Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study

Müter, Dirk; Rother, Gernot; Bock, Henry; Schoen, Martin; Findenegg, Gerhard H.

doi:10.1021/acs.langmuir.7b02262

Title: Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study

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Abstract

Adsorption and aggregation of nonionic surfactants at oxide surfaces has been studied extensively in the past, but only for concentrations below and near the critical micelle concentration. In this paper, we report an adsorption study of a short-chain surfactant (C₆E₃) in porous silica glass of different pore sizes (7.5 to 50 nm), covering a wide composition range up to 50 wt % in a temperature range from 20 °C to the LCST. Aggregative adsorption is observed at low concentrations, but the excess concentration of C₆E₃ in the pores decreases and approaches zero at higher bulk concentrations. Strong depletion of surfactant (corresponding to enrichment of water in the pores) is observed in materials with wide pores at high bulk concentrations. We propose an explanation for the observed pore-size dependence of the azeotropic point. Mesoscale simulations based on dissipative particle dynamics (DPD) were performed to reveal the structural origin of this transition from the adsorption to the depletion regime. The simulated adsorption isotherms reproduce the behavior found in the 7.5 nm pores. Finally, the calculated bead density profiles indicate that the repulsive interaction of surfactant head groups causes a depletion of surfactant in the region around the corona of the surface micelles.

Authors:

Müter, Dirk ^[1];

^[2]; Bock, Henry ^[3]; Schoen, Martin ^[4];

^[4]

Univ. of Copenhagen (Denmark). Nano-Science Center, Dept. of Chemistry
Technical Univ. of Berlin (Germany); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Heriot-Watt Univ., Edinburgh, Scotland (United Kingdom)
Technical Univ. of Berlin (Germany)

Publication Date:: Tue Aug 15 00:00:00 EDT 2017

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); German Research Foundation (DFG)

OSTI Identifier:: 1394384

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Langmuir

Additional Journal Information:: Journal Volume: 33; Journal Issue: 42; Journal ID: ISSN 0743-7463

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Müter, Dirk, Rother, Gernot, Bock, Henry, Schoen, Martin, and Findenegg, Gerhard H. Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.langmuir.7b02262.

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                    Müter, Dirk, Rother, Gernot, Bock, Henry, Schoen, Martin, & Findenegg, Gerhard H. Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study.  United States.  https://doi.org/10.1021/acs.langmuir.7b02262

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                    Müter, Dirk, Rother, Gernot, Bock, Henry, Schoen, Martin, and Findenegg, Gerhard H. Tue .  
"Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study".  United States.  https://doi.org/10.1021/acs.langmuir.7b02262.  https://www.osti.gov/servlets/purl/1394384.

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@article{osti_1394384,

  title        = {Adsorption and Depletion Regimes of a Nonionic Surfactant in Hydrophilic Mesopores: An Experimental and Simulation Study},

  author       = {Müter, Dirk and Rother, Gernot and Bock, Henry and Schoen, Martin and Findenegg, Gerhard H.},

  abstractNote = {Adsorption and aggregation of nonionic surfactants at oxide surfaces has been studied extensively in the past, but only for concentrations below and near the critical micelle concentration. In this paper, we report an adsorption study of a short-chain surfactant (C6E3) in porous silica glass of different pore sizes (7.5 to 50 nm), covering a wide composition range up to 50 wt % in a temperature range from 20 °C to the LCST. Aggregative adsorption is observed at low concentrations, but the excess concentration of C6E3 in the pores decreases and approaches zero at higher bulk concentrations. Strong depletion of surfactant (corresponding to enrichment of water in the pores) is observed in materials with wide pores at high bulk concentrations. We propose an explanation for the observed pore-size dependence of the azeotropic point. Mesoscale simulations based on dissipative particle dynamics (DPD) were performed to reveal the structural origin of this transition from the adsorption to the depletion regime. The simulated adsorption isotherms reproduce the behavior found in the 7.5 nm pores. Finally, the calculated bead density profiles indicate that the repulsive interaction of surfactant head groups causes a depletion of surfactant in the region around the corona of the surface micelles.},

  doi          = {10.1021/acs.langmuir.7b02262},

  journal      = {Langmuir},

  number       = 42,

  volume       = 33,

  place        = {United States},

  year         = {Tue Aug 15 00:00:00 EDT 2017},

  month        = {Tue Aug 15 00:00:00 EDT 2017}

}

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