Abstract
The adsorption and desorption behavior of anionic and cationic spherical polyelectrolyte brushes (SPB) on mica surfaces in an aqueous medium is discussed. The SPB consist of a polystyrene core with diameters of 136 nm (anionic SPB) and 90 nm (cationic SPB), respectively, on to which linear polyelectrolyte chains are affixed by a grafting-from technique. Negatively charged particles consist of polystyrene–sulfonate chains and positively charged SPB consist of cationic polyelectrolyte chains (poly((2-acryloxy)ethyl)-trimethylammonium-chloride). The SPB are extensively characterized in aqueous dispersion whereas their interaction with mica surfaces is investigated by atomic force microscopy (AFM) in intermittent contact mode both ex situ and in situ. In the first case it is shown that negatively charged SPB only weakly interact with the negatively charged surface and exhibit a long-range two-dimensional surface order observed by atomic force microscopy. In comparison the phase information obtained by AFM is strikingly different on the particles of both SPB types. The positive polyelectrolyte chains of the cationic SPB spread on the surface and are responsible for a corona around the particles as revealed by AFM. In this case no long-range order was observed. The shell of the SPB and its charge hence can be used to tune the interaction of the particles with solid substrates within a wide range.
In the second part we demonstrate that the adsorption of the cationic spherical polyelectrolyte brushes (SPB) on negatively charged mica substrates can be controlled in situ by the ionic strength of the suspension. The particles are suspended in aqueous solution with a fixed ionic strength. Atomic force microscopy in suspension as well as in air was used for surface characterization. In pure water the polymer particles exhibit a strong adhesion to the mica surface. AFM investigations of the dry samples show that the particles occupy the identical positions as they did in liquid. They were not removed by the capillary forces within the receding water front during the drying process. Moreover, in situ AFM measurements showed that particles which adsorb under liquid in a stable manner are easily desorbed from the surface as soon as electrolyte is added to the suspension. This finding is explained by a decreasing attractive particle–substrate interaction, and the removal of the particles from the surface is due to the significant reduction of the activation barrier of the particle desorption. All findings can be explained in terms of the counterion release force.
As it is shown in this work, atomic force microscopy is a key technology for the investigation of surfaces on the nanometer scale. Therefore, a brief introduction is given to explain the principal of this technique.
Keywords
- Atomic Force Microscopy
- Ionic Strength
- Polymer Particle
- Mica Surface
- Atomic Force Microscopy Investigation
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Acknowledgment
This work was financially supported within the DFG-Center for Functional Nanostructures (CFN), by the Research Prize for Applied Science (“Landesforschungspreis”) Baden-Württemberg, by the Deutsche Forschungsgemeinschaft (SFB 481, Bayreuth), by the European Community (Project “POLYAMPHI”), by the Fonds der Chemischen Industrie, and by the Landesstiftung Baden-Württemberg within the Research Network of Excellence “Functional Nanostructures”.
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Gliemann, H., Ballauff, M., Schimmel, T. (2010). Adsorption/Desorption Behavior of Charged Polymer Nanoparticles on a Mineral Surface in an Aqueous Environment. In: Frimmel, F., Niessner, R. (eds) Nanoparticles in the Water Cycle. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-10318-6_6
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