantioselectivity (E >200) and high enantiomeric excess (up to >99%) of both the remaining amines and amides were obtained using ethyl acetate as both acyl donor and the reaction solvent. Additionally, the bioreduction of pro-chiral boron-containing ketones was investigated. The best results were obtained with purified alcohol dehydrogenases (ADH) from Rhodococcus ruber and Lactobacillus brevis. The ADH from R. ruber (ADH-A) mediated the bioreduction of ketones to their respective (R)-alcohols with excellent enantioselectivity (ee >99%), while the ADH from L. brevis (ADH-LB) catalyzed the reduction of some ketones to their respective (S)-alcohols, also with excellent enantioselectivity (ee >99%).