The influence of spacer composition on thermomechanical properties, crystallinity, and morphology in ionene segmented copolymers.

A series of segmented ammonium ionenes with varying weight fractions of 2000 g mol-1 poly(ethylene glycol) (PEG) or poly(tetramethylene oxide) (PTMO) soft segments were synthesized, and a simplified coarse-grained model of these materials was implemented using molecular dynamics simulations. In addition to varying soft segment type (PTMO vs. PEG), charge density and soft segment content were varied to create a comprehensive series of segmented ammonium ionenes; thermogravimetric analysis reveals that all segmented ionenes in the series are thermally stable up to 240 °C. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) show the formation of phase separated microdomains at low soft segment content. In particular, DSC shows that the hard and soft domains have distinct glass transition temperatures. Similarly, simulations show that reduced soft segment content induces stronger microphase separation, reduces soft segment mobility, and increases ionic aggregate connectivity and size. These increased ionic associations result in elastomeric behavior, as evidenced by the higher rubbery plateau moduli observed at lower soft segment contents through DMA. Moreover, simulations show that ionic aggregation increases when switching from PEG to the less polar PTMO repeat units, which is consistent with DMA results showing higher plateau moduli for PTMO-based ionenes relative to PEG ionenes. DSC and X-ray diffraction determined that the degree of crystallinity increased with soft segment content regardless of segment type. Overall, these results suggest a semi-crystalline microphase-separated morphology strongly influenced by charge density, the degree of ionic aggregation, and the resulting level of confinement and mobility of the soft segments.

Measurement and prediction of kinematic viscosity for linear ethers.

Using the methods of equilibrium and non-equilibrium molecular dynamics alongside capillary viscometer experiments, we explore differences between united and all-atom models of a series of linear ethers. The models are based on two transferable force fields, and changes in viscosity and diffusion are studied across a wide range of temperatures and shear rates. We analyze diffusivity and viscosity data by means of the rotational relaxation time and Arrhenius equation. Rotational relaxation times are calculated explicitly from the ether chain's end-to-end vectors, and self-diffusion values are calculated from the mean square displacement. We find an increase in orientational alignment as temperature drops in both models and consistent differences in activation energies across the models and experiment. A clear relationship is observed between viscosity, rotational relaxation time, and diffusion time. These time constants also impact the reliability of the viscosity value determined by the Green-Kubo method. We also study the trends in zero-shear viscosity as chain length increases and force field performance relative to experiment as this length changes.

Integrating dissipative particle dynamics with energy conservation.

To suppress secular energy drift in dissipative particle dynamics simulations with energy conservation, we introduce an additional pairwise particle dynamics that allows for a microscopic energy fluctuation while conserving the total linear momentum of the system exactly. The pairwise dynamics may be regarded as an adaptation of the thermostat in isothermal dissipative particle dynamics, but leads to microcanonical instead of canonical ensemble at equilibrium and allows for a nonuniform temperature field at a steady state. The method is also effective in suppressing secular energy drift when used in combination with reverse nonequilibrium molecular dynamics moves. All of the equilibrium and transport properties we computed were unaffected by this additional pairwise dynamics.