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HYPOTHESIS: Small scale Marangoni motors, which self-generate motion by inducing surface tension gradients on water interfaces through release of surface-active "fuels", have recently been proposed as self-powered mixing devices for low volume fluids. Such devices however, often show self-limiting lifespans due to the rapid saturation of surface-active agents. A potential solution to this is the use volatile surface-active agents which do not persist in their environment. Here we investigate menthyl acetate (MA) as a safe, inexpensive and non-persistent fuel for Marangoni motors. EXPERIMENTS: MA was loaded asymmetrically into millimeter scale silicone sponges. Menthyl acetate reacts slowly with water to produce the volatile surface-active menthol, which induces surface tension gradients across the sponge to drive motion by the Marangoni effect. Videos were taken and trajectories determined by custom software. Mixing was assessed by the ability of Marangoni motors to homogenize milliliter scale aqueous solutions containing colloidal sediments. FINDINGS: Marangoni motors, loaded with asymmetric "Janus" distributions of menthyl acetate show velocities and rotational speeds up to 30 mm s-1 and 500 RPM respectively, with their functional lifetimes scaling linearly with fuel volume. We show these devices are capable of enhanced mixing of solutions at orders of magnitude greater rates than diffusion alone.
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HYPOTHESIS: Self-driven actions, like motion, are fundamental characteristics of life. Today, intense research focuses on the kinetics of droplet motion. Quantifying macroscopic motion and exploring the underlying mechanisms are crucial in self-structuring and self-healing materials, advancements in soft robotics, innovations in self-cleaning environmental processes, and progress within the pharmaceutical industry. Usually, the driving forces inducing macroscopic motion act at the molecular scale, making their real-time and high-resolution investigation challenging. Label-free surface sensitive measurements with high lateral resolution could in situ measure both molecular-scale interactions and microscopic motion. EXPERIMENTS: We employ surface-sensitive label-free sensors to investigate the kinetic changes in a self-assembled monolayer of the trimethyl(octadecyl)azanium chloride surfactant on a substrate surface during the self-propelled motion of nitrobenzene droplets. The adsorption-desorption of the surfactant at various concentrations, its removal due to the moving organic droplet, and rebuilding mechanisms at droplet-visited areas are all investigated with excellent time, spatial, and surface mass density resolution. FINDINGS: We discovered concentration dependent velocity fluctuations, estimated the adsorbed amount of surfactant molecules, and revealed multilayer coverage at high concentrations. The desorption rate of surfactant (18.4 s-1) during the microscopic motion of oil droplets was determined by in situ differentiating between droplet visited and non-visited areas.
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The inherent instability of laser welding, particularly keyhole instability, poses significant challenges in industrial applications, leading to defects such as porosities that compromise weld quality. Various forces act on the keyhole and molten pool during laser welding, influencing process stability. These forces are categorized into those promoting keyhole opening and penetration (e.g., recoil pressure) and those promoting keyhole collapse (e.g., surface tension, Darcy's damping forces), increasing instability and defect likelihood. This paper provides a comprehensive instability analysis to uncover key factors affecting keyhole and process instability, presenting future avenues for improving laser welding stability. Using a novel numerical method for simulating laser spot welding on aluminum with COMSOL Multiphysics 5.6, we investigated the effect of laser pulse shaping on keyhole and process instability. Our analysis focused on keyhole morphology, fluid flow behaviour, and force analysis. The results indicated that the curvature effect, Marangoni effect, and Darcy's damping force are primary contributors to instability, with the curvature effect and Darcy's damping force being the most dominant. Additionally, erratic and high-velocity magnitudes induce intense fluid flow behaviour, exacerbating keyhole instability. Moreover, single/quadruple peak triangular and variant rectangular ramp-down pulse shapes produced the least instability, while multi-pulse rectangular shapes exhibited intense instability. It was found that combining triangular/rectangular pulse shapes can reduce force and keyhole instability by smoothing spontaneous force spikes, resulting in a more stabilized welding process. Controlling fluid flow and abrupt force changes with appropriate pulse shaping is key to defect-free welded products.
