Excess Surface Energy Research Articles

Convergence to the planar interface for a nonlocal free‐boundary evolution

AbstractWe capture optimal decay for the Mullins–Sekerka evolution, a nonlocal, parabolic free boundary problem from materials science. Our main result establishes convergence of BV solutions to the planar profile in the physically relevant case of ambient space dimension three. Far from assuming small or well‐prepared initial data, we allow for initial interfaces that do not have graph structure and are not connected, hence explicitly including the regime of Ostwald ripening. In terms only of initially finite (not small) excess mass and excess surface energy, we establish that the surface becomes a Lipschitz graph within a fixed timescale (quantitatively estimated) and remains trapped within this setting. To obtain the graph structure, we leverage regularity results from geometric measure theory. At the same time, we extend a duality method previously employed for one‐dimensional PDE problems to higher dimensional, nonlocal geometric evolutions. Optimal algebraic decay rates of excess energy, dissipation, and graph height are obtained.

Enhanced coalescence-induced droplet jumping on superhydrophobic surfaces with stepped structures

The coalescence-induced droplet jumping is a self-propelled water removal phenomenon on superhydrophobic surfaces, which has attracted considerable attention due to its potential in a wide range of applications such as self-cleaning and anti-icing/frosting. Improving the energy conversion efficiency, from the excessive surface energy to the kinetic energy, is pivotal to facilitate droplet jumping. In this study, we numerically investigated the dynamics of droplet coalescence on superhydrophobic surfaces with macro-stepped structures, with particular interest in understanding the role of the stepped structure on the droplet jumping process. Three-dimensional simulations were performed by using the lattice Boltzmann method, with the pseudopotential multiphase model and the multiple-relaxation-time collision operator being adopted to achieve high liquid–gas density/viscosity ratios. A wide range of nondimensional height difference of the stepped structure (0–1.5) and droplet radius ratio (0.5–2) was covered. Results show that adding macro-stepped structures can significantly enhance the droplet-wall interaction, thus yielding increased droplet velocity. The enhancement of droplet jumping is more remarkable for droplets of similar sizes, and the dimensionless height difference of the stepped structure is required to exceed a threshold of approximately 0.5. Among the present simulations, the maximum dimensionless droplet jumping velocity reaches 0.66, corresponding to an energy conversion efficiency of 35%. The present findings are helpful for the development of novel superhydrophobic surfaces that pursue efficient droplet removal.

Magnetic-Actuated Jumping of Droplets on Superhydrophobic Grooved Surfaces: A Versatile Strategy for Three-Dimensional Droplet Transportation.

On-demand droplet transportation is of great significance for numerous applications. Although various strategies have been developed for droplet transportation, out-of-surface three-dimensional (3D) transportation of droplets remains challenging. Here, a versatile droplet transportation strategy based on magnetic-actuated jumping (MAJ) of droplets on superhydrophobic grooved surfaces (SHGSs) is presented, which enables 3D, remote, and precise manipulation of droplets even in enclosed narrow spaces. To trigger MAJ, an electromagnetic field is utilized to deform the droplet on the SHGS with the aid of an attached magnetic particle, thereby the droplet acquires excess surface energy. When the electromagnetic field is quickly removed, the excess surface energy is partly converted into kinetic energy, allowing the droplet to jump atop the surface. Through high-speed imaging and numerical simulation, the working mechanism and size matching effect of MAJ are unveiled. It is found that the MAJ behavior can only be observed if the sizes of the droplets and the superhydrophobic grooves are matched, otherwise unwanted entrapment or pinch-off effects would lead to failure of MAJ. A regime diagram which serves as a guideline to design SHGSs for MAJ is proposed. The droplet transportation capacities of MAJ, including in-surface and out-of-surface directional transportation, climbing stairs, and crossing obstacles, are also demonstrated. With the ability to remotely manipulate droplets in enclosed narrow spaces without using any mechanical moving parts, MAJ can be used to design miniaturized fluidic platforms, which exhibit great potential for applications in bioassays, microfluidics, droplet-based switches, and microreactions.

