Variation in emulsion stabilization behavior of hybrid silicone polymers with change in molecular structure: Phase diagram study.

Silicone oils are widely used in cosmetics and personal care applications to improve softness and condition skin and hair. Being insoluble in water and most hydrocarbons, a common mode of delivering them is in the form of emulsions. Currently most applications use polyoxyethylene (non-ionic) modified siloxanes as emulsifiers to stabilize silicone oil emulsions. However, ionically grafted silicone polymers have not received much attention. Ionic silicones have significantly different properties than the non-ionic counterpart. Thus considerable potential exists to formulate emulsions of silicones with different water/silicone oil ratios for novel applications. In order to understand the mechanisms underlying the effects of hydrophilic modifications on the ability of hybrid silicone polymers to stabilize various emulsions, this article focuses on the phase diagram studies for silicone emulsions. The emulsifying ability of functional silicones was seen to depend on a number of factors including hydrophilicity of the polymer, nature of the functional groups, the extent of modification, and the method of emulsification. It was observed that the region of stable emulsion in a phase diagram expanded with increase in shear rate. At a given shear rate, the region of stable emulsion and the nature of emulsion (water-in-oil or oil-in-water) was observed to depend on hydrophilic-hydrophobic balance of the hybrid silicone emulsifier. At a fixed amount of modification, the non-ionically modified silicone stabilized an oil-in-water emulsion, whereas the ionic silicones stabilized inverse water-in-oil emulsions. This was attributed to the greater hydrophilicity of the polyoxyethylene modified silicones than the ionic counterparts. In general, it is postulated that with progressive increase in hydrophilicity of hybrid silicone emulsifiers, their tendency to stabilize water-in-oil emulsion decreases with corresponding increase in oil-in-water emulsion. Further, this behavior is hypothesized to depend on the nature of modifying functional groups. Thus a hybrid silicone polymer can be tailored by selecting the nature and degree of hydrophilicity to obtain a desired silicone emulsion.

Mechanism of stabilization of silicone oil-water emulsions using hybrid siloxane polymers.

Silicone polymers, due to their high lubricity and good spreading properties, are widely used in industrial applications. Being insoluble in water and most hydrocarbons, a common mode of delivering silicones is in the form of emulsions. To stabilize silicones in the emulsion form more efficiently, it is useful to understand the mechanism of emulsion stabilization. Two different mechanisms of emulsion stabilization have been proposed in the past: film formation and precipitation (known as the Pickering mechanism). These two mechanisms are different, and there is a need to further investigate this issue. The aim of the present work was to investigate the mechanism of stabilizing silicone emulsions and to propose a generalized behavior. Several experiments including the measurement of Langmuir isotherms, rheology experiments, phase diagram studies, and microscopy experiments were conducted. All of the above techniques indicated that the functional groups interact strongly with the water phase. The emulsions were found to be stable only if the emulsifiers were soluble in silicone oil or the water phase, and the stability decreased as the emulsifier precipitated. In most cases tested here, the emulsifiers were not observed to precipitate as reported earlier for the Pickering mechanism, and the emulsion stabilization followed film formation. These results should help to predict emulsion stabilization for unknown systems.

Effects of functional groups on surface pressure-area isotherms of hydrophilic silicone polymers.

Organic/inorganic hybrid silicone polymers are increasingly used in cosmetics, inks and paints, and fabric care applications owing to their special Si-O bond characteristics. Because of the presence of organic as well as inorganic groups, they show the properties of both, and the presence of hydrophobic as well as hydrophilic character makes them behave like a hybrid polymer. Though they are widely used, the utilization of hydrophilically modified silicones on a large scale has mainly been empirical due to lack of fundamental knowledge about variation in their properties with systematic change in their structure. The choice of moieties for hydrophilic modification of silicones in most of the earlier works has been nonionic based on ethylene oxide and propylene oxide groups, however, very little is known about their ionic counterparts. The current work focuses on understanding the behavior of functionally grafted silicone polymers with respect to the variation in the hydrophilic part of the grafting chain. Hydrophilically grafted silicone polymers form monolayers at the air-water interface, which are stabilized by interactions of functional groups with water. The present work examined the effects of functional group modifications on the conformational behavior of chains at the interface. It was observed that the shape of the chain depends on the available area at the interface (or surface pressure), and there are conformational changes with an increase in the number of molecules per unit area. While a poly(dimethylsiloxanes) (PDMS) chain may undergo stretched to helix transition as predicted earlier, this may not be the case for hydrophilically grafted chains. On the basis of the shape of the surface pressure-area isotherm and correlation with the scaling theory, a gradation in hydrophilicity of functional groups and hence modified silicone chains at the air-water interface is predicted.

Silicone emulsions.

Silicone polymers are a class of hybrid organic/inorganic polymers, that show desirable surface properties such as low surface energy and high flexibility, which enables even a very high molecular weight chain to achieve optimal orientation at the interface. They have excellent physical properties such as water repellency, heat stability, and high resistance to chemical and UV attack. Silicone polymers have dual characteristics, because of which they can either be used as emulsifiers or act as the continuous/dispersed phase of the emulsion. The results of an anionically modified silicone polymer indicate that it can stabilize an emulsion of water in cyclic silicone oil (D5) only in a narrow range of compositions around 80% water and 20% oil, formulated at low shear rates. A silicone emulsion stabilized by hydrocarbon emulsifiers shows drastic changes in their electrokinetic and optical properties under external perturbations, for example pH change. Advanced analytical tools such as atomic force microscopy (AFM) illustrated that a coating of silicone emulsion causes a solid substrate like fabric to smoothen out. This article further discusses the various types of silicone emulsions and their applications.

A new model to describe the sorption of surfactants on solids in non-aqueous media.

A new phenomenological model is developed to describe the sorption of surfactants on solids in non-aqueous media. This is based on the use of interaction parameters (delta) among solid, solute and solvent to assess the degree of the various interactions and computing an effective interaction parameter for the entire system represented by delta eff = abs{A|delta solid - delta solvent| + B|delta solute - delta solvent| - C|delta solid - delta solute|}. The effective interaction parameter determines the extent of adsorption that can occur in a given system. Interaction parameters typically account for dispersive interactions between the different components. This new model is used to describe the sorption behavior of a number of surfactant/solvent/solid systems.