A systematic coarse-graining procedure is proposed for the description and simulation of AB diblock copolymers in selective solvents. Each block is represented by a small number, nA or nB, of effective segments or blobs, containing a large number of microscopic monomers. n A and nB are unequivocally determined by imposing that blobs do not, on average, overlap, even if complete copolymer coils interpenetrate (semi-dilute regime). Ultra-soft effective interactions between blobs are determined by a rigorous inversion procedure in the low concentration limit. The methodology is applied to an athermal copolymer model where A blocks are ideal (theta solvent), B blocks self-avoiding (good solvent), while A and B blocks are mutually avoiding. The model leads to aggregation into polydisperse spherical micelles beyond a critical micellar concentration determined by Monte Carlo simulations for several size ratios f of the two blocks. The simulations also provide accurate estimates of the osmotic pressure and of the free energy of the copolymer solutions over a wide range of concentrations. The mean micellar aggregation numbers are found to be significantly lower than those predicted by an earlier, minimal two-blob representation (Capone et al 2009 J.Phys.Chem.B113 3629). © 2011 IOP Publishing Ltd.
Capone, B., Coluzza, I., Hansen, J.-. (2011). A systematic coarse-graining strategy for semi-dilute copolymer solutions: From monomers to micelles. JOURNAL OF PHYSICS. CONDENSED MATTER, 23(19), 194102 [10.1088/0953-8984/23/19/194102].
A systematic coarse-graining strategy for semi-dilute copolymer solutions: From monomers to micelles
Capone B.;
2011-01-01
Abstract
A systematic coarse-graining procedure is proposed for the description and simulation of AB diblock copolymers in selective solvents. Each block is represented by a small number, nA or nB, of effective segments or blobs, containing a large number of microscopic monomers. n A and nB are unequivocally determined by imposing that blobs do not, on average, overlap, even if complete copolymer coils interpenetrate (semi-dilute regime). Ultra-soft effective interactions between blobs are determined by a rigorous inversion procedure in the low concentration limit. The methodology is applied to an athermal copolymer model where A blocks are ideal (theta solvent), B blocks self-avoiding (good solvent), while A and B blocks are mutually avoiding. The model leads to aggregation into polydisperse spherical micelles beyond a critical micellar concentration determined by Monte Carlo simulations for several size ratios f of the two blocks. The simulations also provide accurate estimates of the osmotic pressure and of the free energy of the copolymer solutions over a wide range of concentrations. The mean micellar aggregation numbers are found to be significantly lower than those predicted by an earlier, minimal two-blob representation (Capone et al 2009 J.Phys.Chem.B113 3629). © 2011 IOP Publishing Ltd.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
