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Algebraic repulsions between charged planes with strongly overlapping electrical double layers.

Albert P Philipse1, Bonny W M Kuipers, Agienus Vrij

  • 1Van't Hoff Laboratory for Physical and Colloid Chemistry, Debye Institute for Nanomaterials Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands. a.p.philipse@uu.nl

Langmuir : the ACS Journal of Surfaces and Colloids
|February 7, 2013
PubMed
Summary

This study analytically calculates Langmuir's disjoining pressure, revealing a long-range algebraic repulsion between charged planes. This repulsion, combined with van der Waals attraction, forms a always repulsive zero-field potential, predictable from surface charge and ionic strength.

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Area of Science:

  • Physical Chemistry
  • Colloid Science
  • Surface Science

Background:

  • The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory describes colloidal interactions using van der Waals attraction and electrical double-layer repulsion.
  • Understanding inter-particle forces is crucial for predicting colloidal stability and behavior in various applications.
  • Existing models often focus on screened electrostatic interactions, with less emphasis on zero-field conditions.

Purpose of the Study:

  • To analytically calculate Langmuir's disjoining pressure for strongly overlapping double layers at zero electric field.
  • To characterize the nature and range of the disjoining pressure under these specific conditions.
  • To establish a predictive framework for algebraic repulsions based on easily measurable surface properties.

Main Methods:

  • Analytical calculation of disjoining pressure using Langmuir's model for charged planes.
  • Analysis of ion distribution and thermodynamic equilibrium between interplate ions and the electrolyte reservoir.
  • Mathematical derivation of the force-distance relationship in the zero electric field limit.

Main Results:

  • A long-range algebraic decay in repulsive disjoining pressure was identified.
  • This repulsion arises from the equilibrium between ions within the double layers and the bulk electrolyte.
  • The combined effect with van der Waals attraction results in a zero-field potential that is always repulsive at larger separations.

Conclusions:

  • The study presents a zero-field potential that complements the exponentially screened DLVO potential.
  • Algebraic repulsions are predicted to occur experimentally and can be forecasted using surface charge density and ionic strength.
  • This work provides a more comprehensive understanding of colloidal interactions beyond traditional DLVO theory, particularly in low-field or zero-field scenarios.