Non-equilibrium theory of arrested spinodal decomposition

Abstract

The non-equilibrium self-consistent generalized Langevin equation theory of irreversible relaxation [P. E. Ramŕez-González and M. Medina-Noyola, Phys. Rev. E 82, 061503 (2010); 82, 061504 (2010)] is applied to the description of the non-equilibrium processes involved in the spinodal decomposition of suddenly and deeply quenched simple liquids. For model liquids with hard-sphere plus attractive (Yukawa or square well) pair potential, the theory predicts that the spinodal curve, besides being the threshold of the thermodynamic stability of homogeneous states, is also the borderline between the regions of ergodic and non-ergodic homogeneous states. It also predicts that the high-density liquid-glass transition line, whose high-temperature limit corresponds to the well-known hard-sphere glass transition, at lower temperature intersects the spinodal curve and continues inside the spinodal region as a glass-glass transition line. Within the region bounded from below by this low-temperature glass-glass transition and from above by the spinodal dynamic arrest line, we can recognize two distinct domains with qualitatively different temperature dependence of various physical properties. We interpret these two domains as corresponding to full gas-liquid phase separation conditions and to the formation of physical gels by arrested spinodal decomposition. The resulting theoretical scenario is consistent with the corresponding experimental observations in a specific colloidal model system.

Kinetics of liquid–liquid phase separation in protein solutions exhibiting LCST phase behavior studied by time-resolved USAXS and VSANS

“…This later stage behavior could be due to migration and coalescence of minority phase droplets through a glassy phase 60 or rearrangements of the majority phase due to mechanical stress relaxation. 57,62 Olais-Govea et al have recently proposed a non-equilibrium theory of arrested spinodal decomposition, 63 which reproduces the main experimental observations in colloid and protein systems. 9,10,12,64 In their framework, the dynamic arrest of a solution undergoing LLPS can lead to three scenarios, depending on the quench depth.…”

Nonequilibrium kinetics of the transformation of liquids into physical gels

“…This maximum size ξ a (T ) depends on the depth T of the quench, and as discussed in Ref. [27], it is finite for T smaller than the spinodal temperature T s , but diverges when T reaches T s from below. Thus, although for T < T s the emer-gence of dynamic arrest cancels the possibility of longtime asymptotic divergence of ξ(t), before its saturation ξ(t) appears to follow an apparent algebraic functional form ξ(t) ∝ t α within a limited time-interval, with an exponent α that decreases with the depth of the quench, attaining its maximum value when T approaches T s .…”

Equilibration and Aging of Liquids of Non-Spherically Interacting Particles

“…(2.1)-(2.6) of Ref. [25]). Although the physical meaning of these two sets of equations is totally different, their mathematical similarity allows us to implement the same method of solution described in Ref.…”

“…(39)- (45) describe coupled translational and rotational dynamics, whose particular case l = 0 coincide with the radially-symmetric case, already discussed in detail in Refs. [23,25,27]. Thus, the most novel features are to be expected in the non-equilibrium rotational dynamics illustrated in this exercise.…”

“…In Refs. [25] and [26] it has been shown that the NE-SCGLE theory provides precisely this missing unifying theoretical framework.…”