On the dynamics of coalescence between droplets and partially filled microgrooves

When water vapor condenses on a hydrophobic surface equipped with microgrooves, a unique phenomenon of coalescence between droplets growing on the ridges and the microgrooves partially imbibed with a condensate is manifested. Such coalescence is distinctly different from droplet–droplet coalescence and can trigger rapid removal of the condensate from the surface, a critical requirement for high thermodynamic efficiency of condensation. In this work, we investigate the dynamics of this coalescence process. We develop an experimentally validated, three-dimensional, volume of fluid method-based numerical modeling framework that accounts for dynamic contact angle variation during contact line motion. The condensate wetting the microgroove forms a liquid column with a meniscus pinned to the microgroove edges. We show that ridge droplet coalescence with this pinned meniscus triggers capillary ripples that traverse the microgroove in transverse and longitudinal directions and can trigger the depinning of the contact line from the opposing edge depending on the size of the coalescing droplet. The contact line depins when the local contact angle at the opposing edge reaches ∼180° and, simultaneously, the kinetic energy converted from the excess surface energy available reaches a maximum. Additionally, we show that the overall coalescence process is significantly affected by the microgroove aspect ratio. For the same liquid volume, relatively shallower microgrooves cause the condensate to overflow, thus attaining a morphology akin to large droplets in the Wenzel state. As a result, the coalescence dynamics on such microgrooved surfaces are similar to that on a planar surface.

Condensation heat transfer enhancement through durable, self-propelling fluorine-free silane-treated anodized surfaces

When two or more adjacent droplets coalesce, excess surface energy is generated, which can be converted into the kinetic energy of the merged droplet through a suitable nanostructure and the superhydrophobicity of the surface.

Coalescence behavior of size-selected gold and tantalum nanoclusters under electron beam irradiation: insights into nano-welding mechanisms.

The emerging technique of nano-welding (NW) via precisely regulating the fusion of nanoclusters (NCs) in nanotechnology has attracted significant attention for its innovative approach. Employing the gas-phase condensation cluster source with a lateral time-of-flight (TOF) mass-selector, size-selected gold (Au), and tantalum (Ta) NCs were prepared. This study explores the coalescence behavior of size-selected Au and Ta NCs under electron beam irradiation, aiming to investigate the related mechanism governing the welding process. Intrinsically driven by the reduction of excess surface energy, electron beam induces atomic thermal migration, fostering sintering neck growth at cluster interfaces. During this process, atomic diffusion and recrystallization enable NCs to alter shape while retaining stable facet planes. Aberration-corrected scanning transmission electron microscopy (AC-STEM) showcases the formation of single or polycrystalline sintered clusters, during which some lattice distortions can be eliminated. Interestingly, oxidized Ta clusters experience knock-on damage caused by elastic scattering of electron beams, partially deoxidizing them. Additionally, electron-phonon inelastic scattering transforms oxidized Ta clusters from amorphous to crystalline structures. Moreover, the quantum size effect and surface effect of NCs facilitate the surpassing of miscibility limits during Au-Ta heterogeneous welding processes. This investigation bridges the gap between fundamental research on cluster materials and their practical applications.

Surface-Energy-Driven Tin Whisker Growth on Pure Tin

Spontaneous Sn whisker growth, as a reliability issue in electronic assemblies, has drawn much attention in the past several decades. However, the underlying mechanism is still ambiguous. Herein, the growth of Sn whiskers on pure Sn with different specific surface areas was studied to elucidate the effect of surface energy on Sn whisker growth. Though fabricated and cultivated using the same parameters, it was found that Sn whiskers were obtained on the sample of nano-Sn, which possesses excess surface energy, while no whiskers were observed on the sample of micro-Sn, indicating that surface energy plays a significant role in Sn whisker growth. In addition, the whiskering phenomenon is confirmed to be an abnormal recrystallization process according to the microstructure of the whisker root. Therefore, a Sn whisker growth mechanism companied with an abnormal recrystallization process is proposed, which is driven by the excess surface energy. This work provides a new perspective on understanding the long-standing Sn whiskering problem.

