On the role of hydrodynamic interactions in block copolymer microphase separation

A melt of linear diblock copolymers (AnBm) can form a diverse range of microphase separated structures. The detailed morphology of the microstructure depends on the length of the polymer blocks An and Bm and their mutual solubility. In this paper, the role of hydrodynamic forces in microphase formation is studied. The microphase separation of block copolymer melts is simulated using two continuum methods: dissipative particle dynamics (DPD) and Brownian dynamics (BD). Although both methods produce the correct equilibrium distribution of polymer chains, the BD simulation does not include hydrodynamic interactions, whereas the DPD method correctly simulates the (compressible) Navier Stokes behavior of the melt. To quantify the mesophase structure, we introduce a new order parameter that goes beyond the usual local segregation parameter and is sensitive to the morphology of the system. In the DPD simulation, a melt of asymmetric block copolymers rapidly evolves towards the hexagonal structure that is predict...

[1]  R. D. Vold,et al.  Phase Rule Studies of Soap. II. The System Sodium Laurate—Sodium Chloride—Water , 1938 .

[2]  I. Lifshitz,et al.  The kinetics of precipitation from supersaturated solid solutions , 1961 .

[3]  Eric D. Siggia,et al.  Late stages of spinodal decomposition in binary mixtures , 1979 .

[4]  L. Leibler Theory of Microphase Separation in Block Copolymers , 1980 .

[5]  Hiroshi Furukawa,et al.  A dynamic scaling assumption for phase separation , 1985 .

[6]  E. Helfand,et al.  Fluctuation effects in the theory of microphase separation in block copolymers , 1987 .

[7]  K. Kawasaki,et al.  Concentration dynamics in polymer blends and block copolymer melts , 1989 .

[8]  Oono,et al.  Cell dynamical system approach to block copolymers. , 1990, Physical review. A, Atomic, molecular, and optical physics.

[9]  G. Fredrickson,et al.  Block copolymer thermodynamics: theory and experiment. , 1990, Annual review of physical chemistry.

[10]  Bates,et al.  Gaussian- to stretched-coil transition in block copolymer melts. , 1990, Physical review letters.

[11]  K. Binder,et al.  The microphase separation transition in symmetric diblock copolymer melts: A Monte Carlo study , 1991 .

[12]  G. Fredrickson,et al.  Collective and single‐chain correlations near the block copolymer order–disorder transition , 1991 .

[13]  Ronald G. Larson,et al.  Monte Carlo simulation of microstructural transitions in surfactant systems , 1992 .

[14]  F. Bates,et al.  Order, disorder, and fluctuation effects in an asymmetric poly(ethylene‐propylene)‐poly(ethylethylene) diblock copolymer , 1992 .

[15]  J. Koelman,et al.  Simulating microscopic hydrodynamic phenomena with dissipative particle dynamics , 1992 .

[16]  T. Hashimoto,et al.  Morphology of block copolymers and mixtures of block copolymers at free surfaces , 1992 .

[17]  R. Larson,et al.  Interdependence of shear deformations and block copolymer morphology , 1993 .

[18]  K. Binder,et al.  Asymmetric block copolymer melts near the microphase separation transition: a Monte Carlo simulation , 1993 .

[19]  F. Bates,et al.  Hexagonal mesophases between lamellae and cylinders in a diblock copolymer melt , 1993 .

[20]  F. Bates,et al.  Influence of Shear on the Hexagonal-to-Disorder Transition in a Diblock Copolymer Melt , 1994 .

[21]  R. Larson Simulation of lamellar phase transitions in block copolymers , 1994 .

[22]  A. Bray Theory of phase-ordering kinetics , 1994, cond-mat/9501089.

[23]  T. Tadros,et al.  Investigations of the Phase Changes of Nonionic Surfactants Using Microscopy, Differential Scanning Calorimetry, and Rheology. 1. Synperonic A7, a C13/C15 Alcohol with 7 mol of Ethylene Oxide , 1995 .

[24]  P. Español,et al.  Statistical Mechanics of Dissipative Particle Dynamics. , 1995 .

[25]  R. D. Groot,et al.  Dynamic Viscoelastic Modulus of Associative Polymer Networks: Off-Lattice Simulations, Theory and Comparison to Experiments , 1995 .

[26]  Español,et al.  Hydrodynamics from dissipative particle dynamics. , 1995, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[27]  R. D. Groot,et al.  Molecular theory of strain hardening of a polymer gel: Application to gelatin , 1996 .

[28]  F. Bates,et al.  Unifying Weak- and Strong-Segregation Block Copolymer Theories , 1996 .

[29]  T. Dotera,et al.  The diagonal bond method: A new lattice polymer model for simulation study of block copolymers , 1996 .

[30]  A. Valiente,et al.  Rheological Properties of the L Phase and the Hexagonal, Lamellar, and Cubic Liquid Crystals of the CTAB/Benzyl Alcohol/Water System , 1996 .

[31]  F. Bates,et al.  Phase Behavior of Pure Diblocks and Binary Diblock Blends of Poly(ethylene)−Poly(ethylethylene) , 1996 .

[32]  J. Noolandi,et al.  Stability of Ordered Phases in Diblock Copolymer Melts , 1997 .

[33]  A. Blumen,et al.  Computer simulations of asymmetric block copolymers , 1997 .

[34]  Zhen‐Gang Wang,et al.  KINETICS OF PHASE TRANSITIONS IN WEAKLY SEGREGATED BLOCK COPOLYMERS : PSEUDOSTABLE AND TRANSIENT STATES , 1997 .

[35]  P. B. Warren,et al.  DISSIPATIVE PARTICLE DYNAMICS : BRIDGING THE GAP BETWEEN ATOMISTIC AND MESOSCOPIC SIMULATION , 1997 .

[36]  Muñoz,et al.  Linear Viscoelasticity of the Direct Hexagonal Liquid Crystalline Phase for a Heptane/Nonionic Surfactant/Water System , 1997, Journal of colloid and interface science.

[37]  B. Stühn,et al.  Asymmetric diblock copolymers-phase behaviour and kinetics of structure formation , 1997 .

[38]  S. Milner,et al.  Dynamics of the Lamellar-Cylindrical Transition in Weakly Segregated Diblock Copolymer Melts , 1997 .

[39]  K. Karatasos,et al.  Computer simulation of static and dynamic behavior of diblock copolymer melts , 1997 .

[40]  Ignacio Pagonabarraga,et al.  Self-consistent dissipative particle dynamics algorithm , 1998 .

[41]  M. Matsen CYLINDER GYROID EPITAXIAL TRANSITIONS IN COMPLEX POLYMERIC LIQUIDS , 1998 .

[42]  T. Hashimoto,et al.  Small-angle X-ray scattering and rheological studies on the ordering process of cylindrical microdomains in a polystyrene-block-polyisoprene copolymer , 1998 .

[43]  Ian W. Hamley,et al.  Transformations to and from the Gyroid Phase in a Diblock Copolymer , 1998 .

[44]  Timothy J. Madden,et al.  Dynamic simulation of diblock copolymer microphase separation , 1998 .

[45]  Evolution of microstructure in the liquid and crystal directions in a quenched block copolymer melt , 1998 .

[46]  B. A. Garetz,et al.  Identification of the Molecular Parameters that Govern Ordering Kinetics in a Block Copolymer Melt , 1998 .

[47]  T. Lodge,et al.  Micellar Ordering in Concentrated Solutions of Di- and Triblock Copolymers in a Slightly Selective Solvent , 1998 .

[48]  H. Hasegawa Block copolymers: Generic phase behaviour compared to surfactant phase behaviour , 1998 .