arXiv subjects

Xuehua Zhang

Publications and source records attributed to Xuehua Zhang.

At least 55 records · Page 3Linked to original sources

arXiv2020

Integrated nanoextraction and colorimetric reactions in surface nanodroplets for combinative analysis

A combinative approach for chemical analysis makes it possible to distinguish a mixture of a large number of compounds from other mixtures in a single step. This work demonstrates a combinative analysis approach by using surface nanodroplets for integrating nanoextraction and colorimetric reactions for the identification of multi-component mixtures. The model analytes are acidic compounds dissolved in oil that are extracted into aqueous droplets on a solid substrate. The proton from acid dissociation reacts with the halochromic chemical compounds inside the droplets, leading to the color change of the droplets. The rate of the colorimetric reaction exhibits certain specificity for the acid type, distinguishing acid mixtures with the same pH value. The underlying principle is that the acid transport rate is associated with the partition coefficient and the dissociation constant of the acid, in addition to the concentration in oil. As a demonstration, we showed that droplet-based combinative analysis can be applied for anti-counterfeiting of various alcoholic spirits by comparing decolor time of organic acid mixtures in the spirits. The readout can be done by using a common hand-hold mobile phone.

cond-mat.soft↗

arXiv2020

Oiling-out Crystallization of Beta-Alanine onSolid Surfaces Controlled by Solvent Exchange

Droplet formation in oiling-out crystallization has important implication for separation and purification of pharmaceutical active ingredients by using an antisolvent. In this work, we report the crystallization processes of oiling-out droplets on surfaces during solvent exchange. Our model ternary solution is beta-alanine dissolved in isopropanol and water mixture. As the antisolvent isopropanol displaced the alanine solution pre-filled in a microchamber, liquid-liquid phase separation occurred at the mixing front. The alanine-rich subphase formed surface microdroplets that subsequently crystallized with progression of solvent exchange. We find that the flow rates have significant influence on the droplet size, crystallization process, and growth rate, and final morphology of the crystals. At fast flow rates the droplets solidified rapidly and formed spherical-cap structures resembling the shape of droplets, in contrast to crystal microdomains or thin films formed at slow flow rates. On a highly hydrophilic surface, the crystals formed thin film without droplets formed on the surface. We further demonstrated that by the solvent exchange crystals can be formed by using a stock solution with a very low concentration of the precursor, and the as-prepared crystals can be used as seeds to trigger crystallization in bulk solution. Our results suggest that the solvent exchange has the potential to be an effective approach for controlling oiling-out crystallization, which can be applied in wide areas, such as separation and purification of many food, medical, and therapeutic ingredients.

cond-mat.soft↗

arXiv2020

Accelerated Formation of H2 Nanobubbles from a Surface Nanodroplet Reaction

The compartmentalization of chemical reactions within droplets has advantages in low costs, reduced consumption of reagents and increased throughput. Reactions in small droplets have also been shown to greatly accelerate the rate of many chemical reactions. The accelerated growth rate of nanobubbles from nanodroplet reactions is demonstrated in this work. The gaseous products from the reaction at the nanodroplet surface promoted nucleation of hydrogen nanobubbles within multiple organic liquid nanodroplets. The nanobubbles were confined within the droplets and selectively grew and collapsed at the droplet perimeter, as visualized by microscopy with high spatial and temporal resolutions. The growth rate of the bubbles was significantly accelerated within small droplets and scaled inversely with droplet radius. The acceleration was attributed to confinement from the droplet volume and effect from the surface area on the interfacial chemical reaction for gas production. The results of this study provide further understanding for applications in droplet enhanced production of nanobubbles and the on-demand liberation of hydrogen.

cond-mat.soft↗

arXiv2020

Speeding up biphasic reactions with surface nanodroplets

Biphasic chemical reactions compartmentalized in small droplets offer advantages, such as streamlined procedures for chemical analysis, enhanced chemical reaction efficiency and high specificity of conversion. In this work, we experimentally and theoretically investigate the rate for biphasic chemical reactions between acidic nanodroplets on a substrate surface and basic reactants in a surrounding bulk flow. The reaction rate is measured by droplet shrinkage as the product is removed from the droplets by the flow. In our experiments, we determine the dependence of the reaction rate on the flow rate and the solution concentration. The theoretical analysis predicts that the life time $τ$ of the droplets scales with Peclet number $Pe$ and the reactant concentration in the bulk flow $c_{re,bulk}$ as $τ\propto Pe^{-3/2}c_{re,bulk}^{-1}$, in good agreement with our experimental results. Furthermore, we found that the product from the reaction on an upstream surface can postpone the droplet reaction on a downstream surface, possibly due to the adsorption of interface-active products on the droplets in the downstream. The time of the delay decreases with increasing $Pe$ of the flow and also with increasing reactant concentration in the flow, following the scaling same as that of the reaction rate with these two parameters. Our findings provide insight for the ultimate aim to enhance droplet reactions under flow conditions.