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We present a novel miniaturized, gear-shaped, fuel-free actuator capable of autonomously propelling itself in an aquatic environment to absorb heavy metals, such as copper ions. While hydrogel-based absorbents are promising solutions for cationic pollutant remediation, their stationary nature limits their effectiveness in areas where contaminants are unevenly distributed. To address this, we developed a bio-inspired soft actuator that mimics natural propulsion mechanisms. The Marangoni effect, driven by its inherent chemical properties, demonstrated a self-propelled motion without requiring external fuel. The proof-of-concept actuator generated a plane motion lasting up to 2 h and swept over an area approximately 400 times bigger than its size. By harnessing the chemical and optical properties of the hydrogel, we efficiently removed and quantitatively analyzed copper ions through a colorimetric method. This innovative integration of self-propelled movement and efficient copper ion absorption underscores its potential for advancing miniaturized devices in environmental remediation, paving the way for more active and efficient pollutant removal systems in challenging aquatic environments.
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This study introduces magnetized EGaIn@Fe, an innovative material synthesized by incorporating iron powder into the eutectic gallium-indium alloy (EGaIn). Unlike traditional methods requiring electrolyte environments for electrical control, EGaIn@Fe can be manipulated using external magnetic fields, expanding control from 2D to 3D spaces. The material exhibits both active and passive splitting capabilities under magnetic and electrical control, demonstrating exceptional deformability, precision, and flexibility. EGaIn@Fe shows significant promise in applications such as microfluidic channels, circuit repair, and soft robotics. Specifically, 5 wt.% EGaIn@Fe is optimal for microfluidic tasks and circuit repairs in confined spaces, while higher concentrations (10 and 15 wt.%) enhance 3D control and reduce material usage. Additionally, 20 wt.% EGaIn@Fe displays octopus-like movements for navigating impassable channels. EGaIn@Fe can enhance fluid manipulation in microfluidics, bridge gaps in circuit repairs, and enable flexible actuators in soft robotics, driving advancements in adaptive materials and technologies.
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Smart actuators hold great potential in soft robotics and sensors, but their movement at the fluid interface is less understood and controlled, hindering their performances and applications in complicated fluids. Here an ethanol-containing polyelectrolyte actuator is prepared that demonstrates excellent actuating performance via the Marangoni effect. These actuators exhibit enduring (17 min), repeatable (50 cycles), and autonomous motion on the water surface. More importantly, the motion of actuators are dependent on their shapes. Polygonal actuators with more edges exhibit round motion attached to walls of containers, while the actuators with few edges move randomly. On the basis of this property, the circular actuators can pass through pipe bends with S-shaped complex geometry. These unique advantages lend the actuators to successful applications in wireless sensing (standard 0-5 V level signals) for locating obstructions inside invisible pipes and continuous energy harvesting (7700 nC per cycle) for micro mechanical energy.
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Positional information is key for particles to adapt their behavior based on their position in external concentration gradients, and thereby self-organize into complex patterns. Here, position-dependent behavior of floating surfactant droplets that self-organize in a pH gradient is demonstrated, using the Marangoni effect to translate gradients of surface-active molecules into motion. First, fields of surfactant microliter-droplets are generated, in which droplets floating on water drive local, outbound Marangoni flows upon dissolution of surfactant and concomitantly grow myelin filaments. Next, a competing surfactant based on a hydrolysable amide is introduced, which is more surface active than the myelin surfactant and thereby inhibits the local Marangoni flows and myelin growth from the droplets. Upon introducing a pH gradient, the amide surfactant hydrolyses in the acidic region, so that the local Marangoni flows and myelin growth are reestablished. The resulting combination of local and global surface tension gradients produces a region of myelin-growing droplets and a region where myelin growth is suppressed, separated by a wave front of closely packed droplets, of which the position can be controlled by the pH gradient. Thereby, it is shown how "French flag"-patterns, in synthetic settings typically emerging from reaction-diffusion systems, can also be established via surfactant droplet systems.
