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.

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.

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. This journal is

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.,et al. Nature 2015, 528, 392; Cholakova, D.,et al. 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.,et al. Proc. Natl. Acad. Sci. USA 2016 113, 493; Guttman, S.,et al. 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.

Shape-anisotropic polymeric micro- and nanoparticles are of significant interest for the development of novel composite materials, lock-and-key assemblies, and drug carriers. Currently, syntheses require external confinement in microfluidic devices or lithographic techniques associated with significant infrastructure and low productivity, so new methods are necessary to scale-up such production efficiently. Here we report bottom-up polymerization of regular shape-anisotropic particles (polygonal platelets with different numbers of edges, with and without protruding asperities, and fibrilar particles with controllable aspect ratios), with size control over 4 orders of magnitude (∼50 nm-1 mm). Polymerization also enables the study of much smaller shapes than could previously be studied in water suspensions, and we study the fundamental limits of the self-shaping transition process driving these transformations for monomer oil droplets of stearyl methacrylate (SMA) monomer oil. We show the method is compatible with a variety of polymerizing monomers and functional modifications of the particles (e.g., composites with magnetic nanoparticles, oil-soluble additives, etc.). We also describe postsynthetic surface modifications that lead to hierarchical superstructures. The synthesis procedure has great potential in efficient nanomanufacturing as it can achieve scalable production of the above shapes in a wide range of sizes, with minimum infrastructure and process requirements and little maintenance of the equipment.