Issue 7, 2015

Vermicious thermo-responsive Pickering emulsifiers


Thermo-responsive vermicious (or worm-like) diblock copolymer nanoparticles prepared directly in n-dodecane via polymerisation-induced self-assembly (PISA) were used to stabilise water-in-oil Pickering emulsions. Mean droplet diameters could be tuned from 8 to 117 μm by varying the worm copolymer concentration and the water volume fraction and very high worm adsorption efficiencies (∼100%) could be obtained below a certain critical copolymer concentration (∼0.50%). Heating a worm dispersion up to 150 °C led to a worm-to-sphere transition, which proved to be irreversible if conducted at sufficiently low copolymer concentration. This affords a rare opportunity to directly compare the Pickering emulsifier performance of chemically identical worms and spheres. It is found that the former nanoparticles are markedly more efficient, since worm-stabilised water droplets are always smaller than the equivalent sphere-stabilised droplets prepared under identical conditions. Moreover, the latter emulsions are appreciably flocculated, whereas the former emulsions proved to be stable. SAXS studies indicate that the mean thickness of the adsorbed worm layer surrounding the water droplets is comparable to that of the worm cross-section diameter determined for non-adsorbed worms dispersed in the continuous phase. Thus the adsorbed worms form a monolayer shell around the water droplets, rather than ill-defined multilayers. Under certain conditions, demulsification occurs on heating as a result of a partial worm-to-sphere morphological transition.

Graphical abstract: Vermicious thermo-responsive Pickering emulsifiers

Supplementary files

Article information

Article type
Edge Article
16 Feb 2015
07 May 2015
First published
07 May 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2015,6, 4207-4214

Author version available

Vermicious thermo-responsive Pickering emulsifiers

K. L. Thompson, L. A. Fielding, O. O. Mykhaylyk, J. A. Lane, M. J. Derry and S. P. Armes, Chem. Sci., 2015, 6, 4207 DOI: 10.1039/C5SC00598A

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