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Microscopic Origin of the Hofmeister Effect in Gelation Kinetics of Colloidal Silica.


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Authors

van der Linden, Marte 
Conchúir, Breanndán O 
Spigone, Elisabetta 
Niranjan, Arun 
Zaccone, Alessio 

Abstract

The gelation kinetics of silica nanoparticles is a central process in physical chemistry, yet it is not fully understood. Gelation times are measured to increase by over 4 orders of magnitude, simply changing the monovalent salt species from CsCl to LiCl. This striking effect has no microscopic explanation within current paradigms. The trend is consistent with the Hofmeister series, pointing to short-ranged solvation effects not included in the standard colloidal (DLVO) interaction potential. By implementing a simple form for short-range repulsion within a model that relates the gelation timescale to the colloidal interaction forces, we are able to explain the many orders of magnitude difference in the gelation times at fixed salt concentration. The model allows us to estimate the magnitude of the non-DLVO hydration forces, which dominate the interparticle interactions on the length scale of the hydrated ion diameter. This opens the possibility of finely tuning the gelation time scale of nanoparticles by just adjusting the background electrolyte species.

Description

Keywords

Hofmeister series, gelation time, hydration forces, silica nanoparticle gel

Journal Title

J Phys Chem Lett

Conference Name

Journal ISSN

1948-7185
1948-7185

Volume Title

6

Publisher

American Chemical Society (ACS)
Sponsorship
We acknowledge financial support from: Unilever Plc (E.S.); the Ernest Oppenheimer Fellowship at Cambridge (to 1st June 2014), and by the Technische Universität München Institute for Advanced Study, funded by the German Excellence Initiative and the European Union Seventh Framework Programme under grant agreement 291763 (A.Z.); the Winton Programme for the Physics of Sustainability (B.O.C.).