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.
ABSTRACT
Interest in the protein folding problem has motivated a wide range of theoretical and experimental studies of the kinetics of the collapse of flexible homopolymers. In this paper, a phenomenological model is proposed for the kinetics of the early stages of homopolymer collapse following a quench from temperatures above to below the straight theta temperature. In the first stage, nascent droplets of the dense phase are formed, with little effect on the configurations of the bridges that join them. The droplets then grow by accreting monomers from the bridges, thus causing the bridges to stretch. During these two stages, the overall dimensions of the chain decrease only weakly. Further growth of the droplets is accomplished by the shortening of the bridges, which causes the shrinking of the overall dimensions of the chain. The characteristic times of the three stages scale as N0, N(1/5), and N(6/5), respectively, where N is the degree of polymerization of the chain.
ABSTRACT
Randomly cross-linked macromolecules undergo a liquid to amorphous-solid phase transition at a critical cross-link concentration. This transition has two main signatures: the random localization of a fraction of the monomers and the emergence of a nonzero static shear modulus. In this paper, a semimicroscopic statistical mechanical theory of the elastic properties of the amorphous solid state is developed. This theory takes into account both quenched disorder and thermal fluctuations, and allows for the direct computation of the free energy change of the sample due to a given macroscopic shear strain. This leads to an unambiguous determination of the static shear modulus. At the level of mean field theory, it is found (i) that the shear modulus grows continuously from zero at the transition, and does so with the classical exponent, i.e., with the third power of the excess cross-link density and, quite surprisingly, (ii) that near the transition the external stresses do not spoil the spherical symmetry of the localization clouds of the particles.
