Spontaneously foaming oil systems have been formulated from water‐in‐oil emulsions by the controlled release and entrapment of gas in emulsified water droplets contained within the oil. The cascade of events leading to their formation is as follows: Two Span 60‐emulsified populations of water droplets, one containing Na2CO3, the other 10% HCl and caseinate, were mixed in miglyol oil; the controlled coalescence of Na2CO3 droplets with the HCl ones served as a microreactor for the pH reduction and the subsequent release of CO2 from Na2CO3; these gas microbubbles were arrested by sodium caseinate, stabilizing a microfoam within the water droplets; these droplets expanded under the rising gas pressure, spontaneously transforming the surrounding oil into a foamy oleogel containing water droplets.
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