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Master's Dissertation
DOI
https://doi.org/10.11606/D.88.2010.tde-03082010-155456
Document
Author
Full name
Rafaela Cristina Sanfelice
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2010
Supervisor
Committee
Oliveira Junior, Osvaldo Novais de (President)
Burtoloso, Antonio Carlos Bender
Curvelo, Antonio Aprigio da Silva
Title in Portuguese
Síntese e fabricação de filmes finos de copolímeros contendo azobenzenos para superfícies hidrofóbicas
Keywords in Portuguese
Azopolímeros
Filmes de Langmuir-Blodgett (LB)
Superficies superhidrofóbicas.
Abstract in Portuguese
A funcionalização de materiais poliméricos para a produção de superfícies superhidrofóbicas é importante para uma série de aplicações, principalmente as associadas com superfícies autolimpantes e anti-aderentes. Uma abordagem para obter superhidrofobicidade é combinar polímeros hidrofóbicos com outros materiais passíveis de ser microestruturados. Neste estudo, copolímeros hidrofóbicos foram sintetizados através de polimerização radicalar convencional usando os monômeros 2,2,3,3,4,4,5,5 octafluorpentil metacrilato (OFPMA) ou 2,2,2 trifluoretil metacrilato (TFEMA) copolimerizado com o azo monômero 4-[N-etil-N-(2-metacriloxi-etil)]amino-4-nitro-azobenzeno (DR13-MA) em proporções distintas. A polimerização foi bem sucedida, apresentando massas molares acima de 10.000 g / mol, com uma polidispersividade relativamente baixa. Os copolímeros e homopolímeros, derivados de OFPMA e TFEMA - usados para comparação tiveram sua estrutura confirmada através de espectroscopia no infravermelho (FTIR) e ressonância magnética nuclear (RMN). A proporção de azo monômero incorporada foi estimada por RMN e espectroscopia no UV-vis e foram condizentes com a relação utilizada, ou seja, 10, 20 e 30% em massa. Foram formados filmes de Langmuir estáveis dos copolímeros na interface ar / água, cuja isoterma de pressão superficial apresentou transição de fase provavelmente atribuída a um rearranjo molecular. O potencial de superfície dos filmes dos copolímeros foi negativo, o que indica que os átomos de flúor estavam direcionados para o ar. Esta organização molecular foi mantida após a transferência de filmes sobre substratos sólidos na forma de filmes Langmuir-Blodgett (LB), formando superfícies hidrofóbicas com ângulos de contato próximos de 90 º para todos os copolímeros, independentemente do número de camadas depositadas. A natureza organizada dos filmes LB não contribuiu para a hidrofobicidade, pois o ângulo de contacto é semelhante ao obtido com filmes cast. Grades de relevo foram inscritas nos filmes cast, mas o ângulo de contato não foi afetado significativamente. Portanto, uma otimização na inscrição de nanoestruturas será necessária para se alcançar a superhidrofobicidade.
Title in English
Synthesis and fabrication of thin films of copolymer contains azobenzene for hydrophobic surface
Keywords in English
Azopolymers
Hydrophobic surface
Langmuir-Blodgett(LB) films
Abstract in English
The functionalization of polymer materials to produce superhydrophobic surfaces is an important goal for a number of applications, especially those associated with self-cleaning and anti-adherent surfaces. A possible approach to achieve superhydrophobicity is to combine hydrophobic polymers with other materials amenable to be microstructured. In this study, hydrophobic copolymers were synthesized through conventional radicalar polymerization using the monomers 2,2,3,3,4,4,5,5 octafluorpenthyl methacrylate (OFPMA) or 2,2,2 trifluorethyl methacrylate (TFEMA) copolymerized with the azomonomer 4-[N-ethyl-N-(2methacryloxy-ethyl)]amine-4-nitrobenzene methacrylate (DR-13MA) in distinct proportions. Polymerization was successful leading to molar masses above 10,000 g/mol, with a relatively low polydispersity. The copolymers and the homopolymers from OFPMA and TFEMA used for comparison had their structure confirmed with Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) measurements. The proportion of azomonomer incorporated estimated via NMR was consistent with that determined with UV-vis. spectroscopy for the relative concentrations used, namely 10, 20 and 30% in mass. The copolymers formed stable Langmuir films at the air/water interface, whose surface pressure isotherms featured a phase transition probably associated with molecular rearrangement. The surface potential of the condensed copolymer Langmuir films was negative, which indicates that the fluorine atoms were directed toward the air. This molecular organization was maintained upon film transfer onto solid substrates in the form of Langmuir-Blodgett (LB) films, leading to hydrophobic surfaces with contact angles close to 90º for both copolymers, which did not depend on the number of layers deposited. The organized nature of the LB films did not contribute to the hydrophobicity, however, as similar contact angles were measured for the cast films made with the copolymers. Surface-relief gratings could be inscribed on the cast films, but the contact angle was not affected significantly. Therefore, an optimization in the inscription of such nanostructures will be required for achieving superhydrophobicity.
 
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Publishing Date
2010-09-01
 
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