Este estudo relata a síntese dos catalisadores heterogêneos Fe3O4@nSiO2@MCM-41-MnP e Fe3O4@nSiO2@MCM-41(E)-MnP. São sistemas que aliam as propriedades catalíticas de metaloporfirinas, com as propriedades magnéticas das nanopartículas de magnetita (Fe3O4) numa matriz estruturada de sílica mesoporosa MCM-41. A síntese das nanopartículas de Fe3O4 foi seguida pelo revestimento de sua superfície com camada fina de sílica (Fe3O4@nSiO2). Em seguida, a estrutura mesoporosa da sílica MCM-41 foi formada sobre as partículas recobertas na presença de brometo de hexadeciltrimetilamônio, como surfatante, e tetraetilortosilicato, como o precursor de sílica, obtendo-se o compósito Fe3O4@nSiO2@MCM-41. No processo de síntese do compósito Fe3O4@nSiO2@MCM-41(E), o mesitileno foi incorporado como agente expansor de estrutura, a fim de se obter poros com diâmetros maiores que os característicos para a sílica mesoporosa MCM-41. Os compósitos foram funcionalizados com o agente sililante 3-aminopropiltrietoxisilano. Esta etapa permitiu a imobilização covalente da [Mn(TF5PP)]Cl nos compósitos através de uma reação de substituição nucleofílica aromática, gerando os catalisadores Fe3O4@nSiO2@MCM-41-MnP e Fe3O4@nSiO2@MCM-41(E)-MnP. Caracterizações por espectroscopia no ultravioleta-visível e no infravermelho, reflectância difusa no UV-Vis, magnetometria de amostra vibrante, difração de raios-X, microscopia eletrônica de varredura e transmissão e isotermas de adsorção-dessorção de N2, permitiram compreender a estrutura e morfologia dos catalisadores. A atividade catalítica dos sistemas na oxidação de hidrocarbonetos ((Z) ciclo-octeno e ciclo-hexano) e na oxidação de fármaco (mirtazapina) foi avaliada; iodosilbenzeno ou ácido meta-cloroperoxibenzóico, foram utilizados como agente doador de oxigênio. Os testes catalíticos com os hidrocarbonetos demonstraram maiores rendimentos de epóxido para o catalisador Fe3O4@nSiO2@MCM-41(E)-MnP do que o catalisador Fe3O4@nSiO2@MCM-41-MnP. Estes rendimentos altos para o primeiro foram atribuídos ao seu maior tamanho de poros. Ambos os catalisadores foram seletivos para o produto ciclo-hexanol, indicando um comportamento biomimético. A oxidação do fármaco, nas condições deste estudo preliminar, gerou um metabólito que difere dos dois principais metabólitos (8-hidroximirtazapina e demetilmirtazapina) obtidos em estudos com enzimas P450. Estudos controle de oxidação do fármaco com manganês porfirina em solução revelaram que este sistema foi seletivo para formação do produto demetilmirtazapina. / This study reports on the preparation of the Fe3O4@nSiO2@MCM-41-MnP and Fe3O4@nSiO2@MCM-41(E)-MnP heterogeneous catalysts. They are systems that allies the catalytic properties of metalloporphyrins with the magnetic properties of magnetite (Fe3O4) nanoparticles in a structured matrix of MCM-41 mesoporous silica. Synthesis of Fe3O4 nanoparticles was followed by surface coating with a thin silica layer (Fe3O4@nSiO2). Then, a MCM-41-type mesoporous silica structure was grown over the coated particles in the presence of hexadecyltrimethylammonium bromide, as surfactant, and tetraethylorthosilicate, as the silica precursor, to yield the Fe3O4@nSiO2@MCM-41 composite. It was incorporated into the synthesis route of Fe3O4@nSiO2@MCM-41(E) composite the mesitylene as expanding agent structure, in order to obtain pores with diameters greater than the characteristic for the MCM-41 mesoporous silica. The resulting composites was functionalized with the silylating agent 3-aminopropyltriethoxysilane. This enabled covalent immobilization of [Mn(TF5PP)]Cl onto the composite via a nucleophilic aromatic substitution reaction, to afford the Fe3O4@nSiO2@MCM-41-MnP and Fe3O4@nSiO2@MCM-41(E)-MnP catalysts. Characterization of the catalysts by ultraviolet-visible and infrared spectroscopies, UV-Vis diffuse reflectance, vibrating sample magnetometer, X-ray diffractometry, scanning and transmission electron microscopies and N2 adsorption-desorption isotherm, aimed to understand the structure and morphology of the catalysts. The catalytic activity of the systems in hydrocarbon oxidation ((Z)-cyclooctene and cyclohexane) and the drug oxidation (mirtazapine) was evaluated; iodosylbenzene or meta-chloroperoxybenzoic acid, were used as the oxygen donor agent. The catalytic tests with the hydrocarbons demonstrated higher yields of epoxide for Fe3O4@nSiO2@MCM-41(E)-MnP than Fe3O4@nSiO2@MCM-41-MnP catalyst. These high yields for the first catalyst, were attributed to larger pore size. Both catalysts were selective for the cyclohexanol product, indicating a biomimetic behavior. The drug oxidation, under the preliminary study conditions, generated a metabolite that differs from the two major metabolites (8-hydroxy mirtazapine and demethylmirtazapine) obtained in studies with P450 enzymes. Control drug oxidation studies with manganese porphyrin solution revealed that this system was selective for formation of demethylmirtazapine product.