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Mastering the self-organization of nanoparticle morphologies is pivotal in soft matter physics and film growth. Silicon dioxide (SiO2) nanoparticles are an archetypical model of nanomotor in soft matter. Here, the emphasis is on the self-organizing behavior of SiO2 nanoparticles under extreme conditions. It is unveiled that manipulating the states of the metal substrate profoundly dictates the motion characteristics of SiO2 nanoparticles. This manipulation triggers the emergence of intricate morphologies and distinctive patterns. Employing a reaction-diffusion model, the fundamental roles played by Brownian motion and Marangoni-driven motion in shaping fractal structures and radial Turing patterns are demonstrated, respectively. Notably, these radial Turing patterns showcase hyperuniform order, challenging conventional notions of film morphology. These discoveries pave the way for crafting non-equilibrium morphological materials, poised with the potential for self-healing, adaptability, and innovative applications.
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In 2D materials, a key engineering challenge is the mass production of large-area thin films without sacrificing their uniform 2D nature and unique properties. Here, it is demonstrated that a simple fluid phenomenon of water/alcohol solvents can become a sophisticated tool for self-assembly and designing organized structures of 2D nanosheets on a water surface. In situ, surface characterizations show that water/alcohol droplets of 2D nanosheets with cationic surfactants exhibit spontaneous spreading of large uniform monolayers within 10 s. Facile transfer of the monolayers onto solid or flexible substrates results in high-quality mono- and multilayer films with high coverages (>95%) and homogeneous electronic/optical properties. This spontaneous spreading is quite general and can be applied to various 2D nanosheets, including metal oxides, graphene oxide, h-BN, MoS2, and transition metal carbides, enabling on-demand smart manufacture of large-size (>4 inchÏ) 2D nanofilms and free-standing membranes.
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The yacon roots are rich in fructooligosaccharides (FOS) and highly perishable. Drying is crucial for food quality and extending shelf life. However, preserving thermosensitive compounds, such as FOS, poses a challenge in conventional drying methods. In this regard, microwave drying and ethanol pretreatment (ET) have emerged as promising solutions for maintaining nutrients and reducing drying time (DT). The objective of this study was to assess how ET and sample temperature affect quality and process parameters during intermittent microwave drying of yacon. Drying at 52°C treated with ethanol was the one that stood out for presenting the highest fructan retention (64.1%), low DT, lower energy consumption (EC) (364.00 ± 5.03 kWh kg water-1), higher retention of antioxidant capacity (73.9%) and total phenolic content (77.5%), and slight variation in color parameters. Therefore, microwave drying with a controlled temperature of yacon pretreated with ethanol effectively reduces DT and EC by maintaining quality parameters.
