The role of ions in the self-healing behavior of soft particle suspensions
Autor: | Alberto Fernandez-Nieves, Emily S. Herman, L. Andrew Lyon, Urs Gasser, Andrea Scotti, Andreas Menzel, Miguel Pelaez-Fernandez, Jun Han |
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Rok vydání: | 2016 |
Předmět: |
chemistry.chemical_classification
Multidisciplinary Small-angle X-ray scattering Scattering Context (language use) 02 engineering and technology Neutron scattering Colloidal crystal 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Suspension (chemistry) Condensed Matter::Soft Condensed Matter Crystallography chemistry Chemical physics Physical Sciences Particle Counterion 0210 nano-technology |
Zdroj: | PNAS |
ISSN: | 1091-6490 0027-8424 |
Popis: | Impurities in crystals generally cause point defects and can even suppress crystallization. This general rule, however, does not apply to colloidal crystals formed by soft microgel particles [Iyer ASJ, Lyon LA (2009) Angew Chem Int Ed 48:4562–4566], as, in this case, the larger particles are able to shrink and join the crystal formed by a majority of smaller particles. Using small-angle X-ray scattering, we find the limit in large-particle concentration for this spontaneous deswelling to persist. We rationalize our data in the context of those counterions that are bound to the microgel particles as a result of the electrostatic attraction exerted by the fixed charges residing on the particle periphery. These bound counterions do not contribute to the suspension osmotic pressure in dilute conditions, as they can be seen as internal degrees of freedom associated with each microgel particle. In contrast, at sufficiently high particle concentrations, the counterion cloud of each particle overlaps with that of its neighbors, allowing these ions to freely explore the space outside the particles. We confirm this scenario by directly measuring the osmotic pressure of the suspension. Because these counterions are then no longer bound, they create an osmotic pressure difference between the inside and outside of the microgels, which, if larger than the microgel bulk modulus, can cause deswelling, explaining why large, soft microgel particles feel the squeeze when suspended with a majority of smaller particles. We perform small-angle neutron scattering measurements to further confirm this remarkable behavior. |
Databáze: | OpenAIRE |
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