Solution Droplets Research Articles

Ultrasound induced grain refinement of crystallization in evaporative saline droplets

We investigate the effect of ultrasound on the evaporation and crystallization of sessile NaCl solution droplets which were positioned in traveling or standing wave ultrasound field. The experimental results indicated that the ultrasound field can significantly accelerate the evaporation rate of the sessile droplets and refine the crystal grains. By adjusting the distance between the sessile droplets and the ultrasound emitter, it is found that, in traveling wave ultrasound field, the sessile droplet evaporation time and the time for the appearance of NaCl grains exhibited a fluctuating increase as the droplet-emitter distance increased. While in the standing wave ultrasound, the sessile droplet evaporation rate increases with the increasing droplet-emitter distance. Overall, the traveling wave ultrasound field has a stronger effect on grain refinement of the sessile droplets than the standing wave ultrasound field. The grain refinement is attributed to the decrease of critical nucleation radius caused by ultrasound energy and the increase of the nucleation rate caused by the accelerated evaporation rate. In addition, the breakage of grains caused by ultrasonic cavitation would also lead to grain refinement.

Comparison of Newtonian and glycerol-water solution-based SiO2 nanofluid droplets impacting on heated spherical surfaces

The dynamic interactions of liquid droplets with heated spherical particles, relevant across various scientific and engineering disciplines, display intriguing collision behaviors whose principles are yet to be fully deciphered. This investigation utilizes high-speed photography to explore the wetting and non-wetting responses of different Newtonian and glycerol-water solution-based SiO2 nanofluid droplets upon contact with heated particles. Findings indicate that nanofluid droplets disrupt the thermal field and modify the surface morphology of particles more extensively under wetting than non-wetting conditions. Wetting conditions lead to significant alterations in the liquid film thickness and notable velocity field disruptions for droplets of deionized water and glycerol solution. Conversely, in the non-wetting phase, droplets nearing full rebound cause less disturbance to the velocity field, a behavior consistent across all fluid types and particle temperatures. The shape changes nanofluid droplets undergo when rebounding and separating from the particle surface are similar to those seen in glycerol solution and water droplets. Droplets in the breakup-rebound phase experience shorter contact times than those merely rebounding. A phase diagram is presented, detailing wetting (receding-deposition and boiling-breakup) and non-wetting (rebound and breakup-rebound) actions. An increase in the Weber number necessitates a higher particle temperature for the transition from rebound to breakup-rebound, which corroborates with theoretical insights. Furthermore, droplets achieve their maximum spreading area during the boiling-breakup mode.

Potensi Pewarna Alami untuk Pengembangan Kemajuan Teknologi Sel Surya Organik

Electrospinning is a modified technology to produce nano-sized fibers which can be used in making thin layers of semiconductor dye sensitized solar cells. Flourate – doped tin oxide (FTO) substrate was placed as a target for deposition of TiO2 nanofiber synthesized from TiO2 solution. The deposition process of a thin layer of TiO2 nanofiber was carried out for 15 minutes. The TiO2 solution synthesized is a mixture of acetic acid, ethanol, polyvinylpyrrolidone (PVP), and titanium tetra – isopropoxide (TTIP). Mixing the synthesis solution was carried out for 24 hours, to obtain a homogeneous TiO2 synthesis solution. The TiO2 nanofiber thin layer deposition process was applied under an electrospinning voltage of 25 kV, the distance of the FTO substrate as the collector layer to the solution syringe was 25 cm to avoid too large solution droplets. Before the deposition stage, the surface of the FTO substrate is first formed using the etching method by coating Zn and removing the conductive layer using HCl, so that a customized conductive layer is obtained. The annealing process of the deposited TiO2 nanofiber layer was carried out for 3 hours at a temperature of 450°C. The spin coating method was carried out to deposit a layer of Poly [2- methoxy- 5- (2- ethyl hexyloxy)- 1,4- phenylene venylene] (MEH-PPV). Coating variations are carried out with 4 different layer thicknesses. MEH – PPV was prepared by mixing chlorobenzene and stirring for 18 hours. Testing and characterization was carried out using current and voltage characterization (I – V meter), as well as image characterization using Scanning Electron Microscopy (SEM) as an analysis of the influence of layers on organic solar cells.

