Adsorbed and spread layers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers at the air-water interface studied by sum-frequency vibrational spectroscopy and tensiometry

E. Kiss, T. Keszthelyi, Gábor Kormány, Orsolya Hakkel

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30 Citations (Scopus)

Abstract

The surface properties of three water-soluble and amphiphilic PEO-PPO-PEO triblock copolymers of different composition (Pluronic 6100, 6400, and 6800) are investigated by tensiometry and sum-frequency vibrational spectroscopy. We compared the concentration dependence of the structure of surface layers prepared by three different methods: (i) adsorption from aqueous solution, (ii) dropwise spreading from an organic solution onto a surface of constant area, and (iii) compression of the spread film in a Langmuir trough. The surface density and conformation of the polymers were deduced from the vibrational band intensities of the methyl groups of the central hydrophobic PPO block and from the surface tension isotherms. A transition range related to a conformational change was observed by tensiometry for the adsorbed and the compressed Langmuir films of Pluronics with short PEO blocks, whereas the Pluronic with longest PEO blocks displays a gradual change of surface pressure without the sign of a phase transition. This difference reveals the effect of the relative lengths of the hydrophilic and hydrophobic blocks on the structural changes in the surface layers of block copolymers. A clear indication of the influence of the hydrophilic blocks on the structure of the whole molecule at the interface was also observed in the sum-frequency experiments. Above a given concentration the Pluronic with longest PEO chains exhibited lower sum-frequency intensities and methyl symmetric/asymmetric amplitude ratios than the other Pluronic compounds for all of the layers formed by the various methods. The differences in the surface properties of the dropwise spread layers and of the compressed Langmuir layers exposed the importance of the kinetic aspects of polymer monolayer formation. In the case of the spread films the possible large degree of nonequilibrium chain entanglements might hinder the accomplishment of preferred orientation and conformation of the polymer chains.

Original languageEnglish
Pages (from-to)9375-9384
Number of pages10
JournalMacromolecules
Volume39
Issue number26
DOIs
Publication statusPublished - Dec 26 2006

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Polypropylene oxides
Poloxamer
Vibrational spectroscopy
Polyethylene oxides
Block copolymers
Water
Polyphenylene oxides
Air
Polymers
Surface properties
Conformations
Langmuir Blodgett films
Crystal orientation
Isotherms
Surface tension
Monolayers
Compaction
Phase transitions
PEO-PPO-PEO
Adsorption

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

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title = "Adsorbed and spread layers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers at the air-water interface studied by sum-frequency vibrational spectroscopy and tensiometry",
abstract = "The surface properties of three water-soluble and amphiphilic PEO-PPO-PEO triblock copolymers of different composition (Pluronic 6100, 6400, and 6800) are investigated by tensiometry and sum-frequency vibrational spectroscopy. We compared the concentration dependence of the structure of surface layers prepared by three different methods: (i) adsorption from aqueous solution, (ii) dropwise spreading from an organic solution onto a surface of constant area, and (iii) compression of the spread film in a Langmuir trough. The surface density and conformation of the polymers were deduced from the vibrational band intensities of the methyl groups of the central hydrophobic PPO block and from the surface tension isotherms. A transition range related to a conformational change was observed by tensiometry for the adsorbed and the compressed Langmuir films of Pluronics with short PEO blocks, whereas the Pluronic with longest PEO blocks displays a gradual change of surface pressure without the sign of a phase transition. This difference reveals the effect of the relative lengths of the hydrophilic and hydrophobic blocks on the structural changes in the surface layers of block copolymers. A clear indication of the influence of the hydrophilic blocks on the structure of the whole molecule at the interface was also observed in the sum-frequency experiments. Above a given concentration the Pluronic with longest PEO chains exhibited lower sum-frequency intensities and methyl symmetric/asymmetric amplitude ratios than the other Pluronic compounds for all of the layers formed by the various methods. The differences in the surface properties of the dropwise spread layers and of the compressed Langmuir layers exposed the importance of the kinetic aspects of polymer monolayer formation. In the case of the spread films the possible large degree of nonequilibrium chain entanglements might hinder the accomplishment of preferred orientation and conformation of the polymer chains.",
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T1 - Adsorbed and spread layers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers at the air-water interface studied by sum-frequency vibrational spectroscopy and tensiometry

AU - Kiss, E.

AU - Keszthelyi, T.

AU - Kormány, Gábor

AU - Hakkel, Orsolya

PY - 2006/12/26

Y1 - 2006/12/26

N2 - The surface properties of three water-soluble and amphiphilic PEO-PPO-PEO triblock copolymers of different composition (Pluronic 6100, 6400, and 6800) are investigated by tensiometry and sum-frequency vibrational spectroscopy. We compared the concentration dependence of the structure of surface layers prepared by three different methods: (i) adsorption from aqueous solution, (ii) dropwise spreading from an organic solution onto a surface of constant area, and (iii) compression of the spread film in a Langmuir trough. The surface density and conformation of the polymers were deduced from the vibrational band intensities of the methyl groups of the central hydrophobic PPO block and from the surface tension isotherms. A transition range related to a conformational change was observed by tensiometry for the adsorbed and the compressed Langmuir films of Pluronics with short PEO blocks, whereas the Pluronic with longest PEO blocks displays a gradual change of surface pressure without the sign of a phase transition. This difference reveals the effect of the relative lengths of the hydrophilic and hydrophobic blocks on the structural changes in the surface layers of block copolymers. A clear indication of the influence of the hydrophilic blocks on the structure of the whole molecule at the interface was also observed in the sum-frequency experiments. Above a given concentration the Pluronic with longest PEO chains exhibited lower sum-frequency intensities and methyl symmetric/asymmetric amplitude ratios than the other Pluronic compounds for all of the layers formed by the various methods. The differences in the surface properties of the dropwise spread layers and of the compressed Langmuir layers exposed the importance of the kinetic aspects of polymer monolayer formation. In the case of the spread films the possible large degree of nonequilibrium chain entanglements might hinder the accomplishment of preferred orientation and conformation of the polymer chains.

AB - The surface properties of three water-soluble and amphiphilic PEO-PPO-PEO triblock copolymers of different composition (Pluronic 6100, 6400, and 6800) are investigated by tensiometry and sum-frequency vibrational spectroscopy. We compared the concentration dependence of the structure of surface layers prepared by three different methods: (i) adsorption from aqueous solution, (ii) dropwise spreading from an organic solution onto a surface of constant area, and (iii) compression of the spread film in a Langmuir trough. The surface density and conformation of the polymers were deduced from the vibrational band intensities of the methyl groups of the central hydrophobic PPO block and from the surface tension isotherms. A transition range related to a conformational change was observed by tensiometry for the adsorbed and the compressed Langmuir films of Pluronics with short PEO blocks, whereas the Pluronic with longest PEO blocks displays a gradual change of surface pressure without the sign of a phase transition. This difference reveals the effect of the relative lengths of the hydrophilic and hydrophobic blocks on the structural changes in the surface layers of block copolymers. A clear indication of the influence of the hydrophilic blocks on the structure of the whole molecule at the interface was also observed in the sum-frequency experiments. Above a given concentration the Pluronic with longest PEO chains exhibited lower sum-frequency intensities and methyl symmetric/asymmetric amplitude ratios than the other Pluronic compounds for all of the layers formed by the various methods. The differences in the surface properties of the dropwise spread layers and of the compressed Langmuir layers exposed the importance of the kinetic aspects of polymer monolayer formation. In the case of the spread films the possible large degree of nonequilibrium chain entanglements might hinder the accomplishment of preferred orientation and conformation of the polymer chains.

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