Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas

Detalhes bibliográficos
Autor(a) principal: Diaz, Julio Cesar Camilo Albornoz
Data de Publicação: 2018
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/10555
Resumo: In the current context of research that points to the development of ecologically correct materials highlights the fact that a single family of materials can not be obtained capable of mimicking all the properties of PZTs (systems based in Pb(Zr1-xTix)O3). However, some studies have generated new expectations regarding the possible multifunctionality in materials based on BNT ((Bi0.5Na0.5)TiO3), being that the doping in BNT and some compositions in the MPB of the BNT-xBT system (BT being the acronym for BaTiO3) with rare earths and some transition metals have shown improvements in some properties and the actual coupling between electrical and optical properties, thus leveraging the interest and diversification of the research on BNT based materials. The general objective was the study of BNT and BNT6 ([(Bi0.5Na0.5)0.94Ba0.06]TiO3, in the MPB of BNT-xBT system) doped with different elements, Sm3+ and La3+ acting as donor elements at position A and Nb5+ being a donor element at position B. The samples were produced by the solid state reaction method. A suitable processing route was determined for producing the studied samples of the systems BNT-100xSm, BNT6-100xSm, BNT6-100xLa and BNT6-100xNb, obtaining samples of high quality, high densification and absence of spurious or secondary phases. In all cases, it was carried out a study including structural characterization at room temperature and dielectric and mechanical characterisations (DMA and flexural) as a function of temperature and for several frequencies. Additional characterizations (TSD current, photoluminescence, and hysteresis P-E measurements) were used when required. It was possible to glimpse a general panorama for the BNT, presenting a consistent physical explanation of all the processes observed in the studied temperature range. In this case, mechanisms of mobility of ionic space charge were observed and described, that were not yet reported in the literature. For BNT6, frequency dependent processes were identified at high temperature through dielectric and mechanical measurements, suggesting the mobility of oxygen vacancies. Effects of substitution of Sm3+, La3+ and Nb5+ on BNT and BNT6 were analysed. X-ray diffraction patterns at room temperature reveal the stabilization of the tetragonal phase with addition of each dopant. Dielectric measurements and anelastic spectra show that the increase of the Sm or Nb content induces monotonous displacement to low temperature of the observed processes, in contrast La induces shifts with a non-monotonous tendency. The compositional disorder induced by addition of the dopant element generates, in all cases, changes in both the relative variation of the elastic modulus and the real part of the permittivity, which may indicate the deterioration of piezoelectric properties. As expected, Sm3+ doping generates photoluminescence. The anelastic and photoluminescence spectra allows us to state that the different mechanisms required for charge balancing in Sm3+ doping in BNT and BNT6 are the reduction of a small amount of Sm3+ together with the preferential substitution of Sm3+ in the Bi3+ position. It can be observed that the shift to low temperature of the processes observed in the dielectric and mechanical measurements, induced by the addition of Nb, occurs together with the consolidation of the tetragonal structure, which may allow the stabilization and correlation between polar nano-regions with phase P4bm in lower temperature, thus favouring the relaxor behaviour in the system BNT6-100xNb. The study of the P-E hysteresis loops as a function of temperature in the BNT6-100xNb system showed promising energy storage properties. Finally, a possible sequence in structural evolution with the addition of La can be indirectly indicated, the stabilization of a major tetragonal ferroelectric phase in BNT6-0.7La and BNT6-1La compositions was unexpectedly observed, which could explain the non-monotony observed in the measurements with the increase of La content.