Droplet Microfluidics-Assisted Fabrication of Shape Controllable Iron-Alginate Microgels with Fluorescent Property.

Droplet-based microfluidics-assisted fabrication of alginate microgels has extensive applications in biomaterials, biomedicines, and related fields. This approach is typically achieved by crosslinking droplets of an aqueous solution of sodium alginate with various divalent and trivalent ions, such as Ca2+, Ba2+, Sr2+, etc. Despite the exceptional features exhibited by bulk alginate hydrogels when using iron ions as the crosslinking reagent, including stimulus responsiveness and complex chemistry, no attention has been given to studying the fabrication of Fe-alginate microgels through droplet microfluidics. In this work, a facile method is presented for fabricating Fe-alginate microgels using single emulsion droplets as templates and an off-chip crosslinking technique to solidify the droplets. The morphologies of the resulting microgels can be systematically adjusted by manipulating different parameters such as viscosities and ionic strength of the collecting solutions. It should be noted that these resulting microgels undergo a color change from light brown to dark brown due to presumed self-oxidation of iron ions within their skeleton structure. Furthermore, these Fe-alginate microgels are functionalized by decorating them with a positively charged linear polymer via electrostatic interactions to impart them with stable fluorescent property. These functionalized Fe-alginate microgels may find potential applications in drug delivery carriers and biomimetic structures.

Effect of the formation of open microcapsules with Mn3O4 walls during hydrolysis of the MnSO4 salt solution droplets deposited on the alkaline solution surface

It was shown for the first time that open microcapsules 1–5 µm in size with Mn3O4 walls and unique morphology are formed as a result of spraying an aqueous MnSO4 solution onto the surface of an alkali solution. The walls have a thickness of 80–120 nm and consist of an array of Mn3O4 nanosheets with a thickness of 2–3 nm, oriented predominantly in the radial direction towards the center of the microcapsule. There is a special rim with a height of 100–200 nm around the hole of the most microcapsules, which can be a kind of ‘ground’ when fixing such microcapsules on the surface of a substrate in the process of application by the Langmuir–Schaefer technique.

Three-dimensional internal flow evolution of an evaporating droplet and its role in particle deposition pattern

The internal flow within an evaporating sessile droplet is one of the driving mechanisms that lead to various particle deposition patterns seen in applications such as inkjet printing, surface patterning, and blood stain analysis. Despite decades of research, the causal link between droplet internal flow and particle deposition patterns has not been fully established. In this study, we employ a three-dimensional (3D) imaging technique based on digital inline holography to quantitatively assess the evolution of internal flow fields and particle migration in three distinct types of wetting droplets, namely water droplets, sucrose aqueous solution droplets, and sodium dodecylsulfate aqueous solution droplets, throughout their entire evaporation process. Our imaging reveals the three-stage evolution of the 3D internal flow regimes driven by changes in the relative importance of capillary flow, Marangoni flow, and droplet boundary movement during evaporation. Moreover, the migration of individual particles from their initial locations to deposition can be divided into five categories, with some particles depositing at the contact line and others inside the droplet. In particular, we observe the changing migration directions of particles due to competing Marangoni and capillary flows. We further develop an analytical model that predicts the droplet internal flow, deposition patterns, and determines the deposition mechanisms depending on their initial locations and evolving internal flow. The model, validated using different types of droplets from our experiment and the literature, can be further expanded to other Newtonian and non-Newtonian droplets, potentially serving as a real-time assessment tool for particle deposition in various applications.

