From aggregative adsorption to surface depletion: Aqueous systems of CnEm amphiphiles at hydrophilic surfaces
Abstract
Adsorption of a short-chain nonionic amphiphile (C6E3) at the surface of mesoporous silica glass (CPG-10) was studied by a combination of adsorption measurements and mesoscale simulations. Adsorption measurements covering a wide composition range of the C6E3 + water system show that no adsorption occurs up to the critical micelle concentration (cmc), at which a sharp increase of adsorption is observed that is attributed to ad-micelle formation at the pore walls. Intriguingly, as the concentration is increased further, the surface excess of the amphiphile begins to decrease and eventually becomes negative, which corresponds to preferential adsorption of water rather than amphiphile at high amphiphile concentrations. The existence of such a surface-azeotropic point has not previously been reported in the surfactant adsorption field. Dissipative particle dynamics (DPD) simulations were performed to reveal the structural origin of this transition from aggregative adsorption to surface depletion. Finally, the simulations indicate that this transition can be attributed to the repulsive interaction between head groups, causing amphiphilic depletion in the region around the corona of the surface micelles.
- Authors:
-
- Technische Univ. Berlin, Berlin (Germany); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Copenhagen, Copenhagen (Denmark)
- Heriot-Watt Univ., Edinburgh (United Kingdom)
- Technische Univ. Berlin, Berlin (Germany)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1349616
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Molecular Physics
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 1; Journal ID: ISSN 0026-8976
- Publisher:
- Taylor & Francis
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; adsorption; ad-micelles; surface azeotrope; surfactant; mesoscale simulations; nanopores
Citation Formats
Rother, Gernot, Müter, Dirk, Bock, Henry, Schoen, Martin, and Findenegg, Gerhard H. From aggregative adsorption to surface depletion: Aqueous systems of CnEm amphiphiles at hydrophilic surfaces. United States: N. p., 2017.
Web. doi:10.1080/00268976.2017.1299234.
Rother, Gernot, Müter, Dirk, Bock, Henry, Schoen, Martin, & Findenegg, Gerhard H. From aggregative adsorption to surface depletion: Aqueous systems of CnEm amphiphiles at hydrophilic surfaces. United States. https://doi.org/10.1080/00268976.2017.1299234
Rother, Gernot, Müter, Dirk, Bock, Henry, Schoen, Martin, and Findenegg, Gerhard H. Mon .
"From aggregative adsorption to surface depletion: Aqueous systems of CnEm amphiphiles at hydrophilic surfaces". United States. https://doi.org/10.1080/00268976.2017.1299234. https://www.osti.gov/servlets/purl/1349616.
@article{osti_1349616,
title = {From aggregative adsorption to surface depletion: Aqueous systems of CnEm amphiphiles at hydrophilic surfaces},
author = {Rother, Gernot and Müter, Dirk and Bock, Henry and Schoen, Martin and Findenegg, Gerhard H.},
abstractNote = {Adsorption of a short-chain nonionic amphiphile (C6E3) at the surface of mesoporous silica glass (CPG-10) was studied by a combination of adsorption measurements and mesoscale simulations. Adsorption measurements covering a wide composition range of the C6E3 + water system show that no adsorption occurs up to the critical micelle concentration (cmc), at which a sharp increase of adsorption is observed that is attributed to ad-micelle formation at the pore walls. Intriguingly, as the concentration is increased further, the surface excess of the amphiphile begins to decrease and eventually becomes negative, which corresponds to preferential adsorption of water rather than amphiphile at high amphiphile concentrations. The existence of such a surface-azeotropic point has not previously been reported in the surfactant adsorption field. Dissipative particle dynamics (DPD) simulations were performed to reveal the structural origin of this transition from aggregative adsorption to surface depletion. Finally, the simulations indicate that this transition can be attributed to the repulsive interaction between head groups, causing amphiphilic depletion in the region around the corona of the surface micelles.},
doi = {10.1080/00268976.2017.1299234},
journal = {Molecular Physics},
number = 1,
volume = 1,
place = {United States},
year = {Mon Mar 27 00:00:00 EDT 2017},
month = {Mon Mar 27 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Design of liquid/solid adsorption isotherms by energy distribution functions
journal, March 2009
- Kalies, Grit; Bräuer, Peter; v. Szombathely, Michael
- Journal of Colloid and Interface Science, Vol. 331, Issue 2
Calorimetric Study of the Micellization of n -Butoxyethanol in Water
journal, June 1997
- Onori, G.; Santucci, A.
- The Journal of Physical Chemistry B, Vol. 101, Issue 23
Particle Diffusion in Complex Nanoscale Pore Networks
journal, April 2015
- Müter, D.; Sørensen, H. O.; Bock, H.
- The Journal of Physical Chemistry C, Vol. 119, Issue 19
Investigation of structure formation mechanism of a mesoporous ZSM-5 zeolite by mesoscopic simulation
journal, February 2015
- Ren, Yanqun; Liu, Baoyu; Kiryutina, Tatyana
- Chemical Physics, Vol. 448
2 H NMR Investigation of the Structure and Dynamics of the Nonionic Surfactant C 12 E 5 Confined in Controlled Pore Glass
journal, July 2003
- Qiao, Ying; Schönhoff, Monika; Findenegg, Gerhard H.
- Langmuir, Vol. 19, Issue 15
Thermodynamic and Dynamic Properties of Micellar Aggregates of Nonionic Surfactants with Short Hydrophobic Tails
journal, June 1997
- Ambrosone, Luigi; Costantino, Lucia; D'errico, Gerardino
- Journal of Colloid and Interface Science, Vol. 190, Issue 2
Influence of Surface Roughness on Cetyltrimethylammonium Bromide Adsorption from Aqueous Solution
journal, May 2011
- Wu, Shuqing; Shi, Liu; Garfield, Lucas B.
