Theory of microphase separation in charged crosslinked polymer blends with arbitrary charge distribution

In this paper, we are interested in the phase behavior and scattering properties of charged crosslinked polymer blends in solution. The system undergoes a microphase separation, below some critical temperature. To study such a transition, use is made of the standard de Gennes theory based on an analogy with a dielectric medium. This analogy is extended to include the effects of the initial composition fluctuations in order to improve its agreement with experimental data in the small wave vector range. The excluded-volume interactions are explicitly introduced through the blob model. The charge effects on the phase behavior are examined, for any charge distribution of polyions and for any salt concentration. This completes a previous study which was concerned with the situation where only one species is charged. The early kinetics of microphase separation is discussed, and the charges contribution to the growth rate is also evaluated.     

Theory of microphase separation in crosslinked polymer blends immersed in a $ \theta$ -solvent

The aim of this work is a theoretical study of the effects of the solvent quality on the microphase separation in crosslinked polymer blends, from a static and kinetics point of view. More precisely, we assume that the crosslinked mixture is trapped in a q \theta -solvent. The static microphase properties are studied through the static structure factor. The latter is computed using an extended blob model, where the crosslinked unlike chains can be viewed as sequences of blobs. We demonstrate that the presence of the q \theta -solvent simply leads to a multiplicative renormalization of these properties, and the renormalization factors are powers of the overall monomer volume fraction. Second, we investigate the early kinetics of the microphase separation, via the relaxation rate, t_q \tau_{q}^{} , which is a function of the wave number q (at fixed temperature and monomer volume fraction). We first show that the kinetics is entirely controlled by local motions of Rouse type, since the slow motions are frozen out by the presence of crosslinks. Using the blob model, we find an explicit form for the growth rate W \Omega(q) = t_q^-1 \tau_{q}^{{-1}} , which depends, in addition to the wave number q , on the overall monomer volume fraction, F \Phi . Also, we discuss the effect of initial entanglements that are trapped when the system is crosslinked. In fact, these play the role of true reticulation points, and then, they quantitatively contribute to the microseparation phenomenon. Finally, the results are compared to their homologous relatively to the molten state and to the good solvent case. The main conclusion is that the quality of the solvent induces drastic changes of the microphase properties.     

Critical behaviour of thin films with quenched impurities

The critical behaviour of thin films containing quenched random impurities and inhomogeneities is investigated by the renormalization-group method to the one-loop order within the framework of the n-component φ⁴-model. The finite-size crossover in impure films has been considered on the basis of the fundamental relationship between the effective dimensionality D_eff and the characteristic lengths of the system. The fixed points, their stability properties and the critical exponents are obtained and analyzed, using an -expansion near the effective spatial dimensionality D_eff of the fluctuation modes in D-dimensional hyperslabs with two types of quenched impurities: point-like impurities with short-range random correlations and extended (linear) impurities with infinite-range random correlations along the small-size spatial direction. The difference between the critical properties of infinite systems and films is demonstrated and investigated. A new critical exponent, describing the scaling properties of the thickness of films with extended impurities has been derived and calculated. A special attention is paid to the critical behaviour of real impure films (D=3).     

Critical properties of the three-dimensional Ising model with quenched disorder

The static critical properties of the three-dimensional Ising model with quenched disorder are studied by the Monte-Carlo (MC) method on a simple cubic lattice, in which the quenched disorder is distributed as nonmagnetic impurities by the canonical manner. The calculations are carried out for systems with periodic boundary conditions and spin concentrations p=1.0; 0.95; 0.9; 0.8; 0.7; 0.6. The systems of non-linear sizes L×L×L, L=20-60 are researched. On the basis of the finite-size scaling (FSS) theory, the static critical exponents of specific heat α, susceptibility γ, magnetization β, and an exponent of the correlation radius in a studied interval of concentrations p are calculated. It is shown that the three-dimensional Ising model with quenched disorder has two regimes of the critical behavior universality in a dependence on nonmagnetic impurities.     

Field-theoretical Renormalization-Group approach to critical dynamics of crosslinked polymer blends

We consider a crosslinked polymer blend that may undergo a microphase separation. When the temperature is changed from an initial value towards a final one very close to the spinodal point, the mixture is out equilibrium. The aim is the study of dynamics at a given time t, before the system reaches its final equilibrium state. The dynamics is investigated through the structure factor, S(q, t), which is a function of the wave vector q, temperature T, time t, and reticulation dose D. To determine the phase behavior of this dynamic structure factor, we start from a generalized Langevin equation (model C) solved by the time composition fluctuation. Beside the standard de Gennes Hamiltonian, this equation incorporates a Gaussian local noise, ζ. First, by averaging over ζ, we get an effective Hamiltonian. Second, we renormalize this dynamic field theory and write a Renormalization-Group equation for the dynamic structure factor. Third, solving this equation yields the behavior of S(q, t), in space of relevant parameters. As result, S(q, t) depends on three kinds of lengths, which are the wavelength q ⁻¹, a time length scale R(t) ∼ t ^1/z , and the mesh size ξ ^*. The scale R(t) is interpreted as the size of growing microdomains at time t. When R(t) becomes of the order of ξ ^*, the dynamics is stopped. The final time, t ^*, then scales as t ^* ∼ ξ ^{* z}, with the dynamic exponent z = 6−η. Here, η is the usual Ising critical exponent. Since the final size of microdomains ξ ^* is very small (few nanometers), the dynamics is of short time. Finally, all these results we obtained from renormalization theory are compared to those we stated in some recent work using a scaling argument.     