One step synthesis of durable slippery, oil/water selective, corrosion-resistant silicone coatings with grafted flexible sidechains

Slippery liquid-infused porous surfaces (SLIPSs) based on polymer matrices impregnated with liquid lubricants are multifunctional and provide a wide range of useful properties such as low adhesion of water and other liquids, selectivity, high corrosion resistance, etc. However, these properties vanish quickly due to the gradual depletion of lubricant from the matrix. This issue could be resolved by attaching lubricant molecules to the matrix as flexible, liquid-like sidechains. In the present work, thin silicone films with grafted sidechains are fabricated. The uniform coatings are obtained in “eco-friendly” pressurized (subcritical) CO2 on smooth silicon wafers as well as on rough porous substrates such as carbon aerogels. The possibility of applying films by the traditional dip-coating method is also demonstrated on titanium slides. The coatings demonstrate low sliding angles for water and water/alcohol solution droplets. Coated aerogels preserve high porosity. It is demonstrated that initially hydrophilic aerogels become highly hydrophobic after coating and selectively absorb oil from water/oil mixtures. The tests of obtained coatings on titanium substrates demonstrate a significant increase in corrosion resistance. The proposed technique has a wide range of potential applications where such slippery coatings should be applied on complex rough substrates: from filtration materials production to textile finishing.

Characterizing boiling behaviors in water/ethanol binary droplet impact on a heated plate

This work experimentally investigates the transition boiling behaviors of water/ethanol binary droplets impact on a heated smooth aluminum alloy plate with a high-speed imaging system, forming a more finely defined impact behavior regime map. The dynamic Leidenfrost point temperature exhibits a non-monotonic variation trend with ethanol fraction. Binary droplets exhibit two characteristic boiling behaviors at specific temperatures (Ts) and droplet compositions (Φe), including corona boiling and prompt boiling, distinguished by the elevation of a crown-shaped thick liquid lamella and the prompt generation of numerous secondary droplets from the contact line, respectively. Both boiling behaviors are featured with the violent breakup of parent droplet into about 10 or more fragment droplets (secondary droplets with D ≥ 0.3 mm) and the short residence times on the wall, while exhibiting different splash angle distributions of satellite droplets (secondary droplets with D < 0.3 mm). Characteristic parameter analysis of the two boiling behaviors is conducted to provide qualitative mechanistic explanations. Corona boiling occurs at Φe = 25% & 50% with a lower temperature range (Ts ≤ 200 ℃), the liftoff of the liquid layer is attributed to the combined effect of decelerated wetting speed caused by evaporation and the vapor-induced lift. Prompt boiling occurs at Φe = 25% & 50% with Ts ≥ 220 °C and Φe = 75% with Ts < 200 °C, the intensity of the bubble cloud determines whether the central part of the droplet forms a jet or a liquid bulk filled with microbubbles. This work will provide some new insights into the boiling behaviors and the regulation of secondary atomization of binary solution droplets impact studies.

Wetting Properties of Black Silicon Layers Fabricated by Different Techniques

The wettability of black silicon (BSi) layers fabricated by reactive ion etching (RIE), metal‐assisted chemical etching (MACE), and laser‐induced etching (LIE) techniques is studied. The contact angles of wetting on the samples with deionized water and methylammonium iodide‐based perovskite solutions are determined. It is found that the element composition and the enlargement area factor of BSi layers have a significant effect on their wettability. When tested with water, the RIE and MACE BSi layers exhibit hydrophobic properties, while the LIE BSi layer demonstrates hydrophilic properties due to the SiOx‐rich surface structures. It is also shown that aging leads to a decrease in the water contact angle. Upon exposure to perovskite solution droplets, BSi layers become highly lyophilic. Based on the Wenzel and Cassie–Baxter models, the mechanisms responsible for the wetting states of the fabricated samples are identified. In the results obtained, valuable insights are provided into the potential of using these layers in tandem perovskite/silicon solar cells.

