Droplet-on-chip electro-spectroscopy detects the ultra-short relaxation time of a dilute polymer solution.

We report an electrode-embedded on-chip platform technology for the precise determination of ultra-short (of the order of a few nanoseconds) relaxation times of dilute polymer solutions, by deploying time-alternating electrical voltages. Our methodology delves into the sensitive dependence of the contact line dynamics of a droplet of the polymer solution atop a hydrophobic interface in response to the actuation voltage, resulting in a non-trivial interplay between the time-evolving electrical, capillary, and viscous forces. This culminates into a time-decaying dynamic response that mimics the features of a damped oscillator having its 'stiffness' mapped with the polymeric content of the droplet. The observed electro-spreading characteristics of the droplet are thus shown to correlate explicitly with the relaxation time of the polymer solution, drawing analogies with a damped electro-mechanical oscillator. By corroborating well with the reported values of the relaxation times as obtained from more elaborate and sophisticated laboratory set-ups. Our findings provide perspectives for a unique and simple approach towards electrically-modulated on-chip-spectroscopy for deriving ultra-short relaxation times of a broad class of viscoelastic fluids that could not be realized thus far.

Effect of gravity on the spreading of a droplet deposited by liquid needle deposition technique.

This study represents an experimental investigation, complemented with a mathematical model, to decipher the effect of gravity on the spreading dynamics of a water droplet. For the theoretical discussion, an overall energy balance approach is adopted to explain the droplet spreading under both microgravity (µg) and terrestrial gravity condition. Besides explaining the mechanism of the droplet spreading under microgravity condition achieved during the parabolic flight, a technique with a detailed experimental set-up has also been developed for the successful deposition of droplet. A rational understanding is formulated through experimental investigation and theoretical analysis, which allows us to distinguish the transient variation of the spreading of a droplet, between microgravity and terrestrial gravity condition. The spreading of the droplet is predicted by the non-linear overall energy balance equation, which accounts for the operating parameters in the form of non-dimensional groups like Reynolds number ([Formula: see text]), Weber number (We) and Bond number (Bo). To distinctly identify the difference in the drop spreading at terrestrial and microgravity conditions, the Bo with transient gravitational field obtained through the on-board accelerometer is considered. The obtained theoretical results are further corroborated by experimental results which are obtained from the parabolic flight.

Electrowetting-Induced Coalescence of Sessile Droplets in Viscous Medium.

Manipulating the coalescence of microdroplets has recently gained enormous attention in digital microfluidics and biological and chemical industries. Here, coalescence between two sessile droplets is induced by spreading them due to electrowetting. The electrocoalescence dynamics is investigated for a wide range of operating parameters such as electrowetting number, Ohnesorge number, driving frequency, and drop to surrounding medium viscosity ratio. Here, the characteristic time scale from the classical lubrication theory is modified with an additional driving and resisting force due to the electrostatic pressure force and liquid-liquid viscous dissipation, respectively. With the revised characteristic time scale, a universal bridge growth is shown between the two merging droplets following a 1/3 power law during early coalescence followed by a long-range linear variation. To ensure precise control on droplet coalescence, a geometric analysis is also performed to define the initial separation distance.

The effect of dynamic wetting pressure on contact angle measurements.

HYPOTHESIS: The drop deposition technique can impact contact angle measurements. We hypothesized that the drop pinch-off, during the traditionally used pendant drop technique, significantly alters the static contact angle. The capillary waves and dynamic wetting pressure generated during the pendant drop deposition are the source for forced spreading, which can be circumvented by alternative liquid-needle drop deposition techniques. EXPERIMENTS: To compare the role of drop pinch-off and resultant dynamic wetting pressure, we meticulously observed and quantified the entire drop deposition process using high speed imaging until the drop attains the static contact angle in both cases, namely pendant drop and liquid needle deposition technique. Conventionally used standard substrates are compared using both techniques and further compared using literature data. The capillary waves and corresponding drop shape variations are analysed for quantifying the dynamic wetting pressure by measuring drop base diameter, contact angle and centre of mass. FINDINGS: We compared three parameters - drop pinch-off, spreading behaviour and respective static contact angles along with the resultant dynamic wetting pressure for both the techniques, i.e., pendant drop and liquid-needle. For the pendant drop technique we observed a pronounced drop volume dependency of these parameters even though the corresponding Bond numbers are less than unity. In contrast, for the liquid needle there is no such dependency. With a theoretical argument corroborating experimental observations, this work highlights the importance of a well controlled drop deposition, with a minimum wetting pressure, in order to guarantee contact angle data that is independent of drop deposition effects, thereby only reflecting the substrate properties.

