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Superhydrophobic surfaces are often seen as frictionless materials, on which water is highly mobile. Understanding the nature of friction for such water-repellent systems is central to further minimize resistance to motion and energy loss in applications. For slowly moving drops, contact-line friction has been generally considered dominant on slippery superhydrophobic surfaces. Here, we show that this general rule applies only at very low speed. Using a micropipette force sensor in an oscillating mode, we measure the friction of water drops approaching or even equaling zero contact-line friction. We evidence that dissipation then mainly stems from the viscous shearing of the air film (plastron) trapped under the liquid. Because this force is velocity dependent, it can become a serious drag on surfaces that look highly slippery from quasi-static tests. The plastron thickness is found to be the key parameter that enables the control of this special friction, which is useful information for designing the next generation of ultraslippery water-repellent coatings.
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Immiscible fluid-fluid displacement in confined geometries is a fundamental process occurring in many natural phenomena and technological applications, from geological CO2 sequestration to microfluidics. Due to the interactions between the fluids and the solid walls, fluid invasion undergoes a wetting transition from complete displacement at low displacement rates to leaving a film of the defending fluid on the confining surfaces at high displacement rates. While most real surfaces are rough, fundamental questions remain about the type of fluid-fluid displacement that can emerge in a confined, rough geometry. Here, we study immiscible displacement in a microfluidic device with a precisely controlled structured surface as an analogue for a rough fracture. We analyze the influence of the degree of surface roughness on the wetting transition and the formation of thin films of the defending liquid. We show experimentally, and rationalize theoretically, that roughness affects both the stability and dewetting dynamics of thin films, leading to distinct late-time morphologies of the undisplaced (trapped) fluid. Finally, we discuss the implications of our observations for geologic and technological applications.
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Biomolecular phase separation has emerged as an essential mechanism for cellular organization. How cells respond to environmental stimuli in a robust and sensitive manner to build functional condensates at the proper time and location is only starting to be understood. Recently, lipid membranes have been recognized as an important regulatory center for biomolecular condensation. However, how the interplay between the phase behaviors of cellular membranes and surface biopolymers may contribute to the regulation of surface condensation remains to be elucidated. Using simulations and a mean-field theoretical model, we show that two key factors are the membrane's tendency to phase-separate and the surface polymer's ability to reorganize local membrane composition. Surface condensate forms with high sensitivity and selectivity in response to features of biopolymer when positive co-operativity is established between coupled growth of the condensate and local lipid domains. This effect relating the degree of membrane-surface polymer co-operativity and condensate property regulation is shown to be robust by different ways of tuning the co-operativity, such as varying membrane protein obstacle concentration, lipid composition, and the affinity between lipid and polymer. The general physical principle emerged from the current analysis may have implications in other biological processes and beyond.
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Proteínas de Membrana , Polímeros , Membrana Celular , Membranas , LipídeosRESUMO
The interplay between phase separation and wetting of multicomponent mixtures is ubiquitous in nature and technology and recently gained significant attention across scientific disciplines, due to the discovery of biomolecular condensates. It is well understood that sessile droplets, undergoing phase separation in a static wetting configuration, exhibit microdroplet nucleation at their contact lines, forming an oil ring during later stages. However, very little is known about the dynamic counterpart, when phase separation occurs in a nonequilibrium wetting configuration, i.e., spreading droplets. Here we show that liquid-liquid phase separation strongly couples to the spreading motion of three-phase contact lines. Thus, the classical Cox-Voinov law is not applicable anymore, because phase separation adds an active spreading force beyond the capillary driving. Intriguingly, we observe that spreading starts well before any visible nucleation of microdroplets in the main droplet. Using high-speed ellipsometry, we further demonstrate that the evaporation-induced enrichment, together with surface forces, causes an even earlier nucleation in the wetting precursor film around the droplet, initiating the observed wetting transition. We expect our findings to improve the fundamental understanding of phase separation processes that involve dynamical contact lines and/or surface forces, with implications in a wide range of applications, from oil recovery or inkjet printing to material synthesis and biomolecular condensates.
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SignificanceThe shape and dynamics of small sessile droplets are dictated by capillary forces. For liquid mixtures, evaporation adds spatio-temporal modulation to these forces that can either enhance or inhibit droplet spreading, depending on the direction of the resulting Marangoni flow. This work experimentally and numerically demonstrates the coexistence of two antagonistic Marangoni flows in a ternary mixture. Played against each other, they can choreograph a boomerang-like wetting motion: Droplets initially rapidly spread, then contract into a compact cap shape. While such a behavior has been impossible in wetting scenarios of simple liquids, it enables spread-retract-remove surface processing with the addition of a single small liquid volume, demonstrated here in a surface-cleaning experiment.
