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Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate
Abstract
The linear viscoelastic response, LVR, of a hydrated polyelectrolyte complex coacervate, PEC, was evaluated over a range of frequencies, temperatures, and salt concentrations. The PEC was a nearly stoichiometric blend of a quaternary ammonium poly([3-(methacrylamido)propyl]trimethylammonium chloride), PMAPTAC, and poly(2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt), PAMPS, an aliphatic sulfonate, selected because they remain fully charged over the conditions of use. Narrow molecular weight distribution polyelectrolytes were prepared using fractionation techniques. A partially deuterated version of PMAPTAC was incorporated to determine its coil radius of gyration, Rg, within PECs using small-angle neutron scattering. Chain dimensions were determined to be Gaussian with a Kuhn length of 2.37 nm, which remained constant from 25 to 65 °C. The LVR for a series of matched molecular weight PECs, mostly above the entanglement threshold, exhibited crossovers of modulus versus frequency classically attributed to the reptation time, relaxation between entanglements, and the relaxation of a Kuhn length of units (the “monomer” time). The scaling for zero shear viscosity, η0, versus chain length, N, was η0 ~ N3.1, in agreement with “sticky reptation” theory. The lifetime and activation energy, Ep, of a pair between polyanion and polycation repeat units, Pol+Pol–, were determined from diffusion coefficients of salt ions within themore »
- Authors:
-
[1];
[2];
[1]
- Florida State Univ., Tallahassee, FL (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- OSTI Identifier:
- 2317732
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 3; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; diffusion; ions; polyelectrolytes; polymers; salts
Citation Formats
Akkaoui, Khalil, Digby, Zachary A., Do, Changwoo, and Schlenoff, Joseph B. Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate. United States: N. p., 2024.
Web. doi:10.1021/acs.macromol.3c01540.
Akkaoui, Khalil, Digby, Zachary A., Do, Changwoo, & Schlenoff, Joseph B. Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate. United States. https://doi.org/10.1021/acs.macromol.3c01540
Akkaoui, Khalil, Digby, Zachary A., Do, Changwoo, and Schlenoff, Joseph B. Wed .
"Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate". United States. https://doi.org/10.1021/acs.macromol.3c01540.
@article{osti_2317732,
title = {Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate},
author = {Akkaoui, Khalil and Digby, Zachary A. and Do, Changwoo and Schlenoff, Joseph B.},
abstractNote = {The linear viscoelastic response, LVR, of a hydrated polyelectrolyte complex coacervate, PEC, was evaluated over a range of frequencies, temperatures, and salt concentrations. The PEC was a nearly stoichiometric blend of a quaternary ammonium poly([3-(methacrylamido)propyl]trimethylammonium chloride), PMAPTAC, and poly(2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt), PAMPS, an aliphatic sulfonate, selected because they remain fully charged over the conditions of use. Narrow molecular weight distribution polyelectrolytes were prepared using fractionation techniques. A partially deuterated version of PMAPTAC was incorporated to determine its coil radius of gyration, Rg, within PECs using small-angle neutron scattering. Chain dimensions were determined to be Gaussian with a Kuhn length of 2.37 nm, which remained constant from 25 to 65 °C. The LVR for a series of matched molecular weight PECs, mostly above the entanglement threshold, exhibited crossovers of modulus versus frequency classically attributed to the reptation time, relaxation between entanglements, and the relaxation of a Kuhn length of units (the “monomer” time). The scaling for zero shear viscosity, η0, versus chain length, N, was η0 ~ N3.1, in agreement with “sticky reptation” theory. The lifetime and activation energy, Ep, of a pair between polyanion and polycation repeat units, Pol+Pol–, were determined from diffusion coefficients of salt ions within the PEC. The activation energy for LVR of salt-free PECs was 2Ep, showing that the key mechanism limiting the dynamics of undoped PECs is pair exchange. An FTIR technique was used to distinguish whether SCN– acts as a counterion or a co-ion within PECs. Doping of PECs with NaSCN breaks Pol+Pol– pairing efficiently, which decreases effective cross-linking and decreases viscosity. Finally, an equation was derived that quantitatively predicts this effect.},
doi = {10.1021/acs.macromol.3c01540},
journal = {Macromolecules},
number = 3,
volume = 57,
place = {United States},
year = {Wed Jan 24 00:00:00 EST 2024},
month = {Wed Jan 24 00:00:00 EST 2024}
}
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