Droplet Periphery Research Articles

Assessing Activation Quality through Evaporative Drying Patterns of Zr-MOF (UiO-66) Colloidal Droplets.

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 Bro̷nsted 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.

Exploring impact, spreading, and bonding dynamics in molten metal deposition for novel drop-on-demand printing

This study delves into the dynamics of molten metal deposition (MMD)-based drop-on-demand (DoD) printing, focusing on the interaction between aluminum droplets and substrates. Nozzle-to-substrate distances below 20 mm prevent droplet pinch-off, while distances exceeding 40 mm result in no droplet-substrate adhesion. Operating within the substrate temperature range of 350–550 °C is crucial, avoiding delamination, and shrinkage pits at lower temperatures, and substrate deformation and heightened oxidation at higher temperatures. Droplet adhesion is impeded at nozzle temperatures below 700 °C. Impact-driven and inviscid, DoD-MMD exhibits spreading outpacing overall solidification, particularly at higher temperatures. Surface tension forces dominate, influencing droplet spreading and leading to underdamped interfacial oscillations. Weak droplet-substrate adherence, facilitated by Van der Waals forces, allows easy droplet detachment, beneficial for successive drop-on-drop deposition. Unique to DoD-MMD, ridges along the droplet periphery act as solidification paths, influenced by thermal contraction and surface tension. The spherical pancake shape of the droplet, characterized by a solidification angle >90°, is elucidated through Weber and Freezing numbers. The final deposited droplet width to initial diameter ratio increases with the droplet temperature and deposition height. In contrast to other metal DoD studies, the spreading factor decreases with a rise in substrate temperature, attributed to intensified oxidation at higher substrate temperatures.

Digital holographic microscopy for measurement of instantaneous contact angle of an evaporating droplet

Despite the apparent simplicity of the process of a droplet evaporating on a substrate, the temporal evolution of the local contact angle along the droplet periphery during the evaporation is still not fully understood. In this work, digital holographic microscopy is used for capturing the time evolution of the droplet surface at submicron resolution. The three-dimensional surface provides the information for determining the instantaneous three-phase contact line and the local apparent contact angle along the whole droplet periphery. The apparent contact angle is computed from the gradient of the droplet surface and defined as the maximum slope of this function along the periphery of the droplet. The method is then applied to study the diffusion dominated evaporation of nanoliter droplets on a hydrophilic substrate. For the case of a non-axisymmetric droplet, differences of up to 10^circ in contact angle along the contact line were identified when the contact line went from one pinning position to another. Digital holographic microscopy allowed us to characterize the irregular motion of the contact line and local changes in contact angle during the evaporation process.

Evaporation-induced hydrodynamics control plasmid transfer during surface-associated microbial growth

Droplet evaporation is a general process in unsaturated environments that results in micro-scale hydrodynamic flows which in turn determine the spatial distributions of microbial cells across surfaces. These spatial distributions can have significant effects on the development and functioning of surface-associated microbial communities, with consequences for important processes such as the spread of plasmids. Here, we experimentally quantified how evaporation-induced hydrodynamic processes modulate the initial deposition patterns of microbial cells (via the coffee ring effect and Marangoni convection) and how these patterns control the spread of an antibiotic resistance-encoding plasmid during surface-associated growth. We found that plasmid spread is a function of the initial density of cells deposited along the droplet periphery, which is a manifestation of the coffee ring effect. Using an individual-based model, we systematically linked how the different initial cell deposition patterns caused by the relative strengths of the coffee ring effect and Marangoni convection determine the extent of plasmid transfer during surface-associated growth. Our study demonstrates that evaporation-induced hydrodynamic processes that are common in nature can alter crucial ecological properties of surface-associated microbial communities and control the proliferation of plasmids, with consequences on the spread of antibiotic resistance and other plasmid-encoded traits.

