Preparação e caracterização de blendas de PANI/ABS

Detalhes bibliográficos
Autor(a) principal: Cristovan, Fernando Henrique
Data de Publicação: 2009
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/6116
Resumo: Polyaniline (PANI) chemical synthesis was monitored in situ by means of electrochemical impedance, open circuit potential (Voc) and mass variation. We verify that the final properties of the polymer could be practically defined after inflection point in the potential profile. The impedance data were decisive to understand this behavior, showing only a small change after inflection point. Impedance results and mass variations during the synthesis contributed to understand the induction mechanisms that occur in the initial stages of the polymerization process. Also, it was performed an investigation on the influence of different variables (temperature, monomer:oxidant molar ratio, oxidant, pH value, use of inert salts at high concentrations) in the PANI chemical synthesis process as well as in its physicochemical properties. In this work, it was estimated the characteristic points of PANI through the Voc measurements during the chemical synthesis, based on an experimental design methodology. This methodology allowed an efficient mapping of PANI synthesis process as well as its interactions with each variable previously described. The results indicated that the oxidant employed in the synthesis influences in the final chemical and physical properties of this polymer. The studies performed on the final properties of PANI were the degree of oxidation and electric resistivity. Moreover, the yield the degree of polymerization was also evaluated. The experimental design methodology was also used in order to understand the influence of the preparation conditions on the final properties of the blends in poly(acrylonitrile-butadiene-styrene) (ABS) and polyaniline obtained by the co-dissolving components in a common organic solvent. The variables evaluated were the PANI content in the blend, m-cresol:chloroform rate (solvent ratio), dopant (DBSA or CSA) and acrylonitrile content in the ABS. The results showed that these variables are able to change significantly the flexibility and electric conductivity of the blends. On the other hand, the dopant used mainly influences in the conductivity, suggesting that the DBSA is the better for the development of PANI/ABS blends more conductive. After better prepare conditions of the blends, the percolation threshold was established at around 3 wt% of PANI, forming a flexible blend with conductivity of approximately 3 S.cm-1. The optical properties of the blend films were characterized by UV Vis-NIR. The conduction mechanisms of the blends were investigated using a dc electric conductivity in the range from 80 to 320 K. Using the Mott s theory, it was found that the conductivity in the blends is a threedimensional variable range hopping mechanism. The Mott s temperature values, density of states at the Fermi energy, average hopping distance and barrier height for the blends were calculated and discussed in this work. Also, two possible technological applications were proposed to the PANI/ABS system, including: composite varistors and antistatic or electromagnetic protection of electronic devices. The varistors were prepared with 30% of PANI, which showed a low rupture voltage at around 10 V and a non linearity coefficient of approximately 9,2. On the paint shape and when deposited on cardboard, this material can be employed as protector system of electronic devices. Another important characteristic is the conductivity of this material, which is controlled by the number of paint layers deposited on the cardboard.
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spelling Cristovan, Fernando HenriqueSouza, Ernesto Chaves Pereira dehttp://lattes.cnpq.br/1505400360366643http://lattes.cnpq.br/541065230756235479bed996-3e56-464c-84b0-56b334543a482016-06-02T20:34:11Z2009-09-152016-06-02T20:34:11Z2009-03-16CRISTOVAN, Fernando Henrique. Preparação e caracterização de blendas de PANI/ABS. 2009. 208 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2009.https://repositorio.ufscar.br/handle/ufscar/6116Polyaniline (PANI) chemical synthesis was monitored in situ by means of electrochemical impedance, open circuit potential (Voc) and mass variation. We verify that the final properties of the polymer could be practically defined after inflection point in the potential profile. The impedance data were decisive to understand this behavior, showing only a small change after inflection point. Impedance results and mass variations during the synthesis contributed to understand the induction mechanisms that occur in the initial stages of the polymerization process. Also, it was performed an investigation on the influence of different variables (temperature, monomer:oxidant molar ratio, oxidant, pH value, use of inert salts at high concentrations) in the PANI chemical synthesis process as well as in its physicochemical properties. In this work, it was estimated the characteristic points of PANI through the Voc measurements during the chemical synthesis, based on an experimental design methodology. This methodology allowed an efficient mapping of PANI synthesis process as well as its interactions with each variable previously described. The results indicated that the oxidant employed in the synthesis influences in the final chemical and physical properties of this polymer. The studies performed on the final properties of PANI were the degree of oxidation and electric resistivity. Moreover, the yield the degree of polymerization was also evaluated. The experimental design methodology was also used in order to understand the influence of the preparation conditions on the final properties of the blends in poly(acrylonitrile-butadiene-styrene) (ABS) and polyaniline obtained by the co-dissolving components in a common organic solvent. The variables evaluated were