The Use of Phase-Inverting Emulsions to Show the Phenomenon of Interfacial Crystallization on Both Heating and Cooling

• Published in: Journal of the American Chemical Society 2005-08, Vol.127 (34), p.11894-11895
• Main Authors: Nicholson, Catherine E, Cooper, Sharon J, Marcellin, Claire, Jamieson, Matthew J
• Format: Article
• Language: English
• Subjects: Chemistry; Colloidal state and disperse state; Emulsions. Microemulsions. Foams; Exact sciences and technology; General and physical chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0526012

Highly anomalous crystallization behavior has been achieved in phase-inverting emulsion systems by using nonionic surfactants that induce nucleation. In particular, nucleation can be inhibited at the phase inversion, allowing systems held at, or near, this temperature to undergo crystallization either on heating or cooling. This new phenomenon is demonstrated for 27.4 wt % aqueous glycine solutions emulsified in decane using Span 20 Tween 20 blends. The inhibitory effect on interfacial nucleation at/near the phase inversion is readily shown by the maximum in the induction time for crystallization found in systems at/near the phase-inversion temperature. These findings are unprecedented. An extremely rapid rise in nucleation rate is expected on cooling glycine solutions, owing to the associated increase in supersaturation, the driving force for crystallization. The origin of this highly anomalous behavior is thought to be the low droplet interfacial tension, γ ow, that occurs at the phase-inversion temperature, which results primarily in a substantially increased contact angle between the glycine critical nucleus and the droplet interface. This may present a paradigm shift in crystallization strategies through the use of tunable contact-angle nucleators.