Thickness, composition, and molecular structure of residual thin films formed by forced dewetting of Ag from glycerol/D2O solutions

Jeanne E Pemberton, Anoma Mudalige, Heemin Yoo

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The thickness, composition, and interfacial molecular structure of residual thin films retained on the surface of polycrystalline Ag substrates after being forcibly dewet from glycerol/D2O solutions are investigated using contact angle measurements, ellipsometry, and polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS). Residual film thicknesses are rationalized on the basis of the relevant long-range van der Waals and structural forces leading to residual film formation along with the interfacial glycerol and D2O structure. Unique interfacial composition, wherein glycerol preferentially segregates to the residual film interfaces, is substantiated by PM-IRRAS. Thus, the residual films possess composition and molecular structure that differ from those of bulk solution. Specifically, in the thinnest residual films, glycerol interacts strongly with the Ag substrate, leading to glycerol that is more ordered than the bulk liquid that coexists with bulk-like D2O. In thicker residual films, the glycerol mole fraction is still enhanced relative to the bulk solution, but both ordered and liquid-like glycerol species are observed along with D2O that is more strongly hydrogen-bonded than in the bulk. The creation of residual films by forced dewetting and their interrogation by spectroscopic methods are thus demonstrated to represent a powerful approach for characterizing interfacial liquid molecular structure near solid surfaces but beyond the first monolayer under ambient conditions.

Original languageEnglish (US)
Pages (from-to)15181-15192
Number of pages12
JournalLangmuir
Volume30
Issue number50
DOIs
StatePublished - Dec 23 2014

Fingerprint

glycerols
Glycerol
Molecular structure
drying
molecular structure
Thin films
thin films
Chemical analysis
polarization modulation
infrared reflection
Absorption spectroscopy
absorption spectroscopy
Liquids
liquids
Modulation
Polarization
Infrared radiation
modulation
interrogation
Ellipsometry

ASJC Scopus subject areas

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

Cite this

Thickness, composition, and molecular structure of residual thin films formed by forced dewetting of Ag from glycerol/D2O solutions. / Pemberton, Jeanne E; Mudalige, Anoma; Yoo, Heemin.

In: Langmuir, Vol. 30, No. 50, 23.12.2014, p. 15181-15192.

Research output: Contribution to journalArticle

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