Ben Ocko

Atomic-Scale Surface Demixing in a Eutectic Liquid BiSn Alloy

Resonant x-ray reflectivity of the surface of the liquid phase of the Bi(43)Sn(57) eutectic alloy reveals atomic-scale demixing extending over three near-surface atomic layers. Because of the absence of an underlying atomic lattice which typically defines adsorption in crystalline alloys, studies of adsorption in liquid alloys provide unique insight on interatomic interactions at the surface. The observed composition modulation could be accounted for quantitatively by the Defay-Prigogine and Strohl-King multilayer extensions of the single-layer Gibbs model, revealing a near-surface domination of the attractive Bi-Sn interaction over the entropy.

Anomalous layering at the liquid sn surface

X-ray reflectivity measurements on the free surface of liquid Sn are presented. They exhibit the high-angle peak, indicative of surface-induced layering, also found for other pure liquid metals (Hg, Ga, and In). However, a low-angle shoulder, not hitherto observed for any pure liquid metal, is also found, indicating the presence of a high-density surface layer. Fluorescence and resonant reflectivity measurements rule out the assignment of this layer to surface segregation of impurities. The reflectivity is modeled well by a 10% contraction of the spacing between the first and second atomic surface layers, relative to that of subsequent layers. Possible reasons for this are discussed.

Surface Layering of Liquids: The Role of Surface Tension

Recent measurements show that the free surfaces of liquid metals and alloys are always layered, regardless of composition and surface tension; a result supported by three decades of simulations and theory. Recent theoretical work claims, however, that at low enough temperatures the free surfaces of all liquids should become layered, unless preempted by bulk freezing. Using x-ray reflectivity and diffuse scattering measurements we show that there is no observable surface-induced layering in water at T=298 K, thus highlighting a fundamental difference between dielectric and metallic liquids. The implications of this result for the question in the title are discussed.

Short-Range Wetting at Liquid Gallium-Bismuth Alloy Surfaces: X-Ray Measurements and Square-Gradient Theory

We present an x-ray reflectivity study of wetting at the free surface of the binary liquid metal gallium-bismuth (Ga-Bi) in the region where the bulk phase separates into Bi-rich and Ga-rich liquid phases. The measurements reveal the evolution of the microscopic structure of wetting films of the Bi-rich, low-surface-tension phase along different paths in the bulk phase diagram. A balance between the surface potential preferring the Bi-rich phase and the gravitational potential which favors the Ga-rich phase at the surface pins the interface of the two demixed liquid metallic phases close to the free surface. This enables us to resolve it on an Ångström level and to apply a meanfield, square gradient model extended by thermally activated capillary waves as dominant thermal fluctuations. The sole free parameter of the gradient model, i.e. the so-called influence parameter, κ, is determined from our measurements. Relying on a calculation of the liquid/liquid interfacial tension that makes it possible to distinguish between intrinsic and capillary wave contributions to the interfacial structure we estimate that fluctuations affect the observed short-range, complete wetting phenomena only marginally. A critical wetting transition that should be sensitive to thermal fluctuations seems to be absent in this binary metallic alloy.

Nanoscale structure of the oil-water interface

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. The XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.