We report here on the influence of changes in the solution salt concentration on the structure of multilayers
of weak polyelectrolytes. For poly(acrylic acid) (PAA) and poly(allylamine) (PAH) multilayers assembled
by the layer-by-layer process in the presence of sodium chloride, washing with pure water after deposition
of each layer produces films with considerable surface roughness (root-mean-squared (rms) roughness ∼17
nm for a 10 layer film), as assessed by scanning force microscopy. In contrast, relatively smooth (rms
roughness ∼1 nm) and homogeneous PAH/PAA multilayer films are formed when the salt concentration
is kept constant both during the assembly process and in the washing steps. For such smooth films,
subsequent exposure to pure water leads to the introduction of regular, discrete, nanometer-sized pores,
thus providing a means of introducing lateral structure into the PAH/PAA multilayer films. Electrochemical
measurements revealed that the pores formed in less than 10 min. The sensitivity of the multilayer films
to salt as well as the subsequent creation of nanopores potentially makes them attractive candidates for
use in controlled-release applications where defined permeability characteristics are desired.
Hollow polyelectrolyte microcapsules containing diazoresins (DZR) were fabricated by the layer‐by‐layer self‐assembly of a polycation, DZR, in alternation with poly(styrenesulfonate) (PSS) onto polystyrene (PS) particles, followed by dissolution of the PS core by tetrahydrofuran (THF). The multilayer film buildup on the colloids was observed by UV‐visible spectroscopy, single particle light scattering (SPLS), and transmission electron microscopy (TEM). The data confirmed regular and stepwise layer formation of DZR and PSS on the colloid particles, with a thickness of about 10 nm for each DZR/PSS bilayer when exposed to aqueous solution, and approximately 5 nm in the “dry state”. The photosensitive nature of the DZR layers was exploited to construct highly stable, covalently attached (polymerized) films by exposure of the ionic self‐assembled DZR/PSS multilayer films to UV‐irradiation. TEM and atomic force microscopy (AFM) confirmed the formation of hollow DZR/PSS multilayer capsules. Osmotic pressure experiments followed by confocal laser scanning microscopy revealed a high mechanical stability of the hollow DZR/PSS capsules. The mechanically robust polymerized multilayer films on the colloids and as free‐standing three‐dimensional hollow capsules are more stable in various chemical environments (i.e., resistant to etching by solvents) than their ionically linked counterparts.
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