Phase behavior and charge regulation of weak polyelectrolyte grafted layers

• Published in: Physical review letters Vol. 98; no. 1; p. 018302
• Main Authors: Gong, Peng, Genzer, Jan, Szleifer, I
• Format: Journal Article
• Language: English
• Published: United States 05.01.2007
• Subjects: Biophysics - instrumentation; Biophysics - methods; Electrolytes - chemistry; Hydrogen-Ion Concentration; Ions; Models, Chemical; Models, Statistical; Polymers - chemistry; Salts - chemistry; Salts - pharmacology; Solvents; Static Electricity; Surface Properties; Temperature; Thermodynamics
• ISSN: 0031-9007
• DOI: 10.1103/physrevlett.98.018302

The stability of weak polyelectrolytes end grafted to a planar surface has been studied with a molecular theory. The effective quality of the solvent is found to depend on the interplay between polymer grafting density, acid-base equilibrium, and salt concentration. Our results reveal that increasing salt concentration results in a thermodynamically more stable layer. This reverse salt effect is due to the competition between the solvent quality and the dual role of the ionic strength in screening the electrostatic interactions (reducing stability with increasing salt concentration), and regulating the charge on the polymer (increasing charge with increasing salt concentration). Grafted weak polyelectrolyte layers are found to be thermodynamically unstable at intermediate surface coverages. Additionally, it is established that the increased solubility of the layer at low surface coverage is due to the relatively large charge of the grafted polymers. The range of stability of the film with regard to polymer surface coverage, temperature, bulk pH and salt concentration is demonstrated.