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Dynamics in water-AOT-n-decane microemulsions with poly(ethylene glycol) probed by dielectric spectroscopy

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Abstract

Water in oil microemulsions, consisting of water, AOT and n-decane, have been used as a model system to investigate the influence of the water soluble polymer PEO on the dynamical behavior of the system. Therefore dielectric relaxation spectroscopy and conductivity, extracted from dielectric spectroscopy, measurements in a wide frequency and temperature range have been applied. The pure microemulsion displays the known phenomenon of percolation that manifests in a steep increase of conductivity at the percolation temperature \(T_\text{P}\). The percolation temperature has been found to be strongly dependent on droplet volume fraction and droplet size. The latter additionally shows that percolation temperature and surfactant film rigidity are proportional. Far from percolation water-AOT-n-decane microemulsions display two dielectric relaxations. The slower one has a relaxation time of \(\tau \approx 3\cdot 10^{-6}~\text{s}\) and can be related to an interfacial polarization at the interface of the water core and the AOT shell (core relaxation). The faster one has a relaxation time of \(\tau \approx 10^{-9}~\text{s}\) and can be related to the ions in the AOT shell(shell or cluster relaxation). While the first is mainly untouched by the percolation phenomenon, the latter undergoes a slowdown and an increase of relaxation strength, both over about two decades, on approaching the percolation transition. Addition of PEO tremendously shifts the percolation transition to higher temperatures, due to adsorption at the AOT layer which leads to an increase in rigidity. Furthermore a lower phase boundary temperature evolves, below which the microemulsion phase separates. The conductivity of the microemulsion is also slightly increased with polymer. The effect on the dielectric properties is only small, where dielectric relaxation times are reduced by the polymer, while only the relaxation strength of the faster relaxation is influenced and also decreases with polymer. The decreased relaxation time of core relaxation can be either due to changes in the core to shell volume ratio or an increased conductivity of the water core. The decrease in relaxation time and strength of the shell relaxation suggest that the ion mobility in the shell increase, while the dipole moment is reduced. Additionally we applied a cluster relaxation model proposed by Cametti et al. (Phys Rev Lett 75(3):569, 1995) and Bordi et al. (J Phys, Condens Matter 8:A19, 1996) to estimate the cluster size evolution.

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Authors and Affiliations

  1. Institut für Festkörperphysik, Technische Universität Darmstadt, Hochschulstrasse 8, 64289, Darmstadt, Germany

    Robert Wipf, Sebastian Jaksch & Bernd Stühn

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  1. Robert Wipf
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  2. Sebastian Jaksch
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  3. Bernd Stühn
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Correspondence to Robert Wipf.

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Wipf, R., Jaksch, S. & Stühn, B. Dynamics in water-AOT-n-decane microemulsions with poly(ethylene glycol) probed by dielectric spectroscopy. Colloid Polym Sci 288, 589–601 (2010). https://doi.org/10.1007/s00396-010-2199-5

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