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In principle, there can be additional macrophase separation inside the polymer-rich regions (for example, between cross-linking acrylate matrix and PCL chains). This type of phase separation, however, would start at a later time than the solvent-polymer one and would be substantially slowed down by the vitrification of polymer-rich domains. Thus, PCL-rich and PMMA-rich domains would probably grow only within nanometer range (< 100 nm), while the polymer - solvent phase separation would be primarily responsible for the structures developing on the micron length scale.
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On the basis of thermodynamic considerations alone (Figure 2b), one could conjecture that cascading phase separation could occur even without cross-linking (driven purely by solvent evaporation). In that case, though, it is more likely that coalescence of polymer-rich domains would preempt their vitrification, and the multiscale pattern would not be observed. A comprehensive kinetic model combining the description of PIPS and solvent evaporation would be required to determine which conditions are necessary for the formation of multiscale nodules. To our knowledge, no such model exists at present time.
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33745741411
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note
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In a similar cross-linking acrylate/PCL/BuAc system without gold particles, no nodules or multiscale self-similar structures were seen (films were either translucent or milky white, indicating some degree of macrophase separation). It is likely, therefore, that particles act as nuclei to start the phase separation and speed up its kinetics. Thus, in a system without particles, vitrification arrests the phase separation relatively early; in the presence of particles, vitrification stops the process only at its relatively late stage, with primary, secondary, and even tertiary phase separation well under way.
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Our estimates of the dielectric constant of the nodule assume that dielectric properties inside the nodule remain constant or vary smoothly as a function of position. Further investigation is needed to confirm or disprove this assumption.
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