The objective of the proposed research is to design and develop a series of radio frequency identification (RFID) tag structures that exhibit good performance characteristics with cost optimization and can be realized on flexible substrates such as liquid crystal polymer (LCP), paper-based substrate and magnetic composite material for conformal applications. The demand for flexible RFID tags has recently increased tremendously due to the requirements of automatic identification in various areas. Several major challenges existing in today's RFID technologies need to be addressed before RFID can eventually march into everyone's daily life, such as how to design high performance tag antennas with effective impedance matching for passive RFID IC chips to optimize the power performance, how to fabricate ultra-low-cost RFID tags in order to facilitate mass production, how to integrate sensors with passive RFID tags for pervasive sensing applications, and how to realize battery-free active RFID tags in which changing battery is not longer needed. In this research, different RFID tag designs are realized on flexible substrates. The design techniques presented set the framework for answering these technical challenges for which, the focus will be on RFID tag structure design, characterization and optimization from the perspectives of both costs involved and technical constraints.

Este estudo relata a síntese dos catalisadores heterogêneos Fe3O4@nSiO2@MCM-41-MnP e Fe3O4@nSiO2@MCM-41(E)-MnP. São sistemas que aliam as propriedades catalíticas de metaloporfirinas, com as propriedades magnéticas das nanopartículas de magnetita (Fe3O4) numa matriz estruturada de sílica mesoporosa MCM-41. A síntese das nanopartículas de Fe3O4 foi seguida pelo revestimento de sua superfície com camada fina de sílica (Fe3O4@nSiO2). Em seguida, a estrutura mesoporosa da sílica MCM-41 foi formada sobre as partículas recobertas na presença de brometo de hexadeciltrimetilamônio, como surfatante, e tetraetilortosilicato, como o precursor de sílica, obtendo-se o compósito Fe3O4@nSiO2@MCM-41. No processo de síntese do compósito Fe3O4@nSiO2@MCM-41(E), o mesitileno foi incorporado como agente expansor de estrutura, a fim de se obter poros com diâmetros maiores que os característicos para a sílica mesoporosa MCM-41. Os compósitos foram funcionalizados com o agente sililante 3-aminopropiltrietoxisilano. Esta etapa permitiu a imobilização covalente da [Mn(TF5PP)]Cl nos compósitos através de uma reação de substituição nucleofílica aromática, gerando os catalisadores Fe3O4@nSiO2@MCM-41-MnP e Fe3O4@nSiO2@MCM-41(E)-MnP. Caracterizações por espectroscopia no ultravioleta-visível e no infravermelho, reflectância difusa no UV-Vis, magnetometria de amostra vibrante, difração de raios-X, microscopia eletrônica de varredura e transmissão e isotermas de adsorção-dessorção de N2, permitiram compreender a estrutura e morfologia dos catalisadores. A atividade catalítica dos sistemas na oxidação de hidrocarbonetos ((Z) ciclo-octeno e ciclo-hexano) e na oxidação de fármaco (mirtazapina) foi avaliada; iodosilbenzeno ou ácido meta-cloroperoxibenzóico, foram utilizados como agente doador de oxigênio. Os testes catalíticos com os hidrocarbonetos demonstraram maiores rendimentos de epóxido para o catalisador Fe3O4@nSiO2@MCM-41(E)-MnP do que o catalisador Fe3O4@nSiO2@MCM-41-MnP. Estes rendimentos altos para o primeiro foram atribuídos ao seu maior tamanho de poros. Ambos os catalisadores foram seletivos para o produto ciclo-hexanol, indicando um comportamento biomimético. A oxidação do fármaco, nas condições deste estudo preliminar, gerou um metabólito que difere dos dois principais metabólitos (8-hidroximirtazapina e demetilmirtazapina) obtidos em estudos com enzimas P450. Estudos controle de oxidação do fármaco com manganês porfirina em solução revelaram que este sistema foi seletivo para formação do produto demetilmirtazapina. / This study reports on the preparation of the Fe3O4@nSiO2@MCM-41-MnP and Fe3O4@nSiO2@MCM-41(E)-MnP heterogeneous catalysts. They are systems that allies the catalytic properties of metalloporphyrins with the magnetic properties of magnetite (Fe3O4) nanoparticles in a structured matrix of MCM-41 mesoporous silica. Synthesis of Fe3O4 nanoparticles was followed by surface coating with a thin silica layer (Fe3O4@nSiO2). Then, a MCM-41-type mesoporous silica structure was grown over the coated particles in the presence of hexadecyltrimethylammonium bromide, as surfactant, and tetraethylorthosilicate, as the silica precursor, to yield the Fe3O4@nSiO2@MCM-41 composite. It was incorporated into the synthesis route of Fe3O4@nSiO2@MCM-41(E) composite the mesitylene as expanding agent structure, in order to obtain pores with diameters greater than the characteristic for the MCM-41 mesoporous silica. The resulting composites was functionalized with the silylating agent 3-aminopropyltriethoxysilane. This enabled covalent immobilization of [Mn(TF5PP)]Cl onto the composite via a nucleophilic aromatic substitution reaction, to afford the Fe3O4@nSiO2@MCM-41-MnP and Fe3O4@nSiO2@MCM-41(E)-MnP