TY - JOUR
T1 - Micellization kinetics of diblock copolymers in a homopolymer matrix
T2 - Aself-consistent field study
AU - Thiagarajan, Raghuram
AU - Morse, David C.
PY - 2011/7/20
Y1 - 2011/7/20
N2 - Self-consistent field theory is used to calculate free energy barriers and reaction rates for the spontaneous association and dissociation of micelles formed of block copolymers in a homopolymer matrix. The barriers are prohibitively large for copolymers of typical molecular weights when the unimer (free surfactant) concentration is near the equilibrium critical micelle concentration (CMC). As a result, polymeric micelles normally cannot reach true thermodynamic equilibrium. The rates of association and dissociation are, however, sensitive to unimer concentration, making it possible to form or destroy micelles at observable rates in sufficiently highly supersaturated or subsaturated solutions, respectively, even when both reactions are suppressed near the equilibrium CMC. The barrier to dissociation is particularly sensitive to unimer concentration, and vanishes when the unimer concentration is only slightly (for example, a percentage of a few tens) below the equilibrium CMC.
AB - Self-consistent field theory is used to calculate free energy barriers and reaction rates for the spontaneous association and dissociation of micelles formed of block copolymers in a homopolymer matrix. The barriers are prohibitively large for copolymers of typical molecular weights when the unimer (free surfactant) concentration is near the equilibrium critical micelle concentration (CMC). As a result, polymeric micelles normally cannot reach true thermodynamic equilibrium. The rates of association and dissociation are, however, sensitive to unimer concentration, making it possible to form or destroy micelles at observable rates in sufficiently highly supersaturated or subsaturated solutions, respectively, even when both reactions are suppressed near the equilibrium CMC. The barrier to dissociation is particularly sensitive to unimer concentration, and vanishes when the unimer concentration is only slightly (for example, a percentage of a few tens) below the equilibrium CMC.
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U2 - 10.1088/0953-8984/23/28/284109
DO - 10.1088/0953-8984/23/28/284109
M3 - Article
C2 - 21709331
AN - SCOPUS:79960473104
SN - 0953-8984
VL - 23
JO - Journal of Physics Condensed Matter
JF - Journal of Physics Condensed Matter
IS - 28
M1 - 284109
ER -