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Development of nanogels from nanoemulsions and investigation of their rheology and stability



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Nanoemulsions with extremely small droplet sizes (<100 nm) have shown several advantages over conventional emulsions. However, almost all nanoemulsions in usage are liquids that restrict their use in many soft materials. The aim of this thesis is to understand the formation and long-term stability of viscoelastic nanogels developed from liquid nanoemulsions. At first, gelation in 40 wt% canola oil-in-water nanoemulsions were investigated as a function of emulsifier type (anionic sodium dodecyl sulfate (SDS) or nonionic Tween 20) and concentration. Three different regimes of colloidal interactions were observed as a function of SDS concentration. 1) At low SDS concentration (0.5 – 2 times CMC) the counterion shell layer increased the effective volume fraction of the dispersed phase (eff) close to the random jamming, resulting in repulsive gelation. 2) At SDS concentration between 5 – 15 times CMC, micelle induced depletion attractions led to extensive droplet aggregation and gelation. 3) At very high SDS concentration, however, oscillatory structural forces (OSF) due to layered-structuring of excess micelles in the interdroplet regions led to loss of gelation. In repulsive gelation, reduction in droplet size coupled with the electrical double layer resulted in a linear increase of Gʹ. On the contrary, attractive nanoemulsions showed rapid increase in gel strength below a critical droplet radius, and was explained by transformation of OSF into depletion attraction. No gelation was seen in Tween 20 nanoemulsions, due to lack of repulsive interactions and weak depletion attraction. Next the influence of the dispersed phase volume fraction () on repulsive nanoemulsion gelation was investigated and the Gʹ values were modeled using empirical scaling law developed by Mason et al. (1995). It was found that an initial liquid regime transformed into glassy phase at a eff = g ~ 0.58, where droplets are entrapped in a cage of neighbouring droplets due to crowding. It was followed by jamming transition at a critical volume fraction (j), where droplet deformation led to large increase in elasticity. The model predicted j = 0.7, which is close to the predictions for repulsive polydispersed emulsions found in the literature. In the final phase long-term stability of the nanogels was evaluated until 90 days, during which the nanogels remained stable to creaming and coalescence. However, repulsive nanogels showed a significant decrease in Gʹ and the gels converted into flowable liquids over time. For attractive nanogels decrease in Gʹ was much less, although given enough time they would also transformed into weak gels. It was hypothesized that surface active compounds generated due to lipid oxidation altered interfacial charge cloud leading to loss of gel strength for repulsive nanogels. For attractive nanogels slippery bonds in the aggregates permitted rotational and translational diffusion of nanodroplets on the surface of each other leading to network compactness and a decrease in gel strength with time. Overall, it was concluded that it is possible to form nanogels from canola oil nanoemulsions using ionic emulsifiers. The gel strength and stability of the nanogels depends on emulsifier concentration, droplet size,  and the chemical stability of the oil used. More investigation is needed in order to improve the long-term stability of the nanogels. The nanogels possess high potential for use in low-fat foods, pharmaceuticals, and cosmetic products.



nanoemulsions, nanogels, maximal random jamming, depletion attraction, oscillatory structural forces



Master of Science (M.Sc.)


Food and Bioproduct Sciences


Food Science



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