Evidence for global circuit current flow through water droplet layers

Abstract Foggy air and clear air have appreciably different electrical conductivities. The conductivity gradient at horizontal droplet boundaries causes droplet charging, as a result of vertical current flow in the global atmospheric electrical circuit. The charging is poorly known, as both the current flow through atmospheric water droplet layers and the air conductivity are poorly characterised experimentally. Surface measurements during three days of continuous fog using new instrument techniques show that a shallow (of order 100 m deep) fog layer still permits the vertical conduction current to pass. Further, the conductivity in the fog is estimated to be approximately 20% lower than in clear air. Assuming a fog transition thickness of one metre, this implies a vertical conductivity gradient of order 10 fS m−2 at the boundary. The actual vertical conductivity gradient at a cloud boundary would probably be greater, due to the presence of larger droplets in clouds compared to fog, and cleaner, more conductive clear air aloft.

A new oxidation catalyst system using fluorous cobalt(II) species in water-supercritical carbon dioxide (C-H free environment)

Stabilized water droplet dispersed in supercritical carbon dioxide fluid is demonstrated to be an excellent alternative solvent system to acetic acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions.

Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C-H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this 'greener' catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

Phase behavior of the orange essential oil/sodium bis(2-ethylhexyl)sulfosuccinate/water system

The ternary phase diagram for the orange essential oil (OEO)/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water system was constructed at 25 degrees C. It indicates a large single phase region, comprising an isotropic water-in-oil (W/O) microemulsion (ME) phase (L(2)), a liquid crystal (LC) (lamellar or hexagonal) and a large unstable emulsion phase that separates in two phases of normal and reverse micelles (L(1) and L(2)). In this communication the properties of the ME are investigated by viscosity, electric conductivity and small angle X-ray scattering (SAXS) indicating that the isotropic ME phase exhibits different behaviors depending on composition. At low water content low viscous ""dry"" surfactant structures are formed, whereas at higher water content higher viscous water droplets are formed. The experimental data allow the determination of the transition from ""dry"" to the water droplet structures within the L(2) phase. SAXS analyses have also been performed for selected LC samples. (C) 2009 Elsevier B.V. All rights reserved.

Phase behavior of the orange essential oil/sodium bis(2-ethylhexyl)sulfosuccinate/water system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Implementation of a phenomenological evaporation model into a porous network simulation for water management in low temperature fuel cells

A phenomenological transition film evaporation model was introduced to a pore network model with the consideration of pore radius, contact angle, non-isothermal interface temperature, microscale fluid flows and heat and mass transfers. This was achieved by modeling the transition film region of the menisci in each pore throughout the porous transport layer of a half-cell polymer electrolyte membrane (PEM) fuel cell. The model presented in this research is compared with the standard diffusive fuel cell modeling approach to evaporation and shown to surpass the conventional modeling approach in terms of predicting the evaporation rates in porous media. The current diffusive evaporation models used in many fuel cell transport models assumes a constant evaporation rate across the entire liquid-air interface. The transition film model was implemented into the pore network model to address this issue and create a pore size dependency on the evaporation rates. This is accomplished by evaluating the transition film evaporation rates determined by the kinetic model for every pore containing liquid water in the porous transport layer (PTL). The comparison of a transition film and diffusive evaporation model shows an increase in predicted evaporation rates for smaller pore sizes with the transition film model. This is an important parameter when considering the micro-scaled pore sizes seen in the PTL and becomes even more substantial when considering transport in fuel cells containing an MPL, or a large variance in pore size. Experimentation was performed to validate the transition film model by monitoring evaporation rates from a non-zero contact angle water droplet on a heated substrate. The substrate was a glass plate with a hydrophobic coating to reduce wettability. The tests were performed at a constant substrate temperature and relative humidity. The transition film model was able to accurately predict the drop volume as time elapsed. By implementing the transition film model to a pore network model the evaporation rates present in the PTL can be more accurately modeled. This improves the ability of a pore network model to predict the distribution of liquid water and ultimately the level of flooding exhibited in a PTL for various operating conditions.

