Freeze–thaw stability of water-in-oil emulsions

Factors influencing water-in-oil emulsion stability during freeze/thaw-cycling, namely interfacial crystallization vs. network crystallization and the sequence of crystallization events (i.e., dispersed vs. continuous phase or vice versa), are assessed. We show that destabilization is most apparent with a liquid-state emulsifier and a continuous oil phase that solidifies prior to the dispersed phase. Emulsions stable to F/T-cycling are obtained when the emulsifier crystallizes at the oil-water interface or in emulsions where the continuous phase crystallizes after the dispersed aqueous phase. The materials used are two food-grade oil-soluble emulsifiers - polyglycerol polyricinoleate (PGPR) and glycerol monostearin (GMS) and two continuous oil phases with differing crystallization temperatures - canola oil and coconut oil. Emulsion stability is assessed with pulsed field gradient NMR droplet size analysis, sedimentation, microscopy and differential scanning calorimetry. This study demonstrates the sequence of crystallization events and the physical state of the surfactant at the oil-water interface strongly impact the freeze-thaw stability of water-in-oil emulsions.