catalysts. Characterization of the catalysts by ultraviolet-visible and infrared spectroscopies, UV-Vis diffuse reflectance, vibrating sample magnetometer, X-ray diffractometry, scanning and transmission electron microscopies and N2 adsorption-desorption isotherm, aimed to understand the structure and morphology of the catalysts. The catalytic activity of the systems in hydrocarbon oxidation ((Z)-cyclooctene and cyclohexane) and the drug oxidation (mirtazapine) was evaluated; iodosylbenzene or meta-chloroperoxybenzoic acid, were used as the oxygen donor agent. The catalytic tests with the hydrocarbons demonstrated higher yields of epoxide for Fe3O4@nSiO2@MCM-41(E)-MnP than Fe3O4@nSiO2@MCM-41-MnP catalyst. These high yields for the first catalyst, were attributed to larger pore size. Both catalysts were selective for the cyclohexanol product, indicating a biomimetic behavior. The drug oxidation, under the preliminary study conditions, generated a metabolite that differs from the two major metabolites (8-hydroxy mirtazapine and demethylmirtazapine) obtained in studies with P450 enzymes. Control drug oxidation studies with manganese porphyrin solution revealed that this system was selective for formation of demethylmirtazapine product.

Polymer magnetic composite (PMC) nanoparticles have gained a large attention due to their potential use in several biomedical applications from biomedical to engineering field. Among the different heterogeneous polymerization techniques that are generally used to prepare hybrid polymer particles, miniemulsion polymerization is proved to be an efficient one. The occurrence of preferential droplet nucleation in case of miniemulsion polymerization results in a 1:1 copy of monomer droplets to the polymer particles and such a mechanistic pathway offers a suitable environment for the preparation of hybrid polymer nanoparticles in the range between 50 to 500 nm. The surfactant in miniemulsoin plays a significant role to stabilize the droplets/particles and also in the encapsulation of nanoparticles. In the present study, a new class of surfactant, called amphiphilic ionic liquid, has been employed in the field of miniemulsion. The amphiphilic ionic liquid has amazing ability to impart surface tunable characteristics to the polymer particles when present on the surface of the particles. Thus the aim of the present work is to synthesize polymer magnetic composite nanoparticles with good colloidal stability, high content of magnetic nanoparticles as well as the chance for further surface functionality. Such magnetic nanoparticles may find applications in various fields. At first, the aim of the work was to establish a suitable recipe with ionic liquid as surfactant for the execution of miniemulsion polymerization. Monodisperse polystyrene nanoparticles were possible to be synthesized reproducibly. The established recipe was utilized to carry out the synthesis of PMC nanoparticles. Iron oxide (Fe3O4) was taken as magnetic nanoparticles (MNP) and it was hydrophobized with oleic acid to disperse in styrene. The concentration of feed MNP was varied to observe its influence on the characteristics of PMC nanoparticles. Stable dispersion of magnetic polystyrene particles was possible to be synthesized up to 8 wt% feed MNP. But feeding 12 wt% MNP resulted in the development of large amount of coagulum associated with instability in the dispersion. TGA investigation confirmed a significantly lower MNP content (8.2 wt%) of the composite compared to the feed amount. TEM investigation showed inhomogeneous distribution of MNP among polystyrene particles and agglomeration of MNP was observed on the surface of polystyrene particles. Considering the inability of the single step miniemulsion polymerization for the preparation of high MNP content polymer particles, it was aimed to find a new strategy which can produce such material. Inspired from the affinity of carboxylic acid group towards the surface of MNP, it was aimed to synthesize carboxyl functionalized polystyrene which was expected to improve the interaction between polymer and magnetic nanoparticles. For this purpose, RAFT mediated miniemulsion polymerization was performed in presence of a carboxyl functionalized chain transfer agent (CTA). The colloidal stability was much better compared to the previous case of non-RAFT experiments. From a feed MNP of 8 wt%, a high final MNP content up to ~27 wt% could be achieved and all the dispersions were highly stable. The higher MNP content in the final composites compared to the feed ratio was a result of the low monomer conversion and could be adjusted by a proper tuning of AIBN to CTA mole ratio. Another significant influence of the carboxyl functionalized CTA was observed on the morphology of the composite nanoparticles. The MNP were distributed homogeneously among the PS particles. Regarding the dispersion of MNP in the individual polystyrene particles, it was observed that higher amount of CTA resulted in a homogeneous dispersion of MNP whereas higher amount of initiator ended up producing asymmetric Janus like morphology. Apart from that, due to