Enthalpy relaxation in poly(4-hydroxystyrene)/poly(methyl methacrylate) blends

I. M G Cowie, Valeria Arrighi, Elizabeth Anne McGonigle

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14 Citations (Scopus)


The influence of blend composition on enthalpy relaxation behaviour was assessed for miscible blends of poly(4-hydroxystyrene)/poly(methyl methacrylate) (PHS/PMMA). Values of enthalpy lost (?H(Ta, ta)) were calculated from experimental data plotted against log10(t a) and modelled using the Cowie-Ferguson (CF) semi-empirical model. This gives a set of values for three adjustable parameters, ?H 8(Ta), log10(tc) and ß. The blends relaxed more slowly than PMMA, but more quickly and less co-operatively than PHS. Moreover, the blends released more enthalpy than PMMA, but less than PHS. The enthalpy lost by the fully relaxed glass (?H8(T a)) was less than the theoretical amount possible on reaching the state defined by the liquid enthalpy line extrapolated into the glassy region (?Hmax(Ta)). Infrared spectroscopy was used for assessing the hydrogen bonding interactions in the blends. The ageing results are discussed with reference to the hydrogen bonding interactions. © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original languageEnglish
Pages (from-to)767-776
Number of pages10
JournalMacromolecular Chemistry and Physics
Issue number7
Publication statusPublished - 6 Apr 2005


  • Ageing
  • Blends
  • Enthalpy relaxation
  • Hydrogen bonding


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