0000000000496209
AUTHOR
John M. Zielinski
An Alternate Interpretation of Polymer/Solvent Jump Size Units for Free-Volume Diffusion Models
Polystyrene/toluene mutual-diffusion coefficients have been measured as a function of temperature in the limit of infinite solvent dilution. The solvent to polymer jump size unit ratio (ξ) was determined from the Vrentas−Duda free-volume diffusion model for polymer self-diffusion and is in excellent agreement with values evaluated from solvent self- and binary mutual-diffusion coefficient data. Comparison of the free-volume model to a version of the Kirkwood−Riseman theory, modified for diffusion at infinite dilution under non-ϑ conditions, suggests that ξ follows the temperature dependence of the root-mean-squared end-to-end distance of the polystyrene and can be estimated without the use …
Probe diffusion in homogeneous diblock copolymers
Forced Rayleigh scattering was used to investigate the diffusion of a photoreactive dye molecule in two homogeneous poly(styrene-b-isoprene) (SI) diblock copolymers with overall molecular weights of approximately 2000. Although diffusion rates were intermediate to TTI transport in homopolymer polystyrene (PS) and polyisoprene (PI), system dynamics appear to be largely dictated in each case by the PI block. The size of the polymer jumping unit, on the other hand, is evaluated from a free-volume analysis of the data, and is found to be governed predominantly by the PS component of the copolymer. The mechanism for tracer diffusion in low-molecular-weight block copolymers appears analogous to t…
1,3,5-triisopropylbenzene diffusion in polystyrene solutions
Self-diffusion coefficients of 1,3,5-triisopropylbenzene (TIB) in binary solutions with polystyrene and ternary mixtures comprised of TIB, toluene, and polystyrene have been measured by static gradient nuclear magnetic resonance (SG-NMR) techniques. These data, as well as mutual-diffusion coefficient data measured by capillary column inverse gas chromatography (CCIGC), have been analyzed here with the Vrentas-Duda free-volume diffusion model. Although both binary and ternary diffusion coefficient data can be accurately correlated with the model, the results contradict those of an earlier investigation, which suggested that TIB diffuses as a single unit in polystyrene solutions. The new data…
A friction factor analysis of the coupling between polymer/solvent self- and mutual-diffusion: polystyrene/toluene
The Bearman statistical mechanical theory, which couples the mutual-diffusion and self-diffusion coefficients via friction factors, has been applied to polystyrene/toluene solutions with polystyrene molecular weights of 18 kDa and 900 kDa. Toluene and polystyrene self-diffusion coefficients, obtained from the literature and measured here, along with polystyrene/toluene binary mutual-diffusion coefficients and thermodynamic data, were employed to independently calculate the three friction coefficients (ξ 12 , ξ 11 , and ξ 22 ) required to describe transport within binary solutions. Results reveal that the frequently used geometric mean approximation (GMA) for relating the friction coefficien…