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A carbon nanotube (CNT) may facilitate near-frictionless water transport within it. In this work, we elucidate the slip flow characteristics for a CNT embedded in a silicon nitride matrix using the molecular dynamics (MD) method. We reveal that the wetting transparency of a CNT, the transmission of the membrane matrix wetting property over a CNT, cannot be ignored. Due to the effect of CNT wetting transparency, the orientation flip behavior of water molecules should be the primary cause of the entrance and exit losses, which is a dominant factor influencing the interfacial friction coefficient for the thin CNT membrane. The relationship between the friction coefficient and pore size follows a logarithmic function, which agrees well with the reported experimental data. Our findings bridge the gap between the MD prediction and experimental observation for water transport in a CNT membrane and provide a clear understanding of the mechanism behind its ultrafast flow performance.
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Realizing jumping detachment of condensed droplets from solid surfaces at the smallest sizes possible is vital for applications such as antifogging/frosting and heat transfer. For instance, if droplets uniformly jump at sizes smaller than visible light wavelengths of 400-720 nm, antifogging issues could be resolved. In comparison, the smallest droplets experimentally observed so far to jump uniformly were around 16 µm in radius. Here, we show molecular dynamics (MD) simulations of persistent droplet jumping with a uniform radius down to only 3.6 nm on superhydrophobic thin-walled lattice (TWL) nanostructures integrated with superhydrophilic nanospots. The size cutoff is attributed to the preferential cross-lattice coalescence of island droplets. As an application, the MD results exhibit a 10× boost in the heat transfer coefficient (HTC), showing a -1 scaling law with the maximum droplet radius. We provide phase diagrams for jumping and wetting behaviors to guide the design of lattice structures with advanced antidew performance.
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Surface effects of low-surface-tension contaminants accumulating at the evaporation surface easily induce wetting in membrane distillation, especially in hypersaline scenarios. Herein, we propose a novel strategy to eliminate the surface effect and redistribute contaminants at the evaporation interface simply by incorporating a layer of hydrogel. The as-fabricated composite membrane exhibits remarkable stability, even when exposed to solution with salt concentration of 5 M and surfactant concentration of 8 mM. Breakthrough pressure of the membrane reaches 20 bar in the presence of surfactants, surpassing commercial hydrophobic membranes by one to two magnitudes. Density functional theory and molecular dynamics simulations reveal the important role of the hydrogel-surfactant interaction in suppressing the surface effect. As a proof of concept, we demonstrate the membrane in stably processing synthetic wastewater containing 144 mg L-1 surfactants, 1 g L-1 mineral oils, and 192 g L-1 NaCl, showing its potential in addressing challenges of hypersaline water treatment.
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A bio-inspired approach to fabricate robust superhydrophobic (SHB) surfaces with anisotropic properties replicated from a leek leaf is presented. The polydimethylsiloxane (PDMS) replica surfaces exhibit anisotropic wetting, anti-icing, and light scattering properties due to microgrooves replicated from leek leaves. Superhydrophobicity is achieved by a novel modified candle soot (CS) coating that mimics leek's epicuticular wax. The resulting surfaces show a contact angle (CA) difference of ≈30° in the directions perpendicular and parallel to the grooves, which is similar to the anisotropic properties of the original leek leaf. The coated replica is durable, withstanding cyclic bending tests (up to 10 000 cycles) and mechanical sand abrasion (up to 60 g of sand). The coated replica shows low ice adhesion (10 kPa) after the first cycle; and then, increases to ≈70 kPa after ten icing-shearing cycles; while, anisotropy in ice adhesion becomes more evident with more cycles. In addition, the candle soot-coated positive replica (CS-coated PR) demonstrates a transmittance of ≈73% and a haze of ≈65% at the wavelength of 550 nm. The results show that the properties depend on the replicated surface features of the leek leaf, which means that the leek leaf appears to be a highly useful template for bioinspired surfaces.
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Hydrophobic polymer plates with smooth and rough surfaces are used as a stabilizer for cubic liquid marbles (LMs) to study the effect of surface roughness on their formation. The smooth and rough polymer plates can stabilize LMs using liquids with surface tensions of 72.8-26.6 and 72.8-22.9 mN m-1, respectively. It is clarified that the higher the surface roughness, the lower the surface tension of the liquids are stabilized to form the LMs. These results indicated that the introduction of surface roughness improves the hydrophobicity of the polymer plates and the rough polymer plates can stabilize LMs using liquids with a wider surface tension range. Electron microscopy studies and numerical analyses confirmed that the LMs can be formed, when the Cassie-Baxter wetting state, where θY>90° (θY: the contact angle on smooth surfaces) and θR>90° (θR: the contact angle on rough surfaces), and the metastable Cassie-Baxter wetting state, where θY<90° and θR>90°, are realized. Finally, the synthesis of cubic polymer particles are succeeded by free radical polymerization of the cubic LMs containing a hydrophobic vinyl monomer (dodecyl acrylate) in a solvent-free manner.