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spelling Diaz, Julio Cesar Camilo AlbornozSilva Junior, Paulo Sergio dahttp://lattes.cnpq.br/7418621942217628http://lattes.cnpq.br/5796421075622433329a6528-ad89-4549-971e-6efc839a26ab2018-10-06T00:00:43Z2018-10-06T00:00:43Z2018-08-30DIAZ, Julio Cesar Camilo Albornoz. Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas. 2018. Tese (Doutorado em Física) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10555.https://repositorio.ufscar.br/handle/ufscar/10555In the current context of research that points to the development of ecologically correct materials highlights the fact that a single family of materials can not be obtained capable of mimicking all the properties of PZTs (systems based in Pb(Zr1-xTix)O3). However, some studies have generated new expectations regarding the possible multifunctionality in materials based on BNT ((Bi0.5Na0.5)TiO3), being that the doping in BNT and some compositions in the MPB of the BNT-xBT system (BT being the acronym for BaTiO3) with rare earths and some transition metals have shown improvements in some properties and the actual coupling between electrical and optical properties, thus leveraging the interest and diversification of the research on BNT based materials. The general objective was the study of BNT and BNT6 ([(Bi0.5Na0.5)0.94Ba0.06]TiO3, in the MPB of BNT-xBT system) doped with different elements, Sm3+ and La3+ acting as donor elements at position A and Nb5+ being a donor element at position B. The samples were produced by the solid state reaction method. A suitable processing route was determined for producing the studied samples of the systems BNT-100xSm, BNT6-100xSm, BNT6-100xLa and BNT6-100xNb, obtaining samples of high quality, high densification and absence of spurious or secondary phases. In all cases, it was carried out a study including structural characterization at room temperature and dielectric and mechanical characterisations (DMA and flexural) as a function of temperature and for several frequencies. Additional characterizations (TSD current, photoluminescence, and hysteresis P-E measurements) were used when required. It was possible to glimpse a general panorama for the BNT, presenting a consistent physical explanation of all the processes observed in the studied temperature range. In this case, mechanisms of mobility of ionic space charge were observed and described, that were not yet reported in the literature. For BNT6, frequency dependent processes were identified at high temperature through dielectric and mechanical measurements, suggesting the mobility of oxygen vacancies. Effects of substitution of Sm3+, La3+ and Nb5+ on BNT and BNT6 were analysed. X-ray diffraction patterns at room temperature reveal the stabilization of the tetragonal phase with addition of each dopant. Dielectric measurements and anelastic spectra show that the increase of the Sm or Nb content induces monotonous displacement to low temperature of the observed processes, in contrast La induces shifts with a non-monotonous tendency. The compositional disorder induced by addition of the dopant element generates, in all cases, changes in both the relative variation of the elastic modulus and the real part of the permittivity, which may indicate the deterioration of piezoelectric properties. As expected, Sm3+ doping generates photoluminescence. The anelastic and photoluminescence spectra allows us to state that the different mechanisms required for charge balancing in Sm3+ doping in BNT and BNT6 are the reduction of a small amount of Sm3+ together with the preferential substitution of Sm3+ in the Bi3+ position. It can be observed that the shift to low temperature of the processes observed in the dielectric and mechanical measurements, induced by the addition of Nb, occurs together with the consolidation of the tetragonal structure, which may allow the stabilization and correlation between polar nano-regions with phase P4bm in lower temperature, thus favouring the relaxor behaviour in the system BNT6-100xNb. The study of the P-E hysteresis loops as a function of temperature in the BNT6-100xNb system showed promising energy storage properties. Finally, a possible sequence in structural evolution with the addition of La can be indirectly indicated, the stabilization of a major tetragonal ferroelectric phase in BNT6-0.7La and BNT6-1La compositions was unexpectedly observed, which