Suppressed grain growth and enhanced irradiation resistance of nano-grained waste form under electronic energy loss

The effects of both nuclear energy loss and electronic energy loss need to be taken into consideration in the ceramic-based waste forms under repository environment. However, the irradiation responses of ceramic-based waste forms to each type of energy loss are somewhat different. In this study, the microstructure evolutions of ultrafine nano and micro Gd2Zr2O7-based waste forms were systematically studied under predominant electronic energy loss simulated by multi-energy He+ irradiation, and compared to those under predominant nuclear energy loss. The results reveal that the fewer He bubble chains, ribbon-like He bubbles and smaller microcracks were observed in the irradiated nano-grained sample. Additionally, nano-grained sample displayed a lower degree of amorphization and higher atomic order compared to micro-grained samples when subjected to predominant electronic energy loss. Moreover, the irradiation dominated by nuclear energy loss can easily induce the grain growth of nano-grained Gd2Zr2O7-based waste form, but in the present study this phenomenon was not observed under multi-energy He+ irradiation. Consequently, under predominant electronic energy loss, the thermodynamic instability and driving force for grain growth due to excess surface energy in the ultrafine nano sample can be suppressed. As a result, the sample demonstrated enhanced irradiation resistance due to the more efficient absorption and elimination of defects at grain boundaries induced by electronic excitation. We elucidated that enhanced irradiation resistance of the waste forms by tailoring the grain size requires the consideration of the effects of electronic energy loss and nuclear energy loss, which can provide guidance for the design and optimization of highly irradiation-resistant nuclear waste forms.

Electrochemical-Memristor-Based Artificial Neurons and Synapses-Fundamentals, Applications, and Challenges.

Artificial neurons and synapses are considered essential for the progress of the future brain-inspired computing, based on beyond von Neumann architectures. Here, a discussion on the common electrochemical fundamentals of biological and artificial cells is provided, focusing on their similarities with the redox-based memristive devices. The driving forces behind the functionalities and the ways to control them by an electrochemical-materials approach are presented. Factors such as the chemical symmetry of the electrodes, doping of the solid electrolyte, concentration gradients, and excess surface energy are discussed as essential to understand, predict, and design artificial neurons and synapses. A variety of two- and three-terminal memristive devices and memristive architectures are presented and their application for solving various problems is shown. The work provides an overview of the current understandings on the complex processes of neural signal generation and transmission in both biological and artificial cells and presents the state-of-the-art applications, including signal transmission between biological and artificial cells. This example is showcasing the possibility for creating bioelectronic interfaces and integrating artificial circuits in biological systems. Prospectives and challenges of the modern technology toward low-power, high-information-density circuits are highlighted.

Sequential self-propelled morphology transitions of nanoscale condensates enable a cascade jumping-droplet condensation

Jumping-droplet condensation, namely the out-of-plane jumping of condensed droplets upon coalescence, has been a promising technical innovation in the fields of energy harvesting, droplet manipulation, thermal management, etc., yet is limited owing to the challenge of enabling a sustainable and programmable control. Here, we characterized the morphological evolutions and dynamic behaviors of nanoscale condensates on different nanopillar surfaces, and found that there exists an unrevealed domino effect throughout the entire droplet lifecycle and the coalescence is not the only mechanism to access the droplet jumping. The vapor nucleation preferentially occurs in structure intervals, thus the formed liquid embryos incubate and grow in a spatially confined mode, which stores an excess surface energy and simultaneously provides a asymmetric Laplace pressure, stimulating the trapped droplets to undergo a dewetting transition or even a self-jumping, which can be facilitated by the tall and dense nanostructures. Subsequently, the adjacent droplets merge mutually and further trigger more multifarious self-propelled behaviors that are affected by underlying surface nanostructure, including dewetting transition, coalescence-induced jumping and jumping relay. Moreover, an improved energy-based model was developed by considering both the surface structure properties and the nano-physical effects, the theoretical prediction not only extends the coalescence-induced jumping to the nanometer-sized droplets but also correlates the surface nanostructure topology to the jumping velocity. Such a domino effect of nucleation-growth-coalescence on the ultimate morphology of droplet may offer a new strategy for designing functional nanostructured surfaces that serve to orientationally manipulate, transport and collect droplets, and motivate surface engineers to realize a stable cascade jumping-droplet condensation and achieve its performance ceiling.

