Renormalization-group approach to the vulcanization transition

Abstract

The vulcanization transition-the cross-link-density-controlled equilibrium phase transition from the liquid to the amorphous solid state-is explored analytically from a renormalization-group perspective. The analysis centers on a minimal model which has previously been shown to yield a rich and informative picture of vulcanized matter at the mean-field level, including a connection with mean-field percolation theory (i.e., random graph theory). This minimal model accounts for both the thermal motion of the constituents and the quenched random constraints imposed on their motion by the cross-links, as well as particle-particle repulsion which suppresses density fluctuations and plays a pivotal role in determining the symmetry structure (and hence properties) of the model. A correlation function involving fluctuations of the amorphous solid order parameter, the behavior of which signals the vulcanization transition, is examined, its physical meaning is elucidated, and the associated susceptibility is constructed and analyzed. A Ginzburg criterion for the width (in cross-link density) of the critical region is derived and is found to be consistent with a prediction due to de Gennes. Inter alia, this criterion indicates that the upper critical dimension for the vulcanization transition is 6. Certain universal critical exponents characterizing the vulcanization transition are computed, to lowest nontrivial order, within the framework of an expansion around the upper critical dimension. This expansion shows that the connection between vulcanization and percolation extends beyond mean-field theory, surviving the incorporation of fluctuations in the sense that pairs of physically analogous quantities (one percolation related and one vulcanization related) are found to be governed by identical critical exponents, at least to first order in the departure from the upper critical dimension (and presumably beyond). The relationship between the present approach to vulcanized matter and other approaches, such as those based on gelation-percolation ideas, is explored in the light of this connection. To conclude, some expectations for how the vulcanization transition is realized in two dimensions, developed with H. E. Castillo, are discussed.