Spinodal decomposition of a symmetric critical mixture of deuterated and protonated polymer

A nearly symmetric critical mixture (φ_c = 0.486) of perdeuterated and protonated 1,4-polybutadiene exhibiting an upper critical solution temperature T_c = 61.5 ± 1.5 °C has been quenched from the homogeneous state (≃75 °C) to various temperatures between 25 and 57.5 °C. Light scattering measurements document the subsequent spinodal decomposition process which we describe based on a four-stage model: early, intermediate, transition, and final. The early stage is accounted for by the Cahn theory, yielding initial correlation lengths and effective diffusion coefficients in quantitative agreement with mean-field predictions. Nonlinear effects mark the beginning of the intermediate stage, which exhibits a simple power-law growth of heterogeneity length L_m (t) ∼ ^tneff, but with a temperature dependent exponent n_eff. As the composition fluctuation amplitude approaches the equilibrium values, the spinodal decomposition process enters the transition stage, characterized by a decreasing interfacial thickness and an increasing L_m (t). Once the interfacial profile equilibrates, a crossover to the final stage occurs. Subsequent growth of L(t) leaves the morphology unaffected as evidenced by a universal structure factor. These findings are discussed in the context of the current theory and are compared with prior studies involving polymer-polymer and simple liquid mixtures.