CGAS phase separation inhibits TREX1-mediated DNA degradation and enhances cytosolic DNA sensing

Cyclic GMP-AMP synthase (cGAS) recognition of cytosolic DNA is critical for the immune response to cancer and pathogen infection. Here, we discover that cGAS-DNA phase separation is required to resist negative regulation and allow efficient sensing of immunostimulatory DNA. We map the molecular determinants of cGAS condensate formation and demonstrate that phase separation functions to limit activity of the cytosolic exonuclease TREX1. Mechanistically, phase separation forms a selective environment that suppresses TREX1 catalytic function and restricts DNA degradation to an outer shell at the droplet periphery. We identify a TREX1 mutation associated with the severe autoimmune disease Aicardi-Goutières syndrome that increases penetration of TREX1 into the repressive droplet interior and specifically impairs degradation of phase-separated DNA. Our results define a critical function of cGAS-DNA phase separation and reveal a molecular mechanism that balances cytosolic DNA degradation and innate immune activation.

Disk-Ring Deposition in Drying a Sessile Nanofluid Droplet with Enhanced Marangoni Effect and Particle Surface Adsorption.

The present study is to explore the central particle deposition from drying a sessile nanofluid droplet experimentally and theoretically. Normally, a pinned colloidal droplet dries into a coffee-ring pattern as a result of moving the particles to a three-phase line by the radial direction capillary flow. However, the strong evaporation can generate the nonuniform temperature at the evaporating droplet interface and the droplet periphery temperature is higher than that close to the droplet centerline. The induced Marangoni flow would reversibly transport the particles at the periphery toward the centerline. We have thus designed the experiments to increase the droplet evaporation rate in vacuum conditions and accordingly to enhance the Marangoni effect. We have observed distinguishable disk deposition inside the outer coffee ring. A three-dimensional diffusion-limited cluster-cluster aggregation Monte Carlo model has been developed to simulate the deposition process. With modeling the Marangoni effect, particle adsorption at the liquid-air interface and particle aggregation behaviors, the formation of the disk pattern inside a coffee ring has been simulated. The qualitative agreement has been found in the comparison of local deposition distribution between the related experiment and simulation.

Scavenging One of the Liquids versus Emulsion Stabilization by Microgels in a Mixture of Two Immiscible Liquids.

It is known that microgels can serve as soft, permeable and stimuli-responsive alternative of solid colloidal particles to stabilize oil-water emulsions. The driving force for the adsorption of the microgels on interface of two immiscible liquids is a shielding of unfavorable oil-water contacts by adsorbed subchains, that is, the decrease of the surface tension between the liquids. Such phenomenon usually proceeds if volume fractions of the two liquids are comparable with each other and the microgel concentration is not high enough. The natural question arises: what is going on with the system in the opposite case of strongly asymmetric mixture (one of the liquids (oil) has a very small fraction) or high microgel concentration (the overall volume of the microgels exceeds the volume of the minor oil component)? Here we demonstrate that the microgels uptake the oil whose concentration within the microgels can be orders of magnitude higher than outside, leading to the additional microgel swelling (in comparison with the swelling in water). Thus, the microgels can serve as scavengers and concentrators of liquids dissolved in water. At first glance, this effect seems counterintuitive. However, it has a clear physical reason related to the incompatibility of oil and water. Absorption of the oil by microgels reduces unfavorable oil-water contacts by microgel segments: the microgels have a higher concentration of the segments at the periphery, forming a shell. The microgels with uptaken oil are stable toward aggregation at very small oil concentration in the mixture. However, an increase in the oil concentration can lead to aggregation of the microgels into dimers, trimers, and so on. The increasing concentration of oil mediates the attraction between the microgels: the oil in the aggregates appears to be localized in-between the microgels instead of their interior, which is accompanied by the release of the elastic stress of the microgels. A further increase in the oil concentration results in a growth of the size of the oil droplets between the microgels and the number of the microgels at the droplet's periphery, that is, the emulsion is formed.

