Controlling the Localization of Liquid Droplets in Polymer Matrices by Evaporative Lithography

Localized inclusions of liquids provide solid materials with many functions, such as self‐healing, secretion, and tunable mechanical properties, in a spatially controlled mode. However, a strategy to control the distribution of liquid droplets in solid matrices directly obtained from a homogeneous solution has not been reported thus far. Herein, we describe an approach to selectively localize liquid droplets in a supramolecular gel directly obtained from its solution by using evaporative lithography. In this process, the formation of droplet‐embedded domains occurs in regions of free evaporation where the non‐volatile liquid is concentrated and undergoes a phase separation to create liquid droplets prior to gelation, while a homogeneous gel matrix is formed in the regions of hindered evaporation. The different regions of a coating with droplet embedment patterns display different secretion abilities, enabling the control of the directional movement of water droplets.     

Simultaneous generation of multiple aqueous droplets in a microfluidic device

This paper describes a microfluidic platform for the on-demand generation of multiple aqueous droplets, with varying chemical contents or chemical concentrations, for use in droplet based experiments. This generation technique was developed as a complement to existing techniques of continuous-flow (streaming) and discrete-droplet generation by enabling the formation of multiple discrete droplets simultaneously. Here sets of droplets with varying chemical contents can be generated without running the risk of cross-contamination due to the isolated nature of each supply inlet. The use of pressure pulses to generate droplets in parallel is described, and the effect of droplet size is examined in the context of flow rates and surfactant concentrations. To illustrate this technique, an array of different dye-containing droplets was generated, as well as a set of droplets that displayed a concentration gradient of a fluorescent dye.     

Droplets wetting on filament rails: Surface energy and morphology transition

The morphology of liquid droplets wetting on filaments depends on the filament configuration, droplet volume, and contact angle. A stable morphology is the one that minimizes the potential energy of the droplet–filament system, while morphology transition may happen when an intermediate state exists which corresponds to a higher potential energy. This paper aims to explore such morphology transition of droplet wetting on filament rails made of two parallel identical microfilaments. Detailed numerical simulations were performed to extract the surface energy of the droplet–filament system at varying filament spacings, droplet volumes, and contact angles. Critical conditions of the morphology transition between two symmetrical wetting morphologies (i.e., liquid droplet bridge and barrel-shaped droplet) were determined. A family of characteristic curves in terms of the dimensionless droplet volume vs the filament spacing at varying contact angles was obtained, which can be used as a universal law to govern the morphology transition for such droplet–filament rail systems. The results and concepts presented in this work can be extended to broad wetting systems and utilized for the analysis and design of microfluidic devices and testers based on droplet–filament systems.     

Photon control of liquid motion on reversibly photoresponsive surfaces

The movement of a liquid droplet on a flat surface functionalized with a photochromic azobenzene may be driven by the irradiation of spatially distinct areas of the drop with different UV and visible light fluxes to create a gradient in the surface tension. In order to better understand and control this phenomenon, we have measured the wetting characteristics of these surfaces for a variety of liquids after UV and visible light irradiation. The results are used to approximate the components of the azobenzene surface energy under UV and visible light using the van Oss-Chaudhury-Good equation. These components, in combination with liquid parameters, allow one to estimate the strength of the surface interaction as given by the advancing contact angle for various liquids. The azobenzene monolayers were formed on smooth air-oxidized Si surfaces through 3-aminopropylmethyldiethoxysilane linkages. The experimental advancing and receding contact angles were determined following azobenzene photoisomerization under visible and ultraviolet (UV) light. Reversible light-induced advancing contact-angle changes ranging from 8 to 16 degrees were observed. A large reversible change in contact angle by photoswitching of 12.4 degrees was achieved for water. The millimeter-scale transport of 5 microL droplets of certain liquids was achieved by creating a spatial gradient in visible/UV light across the droplets. A criterion for light-induced motion of droplets is shown to be consistent with the response of a variety of liquids. The type of light-driven fluid movement observed could have applications in microfluidic devices.     

Controlled Directional Water‐Droplet Spreading on a High‐Adhesion Surface

Controlled directional spreading of a droplet on a smart high‐adhesion surface was made possible by simply controlling anodic oxidation. The wettability gradient of the surface was controlled from 0.14 to 3.38° mm^?1 by adjusting the anodic oxidation conditions. When a water droplet made contact with the substrate, the droplet immediately spread in the direction of the wettability gradient but did not move in other directions, such as those perpendicular to the gradient direction, even when the surface was turned upside down. The spreading behavior was mainly controlled by the wettability gradient. Surfaces with a V‐ or inverse‐V‐shaped wettability gradient were also formed by the same method, and two droplets on these surfaces spread either toward or away from one another as designed. This method could be used to oxidize many conductive substrates (e.g., copper, aluminum) to form surfaces with variously shaped wettability gradients. It has potential for application in microfluidic devices.     

