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One of the major environmental issues related to spraying of pesticides on cultivated crops is the drift phenomenon. Because of the wind, small droplets may drift away from the targeted crop and cause contamination. One way to reduce the drift is to control the spray drop size distribution and reduce the proportion of small drops. In this context, anti-drift additives have been developed, including dilute oil-in-water emulsions. Although being documented, the effects of oil-in-water emulsions on spray drop size distribution are not yet understood. The objective of this work is to determine the mechanisms at the origin of the changes of the spray drop size distribution for emulsion-based sprays. Agricultural spraying involves atomizing a liquid stream through a hydraulic nozzle. At the exit of the nozzle, a free liquid sheet is formed, which is subsequently destabilized into droplets.In order to elucidate the mechanisms causing the changes of the spray drop size distribution, we investigate the influence of emulsions on the destabilization mechanisms of liquid sheets. Model single-tear experiments based on the collision of one tear of liquid on a small solid target are used to produce and visualize liquid sheets with a fast camera. Upon impact, the tear flattens into a sheet radially expanding in the air bounded by a thicker rim. Different destabilization mechanisms of the sheet are observed depending on the fluid properties. A pure water sheet spreads out radially and then retracts due to the effect of surface tension. Simultaneously, the rim corrugates forming radial ligaments, which are subsequently destabilized into droplets. The destabilization mechanism is drastically modified when a dilute oil-in-water emulsion is used. Emulsion-based liquid sheets are destabilized through the nucleation of holes within the sheet that perforate the sheet during its expansion. The holes grow until they merge together and form a web of ligaments, which are then destabilized into drops.The physical-chemical parameters of the emulsion, such as emulsion concentration and emulsion droplet size distribution, are modified to rationalize their influence on the perforation mechanism. We correlate the size distribution of drops issued from conventional agricultural spray with the amount of perforation events in single-tear experiments, demonstrating that the single-tear experiment is an appropriate model experiment to investigate the physical mechanisms governing the spray drop size distribution of anti-drift formulations. We show that the relevant mechanism causing the increase of drops size in the emulsion-based spray is a perforation mechanism.To gain an understanding of the physical mechanisms at the origin of the perforation events, we develop an optical technique that allows the determination of the time and space-resolved thickness of the sheet. We find that the formation of a hole in the sheet is systematically preceded by a localized thinning of the liquid film. We show that the thinning results from the entering and Marangoni-driven spreading of emulsion oil droplet at the air/water interface. The localized thinning of the liquid film ultimately leads to the rupture of the film. We propose the perforation mechanism as a sequence of two necessary steps: the emulsion oil droplets (i) enter the air/water interface, and (ii) spread at the interface. We show that the formulation of the emulsion is a critical parameter to control the perforation. The addition of salt or amphiphilic copolymers can trigger or completely inhibit the perforation mechanism. We show that the entering of oil droplets at the air/water interface is the limiting step of the mechanism. Thin-film forces such as electrostatic or steric repulsion forces stabilize the thin film formed between the interface and the approaching oil droplets preventing the entering of oil droplets at the interface and so inhibit the perforation process.

Ultrasound-modulated optical tomography (UOT) is a technique that images optical contrast deep inside scattering media. Heterodyne holography is a promising tool able to detect the UOT tagged photons with high efficiency. In this work, we describe theoretically the detection of the tagged photon in heterodyne holography based UOT, show how to filter the untagged photon discuss, and discuss the effect of speckle decorrelation. We show that optimal detection sensitivity can obtain, if the frame exposure time is of the order of the decorrelation time.