Programmable Functionalization of Surfactant‐Stabilized Microfluidic Droplets via DNA‐Tags

AbstractDroplet‐based microfluidics has emerged as a powerful tool in synthetic biology. For many applications, chemical functionalization of the droplets is a key process. Therefore, a straightforward and broadly applicable approach is developed to functionalize the inner periphery of microfluidic droplets with diverse reactive groups and components. Instead of covalent modification of the droplet‐stabilizing surfactants, this method relies on cholesterol‐tagged DNA that self‐assembles at the droplet periphery. The cholesterol‐tagged DNA serves as an attachment handle for the recruitment of complementary DNA. The complementary DNA can carry diverse functional groups. We exemplify our method by demonstrating the attachment of amine groups, DNA nanostructures, microspheres, a minimal actin cortex, and leukemia cells to the droplet periphery. It is further shown that the DNA‐mediated attachment to the droplet periphery is temperature‐responsive and reversible. It is envisioned that droplet functionalization via DNA handles will help to tailor droplet interfaces for diverse applications—featuring programmable assembly, unique addressability, and stimuli‐responsiveness.

Numerical simulation of EWOD on a printed circuit board for cleanroom-less digital fluidic manufacturing applications

PurposeDigital microfluidic devices have been demonstrated to have great potential for a wide range of applications. These devices need expensive photolithography process and clean room facilities, while printed circuit board (PCB) technology provides high configurability and at low cost. This study aims to investigate the mechanism of electrowetting-on-a-dielectric (EWOD) on PCB by solving the multiphysics interaction between fluid droplet and electric field. The performance of system will be improved by inducing an efficient electric field inside the droplet.Design/methodology/approachTo induce an electric field inside the droplet on a PCB and change the initial contact angle, the mechanism of EWOD is studied based on energy minimization method and a set of simulations are carried out by considering multiphysics interaction between the fluid droplet and external electric field. The performance of EWOD on a PCB system is investigated using different electrode structures.FindingsSurface tension plays an efficient role in smaller sizes and can be used to move and control a fluid droplet on a surface by changing the interfacial surface tension. EWOD on a PCB system is studied. and it revealed that any change in electric field affects the droplet contact angle and as a result droplet deformation and movement. The electrode pattern is an important parameter which could change the electric potential distribution inside the droplet. Array of electrodes with square, zigzag interdigitated and crescent shapes are studied to enhance the EWOD force on a PCB substrate. Based on the results, the radial shape of the crescent electrodes keeps almost the same actuated contact line, applies uniform force on the droplet periphery and prevents the droplet from large deformation. A droplet velocity of 0.6 mm/s is achieved by exciting the crescent electrodes at 315 V. Furthermore, the behavior of system is characterized for process parameters such as actuation voltage, dielectric constant of insulator layer, fluidic material properties and the resultant velocity and contact angle. The study of contact angle distribution and droplet motion revealed that it is helpful to generate EWOD mechanism on a PCB which does not need more complicated fabrication processes.Originality/valueThe ability to handle and manipulate the droplets is very important for chemistry on-chip analysis such as immunoassay chips. Furthermore, a PCB-based electrowetting-on-dielectric device is of high interest because it does not need cleanroom facilities and avoids additional high-cost fabrication processes. In the present research, the EWOD mechanism is studied on a PCB by using different electrode patterns.

Suppression of the coffee-ring effect by sugar-assisted depinning of contact line

Inkjet printing is of growing interest due to the attractive technologies for surface patterning. During the printing process, the solutes are transported to the droplet periphery and form a ring-like deposit, which disturbs the fabrication of high-resolution patterns. Thus, controlling the uniformity of particle coating is crucial in the advanced and extensive applications. Here, we find that sweet coffee drops above a threshold sugar concentration leave uniform rather than the ring-like pattern. The evaporative deposit changes from a ring-like pattern to a uniform pattern with an increase in sugar concentration. We moreover observe the particle movements near the contact line during the evaporation, suggesting that the sugar is precipitated from the droplet edge because of the highest evaporation and it causes the depinning of the contact line. By analyzing the following dynamics of the depinning contact line and flow fields and observing the internal structure of the deposit with a FIB-SEM system, we conclude that the depinned contact line recedes due to the solidification of sugar solution without any slip motion while suppressing the capillary flow and homogeneously fixing suspended particles, leading to the uniform coating. Our findings show that suppressing the coffee-ring effect by adding sugar is a cost-effective, easy and nontoxic strategy for improving the pattern resolution.

