Effect of side chain architecture on dielectric relaxation in polyhedral oligomeric silsesquioxane/polypropylene oxide nanocomposites

Yu Bian, Jovan Mijovic

Research output: Contribution to journalArticle

Abstract

Segmental and normal mode dynamics in polyhedral oligomeric silsesquioxane (POSS)/poly(propylene oxide) (PPO) non-reactive and reactive nanocomposites were investigated using a broadband dielectric relaxation spectroscopy (DRS) over wide ranges of frequency and temperature. Three POSS reagents with varying side chain architecture were selected for the study: OctaGlycidyldimethylsilyl (OG), TrisGlycidylEthyl (TG) and MonoGlycidylEthyl (MG). Spectra of OG and TG show a segmental (α) process at lower frequency and a local (β) relaxation at higher frequency, while MG displays only a local relaxation. Neat PPO has both segmental and normal mode (αN) process. In POSS/PPO non-reactive nanocomposites, the presence of OG and TG causes a decrease in the time scale of αN and α relaxation, while MG has no impact on the dynamics of PPO. Chemical reactions in POSS/PPO reactive nanocomposites lead to the formation of nanonetworks. Prior to the onset of reaction, POSS nanoparticles promote the motions of PPO chains, decrease the time scale of relaxation and give rise to thermodielectrically simple spectra. During the reaction, however, the network formation leads to spectral broadening and a gradual increase in the time scale of both segmental (α) and normal mode (αN) relaxation. A detailed account of the effects of structure, concentration and dispersion of POSS in the matrix, molecular weight of PPO, extent of reaction and temperature on the molecular origin, temperature dependence and spectral characteristics of relaxation processes in POSS/PPO nanocomposites is provided.

Original languageEnglish (US)
Pages (from-to)1541-1547
Number of pages7
JournalPolymer
Volume50
Issue number6
DOIs
StatePublished - Mar 6 2009

Fingerprint

Polypropylene oxides
Dielectric relaxation
Nanocomposites
polypropylene glycol
Relaxation processes
Temperature
Chemical reactions
Molecular weight
Spectroscopy
Nanoparticles

Keywords

  • Dielectric spectroscopy
  • POSS
  • Relaxation dynamics

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics

Cite this

Effect of side chain architecture on dielectric relaxation in polyhedral oligomeric silsesquioxane/polypropylene oxide nanocomposites. / Bian, Yu; Mijovic, Jovan.

In: Polymer, Vol. 50, No. 6, 06.03.2009, p. 1541-1547.

Research output: Contribution to journalArticle

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N2 - Segmental and normal mode dynamics in polyhedral oligomeric silsesquioxane (POSS)/poly(propylene oxide) (PPO) non-reactive and reactive nanocomposites were investigated using a broadband dielectric relaxation spectroscopy (DRS) over wide ranges of frequency and temperature. Three POSS reagents with varying side chain architecture were selected for the study: OctaGlycidyldimethylsilyl (OG), TrisGlycidylEthyl (TG) and MonoGlycidylEthyl (MG). Spectra of OG and TG show a segmental (α) process at lower frequency and a local (β) relaxation at higher frequency, while MG displays only a local relaxation. Neat PPO has both segmental and normal mode (αN) process. In POSS/PPO non-reactive nanocomposites, the presence of OG and TG causes a decrease in the time scale of αN and α relaxation, while MG has no impact on the dynamics of PPO. Chemical reactions in POSS/PPO reactive nanocomposites lead to the formation of nanonetworks. Prior to the onset of reaction, POSS nanoparticles promote the motions of PPO chains, decrease the time scale of relaxation and give rise to thermodielectrically simple spectra. During the reaction, however, the network formation leads to spectral broadening and a gradual increase in the time scale of both segmental (α) and normal mode (αN) relaxation. A detailed account of the effects of structure, concentration and dispersion of POSS in the matrix, molecular weight of PPO, extent of reaction and temperature on the molecular origin, temperature dependence and spectral characteristics of relaxation processes in POSS/PPO nanocomposites is provided.

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