Disentangling and Lamellar Thickening of Linear Polymers during Crystallization: Simulation of Bimodal and Unimodal Molecular Weight Distribution Systems.

We have performed coarse-grained molecular dynamics simulations to study the isothermal crystallization of bimodal and unimodal molecular weight distribution (MWD) polymers with equivalent average molecular weight (Mw). By using primitive path analysis, we can monitor the entanglement evolution during the process of crystallization. We have discovered a quantitative correlation between the degree of disentanglement and crystallinity, indicating that chain disentanglement permits the process of crystallization. In addition, the crystalline stem length also displays a linear relation with the degree of disentanglement at different temperatures. Based on the observation in our simulations, we can build a scenario of the whole process of chain disentangling and lamellar thickening on the basis of chain sliding diffusion. Furthermore, we have enough evidence to infer that the temperature dependence of crystalline stem length is basically a result of temperature dependence of chain sliding diffusion. Our observations are also in agreement with Hikosaka's sliding diffusion theory. Compared to the unimodal system, the disentanglement degree of the bimodal system is more delayed than its crystallinity due to the slower chain sliding of the long-chain component; the bimodal system reaches a larger crystalline stem length at all temperatures due to the promotion of higher chain sliding mobility of the short-chain component.

Crystallization of finite-extensible nonlinear elastic Lennard-Jones coarse-grained polymers.

The ability of a simple coarse-grained finite-extensible nonlinear elastic (FENE) Lennard-Jones (LJ) polymer model to be crystallized is investigated by molecular dynamics simulations. The optimal FENE Lennard-Jones parameter combinations (ratio between FENE and LJ equilibrium distances) and the optimal lattice parameters are calculated for five different perfect crystallite structures: simple tetragonal, body-centered tetragonal, body-centered orthorhombic, hexagonal primitive, and hexagonal close packed. It was found that the most energetically favorable structure is the body-centered orthorhombic. Starting with an equilibrated polymer liquid and with the optimal parameters found for the body-centered orthorhombic, an isothermal treatment led to the formation of large lamellar crystallites with a typical chain topology: folded, loop, and tie chains, and with a crystallinity of about 60%-70%, similar to real semicrystalline polymers. This simple coarse-grained Lennard-Jones model provides a qualitative tool to study semicrystalline microstructures for polymers.

A novel method for calculating the energy barriers for carbon diffusion in ferrite under heterogeneous stress.

A novel method for accurate and efficient evaluation of the change in energy barriers for carbon diffusion in ferrite under heterogeneous stress is introduced. This method, called Linear Combination of Stress States, is based on the knowledge of the effects of simple stresses (uniaxial or shear) on these diffusion barriers. Then, it is assumed that the change in energy barriers under a complex stress can be expressed as a linear combination of these already known simple stress effects. The modifications of energy barriers by either uniaxial traction/compression and shear stress are determined by means of atomistic simulations with the Climbing Image-Nudge Elastic Band method and are stored as a set of functions. The results of this method are compared to the predictions of anisotropic elasticity theory. It is shown that, linear anisotropic elasticity fails to predict the correct energy barrier variation with stress (especially with shear stress) whereas the proposed method provides correct energy barrier variation for stresses up to ∼3 GPa. This study provides a basis for the development of multiscale models of diffusion under non-uniform stress.

Hydrodynamic attraction of immobile particles due to interfacial forces.

Applying the method of reflections, we derive the flow pattern around a confined colloidal particle with quasislip conditions at its surface, in powers of the ratio a/h of particle radius and wall distance. The lowest order corresponds to a single reflection at the confining wall. Significant corrections occur at higher order: the linear term in a/h modifies the amplitudes of the well-known one-reflection approximation, whereas new features arise in quadratic order. Our results agree with recent experiments where thermo-osmosis drives hydrodynamic attractive forces in confined colloids.

Thermophoresis at a charged surface: the role of hydrodynamic slip.

By matching boundary layer hydrodynamics with slippage to the force-free flow at larger distances, we obtain the thermophoretic mobility of charged particles as a function of the Navier slip length b. A moderate value of b augments Ruckenstein's result by a term 2b/λ, where λ is the Debye length. If b exceeds the particle size a, the enhancement coefficient a/λ is independent of b but proportional to the particle size. Similar effects occur for transport driven by a salinity gradient or by an electric field.