cond-mat.soft↗

arXiv2020

Viscosity-Mediated Growth and Coalescence of Surface Nanodroplets

Solvent exchange is a simple method to produce surface nanodroplets on a substrate for a wide range of applications by displacing a solution of good solvent, poor solvent and oil (Solution A) by a poor solvent (Solution B). In this work, we show that the growth and coalescence of nanodroplets on a homogeneous surface is mediated by the viscosity of the solvent. We show that at high flow rates of viscous Solution B, the final droplet volume deviates from the scaling law that correlates final droplet volume to the flow rate of non-viscous Solution B, reported in previous work. We attribute this deviation to a two-regime growth in viscous Solution B, where transition from an initial, fast regime to a final slow regime influenced by the flow rate. Moreover, viscous solution B hinders the coalescence of growing droplets, leading to a distinct bimodal distribution of droplet size with stable nanodroplets, in contrast to a continuous size distribution of droplets in non-viscous case. We demonstrate that the group of small droplets produced in high viscosity environment may be applied for enhanced fluorescence detection with higher sensitivity and shorter response time. The finding of this work can potentially be applied for mediating the size distribution of surface nanodroplets on homogeneous surface without templates.

cond-mat.soft↗

arXiv2020

Physicochemical Hydrodynamics of Droplets out of Equilibrium: A Perspective Review

Droplets abound in nature and technology. In general, they are multicomponent, and, when out of equilibrium, with gradients in concentration, implying flow and mass transport. Moreover, phase transitions can occur, with either evaporation, solidification, dissolution, or nucleation of a new phase. The droplets and their surrounding liquid can be binary, ternary, or contain even more components, and with several even in different phases. In the last two decades the rapid advances in experimental and numerical fluid dynamical techniques has enabled major progress in our understanding of the physicochemical hydrodynamics of such droplets, further narrowing the gap from fluid dynamics to chemical engineering and colloid & interfacial science and arriving at a quantitative understanding of multicomponent and multiphase droplet systems far from equilibrium, and aiming towards a one-to-one comparison between experiments and theory or numerics. This review will discuss various examples of the physicochemical hydrodynamics of droplet systems far from equilibrium and our present understanding of them. These include immiscible droplets in a concentration gradient, coalescence of droplets of different liquids, droplets in concentration gradients emerging from chemical reactions (including droplets as microswimmers) and phase transitions such as evaporation, solidification, dissolution, or nucleation, and droplets in ternary liquids, including solvent exchange, nano-precipitation, and the so-called ouzo effect. We will also discuss the relevance of the physicochemical hydrodynamics of such droplet systems for many important applications, including in chemical analysis and diagnostics, microanalysis, pharmaceutics, synthetic chemistry and biology, chemical and environmental engineering, the oil and remediation industries, inkjet-printing, for micro- and nano-materials, and in nanotechnolgoy.

physics.flu-dyn↗

arXiv2020

Gas-Vapor Interplay in Plasmonic Bubble Shrinkage

The understanding of the shrinkage dynamics of plasmonic bubbles formed around metallic nanoparticles immersed in liquid and irradiated by a resonant light source is crucial for the usage of these bubbles in numerous applications. In this paper we experimentally show and theoretically explain that a plasmonic bubble during its shrinkage undergoes two different phases: first, a rapid partial bubble shrinkage governed by vapor condensation and, second, a slow diffusion-controlled bubble dissolution. The history of the bubble formation plays an important role in the shrinkage dynamics during the first phase, as it determines the gas-vapor ratio in the bubble composition. Higher laser powers lead to more vaporous bubbles, while longer pulses and higher dissolved air concentrations lead to more gaseous bubbles. The dynamics of the second phase barely depends on the history of bubble formation, i.e. laser power and pulse duration, but strongly on the dissolved air concentration, which defines the concentration gradient at the bubble interface. Finally, for the bubble dissolution in the second phase, with decreasing dissolved air concentration, we observe a gradual transition from a $R(t) \propto (t_0 - t) ^{1/3}$ scaling law to a $R(t) \propto (t_0 - t) ^{1/2}$ scaling law, where $t_0$ is the lifetime of the bubble and theoretically explain this transition.

