Droplet shape of an anisotropic liquid

We investigate how a droplet of a complex liquid is modified by its internal nanoscale structure. As the liquid passes from an isotropic disordered state to an anisotropic layered morphology, the droplet shape switches from a smooth spherical cap to a terraced hyperbolic profile, which can be modeled as a stack of thin concentric circular disks with a repulsion between adjacent disk edges. Our ability to resolve the detailed shape of these defect-free droplets offers a unique opportunity to explore the underlying physics.

Liquid matrix deposition on conductive hydrophobic surfaces for tuning and quantitation in UV-MALDI mass spectrometry

With its highly fluctuating ion production matrix-assisted laser desorption/ionization (MALDI) poses many practical challenges for its application in mass spectrometry. Instrument tuning and quantitative ion abundance measurements using ion signal alone depend on a stable ion beam. Liquid MALDI matrices have been shown to be a promising alternative to the commonly used solid matrices. Their application in areas where a stable ion current is essential has been discussed but only limited data have been provided to demonstrate their practical use and advantages in the formation of stable MALDI ion beams. In this article we present experimental data showing high MALDI ion beam stability over more than two orders of magnitude at high analytical sensitivity (low femtomole amount prepared) for quantitative peptide abundance measurements and instrument tuning in a MALDI Q-TOF mass spectrometer. Samples were deposited on an inexpensive conductive hydrophobic surface and shrunk to droplets <10 nL in size. By using a sample droplet <10 nL it was possible to acquire data from a single irradiated spot for roughly 10,000 shots with little variation in ion signal intensity at a laser repetition rate of 5-20 Hz.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Droplets of structured fluid on a flat substrate

We study the equilibrium morphology of droplets of symmetric AB diblock copolymer on a flat substrate. Using self-consistent field theory (SCFT), we provide the first predictions for the equilibrium droplet shape and its internal structure. When the sustrate affinity for the A component, $\eta_A$, is small, the droplet adopts a nearly spherical shape much like that of simple fluids. Inside the spherical droplet, however, concentric circular lamellar layers stack on top of each other; hence the thickness of the droplet is effectively quantized by a half-integer or integer number of layers. At larger $\eta_A$ and smaller contact angle, the area of the upper-most layer becomes relatively large, resulting in a nearly flat, faceted top surface, followed by a semi-spherical slope. This geometry is remarkably reminiscent of the droplet shapes observed with smetic liquid crystals.

Evidence that ice forms primarily in supercooled liquid clouds at temperatures > -27C

Using 4 years of radar and lidar observations of layer clouds from the Chilbolton Observatory in the UK, we show that almost all (95%) ice particles formed at temperatures >-20°C appear to originate from supercooled liquid clouds. At colder temperatures, there is a monotonic decline in the fraction of liquid-topped ice clouds: 50% at -27°C, falling to zero at -37°C (where homogeneous freezing of water droplets occurs). This strongly suggests that deposition nucleation plays a relatively minor role in the initiation of ice in mid-level clouds. It also means that the initial growth of the ice particles occurs predominantly within a liquid cloud, a situation which promotes rapid production of precipitation via the Bergeron-Findeison mechanism.

A transmission electron microscopy study of polymer-stabilised liquid crystal structure

A method has been established for observing the internal structure of the network component of polymer-stabilised liquid crystals. In situ photopolymerisation of a mesogenic diacrylate monomer using ultraviolet light leads to a sparse network (∼1 wt%) within a nematic host. Following polymerisation, the host was removed through dissolution in heptane, revealing the network. In order to observe a cross-section through the network, it was embedded in a resin and then sectioned using an ultramicrotome. However, imaging of the network was not possible due to poor contrast. To improve this, several reagents were used for network staining, but only one was successful: bromine. The use of a Melinex-resin composite for sectioning was also found to be advantageous. Imaging of the network using transmission electron microscopy revealed solid “droplets” of width 0.07–0.20 μm, possessing an open, yet homogeneous structure, with no evidence for any large-scale internal structures.

