Stabilization of Solutions to a FitzHugh-Nagumo Type System

We consider a bistable reaction-diffusion system arising in the theory of phase transitions; it appears in several physical contexts such as thin magnetic films and the microphase separation in diblock copolymer melts. Mathematically it takes the form of an Allen-Cahn equation coupled to an elliptic equation. This system possesses a Lyapunov functional which represents the Gibbs free energy of the phase separation problem. We study the large time behavior of the solution orbits, and use the fact that the problem has a gradient structure to prove their stabilization by means of a version of ?ojasiewicz inequality.     

Selectivity and temperature dependence of phase and phase transition in diblock copolymer solution

In order to study the effects of solvent selectivity and temperature on phase behavior and transition of diblock copolymer solution, self-consistent field theory is modified to incorporate the short-range interaction and non-local effects. Inhomogeneous free-energy density is shown to be dependent on solvent selectivity, temperature and copolymer concentration. Enthalpic quantity and entropic contributions are crucial to phase diagrams of diblock copolymer solution. Three selective strengths of solvent --weak, moderate and strong-- are chosen for comparison. For a weakly selective solvent, theoretical and experimental results illustrate the same variation tendency in the phase boundary of the order-disorder transition for a symmetric diblock of polystyrene and polyisoprene. Self-consistent field equations can be used to calculate the exact FCC-BCC structural phase transition temperatures in moderately and strongly selective solvents. Detailed comparison with the experimental phase diagrams including lamellar, cylindrical and spherical structures is presented.     

Spherical/gyroid phase diagram of the diblock copolymer in the median selective solvent

The effect of the median selective solution on the lamellar, spherical and gyroid structures is studied. The self-consistent field equations of the diblock copolymer solution are solved by using the reciprocal space method. It is shown that the spherical and gyroid phases have the lowest free energy in the certain range of the solution concentration. Furthermore, the phase diagram of the ordered structures in the diblock copolymer solution with the median selective solvent is calculated, which is consistent with the experimental results. Supported by the National Natural Science Foundation of China (Grant Nos. 10834014, 10674173, and 30770517) and the National Basic Research Program of China (Grant No. 2009CB930704)     

Spectral method for exploring patterns of diblock copolymers

A numerical method in Fourier-space is developed to solve the polymeric self-consistent field equations. The method does not require a priori symmetric information. More significantly, periodic structure can be adjusted automatically during the iteration process. In this article, we apply our method to AB linear diblock copolymer melt, thus reproduce all known stable phases, and reveal some meta-stable phases. It is worthy to point out that we also give an efficient strategy to estimating initial values for diblock copolymer system. Finally, by comparing with Matsen–Schick’s method, we show some advantages of our method.     

Identification of micellar stability zones and structural inversion process of thermoresponsive polymeric micelles by dissipative particle dynamics simulations

The stimuli-sensitive polymeric micelles have huge applications to industrial and technological level, know their behaviour under the influence of a pure stimulus, such as the temperature is an important aspect to control and amplify its application field. In this paper, we investigate the micellar stability zones together with the structural inversion process of thermoresponsive polymeric micelles formed by a diblock copolymer (poly(N-isopropylacrylamide-b-3-[N-(3-methacrylamidopropyl)-N,N-dimethyl]ammoniopropane sulphonate (PNIPA-b-PSPP)) in an aqueous environment employing dissipative particle dynamics simulations. Our outcomes show that the PNIPA-b-PSPP copolymer has the ability to form thermodynamically stable micelles with different core-shell structure (PSPP-core/PNIPA-shell and PNIPA-core/PSPP-shell) depending on the direction of the applied stimulus (low or high temperature), the duality of this micellar behaviour is controlled by temperature effect and by the double hydrophilic character that exhibit the PNIPA and PSPP polymeric segments. Four micellar stability zones and one zone where only exist free unimer chains were detected during the thermal scan. The micellar inversion process is triggered by purely temperature effect, is totally reversible and involves three main stages: (1) micellar dissociation, (2) stabilisation of free unimer chains and (3) formation of inverse micelles, all transitory and metastable stages of micellar inversion process are described and analysed in this paper.     

