Synthetic and biopolymeric microgels: Review of similarities and difference in behaviour in bulk phases and at interfaces.

This review discusses the current knowledge of interfacial and bulk interactions of biopolymeric microgels in relation to the well-established properties of synthetic microgels for applications as viscosity modifiers and Pickering stabilisers. We present a timeline showing the key milestones in designing microgels and their bulk/ interfacial performance. Poly(N-isopropylacrylamide) (pNIPAM) microgels have remained as the protagonist in the synthetic microgel domain whilst proteins or polysaccharides have been primarily used to fabricate biopolymeric microgels. Bulk properties of microgel dispersions are dominated by the volume fraction (ϕ) of the microgel particles, but ϕ is difficult to pinpoint, as addressed by many theoretical models. By evaluating recent experimental studies over the last five years, we find an increasing focus on the analysis of microgel elasticity as a key parameter in modulating their packing at the interfaces, within the provinces of both synthetic and biopolymeric systems. Production methods and physiochemical factors shown to influence microgel swelling in the aqueous phase can have a significant impact on their bulk as well as interfacial performance. Compared to synthetic microgels, biopolymer microgels show a greater tendency for polydispersity and aggregation and do not appear to have a core-corona structure. Comprehensive studies of biopolymeric microgels are still lacking, for example, to accurately determine their inter- and intra- particle interactions, whilst a wider variety of techniques need to be applied in order to allow comparisons to real systems of practical usage.