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Antioxidantes , Desecación , Etanol , Microondas , Etanol/química , Desecación/métodos , Antioxidantes/química , Fenoles/análisis , Raíces de Plantas/química , Oligosacáridos/química , Temperatura , Fructanos/química , Fructanos/análisis , Manipulación de Alimentos/métodos , Conservación de Alimentos/métodosRESUMEN
We demonstrate a simple droplet diagnostic approach to monitor the UiO-66 MOF (metal-organic framework) synthesis and its quality using the sessile droplet drying phenomenon. Drying a sessile droplet involves evaporation-driven hydrodynamic flow and particle-nature-dependent self-assembled deposition. In general, the MOF synthesis process involves different sizes and physicochemical nature of particles in every synthesis stage. Equivalent quantities of each of purified pore-activated UiO-66 MOF, yet-to-be-purified pore-inactivated UiO-66 MOF, and reaction precursors of UiO-66 MOF give different deposition patterns when a well-dispersed aqueous droplet of these materials undergoes drying over substrates of varying stiffness and wettability. Yet-to-be-purified, pore-inactivated UiO-66 MOF nanoparticles undergo transport toward the droplet periphery, leading to a thick ring-like deposition at the dried droplet edge. Under appropriate drying conditions, such a deposit leads to desiccation-type mud-like reticular cracking. We study the origin of such ring-like deposits and cracks to understand how the surface charge density of UiO-66 particles controls their stability. We demonstrate that ZrOCl2 salt trapped in a nonpurified pore-inactivated UiO-66 MOF moiety is the principal reason for ring-like deposit formation and subsequent cracking in its dried aqueous droplet edge. Qualitatively, we identified Lewis acid salts that are capable of acting as BroÌ·nsted acid upon hydrolysis (like FeCl3, SnCl2, and ZrOCl2), influence surface charge density and colloidal stability of dispersed UiO-66 MOF particles. As a result, immediate particle coagulation is avoided, so those travel to the droplet edge, forming ring-like deposition and subsequent cracking upon drying. Further, we show that crack patterns on such deposits are highly dependent on the stiffness and temperature of depositing substrates via a competition between axial and lateral strains at the deposit-substrate interface.
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Quorum sensing enables unicellular organisms to probe their population density and perform behavior that exclusively occurs above a critical density. Quorum sensing is established in emulsion droplet swarms that float at a water surface and cluster above a critical density. The design involves competition between 1) a surface tension gradient that is generated upon release of a surfactant from the oil droplets, and thereby drives their mutual repulsion, and 2) the release of a surfactant precursor from the droplets, that forms a strong imine surfactant which suppresses the surface tension gradient and thereby causes droplet clustering upon capillary (Cheerios) attraction. The production of the imine-surfactant depends on the population density of the droplets releasing the precursor so that the clustering only occurs above a critical population density. The pH-dependence of the imine-surfactant formation is exploited to trigger quorum sensing upon a base stimulus: dynamic droplet swarms are generated that cluster and spread upon spatiotemporally varying acid and base conditions. Next, the clustering of two droplet subpopulations is coupled to a chemical reaction that generates a fluorescent signal. It is foreseen that quorum sensing enables control mechanisms in droplet-based systems that display collective responses in contexts of, e.g., sensing, optics, or dynamically controlled droplet-reactors.
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With the advent of new media art, artists have harnessed fluid dynamics to create captivating visual narratives. A striking technique known as dendritic painting employs mixtures of ink and isopropanol atop paint, yielding intricate tree-like patterns. To unravel the intricacies of that technique, we examine the spread of ink/alcohol droplets over liquid substrates with diverse rheological properties. On Newtonian substrates, the droplet size evolution exhibits two power laws, suggesting an underlying interplay between viscous and Marangoni forces. The leading edge of the droplet spreads as a precursor film with an exponent of 3/8, while its main body spreads with an exponent of 1/4. For a weakly shear-thinning acrylic resin substrate, the same power laws persist, but dendritic structures emerge, and the texture of the precursor film roughens. The observed roughness and growth exponents (3/4 and 3/5) suggest a connection to the quenched Kardar-Parisi-Zhang universality class, hinting at the existence of quenched disorder in the liquid substrate. Mixing the resin with acrylic paint renders it more viscous and shear-thinning, refining the dendrite edges and further roughening the precursor film. At larger paint concentrations, the substrate becomes a power-law fluid. The roughness and growth exponents then approach 1/2 and 3/4, respectively, deviating from known universality classes. The ensuing structures have a fractal dimension of 1.68, characteristic of diffusion-limited aggregation. These findings underscore how the nonlinear rheological properties of the liquid substrate, coupled with the Laplacian nature of Marangoni spreading, can overshadow the local kinetic roughening of the droplet interface.
