Doping and Diffusion in an Extruded Saloplastic Polyelectrolyte Complex

Abstract

Doping constants and diffusion coefficients for an extruded, stoichiometric, dense polyelectrolyte complex, PEC, were determined for a Hofmeister series of anions. These thermodynamic and kinetic parameters describe the extent and speed to which a c o m p l e x o f p o l y ( s t y r e n e s u l f o n a t e ) a n d p o l y -(diallyldimethylammonium) may be doped. Both parameters followed a Hofmeister ordering and covered a wide range of response. Differences between doping and undoping kinetics were observed, with the latter adhering well to classical diffusion from the cylindrical geometry employed. Tracer diffusion of radiolabeled Na + , compared with coupled diffusion of NaCl, revealed slightly faster diffusion of Na + compared to Cl − ions within the PEC.

Underwater Adhesion of Multiresponsive Complex Coacervates

“…In line with similar experiments, [39] the whole transition visually takes ≈45 min, both in graft copolymer and in homopolymer complex coacervates, while, mechanically, according to the rheology data, the moduli, after a dramatic increase in the first 10 min ( Figure S3 Figure S4, Supporting Information), it is observed that the moduli still increase at longer times, albeit with a slower pace. Initially, diffusion is fast because the sample is liquid: the abrupt increase in moduli by more than an order of magnitude at the beginning of the experiment is due to the formation of solid regions at the edges of the sample, which coexist with liquid zones and which dominate the average moduli.…”

“…In line with similar experiments, the whole transition visually takes ≈45 min, both in graft copolymer and in homopolymer complex coacervates, while, mechanically, according to the rheology data, the moduli, after a dramatic increase in the first 10 min (Figure S3, Supporting Information), head toward a plateau. However, when plotted in a lin–lin scale (Figure S4, Supporting Information), it is observed that the moduli still increase at longer times, albeit with a slower pace.…”

“…As previously mentioned, the salt‐triggered setting mechanism is driven by the ion diffusion out of the complex coacervate phase . In order to determine the end of the transition, the adhesive is loaded into a glass container which is part of a custom‐made adhesion setup allowing visualization from the bottom (Figure S6, Supporting Information).…”

“…[15,37,38] As previously mentioned, the salt-triggered setting mechanism is driven by the ion diffusion out of the complex coacervate phase. [39] In order to determine the end of the transition, the adhesive is loaded into a glass container which is part of a custom-made adhesion setup allowing visualization from the bottom ( Figure S6, Supporting Information). As preload is impossible due to the viscous nature of the sample which relaxes over time, contact with a mica probe is performed imposing a final adhesive thickness of 0.2 mm.…”

Saloplastics: Processing Compact Polyelectrolyte Complexes

“…This is the condition reached by the ternary solvents (e.g., water, acetone, and salt) developed by Michaels to dissolve complexes . The effectiveness of doping was found to follow a Hofmeister series, where SCN − and ClO 4 − doped complexes most efficiently ( Figure ) . The rate of diffusion of ions through stoichiometric, cylindrical samples of PDADMA/PSS complex was measured by electrical conductivity of released ions ( Table 1 ).…”