Positron annihilation lifetime spectroscopy and large molecule diffusion into a polyurethane matrix

S. A. Ward, R. A. Pethrick

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Positron annihilation lifetime spectroscopy (PALS) measurements are reported on a three polyurethane (PU) materials created by the reaction of polymeric toluene diisocyanate with either ethylene glycol, 1,10-decanediol, or a silicone containing diol. Dynamical mechanical analysis indicated that the glass transition temperature of the PU’s were respectively 118, 95, and −40 °C. Whereas the ethylene glycol and 1,10-decanediol materials exhibited a glass–rubber transition, the silicone containing PU showed rubber characteristics over the temperature 0–180 °C. The PALS measurements on the silicone-based PU’s showed significantly larger voids dimensions than the other PU’s. Void collapse is observed to occur on the time scale of the oPs measurements. The permeation of dioctyl phthalate, 2-ethylhexylbenzyl phthalate, nonylphenol ethoxylate, isopropyl myristate, and oleic acid into a polyurethane matrix was measured gravimetrically. The silicone containing material at low temperatures exhibits relative simple permeation behavior however deviations from simple Fickian-type behavior are observed at higher temperature. Surprisingly, the ethylene glycol and 1,10-decanediol exhibited no significant absorption over a period of 5 months with the exception being nonylphenol ethoxylate. A comparison of the void sizes with the molecular dimensions for the lowest energy conformations of the permeants obtained using theoretical calculations indicate that for the silicone-based material the diffusion cross section for the permeants is larger than the available void size. The permeation process is considered to occur by a reptation type of motion of the permeants into channels created by the phase segregation of the flexible segments.
LanguageEnglish
Pages8479-8486
Number of pages8
JournalMacromolecules
Volume44
Issue number21
DOIs
Publication statusPublished - 2011

Fingerprint

Polyurethanes
Positron annihilation
Silicones
Spectroscopy
Molecules
Ethylene Glycol
Ethylene glycol
Permeation
Rubber
Diethylhexyl Phthalate
Toluene 2,4-Diisocyanate
Oleic acid
Oleic Acid
Temperature
Toluene
Conformations
Glass
1,10-decanediol

Keywords

  • membranes
  • starvation kinetics
  • free-volume
  • polymers
  • chain entanglement
  • probe
  • water-vapor permeability

Cite this

Ward, S. A. ; Pethrick, R. A. / Positron annihilation lifetime spectroscopy and large molecule diffusion into a polyurethane matrix. In: Macromolecules. 2011 ; Vol. 44, No. 21. pp. 8479-8486.
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Positron annihilation lifetime spectroscopy and large molecule diffusion into a polyurethane matrix. / Ward, S. A.; Pethrick, R. A.

In: Macromolecules, Vol. 44, No. 21, 2011, p. 8479-8486.

Research output: Contribution to journalArticle

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