Effects of counterion size and backbone rigidity on the dynamics of ionic polymer melts and glasses

Abstract

It is well-known that the nature and size of the counterions affect the ionic conductivity and glass transition temperature of ionic polymers in a significant manner. However, the microscopic origin of the underlying changes in the dynamics of chains and counterions is far from completely understood. Using coarse-grained molecular dynamics simulations of flexible and semi-flexible ionic polymers, we demonstrate that the glass transition temperature of ionic polymeric melts depends on the size of monovalent counterions in a non-monotonic manner. The glass transition temperature is found to be the highest for the smallest counterions and decreases with an increase in the counterion radii up to a point, after which the glass transition temperature increases with a further increase in the radii. This behavior is because the counterions have significant effects on the coupled dynamics of the charges on the chains and counterions. In particular, increase in the radii of the counterions leads to strongly coupled dynamics between the charges on the chains and the counterions. The static dielectric constant of the polymer melts also has a significant effect on the coupling and the glass transition temperature. The glass transition temperature is predicted to decrease with an increase in the dielectric constant. This, in turn, leads to an increase in the diffusion constant of the counterions at a given temperature. Backbone rigidity is shown to increase the glass transition temperature and decrease the coupling. Furthermore, faster counterion dynamics is predicted for the melts of semi-flexible chains in comparison with flexible chains at the same segmental relaxation time. As the semi-flexible chains tend to have a longer segmental relaxation time, semi-flexible polymers with high dielectric constants are predicted to have diffusion constants of counterions comparable with flexible polymers.

Structural and Mechanical Properties of Ionic Di-block Copolymers via a Molecular Dynamics Approach

“…Tg of both charged HPs and BCPs gradually increase with charge ratio. These results are in agreement with our previous study in the ionic homopolymer system, where an increase in the glass transition temperature of charged HPs was found as compared to their neutral counterpart [32,33]. At the same charge ratio, the Tg of BCPs is lower than that of HPs due to the lower Tg of B block.…”

“…Figure 4 demonstrates density versus temperature relation of both HPs and di-BCPs with varying charge ratio. Glass transition temperature (Tg) can be obtained by the change in the thermal expansion coefficient [32,33,34]. Tg of both charged HPs and BCPs gradually increase with charge ratio.…”

Miscibility and Nanoparticle Diffusion in Ionic Nanocomposites

“…The particle mesh Ewald (PME) method [96,97,98] has been used to treat the long range electrostatics with a Fourier-spacing of 0.12 nm and an order of interpolation 4. The dielectric constant of the coulombic part is ϵr=50 [99,100]. The Bjerrum length lB/σm=Zqiqj/ϵrkBT<1 (for R=2) signals weak electrostatic strength between monomers and nanoparticles.…”

Polymerized ionic liquids: Effects of counter‐anions on ion conduction and polymerization kinetics

“…Table 1 and Figure S5, Supporting Information confirms the T g s were dependent on the counter-ion and varied from 10 8C (1BDIMABr) to 242 8C (1BDI-MATf 2 N), where larger counter-ion size facilitated long range segmental motion and led to weaker ion associations, resulting in a lower T g . 24,[40][41][42][43][44][45] Previous works have attributed the counter-ion effect on T g to size, where larger counter-ions (Tf 2 N) tended to plasticize the polymer matrices more than smaller, tightly bound ions (Br), leading to a decrease in T g . 24 When comparing PILs with the same counter-ions but different molecular weights, the T g showed no significant variation.…”