Coarse-grained Description of Polymer Blends as Interacting Soft-Colloidal Particles

We present a theoretical approach which maps polymer blends onto mixtures of soft-colloidal particles. The analytical mesoscale pair distribution functions reproduce well data from united atom molecular dynamics simulations of polyolefin mixtures without fitting parameters. The theory exactly recovers the analytical expressions for density and concentration fluctuation structure factors of soft colloidal mixtures (liquid alloys).Comment: 27 REVTex4 pages, 8 PostScript figures, 1 table accepted for publication in Journal of Chemical Physic

Theory of the Spatial Transfer of Interface-Nucleated Changes of Dynamical Constraints and Its Consequences in Glass-Forming Films

We formulate a new theory for how caging constraints in glass-forming liquids at a surface or interface are modified and then spatially transferred, in a layer-by-layer bootstrapped manner, into the film interior in the context of the dynamic free energy concept of the Nonlinear Langevin Equation theory approach. The dynamic free energy at any mean location involves contributions from two adjacent layers where confining forces are not the same. At the most fundamental level of the theory, the caging component of the dynamic free energy varies essentially exponentially with distance from the interface, saturating deep enough into the film with a correlation length of modest size and weak sensitivity to thermodynamic state. This imparts a roughly exponential spatial variation of all the key features of the dynamic free energy required to compute gradients of dynamical quantities including the localization length, jump distance, cage barrier, collective elastic barrier and alpha relaxation time. The spatial gradients are entire of dynamical, not structural nor thermodynamic, origin. The theory is implemented for the hard sphere fluid and diverse interfaces which can be a vapor, a rough pinned particle solid, a vibrating pinned particle solid, or a smooth hard wall. Their basic description at the level of the spatially-heterogeneous dynamic free energy is identical, with the crucial difference arising from the first layer where dynamical constraints can be weakened, softened, or hardly changed depending on the specific interface. Numerical calculations establish the spatial dependence and fluid volume fraction sensitivity of the key dynamical property gradients for five different model interfaces. Comparison of the theoretical predictions for the dynamic localization length and glassy modulus with simulations and experiments for systems with a vapor interface reveals good agreement.Comment: 17 pages, 11 figures, Accepted on Journal of Chemical Physic

Site-averaging in the integral equation theory of interaction site models of macromolecular fluids: An exact approach

A simple "trick" is proposed, which allows to perform exactly the site-averaging procedure required when developing integral equation theories of interaction site models of macromolecular fluids. It shows that no approximation is involved when the number of Ornstein-Zernike equations coupling the site-site correlation functions is reduced to one. Its potential practical interest for future theoretical developments is illustrated with a rederivation of the so-called molecular closures.Comment: 2 pages, revTeX

Polymer-Mode-Coupling Theory of Finite-Size-Fluctuation Effects in Entangled Solutions, Melts and Gels. I. General Formulation and Predictions

The transport coefficients of dense polymeric fluids are approximately calculated from the microscopic intermolecular forces. The following finite molecular weight effects are discussed within the Polymer-Mode-Coupling theory (PMC) and compared to the corresponding reptation/ tube ideas: constraint release mechanism, spatial inhomogeneity of the entanglement constraints, and tracer polymer shape fluctuations. The entanglement corrections to the single polymer Rouse dynamics are shown to depend on molecular weight via the ratio N/N_e, where the entanglement degree of polymerization, N_e, can be measured from the plateau shear modulus. Two microscopically defined non-universal parameters, an entanglement strength 1/alpha and a length scale ratio, delta= xi_rho/b, where xi_rho and b are the density screening and entanglement length respectively, are shown to determine the reduction of the entanglement effects relative to the reptation- -like asymptotes of PMC theory. Large finite size effects are predicted for reduced degrees of polymerization up to N/N_e\le10^3. Effective power law variations for intermediate N/N_e of the viscosity, eta\sim N^x, and the diffusion constant, D\sim N^{-y}, can be explained with exponents significantly exceeding the asymptotic, reptation-like values, x\ge 3 and y\ge2, respectively. Extensions of the theory to treat tracer dielectric relaxation, and polymer transport in gels and other amorphous systems, are also presented.Comment: Latex, figures and styles files included; Macromolecules, in press (1997

Mode-coupling theory for structural and conformational dynamics of polymer melts

A mode-coupling theory for dense polymeric systems is developed which unifyingly incorporates the segmental cage effect relevant for structural slowing down and polymer chain conformational degrees of freedom. An ideal glass transition of polymer melts is predicted which becomes molecular-weight independent for large molecules. The theory provides a microscopic justification for the use of the Rouse theory in polymer melts, and the results for Rouse-mode correlators and mean-squared displacements are in good agreement with computer simulation results.Comment: 4 pages, 3 figures, Phys. Rev. Lett. in pres