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Sodium naphthenates (NaNs), found in crude oils and oil sands process-affected water (OSPW), can act as surfactants and stabilize undesirable foams and emulsions. Despite the critical impact of soap-like NaNs on the formation, properties, and stability of petroleum and OSPW foams, there is a significant lack of studies that characterize foam film drainage, motivating this study. Here, we contrast the drainage of aqueous foam films formulated with NaN with foams containing sodium dodecyl sulfate (SDS), a well-studied surfactant system, in the relatively low concentration regime ( c /CMC < 12.5). The foam films exhibit drainage via stratification, displaying step-wise thinning and coexisting thick–thin regions manifested as distinct shades of gray in reflected light microscopy due to thickness-dependent interference intensity. Using IDIOM (interferometry digital imaging optical microscopy) protocols that we developed, we analyze pixel-wise intensity to obtain thickness maps with high spatiotemporal resolution (thickness <1 nm, lateral ∼500 nm, time ∼10 ms). The analysis of interference intensity variations over time reveals that the aqueous foam films of both SDS and NaN possess an evolving, dynamic, and rich nanoscopic topography. The nanoscopic thickness transitions for stratifying SDS foam films are attributed to the role played by damped supramolecular oscillatory structural disjoining pressure contributed by the confinement-induced layering of spherical micelles. In comparison with SDS, we find smaller concentration-dependent step size and terminal film thickness values for NaN, implying weaker intermicellar interactions and oscillatory structural disjoining pressure with shorter decay length and periodicity.
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Surface forces and stratification in foam films formed with bile salts
Bile salts, especially in their aggregated or micellar form, play a critical role in health and medicine by solubilizing cholesterol, fat-soluble vitamins, and drugs. However, in contrast to the head–tail (HT) surfactants like sodium dodecyl sulfate (SDS), amphiphilic bile salts have an unusual steroid structure and exhibit a smaller aggregation number ( N agg < 20 molecules per micelle vs. N agg > 50 for SDS). Foam films formed by micellar solutions of typical surfactants like SDS exhibit stratification manifested as stepwise thinning and coexistence of flat thick–thin regions that differ by a step-size proportional to the intermicellar distance. We consider drainage via stratification studies as an effective and insightful probe of the strength and magnitude of intermicellar interactions and resulting supramolecular oscillatory structural (SOS) surface force contribution to disjoining pressure. However, there are neither prior reports of stratification in foam films formed with bile salt solutions nor measurements of SOS surface forces. Here we report the discovery and characterization of stratification in foam films formed by aqueous solutions of four bile salts – sodium cholate (NaC), sodium taurocholate (NaTC), sodium deoxycholate (NaDC), and sodium glycodeoxycholate (NaGDC) – that have a similar steroid nucleus, but difference in conjugation sites and the number of hydroxyl groups (3 for NaC and NaTC, 2 for NaDC and NaGC). Using IDIOM (interferometry digital imaging optical microscopy) protocols we developed recently to characterize and analyze thickness variations and transitions, we find that foam films made with bile salts exhibit fewer stepwise transitions and smaller step-size than SDS solutions. Also, we measured a lower drop in surface tension and lower magnitude of thickness-dependent disjoining pressure compared to SDS solutions. We find that the bile salts with a matched number of hydroxyl groups exhibit similar properties in tensiometry and foam film studies. We show that the stratification studies can characterize the influence of chemical structure on the magnitude and range of intermicellar interactions as well their influence on drainage and stability of foam films.
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- Award ID(s):
- 1806011
- PAR ID:
- 10286237
- Date Published:
- Journal Name:
- Molecular Systems Design & Engineering
- Volume:
- 6
- Issue:
- 7
- ISSN:
- 2058-9689
- Page Range / eLocation ID:
- 520 to 533
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0me00024h
