Mathieu Destribats

Pickering emulsions stabilized by soft microgels: influence of the emulsification process on particle interfacial organization and emulsion properties.

This work reports a new evidence of the versatility of soft responsive microgels as stabilizers for Pickering emulsions. The organization of microgels at the oil-water interface is a function of the preparation pathway. The present results show that emulsification energy can be used as a trigger to modify microgel deformation at the oil-water interface and their packing density: high shear rates bring strong flattening of the microgels, whereas low shear rates lead to dense monolayers, where the microgels are laterally compressed. As a consequence, the resulting emulsions have opposite behavior in terms of flocculation, which arises from bridging between neighboring drops and is strongly dependent on their surface coverage. This strategy can be applied to any microgel which can sufficiently adsorb at low shear rates, i.e. small microgels or lightly cross-linked ones. The control of the organization of microgels at the interface does not only modify emulsion end-use properties but also constitutes a new tool for the development of Janus-type microgels, obtained by chemical modification of the adsorbed microgels.

Water-in-oil emulsions stabilized by water-dispersible poly(N-isopropylacrylamide) microgels: understanding anti-Finkle behavior.

Emulsions were prepared using poly(N-isopropylacrylamide) microgels as thermoresponsive stabilizers. The latter are well-known for their sensitivity to temperature: they are swollen by water below the so-called volume phase transition temperature (VPTT = 33 °C) and shrink when heated above it. Most of the studies reported in the literature reveal that the corresponding emulsions are of the oil-in-water type (O/W) and undergo fast destabilization upon warming above the VPTT. In the present study, whereas O/W emulsions were obtained with a wide panel of oils of variable polarity and were all thermoresponsive, water-in-oil (W/O) emulsions were found only in the presence of fatty alcohols and did not exhibit any thermal sensitivity. To understand the peculiar behavior of emulsions based on fatty alcohols, we investigated the organization of microgels at the oil-water interface and we studied the interactions of pNIPAM microgels with octanol. By combining several microscopy methods and by exploiting the limited coalescence process, we provided evidence that W/O emulsions are stabilized by multilayers of nondeformed microgels located inside the aqueous drops. Such behavior is in contradiction with the empirical Finkle rule stating that the continuous phase of the preferred emulsion is the one in which the stabilizer is preferentially dispersed. The study of microgels in nonemulsified binary water/octanol systems revealed that octanol diffused through the aqueous phase and was incorporated in the microgels. Thus, W/O emulsions were stabilized by microgels whose properties were substantially different from the native ones. In particular, after octanol uptake, they were no longer thermoresponsive, which explained the loss of responsiveness of the corresponding W/O emulsions. Finally, we showed that the incorporation of octanol modified the interfacial properties of the microgels: the higher the octanol uptake before emulsification, the lower the amount of particles in direct contact with the interface. The multilayer arrangement was thus necessary to ensure efficient stabilization against coalescence, as it increased interface cohesiveness. We discussed the origin of this counterexample of the Finkles rule.

Impact of pNIPAM Microgel Size on Its Ability To Stabilize Pickering Emulsions

We study the influence of the particle size on the ability of poly(N-isoprolylacrylamide) microgels to stabilize direct oil-in-water Pickering emulsions. The microgel size is varied from 250 to 760 nm, the cross-linking density being kept constant. The emulsion properties strongly depend on the stabilizer size: increasing the particle size induces an evolution from dispersed drops and fluid emulsions toward strongly adhesive drops and flocculated emulsions. In order to get insight into this dependency, we study how particles adsorb at the interface and we determine the extent of their deformation. We propose a correlation between microgel ability to deform and emulsion macroscopic behavior. Indeed, as the microgels size increases, their internal structure becomes more heterogeneous and so does the polymeric interfacial layer they form. The loss of a uniform dense layer favors bridging between neighboring drops, leading to flocculated and therefore less handleable emulsions.

Thermostimulable Wax@SiO2 Core-Shell Particles

We propose a new synthesis pathway without any sacrificial template to prepare original monodisperse thermoresponsive capsules made of a wax core surrounded by a silica shell. Under heating, the inner wax expands and the shell breaks, leading to the liquid oil release. Such capsules that allow triggered deliverance provoked by an external stimulus belong to the class of smart materials. The process is based on the elaboration of size-controlled emulsions stabilized by particles (Pickering emulsions) exploiting the limited coalescence phenomenon. Then the emulsions are cooled down and the obtained suspensions are mineralized by the hydrolysis and condensation of a monomer at the wax-water interface, leading to the formation of capsules. The shell break and the liquid oil release are provoked by heating above the wax melting temperature. We characterize the obtained materials and examine the effect of processing parameters and heating history. By an appropriate choice of the wax, the temperature of release can easily be tuned.

A novel three-dimensional macrocellular carbonaceous biofuel cell

Here we report the first membrane-free biofuel cell obtained using three-dimensional carbonaceous foam electrodes. We first developed a new synthetic pathway to produce a new carbonaceous foam electrode material bearing porosity both on the meso and macroporous scales. We proved that by increasing the porosity of our three-dimensional foams we could increase the current density of our modified electrodes. Then, by choosing the right combination of enzyme and mediator, and the right loading of active components, we achieved high current densities for an anodic system. Finally, we combined the improved cathode and anode to build a new membrane-free hybrid enzymatic biofuel cell consisting of a mediated anode and a mediator-free cathode.

Outstanding Stability of Poorly-protected Pickering Emulsions

Pickering emulsions are surfactant-free emulsions, stabilized solely by colloidal particles. Most of these emulsions exhibit exceptionally high stability and bulk elasticity. In order to investigate the effect of interfacial particle interactions and structure on the emulsions properties, we synthesized particles (silica, core-shell latexes, neighborite cubes) whose interactions can be tuned by a composition variable (pH, ionic strength…) leading to stimulus-responsive materials. The systems could switch from kinetically stable to unstable on demand. Surprisingly, some kinetically stable emulsions were obtained at very low interfacial particle coverage. We demonstrate the generality of this phenomenology using different types of particles and we discuss the origin of the stabilization in the poorly-covered regime.