Soret coefficients of the ternary system of poly(ethylene oxide) in mixed water/ethanol solvent were measured over a wide solvent composition range by means of thermal diffusion forced Rayleigh scattering. The Soret coefficient ST of the polymer was found to change sign as the water content of the solvent increases with the sign change taking place at a water mass fraction of 0.83 at a temperature of 22 °C. For high water concentrations, the value of ST of poly(ethylene oxide) is positive, i.e., the polymer migrates to the cooler regions of the fluid, as is typical for polymers in good solvents. For low water content, on the other hand, the Soret coefficient of the polymer is negative, i.e., the polymer migrates to the warmer regions of the fluid. Measurements for two different polymer concentrations showed a larger magnitude of the Soret coefficient for the smaller polymer concentration. The temperature dependence of the Soret coefficient was investigated for water-rich polymer solutions and revealed a sign change from negative to positive as the temperature is increased. Thermodiffusion experiments were also performed on the binary mixture water/ethanol. For the binary mixtures, the Soret coefficient of water was observed to change sign at a water mass fraction of 0.71. This is in agreement with experimental results from the literature. Our results show that specific interactions (hydrogen bonds) between solvent molecules and between polymer and solvent molecules play an important role in thermodiffusion for this system.
Thermal diffusion forced Rayleigh scattering results on thermal diffusion of poly(ethylene oxide) (PEO) in ethanol/water mixtures are presented. In water-rich solvent mixtures, PEO is found to migrate towards regions of lower temperature. This is typical for polymer solutions and corresponds to a positive Soret coefficient of PEO. In solvent mixtures with low water content, however, the polymer is found to migrate towards higher temperatures, corresponding to a negative Soret coefficient of PEO in ethanol-rich solutions. To our knowledge, this is the first observed sign change of the Soret coefficient of a polymer in solution. We also present a simple lattice model for the polymer solvent system and calculate Soret coefficients with statistical mechanics methods. The calculated values agree qualitatively with the experimental results.
A novel polymer host from carboxymethyl cellulose (CMC)/poly(N-isopropylacrylamide) (PNiPAM) was developed for a high safety solid polymer electrolyte (SPE) in a zinc ion battery. Effects of the PNiPAM loading level in the range of 0–40% by weight ( wt%) on the chemical, mechanical, thermal, and morphological properties of the CMC/PNiPAMx films (where x is the wt% of PNiPAM) were symmetrically investigated. The obtained CMC/PNiPAMx films showed a high compatibility between the polymers. The CMC/PNiPAM20 blend showed the greatest tensile strength and modulus at 37.9 MPa and 2.1 GPa, respectively. Moreover, the thermal degradation of CMC was retarded by the addition of PNiPAM. Scanning electron microscopy images of CMC/PNiPAM20 revealed a porous structure that likely supported Zn2+ movement in the SPEs containing zinc triflate, resulting in the high Zn2+ ion transference number (0.56) and ionic conductivity (1.68 × 10–4 S cm−1). Interestingly, the presence of PNiPAM in the CMC/PNiPAMx blends showed a greater stability during charge–discharge cyclic tests, indicating the ability of PNiPAM to suppress dendrite formation from causing a short circuit. The developed CMC/PNiPAM20 based SPE is a promising material for high ionic conductivity and stability in a Zn ion battery.
Results on thermodiffusion of poly(ethylene oxide) and colloidal boehmite (γ-AlOOH) rods in ethanol/water mixtures are presented. Data were obtained using thermal diffusion forced Rayleigh scattering. The sign of the Soret coefficient of the boehmite rods changes from positive to negative with increasing water content, i.e., at sufficiently high water content the colloidal particles move to higher temperatures. The sign of the Soret coefficient of the poly(ethylene oxide) in ethanol/water mixtures is negative, i.e., the poly(ethylene oxide) molecules move to higher temperatures, whereas in pure water the sign is positive. To our knowledge this is the first time that a sign change has been observed for polymers in solution. The analysis of the static light scattering on poly(ethylene oxide) allows the determination of the preferentially solvating solvent. In the investigated concentration range the preferentially solvating solvent is ethanol, in spite of being the poorer solvent for poly(ethylene oxide).