Rheology of Cellulose Nanocrystal and Fumed Silica Suspensions: Influence of Ionic Surfactants

Nanomaterials such as cellulose nanocrystals and fumed silica are emerging as excellent thickeners for liquids in a variety of practical applications. Surfactants are often incorporated into the thickening fluids to provide stabilizing components and to control the surface activity of fluids. To develop new thickening materials with desired surface-active properties, it is important to understand the interactions between surfactants and nanoparticles in suspensions. In this work, the interactions between surfactants and nanocrystals/nanoparticles were investigated. Two surfactants, anionic sodium lauryl sulfate-based surfactant (referred to as Stepanol) and cationic hexadecyltrimethylammonium bromide (referred to as HTAB), were studied. Cellulose nanocrystals (referred to as NCC) and fumed-silica nanoparticles (referred to as N20) were used as nanomaterials. The unique feature of this study is that it simultaneously measures rheology, surface activity, and electrical conductivity to determine the influence of ionic surfactants on the behavior and properties of cellulose nanocrystal and fumed silica nanoparticle suspensions. Furthermore, the interactions are observed in the low surfactant concentration range of 0 to 500 ppm. The NCC concentration of NCC-surfactant mixtures was fixed at 1 wt%. Two concentrations of N20 (2 and 5 wt%) were used for N20-surfactant mixtures. The influence of Stepanol was found to be weak whereas HTAB had a strong influence on the rheology of NCC and N20 suspensions. The NCC suspension and surfactant-NCC suspensions were highly non-Newtonian shear-thinning. The N20 suspensions and N20-Stepanol mixtures were nearly Newtonian. The N20-HTAB mixtures were shear-thinning at high HTAB concentrations. The power law model described the rheological behavior of non-Newtonian systems adequately. The consistency and flow behavior indices varied only marginally with the addition of the anionic surfactant Stepanol to NCC and N20 suspensions. With the addition of cationic surfactant HTAB to NCC and N20 suspensions, however, a large increase (20- to 70-fold) in consistency index was observed at high surfactant concentrations. The critical surfactant concentrations where sharp transitions in the rheological properties took place were identified using break points in surface tension and electrical conductivity plots. This study offers valuable insights into tailoring surfactant-nanoparticle systems for practical applications, where precise control of rheological and interfacial properties may be required.