Underwater Oil Drop Storage, Guided Transport, and Oil/Water Separation Using Surfaces with Wettability Contrast Prepared through a Vapor-Based Etching Method.

A facile vapor-based etching method is introduced to design surfaces with underwater wettability contrast. The method involves exposure of the masked copper surface to acetic acid vapors for growing nano- and microstructures; additional modification with stearic acid (STA) produced a superhydrophobic exposed area, while the masked surface remained hydrophobic. Dot- as well dumbbell-shaped patterns were prepared and used for oil drop storage and transfer, respectively. The influence of buoyancy on the storage capacity of the dot patterns and transfer rate of the channels is investigated. Buoyancy-driven partial channel-less transport of oil droplets by using a strategic arrangement of donor and receptor channels is also demonstrated. Patterns are also designed on flexible substrates to enable easy fabrication of complex three-dimensional fluidic pathways having both horizontal and vertical tracks. The flexibility of the substrates enabled the design of an electric switch-type configuration for the oil drop transport between two channels. In the end, a strategy for the removal of water from a water-in-oil emulsion using channels is introduced. A unique phenomenon of spontaneous bursting out of a water drop from inside an oil drop is also demonstrated.

Double-Emulsion Drop Evaporation and Formation of a Daughter Droplet.

In this study, we present experimental and theoretical analyses of evaporating a double-emulsion drop resting on a substrate. Multistage evaporation of the outer and inner droplet is witnessed. The complete evaporation of the outer drop and the initialization of the inner drop evaporation demonstrate an interesting transition dynamics. After the apparent completion of evaporation of the inner phase of a double-emulsion drop, surprisingly, formation of a daughter droplet is observed. We further investigated to hypothesize this phenomenon and achieved the formation of the daughter droplet for a single-phase drop as well. While engineering the "daughter drop formation" phenomena, we also proposed a way to obtain prolonged fixed contact line evaporation for a single-phase drop.

Effects of magnetic field on the spreading dynamics of an impinging ferrofluid droplet.

This paper presents a comprehensive experimental study of the effects of vertically and horizontally applied magnetic fields on the dynamics of magnetowetting and the formation of satellite droplet. Besides explaining the physics of the transient variation of different drop shape parameters, the role of a magnetic field on controlling the dynamics of spreading is also presented. Ultimately the magnetic field maneuvers the droplet spreading without altering the surface chemistry. The morphological evolution and dynamics of an impacting ferrofluid droplet has also been studied. By observing the spreading at an appropriate time scale, the contrary spreading behavior of the paramagnetic ferrofluid under the effect of magnetic field is noticed. Special attention is given to the droplet break-up and satellite droplet formation. A universal relationship is presented between the drop shape parameters before and after the impact. The destination and travel path of the satellite droplet is also analyzed in a vertical as well as horizontal magnetic field, which governs the satellite droplet merging with the already deposited parent droplet.

Application of oil-swollen surfactant gels as a growth medium for metal nanoparticle synthesis, and as an exfoliation medium for preparation of graphene.

Gel is an intermediate phase of solid and liquid, which exhibits properties of both, and this unique feature of gel has made it an excellent choice as a reaction medium for the nanomaterials synthesis. Herein, we report use of oil swollen surfactant gels as reaction medium and exfoliation medium, for the synthesis of metals (Au, Ag) nanoparticles and graphene, respectively. Confined growth of metals (Au and Ag) nanoparticles, has been achieved by exploring tween 80 based surfactant gel as a reaction medium. Au NPs prepared within tween 80 gel were found to be spherical with size ∼5nm, arranged in template micelles. Heating triggered the growth of Au nanoparticles and particles of various shapes including triangles, rods and pentagonal, were produced. Au and Ag containing tween 80 gels were found to be promising as catalysts for the nitrophenol reduction. Apart from separate synthesis of Au and Ag nanoparticles, bimetallic (Au-Ag) nanoparticles have also been synthesized by taking advantage of selective reducing property of tween 80. First time CTAB gel has been utilized as an exfoliation medium for the quick exfoliation of graphite into graphene sheets, eliminating the necessity of any external driving force such as sonication or heating, to reinforce exfoliation.

Under-water superoleophobicity of fish scales.

Recent surge in the development of superhydrophobic/superoleophobic surfaces has been motivated by surfaces like fish scales that have hierarchical structures, which are believed to promote water or oil repellency. In this work, we show that the under-water oil repellency of fish scales is entirely due to the mucus layer formation as part of its defense mechanism, which produces unprecedented contact angle close to 180°. We have identified the distinct chemical signatures that are responsible for such large contact angle, thereby making fish scale behave highly superoleophobic inside the water medium. In absence of the mucus layer, it is found that the contact angle decreases quite dramatically to around 150°, making it less oleophobic, the degree of such oleophobicity can then be contributed to its inherent hierarchical structures. Hence, through this systematic study, for the first time we have conclusively shown the role of the fish's mucus layer to generate superoleophobicity and negate the common notion that hierarchical structure is the only reason for such intrinsic behavior of the fish scales.

Under-water superoleophobic glass: unexplored role of the surfactant-rich solvent.

Preparing low energy liquid-repellant surfaces (superhydrophobic or superoleophobic) have attracted tremendous attention of late. In all these studies, the necessary liquid repellency is achieved by irreversible micro-nano texturing of the surfaces. Here we show for the first time that a glass surface, placed under water, can be made superoleophobic (with unprecedented contact angles close to 180 degrees and roll off angles only a few fractions of 1 degree) by merely changing the surfactant content of the water medium in which the oil (immiscible in water) has been dispersed. Therefore, we propose a paradigm shift in efforts to achieve liquid-repellant systems, namely, altering the solvent characteristics instead of engineering the surfaces. The effect occurs for a surfactant concentration much larger than the critical micelle concentration, and is associated to strong adsorption of surfactant molecules at the solid surface, triggering an extremely stable Cassie-Baxter like conformation of the oil droplets.

Early regimes of capillary filling.

In this paper we analyze the inviscid regime (for which viscosity is unimportant and the flow occurs due to the balance between the capillary and the inertial effects) that invariably precedes the classical century-old Washburn regime during capillary filling. We demonstrate that a new nondimensional number, namely, the product of the Ohnesorge number and the ratio between the filling length (ℓ) and the radius of the capillary (R), dictates the occurrence of this regime and the other well-known regimes in a capillary filling problem. We also identify that this inviscid regime occurs for the time that is of the order of the capillary time scale and, as has been quantified before [Quere, Eur. Phys. Lett. 39, 533 (1997); Joly, J. Chem. Phys. 135, 214705 (2011)], is characterized by the filling length being linearly proportional to the filling time. We establish the universality of this regime by pinpointing the existence of this regime (showing appropriate dependencies of the capillary radii and density) from existing experimental and Molecular Dynamics Simulation results that signify disparate ranges of length and time scales.

Anodic growth of large-diameter multipodal TiO2 nanotubes.

We report on the formation of a new class of nanostructures, namely, multipodal hollow titania nanotubes possessing two or more legs, achieved during the electrochemical anodization of titanium in diethylene glycol (DEG)-based electrolytes. The unique multipodal porous structure is expected to extend and enhance the applications of TiO(2) nanotube arrays. Multipodal nanotubes form by a process we term "nanotube combination", which only occurs in viscous electrolytes at high anodization potentials in the presence of a low concentration of fluoride-bearing species. The mechanism of formation of multipodal nanotubes is considered, and the tube length at which nanotube combination occurs is predicted theoretically using a simplified analytical model. The results suggest that capillary forces strong enough to bend the TiO(2) nanotubes by tens of degrees are generated during the imbibition of electrolyte into and out of the intertubular spaces between adjacent tapered nanotubes.

Contact angle hysteresis of microbead suspensions.