Fluidic oscillator design for water removal enhancement in a PEM fuel cell

This research initiative was triggered by the problems of water management of Polymer Electrolyte Membrane Fuel Cell (PEMFC). In low temperature fuel cells such as PEMFC, some of the water produced after the chemical reaction remains in its liquid state. Excess water produced by the fuel cell must be removed from the system to avoid flooding of the gas diffusion layers (GDL). The GDL is responsible for the transport of reactant gas to the active sites and remove the water produced from the sites. If the GDL is flooded, the supply gas will not be able to reach the reactive sites and the fuel cell fails. The choice of water removal method in this research is to exert a variable asymmetrical force on a liquid droplet. As the drop of liquid is subjected to an external vibrational force in the form of periodic wave, it will begin to oscillate. A fluidic oscillator is capable to produce a pulsating flow using simple balance of momentum fluxes between three impinging jets. By connecting the outputs of the oscillator to the gas channels of a fuel cell, a flow pulsation can be imposed on a water droplet formed within the gas channel during fuel cell operation. The lowest frequency produced by this design is approximately 202 Hz when a 20 inches feed-back port length was used and a supply pressure of 5 psig was introduced. This information was found by setting up a fluidic network with appropriate data acquisition. The components include a fluidic amplifier, valves and fittings, flow meters, a pressure gage, NI-DAQ system, Siglab®, Matlab software and four PCB microphones. The operating environment of the water droplet was reviewed, speed of the sound pressure which travels down the square channel was precisely estimated, and measurement devices were carefully selected. Applicable alternative measurement devices and its application to pressure wave measurement was considered. Methods for experimental setup and possible approaches were recommended, with some discussion of potential problems with implementation of this technique. Some computational fluid dynamic was also performed as an approach to oscillator design.

Performance assessment of electrically small antennas for implantable microsystems with wireless power and communications

Dissertação de mestrado integrado em Engenharia Biomédica (área de especialização em Eletrónica Médica)

Quantifying the importance of galactic cosmic rays in cloud microphysical processes

Galactic Cosmic Rays are one of the major sources of ion production in the troposphere and stratosphere. Recent studies have shown that ions form electrically charged clusters which may grow to become cloud droplets. Aerosol particles charge by the attachment of ions and electrons. The collision efficiency between a particle and a water droplet increases, if the particle is electrically charged, and thus aerosol-cloud interactions can be enhanced. Because these microphysical processes may change radiative properties of cloud and impact Earth's climate it is important to evaluate these processes' quantitative effects. Five different models developed independently have been coupled to investigate this. The first model estimates cloud height from dew point temperature and the temperature profile. The second model simulates the cloud droplet growth from aerosol particles using the cloud parcel concept. In the third model, the scavenging rate of the aerosol particles is calculated using the collision efficiency between charged particles and droplets. The fourth model calculates electric field and charge distribution on water droplets and aerosols within cloud. The fifth model simulates the global electric circuit (GEC), which computes the conductivity and ionic concentration in the atmosphere in altitude range 0–45 km. The first four models are initially coupled to calculate the height of cloud, boundary condition of cloud, followed by growth of droplets, charge distribution calculation on aerosols and cloud droplets and finally scavenging. These models are incorporated with the GEC model. The simulations are verified with experimental data of charged aerosol for various altitudes. Our calculations showed an effect of aerosol charging on the CCN concentration within the cloud, due to charging of aerosols increase the scavenging of particles in the size range 0.1 µm to 1 µm.

