Dielectric spectroscopy of ionic microgel suspensions
Autor: | Maxime J. Bergman, Jan K. G. Dhont, G. Nägele, Rafael Roa, Silvia Arrese-Igor, Angel Alegría, Peter Schurtenberger, Sofi Nöjd, Priti S. Mohanty |
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Přispěvatelé: | Swiss National Science Foundation, Lund University, European Commission, European Research Council, Knut and Alice Wallenberg Foundation, German Research Foundation |
Rok vydání: | 2016 |
Předmět: |
chemistry.chemical_classification
Materials science Scattering Analytical chemistry Ionic bonding 02 engineering and technology General Chemistry Polymer 010402 general chemistry 021001 nanoscience & nanotechnology Condensed Matter Physics 01 natural sciences Spectral line 0104 chemical sciences Dielectric spectroscopy Ion Condensed Matter::Soft Condensed Matter Rheology chemistry Chemical physics Others ddc:530 Physics::Chemical Physics 0210 nano-technology Polarization (electrochemistry) |
Zdroj: | ResearcherID Digital.CSIC: Repositorio Institucional del CSIC Consejo Superior de Investigaciones Científicas (CSIC) Digital.CSIC. Repositorio Institucional del CSIC instname Soft matter 12(48), 9705-9727 (2016). doi:10.1039/C6SM01683A |
ISSN: | 2011-4338 |
DOI: | 10.1039/C6SM01683A |
Popis: | The determination of the net charge and size of microgel particles as a function of their concentration, as well as the degree of association of ions to the microgel backbone, has been pursued in earlier studies mainly by scattering and rheology. These methods suffer from contributions due to inter-particle interactions that interfere with the characterization of single-particle properties. Here we introduce dielectric spectroscopy as an alternative experimental method to characterize microgel systems. The advantage of dielectric spectroscopy over other experimental methods is that the polarization due to mobile charges within a microgel particle is only weakly affected by inter-particle interactions. Apart from electrode polarization effects, experimental spectra on PNIPAM-co-AA [poly(N-isopropylacrylamide-co-acrylic acid)] ionic microgel particles suspended in de-ionized water exhibit three well-separated relaxation modes, which are due to the polarization of the mobile charges within the microgel particles, the diffuse double layer around the particles, and the polymer backbone. Expressions for the full frequency dependence of the electrode-polarization contribution to the measured dielectric response are derived, and a theory is proposed for the polarization resulting from the mobile charges within the microgel. Relaxation of the diffuse double layer is modeled within the realm of a cell model. The net charge and the size of the microgel particles are found to be strongly varying with concentration. A very small value of the diffusion coefficient of ions within the microgel is found, due to a large degree of chemical association of protons to the polymer backbone. This work was supported by the Swiss National Science Foundation, the Swedish Research Council (Project 621-2011-4338), the science faculty of Lund University, the European Research Council (ERC-339678-COMPASS), and the Knut and Alice Wallenberg Foundation (project grant KAW 2014.0052). J. K. G. Dhont, G. Nägele, and R. Roa acknowledge support by the German Research Foundation (SFB 985, Functional Microgels and Microgel Systems, Project B6). The authors acknowledge financial support from the European Commission under the Seventh Framework Program by means of the grant agreement for the Integrated Infrastructure Initiative N. 262348, European Soft Matter Infrastructure (ESMI). |
Databáze: | OpenAIRE |
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