Effect of adjuvants on the amount of air included in droplets generated by spray nozzles

The air included in droplets generated by spray nozzles directly int0erferes in transport, deposition and retention of the droplets after its impact on the target. The objective of this study was to analyze the interference of adjuvants in the amount of air included in droplets generated by spray nozzles. The treatments were composed by four spray solutions containing mineral oil, vegetable oil, surfactant and water, and three spray nozzles, two air induction type and one pre-orifice. The air included was calculated by the difference between the volume of spray mix (air plus liquid) and only the liquid, which was made by means of sprayed samples captured in a funnel and collected in a graduated cylinder. The surface tension was estimated by the gravimetric method using a precision scale and a graduated pipette. The surfactant provided the largest percentage of air included in the spray. For the surface tension, the mineral oil and the surfactant had the lowest values. It was concluded that the use of adjuvants had a direct influence on the percentage of air included. In addition, products with greater ability to reduce surface tension and to form homogeneous solutions provided the increase in the percentage of air included in the droplet.

A dose-controlled system for air-liquid interface cell exposure and application to zinc oxide nanoparticles

BACKGROUND: Engineered nanoparticles are becoming increasingly ubiquitous and their toxicological effects on human health, as well as on the ecosystem, have become a concern. Since initial contact with nanoparticles occurs at the epithelium in the lungs (or skin, or eyes), in vitro cell studies with nanoparticles require dose-controlled systems for delivery of nanoparticles to epithelial cells cultured at the air-liquid interface. RESULTS: A novel air-liquid interface cell exposure system (ALICE) for nanoparticles in liquids is presented and validated. The ALICE generates a dense cloud of droplets with a vibrating membrane nebulizer and utilizes combined cloud settling and single particle sedimentation for fast (~10 min; entire exposure), repeatable (<12%), low-stress and efficient delivery of nanoparticles, or dissolved substances, to cells cultured at the air-liquid interface. Validation with various types of nanoparticles (Au, ZnO and carbon black nanoparticles) and solutes (such as NaCl) showed that the ALICE provided spatially uniform deposition (<1.6% variability) and had no adverse effect on the viability of a widely used alveolar human epithelial-like cell line (A549). The cell deposited dose can be controlled with a quartz crystal microbalance (QCM) over a dynamic range of at least 0.02-200 mug/cm(2). The cell-specific deposition efficiency is currently limited to 0.072 (7.2% for two commercially available 6-er transwell plates), but a deposition efficiency of up to 0.57 (57%) is possible for better cell coverage of the exposure chamber. Dose-response measurements with ZnO nanoparticles (0.3-8.5 mug/cm(2)) showed significant differences in mRNA expression of pro-inflammatory (IL-8) and oxidative stress (HO-1) markers when comparing submerged and air-liquid interface exposures. Both exposure methods showed no cellular response below 1 mug/cm(2 )ZnO, which indicates that ZnO nanoparticles are not toxic at occupationally allowed exposure levels. CONCLUSION: The ALICE is a useful tool for dose-controlled nanoparticle (or solute) exposure of cells at the air-liquid interface. Significant differences between cellular response after ZnO nanoparticle exposure under submerged and air-liquid interface conditions suggest that pharmaceutical and toxicological studies with inhaled (nano-)particles should be performed under the more realistic air-liquid interface, rather than submerged cell conditions.

Pulsating emission of droplets from an electrified meniscus.

A numerical description is given for the pulsating emission of droplets from an electrified meniscus of an inviscid liquid of infinite electrical conductivity which is injected at a constant flow rate into a region of uniform, continuous or time periodic, electric field. Under a continuous field, the meniscus attains a periodic regime in which bursts of tiny droplets are emitted from its tip. At low electric fields this regime consists of sequences of emission bursts interspersed with sequences of meniscus oscillations without droplet emission, while at higher fields the bursts occur periodically. These results are in qualitative agreement with experimental results in the literature. Under a time periodic electric field with square waveform, the electric stress that acts on the surface of the liquid while the field is on may generate a tip that emits tiny droplets or may accelerate part of the meniscus and lead to a second emission mode in which a few large droplets are emitted after the electric field is turned off. Conditions under which each emission mode or a combination of the two are realized are discussed for low frequency oscillatory fields. A simplified model is proposed for high electric field frequencies, of the order of the capillary frequency of the meniscus. This model allows computing the average emission rate as a function of the amplitude, duration and bias of the electric field square wave, and shows that droplet emission fails to follow the applied field above a certain frequency

