Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer

Autores
Dos Santos Claro, Paula Cecilia; Coustet, Marcos Eduardo; Diaz, Carolina; Maza, Eliana María; Cortizo, Maria Susana; Requejo, Felix Gregorio; Pietrasanta, Lia; Ceolin, Marcelo Raul; Azzaroni, Omar
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The aggregation behavior and morphological characteristics of amphiphilic block copolymer polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) at the air-water interface were investigated through surface pressure measurements, atomic force microscopy (AFM) imaging, electrochemical measurements and X-ray reflectivity. Ionization of PDMAEMA blocks significantly affects the isotherms of the surface films at the air-water interface and, consequently, originates different morphologies of Langmuir-Blodgett films obtained under different experimental conditions. At low pH the PDMAEMA blocks are fully protonated and therefore dissolved in the aqueous subphase. Under this condition, the effects of the solubility and electrostatic repulsion of submerged PDMAEMA chains prevail over hydrophobic interactions and the Langmuir film exhibits low surface pressure at large molecular area values. Upon compression, the isotherm shows a pseudoplateau corresponding to the "pancake-to-brush" transition followed by an increase in surface pressure at smaller MMA values. These results were correlated with the morphological features of Langmuir-Blodgett films transferred onto silicon substrates, where dispersed dot-like domains that gradually transformed into an island-like structure, followed by further percolation into a continent-like morphology, were observed through AFM imaging. On the other hand, at high pH the isotherm is more expanded and the film exhibits higher surface pressure at relatively high MMA values due to the strong repulsive interactions between interface-confined hydrophobic aggregates constituted of PBzMA cores and neutral PDMAEMA shells. In this case, the AFM results show a structural evolution from circular and quasi-hexagonally packed micelles, followed by a worm-like structure that collapses into a homogeneous film. Furthermore, the study of the copolymer behavior under different subphase ionic strength conditions confirmed the critical role of electrostatic interactions in determining the characteristics of the isotherm. We could also demonstrate that our system follows accurately the scaling relationship for surface pressure of annealed brushes. Complementary studies performed by means of X-ray reflectivity were carried out to probe the buried interfacial structure of the diblock copolymer film, corroborating that the organization of both blocks on the silicon substrates is strongly dependent on the pH conditions of the subphase during the LB transfer.
Fil: Dos Santos Claro, Paula Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Coustet, Marcos Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Diaz, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Microscopías Avanzadas; Argentina
Fil: Maza, Eliana María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Cortizo, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Pietrasanta, Lia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Microscopías Avanzadas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ceolin, Marcelo Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Langmuir-Blodgett Technique
Block Copolymers
Supramolecular Assembly
Polymer Interfaces
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/4785
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/4785
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transferDos Santos Claro, Paula CeciliaCoustet, Marcos EduardoDiaz, CarolinaMaza, Eliana MaríaCortizo, Maria SusanaRequejo, Felix GregorioPietrasanta, LiaCeolin, Marcelo RaulAzzaroni, OmarLangmuir-Blodgett TechniqueBlock CopolymersSupramolecular AssemblyPolymer Interfaceshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The aggregation behavior and morphological characteristics of amphiphilic block copolymer polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) at the air-water interface were investigated through surface pressure measurements, atomic force microscopy (AFM) imaging, electrochemical measurements and X-ray reflectivity. Ionization of PDMAEMA blocks significantly affects the isotherms of the surface films at the air-water interface and, consequently, originates different morphologies of Langmuir-Blodgett films obtained under different experimental conditions. At low pH the PDMAEMA blocks are fully protonated and therefore dissolved in the aqueous subphase. Under this condition, the effects of the solubility and electrostatic repulsion of submerged PDMAEMA chains prevail over hydrophobic interactions and the Langmuir film exhibits low surface pressure at large molecular area values. Upon compression, the isotherm shows a pseudoplateau corresponding to the "pancake-to-brush" transition followed by an increase in surface pressure at smaller MMA values. These results were correlated with the morphological features of Langmuir-Blodgett films transferred onto silicon substrates, where dispersed dot-like domains that gradually transformed into an island-like structure, followed by further percolation into a continent-like morphology, were observed through AFM imaging. On the other hand, at high pH the isotherm is more expanded and the film exhibits higher surface pressure at relatively high MMA values due to the strong repulsive interactions between interface-confined hydrophobic aggregates constituted of PBzMA cores and neutral PDMAEMA shells. In this case, the AFM results show a structural evolution from circular and quasi-hexagonally packed micelles, followed by a worm-like structure that collapses into a homogeneous film. Furthermore, the study of the copolymer behavior under different subphase ionic strength