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When a multi-component fluid contacts arigid solid substrate, the van der Waals interaction between fluids and substrate induces a depletion/adsorption layer depending on the intrinsic wettability of the system. In this study, we investigate the depletion/adsorption behaviors of A-B fluid system. We derive analytical expressions for the equilibrium layer thickness and the equilibrium composition distribution near the solid wall, based on the theories of de Gennes and Cahn. Our derivation is verified through phase-field simulations, wherein the substrate wettability, A-B interfacial tension, and temperature are systematically varied. Our findings underscore two pivotal mechanisms governing the equilibrium layer thickness. With an increase in the wall free energy, the substrate wettability dominates the layer formation, aligning with de Gennes' theory. When the interfacial tension increases, or temperature rises, the layer formation is determined by the A-B interactions, obeying Cahn's theory. Additionally, we extend our study to non-equilibrium systems where the initial composition deviates from the binodal line. Notably, macroscopic depletion/adsorption layers form on the substrate, which are significantly thicker than the equilibrium microscopic layers. This macroscopic layer formation is attributed to the interplay of phase separation and Ostwald ripening. We anticipate that the present finding could deepen our knowledge on the depletion/adsorption behaviors of immiscible fluids.
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The ability to manipulate the dimensions, areal density, and form of substrate-supported Au and Ag nanoparticles (NPs) is highly desirable for utilizing their plasmonic properties in biosensing, photovoltaics, and nanophotonic applications. The transformation of thin films into the substrate-supported nanostructures by solid-state dewetting (SSD), provides an avenue to manipulate the dimensional aspects of nanostructures simply and cost-effectively on a large scale. However, spontaneous agglomeration of the film produces randomly distributed and non-uniform nanostructures that must be controlled. Here, we have systematically studied the effect of annealing temperature, between 200 °C and 750 °C, on the dewetting morphology evolution of Au, Ag, and Au-Ag bilayer ultrathin films sputter deposited on thec-plane (0001) sapphire substrates. Regardless of the film thickness, Ag films dewet faster than Au films and produce spherical NPs, compared to faceted Au NPs, with broader size distribution. Whereas, by the SSD of Au-Ag bilayer ultrathin films, highly spherical and monodisperse AuAg bimetallic NPs can be fabricated. Furthermore, we have shown the possibility of fabricating the AuAg bimetallic NPs of varying compositions by adjusting the thickness of individual layers, thus enabling us to smoothly tune the spectral location of plasmonic resonance within the visible range.
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Landfill gases can have numerous detrimental effects on the global climate and urban ecological environment. The protective efficacy of the final cover layer against landfill gases, following exposure to periodic natural meteorological changes during long-term service, remains unclear. This study conducted centrifuge tests and gas permeability tests on compacted loess. The experiments examined the impact and relationship of wetting-drying cycles and dry density on the soil water characteristic curve (SWCC) and gas permeability of compacted loess. Research findings reveal that during the dehumidification process of compacted loess, the gas permeability increases non-linearly, varying the gas permeability of soil with different densities to different extents under wetting-drying cycles. Two models were introduced to describe the impact of wetting-drying cycles on gas permeability of loess with various dry densities, where fitting parameters increased with the number of wetting-drying cycles. Sensitivity analysis of the parameters in the Parker-Van Genuchten-Mualem (P-VG-M) model suggests that parameter γ's accuracy should be ensured in practical applications. Finally, from a microstructural perspective, wetting-drying cycles cause dispersed clay and other binding materials coalesce to fill minuscule pores, leading to an increase in the effective pores responsible for the gas permeability of the soil. These research results offer valuable guidance for designing water retention and gas permeability in compacted loess cover layers under wetting-drying cycles.
