Interfacial crystallization at the intersection of thermodynamic and geometry.

Interfacial crystallization appears as a crucial stage in the numeral natural phenomena and technological applications, such as industry of semi-conductors and manufacturing of nano-whiskers. Interfacial aspects of heterogeneous crystallization are surveyed. The review is focused on the interplay of thermodynamic and geometric aspects of the interfacial crystallization. Thermodynamic considerations leading to the Wulff construction are discussed. Equilibrium shape of the crystallized particle in the contact with a foreign substrate giving rise to the Winterbottom construction is treated. The concept of equivalent equilibrium contact angle θeq is introduced. The equivalent contact angle θeq applicable for isotropic crystals does not depend neither on the volume of the crystallized particles nor on the external fields. Bulk contributions to the free energy of the particle such as the bulk heat release in the case of reactive contact or latent heat of crystallization do not influence the equivalent contact angle θeq. Application of the Winterbottom constructions for prediction of the shape of nanoparticles grown on solid substrates is treated. Thermodynamics of interfacial crystallization is discussed. The thermodynamic condition predicting when surface crystallization is thermodynamically favored over homogeneous (bulk) crystallization is supplied. This thermodynamic relation coincides with the condition prescribing the partial wetting of a solid by its melt. Interfacial crystallization in its relation to the "coffee-stain" effect, salt creeping and development of anti-icing surfaces is addressed. Interfacial aspects of epitaxial growth of crystals are considered. The current state-of-art in the field is reviewed.

Measurement of effective wetting area at hydrophobic solid-liquid interface.

HYPOTHESES: The effective wetting area, a parameter somewhat different from the apparent contact area at solid-liquid interfaces, plays a significant role in surface wettability. However, determination of the effective wetting area for hydrophobic surfaces remains an open question. In the present study, we developed an electrochemical impedance method to evaluate the effective wetting area at a hydrophobic solid-liquid interface. EXPERIMENTS: Patterned Si surfaces were prepared using the anisotropic wet etching method, and the water contact angle and electrochemical impedance were measured experimentally. The effective wetting area at the solid-liquid interface was examined based on the wettability and impedance results. FINDINGS: The electrochemical impedance for the patterned Si surfaces increased with increasing surface hydrophobicity, whereas the effective wetting area decreased. The intermediate wetting state (i.e. partial wetting model) was confirmed at the patterned Si surfaces, and the effective wetting area was theoretically estimated. The effective wetting area predicted from the electrochemical impedance agreed well with that predicted from the partial wetting model, thereby demonstrating the validity of the electrochemical impedance method for evaluating the effective wetting area at the hydrophobic solid-liquid interface.

Rotational diffusion of partially wetted colloids at fluid interfaces.

HYPOTHESIS: Rotational Brownian diffusions of colloidal particles at a fluid interface play important roles in particle self-assembly and in surface microrheology. Recent experiments on translational Brownian motion of spherical particles at the air-water interface show a significant slowing down of the translational diffusion with respect to the hydrodynamic predictions (Boniello et al., 2015). For the rotational diffusions of partially wetted colloids, slowing down of the particle dynamics can be also expected. EXPERIMENTS: Here, the rotational dynamics of Janus colloids at the air-water interface have been experimentally investigated using optical microscopy. Bright field and fluorescent microscopies have been used to measure the in-plane and out-of-plane particle rotational diffusions exploiting the Janus geometry of the colloids we fabricated. FINDINGS: Our results show a severe slowing down of the rotational diffusion Dr,⊥ connected to the contact line motion and wetting-dewetting dynamics occurring on particle regions located at opposite liquid wedges. A slowing down of the particle rotational diffusion about an axis parallel to the interfacial normal Dr,|| was also observed. Contact line fluctuations due to partial wetting dynamics lead to a rotational line friction that we have modelled in order to describe our results.

Reducing Surface Wetting Proportion of Soils Irrigated by Subsurface Drip Irrigation Can Mitigate Soil N2O Emission.

To reveal the impact of soil moisture distributions on nitrous oxide (N2O) emissions from wet soils irrigated by sub-surface drip irrigation (SDI) with different surface soil wetting proportions, pot experiments were conducted, with surface irrigation (SI) as a control. Results indicated that irrigation triggered N2O pulsing effect in all SDI treatments, yet N2O values reduced with the decrease of surface soil wetting proportions of SDI irrigated soils, and the occurrence times were lagged. The peak N2O fluxes and the corresponding soil water filled pore space (WFPS), as well as the coefficients of determination (R²) of the exponential function between N2O fluxes and soil WFPS, decreased with the reduction of surface soil wetting proportions with SDI treatment, and from the central sub-region to the periphery sub-region. The pulse period contributed most to the reduction of N2O emissions in SDI compared to SI treatments and should be a key period for N2O emission mitigation. Over the whole experimental period, the area-weighted average cumulative N2O fluxes from SDI treatments were 82.3⁻157.3 mg N2O m-2 lower than those from SI treatment, with periphery sub-regions of R3 and R4 (radius of 19⁻27 cm and 28⁻36 cm from the emitter horizontally) contributing to more than 75.8% of the total N2O emission mitigation. These results suggest that reducing surface soil wetting proportions or the increments of topsoil WFPS for SDI irrigated soils is a promising strategy for N2O emission reduction.

Complex coacervates formed across liquid interfaces: A self-consistent field analysis.

The Scheutjens-Fleer self-consistent field (SF-SCF) theory is used to study complexation between two oppositely charged polyelectrolytes across an interface formed by two solvents, here called oil and water. The focus is on the composition and the lateral stability of such interfacial coacervate. One polyelectrolyte is chosen to be oil soluble and the other one prefers water, whereas the counter and salt ions are taken to distribute ideally over all phases. There exists an electrostatic associative driving force for the formation of the coacervate phase which increases with decreasing ionic strength and may be assisted by some specific affinity between the associating units and an effective poor solvency for the coacervate. As with respect to the lateral stability an unusual wetting scenario, called pseudo-partial wetting, presents itself, which results from interactions on two different length scales. On the segmental length the screening of oil-water contacts promotes the wetting by the coacervate: a pre-wetting jump-like transition takes place off-coexistence from a microscopically thin to a mesoscopically thin film. Usually this implies complete wetting. However, the mesoscopically thin film is exposed to long-ranged attractive electrostatic interactions and therefore cannot grow to macroscopic dimensions upon approach towards coexistence. Hence the system remains partial wet. The bulk correlation length controls the thickness of the mesoscopically thin film and as a result the wetting transition occurs extremely close to the bulk critical point. We therefore expect that a thick coacervate film typically is laterally inhomogeneous: there are drops on top of a mesoscopically thin coacervate film. This conclusion qualitatively explains the experimental observation that such a coacervate film scatters visible light.

Thermodynamic origin of surface melting on ice crystals.

Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice-vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs.