Structure of the Hexadecane Rotator Phase: Combination of X-ray Spectra and Molecular Dynamics Simulation.

Rotator phases are rotationally disordered plastic crystals, some of which can form upon freezing of alkane at alkane-water interfaces. Existing X-ray diffraction studies show only partial unit cell information for rotator phases of some alkanes. This includes the rotator phase of n-hexadecane, which is a transient metastable phase in pure alkane systems, but shows remarkable stability at interfaces when mediated by a surfactant. Here, we combine synchrotron X-ray diffraction data and molecular dynamics (MD) simulations, reporting clear evidence of the face-centered orthorhombic RI rotator phase from spectra for two hexadecane emulsions, one stabilized by Brij C10 and another by Tween 40 surfactants. MD simulations of pure hexadecane use the recently developed Williams 7B force field, which is capable of reproducing crystal-to-rotator phase transitions, and it also predicts the crystal structure of the RI phase. Full unit cell information is obtained by combining unit cell dimensions from synchrotron data and molecular orientations from MD simulations. A unit cell model of the RI phase is produced in the crystallographic information file (CIF) format, with each molecule represented by a superposition of four rotational positions, each with 25% occupancy. Powder diffraction spectra computed using this model are in good agreement with the experimental spectra

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

Theory of Shape-Shifting Droplets

Recent studies of cooled oil emulsion droplets uncovered transformations into a host of flattened shapes with straight edges and sharp corners, driven by a partial phase transition of the bulk liquid phase. Here, we explore theoretically the simplest geometric competition between this phase transition and surface tension in planar polygons and recover the observed sequence of shapes and their statistics in qualitative agreement with experiments. Extending the model to capture some of the three-dimensional structure of the droplets, we analyze the evolution of protrusions sprouting from the vertices of the platelets and the topological transition of a puncturing planar polygon.This work was supported in part by the Engineering and Physical Sciences Research Council (P. A. H.), an Established Career Fellowship from the EPSRC (R. E. G.), and the European Research Council (Grant EMATTER No. 280078 to S. K. S.)

Seventh to eleventh century CE glass from Northern Italy: between continuity and innovation

Previous analytical studies show that most of Northern Italian glass has been heavily recycled and that mixing of natron and plant ash glass was occurring (Verità and Toninato 1990; Verità et al. 2002; Uboldi and Verità 2003; Andreescu-Treadgold and Henderson 2006; Silvestri and Marcante 2011). The re-use of “old Roman glass” has been interpreted as stagnation in glass trade from the primary production areas. However, the reintroduction of plant ash glass on sites such as Torcello, Nogara, and in Lombardy at the same time as it was reintroduced in the Levant, strongly indicates long-distance contacts with the Levant at least from the eighth century CE. This paper addresses the key issue of recycling by focusing on the compositional nature of glass traded and reworked in Northern Italy after the seventh century CE set in a broad Mediterranean context by analysing major, minor, and trace elements in eighty-nine glass samples (seventh to the eleventh century AD) from the glass workshop of Piazza XX Settembre, Comacchio. Five major previously proposed compositional groups of glass have been identified from Comacchio (Levantine Apollonia and Jalame types, HIMT, Foy-2, and plant ash glass). The impact of recycling and mixing practices in Comacchio glass is also discussed with the help of known recycling markers and selected ratios (major and trace elements). The mixing between Levantine, HIMT, and plant ash glass is highlighted and end-members of potential natron to natron mixing compositional groups have been identified. The compositional nature of plant ash glass from Northern Italy is discussed in light of their trace element content and production areas

Self-shaping of oil droplets via the formation of intermediate rotator phases upon cooling.

Revealing the chemical and physical mechanisms underlying symmetry breaking and shape transformations is key to understanding morphogenesis. If we are to synthesize artificial structures with similar control and complexity to biological systems, we need energy- and material-efficient bottom-up processes to create building blocks of various shapes that can further assemble into hierarchical structures. Lithographic top-down processing allows a high level of structural control in microparticle production but at the expense of limited productivity. Conversely, bottom-up particle syntheses have higher material and energy efficiency, but are more limited in the shapes achievable. Linear hydrocarbons are known to pass through a series of metastable plastic rotator phases before freezing. Here we show that by using appropriate cooling protocols, we can harness these phase transitions to control the deformation of liquid hydrocarbon droplets and then freeze them into solid particles, permanently preserving their shape. Upon cooling, the droplets spontaneously break their shape symmetry several times, morphing through a series of complex regular shapes owing to the internal phase-transition processes. In this way we produce particles including micrometre-sized octahedra, various polygonal platelets, O-shapes, and fibres of submicrometre diameter, which can be selectively frozen into the corresponding solid particles. This mechanism offers insights into achieving complex morphogenesis from a system with a minimal number of molecular components.European Research Council (Grant ID: EMATTER 280078), European networks COST MP 1106 and 1305 and the capacity building project BeyondEverest of the European Commission (Grant ID: 286205)This is the author accepted manuscript. The final version is available from Nature Publishing Group via http://dx.doi.org/10.1038/nature1618