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Permeabilidade , Solo , Solo/química , Água/química , Molhabilidade , Eliminação de Resíduos/métodos , Gases , Dessecação/métodos , Poluentes Atmosféricos/análiseRESUMO
Seeds of dicotyledonous plants store proteins in dedicated membrane-bounded organelles called protein storage vacuoles (PSVs). Formed during seed development through morphological and functional reconfiguration of lytic vacuoles in embryos [M. Feeney et al., Plant Physiol. 177, 241-254 (2018)], PSVs undergo division during the later stages of seed maturation. Here, we study the biophysical mechanism of PSV morphogenesis in vivo, discovering that micrometer-sized liquid droplets containing storage proteins form within the vacuolar lumen through phase separation and wet the tonoplast (vacuolar membrane). We identify distinct tonoplast shapes that arise in response to membrane wetting by droplets and derive a simple theoretical model that conceptualizes these geometries. Conditions of low membrane spontaneous curvature and moderate contact angle (i.e., wettability) favor droplet-induced membrane budding, thereby likely serving to generate multiple, physically separated PSVs in seeds. In contrast, high membrane spontaneous curvature and strong wettability promote an intricate and previously unreported membrane nanotube network that forms at the droplet interface, allowing molecule exchange between droplets and the vacuolar interior. Furthermore, our model predicts that with decreasing wettability, this nanotube structure transitions to a regime with bud and nanotube coexistence, which we confirmed in vitro. As such, we identify intracellular wetting [J. Agudo-Canalejo et al., Nature 591, 142-146 (2021)] as the mechanism underlying PSV morphogenesis and provide evidence suggesting that interconvertible membrane wetting morphologies play a role in the organization of liquid phases in cells.
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Magnoliopsida/metabolismo , Sementes/crescimento & desenvolvimento , Vacúolos/metabolismo , Membranas Intracelulares/metabolismo , Nanotubos , Proteínas de Plantas/metabolismo , Plantas/metabolismo , Sementes/metabolismo , MolhabilidadeRESUMO
The spreading of a liquid droplet on flat surfaces is a well-understood phenomenon, but little is known about how liquids spread on a rough surface. When the surface roughness is of the nanoscopic length scale, the capillary forces dominate and the liquid droplet spreads by wetting the nanoscale textures that act as capillaries. Here, using a combination of advanced nanofabrication and liquid-phase transmission electron microscopy, we image the wetting of a surface patterned with a dense array of nanopillars of varying heights. Our real-time, high-speed observations reveal that water wets the surface in two stages: 1) an ultrathin precursor water film forms on the surface, and then 2) the capillary action by nanopillars pulls the water, increasing the overall thickness of water film. These direct nanoscale observations capture the previously elusive precursor film, which is a critical intermediate step in wetting of rough surfaces.
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Methods for fabricating super-liquid-repellent surfaces have typically relied on perfluoroalkyl substances. However, growing concerns about the environmental and health effects of perfluorinated compounds have caused increased interest in fluorine-free alternatives. Polydimethylsiloxane (PDMS) is most promising. In contrast to fluorinated surfaces, PDMS-coated surfaces showed only superhydrophobicity. This raises the question whether the poor liquid repellency is caused by PDMS interacting with the probe liquid or whether it results from inappropriate surface morphology. Here, we demonstrate that a well-designed two-tier structure consisting of silicon dioxide nanoparticles combined with surface-tethered PDMS chains allows super-liquid-repellency toward a range of low surface tension liquids. Drops of water-ethanol solutions with surface tensions as low as 31.0 mN m-1 easily roll and bounce off optimized surface structures. Friction force measurements demonstrate excellent surface homogeneity and easy mobility of drops. Our work shows that fluorine-free super-liquid-repellent surfaces can be achieved using scalable fabrication methods and environmentally friendly surface functionalization.
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As global climate change progresses, soil will experience prolonged periods of both drought and heavy rainfall, leading to a more frequent drought-re-wetting process that may impact the ecosystem's carbon (C) cycle. However, understanding the extent to which different water conditions and wet-dry cycles alter the process of soil organic carbon (SOC) mineralization remains limited. Therefore, our study focused on the dammed land unique to the Loess Plateau, silted by check dams constructed for erosion control. We implemented three water gradients-drought (30% WHC), water stress (100% WHC), and wet-dry cycling (30-100%)-indoors to observe the SOC mineralization process five times. We identified a transient excitation effect of the wet-dry cycles on SOC mineralization. Soil mineralization decreased gradually with the alternation of wet-dry cycles. The wet-dry cycles not only significantly impacted the contents of SOC and TN but also stimulated the activities of enzymes related to C and N cycles. As the cycle frequency increased, the utilization of C sources by soil microorganisms gradually decreased, and the dominance of carbohydrates, amines, and acids evolved into a single acid, esters, or alcohols. Phosphatase and Chloroflexi were the main factors influencing SOC mineralization under drought stress, while TN and Ascomycota were the primary factors under water stress. SOC and Gemmatimonadetes were the main limiting factors for SOC mineralization under the wet-dry cycles. Additionally, we quantified the direct and interactive contributions of each factor to SOC mineralization. The direct contributions of drought stress, water stress, and the wet-dry cycles to SOC mineralization were 0.961, 0.736, and 0.942, respectively. This study contributes to a more comprehensive understanding of the mechanisms underlying SOC mineralization in the Loess Plateau under changing conditions.