physics.flu-dyn↗

arXiv2020

Morphology of Evaporating Sessile Microdroplets on Lyophilic Elliptical Patches

The evaporation of droplets occurs in a large variety of natural and technological processes such as medical diagnostics, agriculture, food industry, printing, and catalytic reactions. We study the different droplet morphologies adopted by an evaporating droplet on a surface with an elliptical patch with a different contact angle. We perform experiments to observe these morphologies and use numerical calculations to predict the effects of the patched surfaces. We observe that tuning the geometry of the patches offers control over the shape of the droplet. In the experiments, the drops of various volumes are placed on elliptical chemical patches of different aspect ratios and imaged in 3D using laser scanning confocal microscopy, extracting the droplets shape. In the corresponding numerical simulations, we minimize the interfacial free energy of the droplet, by employing Surface Evolver. The numerical results are in good qualitative agreement with our experimental data and can be used for the design of micropatterned structures, potentially suggesting or excluding certain morphologies for particular applications. However, the experimental results show the effects of pinning and contact angle hysteresis, which are obviously absent in the numerical energy minimization. The work culminates with a morphology diagram in the aspect ratio vs relative volume parameter space, comparing the predictions with the measurements.

cond-mat.soft↗

arXiv2020

Solvent Exchange in a Hele-Shaw Cell Universality of Surface Nanodroplet Nucleation

Solvent exchange (also called solvent shifting or Ouzo effect) is a generally used bottom-up process to mass-produce nanoscale droplets. In this process, a good solvent for some oil is displaced by a poor one, leading to oil nanodroplet nucleation and subsequent growth. Here we perform this process on a hydrophobic substrate so that sessile droplets so-called surface nanodroplets-develop, following the work of Zhang et al. [Zhang, X.; Lu, Z.; Tan, H.; Bao, L.; He, Y.; Sun, C.; Lohse, D. Proc. Natl. Acad. Sci. U.S.A. 2015, 122, 9253-9257]. In contrast to what was done in that paper, we chose a very well-controlled Hele-Shaw geometry with negligible gravitational effects, injecting the poor solvent in the center of the Hele-Shaw cell, and characterize the emerging nanodroplets as a function of radial distance and flow rates. We find that the mean droplet volume per area _area strongly depends on the local Peclet number Pe and follows a universal scaling law _area~Pe^(3/4). Moreover, the probability distribution function of the droplet volume strongly depends on the local Pe as well, regardless of the flow rates and radial distance, giving strong support to the theoretical model of the solvent exchange process developed in Zhang et al.'s work.

cond-mat.soft↗

arXiv2020

Diffusive interaction of multiple surface nanobubbles and nanodroplets: shrinkage, growth, and coarsening

Surface nanobubbles are nanoscopic spherical-cap shaped gaseous domains on immersed substrates which are stable, even for days. After the stability of a {\it single} surface nanobubble has been theoretically explained, i.e. contact line pinning and gas oversaturation are required to stabilize them against diffusive dissolution [Lohse and Zhang, Phys.\ Rev.\ E 91, 031003 (R) (2015)], here we focus on the {\it collective} diffusive interaction of {\it multiple} nanobubbles. For that purpose we develop a finite difference scheme for the diffusion equation with the appropriate boundary conditions and with the immersed boundary method used to represent the growing or shrinking bubbles. After validation of the scheme against the exact results of Epstein and Plesset for a bulk bubble [J. Chem. Phys. 18, 1505 (1950)] and of Lohse and Zhang for a surface bubble, the framework of these simulations is used to describe the coarsening process of competitively growing nanobubbles. The coarsening process for such diffusively interacting nanobubbles slows down with advancing time and thus increasing bubble distance. The present results for surface nanobubbles are also applicable for immersed surface nanodroplets, for which better controlled experimental results of the coarsening process exist.

