Water-in-Oil Microstructures Formed by Marine Oil Dispersants in a Model Crude Oil

David A. Riehm, David J. Rokke, Alon V McCormick

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

DOSS (dioctyl sodium sulfosuccinate), Tween 80, and Span 80, surfactants commonly used in marine crude oil spill dispersants, have been mixed into a model oil at a total surfactant concentration of 2 wt %, typical for dispersant-treated oil slicks. These surfactant-oil blends also contained 0.5-1.5 wt % synthetic seawater to enable formation of water-in-oil (W/O) microstructures. Trends in dynamic oil-seawater interfacial tension (IFT) as a function of surfactant blend composition are similar to those observed in prior work for crude oil treated with similar blends of these surfactants. In particular, Span 80-rich surfactant blends exhibit much slower initial dynamic IFT decline than DOSS-rich surfactant blends in both model oil and crude oil, and surfactant blends containing 50 wt % Tween 80 and a DOSS:Span 80 ratio near 1:1 produce ultralow IFT in the model oil (<10-4 mN/m) just as similar surfactant blends do in crude oil. At all DOSS:Span 80 ratios, surfactant blends containing 50 wt % Tween 80 form clear solutions with seawater in the model oil. Cryo-transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) show that these solutions contain spherical W/O microstructures, the size and dispersity of which vary with surfactant blend composition and surfactant:seawater molar ratio. Span 80-rich microstructures exhibit high polydispersity index (PDI > 0.2) and large diameters (≥100 nm), whereas DOSS-rich microstructures exhibit smaller diameters (20-40 nm) and low polydispersity index (PDI < 0.1), indicating a narrow microstructure size distribution. The smaller diameters of DOSS-rich microstructures, as well as the fact that DOSS molecules, being oil-soluble, can diffuse to a bulk oil-water interface as monomers much faster than any of these microstructures, may explain why DOSS-rich blends adsorb to the oil-water interface more quickly than Span 80-rich blends, a phenomenon which has been linked in prior work to the higher effectiveness of DOSS-rich Tween/Span/DOSS-based oil dispersants.

Original languageEnglish (US)
Pages (from-to)3954-3962
Number of pages9
JournalLangmuir
Volume32
Issue number16
DOIs
StatePublished - May 3 2016

Bibliographical note

Funding Information:
This work was supported in part by a grant from the Gulf of Mexico Research Initiative (GoMRI) through the Consortium for the Molecular Engineering of Dispersants (CMEDS) and in part by the Nanostructured Materials and Processes Program of the IPRIME industrial consortium at the University of Minnesota. Data are publicly available through the Gulf of Mexico Research Initiative Information & Data Cooperative (GRIIDC) at https://data.gulfresearchinitiative. org (doi: 10.7266/N7VT1Q2D). Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program.

Publisher Copyright:
© 2016 American Chemical Society.

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