Isotopic analysis of uranium at the picogram level with single-shot laser induced breakdown spectroscopy

Uranium was measured by laser induced breakdown spectroscopy (LIBS) with a limit of detection of 1.3 picograms with spectral-peak height as the analytical parameter, which shows an improvement of several orders of magnitude compared to other reports in the literature. The improvement is a result of optimizing the choice of the U analytical line, the system hardware, and the light collection and detection efficiency. The research established properties of U line emission (intensity, signal-to-background ratio, isotopic splitting, and spectral interferences) to select an optimum wavelength for analysis. The samples were mock particles from dried, monodispersed U solution droplets (∼65 pL in volume) deposited on Si wafers. LIBS emission spectra from several 235U-enriched samples were measured to demonstrate the performance for isotopic analysis. For isotopic measurements, two masses for total U, 100 pg and 325 pg, were studied. The 235U: 238U isotopic ratio was obtained by peak fitting the LIBS spectra without requiring calibration with the use of enriched standards. Depending on the total U mass and the 235U enrichment, typical relative standard deviations of the isotopic analysis ranged from several percent down to about 1%. Further, the developed method and the reported analytical performance were all based on single-shot LIBS. Overall, the study highlights the potential of LIBS as a robust and sensitive technique for isotopic analysis of U-containing particles.

The Numerical Simulation of Marangoni Problems Employing Multi-phase Parallel SPH Method

When facing microscale problems, the phenomenon of droplet movement caused by temperature gradients is usually attributed to the Marangoni effect. This study first constructed a multiphase smoothed particle fluid dynamics (SPH) system structure, integrating continuous surface force (CSF) model and multiphase model to explore the behavior of droplets under Marangoni effect. To further improve computational efficiency, this study also utilized the Open Multi Processing (OpenMP) parallel computing framework to perform parallel optimization on the SPH algorithm. Subsequently, the effectiveness of the constructed SPH framework in addressing thermal capillary phenomena was verified by simulating the Marangoni migration phenomenon of silicone oil droplets in fluorine solutions. In addition, this study also investigated the polymerization process of two droplets in microchannels under the Marangoni effect, and obtained the complete dynamic changes of droplets from motion to polymerization. During this period, we conducted a detailed analysis of the variation process of the velocity vector field, the spatial distribution of the temperature field, and the evolution characteristics of the surface tension gradient during the droplet movement process, thereby comprehensively revealing how the Marangoni effect drives the phenomenon of droplet movement and aggregation.

Soot aerosols from commercial aviation engines are poor ice-nucleating particles at cirrus cloud temperatures

Abstract. Ice-nucleating particles catalyze ice formation in clouds, affecting climate through radiative forcing from aerosol–cloud interactions. Aviation directly emits particles into the upper troposphere where ice formation conditions are favorable. Previous studies have used proxies of aviation soot to estimate their ice nucleation activity; however, investigations with commercial aircraft soot from modern in-use aircraft engines have not been quantified. In this work, we sample aviation soot particles at ground level from different commercial aircraft engines to test their ice nucleation ability at temperatures ≤228 K as a function of engine thrust and soot particle size. Additionally, soot particles were catalytically stripped to reveal the impact of mixing state on their ice nucleation ability. Particle physical and chemical properties were further characterized and related to the ice nucleation properties. The results show that aviation soot nucleates ice at or above relative humidity conditions required for homogeneous freezing of solution droplets (RHhom). We attribute this to a mesopore paucity inhibiting pore condensation and the sulfur content which suppresses freezing. Only large soot aggregates (400 nm) emitted under 30 %–100 % thrust conditions for a subset of engines (2 out of 10) nucleate ice via pore condensation and freezing. For those specific engines, the presence of hydrophilic chemical groups facilitates the nucleation. Aviation soot emitted at thrust ≥ 100 % (sea level thrust) nucleates ice at or above RHhom. Overall, our results suggest that aviation soot will not contribute to natural cirrus formation and can be used in models to update impacts of soot–cirrus clouds.