Microstructural transformations of swelling clay minerals

An original model of microstructural transformations during clay swelling is considered, a thermodynamic and physical-mechanical description of the properties of clays during the process of swelling in vapors and aqueous solutions is given. The model proposed to explain these properties is based on the concept of mutual displacement of clay particles in clay rock aggregates during swelling with the formation of new pores between clay particles forming crystallites and aggregates. The model is based on the mechanism of utilization of the excess surface energy of clay particles during hydration, taking into account the influence of certain environmental parameters, for example, the concentration of the solution, through a change in the mutual orientation of clay particles, mainly due to rotations or shifts relative to each other, with the formation of an area available for further wetting free surface. In the thermodynamic description, such a process will manifest itself in a change in the surface interaction energy on the wetted areas of the particles when moving during mutual shifts and rotations. At the same time, one of the most important parameters of clay rock, microporosity, also changes. In this work, this phenomenon was experimentally studied using the methods of static moisture capacity and Mössbauer (NGR) spectroscopy. The proposed model makes it possible to explain the features of the clay hydration process and to compare the observed experimental data with the theoretical description of the clay swelling process.

Coalescence-induced jumping of bubbles in shear flow in microgravity

Bubble removal from a solid surface is of significant importance to many technical processes and applications. In addition to the conventional buoyancy-aided bubble removal, there is also a passive strategy to remove bubbles from a solid surface via coalescence. However, likewise several processes, the coalescence-induced removal of bubbles from the solid surface is masked by the dominant buoyancy, hence, difficult to observe in terrestrial conditions. Microgravity condition offers a unique opportunity to investigate such phenomenon in great detail that can significantly improve our fundamental understanding. In this work, we report coalescence-induced jumping of isolated vapor bubbles from the heated substrate during shear flow in microgravity condition. We show that, similar to the coalescence-induced jumping droplets, when two bubbles coalesce, the resulting big coalesced bubble jumps from the substrate due to the conversion of excess surface energy into the translational kinetic energy, which provides the requisite initial velocity for jumping. Jumping of bubbles over a wide range of bubble size (post-coalescence radius ≈0.9–3.4 mm) is observed. Bubbles oscillate continuously while rising through certain height post-coalescence. We perform force balance and scaling analysis to develop a model to predict the maximum jumping height of bubbles. We show that the jumping height is strongly related to the bubble size and the non-dimensional Ohnesorge number, which captures the role of fluid properties governing the coalescence. The physical insight presented in this work has implication for the design of energy systems and microfluidic devices for the earth and space-based applications.

Theoretical study on the correlation between the structure, excess energy, surface energy, electronic structure, nitro charge, and friction sensitivity of N,N'-dinitroethylenediamine (EDNA).

The sensitivity of energetic materials along different crystal directions is not the same and is anisotropic. In order to explore the difference in friction sensitivity of different surfaces, we calculated the structure, excess energy, surface energy, electronic structure, and the nitro group along (1 1 1), (1 1 0), (1 0 1), (0 1 1), (0 0 1), (0 1 0), and (1 0 0) surfaces of EDNA based on density functional theory. The analysis results showed that relative to other surfaces, the (0 0 1) surface has the shortest N-N average bond length, largest N-N average bond population, smallest excess energy and surface energy, widest band gap, and the largest nitro group charge value, which indicates that the (0 0 1) surface has the lowest friction sensitivity compared to other surfaces. Furthermore, the conclusions obtained by analyzing the excess energy are consistent with the results of the N-N bond length and bond population, band gap, and nitro charge. Therefore, we conclude that the friction sensitivity of different surfaces of EDNA can be evaluated using excess energy.

