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ATR-IR Investigation of Solvent Interactions with Surface-Bound Polymers.

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Title: ATR-IR Investigation of Solvent Interactions with Surface-Bound Polymers.
Authors: Mathis, Christian H.1, Divandari, Mohammad1, Simic, Rok1, Naik, Vikrant V.1, Benetti, Edmondo M.1, Isa, Lucio2, Spencer, Nicholas D.1 nspencer@ethz.ch
Source: Langmuir. Aug2016, Vol. 32 Issue 30, p7588-7595. 8p.
Subjects: Infrared spectroscopy, Solvents, Thermoresponsive polymers, Adhesion, Atomic force microscopy, Ultraviolet spectrophotometry
Abstract: Solvent interactions with bulk and surface-bound polymer brushes are crucial for functionalities such as controlled friction and thermoresponsive adhesion. To study such interactions, the temperature-induced solvent-quality changes and the effect of surface tethering on the mechanical and tribological properties of poly(dodecyl methacrylate) (P12MA) brushes have been investigated by means of attenuated total reflection infrared spectroscopy (ATR-IR), as well as atomic force microscopy (AFM) and lateral force microscopy (LFM). These results have been compared with temperature-dependent UV-visible spectrophotometry (UV-vis) data for the corresponding bulk polymer solutions. The ATR-IR results clearly show that increasing temperature enhances ethanol uptake in P12MA, which results in film swelling. This is accompanied by a marked increase in both adhesion and friction. We have also shown that a combination of solvents, such as toluene and ethanol, can lead to a temperature-dependent solvent partitioning within the polymer brush. To our knowledge this is the first time preferential solvent uptake in a grafted-from brush has been monitored via in situ ATR-IR. Moreover, we have observed remarkably different behavior for polymer chains in solution compared to the behavior of similar chains bound to a surface. The presented findings on the temperature-dependent solvent interactions of surface-grafted P12MA reveal previously unknown solvation phenomena and open up a range of possible applications in the area of stimuli-responsive materials. [ABSTRACT FROM AUTHOR]
Copyright of Langmuir is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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DbLabel: Engineering Source
An: 117172329
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PubType: Academic Journal
PubTypeId: academicJournal
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  Data: ATR-IR Investigation of Solvent Interactions with Surface-Bound Polymers.
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  Data: <searchLink fieldCode="AR" term="%22Mathis%2C+Christian+H%2E%22">Mathis, Christian H.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Divandari%2C+Mohammad%22">Divandari, Mohammad</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Simic%2C+Rok%22">Simic, Rok</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Naik%2C+Vikrant+V%2E%22">Naik, Vikrant V.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Benetti%2C+Edmondo+M%2E%22">Benetti, Edmondo M.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Isa%2C+Lucio%22">Isa, Lucio</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Spencer%2C+Nicholas+D%2E%22">Spencer, Nicholas D.</searchLink><relatesTo>1</relatesTo><i> nspencer@ethz.ch</i>
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  Data: <searchLink fieldCode="JN" term="%22Langmuir%22">Langmuir</searchLink>. Aug2016, Vol. 32 Issue 30, p7588-7595. 8p.
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  Data: <searchLink fieldCode="DE" term="%22Infrared+spectroscopy%22">Infrared spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Solvents%22">Solvents</searchLink><br /><searchLink fieldCode="DE" term="%22Thermoresponsive+polymers%22">Thermoresponsive polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Adhesion%22">Adhesion</searchLink><br /><searchLink fieldCode="DE" term="%22Atomic+force+microscopy%22">Atomic force microscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Ultraviolet+spectrophotometry%22">Ultraviolet spectrophotometry</searchLink>
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  Data: Solvent interactions with bulk and surface-bound polymer brushes are crucial for functionalities such as controlled friction and thermoresponsive adhesion. To study such interactions, the temperature-induced solvent-quality changes and the effect of surface tethering on the mechanical and tribological properties of poly(dodecyl methacrylate) (P12MA) brushes have been investigated by means of attenuated total reflection infrared spectroscopy (ATR-IR), as well as atomic force microscopy (AFM) and lateral force microscopy (LFM). These results have been compared with temperature-dependent UV-visible spectrophotometry (UV-vis) data for the corresponding bulk polymer solutions. The ATR-IR results clearly show that increasing temperature enhances ethanol uptake in P12MA, which results in film swelling. This is accompanied by a marked increase in both adhesion and friction. We have also shown that a combination of solvents, such as toluene and ethanol, can lead to a temperature-dependent solvent partitioning within the polymer brush. To our knowledge this is the first time preferential solvent uptake in a grafted-from brush has been monitored via in situ ATR-IR. Moreover, we have observed remarkably different behavior for polymer chains in solution compared to the behavior of similar chains bound to a surface. The presented findings on the temperature-dependent solvent interactions of surface-grafted P12MA reveal previously unknown solvation phenomena and open up a range of possible applications in the area of stimuli-responsive materials. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>Copyright of Langmuir is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/acs.langmuir.6b02086
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        Text: English
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        Type: general
      – SubjectFull: Solvents
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      – SubjectFull: Thermoresponsive polymers
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      – SubjectFull: Adhesion
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      – SubjectFull: Atomic force microscopy
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      – SubjectFull: Ultraviolet spectrophotometry
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      – TitleFull: ATR-IR Investigation of Solvent Interactions with Surface-Bound Polymers.
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              Text: Aug2016
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              Y: 2016
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