Local liquid holdups and hysteresis in a 2-D packed bed using X-ray radiography

An X-ray visualization technique has been used for the quantitative determination of local liquid holdups distribution and liquid holdup hysteresis in a nonwetting two-dimensional (2-D) packed bed. A medical diagnostic X-ray unit has been used to image the local holdups in a 2-D cold model having a random packing of expanded polystyrene beads. An aqueous barium chloride solution was used as a fluid to achieve good contrast on X-ray images. To quantify the local liquid holdup, a simple calibration technique has been developed that can be used for most of the radiological methods such as gamma ray and neutron radiography. The global value of total liquid holdup, obtained by X-ray method, has been compared with two conventional methods: drainage and tracer response. The X-ray technique, after validation, has been used to visualize and quantify, the liquid hysteresis phenomena in a packed bed. The liquid flows in preferred paths or channels that carry droplets/rivulets of increasing size and number as the liquid flow rate is increased. When the flow is reduced, these paths are retained and the higher liquid holdup that persists in these regions leads to the holdup hysteresis effect. Holdup in some regions of the packed bed may be an order of magnitude higher than average at a particular flow rate. (c) 2005 American Institute of Chemical Engineers

A parametric study of droplet deformation through a microfluidic contraction: Low viscosity Newtonian droplets

Numerical simulations are conducted to investigate how a droplet of Newtonian liquid. entrained in a higher viscosity Newtonian liquid, behaves when passing through an axisymmetric microfluidic contraction. Simulations are performed using a transient Volume of Fluid finite volume algorithm, and cover ranges of Reynolds and Weber numbers relevant to microfluidic flows. Results are presented for a droplet to surrounding fluid viscosity ratio of 0.001. In contrast to behaviour at higher viscosity ratios obtained previously by the authors, shear and interfacial tension driven instabilities often develop along the droplet Surface. leading to complex shape development, and in some instances, droplet breakup. (c) 2006 Elsevier Ltd. All rights reserved.

The hydrodynamic behaviour and mass transfer characteristics of single droplets in a pulsed sieve plate column

The literature relating to the performance of pulsed sieve plate liquid-liquid extraction columns and the relevant hydrodynamic phenomenon have been surveyed. Hydrodynamic behaviour and mass transfer characteristics of droplets in turbulent and non-turbulent conditions have also been reviewed. Hydrodynamic behaviour, i.e. terminal and characteristic velocity of droplets, droplet size and droplet breakup processes, and mass transfer characteristics of single droplets (d≤0.6 cm) were investigated under pulsed (mixer-settler & transitional regimes) and non-pulsed conditions in a 5.0 cm diameter, 100 cm high, pulsed sieve plate column with three different sieve plate types and variable plate spacing. The system used was toluene (displaced) - acetone - distilled water. Existing photographic techniques for following and recording the droplet behaviour, and for observing the parameters of the pulse and the pulse shape were further developed and improved. A unique illumination technique was developed by which a moving droplet could be photographed using cine or video photography with good contrast without using any dye. Droplet size from a given nozzle and droplet velocity for a given droplet diameter are reduced under pulsing condition, and it was noted that this effect is enhanced in the presence of sieve plate. The droplet breakup processes are well explained by reference to an impact-breakup mechanism. New correlations to predict droplet diameter based on this mechanism are given below.vskip 1.0cm or in dimensionless groups as follows:- (We)crit= 3.12 - 1.79 (Eo)crit A correlation based on the isotropic turbulence theory was developed to calculate droplet diameter in the emulsion regime.vskip 1.0cm Experimental results show that in the mixer-settler and transitional regimes, pulsing parameters had little effect on the overall dispersed phase mass transfer coefficient during the droplet formation and unhindered travel periods.

