Thermal Transitions in Polyelectrolyte Assemblies Occur via a Dehydration Mechanism


Yildirim E., Zhang Y., Lutkenhaus J. L., Sammalkorpi M.

ACS MACRO LETTERS, cilt.4, sa.9, ss.1017-1021, 2015 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 4 Sayı: 9
  • Basım Tarihi: 2015
  • Doi Numarası: 10.1021/acsmacrolett.5b00351
  • Dergi Adı: ACS MACRO LETTERS
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.1017-1021
  • Orta Doğu Teknik Üniversitesi Adresli: Hayır

Özet

Hydrated polyelectrolyte (PE) complexes and multilayers undergo a well-defined thermal transition that bears resemblance to a glass transition. By combining molecular simulations and differential scanning calorimetry (DSC) of poly(diallyldimethylammonium) (PDAC) and poly(styrenesulfonate) (PSS) multilayers, we establish for the first time that dehydration drives the thermally induced change in plasticization of the complex and in the diffusion behavior of its components. DSC experiments show that the thermal transition appears when the assemblies are hydrated in water but not in the presence of alcohols, which supports that water is required for this transition. These findings connect PE complexes more generally to thermoresponsive polymers and liquid crystal phases, which bear phase transitions driven by the (de)hydration of functional groups, thus forming a fundamental link toward an integrated understanding of the thermal response of molecular materials in aqueous environments.