Submitted by Alison Vanceto (alison-vanceto@hotmail.com) on 2016-09-27T14:07:25Z No. of bitstreams: 1 TeseDMSC.pdf: 11591276 bytes, checksum: fcc4bd05d0e7049f1fe48d00e99712c5 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-04-24T19:11:09Z (GMT) No. of bitstreams: 1 TeseDMSC.pdf: 11591276 bytes, checksum: fcc4bd05d0e7049f1fe48d00e99712c5 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-04-24T19:11:18Z (GMT) No. of bitstreams: 1 TeseDMSC.pdf: 11591276 bytes, checksum: fcc4bd05d0e7049f1fe48d00e99712c5 (MD5) / Made available in DSpace on 2017-04-24T19:24:55Z (GMT). No. of bitstreams: 1 TeseDMSC.pdf: 11591276 bytes, checksum: fcc4bd05d0e7049f1fe48d00e99712c5 (MD5) Previous issue date: 2015-05-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The purpose of this thesis was to develop a microwave dilatometer and to study the non-isothermal sintering kinetics of multiferroic composite ceramics. The multiferroic system used to study the sintering kinetics was a composite of two crystalline phases: piezo BaTiO3 and magnetostrictive CoxNi(1-x)Fe2O4 (where x = 0, 0.25, 0.5, 0.75 and 1 and molar ratios of 80/20, 70/30 and 50/50). A method was developed for the synthesis step, called in situ synthesis, to produce the two crystalline phases from a single solution in which the starting materials were completely dissolved. In this synthesis step, a groundbreaking method was developed for the in situ sol-gel synthesis of lead-free BaTiO3/CoxNi(1-x)Fe2O4 composites, applying synthesis control parameters such as basic pH and the amount of polyacrylic acid (PAA) added as a chelating agent. The use of basic pH and PAA as chelating agent enabled the simultaneous formation of two high purity crystalline phases with nanometric particles, spheroidal morphologies, and controlled stoichiometry. The microwave dilatometer measurement device was developed using a pyrometer sensing system, which enabled temperature measurements to be taken without the need for direct contact with the sample, and with greater accuracy, since it prevents direct interaction between the sensor and the microwave field. The effectiveness of the newly developed microwave dilatometer was tested in a study of the shrinkage behavior of the samples, which was compared with their behavior in a conventional dilatometer. The results revealed that shrinkage of the BaTiO3/CoxNi(1-x)Fe2O4 composites during microwave heating occurred at a lower sintering temperature than in conventional sintering, indicating the existence of “non-thermal” effects caused by the interaction of the sample with the microwaves. The “microwave effect” directly affected the sintering mechanisms, as evidenced by the activation energy in the initial stage of sintering. The development of the microwave heated dilatometer provided groundbreaking results in terms of reliable and reproducible dilatometric data. In addition, the in situ sol-gel synthesis of BaTiO3/CoxNi(1-x)Fe2O4 powders enabled a systematic study of the non-isothermal sintering kinetics of this material, opening up excellent prospects for the application of this technique to other materials. / A presente tese teve como objetivo o desenvolvimento de um dilatômetro aquecido por micro-ondas e o estudo cinético da sinterização por método não isotérmico de materiais cerâmicos multiferroicos. O sistema multiferroico utilizado foi um compósito constituído por duas fases cristalinas, uma piezelétrica de BaTiO3 e a outra magnetostritiva de CoxNi(1-x)Fe2O4 (com x = 0; 0,25; 0,5; 0,75 e 1 e proporções de porcentagem molar: 80/20, 70/30 e 50/50), sintetizadas pelo método sol-gel. Na etapa da síntese, desenvolveu-se um método que permitiu a obtenção das duas fases cristalinas através de uma única solução, denominado síntese in situ, com parâmetros controlados, tais como o pH básico (>9,5) e ácido poliacrílico (PAA) como agente quelante. Esses parâmetros possibilitaram a formação simultânea das duas fases cristalinas com pós de partículas nanométricos (20 nm). Na sinterização, foi utilizado um sistema de sensoriamento pirométrico acoplado ao forno de micro-ondas, permitindo medidas de temperatura sem contato direto com a amostra, e com maior precisão. A retração dos compósitos de BaTiO3/CoxNi(1-x)Fe2O4 durante o aquecimento por micro-ondas revelou redução na temperatura necessária de sinterização na faixa de 80–100 °C, quando comparada com uma sinterização convencional, o que indica a existência de efeitos não térmicos devido à interação da amostra com as micro-ondas. Esses efeitos incidiram diretamente nos mecanismos de sinterização, que foi evidenciado na diminuição da energia de ativação de densificação no estágio inicial da sinterização tanto nos compósitos como nas fases puras do sistema cerâmico estudado, por conseguinte o desenvolvimento do dilatômetro aquecido por micro-ondas permitiu de forma inédita medidas de retração confiáveis e reprodutíveis, e os pós sintetizados aqui permitiram o estudo sistemático da cinética de sinterização pelo método não isotérmico, abrindo excelentes perspectivas para o uso dessa técnica em outros materiais.

Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-05-17T17:35:18Z No. of bitstreams: 1 teseDSFV.pdf: 5669668 bytes, checksum: 165ca1333f2345e5e1406b40a2c0548c (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-22T13:43:35Z (GMT) No. of bitstreams: 1 teseDSFV.pdf: 5669668 bytes, checksum: 165ca1333f2345e5e1406b40a2c0548c (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-22T13:43:44Z (GMT) No. of bitstreams: 1 teseDSFV.pdf: 5669668 bytes, checksum: 165ca1333f2345e5e1406b40a2c0548c (MD5) / Made available in DSpace on 2017-05-22T13:49:08Z (GMT). No. of bitstreams: 1 teseDSFV.pdf: 5669668 bytes, checksum: 165ca1333f2345e5e1406b40a2c0548c (MD5) Previous issue date: 2016-04-08 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / In the case of composites materials, which presents the magnetoelectric coupling, there are so many questions about the influence of the microstructure on the coupled and uncoupled properties. Thereby, this work proposes the study of the grain size influence, of ferroelectric and magnetic phases, on the magnetic, electric and coupled properties in particulate magnetoelectric composites. In order to study the relationship property/microstructure in volumetric magnetoelectric composites, it was necessary to prepare samples with different average grain sizes, ie, the phases having average grain size in the order of micrometers or nanometers. To perform this study it was used as magnetic phase the CoFe2O4 and, as the ferroelectric phase, the [0,675] Pb(Mg1/3Nb2/3)O3 – [0,325] PbTiO3, mixed in molar ratio 20/80 %, using techniques like micro ball milling (to reduce particle size) and high energy ball milling (to mixture the phases) during the powder syntheses, and Spark Plasma Sintering (SPS) to densify the bulk. Due the presence of secondary phases in sintered composites generated during the application of SPS, a processing protocol was created based on a post sintering thermal treatment, in PbO rich atmosphere, which allowed the reduction of secondary phases without, however, changing the average size of grain. These procedures resulted in composite material suitable for the investigations of the electrical, magnetic and magnetoelectric properties, considering the different microstructures obtained. The magnetoelectric composites showed the self-biased effect arising from the intrinsic strain generated in one phase over the other. It was observed the properties dependence, coupled or uncoupled, with average grain size of both phases. Furthermore, the magnetoelectric composites presented the selfbiased effect that appears due to intrinsic strain generated from one phase over the other. Moreover, the evolution of the magnetoelectric coefficient behavior as a function of temperature and applied magnetic field has been more dependent on the variation of the average grain size of the ferroelectric phase than the ferrimagnetic phase, which can be attributed to the largest amount of ferroelectric phase in the structure compound. / No caso de materiais compósitos, que apresentam o acoplamento magnetoelétrico, existem muitas questões sobre influência da microestrutura nas propriedades independentes e acopladas das fases. Dessa forma, este trabalho propõe o estudo da influência do tamanho médio de grão, tanto da fase ferroelétrica quanto da magnética, nas propriedades elétricas, magnéticas e de acoplamento em compósitos magnetoelétricos particulados. Com o objetivo de estudar a relação propriedade / microestrutura em compósitos magnetoelétricos volumétricos, fez-se necessária a preparação de amostras com tamanho médio de grão distintos, ou seja, as fases possuindo tamanho médio de grão na ordem de micrômetros ou nanômetros. Para a realização deste estudo, foi utilizada como fase magnética o CoFe2O4 e, como fase ferroelétrica, o [0,675] Pb(Mg1/3Nb2/3)O3 – [0,325] PbTiO3, misturados na proporção molar 20/80, utilizando técnicas como micromoagem (para redução de partículas) e moagem de altas energias (para a mistura homogênea das fases) durante