A study of the drying of single droplets in free-flight

The literature relating to evaporation from single droplets of pure liquids and the drying of solution and slurry droplets, and of droplet sprays has been reviewed. The heat and mass transfer rates for individual droplets suspended in free-flight, were investigated using a specially-designed vertical wind tunnel, to simulate conditions in a spray drier. The technique represented a unique alternative method for investigating evaporation from unrestrained single droplets with variable residence times. The experiments covered droplets of pure liquid allowbreak (water, isopropanol) allowbreak and of significantly different solutions (sucrose, potassium sulphate) over a range of temperatures of 37oC to 97oC, initial concentrations of 5 to 40wt/wt% , and initial drop sizes of 2.8 to 4.6mm. Drop behaviour was recorded photographically and dried particles were examined by Scanning Electron Microscopy. Correlations were developed for mass transfer coefficients for pure water droplets in free-flight; (i) experiencing oscillations, rotation and deformation, Sh = -105 + 3.9 [Ta - Td/Tamb]0.18Re0.5Sc033 for Re approx. > 1380 (ii) when these movements had ceased or diminished, Sh = 2.0 + 0.71 [Ta - Td/Tamb]0.18Re0.5Sc033 for Re approx. < 1060. Data for isopropanol drops were correlated resonably well by these equations. The heat transfer data showed a similar transition range. The drying rate curves for drops of sucrose and potassium sulphate solution exhibited three distinct stages; an initial increase in the drying rate as drop temperature reduced to the wet-bulb temperature, a short constant-rate period and a falling-rate period characterised by formation of a crust which controlled the mass transfer rate. Due to drop perturbation the rates in the high Re number region were up to 5 times greater than predicted from theory for spherical droplets. In the case of sucrose solution a `skin' formed over the drop surface prior to crust formation. This provided an additional resistance to mass transfer and resulted in extended drying times and a smooth crust of low porosity. The relevance of the results to practical spray drying operations is discussed.

A study of liquid-liquid extraction in a sieve plate column

The literature relating to sieve plate liquid extraction columns and relevant hydrodynamic phenomena have been surveyed. Mass transfer characteristics during drop formation, rise and coalescence, and related models were also reviewed. Important design parameters i.e. flooding, dispersed phase hold-up, drop size distribution, mean drop size, coalescence/flocculation zone height beneath a plate and jetting phenomena were investigated under non-mass transfer and mass transfer conditions in a 0.45m diameter, 2.3m high sieve plate column. This column had provision for four different plate designs, and variable plate spacing and downcomer heights, and the system used was Clairsol `350' (dispersed) - acetone - deionised water (continuous) with either direction of mass transfer. Drop size distributions were best described by the functions proposed by Gal-or, and then Mugele-Evans. Using data from this study and the literature, correlations were developed for dispersed phase hold-up, mean drop size in the preferred jetting regime and in the non-jetting regime, and coalescence zone height. A method to calculate the theoretical overall mass transfer coefficient allowing for the range of drop sizes encountered in the column gave the best fit to experimental data. This applied the drop size distribution diagram to estimate the volume percentage of stagnant, circulating and oscillating drops in the drop population. The overall coefficient Kcal was then calculated as the fractional sum of the predicted individual single drop coefficients and their proportion in the drop population. In a comparison between the experimental and calculated overall mass transfer coefficients for cases in which all the drops were in the oscillating regime (i.e. 6.35mm hole size plate), and for transfer from the dispersed(d) to continuous(c) phase, the film coefficient kd predicted from the Rose-Kintner correlation together with kc from that of Garner-Tayeban gave the best representation. Droplets from the 3.175mm hole size plate, were of a size to be mainly circulating and oscillating; a combination of kd from the Kronig-Brink (circulating) and Rose-Kintner (oscillating) correlations with the respective kc gave the best agreement. The optimum operating conditions for the SPC were identified and a procedure proposed for design from basic single drop data.