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Full-Stokes polarization detection, with high integration and portability, offers an efficient path toward next-gen multi-information optoelectronic systems. Nevertheless, current techniques relying on optical filters create rigid and bulky configurations, limiting practicality. Here, a flexible, filter-less full-Stokes polarimeter featuring a uniaxial-oriented chiral perovskite film is first reported. It is found that, the strategic manipulation of the surfactant-mediated Marangoni effect during blade coating, is crucial for guiding an equilibrious mass transport to achieve oriented crystallization. Through this approach, the obtained uniaxial-oriented chiral perovskite films inherently possess anisotropy and chirality, and thereby with desired sensitivity to both linearly polarized light and circularly polarized light vectors. The uniaxial-oriented crystalline structure also improves photodetection, achieving a specific detectivity of 5.23 × 1013 Jones, surpassing non-oriented devices by 10×. The as-fabricated flexible polarimeters enable accurate capture of full-Stokes polarization without optical filters, exhibiting slight detection errors for the Stokes parameters: ΔS1 = 9.2%, ΔS2 = 8.6%, and ΔS3 = 6.5%, approaching the detection accuracy of optics-filter polarimeters. This proof of concept also demonstrates applications in matrix polarization imaging.
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Aquatic actuators based on the light-to-work conversion are of paramount significance for the development of cutting-edge fields including robots, micromachines, and intelligent systems. Herein, we report the design and synthesis of near-infrared light-driven hydrogel actuators through loading with lightweight polydopamine-modified hollow glass microspheres (PDA-HGMPs) into responsive poly(N-isopropylacrylamide) (PNIPAM) hydrogels. These PDA-HGMPs can not only function as an excellent photothermal agent but also accelerate the swelling/desewlling of hydrogels due to their reconstruction for polymer gel skeleton, which speeds up the response rate of hydrogel actuators. The resulting hydrogel actuator shows controlled movements under light illumination, including complex self-propellant and floating/sinking motions. As the proof-of-concept demonstrations, a self-sensing robot is conceptualized by integrating the PDA-HGMP-containing hydrogel actuator with an ultrathin and miniature pressure sensor. Hopefully, this work can offer some important insights into the research of smart aquatic soft actuators, paving the way to the potential applications in emerging fields including micromachines and intelligent systems.
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Marangoni actuators that are propelled by surface tension gradients hold significant potential in small-scale swimming robots. Nevertheless, the release of "fuel" for conventional chemical Marangoni actuators is not easily controllable, and the single swimming function also limits application areas. Constructing controllable Marangoni robots with multifunctions is still a huge challenge. Herein, inspired by water striders, electricity-driven strategies are proposed for a multifunctional swimming Marangoni robot (MSMR), which is fabricated by super-aligned carbon nanotube (SACNT) and polyimide (PI) composite. The MSMR consists of a Marangoni actuator and air-ambient actuators. Owing to the temperature gradient generated by the electrical stimulation on the water surface, the Marangoni actuators can swim controllably with linear, turning, and rotary motions, mimicking the walking motion of water striders. In addition, the Marangoni actuators can also be driven by light. Importantly, the air-ambient actuators fabricated by SACNT/PI bilayer structures demonstrate the function of grasping objects on the water surface when electrically Joule-heated, mimicking the predation behavior of water striders. With the synergistic effect of the Marangoni actuator and air-ambient actuators, the MSMR can navigate mazes with tunnels and grasp objects. This research will provide a new inspiration for smart actuators and swimming robots.
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The measurement of in-plane mechanical properties, such as Young's modulus and strength, of thin and stretchable materials has long been a challenge. Existing measurements, including wrinkle instability and nano indentation, are either indirect or destructive, and are inapplicable to meshes or porous materials, while the conventional tension test fails to measure the mechanical properties of nanoscale films. Here, we report a technique to test thin and stretchable films by loading a thin film afloat via differential surface tension and recording its deformation. We have demonstrated the method by measuring the Young's moduli of homogeneous films of soft materials including polydimethylsiloxane and Ecoflex and verified the results with known values. We further measured the strain distributions of meshes, both isotropic and anisotropic, which were otherwise nearly impossible to measure. The method proposed herein is expected to be generally applicable to many material systems that are thin, stretchable, and water-insoluble.