Physiologically Important Electrolytes as Regulators of TDP-43 Aggregation and Droplet-Phase Behavior.

Intraneuronal aggregation of TDP-43 is seen in 97% of all amyotrophic lateral sclerosis cases and occurs by a poorly understood mechanism. We developed a simple in vitro model system for the study of full-length TDP-43 aggregation in solution and in protein droplets. We found that soluble, YFP-tagged full-length TDP-43 (yTDP-43) dimers can be produced by refolding in low-salt HEPES buffer; these solutions are stable for several weeks. We found that physiological electrolytes induced reversible aggregation of yTDP-43 into 10-50 nm tufted particles, without amyloid characteristics. The order of aggregation induction potency was K+ < Na+ < Mg2+ < Ca2+, which is the reverse of the Hofmeister series. The kinetics of aggregation were fit to a single-step model, and the apparent rate of aggregation was affected by yTDP-43 and NaCl concentrations. While yTDP-43 alone did not form stable liquid droplets, it partitioned into preformed Ddx4N1 droplets, showing dynamic diffusion behavior consistent with liquid-liquid phase transition, but then aggregated over time. Aggregation of yTDP-43 in droplets also occurred rapidly in response to changes in electrolyte concentrations, mirroring solution behavior. This was accompanied by changes to droplet localization and solvent exchange. Exposure to extracellular-like electrolyte conditions caused rapid aggregation at the droplet periphery. The aggregation behavior of yTDP-43 is controlled by ion-specific effects that occur at physiological concentrations, suggesting a mechanistic role for local electrolyte concentrations in TDP-43 proteinopathies.

Corrosion Driven Drying Phenomena Occurring during the Atmospheric Corrosion of Magnesium Containing Galvanized Steel

The corrosion behaviour of various Zn-Mg-Al hot-dip galvanised coatings on steel substrates were studied using a combination of time-lapse photography (TLP), the scanning Kelvin probe (SKP) and non-contact height profiling. In a standard experiment 1uL electrolytic droplets comprising varying concentrations of aqueous NaCl were deposited onto the surface of the Zn-Mg-Al alloy coating held in a humid air atmosphere maintained in isopiestic equilibrium (equilibrium with respect to the vapour pressure of water) with a large remote reservoir of aqueous electrolyte which had the same composition as the original droplet. The progress of atmospheric corrosion was then followed using TLP with photographs taken at 2-minute intervals for a period of up to 60 hours. When required, in-situ SKP was used to produce area maps of electrochemical potential if in the vicinity of the electrolytic droplets over a similar period of time. The SKP probe could also be used as a non-contact height profilometer which allowed the topography of the electrolytic droplet and the surrounding Zn-Mg-Al alloy surface to be mapped. This made it possible to study time-dependent changes in droplet volume and shape as atmospheric corrosion proceeds. In most cases the phenomenon known as cathodic secondary spreading was observed at the droplet periphery, where a thin film (microns) of electrolyte develops and advances away from the droplet as time proceeds. The presence of this thin electrolyte film changes the reflectivity of the Zn-Mg-Al alloy surface with respect to visible light and also produces a marked reduction (drop) in local electrochemical potential. The kinetics of secondary spreading could therefore be followed using a combination of TLP and in-situ SKP. Results are presented which show the dependence of spreading rate on: time, original NaCl concentration and Zn-Mg-Al alloy composition. The role of aluminium and magnesium in modifying (reducing) rates of secondary spreading is discussed in relation to their relative electrocatalytic activities for cathodic oxygen reduction and their distribution within the microstructure of the various alloy coatings. It is shown, using in-situ profilometry, that at lower initial concentrations of NaCl (and consequently higher relative humidity under isopiestic conditions) the original electrolyte droplets dry out within approximately 2-3 hours of being deposited on the alloy surface. The mechanism of this drying phenomenon is discussed in relation to the relevant mechanisms of atmospheric corrosion. It is proposed that as corrosion proceeds all the Na+ cations originally present in the droplet migrate out into the region of secondary cathodic spreading. Conversely, Cl- anions migrating towards the anodic sites at the droplet centre become sequestered as insoluble (or poorly soluble) zinc corrosion products such as Simonkolleite, Zn(OH)Cl. (The presence of Simonkollite is confirmed using grazing angle Z-ray diffraction.) As these corrosion products precipitate the activity of water in the droplet (and its associated vapour pressure) increase and water evaporates from the droplet as it tries to maintain isopiestic equilibrium with the experimental atmosphere. Corrosion-driven drying was also seen for higher initial concentrations of NaCl but at considerably slower rates. The drying effect, caused by the secondary spreading phenomena, may be an important self-limiting mechanism of atmospheric corrosion affecting Zn-Mg-Al alloy coatings.

