Dissipative Particle Dynamics Approaches to Modeling …
85
of varying architectures, block length, block ratio and solvent type on mesoscale
morphologies of self-assembled BCP aggregates.
DPD simulations can probe micellization and interactions between micelles in
solution. Early work by Cao et al. on the self-assembly of three BCPs, (EO) 16 (PO) 18 ,
(EO) 8 (PO) 18 (EO) 8 , and (PO) 9 (EO) 16 (PO) 9 , in aqueous solutions demonstrated the
formation of spherical micelles at low concentrations, and cylindrical micelles and
lamellar phases at increasing concentration [123]. In addition, the diblock copolymers
form intercluster micelles at a certain concentration range, whereas the triblock
copolymers formed intercluster aggregates and gels. Results from this investigation
suggested two mechanisms for the formation of inter-cluster aggregates: sharing of
the hydrated shells for both the diblock and triblock copolymers, with the hydrophilic
blocks serving as a bridge for the triblock copolymers.
DPD simulations can investigate the chain exchange kinetics between micelles
in solution. Experimentally validated studies by Prhashanna et al. demonstrated
that the change chain exchange kinetics (Fig. 2a) depends upon the equilibrium
diblock copolymer chain conformation (namely, tadpole and linear chains) and the
composition of the micelles [124]. The exchange kinetics is faster between micelles
encompassing mixtures of diblock copolymers than micelles encompassing a single
species. Peters et al. showed that the equilibrium chain exchange kinetics in a B
Fig. 2 a Exchange kinetics of a small aggregate between two tadpole micelles. b Comparison of
the simulated and experimentally determined CAC values of ABA triblock copolymer with various
degrees of polymerization. c Phase diagram of reduced volume (ν) versus reduced area difference
between the exterior and interior layer (α) for a vesicle bilayer encompassing two different
species of amphiphilic diblock copolymers. d Morphological phase diagram of amphiphilic triblock
copolymers (A 1 B 8 A 1 ) as a function of DPD repulsive parameters a AS (between the A block and the
solvent S) and a BS (between the B block and the solvent S). A and B reprinted with permission from
[34, 124] respectively ©2017, 2016 American Chemical Society. C reprinted with permission from
[133] ©2013 Royal Society of Chemistry. D reprinted with permission from [129] ©AIP Publishing
85
of varying architectures, block length, block ratio and solvent type on mesoscale
morphologies of self-assembled BCP aggregates.
DPD simulations can probe micellization and interactions between micelles in
solution. Early work by Cao et al. on the self-assembly of three BCPs, (EO) 16 (PO) 18 ,
(EO) 8 (PO) 18 (EO) 8 , and (PO) 9 (EO) 16 (PO) 9 , in aqueous solutions demonstrated the
formation of spherical micelles at low concentrations, and cylindrical micelles and
lamellar phases at increasing concentration [123]. In addition, the diblock copolymers
form intercluster micelles at a certain concentration range, whereas the triblock
copolymers formed intercluster aggregates and gels. Results from this investigation
suggested two mechanisms for the formation of inter-cluster aggregates: sharing of
the hydrated shells for both the diblock and triblock copolymers, with the hydrophilic
blocks serving as a bridge for the triblock copolymers.
DPD simulations can investigate the chain exchange kinetics between micelles
in solution. Experimentally validated studies by Prhashanna et al. demonstrated
that the change chain exchange kinetics (Fig. 2a) depends upon the equilibrium
diblock copolymer chain conformation (namely, tadpole and linear chains) and the
composition of the micelles [124]. The exchange kinetics is faster between micelles
encompassing mixtures of diblock copolymers than micelles encompassing a single
species. Peters et al. showed that the equilibrium chain exchange kinetics in a B
Fig. 2 a Exchange kinetics of a small aggregate between two tadpole micelles. b Comparison of
the simulated and experimentally determined CAC values of ABA triblock copolymer with various
degrees of polymerization. c Phase diagram of reduced volume (ν) versus reduced area difference
between the exterior and interior layer (α) for a vesicle bilayer encompassing two different
species of amphiphilic diblock copolymers. d Morphological phase diagram of amphiphilic triblock
copolymers (A 1 B 8 A 1 ) as a function of DPD repulsive parameters a AS (between the A block and the
solvent S) and a BS (between the B block and the solvent S). A and B reprinted with permission from
[34, 124] respectively ©2017, 2016 American Chemical Society. C reprinted with permission from
[133] ©2013 Royal Society of Chemistry. D reprinted with permission from [129] ©AIP Publishing