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Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules
Published on: April 28, 2014
How antagonistic salts cause nematic ordering and behave like diblock copolymers
David Jung1, Nicolas Rivas1, Jens Harting1
1Forschungszentrum Jülich, Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IEK-11), Fürther Straße 248, 90429 Nürnberg, Germany.
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 kBT, 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.
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