MilliporeSigma

Surface molecular view of colloidal gelation.

Proceedings of the National Academy of Sciences of the United States of America (2006-08-30)
Sylvie Roke, Otto Berg, Johan Buitenhuis, Alfons van Blaaderen, Mischa Bonn
ABSTRACT

We investigate the phase behavior of surface-functionalized silica colloids at both the molecular and macroscopic levels. This investigation allows us to relate collective properties such as aggregation, gelation, and aging directly to molecular interfacial behavior. By using surface-specific vibrational spectroscopy, we reveal dramatic changes in the conformation of alkyl chains terminating submicrometer silica particles. In fluid suspension at high temperatures, the interfacial molecules are in a liquid-like state of conformational disorder. As the temperature is lowered, the onset of gelation is identified by macroscopic phenomena, including changes in turbidity, heat release, and diverging viscosity. At the molecular level, the onset of this transition coincides with straightening of the carbon-carbon backbones of the interfacial molecules. In later stages, their intermolecular crystalline packing improves. It is the increased density of this ordered boundary layer that increases the van der Waals attraction between particles, causing the colloidal gas to aggregate. The approach presented here can provide insights into phase transitions that occur through surface modifications in a variety of colloidal systems.

MATERIALS
Product Number
Brand
Product Description

Stearyl alcohol, European Pharmacopoeia (EP) Reference Standard
Supelco
Stearyl Alcohol, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
1-Octadecanol, Selectophore, ≥99.0%
Sigma-Aldrich
1-Octadecanol, 95%
Sigma-Aldrich
1-Octadecanol, ReagentPlus®, 99%