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

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

doi:10.1021/ma0713557

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

Abstract

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 language	English (US)
Pages (from-to)	8367-8373
Number of pages	7
Journal	Macromolecules
Volume	40
Issue number	23
DOIs	https://doi.org/10.1021/ma0713557
State	Published - Nov 13 2007
Externally published	Yes

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma0713557

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title = "Tuning the glass transition of and ion transport within hydrogen-bonded layer-by-layer assemblies",

abstract = "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.",

author = "Lutkenhaus, {Jodie L.} and Kathleen McEnnis and Hammond, {Paula T.}",

year = "2007",

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journal = "Macromolecules",

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T1 - Tuning the glass transition of and ion transport within hydrogen-bonded layer-by-layer assemblies

AU - Lutkenhaus, Jodie L.

AU - McEnnis, Kathleen

AU - Hammond, Paula T.

PY - 2007/11/13

Y1 - 2007/11/13

N2 - 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.

AB - 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.

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

Abstract

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