Surfactant-mediated control of colloid pattern assembly and attachment strength in evaporating droplets

Verónica L Morales, Jean-Yves Parlange, Mingming Wu, Francisco J Pérez-Reche, Wei Zhang, Wenjing Sang, Tammo S Steenhuis

Research output: Contribution to journalArticle

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Abstract

This study demonstrates that the pattern assembly and attachment strength of colloids in an evaporating sessile droplet resting on a smooth substrate can be controlled by adding nonionic solutes (surfactant) to the solution. As expected, increasing the surfactant concentration leads to a decrease in initial surface tension of the drop, s(0). For the range of initial surface tensions investigated (39-72 mN m(-1)), three distinct deposition patterns were produced: amorphous stains (s(0) = 63-72 mN m(-1)), coffee-ring stains (s(0) = 48-53 mN m(-1)), and concentric rings (s(0) = 39-45 mN m(-1)). A flow-displacement system was used to measure the attachment strength of the dried colloids. Characteristic drying regimes associated with the three unique pattern formations are attributed to abrupt transitions of contact line dynamics during evaporation. The first transition from slipping- to pinned-contact line was found to be a direct result of the competition between mechanical instability of the droplet and the friction generated by pinned colloids at the contact line. The second transition from pinned- to recurrent-stick-rip-slip-contact line was caused by repeated liquid film rupturing from evaporation-intensified surfactant concentration. Data from flow-displacement tests indicate that attachment strength of dried particles is strongest for amorphous stains (lowest surfactant concentration) and weakest for concentric rings (highest surfactant concentration). The mechanism behind these observations was ascribed to the formation and adsorption of micelles onto colloid and substrate surfaces as the droplet solution evaporates. The range of attachment forces observed between the colloids and the solid substrate were well captured by extended-DLVO interactions accounting for van der Waals attraction, electric double layer repulsion, and micelle-protrusion repulsion. Both empirical and theoretical results suggest that an increasingly dense layer of adsorbed micellar-protrusions on colloid and substrate surfaces acts as a physical barrier that hinders strong van der Waals attractive interactions at close proximity. Thereby, colloid stains dried at higher surfactant concentrations are more easily detached from the substrate when dislodging forces are applied than stains dried at lower surfactant concentrations.
Original languageEnglish
Pages (from-to)1831-1840
Number of pages10
JournalLangmuir
Volume29
Issue number6
DOIs
Publication statusPublished - 17 Jan 2013

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Colloids
Surface-Active Agents
attachment
colloids
Surface active agents
assembly
surfactants
Coloring Agents
Substrates
Micelles
Surface tension
rings
micelles
interfacial tension
Evaporation
evaporation
coffee
rupturing
Coffee
Stick-slip

Cite this

Morales, V. L., Parlange, J-Y., Wu, M., Pérez-Reche, F. J., Zhang, W., Sang, W., & Steenhuis, T. S. (2013). Surfactant-mediated control of colloid pattern assembly and attachment strength in evaporating droplets. Langmuir, 29(6), 1831-1840. https://doi.org/10.1021/la304685b

Surfactant-mediated control of colloid pattern assembly and attachment strength in evaporating droplets. / Morales, Verónica L; Parlange, Jean-Yves; Wu, Mingming; Pérez-Reche, Francisco J; Zhang, Wei; Sang, Wenjing; Steenhuis, Tammo S.

In: Langmuir, Vol. 29, No. 6, 17.01.2013, p. 1831-1840.

Research output: Contribution to journalArticle

Morales, VL, Parlange, J-Y, Wu, M, Pérez-Reche, FJ, Zhang, W, Sang, W & Steenhuis, TS 2013, 'Surfactant-mediated control of colloid pattern assembly and attachment strength in evaporating droplets', Langmuir, vol. 29, no. 6, pp. 1831-1840. https://doi.org/10.1021/la304685b
Morales, Verónica L ; Parlange, Jean-Yves ; Wu, Mingming ; Pérez-Reche, Francisco J ; Zhang, Wei ; Sang, Wenjing ; Steenhuis, Tammo S. / Surfactant-mediated control of colloid pattern assembly and attachment strength in evaporating droplets. In: Langmuir. 2013 ; Vol. 29, No. 6. pp. 1831-1840.
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AB - This study demonstrates that the pattern assembly and attachment strength of colloids in an evaporating sessile droplet resting on a smooth substrate can be controlled by adding nonionic solutes (surfactant) to the solution. As expected, increasing the surfactant concentration leads to a decrease in initial surface tension of the drop, s(0). For the range of initial surface tensions investigated (39-72 mN m(-1)), three distinct deposition patterns were produced: amorphous stains (s(0) = 63-72 mN m(-1)), coffee-ring stains (s(0) = 48-53 mN m(-1)), and concentric rings (s(0) = 39-45 mN m(-1)). A flow-displacement system was used to measure the attachment strength of the dried colloids. Characteristic drying regimes associated with the three unique pattern formations are attributed to abrupt transitions of contact line dynamics during evaporation. The first transition from slipping- to pinned-contact line was found to be a direct result of the competition between mechanical instability of the droplet and the friction generated by pinned colloids at the contact line. The second transition from pinned- to recurrent-stick-rip-slip-contact line was caused by repeated liquid film rupturing from evaporation-intensified surfactant concentration. Data from flow-displacement tests indicate that attachment strength of dried particles is strongest for amorphous stains (lowest surfactant concentration) and weakest for concentric rings (highest surfactant concentration). The mechanism behind these observations was ascribed to the formation and adsorption of micelles onto colloid and substrate surfaces as the droplet solution evaporates. The range of attachment forces observed between the colloids and the solid substrate were well captured by extended-DLVO interactions accounting for van der Waals attraction, electric double layer repulsion, and micelle-protrusion repulsion. Both empirical and theoretical results suggest that an increasingly dense layer of adsorbed micellar-protrusions on colloid and substrate surfaces acts as a physical barrier that hinders strong van der Waals attractive interactions at close proximity. Thereby, colloid stains dried at higher surfactant concentrations are more easily detached from the substrate when dislodging forces are applied than stains dried at lower surfactant concentrations.

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