Influence of assembly pH on compression and Ag nanoparticle synthesis of polyelectrolyte multilayers.

Influence of assembly pH on compression and Ag nanoparticle synthesis of polyelectrolyte multilayers was studied using poly(diallyldimethylammonium chloride) (PDADMAC) and poly(4-styrenesulfonic acid-co-maleic acid, 1:1SS:MA) sodium salt (PSSMA 1:1) as the building blocks. The thickest multilayers turned out at pH 4. A homogeneous compression by a silicone rubber stamp increased significantly the water contact angle to a same value which was independent on the original assembly pH anymore. The multilayers assembled at pH 4 could be maximumly compressed to a ratio of 70% by a silicone rubber stamp with linear patterns, which was considerably larger than those assembled at other pHs (the compression ratio ~50%). The Ag nanoparticles were then synthesized inside the multilayers either flat compressed or not. The results showed that the compression reduced significantly the amount of Ag nanoparticles for the multilayers assembled at pH 2 and pH 4. The particle amount was also decreased significantly when the multilayers were assembled at higher pH, pH 6, for example, regardless of the compression. Substantial alteration of the multilayers in terms of the surface morphology, thickness and refractive index was found during the reduction of Ag(+) containing multilayers by NaBH(4) solution.