Segmental and normal mode dynamics during network formation

Jovan Mijovic, Jo Wing Sy

Research output: Contribution to journalArticlepeer-review


Broad-band dielectric relaxation spectroscopy was used to investigate the molecular dynamics of reactive systems where one of the components exhibits, in addition to the transverse dipole moment component (μ or type B) that gives rise to the segmental α process, a persistent cumulative dipole moment along the chain contour (μ or type A). The systems studied were composed of an amine-terminated poly(propylene oxide) (PPO), that contains type A and B dipoles, and a bifunctional epoxy prepolymer. The segmental and normal mode processes were clearly discernible in the neat PPO and the PPO/epoxy blends with PPO MW > 2000 g/mol. The α process broadens upon mixing. The normal mode has a narrower spectrum than the segmental mode and is not affected by mixing. Cross-linking causes the segmental and normal modes to gradually overlap and we observe a deviation of the normal mode from the Rouse dynamics and a considerable broadening of the α process. The molecular architecture of the growing network plays an important role in determining the dynamics, as the compositional and spatial heterogeneities arise during cross-linking. Interestingly, while the increased heterogeneity results in the broadening of the relaxation spectra, the temperature dependence of the α process remains unaffected by cross-linking. This is a curious finding; the apparent lack of a direct correlation between non-exponentiality and fragility in cross-linking PPO networks may reflect the length scale of relaxation and warrants further investigation.

Original languageEnglish (US)
Pages (from-to)679-687
Number of pages9
JournalJournal of Non-Crystalline Solids
StatePublished - Sep 2002

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Materials Chemistry


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