Alberto Giacomello

Underwater energy harvesting from a heavy flag hosting ionic polymer metal composites

In this paper, we analyze underwater energy harvesting from the flutter instability of a heavy flag hosting an ionic polymer metal composite (IPMC). The heavy flag comprises a highly compliant membrane with periodic metal reinforcements to maximize the weight and minimize the bending stiffness, thus promoting flutter at moderately low flow speed. The IPMC is mechanically attached to the host flag and connected to an external load. The entire structure is immersed in a mean flow whose intensity is parametrically varied to explore the onset of flutter instability along with the relation between the vibration frequency and the mean flow speed. Manageable theoretical models for fluid-structure interaction and IPMC response are presented to inform the harvester design and interpret experimental data. Further, optimal parameters for energy scavenging maximization, including resistive load and flow conditions, are identified.

Cassie–Baxter and Wenzel States on a Nanostructured Surface: Phase Diagram, Metastabilities, and Transition Mechanism by Atomistic Free Energy Calculations

In this work, we study the wetting of a surface decorated with one nanogroove by a bulk Lennard-Jones liquid at various temperatures and densities. We used atomistic simulations aimed at computing the free energy of the stable and metastable states of the system, as well as the intermediate states separating them. We found that the usual description in terms of Cassie-Baxter and Wenzel states is insufficient, as the system presents two states of the Cassie-Baxter type. These states are characterized by different curvatures of the meniscus. The measured free energy barrier separating the Cassie-Baxter from the Wenzel state (and vice versa) largely exceeds the thermal energy, attesting the existence of Cassie-Baxter/Wenzel metastabilities. Finally, we found that the Cassie-Baxter/Wenzel transition follows an asymmetric path, with the formation of a liquid finger on one side of the groove and a vapor bubble on the opposite side.

Geometry as a Catalyst: How Vapor Cavities Nucleate from Defects

The onset of cavitation is strongly enhanced by the presence of rough surfaces or impurities in the liquid. Despite decades of research, the way the geometry of these defects promote the nucleation of bubbles and its effect on the kinetics of the process remains largely unclear. We present here a comprehensive explanation of the catalytic action that roughness elements exert on the nucleation process for both pure vapor cavities and gas ones. This approach highlights that nucleation may follow nontrivial paths connected with a sharp decrease of the free energy barriers as compared to flat surfaces. Furthermore, we demonstrate the existence of intermediate metastable states that break the nucleation process in multiple steps; these states correspond to what is commonly known as cavitation nuclei. A single dimensionless parameter, the nucleation number, is found to control this rich phenomenology. The devised theory allows one to quantify the effect of the geometry and hydrophobicity of surface asperities on nucleation. Within the same framework, it is possible to treat both vapor cavitation, which is relevant, e.g., for organic liquids, and gas-promoted cavitation, which is commonly encountered in water. The theory is shown to be valid from the nano- to the macroscale.

Wetting hysteresis induced by nanodefects

Significance Drops may fail to slide even on extremely smooth surfaces. This fact is due to the ubiquitous imperfections of surfaces: defects of molecular size—here too small to be noticed and experimentally characterizable—can hinder a macroscopic drop. To understand these far-reaching nanoscale phenomena, we combine a molecular description of the liquid with advanced techniques for the study of rare events. This approach allows us to bridge the diverse scales involved, demonstrating that even weak nanometer-sized surface defects can give rise to measurable differences between advancing and receding liquid fronts, i.e., contact angle hysteresis. The present results also shed new light on the unexpectedly long life of surface nanobubbles. Wetting of actual surfaces involves diverse hysteretic phenomena stemming from ever-present imperfections. Here, we clarify the origin of wetting hysteresis for a liquid front advancing or receding across an isolated defect of nanometric size. Various kinds of chemical and topographical nanodefects, which represent salient features of actual heterogeneous surfaces, are investigated. The most probable wetting path across surface heterogeneities is identified by combining, within an innovative approach, microscopic classical density functional theory and the string method devised for the study of rare events. The computed rugged free-energy landscape demonstrates that hysteresis emerges as a consequence of metastable pinning of the liquid front at the defects; the barriers for thermally activated defect crossing, the pinning force, and hysteresis are quantified and related to the geometry and chemistry of the defects allowing for the occurrence of nanoscopic effects. The main result of our calculations is that even weak nanoscale defects, which are difficult to characterize in generic microfluidic experiments, can be the source of a plethora of hysteretical phenomena, including the pinning of nanobubbles.

Unraveling the Salvinia Paradox: Design Principles for Submerged Superhydrophobicity

The complex structure of the Salvinia molesta is investigated via rare event molecular dynamics simulations. Results show that a hydrophilic/hydrophobic patterning together with a re-entrant geometry control the free energy barriers for bubble nucleation and for the Cassie-Wenzel transition. This natural paradigm is translated into simple macroscopic design criteria for engineering robust superhydrophobicity in submerged applications.

Wetting and cavitation pathways on nanodecorated surfaces

Rare event methods combined with molecular dynamics and macroscopic calculations reveal multiple pathways for the breakdown of the superhydrophobic Cassie state through wetting or cavitation.