A new rain-operated seed dispersal mechanism in Bertolonia mosenii (Melastomataceae), a Neotropical rainforest herb

Although widespread among fungi, lichens, liverworts, and mosses, seed dispersal mechanisms operated by rain are unusual among flowering plants. Generally speaking, two mechanisms are involved in seed dispersal by rains: the splash-cup and the springboard. Here we describe a new seed dispersal mechanism operated by rain in a Neotropical rainforest herb Bertolonia mosenii Cogniaux (Melastomataceae). The study was carried out at the lowland Atlantic rainforest, southeastern Brazil. We experimentally demonstrate that rain is necessary to release the seeds from the capsules through what we call squirt-corner seed dispersal mechanism: when a raindrop strikes the mature fruit, the water droplet forces the seeds outward to the angles (corners) of the triangular capsule and the seeds are released. As far as we know squirt-corner represents a new rain-operated seed dispersal mechanism, and a novel seed dispersal mode both for Melastomataceae and for flowering plants from Neotropical forests.

Aplicação do eletrocapilaridade na manipulação de microgotas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Glycaspis brimblecombei Moore, 1964 (Hemiptera: Psyllidae) on eucalyptus: oviposition non-preference and antibiosis

Forest plantations with Eucalyptus spp. (L'H,r) in Brazil are highly yielding. However, this activity is more and more threatened due to interactions with phytophagous insects, especially by exotic species, such as the red gum lerp psyllid Glycaspis brimblecombei Moore (Hemiptera: Psyllidae). This study aimed to evaluate the resistance in eucalyptus against the psyllid in oviposition and biological development assays, attempting to identify potential genotypes resistant to the pest for forest plantations. In addition, we tested the hypothesis of that concentration of total phenolics and lignin, and amount of epicuticular wax were associated with the expression of resistance. Results showed that there was variation in the levels of resistance among the genotypes assessed. Oviposition non-preference was observed on Eucalyptus citriodora (Hook) in free-choice and no-choice tests, and Clone FP10 was least preferred in the no-choice test. The genotypes E. citriodora and Clone FP6 provided 100 % nymphal mortality, and Clones FP7 and FP9 also affected negatively the G. brimblecombei development by lengthening the duration of the nymphal stage and reducing adult emergence. Clone FP6 had higher concentration of total phenolics and larger contact angle formed between the water droplet and leaf surface, which may be associated with thicker layer of epicuticular wax on the leaves, and one of the causes of high nymphal mortality. Thus, the use of the resistant genotypes of eucalyptus screened against G. brimblecombei is a promising and viable alternative for forest plantations infested with this pest.

Photoreactive polyorganosiloxane nanoparticles and the fabrication of photocleavable microcapsules

In this thesis, we have presented the preparation of highly crosslinked spherical photoreactive colloidal particles of radius about 10 nm based on the monomer trimethoxysilane. These particles are labeled chemically with two different dye systems (coumarin, cinnamate) which are known to show reversible photodimerization. By analyzing the change in particle size upon UV irradiation with dynamic light scattering, we could demonstrate that the partially reversible photoreaction in principle can be utilized to control increase and decrease of colloidal clusters. Here, selection of the appropriate wavelengths during the irradiation employing suitable optical filters proved to be very important. Next, we showed how photocrosslinking of our nanoparticles within the micrometer-sized thin oil shell of water-oil-water emulsion droplets leads to a new species of optically addressable microcontainers. The inner water droplet of these emulsions may contain drugs, dyes or other water-soluble components, leading to filled containers. Thickness, mechanical stability and light resistance of the container walls can be controlled in a simple way by the amount and adjustable photoreactivity (= No. of labels/particle) of the nanoparticles. Importantly, the chemical bonds between the nanoparticles constituting the microcapsule shell can be cleaved photochemically by irradiation with uv light. An additional major advantage is that filling our microcapsules with water-soluble substrate molecules is extremely simple using a solution of the guest molecules as inner water phase of the W/O/W-emulsion. This optically controlled destruction of our microcontainers thus opens up a pathway to controlled release of the enclosed components as illustrated by the example of enclosed cyclodextrin molecules.