Anomalous Lehmann Rotation of Achiral Nematic Liquid Crystal Droplets Trapped under Linearly Polarized Optical Tweezers

Continuous rotation of a cholesteric droplet under the heat gradient was observed by Lehmann in 1900. This phenomenon, the so-called Lehmann effect, consists of unidirectional rotation around the heat flux axis. We investigate this gradient heat effect using infrared laser optical tweezers. By applying single trap linearly polarized optical tweezers onto a radial achiral nematic liquid crystal droplet, trapping of the droplet was performed. However, under a linearly polarized optical trap, instead of stable trapping of the droplet with slightly deformed molecular directors along with a radial hedgehog defect, anomalous continuous rotation of the droplet was observed. Under low power laser trapping, the droplet appeared to rotate clockwise. By continuously increasing the laser power, a stable trap was observed, followed by reverse directional rotation in a higher intensity laser trap. Optical levitation of the droplet in the laser beam caused the heat gradient, and a breaking of the symmetry of the achiral nematic droplet. These two effects together led to the rotation of the droplet under linearly polarized laser trapping, with the sense of rotation depending on laser power.     

Chembio extraction on a chip by nanoliter droplet ejection

This paper describes a novel liquid separation technique for chembio extraction by an ultrasonic nanoliter-liquid-droplet ejector built on a PZT sheet. This technique extracts material from an aqueous two-phase system (ATPS) in a precise amount through digital control of the number of nanoliter droplets, without any mixing between the two liquids in the ATPS. The ultrasonic droplet ejector uses an acoustic streaming effect produced by an acoustic beam focused on the liquid surface, and ejects liquid droplets only from the liquid surface without disturbing most of the liquid below the surface. This unique characteristic of the focused acoustic beam is perfect (1) for separating a top-layer liquid (from the bulk of liquid) that contains particles of interest or (2) for recovering a top-layer liquid that has different phase from a bottom-layer liquid. Three kinds of liquid extraction are demonstrated with the ultrasonic droplet ejector: (1) 16 microl of top layer in Dextran-polyethylene glycol-water ATPS (aqueous two-phase system) is recovered within 20 s; (2) micron sized particles that float on water surface are ejected out with water droplets; and (3) oil layer on top of water is separated out.     

Stochastic diffusion interactions and coarsening in a system of droplets growing from a supersaturated gas mixture

In this work we study diffusion interactions among liquid droplets growing in stochastic population by condensation from supersaturated binary gas mixture. During the postnucleation transient regime collective growth of liquid droplets competing for the available water vapor decreases local supersaturation leading to the increase of critical radius and the onset of coarsening process. In coarsening regime the growth of larger droplets is prevailing noticeably broadening the droplet size-distribution function when the condensation process becomes more intensive than the supersaturation yield. Modifications in the kinetic equation are discussed and formulated for a stochastic population of liquid droplets when diffusional interactions among droplets become noteworthy. The kinetic equation for the droplet size-distribution function is solved together with field equations for the mass fraction of disperse liquid phase, mass fraction of water vapor component of moist air, and temperature during diffusion-dominated regime of droplet coarsening. The droplet size and mass distributions are found as functions of the liquid volume fraction, showing considerable broadening of droplet spectra. It is demonstrated that the effect of latent heat of condensation considerably changes coarsening process. The coarsening rate constant, the droplet density (number of droplets per unit volume), the screening length, the mean droplet size, and mass are determined as functions of the temperature, pressure, and liquid volume fraction.     

Highly productive droplet formation by anisotropic elongation of a thread flow in a microchannel

We developed a microfluidic device to form monodisperse droplets with high productivity by anisotropic elongation of a thread flow, defined as a threadlike flow of a dispersed liquid phase in a flow of an immiscible, continuous liquid phase. The thread flow was anisotropically elongated in the depth direction in a straight microchannel with a step, where the microchannel depth changed. Consequently, the elongated thread flow was given capillary instability (Rayleigh-Plateau instability) and was continuously transformed into monodisperse droplets at the downstream area of the step in the microchannel. We examined the effects of the flow rates of the dispersed phase and the continuous phase on the droplet formation behavior, including the droplet diameter and droplet formation frequency. The droplet diameter increased as the fraction of the dispersed-phase flow rate relative to the total flow rate increased and was independent of the total flow rate. The droplet formation frequency proportionally increased with the total flow rate at a constant dispersed-phase flow rate fraction. These results are explained in terms of a mechanism similar to that of droplet formation from a cylindrical liquid thread flow by Rayleigh-Plateau instability. The microfluidic device described was capable of forming monodisperse droplets with a 160-microm average diameter and 3-microm standard deviation at a droplet formation frequency of 350 droplets per second from a single thread flow. The highest total flow rate achieved was 6 mL/h using the present device composed of a straight microchannel with a step. We also demonstrated parallel droplet formation by anisotropic elongation of multiple thread flows; the process was applied to form W/O and O/W droplets. The highly productive droplet formation process presented in this study is expected to be useful for future industrial applications.     