Analytical solutions describing the phase separation driven by a free energy functional containing a long-range interaction term

We are primarily concerned with the variational problem with long-range interaction. This functional represents the Gibbs free energy of the microphase separation of diblock copolymer melts. The critical points of this variational problem can be regarded as the thermodynamic equilibrium state of the phase separation phenomenon. Experimentally it is well-known in the diblock copolymer problem that the final equilibrium state prefers periodic structures such as lamellar, column, spherical, double-diamond geometries and so on. We are interested in the characterization of the periodic structure of the global minimizer of the functional (corresponding to the strong segregation limit). In this paper we completely determine the principal part of the asymptotic expansion of the period with respect to epsilon (interfacial thickness), namely, we estimate the higher order error term of the period with respect to epsilon in a mathematically rigorous way in one space dimension. Moreover, we decide clearly the dependency of the constant of proportion upon the ratio of the length of two homopolymers and upon the quench depth. In the last section, we study the time evolution of the system. We first study the linear stability of spatially homogeneous steady state and derive the most unstable wavelength, if it is unstable. This is related to spinodal decomposition. Then, we numerically investigate the time evolution equation (the gradient flow of the free energy), and see that the free energy has many local minimizers and the system have some kind of sensitivity about initial data. (c) 1999 American Institute of Physics.     

On the structural properties from ring diblock copolymers in bulk and in solution

In order to deepen the fundamental knowledge between the structure of ring diblock copolymers and their physico-chemical properties in bulk and in solution, this paper is devoted to a theoretical approach of the structural properties of such polymeric system. This study based on the equation of Benoît, which is a generalization of the relation of Zimm written in its matrix form. We mainly discuss the case of binary mixtures consisting of a diblock copolymer A-B in solution and in the bulk state. To this end, we have investigated the variations of the partial structure factor S_aa(Q) as a function of the normalized wave-vector for various parameters. In particular, we have emphasized on the position of the scattering peak Q_max, its amplitude S_aa(Q_max) and zero angle signal S_aa(Q=0). The main conclusion is that, the circularity of cyclic chains affects drastically the structural properties of the system under consideration.     

The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock copolymer or a comb copolymer. Due to the presence of the large-scale structure, the chains are stretched. The aim of this paper is to investigate the influence of this chain stretching on the formation of the small-scale structure. To gain insight we study infinite melts of infinitely long copolymer chains that are subjected to a stretching force. For melts of monodisperse multiblock copolymers we find that the stretching destabilizes the homogeneous phase. If the stretching is strong, the lamellar structure is the only stable structure. The periodicity increases with the degree of stretching. For melts of monodisperse comb copolymers the chain stretching has no influence on the stability of the homogeneous phase. If the stretching is strong, the lamellar structure and the hexagonal structure are the only stable structures. The periodicity is independent of the degree of stretching. For the multiblock copolymer we investigated the influence of block length polydispersity. For small polydispersity the period of the structure increases monotonically with the degree of stretching. For intermediate polydispersity, the period initially decreases before it starts to increase. For large polydispersity, the mean-field period at the spinodal is infinite, becoming finite once the stretching force exceeds some critical value. For very large polydispersity the mean-field period at the spinodal remains infinite for any value of the stretching force. Received: 14 February 2002 / Accepted: 24 March 2003 / Published online: 29 April 2003 RID="a" ID="a"e-mail: hindrik.angerman@abp.nl     

Lagrange Structure and Dynamics for Solutions to the Spherically Symmetric Compressible Navier-Stokes Equations

The compressible Navier-Stokes system (CNS) with density-dependent viscosity coefficients is considered in multi-dimension, the prototype of the system is the viscous Saint-Venat model for the motion of shallow water. A spherically symmetric weak solution to the free boundary value problem for CNS with stress free boundary condition and arbitrarily large data is shown to exist globally in time with the free boundary separating fluids and vacuum and propagating at finite speed as particle path, which is continuous away from the symmetry center. Detailed regularity and Lagrangian structure of this solution have been obtained. In particular, it is shown that the particle path is uniquely defined starting from any non-vacuum region away from the symmetry center, along which vacuum states shall not form in any finite time and the initial regularities of the solution is preserved. Starting from any non-vacuum point at a later-on time, a particle path is also uniquely defined backward in time, which either reaches at some initial non-vacuum point, or stops at a small middle time and connects continuously with vacuum. In addition, the free boundary is shown to expand outward at an algebraic rate in time, and the fluid density decays and tends to zero almost everywhere away from the symmetry center as the time grows up. This finally leads to the formation of vacuum state almost everywhere as the time goes to infinity.     

