Supercritical carbon dioxide swelling of fluorinated and hydrocarbon surfactant templates in mesoporous silica thin films

Kaustav Ghosh; Hans Joachim Lehmler; Stephen E. Rankin; Barbara L. Knutson

doi:10.1016/j.jcis.2011.10.051

Supercritical carbon dioxide swelling of fluorinated and hydrocarbon surfactant templates in mesoporous silica thin films

Kaustav Ghosh, Hans Joachim Lehmler, Stephen E. Rankin, Barbara L. Knutson

Chemical and Materials Engineering

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

The penetration of compressed CO ₂ in hydrocarbon and fluorocarbon regions of concentrated surfactant mesophases are interpreted from differences in the CO ₂-processed pore expansion of mesoporous silica thin films templated by three surfactants containing varying degrees of hydrocarbon and fluorocarbon functionality. Ordered silica thin films are synthesized for the first time using the 16-carbon (C ₁₆) partly fluorinated surfactant, 11,11,12,12,13,13,14,14,15,15,16,16,16-tridecafluorocetyl pyridinium bromide (HFCPB), as a templating agent. Silica films templated with surfactants containing a 8-carbon (C ₈) fluorocarbon tail (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl pyridinium chloride (HFOPC)) and a 16-carbon (C ₁₆) hydrocarbon tail (cetyl pyridinium bromide (CPB)) and HFCPB (C ₁₆) are processed in compressed CO ₂ (69-172bar, 25°C and 45°C) during synthesis. CO ₂ processing results in significant pore expansion for films templated with both fluorinated surfactants, while pore expansion is negligible for the hydrocarbon templated material suggesting that preferential CO ₂ penetration occurs in the 'CO ₂-philic' fluorocarbon segments of the surfactant template. The effect of substrate surface energy on the final uniformity of the dip-coated films is studied by varying the substrate from unmodified glass to a fluorocarbon-capped substrate. The ability to create dip-coated thin films on low surface energy substrates through favorable interaction of surfactant template tail with the substrate surface functional groups is demonstrated.

Original language	English
Pages (from-to)	183-192
Number of pages	10
Journal	Journal of Colloid and Interface Science
Volume	367
Issue number	1
DOIs	https://doi.org/10.1016/j.jcis.2011.10.051
State	Published - Feb 1 2012

Bibliographical note

Funding Information:
The authors would like to acknowledge National Science Foundation NIRT Grant # DMR-0210517 and Kentucky Science and Engineering Foundation Grant KSEF-159-RDE-001 for funding this research project. We would also like to thank Dr. Sandhya Vyas for the synthesis of the fluorinated surfactants, Dr. Tonglei Li and Clare Aubrey Medendrop for assistance with the contact angle measurements and Dr. Todd Hastings for help with the profilometer.

Keywords

'CO -philic' surfactants
Carbon-dioxide penetration
Dip-coated films
Surfactant solution spreading
Surfactant templated silica

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Biomaterials
Surfaces, Coatings and Films
Colloid and Surface Chemistry

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10.1016/j.jcis.2011.10.051

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title = "Supercritical carbon dioxide swelling of fluorinated and hydrocarbon surfactant templates in mesoporous silica thin films",

abstract = "The penetration of compressed CO 2 in hydrocarbon and fluorocarbon regions of concentrated surfactant mesophases are interpreted from differences in the CO 2-processed pore expansion of mesoporous silica thin films templated by three surfactants containing varying degrees of hydrocarbon and fluorocarbon functionality. Ordered silica thin films are synthesized for the first time using the 16-carbon (C 16) partly fluorinated surfactant, 11,11,12,12,13,13,14,14,15,15,16,16,16-tridecafluorocetyl pyridinium bromide (HFCPB), as a templating agent. Silica films templated with surfactants containing a 8-carbon (C 8) fluorocarbon tail (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl pyridinium chloride (HFOPC)) and a 16-carbon (C 16) hydrocarbon tail (cetyl pyridinium bromide (CPB)) and HFCPB (C 16) are processed in compressed CO 2 (69-172bar, 25°C and 45°C) during synthesis. CO 2 processing results in significant pore expansion for films templated with both fluorinated surfactants, while pore expansion is negligible for the hydrocarbon templated material suggesting that preferential CO 2 penetration occurs in the 'CO 2-philic' fluorocarbon segments of the surfactant template. The effect of substrate surface energy on the final uniformity of the dip-coated films is studied by varying the substrate from unmodified glass to a fluorocarbon-capped substrate. The ability to create dip-coated thin films on low surface energy substrates through favorable interaction of surfactant template tail with the substrate surface functional groups is demonstrated.",

