Physics – Condensed Matter – Soft Condensed Matter
Scientific paper
2002-06-24
Macromol. Theory Simul. 12 (8), 549-559 (2003) http://www3.interscience.wiley.com/cgi-bin/fulltext/105560220/PDFSTART
Physics
Condensed Matter
Soft Condensed Matter
12 pages, 9 figures
Scientific paper
10.1002/mats.200350014
The quality of solvents of polymers is often described in terms of the Flory chi parameter typically assumed to depend only on the temperature, T. In certain polymer-solvent systems fitting the experimental data enforces the replacement of chi(T) by a concentration dependent chieff. In turn, this modifies the swelling and collapse behavior. These effects are studied, in the framework of a mean-field theory, for isolated coils and for planar brushes. The phi dependence of chieff gives rise to three main consequences: (i) Shift in the cross-over between Gaussian and self-avoidance regimes; (ii) A possibility of first-order collapse transition for isolated flexible coils; (iii) The possibility of a first-order phase transition leading to a vertical phase separation within the brush. The discussion relates these effects directly to thermodynamic measurements and does not involve a specific microscopic model. The implementation for the case of Poly(N-isopropylacrylamide) (PNIPAM) is discussed.
Baulin Vladimir A.
Halperin Avi
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