could explain the non-monotony observed in the measurements with the increase of La content.No contexto atual das pesquisas que apontam para o desenvolvimento de materiais eletrocerâmicos ecologicamente corretos, destaca-se o fato de não se obter uma única família de materiais capaz de mimetizar todas as propriedades dos PZTs (sistemas baseados em Pb(Zr1-xTix)O3). No entanto, alguns estudos têm gerado novas expectativas quanto à possível multifuncionalidade nos materiais baseados em BNT ((Bi0,5Na0,5)TiO3). A dopagem do BNT e de algumas composições no contorno de fase morfotrópico (CFM) do sistema BNT-xBT (sendo BT sigla para o BaTiO3), com terras raras e alguns metais de transição, tem mostrado melhorias em algumas propriedades e o acoplamento real entre propriedades elétricas e ópticas, alavancando assim o interesse e a diversificação da pesquisa em torno dos materiais baseados em BNT. Com isso, a escolha dos dopantes utilizados neste trabalho esteve relacionada com a busca de multifuncionalidade em materiais baseados em BNT. Como objetivo geral tomou-se o estudo do BNT e do BNT6 ([(Bi0,5Na0,5)0,94Ba0,06]TiO3, no CFM do sistema BNT-xBT) dopados com diferentes elementos, o Sm3+ e La3+ atuando como elementos doadores na posição A e o Nb5+ sendo um elemento doador na posição B da estrutura perovskita. As amostras cerâmicas estudadas foram produzidas a partir do método de reação de estado sólido, sendo que uma rota adequada de processamento para os sistemas BNT-100xSm, BNT6-100xSm, BNT6-100xLa e BNT6-100xNb foi determinada. Por meio desta rota, foram obtidos materiais de alta qualidade, alta densificação e ausência de fases espúrias ou secundárias. Para todos os casos em estudo, realizaram-se as caracterizações estrutural (em temperatura ambiente), e dielétrica e mecânica (DMA e flexural) em função da temperatura e para varias frequências. De acordo com a necessidade, caracterizações adicionais (medidas de corrente de depolarização, de fotoluminescência, e de ciclos de histerese P-E) também foram realizadas. Para o BNT, vislumbrou-se um panorama geral dos mecanismos observados no intervalo de temperatura estudado, sendo proposta uma explicação física consistente para todos eles, com destaque para os processos de mobilidade de carga iônica espacial que ainda não haviam sido reportados na literatura. Já para o BNT6, através de medidas dielétricas e mecânicas foram identificados processos dependentes da frequência, em alta temperatura, relacionados com mobilidade de vacâncias de oxigênio. Além disso, os efeitos da substituição do Sm3+, do La3+ e do Nb5+, no BNT e no BNT6 foram analisados. Os padrões de difração de raios-X, em temperatura ambiente, revelaram a estabilização da fase tetragonal com a adição de cada dopante. As medidas dielétricas e os espectros anelásticos apresentaram deslocamento monótono para baixas temperaturas dos processos observados com o aumento do teor de Sm ou Nb. Em contraste, o La induziu deslocamentos com tendência não monótona. A desordem composicional induzida pela adição do elemento dopante gerou, em todos os casos, mudanças tanto na variação relativa do módulo de elasticidade quanto da parte real da permissividade, indicando uma possível deterioração de propriedades piezoelétricas. Como esperado, a dopagem com Sm3+ gerou fotoluminescência. Uma análise conjunta dos espectros anelásticos e dos de fotoluminescência permitiu dizer que os diferentes mecanismos necessários para o balanço de carga na dopagem com Sm3+ como elemento doador em BNT e BNT6 são a redução de uma pequena quantidade de Sm3+ juntamente com a substituição preferencial de Sm3+ na posição do Bi3+. Notou-se que o deslocamento para baixas temperaturas dos processos observados nas medidas dielétrica e mecânica, induzido pela adição do Nb, acontece juntamente com a consolidação da estrutura tetragonal, podendo permitir a estabilização e correlação entre nano regiões polares com fase P4bm em mais baixa temperatura, favorecendo assim o comportamento relaxor no sistema BNT6-100xNb. O estudo dos ciclos de histerese P-E em função da temperatura no sistema BNT6-100xNb, mostrou propriedades de armazenamento de energia muito promissoras. Finalmente, pôde-se indicar de maneira indireta uma possível sequência na evolução estrutural com a adição de La, observando-se, inesperadamente, a estabilização de uma fase ferroelétrica tetragonal maioritária nas composições BNT6-0,7La e BNT6-1La, o que poderia explicar a não monotonia observada na evolução das propriedades estudadas com o aumento do teor de La.