Ref HAL: hal-01329849_v1
DOI: 10.1039/c5nj03248b
WoS: WOS:000375586400041
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3 Citations
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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.

Ref HAL: hal-01324784_v1
DOI: 10.1021/acs.langmuir.6b00380
WoS: WOS:000375243300012
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12 Citations
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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.

Ref HAL: hal-01317973_v1
DOI: 10.1016/j.polymer.2016.04.073
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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.

Ref HAL: hal-01307989_v1
DOI: 10.1039/C5FD00117J
WoS: 000374440100019
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13 Citations
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Polymer nanocomposites are used widely, mainly for the industrial application of car tyres. The rheological behavior of such nanocomposites depends in a crucial way on thedispersion of the hard filler particles – typically silica nanoparticles embedded in a soft polymer matrix. It is thus important to assess the filler structure, which may be quitedifficult for aggregates of nanoparticles of high polydispersity, and with strong interactions at high loading. This has been achieved recently using a coupled TEM/SAXSstructural model describing the filler microstructure of simplified industrial nanocomposites with grafted or ungrafted silica of high structural disorder. Here, wepresent an original method capable of reducing inter-aggregate interactions by swelling of nanocomposites, diluting the filler to low-volume fractions. Note that this isimpossible to reach by solid mixing due to the large differences in viscoelasticity between the composite and the pure polymer. By combining matrix crosslinking,swelling in a good monomer solvent, and post-polymerization of these monomers, it isshown that it is possible to separate the filler into small aggregates. The latter have then been characterized by electron microscopy and small-angle X-ray scattering,confirming the conclusions of the above mentioned TEM-SAXS structural model applied directly to the highly loaded cases.

Ref HAL: hal-01307454_v1
DOI: 10.1039/C5CE02477C
WoS: 000373566300012
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6 Citations
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Single crystals of α-quartz type Si1−xGexO2 with x < 0.2 were grown in 0.05 M NaOH solution. Infrared measurements confirmed that crystals grown at high pressure and high temperature have a low –OH group defect content. After a few millimeters of crystal growth under these conditions, α3500 reaches 0.1 cm−1 and no free –OH are present. The d11 value measured on an X-cut from the crystal with x = 0.0375 is 3.08 pC N−1 (±0.15), in good agreement with the value of 2.97 pC N−1 obtained using density functional theory based calculations. Piezoelectric measurements were performed on the Si1−xGexO2 crystal with x = 0.0375, both at room temperature and after annealing at various temperatures. The piezoelectric signal of the crystal with x = 0.0375 and pure SiO2 disappears after annealing at 635 °C and 545 °C, respectively. Nonlinear optical (NLO) properties of Si1−xGexO2 crystals were measured by Maker's fringe technique on Z-cut χ11(2) and their corresponding values for x = 0.023 and 0.028 are 1.3(2) pm V−1 and 1.6(2) pm V−1, respectively. These values are in good agreement with density functional theory based calculations. The light induced damage threshold values measured on Si1−xGexO2 crystals with x = 0.023 and 0.028 are very similar to that of α-quartz.

Ref HAL: hal-01304654_v1
DOI: 10.1615/AtomizSpr.2015013630
WoS: WOS:000375749100006
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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

Ref HAL: hal-01303522_v1
DOI: 10.3390/ijms17020223
WoS: WOS:000371830800032
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13 Citations
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Surface activity and micelle formation of alkylguanidinium chlorides, containing 10, 12, 14, and 16 carbon atoms in the hydrophobic tail have been studied by combining conductivity and surface tension measurements with isothermal titration calorimetry. The purity of the resulting surfactants, their temperatures of Cr → LC and LC → I transitions, as well as their propensity of forming birefringent phases were assessed based on the results of 1H and 13C NMR, differential scanning calorimetry (DSC), and polarizing microscopy studies. Whenever possible, the resulting values of Krafft temperature (TK), critical micelle concentration (CMC), minimum surface tension above the CMC, chloride counter-ion binding to the micelle, and the standard enthalpy of micelle formation per mole of surfactant (micH°), were compared to those characterizing alkyltrimethylammonium chlorides or bromides with the same tail lengths. The value of TK ranged between 292 and 314 K and increased strongly with increase in the chain length of the hydrophobic tail. Micellization was described as both entropy and enthalpy-driven. Based on the direct calorimetry measurements, the general trends in the CMC with the temperature, hydrophobic tail length and NaCl addition were found to be similar to those of other types of cationic surfactants. The particularly exothermic character of micellization was ascribed to the hydrogen-binding capacity of the guanidinium head-group.