Ultrafast self-transportation and efficient separation of organic droplets on semi-conical asymmetric structure

Manipulating oil droplets in an aqueous solution is highly desirable for organic multiphase liquid separation. Despite substantial works in the realm of organic multiphase liquid manipulation and separation, the ultrafast transportation and efficient and precise separation of these liquids, especially those with varied surface tensions, encounters significant challenges due to little driving forces. To address this issue, a semi-conical structure with pine-needlelike features and incorporated wedge-shaped grooves is fabricated, which could support the ultrafast transport and separation of organic droplets. For pre-wetted superhydrophobic surfaces, organic liquids with lower surface tension can be transported at a speed of 305.6 mm/s. The Laplace pressure difference caused by the conical structure determines the direction of transport of organic liquids, and the capillary force caused by flat wedge-shaped grooves increases the transport speed of organic droplets on the surface. Based on the characteristics of “differential” transportation and directional transportation, the separation of mixed organic liquids is realized. This biomimetic design concept will pave a path for microfluidics, liquid manipulation, and the separation of various organic liquids.

Characterizing the Microparticles Deposition Structure and its Photonic Nature in Surfactant-Laden Evaporating Colloidal Sessile Droplets.

This work presents a simple method to create photonic microstructures via the natural evaporation of surfactant-laden colloidal sessile droplets on a flat substrate. In the absence of dissolved surfactant, the evaporating colloidal droplet forms a well-known coffee ring deposition. In contrast, the presence of surfactant leads to the formation of multiple ring structures due to the repetitive pinning-depinning behavior of the droplet contact line (CL). It is found that the multiring structure shows vibrant iridescent structural colors while the coffee ring lacks a photonic nature. This difference in the structural color for the presence and absence of the surfactant is found to be dependent on the arrangement of the particles in the deposition structure. The particle arrangement in the multirings is monolayered and well-ordered. The ordering of the particles is strongly influenced by the particle dynamics, contact angle (CA), and CL dynamics of the evaporating colloidal solution droplet. Furthermore, the iridescent nature of the multiring deposition is demonstrated and explained. The dependence of the multiring deposition structure on the concentration of the dissolved surfactant and the suspended particles is also studied. The findings demonstrate that an intermediate surfactant concentration is desirable for the formation of a multiring structure. Further, the pinning-depinning CL dynamics that causes the formation of the multiring deposition structure is discussed. Finally, we demonstrate the applicability of the approach to smaller droplet volumes.

An Experimental study on steam explosion of multiple droplets in different chemical solutions

Motivated by the interest in steam explosion in chemical solutions and seawater, a series of tests were carried out in the MISTEE facility at KTH to investigate steam explosion characteristics as multiple molten droplets of tin were falling through a coolant pool containing deionized water, boric acid solution, neutral solution of boric acid and sodium phosphate, and seawater, separately. The experimental results revealed distinct and complex characteristics of steam explosion of multiple droplets, which were not observed in previous single-droplet steam explosion experiments. The tin melt samples of 5 g and 20 g were employed to formulate different numbers of multiple droplets. In the test with 5 g melt, steam explosion was more energetic at a deeper explosion location − a similar trend found in the single-droplet steam explosion test with 1 g melt. However, the test of 20 g melt did not show a clear trend in a wide range of explosion depth. The peak pressure and impulse increased with increasing mass of melt sample. The steam explosion occurred more closely to the coolant pool surfaces in the seawater and chemical solutions than in deionized water. Steam explosion intensity was significantly reduced in a neutral solution containing 1.2 wt.% boric acid and sodium phosphate. The influence of the chemical solutions on steam explosion was diminishing in the tests with multiple droplets.

