nanomaterials Review Microemulsion Microstructure(s): A Tutorial Review Giuseppe Tartaro 1 , Helena Mateos 1 , Davide Schirone 1 , Ruggero Angelico 2 and Gerardo Palazzo 1,* 1 Department of Chemistry, and CSGI (Center for Colloid and Surface Science), University of Bari, via Orabona 4, 70125 Bari, Italy;
[email protected] (G.T.);
[email protected] (H.M.);
[email protected] (D.S.) 2 Department of Agricultural, Environmental and Food Sciences (DIAAA), University of Molise, I-86100 Campobasso, Italy;
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[email protected] Received: 30 June 2020; Accepted: 18 August 2020; Published: 24 August 2020 Abstract: Microemulsions are thermodynamically stable, transparent, isotropic single-phase mixtures of two immiscible liquids stabilized by surfactants (and possibly other compounds). The assortment of very different microstructures behind such a univocal macroscopic definition is presented together with the experimental approaches to their determination. This tutorial review includes a necessary overview of the microemulsion phase behavior including the effect of temperature and salinity and of the features of living polymerlike micelles and living networks. Once these key learning points have been acquired, the different theoretical models proposed to rationalize the microemulsion microstructures are reviewed. The focus is on the use of these models as a rationale for the formulation of microemulsions with suitable features. Finally, current achievements and challenges of the use of microemulsions are reviewed. Keywords: microemulsions; wormlike micelles; packing parameter; flexible surface model; hydrophilic–lipophilic difference (HLD); net average curvature (NAC) 1. Introduction As a matter of fact, water and oil do not mix. There are several applications in which this is a bitter truth and the coexistence of oil and water as separate macroscopic phases, interacting just through a small interface, is highly disappointing.