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)CNPq: 142686/2014-0CAPES: 88887.122662/2016-00FAPESP: 2012/08457 − 7FAPESP: 2013/00134 − 7porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Física - PPGFUFSCarMateriais ecologicamente corretosAnelasticidadeDopagem doadoraFotoluminescênciaComportamento relaxorMultifuncionalidadeEco-friendly materialsAnelasticityDonor dopingPhotoluminescenceRelaxor behaviorMultifunctionalityCIENCIAS EXATAS E DA TERRA::FISICAEletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicasinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnline600644c6b32-c667-415b-99ba-565e93506b0binfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARLICENSElicense.txtlicense.txttext/plain; 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dc.title.por.fl_str_mv Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
title Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
spellingShingle Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
Diaz, Julio Cesar Camilo Albornoz
Materiais ecologicamente corretos
Anelasticidade
Dopagem doadora
Fotoluminescência
Comportamento relaxor
Multifuncionalidade
Eco-friendly materials
Anelasticity
Donor doping
Photoluminescence
Relaxor behavior
Multifunctionality
CIENCIAS EXATAS E DA TERRA::FISICA
title_short Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
title_full Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
title_fullStr Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
title_full_unstemmed Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
title_sort Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas
author Diaz, Julio Cesar Camilo Albornoz
author_facet Diaz, Julio Cesar Camilo Albornoz
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/5796421075622433
dc.contributor.author.fl_str_mv Diaz, Julio Cesar Camilo Albornoz
dc.contributor.advisor1.fl_str_mv Silva Junior, Paulo Sergio da
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/7418621942217628
dc.contributor.authorID.fl_str_mv 329a6528-ad89-4549-971e-6efc839a26ab
contributor_str_mv Silva Junior, Paulo Sergio da
dc.subject.por.fl_str_mv Materiais ecologicamente corretos
Anelasticidade
Dopagem doadora
Fotoluminescência
Comportamento relaxor
Multifuncionalidade
topic Materiais ecologicamente corretos
Anelasticidade
Dopagem doadora
Fotoluminescência
Comportamento relaxor
Multifuncionalidade
Eco-friendly materials
Anelasticity
Donor doping
Photoluminescence
Relaxor behavior
Multifunctionality
CIENCIAS EXATAS E DA TERRA::FISICA
dc.subject.eng.fl_str_mv Eco-friendly materials
Anelasticity
Donor doping
Photoluminescence
Relaxor behavior
Multifunctionality
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::FISICA
description In the current context of research that points to the development of ecologically correct materials highlights the fact that a single family of materials can not be obtained capable of mimicking all the properties of PZTs (systems based in Pb(Zr1-xTix)O3). However, some studies have generated new expectations regarding the possible multifunctionality in materials based on BNT ((Bi0.5Na0.5)TiO3), being that the doping in BNT and some compositions in the MPB of the BNT-xBT system (BT being the acronym for BaTiO3) with rare earths and some transition metals have shown improvements in some properties and the actual coupling between electrical and optical properties, thus leveraging the interest and diversification of the research on BNT based materials. The general objective was the study of BNT and BNT6 ([(Bi0.5Na0.5)0.94Ba0.06]TiO3, in the MPB of BNT-xBT system) doped with different elements, Sm3+ and La3+ acting as donor elements at position A and Nb5+ being a donor element at position B. The samples were produced by the solid state reaction method. A suitable processing route was determined for producing the studied samples of the systems BNT-100xSm, BNT6-100xSm, BNT6-100xLa and BNT6-100xNb, obtaining samples of high quality, high densification and absence of spurious or secondary phases. In all cases, it was carried out a study including structural characterization at room temperature and dielectric and mechanical characterisations (DMA and flexural) as a function of temperature and for several frequencies. Additional characterizations (TSD current, photoluminescence, and