Thermodynamic Free Energy Behavior of Diblock Copolymer Chains Confined Between Planar Surfaces Having End-Tethered Flexible Polymer Molecules

A molecular model for the free energy of a confined system of diblock copolymer chains within a 2D slit with the interior surfaces having end-tethered chains is presented, based on a combined lattice and scaling theory approach. The thermodynamics of a model system, based on a constrained minimization of free energy, is explored as a function of the intermolecular energy parameters for interaction between the segments of block copolymer chains, end-tethered chains, and the surfaces. The effects of chain length and the block length ratio are investigated over a wide range of values. The results obtained are qualitative in nature; however, the model can be implemented to real systems provided appropriate parameterization of the model parameters to real systems can be performed. The phase diagrams obtained here provide ways for designing thermodynamically stable systems within the physical parametric variable space.     

Binary-component micelle and vesicle: Free energy and asymmetric distributions of amphiphiles between monolayers of vesicle

The real-space two-dimensional self-consistent field theory (SCFT) is employed to study the free energies of micelles and vesicles constituted by binary amphiphilic diblock copolymer AB in homopolymer A. With increasing volume fraction of copolymer AB, there are morphological transitions from the circle micelles to oblate circle-like micelles, to compound structure with inverted micelles in the inner center and micelles outer layer, and to vesicles. Special attentions are paid to the role of the copolymer AB in controlling free energies of the micelles and vesicles, by examining the effect of length ratio of A/B with the fixed whole chain length of AB copolymer, the length effect of A or B block with the corresponding fixed length of B or A block, for one component of copolymer, and the effect of different amphiphile compositions for binary-component copolymer system. The quantity η is provided to describe the asymmetric density distribution of amphiphiles between the inner and outer monolayers of vesicles, and to quantify the relative asymmetric extent of the density distribution between two species of copolymers in binary component vesicles.     

Self—assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small—angle x—ray scattering

The aggregation behaviour of styrene-vinyl benzoic acid (PS_m-b-PVBA_n) amphiphilic diblock copolymers in selective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We have carried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymers of narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found that the aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms flat disc objects with the ratio of radius ω=0.4. The average radius gyration R_g of the copolymer decreases as solvents change from isopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with the addition of CoCl_2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h)∝h^{-α} in different selective solutions, suggesting that the PS_m-b-PVBA_n coils have self-similar structure behaviour or a fractal structure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changes dramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (D_m) from 2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course of changing solvents, decreasing surface fractal dimension (D_s) from 2.98 to 2.58 indicates that the copolymer micelle change from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasing D_m and D_s from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rather compact and rough disc form by adding CoCl_2 in ethanol solvents.     

Interface free energies in p-spin glass models

The replica method is used to calculate the interface free energy associated with the change from periodic to antiperiodic boundary conditions in finite-dimensional p-spin glass models in the phase which at mean-field level has one-step replica symmetry breaking (1RSB). In any finite dimension the interface free energy is exponentially small for a large system. This result implies that, in finite dimensions, the 1RSB state does not exist, as it is destroyed by thermal excitation of arbitrarily large droplets. The implications of this for the theory of structural glasses are discussed.     