Thermodynamic study of superoxide dismutase adsorption processes over cysteine-gold electrode

Modification of gold electrodes with cysteine, improve superoxide dismutase (SOD) electron transfer for superoxide quantification in a typical third-generation electrochemical biosensor. However, a thermodynamic study that describes the adsorption processes of this type of assemble, has not been reported. Hence in this work, differential capacitance studies of Au/Cys, Au/SOD and Au/Cys/SOD electrodes are reported to describe the adsorption process during the different steps of the enzyme immobilization, through the calculation of charge density, surface tension, surface excess and adsorption energy. Theoretical electrostatic potential calculations of the protein using X-ray diffraction data were carried out, to rationalize the adsorption orientation of SOD according to experimental data.

How macrostructures enhance droplet coalescence jumping: A mechanism study

Macrostructures exhibit excellent performance in coalescence-induced droplet jumping enhancement. Previous velocity prediction models were mainly established for flat plain surface, which usually set up the balance relationship between excess surface energy, kinetic energy and dissipation. But these models are no longer appropriate in macrostructure cases due to great variation of oscillational kinetic energy and gravitational potential energy caused by textures. In this work, coalescence-induced droplet jumping on macrostructures was investigated numerically on flat, sidewall, string, ridge and egg shape substrates. An energy conversion model based on energy efficiency rather than energy balance was established for departure velocity by proposing three sub-efficiencies to evaluate jumping enhancement. In this model, oscillational kinetic energy was distinguished from dissipation, gravitational potential energy induced by macrostructures were considered, and the real droplet morphology were used to calculate surface energy. By dividing the whole droplet jumping process into merge and contact stage, the influence of macrostructures on duration of each stage was closely connected to the macrostructure effects on dissipation and kinetic energy conversion. Pressure and velocity distributions near the macrostructure were also discussed to further explore the mechanism for droplet jumping enhancement. Further, the significant increase of initial surface energy for egg case points out a possible new approach to enhance jumping velocity. This model helps us understand the determinants of jumping enhancement with macrostructures and it also applies to flat plain.

The Fibrolite Problem: Implications for Reaction Overstep Studies

Abstract Despite several experimental studies the phase relations in aluminosilicates, especially involving the high-temperature polymorph, are not well understood. The widespread occurrence of fibrolite before sillimanite in rocks is described as the ‘fibrolite problem’. Fibrolite is considered to have higher free energy than sillimanite because of the excess surface energy contribution due to the higher surface/volume ratio. Equilibrium thermodynamics fails to reconcile the stability of fibrolite, with higher free energy, at lower temperatures than sillimanite. The existing literature invokes reaction kinetics to suggest that the low energy of {110} faces leads to acicular fibrolite growth rather than prismatic sillimanite. Here the ‘fibrolite problem’ is discussed from a perspective of high nucleation rates and hindered growth rates. An analog to fibrolite-sillimanite crystallization is suggested in the crystallization of mullite, a member of the Al2O3-SiO2 system. The crystallization of fibrolite in rocks shifts the position of the sillimanite producing reactions from the equilibrium PT depending upon the ΔS and ΔV of the reaction. Thermodynamic datasets calibrated using such natural samples tend to produce accurate predictions for sillimanite stability in geological terranes but inherently possess a reaction overstep and hence should be used carefully while quantifying reaction oversteps.

Scandium wetting of tungsten surfaces in “scandate” thermionic cathodes

The surface structure and electron emission mechanism in high-performing “scandate” thermionic cathodes has long been a point of debate, in part due to the challenges inherent in observing emitting surfaces under operational conditions. Critically, the distribution and role of Sc in enabling high emitted current densities at low operating temperatures remains unclear. Here, using density functional theory calculations of the structure and energy of bare and Sc-covered W slabs, the wetting behavior of Sc on W has been explored.Computed surface excess energies reveal that, despite the bulk immiscibility of W and Sc, a single monolayer of Sc wets (001), (110), and (112) W surfaces at very low oxygen chemical potentials. The addition of further layers of Sc was found to be thermodynamically unfavorable. In contrast to previous studies, the present findings suggest the existence of a Sc interlayer directly atop W in scandate cathodes, representing a novel example of surface-energy-driven metal-on-metal wetting leading to self-assembly of atomically-thin layers.

