Equilibration strategies in molecular dynamics simulation of polyethers

A comparison of the NVT and NVE ensemble simulations of tetraglyme showed that, in terms of energy, temperature and most of the structural features the results were very similar. However, major differences were observed in dynamic properties, ie in the mean square displacement and in the O--O distances. A fast equilibration method suitable for amorphous polymer systems is also detailed. This was accomplished by the reassignment of the velocity distribution to the particles, after the interruption of an NVE simulation.

Conductivity and NMR properties of plasticized polyethers complexed with lithium salts

NMR provides a tool whereby the dynamic properties of specific nuclei can be investigated. In the present study, a poly(ethylene oxide-co-propylene oxide) network has been used as the polymer host to prepare solid polymer electrolytes (SPE) containing either LiClO₄ or LiCF₃SO₃. In addition, a low molecular weight plasticizer [propylene carbonate (PC), dimethyl formamide (DMF) or tetraglyme] has been added to several of the samples to enhance the mobility of the polymer and, thus, of the ionic species. The effects of plasticizer and salt concentration on the ionic structure and mobility in these SPEs, as measured by NMR relaxation times, and correlation to the conductivity behaviour in these systems are discussed. Temperature dependent triflate diffusion coefficients, as measured by Pulsed Field Gradient ¹⁹F-NMR, in plasticized SPEs are also reported.

13 C NMR spin–lattice relaxation times as a probeof local polymer dynamics in plasticized polyethers

¹³C NMR spin–lattice relaxation times T₁ are used to investigate the effect of low molecular weight diluents, including N,N-dimethylformamide, N-methylformamide, propylene carbonate, γ-butyrolactone, triglyme and tetraglyme, on the local polymer segmental motion in polyether–urethane networks. In all cases, an increase in the local mobility is deduced from the increasing T₁ measurements consistent with a decreasing glass transition temperature. The extent of plasticization, however, is dependent on the nature of the small molecules. Those molecules which can either form strong polymer-diluent interactions (for example through dipolar interactions) or are themselves rigid, give the least enhancement of polymer mobility and the greatest deviation from the Fox equation for T_g. In the presence of alkali metal salts, N,N-dimethylformamide and propylene carbonate are shown to have opposite effects on the local polymer motion, as seen from the T₁ measurements. In both cases, addition of the plasticizers increases the ¹³C T₁ relaxation times for the plasticizer. However, propylene carbonate decreases the polymer ¹³C T₁ whilst N,N-dimethylformamide results in the expected increase in polymer ¹³C T₁.

A 13C NMR study of the role of plasticizers in the conduction mechanism of solid polymer electrolytes

The addition of low molecular weight solvents such as dimethyl formamide (DMF) and propylene carbonate (PC) to urethane crosslinked polyethers results in enhancement of polymer segmental motion, as determined in this work from polymer ¹³C spin lattice relaxation measurements (T₁) and glass transition temperatures. The formation of salt-polyether complexes results in a decrease in T₁, even in the presence of the plasticizer, indicating that the polymer ether molecules are still involved in the alkali metal coordination. In a polymer electrolyte containing 1 mol kg⁻¹ LiClO₄ the addition of DMF and PC have significantly different affects on the polymer mobility, although they both enhance the conductivity. The conductivity enhancement therefore is not solely the result of an increased solvent mobility.

Structure-property relationships in plasticized solid polymer electrolytes

The addition of various kinds of plasticizers can enhance the conductivity of polymer electrolyte systems, in some cases by many orders of magnitude. The plasticizer may be a low molecular weight solvent, or be a low molecular weight polymer. As the plasticizer concentration increases there is an inevitable deterioration in material properties. In this work we have investigated the effect of plasticizer on the conductivity, thermal properties and matrial properties of a number of systems including urethane cross-linked polyethers and polyacrylates. In some of the systems, in particular the polyether electrolytes, the plasticizer acts to enhance conduction by acting as a cosolvent for the salt as well as increasing chain flexibility. Its efficacy is dependent on its structure and characteristics as a solvent. Although T_g is lowered in a close to linear fashion with increasing plasticizer content and thereby conductivity increased rapidly, the elastic modulus changes more slowly. This reflects the coupling of conduction to the local mobility of the molecular units of the combined solvent system and the relative decoupling of the mobility and glass transition from the material properties. In these systems the latter are a function mainly of the longer range structure of the polymer network. The changes in conductivity and materials properties are interpreted in terms of a configurational entropy model of the solution.