Tuning the glass transition of and ion transport within hydrogen-bonded layer-by-layer assemblies

Jodie L. Lutkenhaus, Kathleen McEnnis, Paula T. Hammond

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65 Scopus citations


The influence of pH and ionic strength on the structure and properties of hydrogen-bonded layer-by-layer (LbL) assemblies of polyethylene oxide) (PEO) and poly(acrylic acid) (PAA) is explored. The degree of inter- and intramolecular hydrogen bonding is estimated from Fourier-transform infrared spectroscopy, the glass transition temperature is measured using differential scanning calorimetry of bulk free-standing films, and ionic conductivity is studied using electrochemical impedance spectroscopy. Results indicate that (PEO/PAA) LbL films assembled without added salt are sensitive to pH, with a T g decrease (59-26°C) and intermolecular hydrogen bonding increase (27 to 51% COOH groups bonding with PEO) with increasing assembly pH (2 to 3). Films assembled in the presence of 0.1 M lithium triflate exhibit properties independent of assembly pH (T g ∼ 48°C and 12% COOH groups bonding with PEO), presumably due to the "screening" of hydrogen bonds. Ionic conductivity is found to range from 10 -6 to 10 -10 S cm -1, depending on humidity, plasticization, and salt content.

Original languageEnglish (US)
Pages (from-to)8367-8373
Number of pages7
Issue number23
StatePublished - Nov 13 2007
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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