Minimum surfactant concentration required for inducing self-shaping of oil droplets and competitive adsorption effects.

Surfactant choice is key in starting the phenomena of artificial morphogenesis, the bottom-up growth of geometric particles from cooled emulsion droplets, as well as the bottom-up self-assembly of rechargeable microswimmer robots from similar droplets. The choice of surfactant is crucial for the formation of a plastic phase at the oil-water interface, for the kinetics, and for the onset temperature of these processes. But further details are needed to control these processes for bottom-up manufacturing and understand their molecular mechanisms. Still unknown are the minimum concentration of the surfactant necessary to induce the processes, or competing effects in a mixture of surfactants when only one is capable of inducing shapes. Here we systematically study the effect of surfactant nature and concentration on the shape-inducing behaviour of hexadecane-in-water emulsions with both cationic (CTAB) and non-ionic (Tween, Brij) surfactants over up to five orders of magnitude of concentration. The minimum effective concentration is found approximately equal to the critical micelle concentration (CMC), or the solubility limit below the Krafft point of the surfactant. However, the emulsions show low stability at the vicinity of CMC. In a mixed surfactant experiment (Tween 60 and Tween 20), where only one (Tween 60) can induce shapes we elucidate the role of competition at the interface during mixed surfactant adsorption by varying the composition. We find that a lower bound of ∼75% surface coverage of the shape-inducing surfactant with C14 or longer chain length is necessary for self-shaping to occur. The resulting technique produces a clear visual readout of otherwise difficult to investigate molecular events. These basic requirements (minimum concentration and % surface coverage to induce oil self-shaping) and the related experimental techniques are expected to guide academic and industrial scientists to formulations with complex surfactant mixtures and behaviour.

Correction: Spontaneous particle desorption and "Gorgon" drop formation from particle-armored oil drops upon cooling.

Correction for 'Spontaneous particle desorption and "Gorgon" drop formation from particle-armored oil drops upon cooling' by Diana Cholakova et al., Soft Matter, 2020, 16, 2480-2496, DOI: 10.1039/C9SM02354B.

Spontaneous particle desorption and "Gorgon" drop formation from particle-armored oil drops upon cooling.

We study how the phenomenon of drop "self-shaping" (Denkov et al., Nature, 528, 2015, 392), in which oily emulsion drops undergo a spontaneous series of shape transformations upon emulsion cooling, is affected by the presence of adsorbed solid particles, like those used in Pickering emulsion stabilization. Experiments with several types of latex particles, and with added surfactant of low concentration to enable drop self-shaping, revealed several new unexpected phenomena: (1) adsorbed latex particles rearranged into regular hexagonal lattices upon freezing of the surfactant adsorption layer. (2) Spontaneous particle desorption from the drop surface was observed at a certain temperature - a remarkable phenomenon, as the solid particles are known to irreversibly adsorb on fluid interfaces. (3) Very strongly adhered particles to drop surfaces acted as a template to enable the formation of tens to hundreds of semi-liquid fibres, growing outwards from the drop surface, thus creating a shape resembling the Gorgon head from Greek mythology. Mechanistic explanations of all observed phenomena are provided using our understanding of the rotator phase formation on the surface of the cooled drops. The surface rotator phase creates positive line tension at the contact line formed between the particle surface and the fluid interface, which causes the particle ejection from the drop surface.

Multilayer Formation in Self-Shaping Emulsion Droplets.

In several recent studies, we showed that micrometer-sized oil-in-water emulsion droplets from alkanes, alkenes, alcohols, triglycerides, or mixtures of these components can spontaneously "self-shape" upon cooling into various regular shapes, such as regular polyhedrons, platelets, rods, and fibers ( Denkov , N. , Nature 2015 , 528 , 392 ; Cholakova , D. , Adv. Colloid Interface Sci. 2016 , 235 , 90 ). These drop-shape transformations were explained by assuming that intermediate plastic rotator phase, composed of ordered multilayers of oily molecules, is formed beneath the drop surface around the oil-freezing temperature. An alternative explanation was proposed ( Guttman , S. , Proc. Natl. Acad. Sci. USA 2016 113 , 493 ; Guttman , S. , Langmuir 2017 , 33 , 1305 ), which is based on the assumption that the oil-water interfacial tension decreases to very low values upon emulsion cooling. Here, we present new results, obtained by differential scanning calorimetry (DSC), which quantify the enthalpy effects accompanying the drop-shape transformations. Using optical microscopy, we related the peaks in the DSC thermograms to the specific changes in the drop shape. Furthermore, from the enthalpies measured by DSC, we determined the fraction of the intermediate phase involved in the processes of drop deformation. The obtained results support the explanation that the drop-shape transformations are intimately related to the formation of ordered multilayers of alkane molecules with thickness varying between several and dozens of layers of alkane molecules, depending on the specific system. The new results provide the basis for a rational approach to the mechanistic explanation and to the fine control of this fascinating and industrially relevant phenomenon.

Mechanisms and Control of Self-Emulsification upon Freezing and Melting of Dispersed Alkane Drops.

