Gelation and critical phenomena

For the critical exponents near the sol-gel phase transition, classical theories like those of Flory and Stockmayer predict one set of exponents, whereas scaling theories based on lattice percolation predict different exponents. The two groups of theories differ in their treatment of intramolecular loops, space dimensionality and excluded volume effects. In this article, the differences and similarities between the results of the competing theories are reviewed. For example, a gel fraction like (p-pc)β vanishes for conversion factors p very close to the gel point pc, the weight average molecular weight diverges as (pc-p)−γ for p very slightly below pc, and the radius of macromolecules at the gel point p=pc varies as the ϱ-th power of the number of monomers in that macromolecule. Classical theories predict β=γ=1 and ϱ=1/4 whereas the percolation theory gives β ≃ 0.45, γ ≃ 1.74 and ϱ ≃ 0.40. We also generalize the percolation concept to include interaction effects and concentration fluctuations; in this case the sol-gel phase transition may be connected with a phase separation.

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