the involvement of CTA in the polymerization, much lower molecular weight of the polystyrene chains was developed compared to the free radical process and the molecular weight distribution of PS in the composite nanoparticles became much narrower through the RAFT polymerization. Thus a relatively good control over the polymerization process was achieved through RAFT polymerization which was confirmed by a nearly linear increase of molecular weight (Mn) with time of polymerization and thus, monomer conversion. In the recipe of miniemulsion, costabilizer plays an important role to retard monomer diffusion from smaller to larger droplets. Hexadecane, being the most frequently used costabilizer for miniemulsion, has been employed in this study so far. But its volatile nature restricts its utilization in several applications. For the replacement of hexadecane, a carboxyl functionalized polystyrene is employed as a costabilizer as well as a macro CTA in miniemulsoin polymerization of styrene. For this purpose, low molecular weight carboxyl bi-functionalized polystyrene (9000 g/mole) was synthesized by thermal bulk RAFT polymerization. The carboxylated polystyrene worked successfully as a costabilizer in miniemulsion and molecular weight investigation confirmed the integration of the carboxyl functionalized macro CTA into the developing polystyrene chain via RAFT polymerization. This strategy was employed successfully to synthesize stable dispersion of PMC nanoparticles with a reasonable content of MNP in the system. A homogeneous morphology was observed regarding the distribution of MNP among the polystyrene particles. The strategy of using macro CTA as costabilizer can be utilized to synthesize various functional copolymers with control architecture without any added monomer and CTA in the system. Moreover, presence of functionality within the monomer droplets can be effective to encapsulate several nanomaterials using miniemulsion polymerization.

No description available.

O presente trabalho trata do estudo, análise, construção e teste de uma nova configuração para um atuador planar. O dispositivo é composto de um núcleo de armadura ferromagnético plano, estático e sem ranhuras sobre o qual são montados dois conjuntos de enrolamentos planares, ortogonais entre si, com quatro bobinas cada, eletricamente independentes entre si. A parte móvel consiste de um carro equipado com ímãs permanentes de alto produto energético responsáveis pela produção de fluxo magnético de excitação. A movimentação bidirecional sobre o plano se dá pela interação entre esse fluxo e a corrente elétrica adequadamente aplicada aos enrolamentos. O atuador apresenta uma distribuição espacial da densidade de fluxo magnético em toda a sua estrutura. Este trabalho preocupa-se em analisar numérica e experimentalmente os fenômenos eletromagnéticos envolvidos, tanto em regime estático como dinâmico. O emprego de dois diferentes materiais utilizados separadamente no núcleo da armadura é investigado: o aço maciço (caso 1) e um compósito magneticamente macio de grão isolado (caso 2). Devido à movimentação do carro e conseqüentemente do fluxo magnético de excitação, uma força eletromotriz induzida aparecerá no núcleo da armadura, sendo responsável pelo estabelecimento de correntes elétricas induzidas no mesmo. Essas correntes, que também dependem da condutividade do material do núcleo, produzem um efeito de frenagem sobre o carro do atuador que afeta a sua dinâmica. Produzem ainda perdas Joule no núcleo da armadura. A redução desses efeitos pode ser obtida com a utilização de um material magnético isotrópico de alta resistividade, caso 2, que possibilita ainda a distribuição tridimensional da densidade de fluxo magnético na estrutura do atuador. Uma análise dinâmica a partir do método dos elementos finitos tornou possível a verificação da distribuição da densidade de corrente elétrica induzida no núcleo da armadura, bem como a obtenção dos seus valores em função da velocidade do carro e do material utilizado. Ainda, o efeito de frenagem foi quantificado em ensaios práticos, propondo-se então um coeficiente de atrito total, k, para cada um dos dois casos em estudo. Nessa caracterização, obteve-se que o coeficiente de atrito eletromagnético, devido às correntes induzidas, de 1,74469 Ns/m para o caso 1, enquanto que para o caso 2 esse valor fica em 0,261285 Ns/m. Os resultados numéricos e experimentais apontam que existem diferenças significativas na utilização dos dois materiais propostos, indicando que o caso 2, quando utilizado de maneira adequada no sistema, reduz as correntes elétricas induzidas minimizando seus efeitos. / The present work deals with the study, analysis, construction and testing of a new configuration of a planar actuator. The device comprehends a static ferromagnetic slotless core in form of slab, on which two sets of planar windings are assembled. They are orthogonal with respect to each other and have four independent coils. The moving part consists of a car, equipped with high energy product permanent magnets that deliver the excitation magnetic flux. The bidirectional