Miscibility and exchange chemical potential of ring polymers in symmetric ring-ring blends.

Generally, differences of polymer topologies may affect polymer miscibility even with the same repeated units. In this study, the topological effect of ring polymers on miscibility was investigated by comparing symmetric ring-ring and linear-linear polymer blends. To elucidate the topological effect of ring polymers on mixing free energy, the exchange chemical potential of binary blends was numerically evaluated as a function of composition ϕ by performing semi-grand canonical Monte Carlo and molecular dynamics simulations of a bead-spring model. For ring-ring blends, an effective miscibility parameter was evaluated by comparing the exchange chemical potential with that of the Flory-Huggins model for linear-linear polymer blends. It was confirmed that in the mixed states satisfying χN > 0, ring-ring blends are more miscible and stable than the linear-linear blends with the same molecular weight. Furthermore, we investigated finite molecular weight dependence on the miscibility parameter, which reflected the statistical probability of interchain interactions in the blends. The simulation results revealed that the molecular weight dependence on the miscibility parameter was smaller in ring-ring blends. The effect of the ring polymers on miscibility was verified to be consistent with the change in the interchain radial distribution function. In ring-ring blends, it was indicated that the topology affected miscibility by reducing the effect of the direct interaction between the components of the blends.

Efficient compressed database of equilibrated configurations of ring-linear polymer blends for MD simulations.

To effectively archive configuration data during molecular dynamics (MD) simulations of polymer systems, we present an efficient compression method with good numerical accuracy that preserves the topology of ring-linear polymer blends. To compress the fraction of floating-point data, we used the Jointed Hierarchical Precision Compression Number - Data Format (JHPCN-DF) method to apply zero padding for the tailing fraction bits, which did not affect the numerical accuracy, then compressed the data with Huffman coding. We also provided a dataset of well-equilibrated configurations of MD simulations for ring-linear polymer blends with various lengths of linear and ring polymers, including ring complexes composed of multiple rings such as polycatenane. We executed 109 MD steps to obtain 150 equilibrated configurations. The combination of JHPCN-DF and SZ compression achieved the best compression ratio for all cases. Therefore, the proposed method enables efficient archiving of MD trajectories. Moreover, the publicly available dataset of ring-linear polymer blends can be employed for studies of mathematical methods, including topology analysis and data compression, as well as MD simulations.

Molecular dynamics studies of entropic elasticity of condensed lattice networks connected with uniform functionality f = 4.

To study the linear region of entropic elasticity, we considered the simplest physical model possible and extracted the linear entropic regime by using the least squares fit and the minimum of the mean absolute error. With regard to the effect of the fluctuation of the strand length Ns, the strand length with fluctuation was set to a form proportional to (1.0 + C (R - 0.5)), where R is a uniform random number between 0 and 1 and C is the amplitude of fluctuation. This form enabled us to analytically calculate the fluctuation dependence of the elastic modulus G. To reveal the linear regions of entropic elasticity as a function of the strand length between neighboring nodes in lattices, molecular dynamics (MD) simulations of condensed lattice networks with harmonic bonds without the excluded volume interactions were performed. Stress-strain curves were estimated by performing uniaxial stretching MD simulations under periodic boundary conditions with a bead number density of 0.85. First, we used a diamond lattice with functionality f = 4. The linear region of the entropic elasticity was found to become larger with the increasing number of beads in a strand Ns. For Ns = 100, the linear region had a strain of up to 8 for a regular diamond lattice. We investigated the effect of strand length fluctuation on the diamond lattice, and we confirmed that the equilibrium shear modulus G increases as the obtained analytical prediction and the linear entropic region in the stress-strain curves becomes narrower with increasing fluctuation of Ns. To investigate the difference in network topology with the same functionality f and uniform strand length Ns, we performed MD simulations on regular networks of the BC-8 structure with f = 4 prepared from the ab initio DFT calculations of carbon at high pressure. We found that the elastic behavior depends on the network connectivity (i.e., topology). This indicates that the network topology plays an important role in the emergence of nonlinearity owing to the crossover from entropic to energetic elasticity.

Thinning Approximation for Calculating Two-Dimensional Scattering Patterns in Dissipative Particle Dynamics Simulations under Shear Flow.

Modifications to improve thinning approximation (TA) were considered in order to calculate two-dimensional scattering patterns (2DSPs) for dissipative particle dynamics (DPD) simulations of polymer melts under a shear flow. We proposed multipoint TA and adaptive TA because the bond lengths in DPD chains vary widely when compared to those in Kremer⁻Grest (KG) chains, and the effectiveness of these two types of TA for the two major DPD parameter sets were investigated. In this paper, we report our findings on the original DPD model with soft bonds and that with rigid bonds. Based on the behavior of the 2DSPs and the distribution of orientations of the bond vectors, two spot patterns originating from the oriented chain correlations were observed when distinct distributions of the highly oriented bond vectors in the shear direction were obtained. For multipoint TA, we concluded that at least two additional midpoints ( n mid ≥ 2 ) are required to clearly observe the two spot patterns. For adaptive TA, a dividing distance of l ATA ≤ 0.4 is sufficient for clear observation, which is consistent with the requirement of n mid ≥ 2 for multipoint TA.

Two-dimensional lattice liquid models.

A family of models of liquid on a two-dimensional lattice (2D lattice liquid models) have been proposed as primitive models of soft-material membrane. As a first step, we have formulated them as single-component, single-layered, classical particle systems on a two-dimensional surface with no explicit viscosity. Among the family of the models, we have shown and constructed two stochastic models, a vicious walk model and a flow model, on an isotropic regular lattice and on some honeycomb lattices of various sizes. In both cases, the dynamics is governed by the nature of the frustration of the particle movements. By simulations, we have found the approximate functional form of the frustration probability and peculiar anomalous diffusions in their time-averaged mean-square displacements in the flow model. The relations to other existing statistical models and possible extensions of the models are also discussed.