Dilatational rheology of water-in-diesel fuel interfaces: Effect of surfactant concentration and bulk-to-interface exchange

Shweta Narayan, Sourav Barman, Davis B. Moravec, Brad G. Hauser, Andrew J. Dallas, Joseph A. Zasadzinski, Cari S. Dutcher

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3 Scopus citations


Micrometer-sized water droplets dispersed in diesel fuel are stabilized by the fuel's surface-active additives, such as mono-olein and poly(isobutylene)succinimide (PIBSI), making the droplets challenging for coalescing filters to separate. Dynamic material properties found from interfacial rheology are known to influence the behavior of microscale droplets in coalescing filters. In this work, we study the interfacial dilatational properties of water-in-fuel interfaces laden with mono-olein and PIBSI, with a fuel phase of clay-treated ultra-low sulphur diesel (CT ULSD). First, the dynamic interfacial tension (IFT) is measured using pendant drop tensiometry, and a curvature-dependent form of the Ward and Tordai diffusion equation is applied for extracting the diffusivity of the surfactants. Additionally, Langmuir kinetics are applied to the dynamic IFT results to obtain the maximum surface concentration (Γ∞) and ratio of adsorption to desorption rate constants (κ). We then use a capillary pressure microtensiometer to measure the interfacial dilatational modulus, and further extract the characteristic frequency of surfactant exchange (ω0) by fitting a model assuming diffusive exchange between the interface and bulk. In this measurement, 50-100 μm diameter water droplets are pinned at the tip of a glass capillary in contact with the surfactant-containing fuel phase, and small amplitude capillary pressure oscillations over a range of frequencies from 0.45-20 rad s-1 are applied to the interface, inducing changes in interfacial tension and area to yield the dilatational modulus, E*(ω). Over the range of concentrations studied, the dilatational modulus of CT ULSD with either mono-olein or PIBSI increases with a decrease in bulk concentration and plateaus at the lowest concentrations of mono-olein. Characteristic frequency (ω0) values extracted from the fit are compared with those calculated using equilibrium surfactant parameters (κ and Γ∞) derived from pendant drop tensiometry, and good agreement is found between these values. Importantly, the results imply that diffusive exchange models based on the equilibrium relationships between surfactant concentration and interfacial tension can be used to infer the dynamic dilatational behavior of complex surfactant systems, such as the water-in-diesel fuel interfaces in this study.

Original languageEnglish (US)
Pages (from-to)4751-4765
Number of pages15
JournalSoft Matter
Issue number18
StatePublished - May 14 2021

Bibliographical note

Funding Information:
The authors would like to thank Michael L. Davidson and Professor Lynn M. Walker for helpful discussions and assistance with the setup. The authors also acknowledge Dr. Wieslaw Suszynski at the Coating Process Fundamentals Lab in the Department of Chemical Engineering and Materials Science at the University of Minnesota. The authors would also like to thank Dr. Yun Chen for helpful discussions. This work was primarily funded by Donaldson Company (Bloomington, MN), including support for S. N., and carried out in the Department of Mechanical Engineering and the Department of Chemical Engineering and Materials Science at the University of Minnesota-Twin Cities, College of Science and Engineering. S. B. was funded by the National Heart, Lung, & Blood Institute of the National Institutes of Health under grant numbers R01HL135065 and R01HL51177 and the National Science Foundation under Grant CBET 170378. None of the authors have recent, present, or anticipated financial gain from this work.

Publisher Copyright:
© The Royal Society of Chemistry.

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  • Journal Article


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