- Langmuir, Vol. 27, Issue 10
Counterion Effects on Hexadecyltrimethylammonium Surfactant Adsorption and Self-Assembly on Silica
journal, March 2000
- Velegol, Stephanie B.; Fleming, Barry D.; Biggs, Simon
- Langmuir, Vol. 16, Issue 6
Self-assembled surfactants on patterned surfaces: confinement and cooperative effects on aggregate morphology
journal, January 2014
- Suttipong, Manaswee; Grady, Brian P.; Striolo, Alberto
- Physical Chemistry Chemical Physics, Vol. 16, Issue 31
Microcalorimetric Study of Some Short-Chain Nonionic Surfactants
journal, July 1998
- Ortona, Ornella; Vitagliano, Vincenzo; Paduano, Luigi
- Journal of Colloid and Interface Science, Vol. 203, Issue 2
Adsorption and wetting transitions at a model of the interface between a solid and a binary fluid mixture
journal, March 1983
- da Gama, M. M. Telo; Evans, R.
- Molecular Physics, Vol. 48, Issue 4
Influence of porosity on the adsorption of a non-ionic surfactant on silica
journal, June 1993
- Giordano, F.; Denoyel, R.; Rouquerol, J.
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 71, Issue 3
Kinetics and Mechanism of Cationic Surfactant Adsorption and Coadsorption with Cationic Polyelectrolytes at the Silica−Water Interface
journal, April 1998
- Pagac, Edward S.; Prieve, Dennis C.; Tilton, Robert D.
- Langmuir, Vol. 14, Issue 9
Surfactant Self-Assembly in Cylindrical Pores: Insights from Mesoscale Simulations
journal, June 2013
- Müter, Dirk; Widmann, Matthias A.; Bock, Henry
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 13
Protein Density Profile at the Interface of Water with Oligo(ethylene glycol) Self-Assembled Monolayers †
journal, April 2009
- Skoda, M. W. A.; Schreiber, F.; Jacobs, R. M. J.
- Langmuir, Vol. 25, Issue 7
Adsorption of nonionic surfactants on hydrophilic surfaces. An experimental and theoretical study on association in the adsorbed layer
journal, September 1992
- Bohmer, Marcel R.; Koopal, Luuk K.; Janssen, Rob
- Langmuir, Vol. 8, Issue 9
Multilayer theory for adsorption from solution. Mixtures of monomers + dimers
journal, January 1968
- Ash, S. G.; Everett, D. H.; Findenegg, G. H.
- Transactions of the Faraday Society, Vol. 64
Adsorption and Aggregation of C 8 E 4 and C 8 G 1 Nonionic Surfactants on Hydrophilic Silica Studied by Calorimetry
journal, June 1997
- Király, Z.; Börner, R. H. K.; Findenegg, G. H.
- Langmuir, Vol. 13, Issue 13
Adsorption Isotherms of Aqueous C 12 E 6 and Cetyltrimethylammonium Bromide Surfactants on Solid Surfaces in the Presence of Low Molecular Weight Coadsorbents
journal, May 2009
- Shi, Liu; Ghezzi, Manuel; Caminati, Gabriella
- Langmuir, Vol. 25, Issue 10
Confinement effect on the adsorption from a binary liquid system near liquid/liquid phase separation
journal, June 2004
- Rother, Gernot; Woywod, Dirk; Schoen, Martin
- The Journal of Chemical Physics, Vol. 120, Issue 24
Adsorption of CTAB on Hydrophilic Silica Studied by Linear and Nonlinear Optical Spectroscopy
journal, December 2008
- Tyrode, Eric; Rutland, Mark W.; Bain, Colin D.
- Journal of the American Chemical Society, Vol. 130, Issue 51
Crossover from Normal to Inverse Temperature Dependence in the Adsorption of Nonionic Surfactants at Hydrophilic Surfaces and Pore Walls †
journal, November 2007
- Dietsch, Oliver; Eltekov, Anton; Bock, Henry
- The Journal of Physical Chemistry C, Vol. 111, Issue 43
Self-Assembly of Surfactants and Polymorphic Transition in Nanotubes
journal, June 2008
- Arai, Noriyoshi; Yasuoka, Kenji; Zeng, X. C.
- Journal of the American Chemical Society, Vol. 130, Issue 25
Directed Self-Assembly of Surfactants in Carbon Nanotube Materials
journal, November 2008
- Angelikopoulos, Panagiotis; Bock, Henry
- The Journal of Physical Chemistry B, Vol. 112, Issue 44
Physical characterization of non-ionic surfactant layers adsorbed at hydrophilic and hydrophobic solid surfaces by time-resolved ellipsometry
journal, January 1996
- Tiberg, Fredrik
- Journal of the Chemical Society, Faraday Transactions, Vol. 92, Issue 4
Fluorescence decay study of the adsorption of nonionic surfactants at the solid-liquid interface. 2. Influence of polar chain length
journal, March 1986
- Levitz, Pierre; Van Damme, Henri
- The Journal of Physical Chemistry, Vol. 90, Issue 7
Interfacial aggregation of nonionic surfactants onto silica gel: Calorimetric evidence
journal, August 1990
- Lindheimer, Marc; Keh, Erlend; Zaini, Sabeeh
- Journal of Colloid and Interface Science, Vol. 138, Issue 1
Thermodynamics of micellization of non-ionic detergents
journal, January 1964
- Corkill, J. M.; Goodman, J. F.; Harrold, S. P.
- Transactions of the Faraday Society, Vol. 60