On the stabilization of emulsions by cellulose nanocrystals and nanofibrils: Interfacial behavior and synergism

Competitive adsorption of cellulose nanofibers at oil-water interface in Pickering emulsion is reported here. Dodecane-in-water emulsions stabilized by either of two types of nanocelluloses, cellulose nanocrystals (CNC) or cellulose nanofibrils (CNF), as well as by their binary mixtures with increasing fractions of CNC, were prepared using particle concentrations of 0.1–0.5 wt% and studied. Despite differences in shape and morphology, both forms of nanofibers produced stable emulsion droplets even at low particle concentrations (0.1 wt%), with CNC producing smaller droplets and emulsions with higher stability. When mixed, an increased fraction of CNC in the mixture reduced the average droplet size, which however applied only for higher contents of oil (30 and 50 wt%) and higher total contents of cellulose particles used under emulsification. The CNC particles controlled the size of emulsion droplets, while the role of CNF contributed to the further surface coverage. When the fraction of CNF in the mixture increased, the capability of CNC particles to readily adsorb at the oil-water interface was reduced by the CNF nanofibrils present in aqueous phase. The stability of emulsions with respect to changes in droplet size and creaming index was influenced more by oil content and total particle concentration than by the fraction of CNC present in the mixture

Pickering emulsions stabilised by hydrophobically modified cellulose nanocrystals: responsiveness to pH and ionic strength

The aims of this study were to hydrophobically modify cellulose nanocrystals (CNCs), investigate the ability of such modified CNCs (MCNCs) to stabilise Pickering oil-in-water (O/W) emulsions and understand their stability at different pHs (2.0–7.0) and ionic strengths (0–150 mM NaCl). Structural changes that resulted from esterifying CNCs with octenyl succinic anhydride (OSA) were determined using Fourier transform infrared (FTIR) spectroscopy, X-ray diffractometry (XRD), transmission electron microscopy (TEM) and wettability analysis. The stability of the Pickering O/W emulsions (20 wt% oil, 0.05–1.00 wt% MCNCs) was assessed using droplet sizing, microscopy, ζ-potential, apparent viscosity and oscillatory rheological measurements. FTIR spectroscopy confirmed a decrease in the intensity of the –OH-associated band because of reaction of the hydroxyl group with OSA. XRD indicated a lower (11.5%) crystallinity index in MCNCs. TEM revealed that there was no change in morphology of the needle-shaped CNCs upon OSA modification (length/diameter = 40–100 nm/2–4 nm). Hydrophobic modification of CNCs with OSA was evidenced by an increase in static water contact angle from 56° (untreated CNCs) to 80.2° (MCNCs) which allowed the MCNCs to be partially wetted by both the phases and stabilise O/W emulsions. The Pickering emulsions showed droplet flocculation at pH < 4.0 (without addition of NaCl) or ionic strength ≥ 20 mM NaCl (pH 7.0), with a predominant elastic gel-like behaviour observed at ≥ 20 mM NaCl. Resistance of MCNC-based Pickering emulsions to coalescence and responsiveness to flocculation at bio-relevant pHs and ionic strengths show promise in the design of delivery vehicles