Concentration-induced spinodal decomposition

Spinodal decomposition is the second mechanism of liquid-liquid phase separation. Here, the solution spontaneously separates into interconnected regions of high and low polymer concentration with intertwined networks. The authors report that for chemically Induced systems (polymer/solvent/nonsolvent), the nucleation and growth kinetics are much too rapid to permit spinodal decomposition. 

A homogeneous mixture quenched from a stable phase into a thermodynamically unstable state within a phase diagram develops into an inhomogeneous system. Spinodal decomposition (SD) is induced by the instability of an order parameter, which is usually concentration [101]. In the early stages, the SD is interpreted within the framework of the Cahn theory for an isotropic SD [102,103]. In contrast, in the late stages, the SD is governed by diffusion or hydrodynamic processes and exhibits slow coarsening [104]. There are two types of order parameters that describe a system. One is a conserved order parameter such as concentration of binary mixtures. The other is a non-conserved order parameter such as the polarization of a ferroelectric... 

A direct link between theoretical and experimental work on depletion-induced phase separation of a colloidal dispersion due to non-adsorbing polymers was made by De Hek and Vrij [56, 109]. They mixed sterically stabilized silica dispersions with polystyrene in cyclohexane and measured the limiting polymer concentration (phase separation threshold). Commonly, one uses the binodal or spinodal as experimental phase boundary. A binodal denotes the condition (compositions, temperature) at which two or more distinct phases coexist, see Chap. 3. A tie-line connects two binodal points. A spinodal corresponds to the boundary of absolute instability of a system to decomposition. At or beyond the spinodal boundary infinitesimally small fluctuations in composition will lead to phase separation. De Hek and Vrij [56] used the pair potential (1.21) to estimate the stability of colloidal spheres in a polymer solution by calculating the second osmotic virial coefhcient B2 ... 

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