On the steady-state approximation in thermal free radical frontal polymerization

C. A. Spade, V. A. Volpert*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Scopus citations


Frontal polymerization is a process in which a spatially localized reaction zone propagates into a monomer converting it into a polymer. We formulate a mathematical model of thermal free radical frontal polymerization involving a five-species reaction mechanism and justify its reduction to a four-species problem by combining the concentrations of two kinds of radicals, primary radicals and polymer radicals. We study the simplified problem both numerically and analytically, and determine such important characteristics of the process as the propagation speed of the wave, the final temperature in the system, and the spatial distributions of all the species in the wave. We perform the analyses with the steady-state approximation (SSA) and without it, and reveal where the SSA solution breaks down. Specifically, the non-SSA solution predicts full monomer conversion and an adiabatic final system temperature, whereas the SSA solution predicts a less-than-adiabatic final temperature and incomplete conversion.

Original languageEnglish (US)
Pages (from-to)641-654
Number of pages14
JournalChemical Engineering Science
Issue number3
StatePublished - Feb 2000


  • Free radical polymerization
  • Frontal polymerization
  • Steady-state assumption

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Industrial and Manufacturing Engineering


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