movement on the plan is a result of the interaction between the excitation magnetic flux and the electric currents that fed the armature windings properly. The actuator features a spatial distribution of the magnetic flux density throughout its structure. This work is concerned with the numerical and experimental analyses of the electromagnetic effects involved in terms of static and dynamic behavior of the actuator. These effects are investigated for two different materials employed separately in the core of the armature: solid steel (case 1) and a grain isolated soft magnetic composite (case 2). Owing to the movement of the car and so the excitation magnetic flux, an induced electromotive force appears on the core of the armature and is responsible for the establishment of induced electrical currents in there. These currents, that also depend on the conductivity of the material of the armature core, produce a braking effect on the car that affects the dynamics of the actuator. It also produces Joule losses on that core. The reduction of those effects can be obtained with the use of an isotropic ferromagnetic material with high resistivity, case 2, that allows the 3d distribution of magnetic flux density on the structure of the actuator. A dynamic analysis by means of the finite element method made possible to verify the distribution of the induced electrical current density in the core of the armature, and to compute its value according to the speed of the car and to the material employed. Still, the effect of the braking force was quantified experimentally; as a result, a total friction coefficient, k, is proposed in order to take into account that force. By doing that, a resulting coefficient of electromagnetic friction due to the induced currents is 1.74469 Ns/m for case 1, while for case 2 it is 0.261285 Ns/m. The numerical and experimental results indicate that exist significant differences in the use of the two materials proposed, indicating that the case 2, when used in an appropriate manner, reduces the induced electrical currents minimizing its effects.

O presente trabalho trata do estudo, análise, construção e teste de uma nova configuração para um atuador planar. O dispositivo é composto de um núcleo de armadura ferromagnético plano, estático e sem ranhuras sobre o qual são montados dois conjuntos de enrolamentos planares, ortogonais entre si, com quatro bobinas cada, eletricamente independentes entre si. A parte móvel consiste de um carro equipado com ímãs permanentes de alto produto energético responsáveis pela produção de fluxo magnético de excitação. A movimentação bidirecional sobre o plano se dá pela interação entre esse fluxo e a corrente elétrica adequadamente aplicada aos enrolamentos. O atuador apresenta uma distribuição espacial da densidade de fluxo magnético em toda a sua estrutura. Este trabalho preocupa-se em analisar numérica e experimentalmente os fenômenos eletromagnéticos envolvidos, tanto em regime estático como dinâmico. O emprego de dois diferentes materiais utilizados separadamente no núcleo da armadura é investigado: o aço maciço (caso 1) e um compósito magneticamente macio de grão isolado (caso 2). Devido à movimentação do carro e conseqüentemente do fluxo magnético de excitação, uma força eletromotriz induzida aparecerá no núcleo da armadura, sendo responsável pelo estabelecimento de correntes elétricas induzidas no mesmo. Essas correntes, que também dependem da condutividade do material do núcleo, produzem um efeito de frenagem sobre o carro do atuador que afeta a sua dinâmica. Produzem ainda perdas Joule no núcleo da armadura. A redução desses efeitos pode ser obtida com a utilização de um material magnético isotrópico de alta resistividade, caso 2, que possibilita ainda a distribuição tridimensional da densidade de fluxo magnético na estrutura do atuador. Uma análise dinâmica a partir do método dos elementos finitos tornou possível a verificação da distribuição da densidade de corrente elétrica induzida no núcleo da armadura, bem como a obtenção dos seus valores em função da velocidade do carro e do material utilizado. Ainda, o efeito de frenagem foi quantificado em ensaios práticos, propondo-se então um coeficiente de atrito total, k, para cada um dos dois casos em estudo. Nessa caracterização, obteve-se que o coeficiente de atrito eletromagnético, devido às correntes induzidas, de 1,74469 Ns/m para o caso 1, enquanto que para o caso 2 esse valor fica em 0,261285 Ns/m. Os resultados numéricos e experimentais apontam que existem diferenças significativas na utilização dos dois materiais propostos, indicando que o caso 2, quando utilizado de maneira adequada no sistema, reduz as correntes elétricas induzidas minimizando seus efeitos. / The present work deals with the study, analysis, construction and testing of a new configuration of a planar actuator. The device comprehends a static ferromagnetic slotless core in form of slab, on which two sets of planar windings are assembled. They are orthogonal with respect to each other and have four independent coils. The moving part consists of a car, equipped