Melting of solvents nanoconfined by polymers and networks

Qin Qian, Gregory B. Mckenna

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


Thermoporosimetry is becoming increasingly used to study nanoscale heterogeneity and structure in polymer networks. The starting point for thermoporosimetry is the Gibbs-Thomson (GT) relation between melting point and inverse crystal size. In the case of polymers, the Flory-Huggins (FH) model also predicts that there is a depression of the melting point because of the mixing of the polymer and the solvent molecules, and this needs to be taken into account. The first step in analysis of size heterogeneity using thermoporosimetry and the GT equation requires that there be quantitative agreement between the FH theory and the melting points of the diluent in the uncrosslinked rubber. We find that both benzene and hexadecane exhibit excessive melting point depressions in uncrosslinked polyisoprene. This may imply that the uncrosslinked polymer is divided into 'nanoheterogeneities'. We further find that the heat of fusion decreases as polymer concentration increases for the benzene, but not for the hexadecane. Finally, we compare pore size distributions obtained for a crosslinked polyisoprene as determined from the melting behavior of n-hexadecane as a diluent, using different references for how the uncrosslinked polymer behaves. While number average distribution is not very different between the different analyses, the weight average distribution is.

Original languageEnglish
Pages (from-to)3475-3486
Number of pages12
JournalJournal of Polymer Science, Part B: Polymer Physics
Issue number24
StatePublished - Dec 15 2006


  • Flory-Huggins
  • Gibbs-Thomson
  • Heterogeneity
  • Nanocrystals
  • Thermoporosimetry


Dive into the research topics of 'Melting of solvents nanoconfined by polymers and networks'. Together they form a unique fingerprint.

Cite this