We consider a microscopic model of a polymer blend that is prone to phase separation. Permanent cross-links are introduced between randomly chosen pairs of monomers, drawn from the Deam-Edwards distribution. Thereby, not only density but also concentration fluctuations of the melt are quenched-in in the gel state, which emerge upon sufficient cross-linking. We derive a Landau expansion in terms of the order parameters for gelation and phase separation, and analyze it on the mean-field level, including Gaussian fluctuations. The mixed gel is characterized by thermal as well as time-persistent (glassy) concentration fluctuations. Whereas the former are independent of the preparation state, the latter reflect the concentration fluctuations at the instant of cross-linking, provided the mesh size is smaller than the correlation length of phase separation. The mixed gel becomes unstable to microphase separation upon lowering the temperature in the gel phase. Whereas the length scale of microphase separation is given by the mesh size, at least close to the transition, the emergent microstructure depends on the composition and compressibility of the melt. Hexagonal structures, as well as lamellas or random structures with a unique wavelength, can be energetically favorable.
The physical properties of blends of distinct homopolymers, cross-linked beyond the gelation point, are addressed via a Landau approach involving a pair of coupled order-parameter fields: one describing vulcanisation, the other describing local phase separation. Thermal concentration fluctuations, present at the time of cross-linking, are frozen in by cross-linking, and the structure of the resulting glassy fluctuations is analysed at the Gaussian level in various regimes, determined by the relative values of certain physical length-scales. The enhancement, due to gelation, of the stability of the blend with respect to demixing is also analysed. Beyond the corresponding stability limit, gelation prevents complete demixing, replacing it by microphase separation, which occurs up to a length-scale set by the rigidity of the network, as a simple variational scheme reveals.
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