Aging dynamics and generalized superposition principles in carbon black-carboxymethylcellulose hydrogels
Abstract
Aqueous dispersions of hydrophobic carbon black (CB) particles can be stabilized by carboxymethylcellulose (CMC), forming CB-CMC hydrogels whose microstructure is controlled by the relative CB-to-polymer content. At low CMC content, CB particles form a percolated, electrically conductive network, whereas at higher polymer content, CB particles act as isolated physical crosslinkers within an electrically insulating polymer matrix [see Legrand \textit{et al.}, Macromolecules 56, 2298-2308 (2023)]. Combining rheology and electrical impedance spectroscopy, we show that these two regimes exhibit markedly different aging dynamics. Conductive hydrogels exhibit logarithmic elastic recovery associated with a percolated CB network, whereas insulating hydrogels exhibit a combination of logarithmic and power-law stiffening, accompanied by dielectric polarization associated with confined ionic motion. The insulating hydrogels further exhibit a time-aging superposition principle, as their viscoelastic spectra measured in a time-resolved fashion can collapse onto a single master curve. Under steady shear, the viscoelastic response measured perpendicular to the flow also obeys a time--shear-rate superposition principle. Remarkably, the scaling between the shift factors under shear is reminiscent of critical-gel behavior, unlike that observed during aging at rest. Finally, time-resolved rheo-USAXS measurements performed during shear-rate cycles reveal structural rearrangements of CB particles and clusters that correlate with rheological hysteresis. These results provide a microstructural basis for understanding the nonlinear rheology of insulating CB-CMC hydrogels and establish generalized superposition principles as a unifying framework for their aging and flow behavior.
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BibTeX
@misc{legrand2026aging,
title = {{Aging dynamics and generalized superposition principles in carbon black-carboxymethylcellulose hydrogels}},
author = {Gauthier Legrand and Guilhem P. Baeza and Jarno L. Waeterloos and Christian Clasen and Sébastien Manneville and Thibaut Divoux},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.33682},
eprint = {2610.33682},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.33682},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - UNPB
TI - Aging dynamics and generalized superposition principles in carbon black-carboxymethylcellulose hydrogels
AU - Gauthier Legrand
AU - Guilhem P. Baeza
AU - Jarno L. Waeterloos
AU - Christian Clasen
AU - Sébastien Manneville
AU - Thibaut Divoux
PY - 2026
DA - 2026/10/24
PB - arXiv
DO - 10.48550/arxiv.2610.33682
UR - https://arxiv.org/abs/2610.33682
AB - Aqueous dispersions of hydrophobic carbon black (CB) particles can be stabilized by carboxymethylcellulose (CMC), forming CB-CMC hydrogels whose microstructure is controlled by the relative CB-to-polymer content. At low CMC content, CB particles form a percolated, electrically conductive network, whereas at higher polymer content, CB particles act as isolated physical crosslinkers within an electrically insulating polymer matrix [see Legrand \textit{et al.}, Macromolecules 56, 2298-2308 (2023)]. Combining rheology and electrical impedance spectroscopy, we show that these two regimes exhibit markedly different aging dynamics. Conductive hydrogels exhibit logarithmic elastic recovery associated with a percolated CB network, whereas insulating hydrogels exhibit a combination of logarithmic and power-law stiffening, accompanied by dielectric polarization associated with confined ionic motion. The insulating hydrogels further exhibit a time-aging superposition principle, as their viscoelastic spectra measured in a time-resolved fashion can collapse onto a single master curve. Under steady shear, the viscoelastic response measured perpendicular to the flow also obeys a time--shear-rate superposition principle. Remarkably, the scaling between the shift factors under shear is reminiscent of critical-gel behavior, unlike that observed during aging at rest. Finally, time-resolved rheo-USAXS measurements performed during shear-rate cycles reveal structural rearrangements of CB particles and clusters that correlate with rheological hysteresis. These results provide a microstructural basis for understanding the nonlinear rheology of insulating CB-CMC hydrogels and establish generalized superposition principles as a unifying framework for their aging and flow behavior.
ER -