with high energy product permanent magnets that deliver the excitation magnetic flux. The bidirectional movement on the plan is a result of the interaction between the excitation magnetic flux and the electric currents that fed the armature windings properly. The actuator features a spatial distribution of the magnetic flux density throughout its structure. This work is concerned with the numerical and experimental analyses of the electromagnetic effects involved in terms of static and dynamic behavior of the actuator. These effects are investigated for two different materials employed separately in the core of the armature: solid steel (case 1) and a grain isolated soft magnetic composite (case 2). Owing to the movement of the car and so the excitation magnetic flux, an induced electromotive force appears on the core of the armature and is responsible for the establishment of induced electrical currents in there. These currents, that also depend on the conductivity of the material of the armature core, produce a braking effect on the car that affects the dynamics of the actuator. It also produces Joule losses on that core. The reduction of those effects can be obtained with the use of an isotropic ferromagnetic material with high resistivity, case 2, that allows the 3d distribution of magnetic flux density on the structure of the actuator. A dynamic analysis by means of the finite element method made possible to verify the distribution of the induced electrical current density in the core of the armature, and to compute its value according to the speed of the car and to the material employed. Still, the effect of the braking force was quantified experimentally; as a result, a total friction coefficient, k, is proposed in order to take into account that force. By doing that, a resulting coefficient of electromagnetic friction due to the induced currents is 1.74469 Ns/m for case 1, while for case 2 it is 0.261285 Ns/m. The numerical and experimental results indicate that exist significant differences in the use of the two materials proposed, indicating that the case 2, when used in an appropriate manner, reduces the induced electrical currents minimizing its effects.

O presente trabalho trata do estudo, análise, construção e teste de uma nova configuração para um atuador planar. O dispositivo é composto de um núcleo de armadura ferromagnético plano, estático e sem ranhuras sobre o qual são montados dois conjuntos de enrolamentos planares, ortogonais entre si, com quatro bobinas cada, eletricamente independentes entre si. A parte móvel consiste de um carro equipado com ímãs permanentes de alto produto energético responsáveis pela produção de fluxo magnético de excitação. A movimentação bidirecional sobre o plano se dá pela interação entre esse fluxo e a corrente elétrica adequadamente aplicada aos enrolamentos. O atuador apresenta uma distribuição espacial da densidade de fluxo magnético em toda a sua estrutura. Este trabalho preocupa-se em analisar numérica e experimentalmente os fenômenos eletromagnéticos envolvidos, tanto em regime estático como dinâmico. O emprego de dois diferentes materiais utilizados separadamente no núcleo da armadura é investigado: o aço maciço (caso 1) e um compósito magneticamente macio de grão isolado (caso 2). Devido à movimentação do carro e conseqüentemente do fluxo magnético de excitação, uma força eletromotriz induzida aparecerá no núcleo da armadura, sendo responsável pelo estabelecimento de correntes elétricas induzidas no mesmo. Essas correntes, que também dependem da condutividade do material do núcleo, produzem um efeito de frenagem sobre o carro do atuador que afeta a sua dinâmica. Produzem ainda perdas Joule no núcleo da armadura. A redução desses efeitos pode ser obtida com a utilização de um material magnético isotrópico de alta resistividade, caso 2, que possibilita ainda a distribuição tridimensional da densidade de fluxo magnético na estrutura do atuador. Uma análise dinâmica a partir do método dos elementos finitos tornou possível a verificação da distribuição da densidade de corrente elétrica induzida no núcleo da armadura, bem como a obtenção dos seus valores em função da velocidade do carro e do material utilizado. Ainda, o efeito de frenagem foi quantificado em ensaios práticos, propondo-se então um coeficiente de atrito total, k, para cada um dos dois casos em estudo. Nessa caracterização, obteve-se que o coeficiente de atrito eletromagnético, devido às correntes induzidas, de 1,74469 Ns/m para o caso 1, enquanto que para o caso 2 esse valor fica em 0,261285 Ns/m. Os resultados numéricos e experimentais apontam que existem diferenças significativas na utilização dos dois materiais propostos, indicando que o caso 2, quando utilizado de maneira adequada no sistema, reduz as correntes elétricas induzidas minimizando seus efeitos. / The present work deals with the study, analysis, construction and testing of a new configuration of a planar actuator. The device comprehends a static ferromagnetic slotless core in form of slab, on which two sets of planar windings are assembled. They are orthogonal with