Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films

Samy Madbouly, Joshua U. Otaigbe, Ajaya K. Nanda, Douglas A. Wicks

Research output: Chapter in Book/Report/Conference proceedingConference contribution

2 Citations (Scopus)

Abstract

Two series of nanostructured polyurethane with reactive diamino-polyhedral oligomeric silsesquioxanes (POSS) hybrid were synthesized via environmentally-friendly aqueous dispersions through two different methods, namely, acetone and prepolymer processes. The resulting PU/POSS nanocomposites prepared via acetone process did show more phase homogeneity compared with that of prepolymer process as confirmed by wide angle X-ray diffraction patterns of the cast films. Rheological behavior of these important classes of materials has been investigated as a function of POSS concentration and preparation method over a wide range of shear frequency and temperature. The complex viscosity and the elastic storage modulus of PU and PU/POSS nanocomposites prepared via prepolymer process were much higher than that of acetone process at a constant temperature due to the difference in the molecular weight and percentage of internal surfactant. For the PU/POSS nanocomposites prepared by the two different methods, the rheological behavior in the melt confirmed the existence of microphase separation of the hard and soft segments. The value of the microphase separation temperature (TMPS) was found to be concentration independent when the POSS concentration is ≤6wt%. For 10 wt% POSS the TMPS shifted by 20 °C to a higher temperature. The effect of POSS on the value of TMPS for prepolymer. samples is considerably different. The value of TMPS of pure PU shifted from 165 °C to 178 °C for all PU/POSS samples regardless of the concentration of POSS as measured from the dynamic heating ramps (2 °C/min heating rate at ω = 1 rad/s) of G'. The shift of TMPS to high temperature in both cases (acetone and prepolymer processes) is attributed to the large surface areas of POSS that produces relatively large interaction zones with the PU hard and soft segments.

Original languageEnglish (US)
Title of host publicationNanotechnology Applications in Coatings
PublisherAmerican Chemical Society
Pages89-107
Number of pages19
ISBN (Print)9780841274488
DOIs
StatePublished - Jun 12 2009

Publication series

NameACS Symposium Series
Volume1008
ISSN (Print)0097-6156
ISSN (Electronic)1947-5918

Fingerprint

Polyurethanes
Microphase separation
Acetone
Temperature
Nanocomposites
Heating rate
Dispersions
Surface-Active Agents
Diffraction patterns
Surface active agents
Elastic moduli
Molecular weight
Viscosity
Heating
X ray diffraction

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Madbouly, S., Otaigbe, J. U., Nanda, A. K., & Wicks, D. A. (2009). Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films. In Nanotechnology Applications in Coatings (pp. 89-107). (ACS Symposium Series; Vol. 1008). American Chemical Society. https://doi.org/10.1021/bk-2009-1008.ch006
Madbouly, Samy ; Otaigbe, Joshua U. ; Nanda, Ajaya K. ; Wicks, Douglas A. / Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films. Nanotechnology Applications in Coatings. American Chemical Society, 2009. pp. 89-107 (ACS Symposium Series).
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abstract = "Two series of nanostructured polyurethane with reactive diamino-polyhedral oligomeric silsesquioxanes (POSS) hybrid were synthesized via environmentally-friendly aqueous dispersions through two different methods, namely, acetone and prepolymer processes. The resulting PU/POSS nanocomposites prepared via acetone process did show more phase homogeneity compared with that of prepolymer process as confirmed by wide angle X-ray diffraction patterns of the cast films. Rheological behavior of these important classes of materials has been investigated as a function of POSS concentration and preparation method over a wide range of shear frequency and temperature. The complex viscosity and the elastic storage modulus of PU and PU/POSS nanocomposites prepared via prepolymer process were much higher than that of acetone process at a constant temperature due to the difference in the molecular weight and percentage of internal surfactant. For the PU/POSS nanocomposites prepared by the two different methods, the rheological behavior in the melt confirmed the existence of microphase separation of the hard and soft segments. The value of the microphase separation temperature (TMPS) was found to be concentration independent when the POSS concentration is ≤6wt{\%}. For 10 wt{\%} POSS the TMPS shifted by 20 °C to a higher temperature. The effect of POSS on the value of TMPS for prepolymer. samples is considerably different. The value of TMPS of pure PU shifted from 165 °C to 178 °C for all PU/POSS samples regardless of the concentration of POSS as measured from the dynamic heating ramps (2 °C/min heating rate at ω = 1 rad/s) of G'. The shift of TMPS to high temperature in both cases (acetone and prepolymer processes) is attributed to the large surface areas of POSS that produces relatively large interaction zones with the PU hard and soft segments.",
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Madbouly, S, Otaigbe, JU, Nanda, AK & Wicks, DA 2009, Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films. in Nanotechnology Applications in Coatings. ACS Symposium Series, vol. 1008, American Chemical Society, pp. 89-107. https://doi.org/10.1021/bk-2009-1008.ch006

Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films. / Madbouly, Samy; Otaigbe, Joshua U.; Nanda, Ajaya K.; Wicks, Douglas A.

