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In recent years, ionic microgels have garnered much attention due to their unique properties, especially their stimulus-sensitive swelling behavior. The tunable response of these soft, permeable, compressible, charged colloidal particles is increasingly attractive for applications in medicine and biotechnologies, such as controlled drug delivery, tissue engineering, and biosensing. The ability to model and predict variation of the osmotic pressure of a single microgel with respect to changes in particle properties and environmental conditions proves vital to such applications. In this work, we apply both nonlinear Poisson–Boltzmann theory and molecular dynamics simulation to ionic microgels (macroions) in the cell model to compute density profiles of microions (counterions, coions), single-microgel osmotic pressure, and equilibrium swelling ratios of spherical microgels whose fixed charge is confined to the macroion surface. The basis of our approach is an exact theorem that relates the electrostatic component of the osmotic pressure to the microion density profiles. Close agreement between theory and simulation serves as a consistency check to validate our approach. We predict that surface-charged microgels progressively deswell with increasing microgel concentration, starting well below close packing, and with increasing salt concentration, in qualitative agreement with experiments. Comparison with previous results for microgels with fixed charge uniformly distributed over their volume demonstrates that surface-charged microgels deswell more rapidly than volume-charged microgels. We conclude that swelling behavior of ionic microgels in solution is sensitive to the distribution of fixed charge within the polymer-network gel and strongly depends on bulk concentrations of both microgels and salt ions.
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Effective interactions, structure, and pressure in charge-stabilized colloidal suspensions: Critical assessment of charge renormalization methods
Charge-stabilized colloidal suspensions display a rich variety of microstructural and thermodynamic properties, which are determined by electro-steric interactions between all ionic species. The large size asymmetry between molecular-scale microions and colloidal macroions allows the microion degrees of freedom to be integrated out, leading to an effective one-component model of microion-dressed colloidal quasi-particles. For highly charged colloids with strong macroion–microion correlations, nonlinear effects can be incorporated into effective interactions by means of charge renormalization methods. Here, we compare and partially extend several practical mean-field methods of calculating renormalized colloidal interaction parameters, including effective charges and screening constants, as functions of concentration and ionic strength. Within the one-component description, we compute structural and thermodynamic properties from the effective interactions and assess the accuracy of the different methods by comparing predictions with elaborate primitive-model simulations [P. Linse, J. Chem. Phys. 113, 4359 (2000)]. We also compare various prescriptions for the osmotic pressure of suspensions in Donnan equilibrium with a salt ion reservoir and analyze instances where the macroion effective charge becomes larger than the bare one. The methods assessed include single-center cell, jellium, and multi-center mean-field theories. The strengths and weaknesses of the various methods are critically assessed, with the aim of guiding optimal and accurate implementations.
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- Award ID(s):
- 1928073
- PAR ID:
- 10559648
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 159
- Issue:
- 20
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 204904-1-26
- Subject(s) / Keyword(s):
- charged colloids renormalization effective charge
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0180914
