Poly(methacrylic acid) Grafts Grown from Designer Surfaces; The Effect of Initiator Coverage on Polymerization Kinetics, Morphology, and Properties

Edmondo Maria Benetti, E. Reimhult, J. de Bruin, S.J. Zapotoczny, M. Textor, Gyula J. Vancso

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Poly(methacrylic acid) (PMAA) films were photografted by iniferter-mediated polymerization from self-assembled monolayers (SAMs) of initiator molecules immobilized on Au via disulfide linkages and mixed with disulfide alkanes. The influence of initiator coverage on the growth rates of film thickness, surface morphology, and nanoscale mechanics was studied. Film thickness was measured by ellipsometry and atomic force microscopy (AFM), whereas mechanical performance was assessed by AFM compression force. Remarkably, the film thickness growth rate by ellipsometry did not show any significant variation with initiator coverage. However, surface morphology visualized by AFM showed clear influences of the composition of the initiating SAMs, which directly affected the rate of termination reactions. To investigate the early stages in the grafting process, polymerization was performed in situ using a quartz crystal microbalance with dissipation monitoring setup (QCM-D). The mass increment during the photografting was evaluated using concentrated and diluted SAMs of the initiator. A remarkably higher number of grafted chains in the case of concentrated SAMs was observed. By comparing this result with the AFM measurements on the obtained films, we recognized a broader chain length distribution, consequent to termination reactions in dense systems, to influence the surface morphology of the layers.
Original languageEnglish
Pages (from-to)1640-1647
Number of pages8
JournalMacromolecules
Volume42
Issue number5
DOIs
Publication statusPublished - 2009

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Self assembled monolayers
Grafts
Atomic force microscopy
Polymerization
Surface morphology
Film thickness
Kinetics
Acids
Ellipsometry
Disulfides
Alkanes
Quartz crystal microbalances
Chain length
Paraffins
Mechanics
Compaction
Molecules
methacrylic acid
Monitoring
Chemical analysis

Keywords

  • METIS-258178

Cite this

Benetti, Edmondo Maria ; Reimhult, E. ; de Bruin, J. ; Zapotoczny, S.J. ; Textor, M. ; Vancso, Gyula J. / Poly(methacrylic acid) Grafts Grown from Designer Surfaces; The Effect of Initiator Coverage on Polymerization Kinetics, Morphology, and Properties. In: Macromolecules. 2009 ; Vol. 42, No. 5. pp. 1640-1647.
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abstract = "Poly(methacrylic acid) (PMAA) films were photografted by iniferter-mediated polymerization from self-assembled monolayers (SAMs) of initiator molecules immobilized on Au via disulfide linkages and mixed with disulfide alkanes. The influence of initiator coverage on the growth rates of film thickness, surface morphology, and nanoscale mechanics was studied. Film thickness was measured by ellipsometry and atomic force microscopy (AFM), whereas mechanical performance was assessed by AFM compression force. Remarkably, the film thickness growth rate by ellipsometry did not show any significant variation with initiator coverage. However, surface morphology visualized by AFM showed clear influences of the composition of the initiating SAMs, which directly affected the rate of termination reactions. To investigate the early stages in the grafting process, polymerization was performed in situ using a quartz crystal microbalance with dissipation monitoring setup (QCM-D). The mass increment during the photografting was evaluated using concentrated and diluted SAMs of the initiator. A remarkably higher number of grafted chains in the case of concentrated SAMs was observed. By comparing this result with the AFM measurements on the obtained films, we recognized a broader chain length distribution, consequent to termination reactions in dense systems, to influence the surface morphology of the layers.",
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Poly(methacrylic acid) Grafts Grown from Designer Surfaces; The Effect of Initiator Coverage on Polymerization Kinetics, Morphology, and Properties. / Benetti, Edmondo Maria; Reimhult, E.; de Bruin, J.; Zapotoczny, S.J.; Textor, M.; Vancso, Gyula J.

In: Macromolecules, Vol. 42, No. 5, 2009, p. 1640-1647.

Research output: Contribution to journalArticleAcademicpeer-review

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T1 - Poly(methacrylic acid) Grafts Grown from Designer Surfaces; The Effect of Initiator Coverage on Polymerization Kinetics, Morphology, and Properties

AU - Benetti, Edmondo Maria

AU - Reimhult, E.

AU - de Bruin, J.

AU - Zapotoczny, S.J.

AU - Textor, M.

AU - Vancso, Gyula J.

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N2 - Poly(methacrylic acid) (PMAA) films were photografted by iniferter-mediated polymerization from self-assembled monolayers (SAMs) of initiator molecules immobilized on Au via disulfide linkages and mixed with disulfide alkanes. The influence of initiator coverage on the growth rates of film thickness, surface morphology, and nanoscale mechanics was studied. Film thickness was measured by ellipsometry and atomic force microscopy (AFM), whereas mechanical performance was assessed by AFM compression force. Remarkably, the film thickness growth rate by ellipsometry did not show any significant variation with initiator coverage. However, surface morphology visualized by AFM showed clear influences of the composition of the initiating SAMs, which directly affected the rate of termination reactions. To investigate the early stages in the grafting process, polymerization was performed in situ using a quartz crystal microbalance with dissipation monitoring setup (QCM-D). The mass increment during the photografting was evaluated using concentrated and diluted SAMs of the initiator. A remarkably higher number of grafted chains in the case of concentrated SAMs was observed. By comparing this result with the AFM measurements on the obtained films, we recognized a broader chain length distribution, consequent to termination reactions in dense systems, to influence the surface morphology of the layers.

AB - Poly(methacrylic acid) (PMAA) films were photografted by iniferter-mediated polymerization from self-assembled monolayers (SAMs) of initiator molecules immobilized on Au via disulfide linkages and mixed with disulfide alkanes. The influence of initiator coverage on the growth rates of film thickness, surface morphology, and nanoscale mechanics was studied. Film thickness was measured by ellipsometry and atomic force microscopy (AFM), whereas mechanical performance was assessed by AFM compression force. Remarkably, the film thickness growth rate by ellipsometry did not show any significant variation with initiator coverage. However, surface morphology visualized by AFM showed clear influences of the composition of the initiating SAMs, which directly affected the rate of termination reactions. To investigate the early stages in the grafting process, polymerization was performed in situ using a quartz crystal microbalance with dissipation monitoring setup (QCM-D). The mass increment during the photografting was evaluated using concentrated and diluted SAMs of the initiator. A remarkably higher number of grafted chains in the case of concentrated SAMs was observed. By comparing this result with the AFM measurements on the obtained films, we recognized a broader chain length distribution, consequent to termination reactions in dense systems, to influence the surface morphology of the layers.

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