Critical properties of random anisotropy magnets

The problem of critical behaviour of three dimensional random anisotropy magnets, which constitute a wide class of disordered magnets is considered. Previous results obtained in experiments, by Monte Carlo simulations and within different theoretical approaches give evidence for a second order phase transition for anisotropic distributions of the local anisotropy axes, while for the case of isotropic distribution such transition is absent. This outcome is described by renormalization group in its field theoretical variant on the basis of the random anisotropy model. Considerable attention is paid to the investigation of the effective critical behaviour which explains the observation of different behaviour in the same universality class.     

Diffusion-induced growth of compositional heterogeneity in polymer blends containing random copolymers

The compositional relaxation in random copolymer systems on a macroscopic scale is considered in theory. A set of diffusion equations is derived that describes the motion of chains of different composition and then converted into coupled equations for statistical moments of the compositional distribution. Several ways to solve the closure problem for these equations are discussed. The simplest is the situation when the shape of the transient compositional distribution can be predicted a priori, for example, a bimodal distribution is kept during interdiffusion of two copolymers that are not very close in composition. For a general case, it is shown that the cumulant-neglect closure based on the truncation of high-order cumulants is an effective method to get an approximate solution in terms of the time-dependent local mean composition and its dispersion. This method is applied to non-homogeneous compatible polymer systems, such as a random copolymer AB of a composition varying in space, a bilayer of Bernoullian copolymers AB of different composition, and a bilayer of homopolymers A and B, in which an autocatalytic polymer-analogous reaction A → B takes place, with possibility of the neighbor group effect. It is found that the interdiffusion can lead to a substantial broadening of the local compositional distribution, which, in turn, accelerates the system dynamics and promotes chemical reactions.     

Magnetic correlations in ferromagnets with quenched random fields

The critical dynamics of the relaxational model for ferromagnets in quenched random fields is studied within the framework of the -expansion (=6–d). The shape functionf _x () is obtained exactly atT _c ; it remains finite when the frequency vanishes. The static and dynamic properties of the model belowT _c are also considered. The equation of state and the static correlation function are related to those of the (d–2)-dimensional pure systems. The dynamic response functionG is obtained for zero momentum. The scaling form of the random correlation functionC ^(s) , which determines the spin-glass order parameter, is obtained. The coexistence curve singularities of ,G andC ^(s) when the number of spin componentsn2, are studied.     

Suppression of antiferromagnetic correlations by quenched dipole-type impurities

The effects of quenched dipole moments on a two-dimensional Heisenberg antiferromagnet are found exactly, by applying the renormalization group to the appropriate classical non-linear sigma model. Such dipole moments represent random fields with power law correlations. At low temperatures, they also represent the long range effects of quenched random strong ferromagnetic bonds on the antiferromagnetic correlation length, , of a two-dimensional Heisenberg antiferromagnet. It is found that the antiferromagnetic long range order is destroyed for any non-zero concentration, x, of the dipolar defects, even at zero temperature. Below a line , where T is the temperature, is independent of T, and decreases exponentially with x. At higher temperatures, it decays exponentially with , with an effective stiffness constant , which decreases with increasing x/T. The latter behavior is the same as for annealed dipole moments, and we use our quenched results to interpolate between the two types of averaging for the problem of ferromagnetic bonds in an antiferromagnet. The results are used to estimate the three-dimensional Néel temperature of a lamellar system with weakly coupled planes, which decays linearly with x at small concentrations, and drops precipitously at a critical concentration. These predictions are shown to reproduce successfully several of the prominent features of experiments on slightly doped copper oxides. Received 22 October 1998     

Statistical mechanics of quenched inhomogeneous systems with random disorder

We propose a method to treat quenched disordered systems within the frame of an inhomogeneous ensemble of configurations. To describe a definite configuration, we make use of occupation numbers. By choosing an appropriate representation of these occupation numbers, we are able to deal with an inhomogeneous ensemble by elementary techniques as for instance used for uncorrelated occupation numbers in the frame of a translation invariant ensemble.     

Critical properties of randomly triangulated planar random surfaces

A discrete version of the Polyakov string is studied by analytical and numerical methods. The role of the intrinsic metric is played by random triangulation. The results only qualitatively agree with the Liouville perturbation theory. In particular, the critical exponents for the solvable cases D = 0 and D = ?2 are shown to be larger than those calculated perturbatively. Our numerical simulations for D = 3 indicate a large but finite Hausdorff dimension dH = 10.0 ±0.2.     

Delocalization in disordered chains with random symmetrical impurities

We study in this paper, with the context of a tight-binding on-side model, the electronic properties of one-dimensional random lattices with correlated impurities. We show that, when symmetrical impurities are inserted in a host chain of site energy and a constant hopping interaction V, diffusion will occur even when is random. We provide analytic expressions for the transmittance and confirm the theoretical results by a great deal of numerical calculations. When = V, we find that the mean-square displacement (MSD) follows the law m ² ∝t ^β with β = 2.0 for = constant and β = 1.0 for = = random, respectively. Received 15 January 2001 and Received in final form 30 April 2001