Colloids and nanoparticles possessing two different faces with distinct properties are called Janus as the Roman God depicted with two faces looking in opposite directions. In this talk a fabrication of Janus particles by droplet based microfluidics will be presented. Silica colloids dispersed in the oil phase and gold nanoparticles dispersed in the aqueous phase meet at the droplet oil-water interface. The contact angle of the silica colloid defines the area of the silica face immersed in water, which can be decorated by the gold nanoparticles, forming the Janus silica-gold particle.Many physical and physicochemical aspects take part in this process. Wetting of the silica and gold particles set the contact angle of the particles at the droplet interface, which depends strongly on the chemical groups used to stabilize the particles, and in principle allow the fabrication of Janus particles of different area ratios. Adsorption onto the oil-water interface is also a key process, which depends not only on the concentration but also on the hydrodynamic flows and geometry present in the microfluidic channels. The role of long range surface forces such as Van der Waals and electrostatic will be also highlighted both for the adsorption kinetics and for the effect on the particle size dependent contact angle.

Commercial carboxymethylcellulose was used to prepare dispersible multi-walled carbon nanotubes-based composites. These composites were employed to prepare Pickering oil-in-water emulsions. Emulsion-templated macroporous materials were then prepared by embedding the oil droplets into a polymer resin arising from the polycondensation of furfural and phloroglucinol within the continuous aqueous phase in the presence of FeCl3 as catalyst. Polymerization afforded organic–inorganic nanocomposite materials in the form of capsules. After pyrolysis, highly microporous, magnetic and electrically conductive micrometric capsules could be obtained. This approach opens interesting prospects for catalysis, separation and electrochemistry applications.

A mild and simple way to prepare stable aqueous colloidal suspensions of composite particles made of a cellulosic material (Sigmacell cellulose) and multiwalled carbon nanotubes (MWCNTs) is reported. These suspensions can be dried and redispersed in water at pH 10.5. Starting with rather crude initial materials, commercial Sigmacell cellulose and MWCNTs, a significant fraction of composite dispersed in water could be obtained. The solid composites and their colloidal suspensions were characterized by electronic microscopy, thermal analyses, FTIR and Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and light scattering. The composite particles consist of tenuous aggregates of CNTs and cellulose, several hundred nanometers large, and are composed of 55 wt % cellulose and 45 wt % CNTs. Such particles were shown to stabilize cyclohexane-in-water emulsions. The adsorption and the elasticity of the layer they form at interface were characterized by the pendant drop method. The stability of the oil-in-water emulsions was attributed to the formation of an elastic network of composite particles at interface. Cyclohexane droplet diameters could be tuned from 20 to 100 μm by adjusting the concentration of composite particles. This behavior was attributed to the limited coalescence phenomenon, just as expected for Pickering emulsions. Interestingly, cyclohexane droplets were stable over time and sustained pH modifications over a wide range, although acidic pH induced accelerated creaming. This study points out the possibility of combining crude cellulose and MWCNTs through a simple process to obtain colloidal systems of interest for the design of functional conductive materials.

Alumina-coated silica nanoparticles (NPs) grafted with phosphonic acids of different hydrophobicitywere used as filler in poly(ethylacrylate) nanocomposites. Phosphonic acids bearing short alkyl chains ora diethylene glycol group have been grafted at densities up to 3.2 P/nm2 on NPs (20 nm) dispersed inwater. Nanocomposites at particle fractions up to 10 vol% have been formulated by casting from thecolloidal mixtures of modified NPs and nanolatex in water. The dispersion of the NPs in the polymermatrix has been studied by TEM combined with small-angle scattering, evidencing aggregation of NPs.TEM shows micrometer-scale inhomogeneities depending on the surface/polymer matrix compatibility.For the local interparticle correlations, a quantitative analysis of the intensity based on the mapping ontothe effective structure factor of polydisperse hard spheres is developed. This mapping allows the modelfreedetermination of the internal volume fraction of aggregates, termed compacity k, to between 10%and 30%, compatible with the TEM analysis. k is found to increase for the higher particle volume fractions,to decrease with grafting density, and to be mostly independent of the nature and mass of thegraft. Preliminary evidence for an improved compatibility of grafted with respect to bare NPs is found, asopposed to their aqueous precursor suspensions where some pre-aggregation is induced by grafting.