Skip to main content
U.S. flag

An official website of the United States government

Official websites use .gov
A .gov website belongs to an official government organization in the United States.

Secure .gov websites use HTTPS
A lock ( ) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.

Equilibrium Polymerization Models of Reentrant Self-Assembly



Jacek Dudowicz, Jack F. Douglas, Karl Freed


As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the 'floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of reentrant phase separation, i.e., reentrant self-assembly upon varying the temperature. In particular, reentrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in the case of equilibrium self-assembly near an adsorbing boundary, where a strong competition exists between adsorption and self-assembly. Apparently, a competition between interactions or equilibria generally underlies reentrant behavior in both liquid-liquid phase separation and self-assembly transitions.
Journal of Chemical Physics


self-assembly, reentrancy, adsorption, gelation, closed loop phase boundary


Dudowicz, J. , Douglas, J. and Freed, K. (2009), Equilibrium Polymerization Models of Reentrant Self-Assembly, Journal of Chemical Physics, [online], (Accessed July 19, 2024)


If you have any questions about this publication or are having problems accessing it, please contact

Created April 23, 2009, Updated October 12, 2021