Ultrastable High Internal Phase Pickering Emulsions: Forming Mechanism, Processability, and Application in 3D Printing

High internal phase Pickering emulsions (HIPPEs) are versatile platforms for various applications owing to their low-density, solid-like structure, and large specific surface area. Here, naturally occurring polysaccharide-protein hybrid nanoparticles (PPH NPs) were used to stabilize HIPPEs with an internal phase fraction of 80% at a PPH NP concentration of 1.5%. The obtained HIPPEs displayed a gel-like behavior with excellent stability against centrifugation (10000g, 10 min), temperature (4–121 °C), pH (1.0–11.0), and ionic strength (0–500 mM). Confocal laser scanning microscope and cryo-scanning electron microscopy results showed that PPH NPs contributed to the stability of HIPPEs by effectively adsorbing and anchoring on the surface of the emulsion droplets layer by layer to form a dense 3D network barrier to inhibit droplet coalescence. The rheological analysis showed that the HIPPEs possessed a higher viscosity and lower frequency dependence with increasing PPH NP concentration, suggesting the potential application of such HIPPEs in three-dimensional (3D) printing, which was subsequently confirmed by a 3D printing experiment. This work provides highly stable and processable HIPPEs, which can be developed as facile and reusable materials for numerous applications. They can also be directly used for future food manufacturing, drug and nutrient delivery, and tissue reconstruction.