Partitioning and Enhanced Self-Assembly of Actin in Polypeptide Coacervates

Biomolecules exist and function in cellular microenvironments that control their spatial organization, local concentration, and biochemical reactivity. Due to the complexity of native cytoplasm, the development of artificial bioreactors and cellular mimics to compartmentalize, concentrate, and control the local physico-chemical properties is of great interest. Here, we employ self-assembling polypeptide coacervates to explore the partitioning of the ubiquitous cytoskeletal protein actin into liquid polymer-rich droplets. We find that actin spontaneously partitions into coacervate droplets and is enriched by up to ∼30-fold. Actin polymerizes into micrometer-long filaments and, in contrast to the globular protein BSA, these filaments localize predominately to the droplet periphery. We observe up to a 50-fold enhancement in the actin filament assembly rate inside coacervate droplets, consistent with the enrichment of actin within the coacervate phase. Together these results suggest that coacervates can serve as a versatile platform in which to localize and enrich biomolecules to study their reactivity in physiological environments.

Self-Organized Micro-Spiral of Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWCNTs) are reported to spontaneously align in a rotational pattern by drying a liquid droplet of toluene containing polyfluorene as a dispersant. By situating a droplet of an SWCNT solution around a glass bead, spiral patterns are generated. The parallel alignment of SWCNTs along one stripe of such a pattern is confirmed using scanning electron microscopy and polarized optical microscopy. The orientation order increases toward the outer edge of a stripe. The stripe width in the pattern is proportional to the solute concentration, and the width and position of the stripes follow geometric sequences. The growth of the rotational pattern is also observed in real time. The process of spiral pattern formation is visualized, indicating the role of the annihilation of counter-traveling accompanied by continuous depinning. The geometric sequences for the stripe width and position are explained by the near-constant traveling speed and solute enrichment at the droplet periphery.

Synthesis of Half-Sphere/Half-Funnel-Shaped Silica Structures by Reagent Localization and the Role of Water in Shape Control.

Shape control of silica structures is demonstrated by localization of the reagents. A uniform dispersion of reagents provided straight silica rods, whereas localization of the reagents in the emulsion droplet periphery provided a new type of half-sphere/half-funnel structure. The effect of water concentration appeared to be related to the ease of diffusion of the silica precursor inside the emulsion droplet (i.e., the higher the water concentration, the lower the silica precursor diffusion).