respect to each other and have four independent coils. The moving part consists of a car, equipped with high energy product permanent magnets that deliver the excitation magnetic flux. The bidirectional movement on the plan is a result of the interaction between the excitation magnetic flux and the electric currents that fed the armature windings properly. The actuator features a spatial distribution of the magnetic flux density throughout its structure. This work is concerned with the numerical and experimental analyses of the electromagnetic effects involved in terms of static and dynamic behavior of the actuator. These effects are investigated for two different materials employed separately in the core of the armature: solid steel (case 1) and a grain isolated soft magnetic composite (case 2). Owing to the movement of the car and so the excitation magnetic flux, an induced electromotive force appears on the core of the armature and is responsible for the establishment of induced electrical currents in there. These currents, that also depend on the conductivity of the material of the armature core, produce a braking effect on the car that affects the dynamics of the actuator. It also produces Joule losses on that core. The reduction of those effects can be obtained with the use of an isotropic ferromagnetic material with high resistivity, case 2, that allows the 3d distribution of magnetic flux density on the structure of the actuator. A dynamic analysis by means of the finite element method made possible to verify the distribution of the induced electrical current density in the core of the armature, and to compute its value according to the speed of the car and to the material employed. Still, the effect of the braking force was quantified experimentally; as a result, a total friction coefficient, k, is proposed in order to take into account that force. By doing that, a resulting coefficient of electromagnetic friction due to the induced currents is 1.74469 Ns/m for case 1, while for case 2 it is 0.261285 Ns/m. The numerical and experimental results indicate that exist significant differences in the use of the two materials proposed, indicating that the case 2, when used in an appropriate manner, reduces the induced electrical currents minimizing its effects.

Submitted by MARCIA ROVADOSCHI (marciar@unifra.br) on 2018-08-17T11:57:07Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_MarcelGoulartFinger.pdf: 1595398 bytes, checksum: 461acc59b7b05e1925aa025d086c4f9b (MD5) / Made available in DSpace on 2018-08-17T11:57:07Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_MarcelGoulartFinger.pdf: 1595398 bytes, checksum: 461acc59b7b05e1925aa025d086c4f9b (MD5) Previous issue date: 2016-08-30 / This work aimed to investigate the adsorption and photocatalysis of solutions containing nimesulide and 17β-estradiol with a composite formed of active charcoal decorated with NiFe2O4 nanoparticles. The composite was prepared by the hydrothermal method using Ni (NO3)2 6H2O and Fe(NO3)3 9H2O as precursors solubilized in basic aqueous medium. The solution was sealed in a Teflon reactor and heated 463.15 K for 10 h. The composite was characterized by X-ray diffraction, the morphology was observed by scanning electron microscopy and the with the vibrating sample magnetometer. Nimesulide and 17β-estradiol adsorb according to a pseudo-second order kinetics. The calculation of the thermodynamic parameters of adsorption indicated that the adsorption of nimesulide occurs in an endothermic, spontaneous and favorable manner in all temperatures investigated. The adsorption enthalpy magnitude between the nimesulide and the active charcoal decorated with ferrite is 90.2 kJ mol-1 which indicates that the adsorption is endothermic and occurs through chemisorption. The initial concentration of nimesulide decays by 70% and the concentration of 17β-estradiol decays by 99% after 60 min of UV light irradiation. / Este trabalho teve como objetivo investigar a adsorção e a fotocatálise de soluções contendo a nimesulida e o 17 -estradiol com um compósito formado por carvão ativo decorado com nanopartículas de NiFe2O4. O compósito foi preparado pelo método hidrotermal utilizando o Ni(NO3)2 6 H2O e o Fe(NO3)3 9 H2O como precursores solubilizados em meio aquoso básico. A solução foi selada em um reator de Teflon e aquecida 463,15 K durante 10 h. O compósito foi caracterizado por difração de raios X, a morfologia foi observada por microscopia eletrônica de varredura e a com o magnetômetro de amostra vibrante. A nimesulida e o 17 -estradiol adsorvem segundo uma cinética de pseudo-segunda ordem. O cálculo dos parâmetros termodinâmicos de adsorção indicou que a adsorção da nimesulida ocorre de forma endotérmica, espontânea e favorável em todas as temperaturas investigadas. A magnitude da entalpia de adsorção entre a nimesulida e o carvão ativo decorado com ferrita é 90,2 kJ mol-1 o que indica que a adsorção é endotérmica e ocorre através de quimissorção. A concentração inicial da nimesulida decai 70% e a concentração do 17 -estradiol decai de 99% após 60 min de irradiação com luz UV.

