Interfacial layers of stimuli-responsive poly-(N-isopropylacrylamide-co-methacrylicacid) (PNIPAM-co-MAA) microgels characterized by interfacial rheology and compression isotherms.

Stimuli-sensitive emulsions stabilized by microgel particles consisting of poly-(N-isopropylacrylamide-co-methacrylicacid) (PNIPAM-co-MAA) and being responsive to both pH and temperature have been investigated with respect to the visco-elastic properties of the interfacial layer. Properties of the interfacial layer were probed by means of shear and dilatational rheology as well as by compression isotherms and are related to the microgel packing at the interface as visualized by cryogenic scanning electron microscopy. The corresponding pH dependent emulsion stability is strongly correlated with the visco-elastic properties of the microgel covered oil-water interface. At high pH when the microgels are charged, a structure of partially interconnected microgels is found that provides elastic, soft gel-like interfaces. At low pH, however, the uncharged microgels are densely packed and the interface is rather brittle. Obviously, these pH dependent visco-elastic properties of the microgel layer at the oil-water interface play a determining role in the stability of emulsion droplets and allow us to prepare very stable emulsions when the microgels are charged and to break the emulsion by changing the pH.

The colloidal suprastructure of smart microgels at oil-water interfaces.

Oil on troubled waters: Stimuli-sensitive emulsions have been used to prepare temperature- and pH-responsive microgels. The emulsion stability at oil-water interfaces is not governed by the particle packing density, and structural changes induced by the interface lead to connections between the individual microgels (see picture; scale bar 1 microm), which behave very differently compared to solid-particle-stabilized emulsions.

Microgels as stimuli-responsive stabilizers for emulsions.

Temperature- and pH-sensitive microgels from cross-linked poly(N-isopropylacrylamide)-co-methacrylic acid are utilized for emulsion stabilization. The pH- and temperature-dependent stability of the prepared emulsion was characterized. Stable emulsions are obtained at high pH and room temperature. Emulsions with polar oils, like 1-octanol, can be broken by either addition of acid or an increase of temperature, whereas emulsions with unpolar oils do not break upon these stimuli. However, complete phase separation, independent of oil polarity, can be achieved by successive acid addition and heating. This procedure also offers a way to recover and recycle the microgel from the sample. Interfacial dilatational rheology data correlate with the stimuli sensitivity of the emulsion, and a strong dependence of the interfacial elastic and loss moduli on pH and temperature was found. The influence of the preparation method on the type of emulsion is demonstrated. The mean droplet size of the emulsions is characterized by means of flow particle image analysis. The type of emulsion [water in oil (w/o) or oil in water (o/w)] depends on the preparation technique as well as on the microgel content. Emulsification with high shear rates allows preparation of both w/o and o/w emulsions, whereas with low shear rates o/w emulsions are the preferred type. The emulsions are stable at high pH and low temperature, but instable at low pH and high temperature. Therefore, we conclude that poly(N-isopropylacrylamide)-co-methacrylic acid microgels can be used as stimuli-sensitive stabilizers for emulsions. This offers a new and unique way to control emulsion stability.

Emulsions stabilized by stimuli-sensitive poly(N-isopropylacrylamide)-co-methacrylic acid polymers: microgels versus low molecular weight polymers.

Responsive polymer microgels can be employed for the preparation of stimuli-sensitive emulsions. The microgels used in this study are based on cross-linked copolymers including N-isopropylacrylamide and methacrylic acid. We conducted the synthesis under acidic and basic conditions to investigate the effect of changes of comonomer solubility on the microgel's composition and ability to stabilize emulsions. The synthesis product was partially divided into two fractions by centrifugation. Raw product, collected supernatant, and purified microgel were characterized by means of light scattering, titration, as well as electrophoretic mobility. The ability of the three components to act as stabilizers was investigated by preparing the octanol/water emulsions and looking at their response to pH and temperature changes. The interfacial activity of the three components was characterized by means of the pendent drop technique. Furthermore, we investigated the response of the interface to dilatational stress using a pendant drop tensiometer equipped with an oscillating drop module. The results demonstrate that the pH during synthesis has a significant impact on the composition and thus the properties of the microgel and its ability to be utilized as a stimuli responsive stabilizer for emulsions. We conclude that microgels can be used as stimuli-sensitive stabilizers for emulsions, if the charges are incorporated in the microgel itself.