a síntese dos pós, e a de Spark Plasma Sintering (SPS) para a densificação dos corpos cerâmicos compósitos. Devido à presença de fases secundárias nos compósitos sinterizados, geradas durante a aplicação de SPS, foi criado um protocolo de processamento baseado em tratamento térmico pós-sinterização, com atmosfera rica em PbO, o qual possibilitou a redução das fases secundárias sem, contudo, alterar os tamanhos médios de grão. Tais procedimentos resultaram em material compósito adequado à realização das investigações das propriedades elétricas, magnéticas e magnetoelétricas, considerando as diferentes microestruturas obtidas. Os compósitos magnetoelétricos apresentaram o efeito self-biased, que aparece devido ao strain intrínseco gerado de uma fase sobre a outra. Foi observada a dependência das propriedades, acopladas ou não, com o tamanho médio de grão de ambas as fases. Além disso, a evolução do comportamento do coeficiente magnetoelétrico em função da temperatura e do campo magnético se mostrou mais dependente da variação do tamanho médio de grão da fase ferroelétrica do que da ferrimagnética, fato que pode ser atribuído à maior quantidade de fase ferroelétrica na estrutura do composto.

Fundação de Apoio a Pesquisa e à Inovação Tecnológica do Estado de Sergipe - FAPITEC/SE / The RMnO3 (R=Y,Lu) compounds, members of the family of hexagonal manganites, are materials which exhibit strong magneto-electric coupling characteristic for multiferroic compounds. Despite the numerous studies with objective to reveal the origin of this phenomenon, the mechanism that is causing it is still not fully understood. The question that attracts special attention of scientific community is about the cause of ferroelectric distortion that occurs at certain temperatures in these materials. Although this issue is discussed in many papers, there is still no consensus what mechanism is responsible for it: (1) hybridization between the Mn dz2 orbital and O pz orbital (Mn d0 –ness model), (2) hybridization between the R dz2 orbital and O pz orbital (R d0 –ness model), (3) geometric effects or (4) charge transfer from Mn-O bonds to R-O bonds. Understanding of the mechanism that leads to ferroelectric polarization is necessary to speed application of these materials in ferroelectric memories or spintronics devices. Objective of the present work was to evaluate the first two possible mechanisms that might cause the ferroelectric distortion in RMnO3. Adopted strategy was to investigate what happens with the Mn-O and R-O chemical bonds after the structural phase transition from paraelectric to ferroelectric phase that occurs at high temperature, at which both phases are characterized by paramagnetic order of the Mn magnetic moments. For that purpose, the first-principles calculations based on density functional theory were carried on, with usage of the most modern exchange-correlation potentials. The chemical bonds were evaluated (1) qualitatively, by analysis of density of electronic states (DOS) and maps of electronic density along the bonds, and (2) quantitatively, in terms of topological analysis of Bader. The results revealed that no significant change occurred with Mn-O bonds, while the R-O bonds were affected by phase transition in the sense that R dz2 and O pz orbital exhibited enhanced hybridization in the ferroelectric phase. Therefore, the present study substantiates the R d0 –ness mechanism as the probable cause of ferroelectric distortions in RMnO3 compounds. / The RMnO3 (R=Y,Lu) compounds, members of the family of hexagonal manganites, are materials which exhibit strong magneto-electric coupling characteristic for multiferroic compounds. Despite the numerous studies with objective to reveal the origin of this phenomenon, the mechanism that is causing it is still not fully understood. The question that attracts special attention of scientific community is about the cause of ferroelectric distortion that occurs at certain temperatures in these materials. Although this issue