Morphological transitions and buckling characteristics in a nanoparticle-laden sessile droplet resting on a heated hydrophobic substrate

In this work, we have established the evaporation-liquid flow coupling mechanism by which sessile nanofluid droplets on a hydrophobic substrate evaporate and agglomerate to form unique morphological features under controlled external heating. It is well understood that evaporation coupled with internal liquid flow controls particle transport in a spatiotemporal sense. Flow characteristics inside the heated droplet are investigated and found to be driven by the buoyancy effects. Velocity magnitudes are observed to increase by an order at higher temperatures with similar looking flow profiles. The recirculating flow induced particle transport coupled with collision of particles and shear interaction between them leads to the formation of dome shaped viscoelastic shells of different dimensions depending on the surface temperature. These shells undergo sol-gel transition and subsequently undergo buckling instability leading to the formation of daughter cavities. With an increase in the surface temperature, droplets exhibit buckling from multiple sites over a larger sector in the top half of the droplet. Irrespective of the initial nanoparticle concentration and substrate temperature, growth of a daughter cavity (subsequent to buckling) inside the droplet is found to be controlled by the solvent evaporation rate from the droplet periphery and is shown to exhibit a universal trend.

Coalescence, Cracking, and Crack Healing in Drying Dispersion Droplets.

The formation of a uniform film from a polymer dispersion is a complex phenomenon involving the interplay of many processes: evaporation and resulting fluid flows through confined geometries, particle packing and deformation, coalescence, and cracking. Understanding this multidimensional problem has proven challenging, precluding a clear understanding of film formation to date. This is especially true for drying dispersion droplets, where the particular geometry introduces additional complexity such as lateral flow toward the droplet periphery. We study the drying of these droplets using a simplified approach in which we systematically vary a single parameter: the glass transition temperature (Tg) of the polymer. We combine optical with scanning electron microscopy to elucidate these processes from the macroscopic down to the single-particle level, both qualitatively and quantitatively, over times ranging from seconds to days. Our results indicate that the polymer Tg has a marked influence on the time evolution of particle deformation and coalescence, giving rise to a distinct and sudden cracking transition. Moreover, in cracked droplets it affects the frequently overlooked time scale of crack healing, giving rise to a second transition from self-healing to permanently cracked droplets. These findings are in line with the classical Routh-Russel model for film formation yet extend its scope from particle-level dynamics to long-range polymer flow.

Agglomeration front dynamics: Drying in sessile nano-particle laden droplets

The drying of sessile, nano-silica laden water droplet is studied under ambient conditions, in the absence of any convection. The drying process can be divided into two distinct regimes. During regime 1, the outer edge of the droplet remains pinned and particles agglomerate at the droplet periphery similar to the traditional coffee ring. However in regime 2, with further evaporation, both the liquid contact line and the agglomeration front starts moving radially inwards from the initial contact edge. The contact between the liquid and the agglomerate is maintained throughout regime 2 and the vaporisation driven liquid edge recession essentially drives the inward growth of the particle deposition. Fast kinetics of particle aggregation results in rapid growth of this agglomeration front as seen from the experiments. A theoretical formulation involving a simplistic model of the agglomeration front growth based on particle mass balance has been proposed.

Controllable Printing Droplets for High‐Resolution Patterns

Inkjet printing has attracted wide attention due to the important applications in fabricating biological, optical, and electrical devices. During the inkjet printing process, the solutes prefer to deposit along the droplet periphery and form an inhomogeneous morphology, known as the coffee-ring effect. Besides, the feature size of printed dots or lines of conventional inkjet printing is usually limited to tens or even hundreds of micrometers. The above two issues greatly restrict the extensive application of printed patterns in high-performance devices. This paper reviews the recent advances in precisely controlling the printing droplets for high-resolution patterns and three-dimensional structures, with a focus on the development to suppress the coffee-ring effect and minimize the feature size of printed dots or lines. A perspective on the remaining challenges of the research is also proposed.

Control of the particle deposition in inkjet-printed droplets

Radial flow in drying droplets forms a ring stain deposit. By controlling the amount of radial flow using an evaporation-driven sol&#x2013;gel transition in laponite suspensions, a uniform deposit can be achieved. Droplets gel from the contact line inwards, reducing particle flow to the droplet periphery. The method is demonstrated for picolitre droplets relevant to inkjet printing. Internal flows are visualized using high-speed imaging techniques. The final deposits are characterized by scanning electron microscopy and white light interferometry.