Theory of Sol-Gel Transition in Thermoreversible Gels with due Regard for Fundamental Role of Mesoscopic Cyclization Effects. I. Thermodynamic and Structural Characteristics of Gel Phase

Details Theory of Sol-Gel Transition in Thermoreversible Gels with due Regard for Fundamental Role of Mesoscopic Cyclization Effects. I. Thermodynamic and Structural Characteristics of Gel Phase Theory of Sol-Gel Transition in Thermoreversible Gels with due Regard for Fundamental Role of Mesoscopic Cyclization Effects. I. Thermodynamic and Structural Characteristics of Gel Phase

2001-04-02

arxiv.org/abs/cond-mat/0104034v1

Macromolecules 2001, v. 34, p. 5653

Physics

Condensed Matter

Soft Condensed Matter

65 pages (including 13 pages with figures)

Scientific paper

10.1021/ma0009911

The sol-gel transition (SGT), upon which the infinite cluster (IC) of thermoreversibly bonded particles (gel fraction) appears against a background of a set of finite clusters (sol fraction), is first quantitatively considered with due regard for large and complicated (mesoscopic) cycles inevitably present in the IC. To this end we present a new approach based on a concept of the monomer identity breaking and density functional description. We strictly derive, via a proper choice of basic structural units of the gel fraction, all statements usually supposed to be just Flory (Stockmayer) assumptions. A further analysis of the IC structure reveals some new IC structural units (those involved into mesoscopic cycles) overlooked in both Flory and Stockmayer approaches and to be described by a new order parameter characteristic only of the gel phase. As a result, the SGT is found to transform from a geometric phenomenon to a genuine 1st order phase transition always followed by a phase separation into sol and gel phases. The free energy, total conversion, volume fractions of the gel fraction and dangling monomers as well as other structural quantities are calculated as functions of a reduced monomer density and analyzed for all the existing models. The Flory approach is found to be superior to the Stockmayer-Tanaka one and satisfactorily describe some of the dense weak gel properties but fail (even qualitatively) in a quite extended vicinity of the SGT.

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