Rheological properties of chitosan–tripolyphosphate complexes: From suspensions to microgels

Abstract

Complex fluids formed by crosslinking of chitosan (CS, 330 kDa) with sodium tripolyphosphate (TPP) have been studied by dynamic light scattering (DLS), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), and rheology. The effects of chitosan/TPP ratios, initial chitosan or TPP concentrations, and ultrasonication time on the chitosan–TPP complex formation have been investigated. It was found that the optimum condition for CS–TPP nanoparticle formation occurred at CS/TPP mass ratio of 3.75 and with 9 min sonication treatment (energy output 3.75 W/mL). At the same initial chitosan concentration, small particle sizes (i.e., particle size < 300 nm) resulted in the formation of CS–TPP nanoparticle suspensions, which showed a lower viscosity than pure chitosan solutions, and their viscosities increased as the CS–TPP nanoparticles sizes increased. Centrifugation of CS–TPP particles of larger particle sizes (i.e., 360–870 nm) at 11,000 × g caused the formation of CS–TPP microgels. Dynamic rheological studies indicated that both storage modulus (G′) and loss modulus (G″) increased with particle sizes. During centrifugation processing, strong centrifugal force surmounted the electrostatic repulsion between CS–TPP particles and caused particles to stick with each other to form CS–TPP microgels. The water contents of microgels negligibly depended on particle size, suggesting that the free volumes of microgels were not affected by particle size, therefore supporting our pseudo-hard sphere assumption for CS–TPP nanoparticles.