Focus Article: Theoretical aspects of vapor/gas nucleation at structured surfaces

Heterogeneous nucleation is the preferential means of formation of a new phase. Gas and vapor nucleation in fluids under confinement or at textured surfaces is central for many phenomena of technological relevance, such as bubble release, cavitation, and biological growth. Understanding and developing quantitative models for nucleation is the key to control how bubbles are formed and to exploit them in technological applications. An example is the in silico design of textured surfaces or particles with tailored nucleation properties. However, despite the fact that gas/vapor nucleation has been investigated for more than one century, many aspects still remain unclear and a quantitative theory is still lacking; this is especially true for heterogeneous systems with nanoscale corrugations, for which experiments are difficult. The objective of this focus article is analyzing the main results of the last 10-20 years in the field, selecting few representative works out of this impressive body of the literature, and highlighting the open theoretical questions. We start by introducing classical theories of nucleation in homogeneous and in simple heterogeneous systems and then discuss their extension to complex heterogeneous cases. Then we describe results from recent theories and computer simulations aimed at overcoming the limitations of the simpler theories by considering explicitly the diffuse nature of the interfaces, atomistic, kinetic, and inertial effects.

Energy harvesting from flutter instabilities of heavy flags in water through ionic polymer metal composites

In this paper, we analyze underwater energy harvesting from the flutter instability of a heavy flag hosting an ionic polymer metal composite (IPMC). The heavy flag comprises a highly compliant membrane with periodic metal reinforcements to maximize the weight and minimize the bending stiffness, thus promoting flutter at moderately low flow speed. An IPMC strip is mechanically attached to the host flag and connected to an external load. The entire structure is immersed in a background flow whose intensity is parametrically varied to explore the onset of flutter instability along with the relation between the vibration frequency and the mean flow speed. Manageable theoretical models for fluid-structure interaction and IPMC response are presented to inform the harvester design and interpret experimental data. Further, optimal parameters for energy scavenging maximization, including resistive load and flow conditions, are identified.

Collapse of superhydrophobicity on nanopillared surfaces

The mechanism of the collapse of the superhydrophobic state is elucidated for submerged nanoscale textures forming a three-dimensional interconnected vapor domain. This key issue for the design of nanotextures poses significant simulation challenges as it is characterized by diverse time and length scales. State-of-the-art atomistic rare events simulations are applied for overcoming the long timescales connected with the large free energy barriers. In such interconnected surface cavities wetting starts with the formation of a liquid finger between two pillars. This break of symmetry induces a more gentle bend in the rest of the liquid-vapor interface, which triggers the wetting of the neighboring pillars. This collective mechanism, involving the wetting of several pillars at the same time, could not be captured by previous atomistic simulations using surface models comprising a small number of pillars (often just one). Atomistic results are interpreted in terms of a sharp-interface continuum model which suggests that line tension, condensation, and other nanoscale phenomena play a minor role in conditions close to coexistence. ∗ alberto.giacomello@uniroma1.it 1 ar X iv :1 70 3. 10 38 9v 1 [ co nd -m at .s of t] 3 0 M ar 2 01 7

Intrusion and extrusion of water in hydrophobic nanopores

Significance Molecular springs, constituted by nanoporous materials immersed in a nonwetting liquid, are compact, economical, and efficient means of storing energy, owing to their enormous surface area. Surface energy is accumulated during liquid intrusion inside the pores and released by decreasing liquid pressure and thus triggering confined cavitation. State-of-the-art atomistic simulations shed light on the intrusion and extrusion of water in hydrophobic nanopores, revealing conspicuous deviations from macroscopic theories, which include accelerated cavitation, increased intrusion pressure, and reversible intrusion and extrusion processes. Understanding these nanoscale phenomena is the key to a better design of molecular springs as it allows relating the characteristics of the materials to the overall properties of the devices, e.g., their operational pressure and efficiency. Heterogeneous systems composed of hydrophobic nanoporous materials and water are capable, depending on their characteristics, of efficiently dissipating (dampers) or storing (“molecular springs”) energy. However, it is difficult to predict their properties based on macroscopic theories—classical capillarity for intrusion and classical nucleation theory (CNT) for extrusion—because of the peculiar behavior of water in extreme confinement. Here we use advanced molecular dynamics techniques to shed light on these nonclassical effects, which are often difficult to investigate directly via experiments, owing to the reduced dimensions of the pores. The string method in collective variables is used to simulate, without artifacts, the microscopic mechanism of water intrusion and extrusion in the pores, which are thermally activated, rare events. Simulations reveal three important nonclassical effects: the nucleation free-energy barriers are reduced eightfold compared with CNT, the intrusion pressure is increased due to nanoscale confinement, and the intrusion/extrusion hysteresis is practically suppressed for pores with diameters below 1.2 nm. The frequency and size dependence of hysteresis exposed by the present simulations explains several experimental results on nanoporous materials. Understanding physical phenomena peculiar to nanoconfined water paves the way for a better design of nanoporous materials for energy applications; for instance, by decreasing the size of the nanopores alone, it is possible to change their behavior from dampers to molecular springs.