Microbead suspensions are often used in microfluidic devices for transporting biomolecules. An experimental investigation on the wettability of microbead suspension is presented in this study. The variation in the surface tension and the equilibrium contact angle with the change in the volume fraction of the microbead is presented here. The surface tension of the microbead suspension is measured with the pendant drop technique, whereas the dynamic contact angle measurements, i.e., advancing and receding contact angles, are measured with the sessile drop technique. An equilibrium contact angle of a suspension with particular volume fraction is determined by computing an average over the measured advancing and receding contact angles. It is observed that the surface tension and the equilibrium contact angle determined from advancing and receding contact angles vary with the magnitude of the microbeads volume fraction in the suspension. A decrease in the surface tension with an increase in the volume fraction of the microbead suspension is observed. The advancement and the recession in contact line for dynamic contact angle measurements are achieved with the motorized dosing mechanism. For microbead suspensions, the advancement of the contact line is faster as compared to the recession of the contact line for the same flow rate. The presence of microbeads assists in the advancement and the recession of the contact line of the suspension. A decrease in the equilibrium contact angles with an increase in the microbead suspension volume fraction is observed. Inclusion of microbeads in the suspension increases the wetting capability for the considered combination of the microbead suspension and substrate. Finally, empirical correlations for the surface tension and the contact angle of the suspension as a function of microbead volume fraction are proposed. Such correlations can readily be used to develop mechanistic models for the capillary transport of microbead suspensions related to LOC applications.

Finite reservoir effect on capillary flow of microbead suspension in rectangular microchannels.

The present study reports a theoretical investigation of capillary transport of microbead suspension in microfluidic channels with finite size reservoirs at the inlet. The reservoir-microchannel combination is often the case in Lab-on-a-Chip (LOC) where biomolecules are transported using capillary force. To demonstrate such finite reservoir effect, the reservoir is placed vertically above the microchannel. Under such condition, the pressure field expression at the rectangular microchannel inlet is deduced. Appropriate correlations for effective physical properties are used to account for the presence of microbeads in the working fluid, mimicking biomolecules in actual LOC. The non-dimensional governing equation for capillary flow with finite size reservoir is derived based on the balance among the surface, viscous and gravity forces acting on the fluid front. The numerical solution of governing equation is obtained to investigate the impact of several operating parameters on the flow front progression. It is observed that the aspect ratio of the microchannel and reservoir play vital roles in deciding the behavior and magnitude of flow front progression in the microfluidic channels. Capillarity and gravity force dominant regions during the progression is observed. The microchannel width and reservoir width decide the interplay between gravity and capillarity. Although higher fluid level in the reservoir has an added advantage for more gravitational head, the resistance from the reservoir makes the flow front progress slowly at the beginning of the capillary transport. It is also found that microbead volume fraction in the working fluid plays an important role in delaying the capillary transport under various operating conditions. Hence, it can be concluded that the use of reservoir at the inlet of microfluidic channels has an impact on the overall capillary transport of biomolecules in LOC devices.

Modeling of combined electroosmotic and capillary flow in microchannels.

In the present study, theoretical model for the transient response of a capillary flow under the combined effects of electroosmotic and capillary forces at low Reynolds number is presented. The governing equation is derived based on the balance among the electrokinetic, surface, viscous and gravity forces. A non-dimensional transient governing equation for the penetration depth as a function of time is obtained by normalizing the viscous, gravity and electroosmotic forces with surface tension force. A new non-dimensional group for the electroosmotic force, E(o), is obtained through the non-dimensional analysis. This new non-dimensional group is a representation of combined electroosmosis and surface tension, i.e., capillarity. The numerical solution of governing equation is obtained to study the effect of different operating parameters on the flow front transport. In a combined flow, it is observed that the flow with positive and low negative magnitude E(o) numbers, the attainment of equilibrium penetration depth is similar to a capillary flow. In case of high negative magnitude E(o) numbers, complete filling of the channel is observed. The electrolyte with lower permittivity delays the progress of the flow front whereas a large EDL transports the electrolyte quickly. Higher viscous and gravity forces also delay the transport process in the combined flow. This model suggests that in combined flow the electrokinetic parameters also play an important role on the capillary flow and experiments are required to confirm this electrokinetic effect on capillary transport.