基于超声振动的微液滴生成装置设计与实验研究

设计了一种基于V型直线超声电机驱动的微液滴生成装置用于制备具有微米级尺寸的微液滴.此装置由基于V型直线超声电机驱动的微液滴生成部件、基于V型直线超声电机的三维位移控制平台和基于压电振子的微液滴分离部件组成.其中,生成部件包含超声电机、医用注射器、硅胶软管和自制的玻璃基微喷嘴.利用控制器驱动直线超声电机高精度地移动,由滑台推动注射器,在玻璃基喷嘴尖端产生附着的微小液滴;再利用压电振子激发杆状喷嘴的固有振型,使得附着的液滴克服粘性力从微喷嘴尖端分离,落在一定的范围内, 并计算生成的球形微液滴的半径.以蒸馏水作为初始液体,探究此装置生成的微液滴的特性.研究结果表明,蒸馏水在直线电机的精密驱动下,在微喷嘴尖端形成附着的球冠状液滴.通过分离部件的振动,附着的液滴克服自身的粘性力从喷嘴尖端分离, 形成球形液滴,通过测量得出此装置生成的球形液滴的半径小于40 μm.     

Tunable wetting mechanism of polypyrrole surfaces and low-voltage droplet manipulation via redox

This paper presents the experimental results and analyses on a controlled manipulation of liquid droplets upon local reduction and oxidation (redox) of a smart polymer-dodecylbenzenesulfonate doped polypyrrole (PPy(DBS)). The electrochemically tunable wetting property of PPy(DBS) permitted liquid droplet manipulation at very low voltages (-0.9 to 0.6 V). A dichloromethane (DCM) droplet was flattened upon PPy(DBS) reduction. It was found that the surface tension gradient across the droplet contact line induced Marangoni stress, which caused this deformation. Further observation of PPy(DBS)'s color change upon the redox process confirmed that the surface tension gradient was the driving force for the droplet shape change.     

Droplet motion on designed microtextured superhydrophobic surfaces with tunable wettability

Superhydrophobic surfaces have shown promising applications in microfluidic systems as a result of their water-repellent and low-friction properties over the past decade. Recently, designed microstructures have been experimentally applied to construct wettability gradients and direct the droplet motion. However, thermodynamic mechanisms responsible for the droplet motion on such regular rough surfaces have not been well understood such that at present specific guidelines for the design of tunable superhydrophobic surfaces are not available. In this study, we propose a simple but robust thermodynamic methodology to gain thorough insight into the physical nature for the controllable motion of droplets. On the basis of the thermodynamic calculations of free energy (FE) and the free-energy barrier (FEB), the effects of surface geometry of a pillar microtexture are systematically investigated. It is found that decreasing the pillar width and spacing simultaneously is required to lower the advancing and receding FEBs to effectively direct droplets on the roughness gradient surface. Furthermore, the external energy plays a role in the actuation of spontaneous droplet motion with the cooperation of the roughness gradient. In addition, it is suggested that the so-called "virtual wall" used to confine the liquid flow along the undesired directions could be achieved by constructing highly advancing FEB areas around the microchannels, which is promising for the design of microfluidic systems.     

Convective rolls and hydrothermal waves in evaporating sessile drops

Recent experiments on the evaporation of sessile droplets have revealed the spontaneous formation of various patterns including the presence of hydrothermal waves. These waves had previously been observed, in the absence of evaporation, in thin liquid layers subjected to an imposed, uniform temperature gradient. This is in contrast to the evaporating droplet case wherein these gradients arise naturally due to evaporation and are spatially and temporally varying. In the present paper, we present a theory of evaporating sessile droplets deposited on a heated surface and propose a candidate mechanism for the observed pattern formation using a linear stability analysis in the quasi-steady-state approximation. A qualitative agreement with experimental trends is observed.     

