Engineering the oil binding capacity and crystallinity of self-assembled fibrillar networks of 12-hydroxystearic acid in edible oils

Abstract

The crystallinity and oil binding capacity of 12-hydroxystearic acid (12HSA)–vegetable oil organogels was modified by changing the post-crystallization annealing temperature from 5 °C to 30 °C for 24 h. The gels stored at 5 °C had a highly branched crystalline structure with small uniform pores, as determined by cryo-scanning electron microscopy. Large T₂proton relaxation peaks at 50 to 70 ms determined by pulse nuclear magnetic resonance (pNMR) suggested the presence of highly immobilized oil at 5 °C. When the gels were stored at 30 °C, longer fibers and a less branched network were observed. At 30 °C, the 12HSA network's crystallinity was enhanced with fewer inclusions of liquid oil as determined by pNMR. When the gels were stored at 30 °C, a significantly shorter T₂ relaxation peak was observed. The increased crystallinity, at 30 °C, was attributed to a reduction in bulk supersaturation, resulting in a very high crystallographic mismatch nucleation barrier (ΔG*) which favored one-dimensional fiber growth. However, at a lower crystallization temperature of 5 °C, there is an increase in the supersaturation and hence the crystallographic mismatch barrier is significantly lower, increasing fiber tip branching. The nucleation-growth–branching-growth model for self-assembled fibrillar networks explains the differences in crystallinity, pore size and oil syneresis observed for the 12HSA–vegetable oil organogels. It was found that the gels stored at 30 °C syneresised 1.35 times faster than the gels stored at 5 °C. Furthermore, the change in the T₂ relaxations and the ratio of the complex viscosity/pore radius were 1.35 and 1.30 respectively.