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Chemically active droplets display complex self-propulsion behavior in homogeneous surfactant solutions, often influenced by the interplay between diffusiophoresis and Marangoni effects. Previous studies have primarily considered these effects separately or assumed axisymmetric motion. To understand the full hydrodynamics, we investigate the motion of a two-dimensional active droplet under their combined influences using weakly nonlinear analysis and numerical simulations. The impact of two key factors, the Péclet number ( P e $Pe$ ) and the mobility ratio between diffusiophoretic and Marangoni effects ( m $m$ ), on droplet motion is explored. We establish a phase diagram in the P e - m $Pe-m$ space, categorizing the boundaries between four types of droplet states: stationary, steady motion, periodic/quasi-periodic motion, and chaotic motion. We find that the mobility ratio does not affect the critical P e $Pe$ for the onset of self-propulsion, but it significantly influences the stability of high-wavenumber modes as well as the droplet's velocity and trajectory. Scaling analysis reveals that in the high P e $Pe$ regime, the Marangoni and diffusiophoresis effects lead to distinct velocity scaling laws: U â¼ P e - 1 / 2 $U\sim Pe^{-1/2}$ and U â¼ P e - 1 / 3 $U\sim Pe^{-1/3}$ , respectively. When these effects are combined, the velocity scaling depends on the sign of the mobility ratio. In cases with a positive mobility ratio, the Marangoni effect dominates the scaling, whereas the negative diffusiophoretic effect leads to an increased thickness of the concentration boundary layer and a flattened scaling of the droplet velocity.
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Motion is an essential feature of living systems. Microorganisms autonomously change their nature in response to slight changes in the surrounding environment induced by external stimuli and exhibit unique motion modes. Various self-propelled objects have been constructed to understand these behaviors. Towards achievement of such purpose, the precise settings of experimental conditions including fabrication of objects with a shape anisotropy have been made attempts in the field of active matter and supramolecular chemistry. This review describes the recent progress in inducing the self-propelled motion of artificial objects. If life-like dynamic behavior such as self-propelled motion can be designed and experimentally induced from molecular properties, it will be easier to control functions expressed as outputs. This will lead to not only a better understanding of the complex functions in living systems, but also the fabrication of exotic materials with life-like properties.
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Anisotropía , Movimiento (Física)RESUMEN
The objective of this study was to evaluate, during the drying of spent coffee grounds, the application of pretreatments with ethanol and the application of ultrasound assisting the refractive window (RW) drying, and to compare with convective drying by hot air (AC). The effect on the kinetics parameters of the Fick and Page models were evaluated, as well as on the content of total phenolics and antioxidant capacity. For AC drying, samples of spent ground coffee were prepared in the form of fixed rectangular beds 0.7 cm high, which were placed on polyester sheets and pretreated up to 10 times sprayed with ethanol, then dried by AC at 80 °C and 0.8 m/s. For RW drying, the samples prepared in the same way as for AC were used. For this case, the application of ethanol as pretreatment and the use of ultrasound during process were tested. As results, regardless of the conditions applied, drying by RW was up to 50 % faster, evidenced in the highest values of effective diffusivity (from the Fick model) and the kinetic parameter (from the Page model). Regarding the treatments applied and their effect on the drying kinetics, any treatment had a significant effect on AC drying. On the contrary, the strategies applied in RW drying had significant effects, both the application of pretreatment with ethanol as well as the application of ultrasound assisting the process accelerated the drying kinetics. However, the treatment with ethanol and RW drying was the one that best preserved the phenolic compounds and the antioxidant capacity in the samples. Therefore, these strategies could be a good option to improve RW drying by accelerating the process and preserving the bioactive compounds in the spent coffee grounds for subsequent utilization.