Dynamics of Diblock Copolymers in Dilute Solutions

We consider the dynamics of freely translating and rotating diblock (A-B), Gaussian copolymers, in dilute solutions. Using the multiple scattering technique, we have computed the diffusion and the friction coefficients D_AB and Zeta_AB, and the change Eta_AB in the viscosity of the solution as functions of x = N_A/N and t = l_B/l_A, where N_A, N are the number of segments of the A block and of the whole copolymer, respectively, and l_A, l_B are the Kuhn lengths of the A and B blocks. Specific regimes that maximize the efficiency of separation of copolymers with distinct "t" values, have been identified.Comment: 20 pages Revtex, 7 eps figures, needs epsf.tex and amssymb.sty, submitted to Macromolecule

Unicyclic Components in Random Graphs

The distribution of unicyclic components in a random graph is obtained analytically. The number of unicyclic components of a given size approaches a self-similar form in the vicinity of the gelation transition. At the gelation point, this distribution decays algebraically, U_k ~ 1/(4k) for k>>1. As a result, the total number of unicyclic components grows logarithmically with the system size.Comment: 4 pages, 2 figure

Critical Dynamics of Gelation

Shear relaxation and dynamic density fluctuations are studied within a Rouse model, generalized to include the effects of permanent random crosslinks. We derive an exact correspondence between the static shear viscosity and the resistance of a random resistor network. This relation allows us to compute the static shear viscosity exactly for uncorrelated crosslinks. For more general percolation models, which are amenable to a scaling description, it yields the scaling relation $k=\phi-\beta$ for the critical exponent of the shear viscosity. Here $\beta$ is the thermal exponent for the gel fraction and $\phi$ is the crossover exponent of the resistor network. The results on the shear viscosity are also used in deriving upper and lower bounds on the incoherent scattering function in the long-time limit, thereby corroborating previous results.Comment: 34 pages, 2 figures (revtex, amssymb); revised version (minor changes

Universality and its Origins at the Amorphous Solidification Transition

Systems undergoing an equilibrium phase transition from a liquid state to an amorphous solid state exhibit certain universal characteristics. Chief among these are the fraction of particles that are randomly localized and the scaling functions that describe the order parameter and (equivalently) the statistical distribution of localization lengths for these localized particles. The purpose of this Paper is to discuss the origins and consequences of this universality, and in doing so, three themes are explored. First, a replica-Landau-type approach is formulated for the universality class of systems that are composed of extended objects connected by permanent random constraints and undergo amorphous solidification at a critical density of constraints. This formulation generalizes the cases of randomly cross-linked and end-linked macromolecular systems, discussed previously. The universal replica free energy is constructed, in terms of the replica order parameter appropriate to amorphous solidification, the value of the order parameter is obtained in the liquid and amorphous solid states, and the chief universal characteristics are determined. Second, the theory is reformulated in terms of the distribution of local static density fluctuations rather than the replica order parameter. It is shown that a suitable free energy can be constructed, depending on the distribution of static density fluctuations, and that this formulation yields precisely the same conclusions as the replica approach. Third, the universal predictions of the theory are compared with the results of extensive numerical simulations of randomly cross-linked macromolecular systems, due to Barsky and Plischke, and excellent agreement is found.Comment: 10 pages, including 3 figures (REVTEX

Elasticity near the vulcanization transition

Signatures of the vulcanization transition--amorphous solidification induced by the random crosslinking of macromolecules--include the random localization of a fraction of the particles and the emergence of a nonzero static shear modulus. A semi-microscopic statistical-mechanical theory is presented of the latter signature that accounts for both thermal fluctuations and quenched disorder. It is found (i) that the shear modulus grows continuously from zero at the transition, and does so with the classical exponent, i.e., with the third power of the excess cross-link density and, quite surprisingly, (ii) that near the transition the external stresses do not spoil the spherical symmetry of the localization clouds of the particles.Comment: REVTEX, 5 pages. Minor change

Multi-Particle Collision Dynamics -- a Particle-Based Mesoscale Simulation Approach to the Hydrodynamics of Complex Fluids

In this review, we describe and analyze a mesoscale simulation method for fluid flow, which was introduced by Malevanets and Kapral in 1999, and is now called multi-particle collision dynamics (MPC) or stochastic rotation dynamics (SRD). The method consists of alternating streaming and collision steps in an ensemble of point particles. The multi-particle collisions are performed by grouping particles in collision cells, and mass, momentum, and energy are locally conserved. This simulation technique captures both full hydrodynamic interactions and thermal fluctuations. The first part of the review begins with a description of several widely used MPC algorithms and then discusses important features of the original SRD algorithm and frequently used variations. Two complementary approaches for deriving the hydrodynamic equations and evaluating the transport coefficients are reviewed. It is then shown how MPC algorithms can be generalized to model non-ideal fluids, and binary mixtures with a consolute point. The importance of angular-momentum conservation for systems like phase-separated liquids with different viscosities is discussed. The second part of the review describes a number of recent applications of MPC algorithms to study colloid and polymer dynamics, the behavior of vesicles and cells in hydrodynamic flows, and the dynamics of viscoelastic fluids

Crossover phenomena in spin models with medium-range interactions and self-avoiding walks with medium-range jumps

We study crossover phenomena in a model of self-avoiding walks with medium-range jumps, that corresponds to the limit $N\to 0$ of an $N$-vector spin system with medium-range interactions. In particular, we consider the critical crossover limit that interpolates between the Gaussian and the Wilson-Fisher fixed point. The corresponding crossover functions are computed using field-theoretical methods and an appropriate mean-field expansion. The critical crossover limit is accurately studied by numerical Monte Carlo simulations, which are much more efficient for walk models than for spin systems. Monte Carlo data are compared with the field-theoretical predictions concerning the critical crossover functions, finding a good agreement. We also verify the predictions for the scaling behavior of the leading nonuniversal corrections. We determine phenomenological parametrizations that are exact in the critical crossover limit, have the correct scaling behavior for the leading correction, and describe the nonuniversal lscrossover behavior of our data for any finite range.Comment: 43 pages, revte

Interfacial Profile and Propagation of Frontal Photopolymerization Waves

We investigate the frontal photopolymerization of a thiol–ene system with a combination of experiments and modeling, focusing on the interfacial conversion profile and its planar wave propagation. We spatially resolve the solid-to-liquid front by FT-IR and AFM mechanical measurements, supplemented by differential scanning calorimetry. A simple coarse-grained model is found to describe remarkably well the frontal kinetics and the sigmoidal interface, capturing the effects of UV light exposure time (or dose) and temperature, as well as the front position and resulting patterned dimensions after development. Analytical solutions for the conversion profile enable the description of all conditions with a single master curve in the moving frame of the front position. Building on this understanding, we demonstrate the design and fabrication of gradient polymer materials, with tunable properties <i>along</i> the direction of illumination, which can be coupled with lateral patterning by modulated illumination or grayscale lithography