Nanotechnology Applications in Coatings. American Chemical Society, 2009. p. 89-107 (ACS Symposium Series; Vol. 1008).

Research output: Chapter in Book/Report/Conference proceedingConference contribution

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T1 - Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films

AU - Madbouly, Samy

AU - Otaigbe, Joshua U.

AU - Nanda, Ajaya K.

AU - Wicks, Douglas A.

PY - 2009/6/12

Y1 - 2009/6/12

N2 - Two series of nanostructured polyurethane with reactive diamino-polyhedral oligomeric silsesquioxanes (POSS) hybrid were synthesized via environmentally-friendly aqueous dispersions through two different methods, namely, acetone and prepolymer processes. The resulting PU/POSS nanocomposites prepared via acetone process did show more phase homogeneity compared with that of prepolymer process as confirmed by wide angle X-ray diffraction patterns of the cast films. Rheological behavior of these important classes of materials has been investigated as a function of POSS concentration and preparation method over a wide range of shear frequency and temperature. The complex viscosity and the elastic storage modulus of PU and PU/POSS nanocomposites prepared via prepolymer process were much higher than that of acetone process at a constant temperature due to the difference in the molecular weight and percentage of internal surfactant. For the PU/POSS nanocomposites prepared by the two different methods, the rheological behavior in the melt confirmed the existence of microphase separation of the hard and soft segments. The value of the microphase separation temperature (TMPS) was found to be concentration independent when the POSS concentration is ≤6wt%. For 10 wt% POSS the TMPS shifted by 20 °C to a higher temperature. The effect of POSS on the value of TMPS for prepolymer. samples is considerably different. The value of TMPS of pure PU shifted from 165 °C to 178 °C for all PU/POSS samples regardless of the concentration of POSS as measured from the dynamic heating ramps (2 °C/min heating rate at ω = 1 rad/s) of G'. The shift of TMPS to high temperature in both cases (acetone and prepolymer processes) is attributed to the large surface areas of POSS that produces relatively large interaction zones with the PU hard and soft segments.

AB - Two series of nanostructured polyurethane with reactive diamino-polyhedral oligomeric silsesquioxanes (POSS) hybrid were synthesized via environmentally-friendly aqueous dispersions through two different methods, namely, acetone and prepolymer processes. The resulting PU/POSS nanocomposites prepared via acetone process did show more phase homogeneity compared with that of prepolymer process as confirmed by wide angle X-ray diffraction patterns of the cast films. Rheological behavior of these important classes of materials has been investigated as a function of POSS concentration and preparation method over a wide range of shear frequency and temperature. The complex viscosity and the elastic storage modulus of PU and PU/POSS nanocomposites prepared via prepolymer process were much higher than that of acetone process at a constant temperature due to the difference in the molecular weight and percentage of internal surfactant. For the PU/POSS nanocomposites prepared by the two different methods, the rheological behavior in the melt confirmed the existence of microphase separation of the hard and soft segments. The value of the microphase separation temperature (TMPS) was found to be concentration independent when the POSS concentration is ≤6wt%. For 10 wt% POSS the TMPS shifted by 20 °C to a higher temperature. The effect of POSS on the value of TMPS for prepolymer. samples is considerably different. The value of TMPS of pure PU shifted from 165 °C to 178 °C for all PU/POSS samples regardless of the concentration of POSS as measured from the dynamic heating ramps (2 °C/min heating rate at ω = 1 rad/s) of G'. The shift of TMPS to high temperature in both cases (acetone and prepolymer processes) is attributed to the large surface areas of POSS that produces relatively large interaction zones with the PU hard and soft segments.

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Madbouly S, Otaigbe JU, Nanda AK, Wicks DA. Effect of method of preparation on the rheological behavior of polyurethane-polyhedral oligomeric silsesquioxanes nanostructured hybrid films. In Nanotechnology Applications in Coatings. American Chemical Society. 2009. p. 89-107. (ACS Symposium Series). https://doi.org/10.1021/bk-2009-1008.ch006