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Divalent-anion salt effects in polyelectrolyte multilayer depositions.

Walter J Dressick¹, Kathryn J Wahl, Nabil D Bassim

¹US Naval Research Laboratory, Washington, DC 20375, United States. walter.dressick@nrl.navy.mil

Langmuir : the ACS Journal of Surfaces and Colloids

|October 31, 2012

Summary

Divalent anions significantly influence polyelectrolyte multilayer assembly by promoting the formation of polyallylamine hydrochloride (PAH) aggregates. This aggregation, driven by electrostatic interactions, impacts film properties like thickness and roughness, offering a new model for multilayer formation.

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Temperature-Controlled Assembly and Characterization of a Droplet Interface Bilayer

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Area of Science:

Materials Science
Polymer Chemistry
Surface Science

Background:

Polyelectrolyte multilayers (PEMs) are versatile materials with applications in coatings, drug delivery, and sensing.
Understanding the factors that control PEM assembly is crucial for tailoring their properties.
Divalent anions are known to affect the solubility and interactions of charged polymers.

Purpose of the Study:

To systematically investigate the impact of various divalent anions on the assembly of polystyrene sulfonate (PSS)/polyallylamine hydrochloride (PAH) multilayer films.
To develop a generic model for PSS/PAH multilayer formation influenced by divalent anions.
To elucidate the role of anion structure in governing aggregate formation and film properties.

Main Methods:

Fabrication of PSS/PAH multilayer films from aqueous solutions containing sulfate, phosphate, or organic dicarboxylate dianions.
Controlled anion concentrations (≤0.05 M) and constant ionic strength (1.00 M NaCl) to isolate anion effects.
Characterization of film properties including UV absorbance, thickness, and roughness.

Main Results:

PEMs fabricated with divalent anions showed increased UV absorbance, thickness, and roughness compared to control films.
A generic model for PSS/PAH multilayer formation was derived, involving PAH aggregates formed via bridging dianions.
Anion structure (separation, rigidity, charge angle) dictates PAH aggregate formation and subsequent film properties.
A universal linear correlation between film UV absorbance and thickness was observed across all tested dianions and concentrations.

Conclusions:

Divalent anions play a critical role in PSS/PAH multilayer assembly by mediating the formation of PAH aggregates.
The structural characteristics of divalent anions are key determinants of aggregate morphology and final film properties.
The developed model provides a framework for predicting and controlling PEM properties through anion selection.