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Carbono , Solo , Solo/química , Secas , Ecossistema , Mudança Climática , Ciclo do Carbono , ÁguaRESUMO
Forcible wetting of hydrophobic pores represents a viable method for energy storage in the form of interfacial energy. The energy used to fill the pores can be recovered as pressure-volume work upon decompression. For efficient recovery, the expulsion pressure should not be significantly lower than the pressure required for infiltration. Hysteresis of the wetting/drying cycle associated with the kinetic barrier to liquid expulsion results in energy dissipation and reduced storage efficiency. In the present work, we use open ensemble (Grand Canonical) Monte Carlo simulations to study the improvement of energy recovery with decreasing diameters of planar pores. Near-complete reversibility is achieved at pore widths barely accommodating a monolayer of the liquid, thus minimizing the area of the liquid/gas interface during the cavitation process. At the same time, these conditions lead to a steep increase in the infiltration pressure required to overcome steric wall/water repulsion in a tight confinement and a considerable reduction in the translational entropy of confined molecules. In principle, similar effects can be expected when increasing the size of the liquid particles without altering the absorbent porosity. While the latter approach is easier to follow in laboratory work, we discuss the advantages of reducing the pore diameter, which reduces the cycling hysteresis while simultaneously improving the stored-energy density in the material.
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Irrigation management controls biogeochemical cycles in rice production. Under flooded paddy conditions, arsenic becomes plant-available as iron-reducing conditions ensue, while oxic conditions lead to increased plant availability of Cd in acidic soils. Because Cd enters rice through Mn transporters, we hypothesized that irrigation resulting in intermediate redox could simultaneously limit both As and Cd in rice grain due to As retention in soil and Mn competition for Cd uptake. In a 2 year field study, we used 6 irrigation managements that varied in extent and frequency of inundation, and we observed strong effects of irrigation management on porewater chemistry, soil redox potentials, plant As and Cd concentrations, plant nutrient concentrations, and methane emissions. Plant As decreased with drier irrigation management, but in the grain this effect was stronger for organic As than for inorganic As. Grain organic As, but not inorganic As, was strongly and positively correlated with cumulative methane emissions. Conversely, plant Cd increased under more aerobic irrigation management and grain Cd was negatively correlated with porewater Mn. A hazard index approach showed that in the tested soil with low levels of As and Cd (5.4 and 0.072 mg/kg, respectively), irrigation management could not simultaneously decrease grain As and Cd. Many soil properties, such as reducible As, available Cd, soil pH, available S, and soil organic matter should be considered when attempting to optimize irrigation management when the goal is decreasing the risk of As and Cd in rice grain.
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Irrigação Agrícola , Arsênio , Cádmio , Oryza , Poluentes do Solo , Solo , Irrigação Agrícola/métodos , Cádmio/metabolismo , Poluentes do Solo/análise , Arsênio/análise , Solo/química , Oxirredução , MetanoRESUMO
Compound droplets have received increasing attention due to their applications in many several areas, including medicine and materials. Previous works mostly focused on compound droplets on planar surfaces and, as such, the effects of curved walls have not been studied thoroughly. In this paper, the influence of the properties of curved solid wall (including the shape, curvature, and contact angle) on the wetting behavior of compound droplets is explored. The axisymmetric lattice Boltzmann method, based on the conservative phase field formulation for ternary fluids, was used to numerically study the wetting and spreading of a compound droplet of the Janus type on various curved solid walls at large density ratios, focusing on whether the separation of compound droplets occurs. Several types of wall geometries were considered, including a planar wall, a concave wall with constant curvature, and a convex wall with fixed or variable curvature (specifically, a prolate or oblate spheroid). The effects of surface wettability, interfacial angles, and the density ratio (of droplet to ambient fluid) on the wetting process were also explored. In general, it was found that, under otherwise identical conditions, droplet separation tends to happen more likely on more hydrophilic walls, under larger interfacial angles (measured inside the droplet), and at larger density ratios. On convex walls, a larger radius of curvature of the surface near the droplet was found to be helpful to split the Janus droplet. On concave walls, as the radius of curvature increases from a small value, the possibility to observe droplet separation first increases and then decreases. Several phase diagrams on whether droplet separation occurs during the spreading process were produced for different kinds of walls to illustrate the influences of various factors.