conditions confirmed the critical role of electrostatic interactions in determining the characteristics of the isotherm. We could also demonstrate that our system follows accurately the scaling relationship for surface pressure of annealed brushes. Complementary studies performed by means of X-ray reflectivity were carried out to probe the buried interfacial structure of the diblock copolymer film, corroborating that the organization of both blocks on the silicon substrates is strongly dependent on the pH conditions of the subphase during the LB transfer.Fil: Dos Santos Claro, Paula Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Coustet, Marcos Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Diaz, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Microscopías Avanzadas; ArgentinaFil: Maza, Eliana María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Cortizo, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Pietrasanta, Lia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Microscopías Avanzadas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ceolin, Marcelo Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaRoyal Society of Chemistry2013-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/zipapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/4785Dos Santos Claro, Paula Cecilia; Coustet, Marcos Eduardo; Diaz, Carolina; Maza, Eliana María; Cortizo, Maria Susana; et al.; Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer; Royal Society of Chemistry; Soft Matter; 9; 45; 10-2013; 10899-109121744-683Xenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlepdf/2013/sm/c3sm52336einfo:eu-repo/semantics/altIdentifier/doi/10.1039/c3sm52336einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:07:15Zoai:ri.conicet.gov.ar:11336/4785instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:07:16.017CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
title Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
spellingShingle Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
Dos Santos Claro, Paula Cecilia
Langmuir-Blodgett Technique
Block Copolymers
Supramolecular Assembly
Polymer Interfaces
title_short Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
title_full Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
title_fullStr Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
title_full_unstemmed Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
title_sort Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer
dc.creator.none.fl_str_mv Dos Santos Claro, Paula Cecilia
Coustet, Marcos Eduardo
Diaz, Carolina
Maza, Eliana María
Cortizo, Maria Susana
Requejo, Felix Gregorio
Pietrasanta, Lia
Ceolin, Marcelo Raul
Azzaroni, Omar
author Dos Santos Claro, Paula Cecilia
author_facet Dos Santos Claro, Paula Cecilia
Coustet, Marcos Eduardo
Diaz, Carolina
Maza, Eliana María
Cortizo, Maria Susana
Requejo, Felix Gregorio
Pietrasanta, Lia
Ceolin, Marcelo Raul
Azzaroni, Omar
author_role author
author2 Coustet, Marcos Eduardo
Diaz, Carolina
Maza, Eliana María
Cortizo, Maria Susana
Requejo, Felix Gregorio
Pietrasanta, Lia
Ceolin, Marcelo Raul
Azzaroni, Omar
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Langmuir-Blodgett Technique
Block Copolymers
Supramolecular Assembly
Polymer Interfaces
topic Langmuir-Blodgett Technique
Block Copolymers
Supramolecular Assembly
Polymer Interfaces
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The aggregation behavior and morphological characteristics of amphiphilic block copolymer polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) at the air-water interface were investigated through surface pressure measurements, atomic force microscopy (AFM) imaging, electrochemical measurements and X-ray reflectivity. Ionization of PDMAEMA blocks significantly affects the isotherms of the surface films at the air-water interface and, consequently, originates different morphologies of Langmuir-Blodgett films obtained under different experimental conditions. At low pH the PDMAEMA blocks are fully protonated and therefore dissolved in the aqueous subphase. Under this condition, the effects of the solubility and electrostatic repulsion of submerged PDMAEMA chains prevail over hydrophobic interactions and the Langmuir film exhibits low surface pressure at large molecular area values. Upon compression, the isotherm shows a pseudoplateau corresponding to the "pancake-to-brush" transition followed by an increase in surface pressure at smaller MMA values. These results were correlated with the morphological features of Langmuir-Blodgett films transferred onto silicon substrates, where dispersed dot-like domains that gradually transformed into an island-like structure, followed by further percolation into a continent-like morphology, were observed through AFM imaging. On the other hand, at high pH the isotherm is more expanded and the film exhibits higher surface pressure at relatively high MMA values due to the strong repulsive interactions between interface-confined hydrophobic aggregates constituted of PBzMA cores and neutral PDMAEMA shells. In this case, the AFM results show a structural evolution from circular and quasi-hexagonally packed micelles, followed by a worm-like structure that collapses into a homogeneous film. Furthermore, the study of the copolymer behavior under different subphase ionic strength conditions confirmed the critical role of electrostatic interactions in determining the characteristics of the isotherm. We could also demonstrate that our system follows accurately the scaling relationship for surface pressure of annealed brushes. Complementary studies performed by means of X-ray reflectivity were carried out to probe the buried interfacial structure of the diblock copolymer film, corroborating that the organization of both blocks on the silicon substrates is strongly dependent on the pH conditions of the subphase during the LB transfer.
