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Simultaneous Multi-surface Anodizations and Stair-like Reverse Biases Detachment of Anodic Aluminum Oxides in Sulfuric and Oxalic Acid Electrolyte
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Theory of Surface Forces in Multivalent Electrolytes.

Rahul Prasanna Misra1, J Pedro de Souza1, Daniel Blankschtein1

  • 1Department of Chemical Engineering , Massachusetts Institute of Technology , 25 Ames Street , Cambridge , Massachusetts 02142 , United States.

Langmuir : the ACS Journal of Surfaces and Colloids
|July 17, 2019
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Summary

Multivalent ions in aqueous solutions cause like-charge attraction between colloidal particles due to strong ion-ion correlations. This new theory explains this phenomenon, challenging classical models of colloidal stability.

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Area of Science:

  • Physical Chemistry
  • Colloid Science
  • Materials Science

Background:

  • Classical theories like Derjaguin-Landau-Verwey-Overbeek (DLVO) predict repulsion between like-charged particles in electrolyte solutions.
  • However, experimental observations show attraction between like-charged colloidal particles, particularly in solutions with multivalent ions.

Purpose of the Study:

  • To formulate a general theory of surface forces that explains the phenomenon of like-charge attraction.
  • To investigate the role of ion-ion correlations and hydration interactions in colloidal stability.

Main Methods:

  • Development of a general theory for surface forces.
  • Analysis of ion-ion correlations and their contribution to disjoining pressure.
  • Inclusion of ion-specific hydration interactions and surface charge regulation.

Main Results:

  • The formulated theory predicts an attractive contribution to disjoining pressure arising from ion-ion correlations.
  • This attractive force can overcome entropic repulsions, explaining like-charge attraction with multivalent ions.
  • The theory accounts for experimental observations in cement pastes involving calcium ions.

Conclusions:

  • Ion-ion correlations are a primary driver of like-charge attraction in multivalent ion solutions.
  • Classical mean-field theories are insufficient to explain these observed phenomena.
  • The developed theory provides a framework for understanding cohesive forces in complex systems like cement pastes.