Chain conformation of poly(dimethyl siloxane) at the air/water interface by sum frequency generation

Chanjoong Kim, Marc C. Gurau, Paul S. Cremer, Hyuk Yu

Research output: Contribution to journalArticle

42 Scopus citations

Abstract

This is to report a study of chain conformation of poly(dimethylsiloxane) (PDMS) in spread monolayers at the air/water interface (A/W) with the aid of vibrational sum frequency spectroscopy (VSFS). We find that methyl groups of PDMS chains at the interface are completely disordered in the dilute regime of the surface density. At higher surface densities, however, the two methyl groups on the repeating unit point into the air asymmetrically; one points more normal to the interface, whereas the other lies more parallel to the interface. In the first collapsed regime, where the surface pressure of the PDMS monolayer reaches a plateau value of 8.7 mN/m, the signal intensity at 2915 cm -1 , assigned to the symmetric vibrational frequency of the methyl groups, is found independent of the surface density. On the basis of this finding, we propose that PDMS chains, in the first collapse regime at the A/W, form asymmetric layers. Thus, our proposal lends support to earlier works by Langevin's group to refute a widely speculated helix model that was based on energy minimization in the crystalline state of PDMS. In short, the energy consideration in the bulk crystalline state does not provide meaningful guidance as to the chain conformation of the monolayer at the A/W.

Original languageEnglish (US)
Pages (from-to)10155-10160
Number of pages6
JournalLangmuir
Volume24
Issue number18
DOIs
StatePublished - Sep 16 2008

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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