The impact of stabilization mechanism on the aggregation kinetics of silver nanoparticles

The use of silver nanoparticles (AgNPs) for various applications is growing drastically. The increase in use will eventually lead to their release into the environment. The tendency of AgNPs to aggregate and the kinetics of aggregation are major factors that govern their fate in the environment. Dynamic light scattering (DLS) was utilized to investigate the electrolyte-induced aggregation kinetics (NaNO₃, NaCl and Ca(NO₃)₂) of coated and uncoated AgNPs which are electrostatically (H₂-AgNPs and Citrate-AgNPs), sterically (polyvinylpyrrolidone (PVP)-AgNPs) and electrosterically (branched polyethyleneimine (BPEI)-AgNPs) stabilized. The aggregation kinetics of the electrostatically stabilized AgNPs was in agreement with the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and the AgNPs exhibited both reaction-limited and diffusion-limited regimes. The H₂-AgNPs had critical coagulation concentrations (CCC) of 25, 30 and 3mM in the presence of NaNO₃, NaCl and Ca(NO₃)₂ salts, respectively. The Citrate-AgNPs had CCC of 70, 70 and 5 mM in the presence of NaNO₃, NaCl and Ca(NO₃)₂ salts, respectively. The values of the Hamaker constant for the electrostatically stabilized AgNPs were also determined and the values were in agreement with the reported values for metallic particles. The aggregation kinetics for both the sterically and electrosterically stabilized AgNPs (PVP-AgNPs and BPEI-AgNPs) was not in agreement with the DLVO theory and the particles were resistant to aggregation even at high ionic strength and electrolyte valence. The PVP-AgNPs and the BPEI-AgNPs had no critical aggregation concentration value at the investigated ionic strength values.