Viscoelasticity of reversible gelation for ionomers

Quan Chen, Chongwen Huang, R. A. Weiss, Ralph H. Colby

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Linear viscoelasticity (LVE) of low-ion-content and low-molecular-weight (nonentangled) randomly sulfonated polystyrene shows a sol-gel transition when the average number of ionic groups per chain approaches unity. This transition can be well understood by regarding the number of ionizable sites over a chain as the relevant functionality for cross-linking. For ionomers below but very close to the gel point, the LVE shows power law relaxation similar to gelation of chemical cross-linking. Nevertheless, ionomers near and beyond the gel point also show terminal relaxation not seen in chemically cross-linking systems, which is controlled by ionic dissociation. Careful analysis of the power law region of the frequency dependence of complex modulus close to the gel point shows a change in exponent from ∼1 at high frequency to ∼0.67 at low frequency, which strongly suggests a transition from mean-field to critical percolation known as the Ginzburg point. A mean-field percolation theory by Rubinstein and Semenov for gelation with effective breakup has been modified to include critical percolation close to the gel point and predicts well the observed LVE of lightly sulfonated polystyrene oligomers.

Original languageEnglish (US)
Pages (from-to)1221-1230
Number of pages10
JournalMacromolecules
Volume48
Issue number4
DOIs
StatePublished - Feb 24 2015

Fingerprint

Ionomers
Viscoelasticity
Gelation
Gels
Polystyrenes
Oligomers
Sol-gels
Molecular weight
Ions

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Chen, Quan ; Huang, Chongwen ; Weiss, R. A. ; Colby, Ralph H. / Viscoelasticity of reversible gelation for ionomers. In: Macromolecules. 2015 ; Vol. 48, No. 4. pp. 1221-1230.
@article{5d246bd9e9f346688d3c305cbce073d7,
title = "Viscoelasticity of reversible gelation for ionomers",
abstract = "Linear viscoelasticity (LVE) of low-ion-content and low-molecular-weight (nonentangled) randomly sulfonated polystyrene shows a sol-gel transition when the average number of ionic groups per chain approaches unity. This transition can be well understood by regarding the number of ionizable sites over a chain as the relevant functionality for cross-linking. For ionomers below but very close to the gel point, the LVE shows power law relaxation similar to gelation of chemical cross-linking. Nevertheless, ionomers near and beyond the gel point also show terminal relaxation not seen in chemically cross-linking systems, which is controlled by ionic dissociation. Careful analysis of the power law region of the frequency dependence of complex modulus close to the gel point shows a change in exponent from ∼1 at high frequency to ∼0.67 at low frequency, which strongly suggests a transition from mean-field to critical percolation known as the Ginzburg point. A mean-field percolation theory by Rubinstein and Semenov for gelation with effective breakup has been modified to include critical percolation close to the gel point and predicts well the observed LVE of lightly sulfonated polystyrene oligomers.",
author = "Quan Chen and Chongwen Huang and Weiss, {R. A.} and Colby, {Ralph H.}",
year = "2015",
month = "2",
day = "24",
doi = "10.1021/ma502280g",
language = "English (US)",
volume = "48",
pages = "1221--1230",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "4",

}

Viscoelasticity of reversible gelation for ionomers. / Chen, Quan; Huang, Chongwen; Weiss, R. A.; Colby, Ralph H.

In: Macromolecules, Vol. 48, No. 4, 24.02.2015, p. 1221-1230.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Viscoelasticity of reversible gelation for ionomers

AU - Chen, Quan

AU - Huang, Chongwen

AU - Weiss, R. A.

AU - Colby, Ralph H.

PY - 2015/2/24

Y1 - 2015/2/24

N2 - Linear viscoelasticity (LVE) of low-ion-content and low-molecular-weight (nonentangled) randomly sulfonated polystyrene shows a sol-gel transition when the average number of ionic groups per chain approaches unity. This transition can be well understood by regarding the number of ionizable sites over a chain as the relevant functionality for cross-linking. For ionomers below but very close to the gel point, the LVE shows power law relaxation similar to gelation of chemical cross-linking. Nevertheless, ionomers near and beyond the gel point also show terminal relaxation not seen in chemically cross-linking systems, which is controlled by ionic dissociation. Careful analysis of the power law region of the frequency dependence of complex modulus close to the gel point shows a change in exponent from ∼1 at high frequency to ∼0.67 at low frequency, which strongly suggests a transition from mean-field to critical percolation known as the Ginzburg point. A mean-field percolation theory by Rubinstein and Semenov for gelation with effective breakup has been modified to include critical percolation close to the gel point and predicts well the observed LVE of lightly sulfonated polystyrene oligomers.

AB - Linear viscoelasticity (LVE) of low-ion-content and low-molecular-weight (nonentangled) randomly sulfonated polystyrene shows a sol-gel transition when the average number of ionic groups per chain approaches unity. This transition can be well understood by regarding the number of ionizable sites over a chain as the relevant functionality for cross-linking. For ionomers below but very close to the gel point, the LVE shows power law relaxation similar to gelation of chemical cross-linking. Nevertheless, ionomers near and beyond the gel point also show terminal relaxation not seen in chemically cross-linking systems, which is controlled by ionic dissociation. Careful analysis of the power law region of the frequency dependence of complex modulus close to the gel point shows a change in exponent from ∼1 at high frequency to ∼0.67 at low frequency, which strongly suggests a transition from mean-field to critical percolation known as the Ginzburg point. A mean-field percolation theory by Rubinstein and Semenov for gelation with effective breakup has been modified to include critical percolation close to the gel point and predicts well the observed LVE of lightly sulfonated polystyrene oligomers.

UR - http://www.scopus.com/inward/record.url?scp=84923336100&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84923336100&partnerID=8YFLogxK

U2 - 10.1021/ma502280g

DO - 10.1021/ma502280g

M3 - Article

AN - SCOPUS:84923336100

VL - 48

SP - 1221

EP - 1230

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 4

ER -