Detection and visualisation of elemental components in various ambient species by synchrotron microbeam technique

This study introduces the application of the synchrotron radiation induced X-ray fluorescence (SR-XRF) microprobe installed at the Super Photon ring-8 GeV (SPring-8), which is the world's largest third-generation synchrotron radiation facility, to the specification of chemical properties of various atmospheric samples. The combination of visual elemental mapping and XRF spectral analyses allows for the interpretation of the nature and composition of individual particles. Individually collected droplets by the replication technique were also irradiated by X-ray microbeam to carry out visual reconstruction of elemental maps for their multiple components. The multielemental peaks corresponding to X-ray energy were also successfully resolved. Because the chemical contents of solute for individual droplets can be definitely clarified in this study, we can describe the mechanisms involved in droplet formation and pollutant scavenging. The point analysis of sand dust collected from the local desert in China confirmed that the fine fragments of sand, which may be lifted and transported over a long distance, are considerably inhomogeneous in elemental component.     

Particle capture processes and evaporation on a microscopic scale in wet filters

This paper details results of an experimental study of the capture of solid and liquid aerosols on fibrous filters wetted with water. A microscopic cell containing a single fibre (made from a variety of materials) was observed via a microscope, with a high speed CCD camera used to dynamically image the interactions between liquid droplets, zeolite and PSL particles and fibres. Variable quantities of liquid irrigation were used, and the possibility for subsequent fibre regeneration after clogging or drying was also studied. It was found that drainage of the wetting liquid (water) from the fibres occurred, even at very low irrigation rates when the droplet consisted almost completely of captured particles. It was also found that the fibre was rapidly loaded with captured particles when the irrigation was not supplied. However, almost complete regeneration (removal of the collected cake) by the liquid droplets occurred shortly after recommencement of the water supply. The study also examined the capture of oily liquid aerosols on fibres wetted with water. A predominance of the barrel shaped droplet on the fibre was observed, with oil droplets displacing water droplets (if the oil and fibre combination created a barrel shaped droplet), creating various compound droplets of oil and water not previously reported in literature. This preferential droplet shape implies that whatever the initial substance wetting a filter, a substance with a greater preferential adherence to the fibre will displace the former one.     

Experimental investigation of droplet acceleration and collision in the gas phase in a microchannel

We developed a novel microfluidic system, termed a micro-droplet collider, by utilizing the spatial-temporal localized liquid energy to realize chemical processes, which achieved rapid mixing between droplets having a large volume ratio by collision. In this paper, in order to clarify the characteristics of the micro-droplet collider, dynamics of droplet acceleration, stationary motion and collision in the gas phase in a microchannel were experimentally investigated with visualized images using a microscope equipped with a high-speed camera. The maximum velocity of 450 mm s(-1) and acceleration of 1500 m s(-2) of a 1.6 nL water droplet were achieved at an air pressure of 100 kPa. Measurement results of dynamic contact angles of droplets indicated that wettability of the surface played an important role in the stability of droplet acceleration and collision. We found that the bullet droplet penetrated into the target droplet at collision, which differed from bulk scale. The deformation of the droplet was strongly suppressed by the channel structure, thus stable collision and efficient utilization of the droplet energy were possible. These results are useful for estimating the localized energy, for improving the system in order to realize extreme performance, and for extending the applications of microfluidic devices.     

Electric field studies of liquid crystal droplet suspensions

The responses of freely-suspended micron-sized liquid crystal droplets subjected to an alternating electric field are presented. By examining droplets of isotropic, nematic bipolar, and nematic radial configurations, we test the effect of anchoring on the droplet response. Specifically, using birefringence and scattering dichroism we measure the relaxation of electric field-induced orientation following a field pulse. Results indicate that bipolar and radial droplets in suspension orient in the field through very different mechanisms. Bipolar droplets are observed to rotate their defect axes in the field while radial droplets orient through a nematic distortion. By varying the field pulse, we observe that droplets also respond differently to the field depending on their relative sizes. In radial droplet suspensions we quantitatively measure time scales associated with the reorientation and restructuring of the defect region.     

Transitions of bipolar to radial orientation of liquid crystal droplets in amphiphilic system of PDLC film

The orientation order of nanoscale droplets of thermotropic liquid crystals (LCs) suspended in polymer dispersed liquid crystal (PDLC) solutions prepared with different medias (e.g., polymers, surfactants, nonpolar materials like dyes) respond sensitively and differently via molecular interactions. Such a valuable knowledge provides basis for understanding the properties of PDLC devices. Previously, many studies have explored the droplets size, electro-optical property variations in PDLC films by varying the materials types and its compositions. However, the variations in droplet orientation order with respect to material type and composition provide a new class of study in this particular field. The current study explored the transition in droplet orientation from bipolar to radial on varying the amphiphilic block copolymer concentrations. Further, the variations in surface energies of LCs in different series of block copolymer medias were investigated by contact angle measurements.