Dynamics of linear poly(N-isopropylacrylamide) in water around the phase transition investigated by dielectric relaxation spectroscopy

J Phys Chem B. 2014 Apr 3;118(13):3750-9. doi: 10.1021/jp501325x. Epub 2014 Mar 20.

Abstract

The molecular dynamics of linear poly(N-isopropylacrylamide) (pNIPAM) in aqueous media at temperatures below and above the lower critical solution temperature (LCST) are investigated using broadband dielectric relaxation spectroscopy in a frequency range from 10(-1) to 10(11) Hz. Below the LCST, two relaxation processes are observed in the megahertz and gigahertz region assigned to the reorientation of dipoles of the solvated polymer segments (p-process) and water molecules (w-process), respectively. Both relaxation processes are analyzed using the Havriliak-Negami (HN) function, taking special attention to the w-process. Above the LCST, the dielectric spectra of the pNIPAM solutions resemble that of pure water, showing only the high frequency relaxation process of the water molecules with a more or less Debye-type behavior. The non-Debye behavior of the w-process below the LCST is mainly induced by the interactions between water and pNIPAM chains via hydrogen bonding. The relaxation time and strength of the w-process is studied with dependence on the concentration, temperature, and the polymer chain length (molecular weight). The information obtained is useful for a deeper understanding of the dehydration behavior at the phase transition. The suggestion of dehydration of the pNIPAM chains at the LCST is confirmed by calculating a dehydration number.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylic Resins / chemistry*
  • Dielectric Spectroscopy
  • Molecular Dynamics Simulation
  • Phase Transition
  • Temperature
  • Water / chemistry*

Substances

  • Acrylic Resins
  • Water
  • poly-N-isopropylacrylamide