is discussed in many papers, there is still no consensus what mechanism is responsible for it: (1) hybridization between the Mn dz2 orbital and O pz orbital (Mn d0 –ness model), (2) hybridization between the R dz2 orbital and O pz orbital (R d0 –ness model), (3) geometric effects or (4) charge transfer from Mn-O bonds to R-O bonds. Understanding of the mechanism that leads to ferroelectric polarization is necessary to speed application of these materials in ferroelectric memories or spintronics devices. Objective of the present work was to evaluate the first two possible mechanisms that might cause the ferroelectric distortion in RMnO3. Adopted strategy was to investigate what happens with the Mn-O and R-O chemical bonds after the structural phase transition from paraelectric to ferroelectric phase that occurs at high temperature, at which both phases are characterized by paramagnetic order of the Mn magnetic moments. For that purpose, the first-principles calculations based on density functional theory were carried on, with usage of the most modern exchange-correlation potentials. The chemical bonds were evaluated (1) qualitatively, by analysis of density of electronic states (DOS) and maps of electronic density along the bonds, and (2) quantitatively, in terms of topological analysis of Bader. The results revealed that no significant change occurred with Mn-O bonds, while the R-O bonds were affected by phase transition in the sense that R dz2 and O pz orbital exhibited enhanced hybridization in the ferroelectric phase. Therefore, the present study substantiates the R d0 –ness mechanism as the probable cause of ferroelectric distortions in RMnO3 compounds.

Orientadora: Profa. Dra. Marcia Tsuyama Escote / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, Santo André, 2017. / Neste trabalho foram estudados os efeitos da substituição do Bi por um elemento terra-rara (R = Pr, Dy) e da adição de polímeros nas propriedades físicas de compostos de BiFeO3 (BFO) sintetizados pelo método hidrotermal assistido por micro-ondas. Inicialmente, amostras de BFO foram preparadas em diferentes condições de síntese (tempo, temperatura e concentração de KOH) e com este estudo escolheu-se os parâmetros de síntese utilizados neste trabalho para síntese de todas as amostras. As sínteses hidrotermais foram realizadas a 200 °C por 120 min com concentração de KOH de 4 M. Os compostos preparados foram avaliados por meio de medidas de difração de raios X (DRX) e de imagens de microscopia eletrônica de varredura (MEV). Na segunda etapa, o efeito da substituição de bismuto (Bi) por praseodímio (Pr) ou disprósio (Dy) foi investigado por meio de medidas das propriedades físicas caracterizadas por medidas de DRX e análise pelo método de refinamento de Rietveld, imagens de MEV, espec-tros de absorção na região UV-Vis, medidas de constante dielétrica em função da frequência e medidas de magnetização em função do campo magnético aplicado (MxH) e da temperatura (MxT). Por meio das análises de DRX das amostras de Bi1-xRxFeO3, foi observado que com a substituição de Bi por R as amostras tendem a cristalizar-se de forma polimórfica, apresentando duas simetrias: uma romboédrica (R3c) e outra monoclínica (Cc), sendo que a proporção da simetria monoclínica tende a aumentar com o aumento de x. Este polimorfismo, em geral, está associado a presença de Fe2+ na estrutura do Bi1-xRxFeO3, que exerce forte influência nas pro-priedades magnéticas destes compostos. As medidas elétricas mostraram uma melhora dos va-lores da constante dielétrica destas amostras quando comparadas a amostras sem substituição e com resultados listados na literatura para compostos BiFeO3 dopados preparados por outras metodologias. Resultados de absorção na região UV-Vis dos compostos Bi1-xRxFeO3 eviden-ciam uma diminuição do gap de energia de 2,1 eV para a amostra com x = 0 a 1,7eV para com x = 0,3 (Pr). Por fim, no estudo do efeito da adição de polímeros ou surfactantes, foram adici-onados os seguintes materiais: polietilenoglicol (PEG), polivinilpirrolidona (PVP), carboxime-tilcelulose de sódio (NaCMC) ou brometo de cetiltrimetilamonio (CTAB) com o objetivo de verificar a influência de diferentes morfologias nas propriedades físicas do BFO. De fato, o surfactante na síntese do BiFeO3 modificou a morfologia destes compostos, sendo que o resul-tado diferencial foi a obtenção do BiFeO3 na forma de nanobastões utilizando o CTAB. Os demais surfactantes apresentaram formatos similares aqueles já descritos na literatura. As me-didas de UV-Vis revelaram que o valor do gap de energia variou de 1,7 a 2,1 eV com a variação da morfologia do BFO, sendo que este resultado já foi observado em compostos de BFO com diferentes morfologias na literatura. As medidas de constante dielétrica em função da frequên-cia apresentaram um comportamento similar àqueles observados para o BFO preparado sem surfactante. As caracterizações magnéticas revelaram modificações nas curvas de MxT e MxH na região de baixa temperatura (<50 K), o que foi atribuído a presença de fases adicionais nestas amostras. / In this work, the effects of chemical substitution and addition of polymers on the physical prop-erties of BiFeO3 (BFO) compounds synthesized by microwave-assisted hydrothermal method were studied. Firstly, samples of BFO were prepared using different synthesis conditions (time, temperature, KOH concentration), with this study we chose the synthesis parameters used in this work to produce all samples. In order to obtain the parameters that allow the production of compounds with the desired crystalline phase. Hydrothermal syntheses were performed at 200°C during 120 min with KOH concentration of 4M. The compounds were evaluated by X-ray diffraction (XRD) measurements and images of Scanning Electronic Microscopy (SEM). In the second step, the effect of bismuth (Bi) substitution by praseodymium (Pr) or dysprosium (Dy) was investigated by measurements of the physical properties characterized by XRD meas-urements, and analysis by the Rietveld method of refinement, SEM images, absorption spectra in the UV-Vis region, dielectric constant measurements as a function of frequency, and mag-netization measurements as a function of the applied magnetic field (MxH) and temperature (MxT). By means of the XRD analysis of Bi1-xRxFeO3 samples, it was observed that with Bi for R substitution these samples are likely to crystallize in a polymorphic way, which present a rhomboedric (R3c) and a monoclinic (Cc) symmetry. The proportion of monoclinic symmetry tends to increase with the increasing of x. In general, such polymorphism is related to the Fe2+ content in the Bi1-xRxFeO3 structure, which provides a strong influence in the magnetic proper-ties of these compounds. Electrical measurements of the samples show dielectric constants val-ues similar to values observed for undopped and dopped-BiFeO3 prepared by other methodologies. UV-vis absorption results of Bi1-xRxFeO3 compounds revealed a decrease of energy gap from 2.1 eV for sample with x =0 to 1.7 eV for x = 0.3 (Pr). Finally, study of the effect of polymers or surfactants addition, the following materials were added: polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (NaCMC) or cetyltrimethylammonium bromide (CTAB) to verify the influence of different morphologies on the physical properties of BFO. In fact, the morphology of BFO was modified through the sur-factant addition, the most remarkable results is the nanostick shape observed for BFO samples prepared with CTAB. Samples prepared using the other surfactants revealed different mor-phology than those reported in literature. UV-vis measurements revealed energy gap varying from 1.7 to 2.1 eV for BFO samples with different morphologies. Dielectric constant measure-ments as function of frequency presents similar behavior than those observed for BFO without surfactant. Magnetic characterizations revealed changes in low temperature region (<50 K), which is attributed to the presence of additional phases in these samples.