the PANI content in the blend, m-cresol:chloroform rate (solvent ratio), dopant (DBSA or CSA) and acrylonitrile content in the ABS. The results showed that these variables are able to change significantly the flexibility and electric conductivity of the blends. On the other hand, the dopant used mainly influences in the conductivity, suggesting that the DBSA is the better for the development of PANI/ABS blends more conductive. After better prepare conditions of the blends, the percolation threshold was established at around 3 wt% of PANI, forming a flexible blend with conductivity of approximately 3 S.cm-1. The optical properties of the blend films were characterized by UV Vis-NIR. The conduction mechanisms of the blends were investigated using a dc electric conductivity in the range from 80 to 320 K. Using the Mott s theory, it was found that the conductivity in the blends is a threedimensional variable range hopping mechanism. The Mott s temperature values, density of states at the Fermi energy, average hopping distance and barrier height for the blends were calculated and discussed in this work. Also, two possible technological applications were proposed to the PANI/ABS system, including: composite varistors and antistatic or electromagnetic protection of electronic devices. The varistors were prepared with 30% of PANI, which showed a low rupture voltage at around 10 V and a non linearity coefficient of approximately 9,2. On the paint shape and when deposited on cardboard, this material can be employed as protector system of electronic devices. Another important characteristic is the conductivity of this material, which is controlled by the number of paint layers deposited on the cardboard.A síntese química da polianilina (PANI) foi monitorada in situ por meio das técnicas de impedância eletroquímica, potencial de circuito aberto (Voc) e variação de massa. Foi detectado que as propriedades finais do polímero são definidas logo após o do máximo da curva de Voc e antes do platô final. Os dados de impedância foram decisivos para o entendimento desta característica, apresentando somente uma pequena variação depois do máximo de Voc. Os dados de impedância e variação de massa durante a síntese também contribuíram para a compreensão dos processos que ocorrem durante o período de indução da síntese da PANI. Em seguida, foi feita uma investigação da influência das variáveis de síntese tais como: temperatura, razão monômero:oxidante, tipo de agente oxidante, pH e o uso de LiCl na síntese química da PANI, bem como nas propriedades físico-químicas do polímero obtido. Para avaliar as influências destas variáveis na síntese da PANI foi utilizada a técnica de Voc e para avaliar pontos característicos foi empregada a metodologia de planejamento fatorial. Esta técnica permitiu estabelecer um rápido e compreensivo mapeamento do processo de síntese da PANI, e a importância de cada variável bem como suas interações. A variável que mais influenciou em todos os estágios do processo foi tipo de agente oxidante. Depois, foram estudas as propriedades finais do polímero tais como grau de oxidação e resistividade elétricas. O rendimento de polimerização também foi avaliado, todas estas respostas também foram avaliadas utilizando um planejamento fatorial que, por sua vez, mostrou que a variável que mais influencia nas propriedades finais do polímero é o tipo de agente oxidante. Em um segundo momento, foram estudadas as influências das condições de preparo das blendas de PANI com o poli(acrilonitrila-butadieno-estireno) (ABS) preparadas pelo método de codissolução de ambos os componentes em um solvente comum através de um planejamento fatorial. As variáveis estudadas foram: quantidade de PANI nas blendas, razão m-cresol;clorofórmio, tipo de dopante (DBSA ou CSA), concentração de dopante e teor de acrilonitrila no ABS. As respostas monitoradas foram a flexibilidade e a condutividade elétrica das blendas obtidas. Os resultados mostraram que a quantidade de PANI nas blendas e o teor de acrilonitrila no ABS foram as variáveis que mais influenciaram em ambas as respostas. O tipo de dopante mostrou somente influência na resposta condutividade, onde o DBSA se mostrou o melhor dopante para se obter blendas de PANI/ABS mais condutoras. Depois das melhores condições de preparo estabelecidas, o limite de percolação do sistema foi determinado, onde o valor estimado foi de 3% em massa de PANI na blenda, apresentando uma condutividade de 3 S.cm-1. Para se compreender o mecanismo de condutividade das amostras, foi feito um estudo da condutividade DC das blendas no intervalo de temperatura de 80-320 K. Os dados foram tratados aplicando a teoria de Mott, onde o mecanismo de condutividade obedece ao modelo de Saltos de Tamanhos Variáveis em três dimensões, e os parâmetros de Mott foram estimados. Duas aplicações para o sistema PANI/ABS foram propostas. Onde preparados compósitos varistores de PANI/ABS, sendo que o material preparado com 30% de PANI apresentou uma tensão de ruptura de aproximadamente 10 V e um coeficiente de não linearidade de 9,2, com estes valores o compósito pode ser utilizado na proteção de equipamentos eletrônicos. Na outra aplicação proposta neste trabalho, foi preparada uma tinta de PANI-DBSA/ABS, que foi depositada sobre papelão, a resistência elétrica do material pode ser controlada pelo número de camadas de tinta. Deste modo o material pode ser utilizado na proteção antiestática e eletromagnética também de componentes eletrônico.Financiadora de Estudos e Projetosapplication/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarBRPolímeros condutoresPolianilinaABSBlendas poliméricasSíntese químicaVaristoresCIENCIAS EXATAS E DA TERRA::QUIMICAPreparação e caracterização de blendas de PANI/ABSinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis-1-116229a12-027e-4f0e-96b0-518d49092280info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL2347.pdfapplication/pdf3292291https://repositorio.ufscar.br/bitstream/ufscar/6116/1/2347.pdfdc54e6d366b7627fc352872ae369e01fMD51THUMBNAIL2347.pdf.jpg2347.pdf.jpgIM Thumbnailimage/jpeg6475https://repositorio.ufscar.br/bitstream/ufscar/6116/2/2347.pdf.jpg3b848ff98eb8107ab1caea3945bc50bfMD52ufscar/61162023-09-18 18:31:41.0oai:repositorio.ufscar.br:ufscar/6116Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:41Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Preparação e caracterização de blendas de PANI/ABS