physics.flu-dyn↗

arXiv2020

Plasmonic Bubble Nucleation and Growth in Water: Effect of Dissolved Air

Under continuous laser irradiation, noble metal nanoparticles immersed in water can quickly heat up, leading to the nucleation of so-called plasmonic bubbles. In this work, we want to further understand the bubble nucleation and growth mechanism. In particular, we quantitatively study the effect of the amount of dissolved air on the bubble nucleation and growth dynamics, both for the initial giant bubble, which forms shortly after switching on the laser and is mainly composed of vapor, and for the final life phase of the bubble, during which it mainly contains air expelled from water. We found that the bubble nucleation temperature depends on the gas concentration: the higher the gas concentration, the lower the bubble nucleation temperature. Also, the long-term diffusiondominated bubble growth is governed by the gas concentration. The radius of the bubbles grows as R(t)~t^1/3 for airequilibrated and air-oversaturated water. In contrast, in partially degassed water, the growth is much slower since, even for the highest temperature we achieve, the water remains undersaturated.

physics.flu-dyn↗

arXiv2020

Time-Resolved In Situ Liquid-Phase Atomic Force Microscopy and Infrared Nanospectroscopy during the Formation of Metal-Organic Framework Thin Films

Metal-organic framework (MOF) thin-films show unmatched promise as smart membranes and photo-catalytic coatings. However, their nucleation and growth resulting from intricate molecular assembly processes are not well understood, yet crucial to control the thin-film properties. Here, we directly observe the nucleation and growth behaviour of HKUST-1 thin-films by real-time in-situ AFM at different temperatures in the Cu-BTC solution. In combination with ex-situ infrared (nano-)spectroscopy, synthesis at 25°C reveals initial nucleation of rapidly growing HKUST-1 islands surrounded by a continuously nucleating, but slowly growing HKUST-1 carpet. Monitoring at 13°C and 50°C shows the strong impact of temperature on thin-film formation, resulting in (partial) nucleation and growth inhibition. The nucleation and growth mechanisms as well as their kinetics provide insights to aid in future rational design of MOF thin-films.

physics.chem-ph↗

arXiv2020

Entrapment and Dissolution of Microbubbles Inside Microwells

The formation and evolution of immersed surface micro- and nanobubbles are essential in various practical applications, such as the usage of superhydrophobic rematerials, drug delivery, and mineral flotation. In this work, we investigate the entrapment of microbubbles on a hydrophobic surface, structured with microwells, when water flow passes along, and the subsequent microbubble dissolution. At entrapment, the microbubble is initially pinned at the edge of the microwell. At some point, the three-phase contact line detaches from one side of the edge and separates from the wall, after which it further recedes. We systematically investigate the evolution of the footprint diameter and the contact angle of the entrapped microbubbles, which reveals that the dissolution process is in the constant contact angle mode. By varying the gas undersaturation level, we quantify how a high gas undersaturation enhances the dissolution process, and compare with simplified theoretical predictions for dissolving bubbles on a plane surface. We find that geometric partial blockage effects of the diffusive flux out of the microbubble trapped in the microwell lead to reduced dissolution rates.

physics.flu-dyn↗

arXiv2020

Splitting droplet through coalescence of two different three-phase contact lines

Moving contact lines of more than two phases dictate a large number of interfacial phenomena. Despite its significance to fundamental and applied processes, the contact lines at a junction of four-phases (two immiscible liquids, solid and gas) have been addressed only in a few investigations. Here, we report an intriguing phenomenon that follows after the four phases of oil, water, solid and gas make contact through the coalescence of two different three-phase contact lines. We combine experimental study and theoretical analysis to reveal and rationalize the dynamics exhibited upon the coalescence between the contact line of a micron-sized oil droplet and the receding contact line of a millimetre-sized water drop that covers the oil droplet on the substrate. We find that after the coalescence a four-phase contact line is formed for a brief period. However, this quadruple contact line is not stable, leading to a `droplet splitting' effect and eventual expulsion of the oil droplet from the water drop. We then show that the interfacial tension between the different phases and the viscosity of oil droplet dictate the splitting dynamics. More viscous oils display higher resistance to the extreme deformations of the droplet induced by the instability of the quadruple contact line and no droplet expulsion is observed for such cases.