Instability of Optical Solitons in the Boundary Value Problem for a Medium of Finite Extension

We consider an integrable nonlinear wave system (anisotropic chiral field model) which exhibits a soliton solution when the Cauchy problem for an infinitely long medium is posed. Whenever the boundary value problem is formulated for the same system but for a medium of finite extension, we reveal that the soliton becomes unstable and the true attractor is a different structure which is called polarization attractor. In contrast to the localized nature of solitons, the polarization attractor occupies the entire length of the medium. By demonstrating the qualitative difference between nonlinear wave propagation in an infinite medium and in a medium of finite extension (with simultaneous change of the initial value problem to the boundary value problem), we would like to point out that solitons may loose their property of being stable attractors. Additionally, our findings show the interest of developing methods of integration for boundary value problems.     

Discovering ordered phases of block copolymers: new results from a generic Fourier-space approach

A generic Fourier-space approach to solve the self-consistent field theory of block copolymers is developed. This approach is based on the fact that, for any computational box with periodic boundary conditions, all spatially varying functions are spanned by the Fourier series determined by the size and shape of the box. The method reproduces all known diblock copolymer phases. The application of this method to a model "frustrated" triblock copolymer leads to a phase diagram with a number of new phases. Furthermore, the capability of the method to reproduce experimentally observed structures is demonstrated using the knitting pattern of triblock copolymers.     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

Free energy evaluation in field-theoretic polymer simulations

We present a thermodynamic integration method for free energy evaluation in field-theoretic simulations of classical fluids and polymers. The approach employs an Einstein crystal reference state, analogous to a method developed for particle simulations of crystals by Frenkel and Ladd, but applies equally well in the present context to ordered and disordered phases. Thermodynamic averages are computed using complex Langevin sampling, which is effective against the sign problem inherent to polymer field theories. Our method is illustrated in the context of a diblock copolymer melt, where we provide a demonstration of the experimentally observed transition between the cubic gyroid and disordered phases.     

Stability of a block-copolymer lamella in a strong electric field

Using self-consistent field theory, we examine the stability of a lamellar layer of diblock copolymer subject to strong orthogonal electric fields. Two competing instabilities are identified; one is a peristaltic mode that leads to perpendicular lamellae, and the other is an undulatory mode that results in the formation of an undesirable grain boundary. The former kinetic pathway is favored when the central domain is relatively thin and composed of the low-dielectric material.     

Nucleation and growth kinetics in diblock styrene-butadiene

Time-resolved small-angle x-ray scattering has been used to study the phase transformation kinetics of a thermally quenched, asymmetric, diblock copolymer. The roles played by homogeneous and heterogeneous nucleation in the microdomain ordering process are considered through comparison of results from pure samples and samples doped with impurities. This crystallization process is unique in that it involves constituent particles (microdomains) that are hundreds of angstroms in size ordering onto a lattice with spacings on a similar length scale. Models derived from classical nucleation and growth theories are used to analyze results from pure and doped samples. Clear experimental evidence of a heterogeneous nucleation process occurring in the doped samples suggests that impurity effects cannot be ignored in these materials. In addition, it is proposed that the late-time coexistence of crystalline and amorphous microdomain structures is due to strain energy effects induced by the volume constraints of the sample cell.     

Influence of Grafting Density of Diblock Copolymers on Interfacial Assembly Behavior and Interfacial Shear Strength of Glass Fiber/Polystyrene Composites

To investigate the influence of the grafting density and the molecular structure of block copolymers on the interfacial assembly behavior and interfacial shear strength, macromolecular coupling agents, hydroxyl-terminated poly(n-butyl acrylate-b-styrene) (HO-P(BA-b-S)) were synthesized by atom transfer radical polymerization, and then chemically anchored on the glass fiber surfaces to form a well-defined monolayer. The phase separation and 'hemispherical' domain morphologies of diblock copolymer brushes at the polystyrene/glass fiber interface were observed. The interfacial assembly morphology differs with changes in the grafting density of diblock copolymers. When the grafting density is greatest, the highest height difference of the hemispherical domain and the largest surface roughness are achieved, as well as the best interface shear strength. It was also found that the copolymer brush with a PBA block of the polymerization degree (Xn) about 77 is the optimal option for the interfacial adhesion of PS/GF composites. Thus, the grafting density and molecular structure of diblock copolymers determines the interfacial assembly behavior of copolymer brushes, and therefore the interfacial shear strength.