Polymer magnetic composite (PMC) nanoparticles have gained a large attention due to their potential use in several biomedical applications from biomedical to engineering field. Among the different heterogeneous polymerization techniques that are generally used to prepare hybrid polymer particles, miniemulsion polymerization is proved to be an efficient one. The occurrence of preferential droplet nucleation in case of miniemulsion polymerization results in a 1:1 copy of monomer droplets to the polymer particles and such a mechanistic pathway offers a suitable environment for the preparation of hybrid polymer nanoparticles in the range between 50 to 500 nm. The surfactant in miniemulsoin plays a significant role to stabilize the droplets/particles and also in the encapsulation of nanoparticles. In the present study, a new class of surfactant, called amphiphilic ionic liquid, has been employed in the field of miniemulsion. The amphiphilic ionic liquid has amazing ability to impart surface tunable characteristics to the polymer particles when present on the surface of the particles. Thus the aim of the present work is to synthesize polymer magnetic composite nanoparticles with good colloidal stability, high content of magnetic nanoparticles as well as the chance for further surface functionality. Such magnetic nanoparticles may find applications in various fields. At first, the aim of the work was to establish a suitable recipe with ionic liquid as surfactant for the execution of miniemulsion polymerization. Monodisperse polystyrene nanoparticles were possible to be synthesized reproducibly. The established recipe was utilized to carry out the synthesis of PMC nanoparticles. Iron oxide (Fe3O4) was taken as magnetic nanoparticles (MNP) and it was hydrophobized with oleic acid to disperse in styrene. The concentration of feed MNP was varied to observe its influence on the characteristics of PMC nanoparticles. Stable dispersion of magnetic polystyrene particles was possible to be synthesized up to 8 wt% feed MNP. But feeding 12 wt% MNP resulted in the development of large amount of coagulum associated with instability in the dispersion. TGA investigation confirmed a significantly lower MNP content (8.2 wt%) of the composite compared to the feed amount. TEM investigation showed inhomogeneous distribution of MNP among polystyrene particles and agglomeration of MNP was observed on the surface of polystyrene particles. Considering the inability of the single step miniemulsion polymerization for the preparation of high MNP content polymer particles, it was aimed to find a new strategy which can produce such material. Inspired from the affinity of carboxylic acid group towards the surface of MNP, it was aimed to synthesize carboxyl functionalized polystyrene which was expected to improve the interaction between polymer and magnetic nanoparticles. For this purpose, RAFT mediated miniemulsion polymerization was performed in presence of a carboxyl functionalized chain transfer agent (CTA). The colloidal stability was much better compared to the previous case of non-RAFT experiments. From a feed MNP of 8 wt%, a high final MNP content up to ~27 wt% could be achieved and all the dispersions were highly stable. The higher MNP content in the final composites compared to the feed ratio was a result of the low monomer conversion and could be adjusted by a proper tuning of AIBN to CTA mole ratio. Another significant influence of the carboxyl functionalized CTA was observed on the morphology of the composite nanoparticles. The MNP were distributed homogeneously among the PS particles. Regarding the dispersion of MNP in the individual polystyrene particles, it was observed that higher amount of CTA resulted in a homogeneous dispersion of MNP whereas higher amount of initiator ended up producing asymmetric Janus like morphology. Apart from that, due to the involvement of CTA in the polymerization, much lower molecular weight of the polystyrene chains was developed compared to the free radical process and the molecular weight distribution of PS in the composite nanoparticles became much narrower through the RAFT polymerization. Thus a relatively good control over the polymerization process was achieved through RAFT polymerization which was confirmed by a nearly linear increase of molecular weight (Mn) with time of polymerization and thus, monomer conversion. In the recipe of miniemulsion, costabilizer plays an important role to retard monomer diffusion from smaller to larger droplets. Hexadecane, being the most frequently used costabilizer for miniemulsion, has been employed in this study so far. But its volatile nature restricts its utilization in several applications. For the replacement of hexadecane, a carboxyl functionalized polystyrene is employed as a costabilizer as well as a macro CTA in miniemulsoin polymerization of styrene. For this purpose, low molecular weight carboxyl bi-functionalized polystyrene (9000 g/mole) was synthesized by thermal bulk RAFT polymerization. The carboxylated polystyrene worked successfully as a costabilizer in miniemulsion and molecular weight investigation confirmed the integration of the carboxyl functionalized macro CTA into the developing polystyrene chain via RAFT polymerization. This strategy was employed successfully to synthesize stable dispersion of PMC nanoparticles with a reasonable content of MNP in the system. A homogeneous morphology was observed regarding the distribution of MNP among the polystyrene particles. The strategy of using macro CTA as costabilizer can be utilized to synthesize various functional copolymers with control architecture without any added monomer and CTA in the system. Moreover, presence of functionality within the monomer droplets can be effective to encapsulate several nanomaterials using miniemulsion polymerization.