Theoretical studies of microfluidics: "walking" drops and "melting" snowflakes.

The present PhD thesis summarizes two examples of research in microfluidics. Both times water was the subject of interest, once in the liquid state (droplets adsorbed on chemically functionalized surfaces), the other time in the solid state (ice snowflakes and their fractal behaviour). The first problem deals with a slipping nano-droplet of water adsorbed on a surface with photo-switchable wettability characteristics. Main focus was on identifying the underlying driving forces and mechanical principles at the molecular level of detail. Molecular Dynamics simulation was employed as investigative tool owing to its record of successfully describing the microscopic behaviour of liquids at interfaces. To reproduce the specialized surface on which a water droplet can effectively “walk”, a new implicit surface potential was developed. Applying this new method the experimentally observed droplet slippage could be reproduced successfully. Next the movement of the droplet was analyzed at various conditions emphasizing on the behaviour of the water molecules in contact with the surface. The main objective was to identify driving forces and molecular mechanisms underlying the slippage process. The second part of this thesis is concerned with theoretical studies of snowflake melting. In the present work snowflakes are represented by filled von Koch-like fractals of mesoscopic beads. A new algorithm has been developed from scratch to simulate the thermal collapse of fractal structures based on Monte Carlo and Random Walk Simulations (MCRWS). The developed method was applied and compared to Molecular Dynamics simulations regarding the melting of ice snowflake crystals and new parameters were derived from this comparison. Bigger snow-fractals were then studied looking at the time evolution at different temperatures again making use of the developed MCRWS method. This was accompanied by an in-depth analysis of fractal properties (border length and gyration radius) in order to shed light on the dynamics of the melting process.

A novel methodology for simulating contact-line behavior in capillary-driven flows

Despite the wide swath of applications where multiphase fluid contact lines exist, there is still no consensus on an accurate and general simulation methodology. Most prior numerical work has imposed one of the many dynamic contact-angle theories at solid walls. Such approaches are inherently limited by the theory accuracy. In fact, when inertial effects are important, the contact angle may be history dependent and, thus, any single mathematical function is inappropriate. Given these limitations, the present work has two primary goals: 1) create a numerical framework that allows the contact angle to evolve naturally with appropriate contact-line physics and 2) develop equations and numerical methods such that contact-line simulations may be performed on coarse computational meshes.

Fluid flows affected by contact lines are dominated by capillary stresses and require accurate curvature calculations. The level set method was chosen to track the fluid interfaces because it is easy to calculate interface curvature accurately. Unfortunately, the level set reinitialization suffers from an ill-posed mathematical problem at contact lines: a ``blind spot'' exists. Standard techniques to handle this deficiency are shown to introduce parasitic velocity currents that artificially deform freely floating (non-prescribed) contact angles. As an alternative, a new relaxation equation reinitialization is proposed to remove these spurious velocity currents and its concept is further explored with level-set extension velocities.

To capture contact-line physics, two classical boundary conditions, the Navier-slip velocity boundary condition and a fixed contact angle, are implemented in direct numerical simulations (DNS). DNS are found to converge only if the slip length is well resolved by the computational mesh. Unfortunately, since the slip length is often very small compared to fluid structures, these simulations are not computationally feasible for large systems. To address the second goal, a new methodology is proposed which relies on the volumetric-filtered Navier-Stokes equations. Two unclosed terms, an average curvature and a viscous shear VS, are proposed to represent the missing microscale physics on a coarse mesh.

All of these components are then combined into a single framework and tested for a water droplet impacting a partially-wetting substrate. Very good agreement is found for the evolution of the contact diameter in time between the experimental measurements and the numerical simulation. Such comparison would not be possible with prior methods, since the Reynolds number Re and capillary number Ca are large. Furthermore, the experimentally approximated slip length ratio is well outside of the range currently achievable by DNS. This framework is a promising first step towards simulating complex physics in capillary-dominated flows at a reasonable computational expense.