Fil: Dos Santos Claro, Paula Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Coustet, Marcos Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Diaz, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Microscopías Avanzadas; Argentina
Fil: Maza, Eliana María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Cortizo, Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Requejo, Felix Gregorio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Pietrasanta, Lia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Microscopías Avanzadas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ceolin, Marcelo Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description The aggregation behavior and morphological characteristics of amphiphilic block copolymer polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) at the air-water interface were investigated through surface pressure measurements, atomic force microscopy (AFM) imaging, electrochemical measurements and X-ray reflectivity. Ionization of PDMAEMA blocks significantly affects the isotherms of the surface films at the air-water interface and, consequently, originates different morphologies of Langmuir-Blodgett films obtained under different experimental conditions. At low pH the PDMAEMA blocks are fully protonated and therefore dissolved in the aqueous subphase. Under this condition, the effects of the solubility and electrostatic repulsion of submerged PDMAEMA chains prevail over hydrophobic interactions and the Langmuir film exhibits low surface pressure at large molecular area values. Upon compression, the isotherm shows a pseudoplateau corresponding to the "pancake-to-brush" transition followed by an increase in surface pressure at smaller MMA values. These results were correlated with the morphological features of Langmuir-Blodgett films transferred onto silicon substrates, where dispersed dot-like domains that gradually transformed into an island-like structure, followed by further percolation into a continent-like morphology, were observed through AFM imaging. On the other hand, at high pH the isotherm is more expanded and the film exhibits higher surface pressure at relatively high MMA values due to the strong repulsive interactions between interface-confined hydrophobic aggregates constituted of PBzMA cores and neutral PDMAEMA shells. In this case, the AFM results show a structural evolution from circular and quasi-hexagonally packed micelles, followed by a worm-like structure that collapses into a homogeneous film. Furthermore, the study of the copolymer behavior under different subphase ionic strength conditions confirmed the critical role of electrostatic interactions in determining the characteristics of the isotherm. We could also demonstrate that our system follows accurately the scaling relationship for surface pressure of annealed brushes. Complementary studies performed by means of X-ray reflectivity were carried out to probe the buried interfacial structure of the diblock copolymer film, corroborating that the organization of both blocks on the silicon substrates is strongly dependent on the pH conditions of the subphase during the LB transfer.
publishDate 2013
dc.date.none.fl_str_mv 2013-10
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/4785
Dos Santos Claro, Paula Cecilia; Coustet, Marcos Eduardo; Diaz, Carolina; Maza, Eliana María; Cortizo, Maria Susana; et al.; Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer; Royal Society of Chemistry; Soft Matter; 9; 45; 10-2013; 10899-10912
1744-683X
url http://hdl.handle.net/11336/4785
identifier_str_mv Dos Santos Claro, Paula Cecilia; Coustet, Marcos Eduardo; Diaz, Carolina; Maza, Eliana María; Cortizo, Maria Susana; et al.; Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air/water interface and deposition on solid substrates via Langmuir-Blodgett transfer; Royal Society of Chemistry; Soft Matter; 9; 45; 10-2013; 10899-10912
1744-683X
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlepdf/2013/sm/c3sm52336e
info:eu-repo/semantics/altIdentifier/doi/10.1039/c3sm52336e
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
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application/pdf
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dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.13397

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