Solid-liquid interactions in microscale structures and devices

Liquid-solid interactions become important as dimensions approach mciro/nano-scale. This dissertation focuses on liquid-solid interactions in two distinct applications: capillary driven self-assembly of thin foils into 3D structures, and droplet wetting of hydrophobic micropatterned surfaces. The phenomenon of self-assembly of complex structures is common in biological systems. Examples include self-assembly of proteins into macromolecular structures and self-assembly of lipid bilayer membranes. The principles governing this phenomenon have been applied to induce self-assembly of millimeter scale Si thin films into spherical and other 3D structures, which are then integrated into light-trapping photovoltaic (PV) devices. Motivated by this application, we present a generalized analytical study of the self-folding of thin plates into deterministic 3D shapes, through fluid-solid interactions, to be used as PV devices. This study consists of developing a model using beam theory, which incorporates the two competing components — a capillary force that promotes folding and the bending rigidity of the foil that resists folding into a 3D structure. Through an equivalence argument of thin foils of different geometry, an effective folding parameter, which uniquely characterizes the driving force for folding, has been identified. A criterion for spontaneous folding of an arbitrarily shaped 2D foil, based on the effective folding parameter, is thus established. Measurements from experiments using different materials and predictions from the model match well, validating the assumptions used in the analysis. As an alternative to the mechanics model approach, the minimization of the total free energy is employed to investigate the interactions between a fluid droplet and a flexible thin film. A 2D energy functional is proposed, comprising the surface energy of the fluid, bending energy of the thin film and gravitational energy of the fluid. Through simulations with Surface Evolver, the shapes of the droplet and the thin film at equilibrium are obtained. A critical thin film length necessary for complete enclosure of the fluid droplet, and hence successful self-assembly into a PV device, is determined and compared with the experimental results and mechanics model predictions. The results from the modeling and energy approaches and the experiments are all consistent. Superhydrophobic surfaces, which have unique properties including self-cleaning and water repelling are desired in many applications. One excellent example in nature is the lotus leaf. To fabricate these surfaces, well designed micro/nano- surface structures are often employed. In this research, we fabricate superhydrophobic micropatterned Polydimethylsiloxane (PDMS) surfaces composed of micropillars of various sizes and arrangements by means of soft lithography. Both anisotropic surfaces, consisting of parallel grooves and cylindrical pillars in rectangular lattices, and isotropic surfaces, consisting of cylindrical pillars in square and hexagonal lattices, are considered. A novel technique is proposed to image the contact line (CL) of the droplet on the hydrophobic surface. This technique provides a new approach to distinguish between partial and complete wetting. The contact area between droplet and microtextured surface is then measured for a droplet in the Cassie state, which is a state of partial wetting. The results show that although the droplet is in the Cassie state, the contact area does not necessarily follow Cassie model predictions. Moreover, the CL is not circular, and is affected by the micropatterns, in both isotropic and anisotropic cases. Thus, it is suggested that along with the contact angle — the typical parameter reported in literature quantifying wetting, the size and shape of the contact area should also be presented. This technique is employed to investigate the evolution of the CL on a hydrophobic micropatterned surface in the cases of: a single droplet impacting the micropatterned surface, two droplets coalescing on micropillars, and a receding droplet resting on the micropatterned surface. Another parameter which quantifies hydrophobicity is the contact angle hysteresis (CAH), which indicates the resistance of the surface to the sliding of a droplet with a given volume. The conventional methods of using advancing and receding angles or tilting stage to measure the resistance of the micropatterned surface are indirect, without mentioning the inaccuracy due to the discrete and stepwise motion of the CL on micropillars. A micronewton force sensor is utilized to directly measure the resisting force by dragging a droplet on a microtextured surface. Together with the proposed imaging technique, the evolution of the CL during sliding is also explored. It is found that, at the onset of sliding, the CL behaves as a linear elastic solid with a constant stiffness. Afterwards, the force first increases and then decreases and reaches a steady state, accompanied with periodic oscillations due to regular pinning and depinning of the CL. Both the maximum and steady state forces are primarily dependent on area fractions of the micropatterned surfaces in our experiment. The resisting force is found to be proportional to the number of pillars which pin the CL at the trailing edge, validating the assumption that the resistance mainly arises from the CL pinning at the trailing edge. In each pinning-and-depinning cycle during the steady state, the CL also shows linear elastic behavior but with a lower stiffness. The force variation and energy dissipation involved can also be determined. This novel method of measuring the resistance of the micropatterned surface elucidates the dependence on CL pinning and provides more insight into the mechanisms of CAH.