Shangying Liu

Double Phase Inversion of Emulsions Containing Layered Double Hydroxide Particles Induced by Adsorption of Sodium Dodecyl Sulfate

A liquid paraffin-water emulsion was investigated using layered double hydroxide (LDH) particles and sodium dodecyl sulfate (SDS) as emulsifiers. Both emulsifiers are well-known to stabilize oil-in-water (o/w) emulsions. Surprisingly, a double phase inversion of the emulsion containing LDH particles is induced by the adsorption of SDS. At a constant LDH concentration, the emulsion is o/w type when SDS concentrations are low. At intermediate SDS concentrations, the first emulsion inversion from o/w to w/o occurs, which is attributed to the enhanced hydrophobicity of LDH particles caused by the desorption of the second layer of surfactant, leaving a densely packed SDS monolayer on the LDH exterior surfaces. The second inversion from water-in-oil (w/o) to o/w occurs at higher SDS concentrations, which may be due to the competitive adsorption at the oil/water interfaces between the LDH particles modified by the SDS bilayers and the free SDS molecules in the bulk solution, but the free SDS molecules dominate and determine the emulsion type. Laser-induced fluorescent confocal micrographs clearly confirm the adsorption of LDH particles on the surfaces of the initial o/w and intermediate w/o emulsion droplets, whereas no LDH particles were adsorbed on the final o/w emulsion droplet surfaces. Also, transmission electron microscopy (TEM) observations indicate that the shape of the final o/w emulsions is similar to that of the monomeric SDS-stabilized emulsion but different from that of the initial o/w emulsions. The adsorption behavior of SDS on LDH particles in water was investigated to offer an explanation for the emulsion double phase inversion. The zeta potential results show that the particles will flocculate first and then redisperse following surfactant addition. Also, X-ray diffraction (XRD) measurements indicate that SDS adsorption on the LDH interior surfaces will be complete at intermediate concentrations.

Phase Behavior of Mixtures of Positively Charged Colloidal Platelets and Nonadsorbing Polymer

We investigated the effect of nonadsorbing polymer on the phase behavior of suspensions of positively charged Mg2Al layered double hydroxide (LDH) platelets by birefringence observations and rheological measurements. We show that the depletion attraction, induced by the addition of a high-molecular-weight polyvinyl pyrrolidone (PVP), enriches the phase behavior of these electrostatically stabilized suspensions. At intermediate LDH and polymer concentration, two isotropic phases (I1-I2) coexist, nematic-nematic (N1-N2) demixing occurs, and a sediment phase is observed, with the appearance of two-, three-, four-, and even six-phase coexistence. Upon increasing the polymer concentration, the I-N phase transition and the sol-gel transition shift to lower LDH concentrations; meanwhile, the I-N coexistent samples enter the purely nematic phase. We explain the richness of the phase behavior in such LDH-PVP mixtures by discussing the interactions among PVP-induced depletion attraction, particle polydispersity, and particle sedimentation.

Rearrangement of layered double hydroxide nanoplatelets during hollow colloidosome preparation

Hollow colloidosomes consisting of plate-like Mg/Al layered double hydroxide (LDH) nanoparticles have been prepared by a facile route from a Pickering emulsion. The particles are first adsorbed onto the surface of paraffin oil-in-water emulsion droplets. After the core oil is dissolved in the surrounding bulk liquid, using solvents that are miscible with both the internal and external phases of the droplets, colloidosomes are formed. In this process, we find that the diameters of the colloidosomes are significantly reduced compared to those of the emulsion droplets. The reduction in the diameter is caused by rearrangement of the LDH platelets. That is, the platelets change their orientation from lying flat on the emulsion droplet surface to standing erect in a dense, face-to-face connecting pattern in the colloidosome shell. The main reason for the particle rearrangement is the increase of the attractive forces among the particles due to the reduced polarity of the solvents used during colloidosome preparation.