From Molecular Constraints to Macroscopic Dynamics in Associative Networks Formed by Ionizable Polymers: A Neutron Spin Echo and Molecular Dynamics Simulations Study
[2];
[3];
[5];
[7];
[1]
- Clemson Univ., SC (United States)
- Clemson Univ., SC (United States); Appalachian State University, Boone, NC (United States)
- Clemson Univ., SC (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Clemson Univ., SC (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Juelich Research Centre (Germany)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
The association of ionizable polymers strongly affects their motion in solutions, where the constraints arising from clustering of the ionizable groups alter the macroscopic dynamics. The interrelation between the motion on multiple length and time scales is fundamental to a broad range of complex fluids including physical networks, gels, and polymer-nanoparticle complexes where long-lived associations control their structure and dynamics. Using neutron spin echo and fully atomistic, multimillion atom molecular dynamics (MD) simulations carried out to times comparable to that of chain segmental motion, the current study resolves the dynamics of networks formed by polystyrene sulfonate solutions for sulfonation fractions 0 ≤ f ≤ 0.09 across time and length scales. The experimental dynamic structure factors were measured and compared with computational ones, calculated from MD simulations, and analyzed in terms of a sum of two exponential functions, providing two distinctive time scales. These time constants capture confined motion of the network and fast dynamics of the highly solvated segments. A unique relationship between the polymer dynamics and the size and distribution of the ionic clusters was 2 established and correlated with the number of polymer chains that participate in each cluster. The correlation of dynamics in associative complex fluids across time and length scales, enabled by combining the understanding attained from reciprocal space through neutron spin echo and real space, through large scale MD studies, addresses a fundamental long-standing challenge that underline the behavior of soft materials and affect their potential uses.
- Research Organization:
- Clemson Univ., SC (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- Grant/Contract Number:
- SC0019284; AC02-05CH11231; NA0003525; MRI-1725573; AC02- 05CH11231.; NA-0003525
- OSTI ID:
- 2311006
- Alternate ID(s):
- OSTI ID: 2301683; OSTI ID: 2335869; OSTI ID: 2338245
- Report Number(s):
- SAND-2024-04642J
- Journal Information:
- ACS Polymers Au, Vol. 4, Issue 2; ISSN 2694-2453
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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