Temperature-Insensitive Nonpolar Suspensions of Polyoxyethylene Alkyl Ether-Grafted Silica Nanoparticles.

Nonpolar suspensions of organically modified particles exhibit a strong temperature sensitivity owing to the high-temperature-induced desorption/decomposition and the low-temperature-induced disorder/order conformational transition of the modifiers. This strong temperature sensitivity limits their applications, such as lubricants and oil-based drilling fluids, which require the suspensions to operate over a wide temperature range (e.g., 0-200 °C). We hypothesize that the introduction of a flexible ethylene oxide (EO) chain into the modifiers can disrupt the low-temperature-induced ordered conformation to improve the stability of the nonpolar suspensions. In this article, nonpolar suspensions with temperature insensitivity in the range of 5-160 °C were obtained via the covalent modification of silica NPs and the introduction of EO chains into the modifier molecules. Here, octadecyl-grafted silica NPs (C18-SiO2) and polyoxyethylene alkyl ether-grafted silica NPs (AEOn-SiO2) were synthesized and subsequently dispersed in mineral oil. The rheological properties of each suspension at different temperatures were evaluated, and the thermal stability of AEOn-SiO2 in mineral oil was investigated along with the conformational changes of the grafted chains. In the temperature range of 5-160 °C, the apparent viscosity and gel strength of the C18-SiO2 suspension changed dramatically, whereas the AEOn-SiO2 suspensions exhibited constant rheological properties over this temperature range. This temperature insensitivity of AEOn-SiO2 suspensions is attributed to the excellent thermal stability of AEOn-SiO2 in mineral oil and the disordered conformation of the EO chains upon cooling. This study provides a novel approach to preparing temperature-insensitive nonpolar suspensions, which have potential applications in the petroleum and lubricant industries.

Bulk and Interfacial Contributions to Stabilization of Cyclodextrin-Based Emulsions Mediated by Bacterial Cellulose.

Cyclodextrin (CD)-based emulsions have a characteristic of rapid droplet flocculation, which limits their application as functional material templates, so it is very important to improve the stability of CD-based emulsions. In this study, we select bacterial cellulose (BC) as a nonadsorbing inhibitor to prevent flocculation of CD-based emulsions. We map a phase diagram of the aqueous dispersions of CD inclusion complexes (ICs) and BC from morphological observations and investigate the effects of BC on properties of the IC-laden films. We further explore the effects of BC concentration on the stability of the CD-based emulsions and investigate rheological behavior of the emulsions through large-amplitude oscillatory shear experiments. It shows that BC can effectively suppress the flocculation of CD-based emulsion droplets even at a concentration as low as 0.01 wt %. We propose that BC has dual effects from bulk and interfacial contributions on increasing emulsion stability. At low concentrations, BC mainly results in higher packing density of ICs on the emulsion droplet surface through excluded volume repulsion, and at high concentrations, BC creates a network structure that confines the motion of emulsion droplets and retards flocculation.

Droplet clustering in cyclodextrin-based emulsions mediated by methylcellulose.

Rapid droplet aggregation in cyclodextrin (CD)-stabilized emulsions limits their practical use as material templates. Herein, we formulate mixtures of submicron CD-based emulsion droplets suspended in aqueous solutions of methylcellulose (MC) with various concentrations and molecular weights. We evaluate the effects of MC on the microstructure and stability of the emulsions using different techniques including optical microscopy, laser particle analysis, confocal laser scanning microscopy and multiple light scattering, explore the rheological behavior of the emulsions through large amplitude oscillatory shear experiments, and study the viscoelastic nonlinearities of the emulsions as a function of strain and strain-rate space through nondimensional elastic and viscous Lissajous-Bowditch plots. It is demonstrated that the emulsion droplets are present in the form of small clusters and their size is almost independent of MC concentration and molecular weight. The clustering pattern is also supported by the changes in viscoelastic properties of the emulsions and the intracycle nonlinear behavior of the Lissajous-Bowditch plots. We propose for the first time that glass-like dynamic arrest takes place with the formation of small equilibrium droplet clusters in the situation where the CD-based emulsion droplets are forced by depletion flocculation and kinetic trapping simultaneously exerted by MC.