Abstract
We present simulation results and an explanatory theory on how antagonistic salts affect the spinodal decomposition of binary fluid mixtures. We find that spinodal decomposition is arrested and complex structures form only when electrostatic ion-ion interactions are small. In this case, the fluid and ion concentrations couple and the charge field can be approximated as a polynomial function of the relative fluid concentrations alone. When the solvation energy associated with transferring an ion from one fluid phase to the other is of the order of a few k B T, the coupled fluid and charge fields evolve according to the Ohta-Kawasaki free energy functional. This allows us to accurately predict structure sizes and reduce the parameter space to two dimensionless numbers. The lamellar structures induced by the presence of the antagonistic salt in our simulations exhibit a high degree of nematic ordering and the growth of ordered domains over time follows a power law. This power law carries a time exponent proportional to the salt concentration. We qualitatively reproduce and interpret neutron scattering data from previous experiments of similar systems. The dissolution of structures at high salt concentrations observed in these experiments agrees with our simulations, and we explain it as the result of a vanishing surface tension due to electrostatic contributions. We conclude by presenting 3D results showing the same morphologies as predicted by the Ohta-Kawasaki model as a function of volume fraction and suggesting that our findings from 2D systems remain valid in 3D.
| Original language | English |
|---|---|
| Article number | 064912 |
| Number of pages | 15 |
| Journal | Journal of Chemical Physics |
| Volume | 150 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - 14 Feb 2019 |
Funding
The authors acknowledge financial support by the Deutsche Forschungsgemeinschaft (DFG) within the Cluster of Excellence “Engineering of Advanced Materials,” the Initiative and Networking Fund of the Helmholtz Association, and the Bavarian Ministry of Economic Affairs and Media, Energy, and Technology for the joint projects in the framework of the Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (No. IEK-11) of Forschungszentrum Jülich. We thank the Jülich Supercomputing Centre and the High Performance Computing Centre, Stuttgart, for the technical support and the allocated CPU time.
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