hysteresis P-E measurements) were used when required. It was possible to glimpse a general panorama for the BNT, presenting a consistent physical explanation of all the processes observed in the studied temperature range. In this case, mechanisms of mobility of ionic space charge were observed and described, that were not yet reported in the literature. For BNT6, frequency dependent processes were identified at high temperature through dielectric and mechanical measurements, suggesting the mobility of oxygen vacancies. Effects of substitution of Sm3+, La3+ and Nb5+ on BNT and BNT6 were analysed. X-ray diffraction patterns at room temperature reveal the stabilization of the tetragonal phase with addition of each dopant. Dielectric measurements and anelastic spectra show that the increase of the Sm or Nb content induces monotonous displacement to low temperature of the observed processes, in contrast La induces shifts with a non-monotonous tendency. The compositional disorder induced by addition of the dopant element generates, in all cases, changes in both the relative variation of the elastic modulus and the real part of the permittivity, which may indicate the deterioration of piezoelectric properties. As expected, Sm3+ doping generates photoluminescence. The anelastic and photoluminescence spectra allows us to state that the different mechanisms required for charge balancing in Sm3+ doping in BNT and BNT6 are the reduction of a small amount of Sm3+ together with the preferential substitution of Sm3+ in the Bi3+ position. It can be observed that the shift to low temperature of the processes observed in the dielectric and mechanical measurements, induced by the addition of Nb, occurs together with the consolidation of the tetragonal structure, which may allow the stabilization and correlation between polar nano-regions with phase P4bm in lower temperature, thus favouring the relaxor behaviour in the system BNT6-100xNb. The study of the P-E hysteresis loops as a function of temperature in the BNT6-100xNb system showed promising energy storage properties. Finally, a possible sequence in structural evolution with the addition of La can be indirectly indicated, the stabilization of a major tetragonal ferroelectric phase in BNT6-0.7La and BNT6-1La compositions was unexpectedly observed, which could explain the non-monotony observed in the measurements with the increase of La content.
publishDate 2018
dc.date.accessioned.fl_str_mv 2018-10-06T00:00:43Z
dc.date.available.fl_str_mv 2018-10-06T00:00:43Z
dc.date.issued.fl_str_mv 2018-08-30
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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format doctoralThesis
status_str publishedVersion
dc.identifier.citation.fl_str_mv DIAZ, Julio Cesar Camilo Albornoz. Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas. 2018. Tese (Doutorado em Física) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10555.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/10555
identifier_str_mv DIAZ, Julio Cesar Camilo Albornoz. Eletrocerâmicas multifuncionais ecologicamente corretas baseadas em (Bi0,5Na0,5)TiO3: a influência da dopagem doadora sobre suas propriedades físicas. 2018. Tese (Doutorado em Física) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10555.
url https://repositorio.ufscar.br/handle/ufscar/10555
dc.language.iso.fl_str_mv por
language por
dc.relation.confidence.fl_str_mv 600
dc.relation.authority.fl_str_mv 644c6b32-c667-415b-99ba-565e93506b0b
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Universidade Federal de São Carlos
Câmpus São Carlos
dc.publisher.program.fl_str_mv Programa de Pós-Graduação em Física - PPGF
dc.publisher.initials.fl_str_mv UFSCar
publisher.none.fl_str_mv Universidade Federal de São Carlos
Câmpus São Carlos
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFSCAR
instname:Universidade Federal de São Carlos (UFSCAR)
instacron:UFSCAR
instname_str Universidade Federal de São Carlos (UFSCAR)
instacron_str UFSCAR
institution UFSCAR
reponame_str Repositório Institucional da UFSCAR
collection Repositório Institucional da UFSCAR
bitstream.url.fl_str_mv https://repositorio.ufscar.br/bitstream/ufscar/10555/3/license.txt
https://repositorio.ufscar.br/bitstream/ufscar/10555/4/DIAZ_Julio%20Cesar_2018.pdf
https://repositorio.ufscar.br/bitstream/ufscar/10555/5/DIAZ_Julio%20Cesar_2018.pdf.txt
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