Ligand-Assisted self-assembly of colloidal Ag2S nanoparticles

Over the last decade, great attention of researchers has been focused on nanoscale self-assembly due to increasingly technology-relevant applications. Pattern formation by colloidal droplet evaporation is one of the fascinating subjects to study. A deep understanding of physical and chemical processes of the deposited structure formation allows the development of bioprinting methods, nanoarchitectures for optics and electronics, methods for detecting the state of peptides, proteins, etc. In the present work, the effect of organic ligands (MPS, BSA, GSH, EDTA, TG) on Ag2S NP self-assembly during solution droplet evaporation was investigated. The synthesis conditions were optimized to minimize or neglect the contribution of surface roughness, substrate thermal conductivity, NP shape and size, type of solvent. Properties of a stabilizer, such as molecular length, reactivity, tendency to polycondensate or chelate, and their relative concentration affect the nanoparticle–nanoparticle interactions, which results in several types of pattern formation. The dominant forces in different regions of the evaporated droplet via ligand were discussed. The models of pattern formation were proposed. Thus, depending on the ligand, Ag2S NPs tend to form rings (MPS, BSA), concentric rings (BSA), net like structures (TG), and chains (MPS, TG). In addition, it was shown that replacing water with deuterium can significantly change self-organized architectures.

Determination of the oil absorption value of inorganic powder by tracer-assisted headspace gas chromatography

This paper reports a method for determining the oil absorption value of inorganic powder based on tracer-assisted headspace gas chromatographic (HS-GC) technique. The method was carried out by adding 25 μL droplet of toluene-Dioctyl Phthalate solution onto the surface of 1.0 g inorganic powder, then sealing the headspace vial and shaking it to make the powder spherical. The amount of toluene that not been adsorbed by inorganic powder was quantified using HS-GC with the optimal equilibrium temperature and time conditions of 100 °C and 7 min, respectively. A new mathematical model shows that the oil absorption value can be determined from the signal of toluene. The results show that the employed method has good precision (the relative standard deviation < 3.6 %) and accuracy (R2 = 0.993). This method is simple and accurate, and can be an reliable tool for testing the oil absorption value of inorganic powder sample.

Deposition Patterns Induced by the Evaporation of the Cyclic Diblock Copolymer Solution Droplet

Deposition Patterns Induced by the Evaporation of the Cyclic Diblock Copolymer Solution Droplet

Micro-sized droplet formation by interaction between dielectric barrier discharge and liquid

Liquid atomization technology is one of the applications in various fields of modern industry because it improves reactivity, diffusion, and permeability of liquids. However, existing atomization technologies are severely limited by the physical and chemical properties of the solution or the object to be treated, and there is a growing need to develop atomization technologies that solve these problems. We have developed a device that atomizes liquids to the nanoscale based on the interaction with a dielectric barrier discharge, which enables the atomization of various types of solutions, including water-based and oil-based solutions. Herein, we report the results of visualizing the dynamics of liquid atomization using a high-speed camera. The device atomizes solutions in three modes: instability of the solution jet; physical fragmentation of the solution droplets by the impact of the plasma streamer; and collapse of the droplet surface and generation of a smoke-like mist during the streamer ejection from the solution droplet. The combined and repeated action of these three modes on the produced microdroplets is expected to result in nano-sized mists of the solution.

Extremely Monodispersed Micrometer-Scale Spherical Particle Synthesis of Ag Inside a Microdroplet Vaporizing in Plasma.

Spherical Ag particles have received considerable attention because of their unique properties as well as their applications in various fields. In the present study, the synthesis of micrometer-scale spherical Ag particles with an extremely narrow size distribution is demonstrated using a simple capacitively coupled atmospheric-pressure plasma reactor with an inkjet head. Droplets of a Ag nitrate aqueous solution are ejected from the inkjet head to synthesize Ag particles. The gaseous temperature in the reactor is adjusted such that Ag can be melted with a negligibly small vapor pressure. These particles exhibit a spherical shape with a smooth surface. The mean diameter of the particles is 0.91 ± 0.013 μm with a small coefficient of variation of 1.5%, the smallest value ever reported for Ag particles of less than 1 μm. The grain sizes of the particles are larger than 100 nm, as expected from the broadening of the X-ray diffraction peaks. The excellent monodispersity of the particles synthesized by this method may expand the applications with micrometer-scale spheres such as ball spacer, microsized ball bearing, and inks for printed electronics.