title Preparação e caracterização de blendas de PANI/ABS
spellingShingle Preparação e caracterização de blendas de PANI/ABS
Cristovan, Fernando Henrique
Polímeros condutores
Polianilina
ABS
Blendas poliméricas
Síntese química
Varistores
CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Preparação e caracterização de blendas de PANI/ABS
title_full Preparação e caracterização de blendas de PANI/ABS
title_fullStr Preparação e caracterização de blendas de PANI/ABS
title_full_unstemmed Preparação e caracterização de blendas de PANI/ABS
title_sort Preparação e caracterização de blendas de PANI/ABS
author Cristovan, Fernando Henrique
author_facet Cristovan, Fernando Henrique
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/5410652307562354
dc.contributor.author.fl_str_mv Cristovan, Fernando Henrique
dc.contributor.advisor1.fl_str_mv Souza, Ernesto Chaves Pereira de
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/1505400360366643
dc.contributor.authorID.fl_str_mv 79bed996-3e56-464c-84b0-56b334543a48
contributor_str_mv Souza, Ernesto Chaves Pereira de
dc.subject.por.fl_str_mv Polímeros condutores
Polianilina
ABS
Blendas poliméricas
Síntese química
Varistores
topic Polímeros condutores
Polianilina
ABS
Blendas poliméricas
Síntese química
Varistores
CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA
description Polyaniline (PANI) chemical synthesis was monitored in situ by means of electrochemical impedance, open circuit potential (Voc) and mass variation. We verify that the final properties of the polymer could be practically defined after inflection point in the potential profile. The impedance data were decisive to understand this behavior, showing only a small change after inflection point. Impedance results and mass variations during the synthesis contributed to understand the induction mechanisms that occur in the initial stages of the polymerization process. Also, it was performed an investigation on the influence of different variables (temperature, monomer:oxidant molar ratio, oxidant, pH value, use of inert salts at high concentrations) in the PANI chemical synthesis process as well as in its physicochemical properties. In this work, it was estimated the characteristic points of PANI through the Voc measurements during the chemical synthesis, based on an experimental design methodology. This methodology allowed an efficient mapping of PANI synthesis process as well as its interactions with each variable previously described. The results indicated that the oxidant employed in the synthesis influences in the final chemical and physical properties of this polymer. The studies performed on the final properties of PANI were the degree of oxidation and electric resistivity. Moreover, the yield the degree of polymerization was also evaluated. The experimental design methodology was also used in order to understand the influence of the preparation conditions on the final properties of the blends in poly(acrylonitrile-butadiene-styrene) (ABS) and polyaniline obtained by the co-dissolving components in a common organic solvent. The variables evaluated were the PANI content in the blend, m-cresol:chloroform rate (solvent ratio), dopant (DBSA or CSA) and acrylonitrile content in the ABS. The results showed that these variables are able to change significantly the flexibility and electric conductivity of the blends. On the other hand, the dopant used mainly influences in the conductivity, suggesting that the DBSA is the better for the development of PANI/ABS blends more conductive. After better prepare conditions of the blends, the percolation threshold was established at around 3 wt% of PANI, forming a flexible blend with conductivity of approximately 3 S.cm-1. The optical properties of the blend films were characterized by UV Vis-NIR. The conduction mechanisms of the blends were investigated using a dc electric conductivity in the range from 80 to 320 K. Using the Mott s theory, it was found that the conductivity in the blends is a threedimensional variable range hopping mechanism. The Mott s temperature values, density of states at the Fermi energy, average hopping distance and barrier height for the blends were calculated and discussed in this work. Also, two possible technological applications were proposed to the PANI/ABS system, including: composite varistors and antistatic or electromagnetic protection of electronic devices. The varistors were prepared with 30% of PANI, which showed a low rupture voltage at around 10 V and a non linearity coefficient of approximately 9,2. On the paint shape and when deposited on cardboard, this material can be employed as protector system of electronic devices. Another important characteristic is the conductivity of this material, which is controlled by the number of paint layers deposited on the cardboard.
publishDate 2009
dc.date.available.fl_str_mv 2009-09-15
2016-06-02T20:34:11Z
dc.date.issued.fl_str_mv 2009-03-16
dc.date.accessioned.fl_str_mv 2016-06-02T20:34:11Z
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dc.identifier.citation.fl_str_mv CRISTOVAN, Fernando Henrique. Preparação e caracterização de blendas de PANI/ABS. 2009. 208 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2009.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/6116
identifier_str_mv CRISTOVAN, Fernando Henrique. Preparação e caracterização de blendas de PANI/ABS. 2009. 208 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2009.
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