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Influence of the degree of ionization on the growth mechanism of poly(diallyldimethylammonium)/poly(acrylic acid) multilayers
Authors:Dörte Bütergerds  Christian Kateloe  Cornelia Cramer  Monika Schönhoff
Affiliation:1. Institute of Physical Chemistry, University of Muenster, Münster, Germany;2. Graduate School of Chemistry, University of Muenster, Münster, Germany
Abstract:pH‐dependent growth laws of the mass coverage Γ(n) of poly(diallyldimethylammonium) chloride and poly(acrylic acid) (PAA) layer‐by‐layer films are analyzed by Quartz Crystal Microbalance‐D. (Attenuated Total Reflection)‐FTIR spectroscopy shows a degree of dissociation of acrylic acid groups in the films identical to that in solution. Apart from pH‐regimes of differently pronounced exponential and linear growth, the corresponding kinetics indicate pH‐dependent adsorption, reorganization, and diffusion processes. As the thickest films form with almost uncharged PAA (low pH), the results can only partly be explained by the dissociation degree of PAA in the film. For intermediate and high pH values chain interdiffusion as a mechanism for nonlinear growth is strongly dependent on the charge density of the PAA chains. However, at low pH other types of interactions, most likely ion–dipole interactions, play a major role in the multilayer growth. Furthermore, a change in the symmetry of growth can be observed in the low to intermediate pH range. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 425–434
Keywords:films  FT-IR  layer growth  infrared spectroscopy  nanolayers  self-assembly  self-organization  thin films
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