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The development of functional materials by taking advantage of the physical properties of nanoparticles needs an optimal control over their size and crystal quality. In this context, the synthesis of crystalline oxide nanoparticles in water at room temperature is a versatile and industrially appealing process but lacks control especially for "large" nanoparticles (>30 nm), which commonly consist of agglomerates of smaller crystalline primary grains. Improvement of these syntheses is hampered by the lack of knowledge on possible intermediate, noncrystalline stages, although their critical importance has already been outlined in crystallization processes. Here, we show that during the synthesis of luminescent Eu-doped YVO4 nanoparticles a transient amorphous network forms with a two-level structuration. These two prestructuration scales constrain topologically the nucleation of the nanometer-sized crystalline primary grains and their aggregation in nanoparticles, respectively. This template effect not only clarifies why the crystal size is found independent of the nucleation rate, in contradiction with the classical nucleation models, but also supports the possibility to control the final nanostructure with the amorphous phase.

We have investigated polyelectrolyte multilayers of poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) in contact with D2O by neutron reflectometry. The study particularly focuses on the changes in the solvent fraction of the system upon addition of a layer. When the layers are deposited at a low salt concentration (0.25 M NaCl), no significant changes in the solvent fraction are detected. In contrast, at a larger salt concentration (1 M NaCl), oscillations in the solvent fraction are detected when a new layer is deposited. In this case, addition of PSS systematically increases the solvent volume fraction, and addition of PAH decreases the solvent fraction. The results suggest that one of the parameters driving the oscillations in solvent fraction is the uncompensated charges present in the layers. This study opens new perspectives on results previously published by other authors: in addition to polymer desorption, water uptake or release might contribute to the different regimes of multilayer growth reported in the literature (linear, asymmetric, or exponential growth). In addition, comparison to NMR results previously reported allows for conclusions about the mobility of the solvent in the multilayers: the average rotational correlation time of the water molecules in the polyelectrolyte layers decreases upon addition of PSS and increases upon addition of PAH.

We report a dramatic increase of foam stability for catanionic mixtures (myristic acid and cetyl trimethylammonium bromide, CTABr) with respect to pristine CTABr solutions. This increase was related to the low surface tension, high surface concentration and high viscoelastic compression moduli, as measured with rising bubble experiments and ellipsometry. Dialysis of the catanionic mixtures has been used to decrease the concentration of free surfactant ions (CTA +). The equilibrium surface tension is reached faster for non dialysed samples, due to the presence of these free ions. As a consequence, the foamability of the dialysed solutions is lower. Foam coarsening has been studied using multiple light scattering: it is similar for dialysed and non dialysed samples and much slower than for pure CTABr foams.

We have studied the dialysis of surfactant mixtures of two oppositely charged surfactants (catanionic mixture) by combining HPLC, neutron activation, confocal microscopy, and NMR. In mixtures of n-alkyl trimethylammonium halides and n-fatty acids, we have demonstrated the existence of a specific ratio between both surfactant contents (anionic/cationic almost equal to 2:1) that determines the morphology, the elimination of ions, and the elimination of the soluble cationic surfactant upon dialysis. In mixtures prepared with lower anionic surfactant contents, ill-defined aggregates are formed, and dialysis quickly eliminates the ion pairs (H+X-) formed upon surfactant association and also the cationic surfactant until a limiting 2:1 ratio is reached. By contrast, mixtures prepared above the anionic/cationic 2:1 ratio form micrometer-sized vesicles resistant to dialysis. These closed aggregates retain a significant number of ions (30%) over 1000 hours, and dialysis is unable to eliminate the soluble surfactant. The interactions between surfactants have been estimated by measuring the partitioning of the CTA molecules between the catanionic bilayer, the bulk solution, and mixed micelles when they exist. The mean extraction free energy per CTA in the membrane has been found to increase by 1 kBT to 2 kBT as the soluble surfactant is depleted from the bilayer, which is enough to stop the dialysis. The vesicles produced above the anionic/cationic 2:1 ratio are formed by frozen bilayers and are resistant to extensive dialysis and therefore show an interesting potential for encapsulation as far as durability is concerned.

We here report on the covalent grafting of various phosphated species (phosphoric acid, phenylphosphonic acid, and octyl phosphate) onto the surface of monoclinic zirconia nanoparticles obtained by hydrothermal treatment of zirconium acetate. The initial particles are 60 nm aggregates of nanometric primary grains and present an inner porosity. Small-angle X-ray scattering shows that the high specific area of the colloidal particles (450 m2·g-1) decreases to 150 m2·g-1 upon drying. Therefore, phosphated reactants can access the whole internal surface of the aggregates only before drying. The surface of the particles can be covered with functional groups bound through a variable number of Zr−O−P bonds. Several factors probably enhance the reaction between the particles and the phosphates or phosphonates:  the large specific area of the particles, a fully accessible porous network, and a large concentration of surface terminal groups. At the same time, the morphology of the particles is well preserved upon grafting. This is due to the good crystallinity of the primary grains that constitute the particles. In addition, the grafting drastically modifies the surface properties of the colloids. For example, the polarizability of the particles decreases in the sequence −POH > as-prepared ZrO2 > −PC6H5 > −POC8H17. Furthermore, the grafting of octyl phosphate allows exclusion of water from pores of 2 nm radius, up to hydrostatic pressures of 20 MPa.

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International audienceVesicles of fatty acids in the fluid state show interesting biomimetic properties and are potentially versatile substitutes to phospholipid vesicles in materials science. However, their use is hindered by a poor stability against variations in pH, ionic strength, temperature etc., which can be improved by using, for instance, mixtures of fatty acids and other amphiphilic molecules. Here we report an original property of fatty acid vesicles with aliphatic chains in the gel state prepared from mixtures of fatty acids and cationic surfactants. Apart from encapsulating added solutes in high yields and showing a high durability, even against drastic dialysis, dilution, concentration etc., these vesicles also spontaneously encapsulate the counter-ions (H+ and halides) released upon surfactant association. This "self-encapsulation'' leads to large and sustainable pH gradients across the bilayer (Delta pH approximate to 3 over months), and is mediated by the formation of gel-phase bilayers with little defects. Both the formation of the vesicles and their ability for self-encapsulation of counter-ions have a broad generality and can be exploited with other surfactants to generate pH gradients ranging from acid to base