Colloids that attractively bond to only a few neighbors (e.g., patchy particles) can form equilibrium gels with distinctive dynamic properties that are stable in time. Here, we use a coarse-grained model to explore the dynamics of linked networks of patchy colloids whose average valence is macroscopically, rather than microscopically, constrained. Simulation results for the model show dynamic hallmarks of equilibrium gel formation and establish that the colloid–colloid bond persistence time controls the characteristic slow relaxation of the self-intermediate scattering function. The model features re-entrant network formation without phase separation as a function of linker concentration, centered at the stoichiometric ratio of linker ends to nanoparticle surface bonding sites. Departures from stoichiometry result in linker-starved or linker-saturated networks with reduced connectivity and shorter characteristic relaxation times with lower activation energies. Underlying the re-entrant trends, dynamic properties vary monotonically with the number of effective network bonds per colloid, a quantity that can be predicted using Wertheim’s thermodynamic perturbation theory. These behaviors suggest macroscopic in situ strategies for tuning the dynamic response of colloidal networks.
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Phase mechanics of colloidal gels: osmotic pressure drives non-equilibrium phase separation
Although dense colloidal gels with interparticle bonds of order several kT are typically described as resulting from an arrest of phase separation, they continue to coarsen with age, owing to the dynamics of their temporary bonds. Here, k is Boltzmann's constant and T is the absolute temperature. Computational studies of gel aging reveal particle-scale dynamics reminiscent of condensation that suggests very slow but ongoing phase separation. Subsequent studies of delayed yield reveal structural changes consistent with re-initiation of phase separation. In the present study we interrogate the idea that mechanical yield is connected to a release from phase arrest. We study aging and yield of moderately concentrated to dense reversible colloidal gels and focus on two macroscopic hallmarks of phase separation: increases in surface-area to volume ratio that accompanies condensation, and minimization of free energy. The interplay between externally imposed fields, Brownian motion, and interparticle forces during aging or yield, changes the distribution of bond lengths throughout the gel, altering macroscopic potential energy. The gradient of the microscopic potential (the interparticle force) gives a natural connection of potential energy to stress. We find that the free energy decreases with age, but this slows down as bonds get held stretched by glassy frustration. External perturbations break just enough bonds to liberate negative osmotic pressure, which we show drives a cascade of bond relaxation and rapid reduction of the potential energy, consistent with renewed phase separation. Overall, we show that mechanical yield of reversible colloidal gels releases kinetic arrest and can be viewed as non-equilibrium phase separation.
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- NSF-PAR ID:
- 10317337
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 17
- Issue:
- 14
- ISSN:
- 1744-683X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sm02180f