Steerable directional bouncing and contact time reduction of impacting droplets on superhydrophobic stepped surfaces

HypothesisThe unbalanced capillary force provided by wettability patterns, non-uniform/asymmetric microtextures enables directional droplet transport, while macrotextures have shown potentials in reducing the contact time. Inspired by these findings, we design millimeter superhydrophobic stepped surfaces to simultaneously achieve highly steerable directional bouncing and contact time reduction of impacting droplets. ExperimentsThe stepped surfaces are fabricated by computerized numerical control, chemical oxidation, hydrophobic treatment. Systematic impact experiments are conducted under Weber number ranging from 10.5 to 20.5, two step heights (0.5 mm and 1.0 mm) and extensive impact positions. FindingsCompared with known microtextured surfaces, the stepped surfaces exhibit excellent performance with the maximum lateral movement distance about 8 times of droplet radius, controllable rebound angle ranging from ∼ 32° to ∼ 90° and up to ∼ 30 % reduction in contact time. Particularly, we divide the directional bouncing characteristics into six regimes and attribute the variation of rebound velocity by the synergistic effects of viscous dissipation, excess surface energy, excess kinetic energy. It is demonstrated that the contact time is reduced by liquid mass redistribution and asymmetry enhancement. Predictive models of contact time that incorporate the coupling effects of impact position, impact velocity and step height are also established.

Coalescence-Induced Droplet Jumping on Honeycomb Bionic Superhydrophobic Surfaces.

Condensation-induced jumping of droplets on superhydrophobic surfaces has received extensive attention because of its great potential for applications in areas such as condensation enhancement and self-cleaning. However, the jumping efficiency of droplets on flat superhydrophobic surfaces is very low, and there is no reliable means of achieving efficient droplet jumping on large scales, which greatly limits its application. To this end, we developed a class of honeycomb bionic superhydrophobic surfaces (HBSS) that enable reliable and efficient droplet jumping on a large scale for the first time and performed experimental and simulation studies on droplet condensation and jumping on this kind of surface. Condensation experiments show that condensate droplets on HBSS can be effectively positioned under the influence of gravity and the uniformity of the droplet diameter is ensured, laying the foundation for achieving efficient jumping. The shape and geometric parameters of HBSS have a significant impact on the droplet jumping efficiency, and the maximum dimensionless jumping velocity of droplet jumping was experimentally measured to be 0.747, corresponding to an efficiency of about 45.25%. Combining with the results of simulation calculations, we found that the surface structure of HBSS can promote more of the excess surface energy to net upward kinetic energy along an extremely efficient and simple pathway (direct conversion), thus achieving an energy conversion efficiency of over 45%.

Invariant surface elastic properties in FCC metals and their correlation to bulk properties revealed by machine learning methods

We present a combination of machine-learned models that predicts the surface elastic properties of general free surfaces in face-centered cubic (FCC) metals. These models are built by combining a semi-analytical method based on atomistic simulations to calculate surface properties with the artificial neural network (ANN) method or the boosted regression tree (BRT) method. The latter is also used to link bulk properties and surface orientation to surface properties. The surface elastic properties are represented by their invariants considering plane elasticity within a polar method. The resulting models are shown to accurately predict the surface elastic properties of seven pure FCC metals (Cu, Ni, Ag, Au, Al, Pd, Pt). The BRT model reveals the correlations between bulk and corresponding surface properties in terms of invariants, which can be used to guide the design of complex nano-sized particles, wires and films. Finally, by expressing the surface excess energy density as a function of surface elastic invariants, fast predictions of surface energy as a function of in-plane deformations can be made from these model constructs.