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Matière molle pour l’agronomie et l’environnement
(43) Production(s) de l'année 2016
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Small angle neutron scattering contrast variation reveals heterogeneities of interactions in protein gels
Auteur(s): Banc A., Charbonneau C., Dahesh M., Appavou Marie-Sousai, Fu Zhendong, Morel Marie-Hélène, Ramos L.
(Article) Publié:
Soft Matter, vol. 12 p.5340-5352 (2016)
Texte intégral en Openaccess :
Ref HAL: hal-01317647_v1
Ref Arxiv: 1605.05867
DOI: 10.1039/c6sm00710d
WoS: 000378934400011
Ref. & Cit.: NASA ADS
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11 Citations
Résumé: The structure of model gluten protein gels prepared in ethanol/water is investigated by small angle X-ray (SAXS) and neutrons (SANS) scattering. We show that gluten gels display radically different SAXS and SANS profiles when the solvent is (at least partially) deuterated. The detailed analysis of the SANS signal as a function of the solvent deuteration demonstrates heterogeneities of sample deuteration at different length scales. The progressive exchange between the protons (H) of the proteins and the deuteriums (D) of the solvent is inhomogeneous and 60 nm large zones that are enriched in H are evidenced. In addition, at low protein concentration, in the sol state, solvent deuteration induces a liquid/liquid phase separation. Complementary biochemical and structure analyses show that the denser protein phase is more protonated and specifically enriched in glutenin, the polymeric fraction of gluten proteins. These findings suggest that the presence of H-rich zones in gluten gels would arise from the preferential interaction of glutenin polymers through a tight network of non-exchangeable intermolecular hydrogen bonds.
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Bursting mechanism of dilute emulsion-based liquid sheets: anti-drift application for agricultural sprays
Auteur(s): Ligoure C.
Conférence invité: 12th SoftComp annual meeting (Ancône, IT, 2016-06-07)
Ref HAL: hal-01331928_v1
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Résumé: 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.
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Microfluidic fabrication of Janus particles: wetting, surface forces and hydrodynamics
Auteur(s): Stocco A.
Conférence invité: EMN Droplets (San Sebastian, ES, 2016-05-09)
Ref HAL: hal-01329861_v1
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Résumé: 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.
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Nanocomposites with both structural and porous hierarchy synthesized from Pickering emulsions
Auteur(s): Avendano Carlos, Brun Nicolas, Mourad Eleonore, Fontaine Olivier, Sarroste Christine Labrugere, Baccour Mohamed, In M., Mehdi Ahmad, Stocco A., Vioux Andre
(Article) Publié:
New Journal Of Chemistry, vol. 40 p.4344-4350 (2016)
Ref HAL: hal-01329849_v1
DOI: 10.1039/c5nj03248b
WoS: WOS:000375586400041
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3 Citations
Résumé: 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.
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Multiwalled Carbon Nanotube/Cellulose Composite: From Aqueous Dispersions to Pickering Emulsions
Auteur(s): Avendano Carlos, Brun Nicolas, Fontaine Olivier, In M., Mehdi Ahmad, Stocco A., Vioux Andre
(Article) Publié:
Langmuir, vol. 32 p.3907-3916 (2016)
Ref HAL: hal-01324784_v1
DOI: 10.1021/acs.langmuir.6b00380
WoS: WOS:000375243300012
Exporter : BibTex | endNote
12 Citations
Résumé: 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.
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DROP IMPACT EXPERIMENT AS A MODEL EXPERIMENT TO INVESTIGATE THE ROLE OF OIL-IN-WATER EMULSIONS IN CONTROLLING THE DROP SIZE DISTRIBUTION OF AN AGRICULTURAL SPRAY
Auteur(s): Vernay C., Ramos L., Douzals Jean-Paul, Goyal Rajesh, Castaing Jean-Christophe, Ligoure C.
(Article) Publié:
Atomization And Sprays, vol. 26 p.827-851 (2016)
Ref HAL: hal-01304654_v1
DOI: 10.1615/AtomizSpr.2015013630
WoS: WOS:000375749100006
Exporter : BibTex | endNote
3 Citations
Résumé: Agricultural spraying involves atomizing a liquid stream through a hydraulic nozzle, thus forming a liquid sheet that is subsequently destabilized into drops. Standard adjuvants such as dilute oil-in- water emulsions are known to influence the spray drop size distribution. Although being documented, the physical mechanisms at the origin of the size increase remain unclear. To elucidate the mechanisms causing the changes on the drop size distribution, we investigate the influence of dilute emulsions on the destabilization mechanisms of liquid sheets. Model laboratory experiments based on the collision of a liquid tear on a small solid target are used to produce and characterize liquid sheets. With dilute oil-in-water emulsions, the liquid sheet is destabilized during its expansion by the nucleation of holes that perforate the sheet and grow. The emulsion concentration and the size of the oil droplet of the emulsion are varied to rationalize their influence on the sheet destabilization mechanisms. The results obtained with the model laboratory experiments are compared to the measurement of the drop size distribution resulting from a conventional agricultural spray. The very good correlation between the number of perforation events and the volume fraction of small drops in the spray suggests (i) that the model experiment on liquid sheet is appropriate to investigate and gain an understanding of the physical mechanisms governing the spray drop size distribution and (ii) that the perforation destabilization mechanism of liquid sheets, which dominates for dilute emulsions, is at the origin of the increase of the size of the spray drops.
Commentaires: [Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]INSPIRE
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