keywords = "'CO -philic' surfactants, Carbon-dioxide penetration, Dip-coated films, Surfactant solution spreading, Surfactant templated silica",

author = "Kaustav Ghosh and Lehmler, {Hans Joachim} and Rankin, {Stephen E.} and Knutson, {Barbara L.}",

note = "Funding Information: The authors would like to acknowledge National Science Foundation NIRT Grant # DMR-0210517 and Kentucky Science and Engineering Foundation Grant KSEF-159-RDE-001 for funding this research project. We would also like to thank Dr. Sandhya Vyas for the synthesis of the fluorinated surfactants, Dr. Tonglei Li and Clare Aubrey Medendrop for assistance with the contact angle measurements and Dr. Todd Hastings for help with the profilometer. ",

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AU - Rankin, Stephen E.

AU - Knutson, Barbara L.

N1 - Funding Information: The authors would like to acknowledge National Science Foundation NIRT Grant # DMR-0210517 and Kentucky Science and Engineering Foundation Grant KSEF-159-RDE-001 for funding this research project. We would also like to thank Dr. Sandhya Vyas for the synthesis of the fluorinated surfactants, Dr. Tonglei Li and Clare Aubrey Medendrop for assistance with the contact angle measurements and Dr. Todd Hastings for help with the profilometer.

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N2 - The penetration of compressed CO 2 in hydrocarbon and fluorocarbon regions of concentrated surfactant mesophases are interpreted from differences in the CO 2-processed pore expansion of mesoporous silica thin films templated by three surfactants containing varying degrees of hydrocarbon and fluorocarbon functionality. Ordered silica thin films are synthesized for the first time using the 16-carbon (C 16) partly fluorinated surfactant, 11,11,12,12,13,13,14,14,15,15,16,16,16-tridecafluorocetyl pyridinium bromide (HFCPB), as a templating agent. Silica films templated with surfactants containing a 8-carbon (C 8) fluorocarbon tail (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl pyridinium chloride (HFOPC)) and a 16-carbon (C 16) hydrocarbon tail (cetyl pyridinium bromide (CPB)) and HFCPB (C 16) are processed in compressed CO 2 (69-172bar, 25°C and 45°C) during synthesis. CO 2 processing results in significant pore expansion for films templated with both fluorinated surfactants, while pore expansion is negligible for the hydrocarbon templated material suggesting that preferential CO 2 penetration occurs in the 'CO 2-philic' fluorocarbon segments of the surfactant template. The effect of substrate surface energy on the final uniformity of the dip-coated films is studied by varying the substrate from unmodified glass to a fluorocarbon-capped substrate. The ability to create dip-coated thin films on low surface energy substrates through favorable interaction of surfactant template tail with the substrate surface functional groups is demonstrated.

AB - The penetration of compressed CO 2 in hydrocarbon and fluorocarbon regions of concentrated surfactant mesophases are interpreted from differences in the CO 2-processed pore expansion of mesoporous silica thin films templated by three surfactants containing varying degrees of hydrocarbon and fluorocarbon functionality. Ordered silica thin films are synthesized for the first time using the 16-carbon (C 16) partly fluorinated surfactant, 11,11,12,12,13,13,14,14,15,15,16,16,16-tridecafluorocetyl pyridinium bromide (HFCPB), as a templating agent. Silica films templated with surfactants containing a 8-carbon (C 8) fluorocarbon tail (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl pyridinium chloride (HFOPC)) and a 16-carbon (C 16) hydrocarbon tail (cetyl pyridinium bromide (CPB)) and HFCPB (C 16) are processed in compressed CO 2 (69-172bar, 25°C and 45°C) during synthesis. CO 2 processing results in significant pore expansion for films templated with both fluorinated surfactants, while pore expansion is negligible for the hydrocarbon templated material suggesting that preferential CO 2 penetration occurs in the 'CO 2-philic' fluorocarbon segments of the surfactant template. The effect of substrate surface energy on the final uniformity of the dip-coated films is studied by varying the substrate from unmodified glass to a fluorocarbon-capped substrate. The ability to create dip-coated thin films on low surface energy substrates through favorable interaction of surfactant template tail with the substrate surface functional groups is demonstrated.

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Supercritical carbon dioxide swelling of fluorinated and hydrocarbon surfactant templates in mesoporous silica thin films

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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