Emulsification requires drop breakage and creation of a large interfacial area between immiscible liquid phases. Usually, high-shear or high-pressure emulsification devices that generate heat and increase the emulsion temperature are used to obtain emulsions with micrometer and submicrometer droplets. Recently, we reported a new, efficient procedure of self-emulsification (Tcholakova et al. Nat. Commun. 2017, 8, 15012), which consists of one to several cycles of freezing and melting of predispersed alkane drops in a coarse oil-in-water emulsion. Within these freeze-thaw cycles of the dispersed drops, the latter burst spontaneously into hundreds and thousands of smaller droplets without using any mechanical agitation. Here, we clarify the main factors and mechanisms, which drive this self-emulsification process, by exploring systematically the effects of the oil and surfactant types, the cooling rate, and the initial drop size. We show that the typical size of the droplets, generated by this method, is controlled by the size of the structural domains formed in the cooling-freezing stage of the procedure. Depending on the leading mechanism, these could be the diameter of the fibers formed upon drop self-shaping or the size of the crystal domains formed at the moment of drop-freezing. Generally, surfactant tails that are 0-2 carbon atoms longer than the oil molecules are most appropriate to observe efficient self-emulsification. The specific requirements for the realization of different mechanisms are clarified and discussed. The relative efficiencies of the three different mechanisms, as a function of the droplet size and cooling procedure, are compared in controlled experiments to provide guidance for understanding and further optimization and scale-up of this self-emulsification process.

"Self-Shaping" of Multicomponent Drops.

In our recent study we showed that single-component emulsion drops, stabilized by proper surfactants, can spontaneously break symmetry and transform into various polygonal shapes during cooling [ Denkov Nature 2015 , 528 , 392 - 395 ]. This process involves the formation of a plastic rotator phase of self-assembled oil molecules beneath the drop surface. The plastic phase spontaneously forms a frame of plastic rods at the oil drop perimeter which supports the polygonal shapes. However, most of the common substances used in industry appear as mixtures of molecules rather than pure substances. Here we present a systematic study of the ability of multicomponent emulsion drops to deform upon cooling. The observed trends can be summarized as follows: (1) The general drop-shape evolution for multicomponent drops during cooling is the same as with single-component drops; however, some additional shapes are observed. (2) Preservation of the particle shape upon freezing is possible for alkane mixtures with chain length difference Δn ≤ 4; for greater Δn, phase separation within the droplet is observed. (3) Multicomponent particles prepared from alkanes with Δn ≤ 4 plastify upon cooling due to the formation of a bulk rotator phase within the particles. (4) If a compound, which cannot induce self-shaping when pure, is mixed with a certain amount of a compound which induces self-shaping, then drops prepared from this mixture can also self-shape upon cooling. (5) Self-emulsification phenomena are also observed for multicomponent drops. In addition to the three recently reported mechanisms of self-emulsification [ Tcholakova Nat. Commun. 2017 , ( 8 ), 15012 ], a new (fourth) mechanism is observed upon freezing for alkane mixtures with Δn > 4. It involves disintegration of the particles due to a phase separation of alkanes upon freezing.

Rotator phases in hexadecane emulsion drops revealed by X-ray synchrotron techniques.

HYPOTHESIS: Micrometer sized alkane-in-water emulsion drops, stabilized by appropriate long-chain surfactants, spontaneously break symmetry upon cooling and transform consecutively into series of regular shapes (Denkov et al., Nature 2015, 528, 392). Two mechanisms were proposed to explain this phenomenon of drop "self-shaping". One of these mechanisms assumes that thin layers of plastic rotator phase form at the drop surface around the freezing temperature of the oil. This mechanism has been supported by several indirect experimental findings but direct structural characterization has not been reported so far. EXPERIMENTS: We combine small- and wide-angle X-ray scattering (SAXS/WAXS) with optical microscopy and DSC measurements of self-shaping drops in emulsions. FINDINGS: In the emulsions exhibiting drop self-shaping, the scattering spectra reveal the formation of intermediate, metastable rotator phases in the alkane drops before their crystallization. In addition, shells of rotator phase were observed to form in hexadecane drops, stabilized by C16EO10 surfactant. This rotator phase melts at ca. 16.6 °C which is significantly lower than the melting temperature of crystalline hexadecane, 18 °C. The scattering results are in a very good agreement with the complementary optical observations and DSC measurements.

Efficient self-emulsification via cooling-heating cycles.

In self-emulsification higher-energy micrometre and sub-micrometre oil droplets are spontaneously produced from larger ones and only a few such methods are known. They usually involve a one-time reduction in oil solubility in the continuous medium via changing temperature or solvents or a phase inversion in which the preferred curvature of the interfacial surfactant layer changes its sign. Here we harness narrow-range temperature cycling to cause repeated breakup of droplets to higher-energy states. We describe three drop breakup mechanisms that lead the drops to burst spontaneously into thousands of smaller droplets. One of these mechanisms includes the remarkable phenomenon of lipid crystal dewetting from its own melt. The method works with various oil-surfactant combinations and has several important advantages. It enables low surfactant emulsion formulations with temperature-sensitive compounds, is scalable to industrial emulsification and applicable to fabricating particulate drug carriers with desired size and shape.