Thermal behavior of polyelectrolyte multilayer microcapsules. 1. The effect of odd and even layer number.

The temperature-dependent behavior of hollow polyelectrolyte multilayer capsules consisting of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sulfonate) (PSS) with a different number of layers was investigated in aqueous media using confocal laser scanning microscopy, scanning and transmission electron microscopy, atomic force microscopy, and elemental analysis. Capsules with an even number of layers exhibited a pronounced shrinking at elevated temperature resulting in a transition to a dense sphere, whereas capsules with an odd number of layers swelled during heating to 5-fold of their initial size followed by their rupture. This effect increases for odd layer numbers and decreases for even layer numbers with increasing layer number. According to elemental analysis, an excess of PDADMAC monomers exists within the multilayers of capsules with an odd number of layers leading to a repulsion between the positive charges, whereas shells with an even number of layers have a balanced ratio between the oppositely charged polyions, so that the temperature-dependent behavior is controlled by the different interactions between polyelectrolytes and the bulk water. At a certain temperature, the polyelectrolyte material softens thus facilitating any rearrangement. Besides incubation temperature, the duration of heating has an influence on the restructuring of the multilayers.