cond-mat.soft↗

arXiv2019

Giant and explosive plasmonic bubbles by delayed nucleation

When illuminated by a laser, nano particles immersed in water can very quickly and strongly heat up, leading to the nucleation of so called vapor bubbles, which have huge application potential in e.g. solar light-harvesting, catalysis, and for medical applications.Whilst the long-time behavior of such bubbles has been well-studied, here, by employing ultra-high-speed imaging, we reveal the nucleation and early life phase of these bubbles. After some delay time after beginning of the illumination, a giant bubble explosively grows, up to a maximal radius of 80 um, and collapses again within 200 us (bubble life phase 1). The maximal bubble volume remarkably increases with decreasing laser power P. To explain this behavior, we measure the delay time from the beginning of the illumination up to nucleation,which drastically increases with decreasing laser power, leading to less total dumped energy . This dumped energy E shows a universal linear scaling relation. This finding supports that the initial giant bubble is a pure vapor bubble. In contrast, the delay time does depend on the gas concentration of the water, as gas pockets in the water facilitate an earlier vapor bubble nucleation, which leads to smaller delay times and lower bubble nucleation temperatures. After the collapse of the initial giant bubbles, first much smaller oscillating bubbles form out of the remaining gas nuclei (bubble life phase 2, up to typically 10 ms). Subsequently the known vaporization dominated growth phase takes over and the bubble stabilizes (life phase 3). In the final life phase 4 the bubble slowly grows by gas expelling due to heating of the surrounding. Our findings on the explosive growth and collapse during the early life phase of a vapor bubble have strong bearings on possible applications of such bubbles, affecting their risk assessment.

physics.app-ph↗

arXiv2019

Plasmonic Bubbles in n-Alkanes

In this paper we study the formation of microbubbles upon the irradiation of an array of plasmonic Au nanoparticles with a laser in n-alkanes ($C_{n}H_{2n+2}$, with n = 5-10). Two different phases in the evolution of the bubbles can be distinguished. In the first phase, which occurs after a delay time τd of about 100 μs, an explosive microbubble, reaching a diameter in the range from 10 μm to 100 μm, is formed. The exact size of this explosive microbubble barely depends on the carbon chain length of the alkane, but only on the laser power $P_l$. With increasing laser power, the delay time prior to bubble nucleation as well as the size of the microbubble both decrease. In the second phase, which sets in right after the collapse of the explosive microbubble, a new bubble forms and starts growing due to the vaporization of the surrounding liquid, which is highly gas rich. The final bubble size in this second phase strongly depends on the alkane chain length, namely it increases with decreasing number of carbon atoms. Our results have important implications for using plasmonic heating to control chemical reactions in organic solvents.

physics.chem-ph↗

arXiv2018

A bouncing oil droplet in a stratified liquid and its sudden death

Droplets can self-propel when immersed in another liquid in which a concentration gradient is present. Here we report the experimental and numerical study of a self-propelling oil droplet in a vertically stratified ethanol/water mixture: At first, the droplet sinks slowly due to gravity, but then, before having reached its density matched position, jumps up suddenly. More remarkably, the droplet bounces repeatedly with an ever increasing jumping distance, until all of a sudden it stops after about 30 min. We identify the Marangoni stress at the droplet/liquid interface as responsible for the jumping: its strength grows exponentially because it pulls down ethanol-rich liquid, which in turn increases its strength even more. The jumping process can repeat because gravity restores the system. Finally, the sudden death of the jumping droplet is also explained. Our findings have demonstrated a type of prominent droplet bouncing inside a continuous medium with no wall or sharp interface.

physics.flu-dyn↗

arXiv2018

Microdroplets nucleation by dissolution of a multicomponent drop in a host liquid

Multicomponent liquid drops in a host liquid are very relevant in various technological applications. Their dissolution or growth dynamics is complex. Differences in solubility between the drop components combined with the solutal Marangoni effect and natural convections contribute to this complexity, which can be even further increased in combination with the ouzo effect, i.e., the spontaneous nucleation of microdroplets due to composition-dependent miscibilities in a ternary system. The quantitive understanding of this combined process is important for applications in industry, particularly for modern liquid-liquid microextraction processes. In this work, as a model system, we experimentally and theoretically explore water/ethanol drops dissolving in anethole oil. During the dissolution, we observed two types of microdroplets nucleation, namely water microdroplet nucleation in the surrounding oil at drop midheight and oil microdroplet nucleation in the aqueous drop, again at midheight. The nucleated oil microdroplets are driven by Marangoni flows inside the aqueous drop and evolve into microdroplets rings. A one-dimensional multiphase and multicomponent diffusion model in combination with thermodynamical equilibrium theory is proposed to predict the behavior of spontaneous emulsification, i.e. the microdroplet nucleation, that is triggered by diffusion. A scale analysis together with experimental investigations of the fluid dynamics of the system reveals that both the solutal Marangoni flow inside the drop and the buoyancy-driven flow in the host liquid influence the diffusion-triggered emulsification process. Our work provides a physical understanding of the microdroplet nucleation by dissolution of a multicomponent drop in a host liquid.

physics.flu-dyn↗