"Foam Marble" Stabilized with One Type of Polymer Particle.

There has been increasing interest in colloidal particles adsorbed at the air-water interface, which lead to stabilization of aqueous foams and liquid marbles. The wettability of the particles at the interface is known to play an important role in determining the type of air/water dispersed system. Foams are preferably formed using relatively hydrophilic particles, and liquid marbles tend to be formed using relatively hydrophobic particles. In this study, submicrometer-sized polystyrene particles carrying poly(N,N-diethylaminoethyl methacrylate) hairs (PDEA-PS particles), which are synthesized by dispersion polymerization, are demonstrated to work as a particulate stabilizer for both aqueous foams and liquid marbles. A key point for the hydrophilic PDEA-PS particles to stabilize both aqueous foams and liquid marbles, which have been generally stabilized with hydrophilic and hydrophobic particles, respectively, is the wetting mode of the particles with respect to water. The flocculates of PDEA-PS particles adsorb to the air-water interface from the aqueous phase to stabilize foam in a Wenzel mode, and the dried PDEA-PS particles adsorb to the interface as aggregates from the air phase to stabilize liquid marbles in a metastable Cassie-Baxter mode. On the basis of the difference in the wetting mode, stabilization of an air-in-water-in-air multiple gas-liquid dispersed system, named "foam marble", is realized. After the evaporation of water from the foam marble, a porous sphere is successfully obtained with pore sizes of a few tens of micrometers (reflecting the bubble sizes) and a few tens of nanometers (reflecting the gap sizes among the PDEA-PS particles).

pH- and temperature-responsive aqueous foams stabilized by hairy latex particles.

Polystyrene (PS) particles carrying pH- and temperature-responsive poly[2-(dimethylamino)ethyl methacrylate] (PDMA) hairs (PDMA-PS particles) were synthesized by dispersion polymerization. The diameter, diameter distribution, morphology, chemical composition and surface chemistry of the particles were characterized using scanning electron microscopy (SEM), elemental microanalysis, dynamic light scattering and zeta potential measurements. The hydrophilicity-hydrophobicity balance of the PDMA could be tuned by varying both pH and temperature and therefore these sterically stabilized particles acted as doubly stimuli-responsive stabilizers for aqueous foams by adsorption and desorption to/from the air-water interface. At and above pH 6.0, in which range the PDMA hairs were either non-protonated or partially protonated, particle-stabilized foams were formed at both 23 and 55 °C. The foam prepared at 55 °C was the more stable of the two, lasting for at least 24 h, whereas the 23 °C foam destabilized within 24 h. SEM studies indicated that the particles adsorbed at the air-water interface as monolayers at 23 °C and as multilayers at 55 °C. At and below pH 5, in which range the hairs were cationic, hydrophilic and water-soluble, no foam was formed irrespective of temperature. Rapid defoaming could be induced by lowering the solution pH at both temperatures, due to rapid in situ protonation of the PDMA hairs, prompting the PDMA-PS particles to desorb from the air-water interface. The foaming and defoaming cycles could be repeated at least five times.

Microcapsules fabricated from liquid marbles stabilized with latex particles.

Millimeter- and centimeter-sized "liquid marbles" were readily prepared by rolling water droplets on a powder bed of dried submicrometer-sized polystyrene latex particles carrying poly[2-(diethylamino)ethyl methacrylate] hairs (PDEA-PS). Scanning electron microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable spherical liquid marbles. The liquid marbles were deformed as a result of water evaporation to adopt a deflated spherical geometry, and the rate of water evaporation decreased with increasing atmospheric relative humidity. Conversely, liquid marbles formed using saturated aqueous LiCl solution led to atmospheric water absorption by the liquid marbles and a consequent mass increase. The liquid marbles can be transformed into polymeric capsules containing water by exposure to solvent vapor: the PDEA-PS particles were plasticized with the solvent vapor to form a polymer film at the air-water interface of the liquid marbles. The polymeric capsules with aqueous volumes of 250 µL or less kept their oblate ellipsoid/near spherical shape even after complete water evaporation, which confirmed that a rigid polymeric capsule was successfully formed. Both the rate of water evaporation from the pure water liquid marbles and the rate of water adsorption into the aqueous LiCl liquid marbles were reduced with an increase of solvent vapor treatment time. This suggests that the number and size of pores within the polymer particles/flocs on the liquid marble surface decreased due to film formation during exposure to organic solvent vapor. In addition, organic-inorganic composite capsules and colloidal crystal capsules were fabricated from liquid marbles containing aqueous SiO2 dispersions.

pH-responsive aqueous foams stabilized by hairy latex particles.

Polystyrene (PS) latex particles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate] (PDEA) hair (PDEA-PS particles) were synthesized by dispersion polymerization and characterized in terms of diameter, diameter distribution, morphology, chemical composition, surface chemistry, and pH-response using scanning electron microscopy (SEM), elemental microanalysis, (1)H nuclear magnetic resonance spectroscopy, the laser diffraction method, and zeta potential measurements. The hairy particles can act as pH-responsive stabilizers of aqueous foams by adsorption at the air-water surface. Above pH 8.0, where particles have nonprotonated PDEA hair, which is relatively hydrophobic, particle-stabilized foams are stable for at least 1 month. Optical microscopy and SEM confirmed that flocculated PDEA-PS latex particles were adsorbed at the air-water interface and stabilized the aqueous foams. At pH 6.1 and 7.1, relatively stable foams can be prepared that remain stable for at least 24 h. SEM studies indicated that the PDEA-PS particles were adsorbed at the air-water interface as a monolayer at pH 6.1. At pH 5.1 and 3.1, where the particles have cationic water-soluble PDEA hairs with hydrophilic character, no foam was formed. Rapid defoamation can be induced by lowering the solution pH; the addition of acid caused the in situ protonation of 2-(diethylamino)ethyl methacrylate residues, which impart water-soluble hydrophilic character to the PDEA hair, and the PDEA-PS particles desorbed from the air-water interface. The foaming and defoaming cycles could be repeated at least five times.

Liquid marbles prepared from pH-responsive sterically stabilized latex particles.

Submicrometer-sized pH-responsive sterically stabilized polystyrene (PS) latex particles were synthesized by dispersion polymerization in isopropyl alcohol with a poly[2-(diethylamino)ethyl methacrylate]- (PDEA-) based macroinitiator. These PDEA-PS latexes were extensively characterized with respect to their particle size distribution, morphology, chemical composition, and pH-responsive behavior. Millimeter- and centimeter-sized "liquid marbles" with aqueous volumes varying between 15 µL and 2.0 mL were readily prepared by rolling water droplets on the dried PDEA-PS latex powder. The larger liquid marbles adopted nonspherical shapes due to gravitational forces; analysis of this deformation enabled the surface tension to be estimated. Scanning electron microscopy and fluorescence microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable liquid marbles. The relative mechanical integrity of the liquid marbles prepared from alkaline aqueous solution (pH 10) was higher than those prepared from acidic aqueous solution (pH 2) as judged by droplet roller experiments. These liquid marbles exhibited long-term stability (over 1 h) when transferred onto the surface of liquid water, provided that the solution pH of the subphase was above pH 8. In contrast, the use of acidic solutions led to immediate disintegration of these liquid marbles within 10 min, with dispersal of the PDEA-PS latex particles in the aqueous solution. Thus the critical minimum solution pH required for long-term liquid marble stability correlates closely with the known pK(a) value of 7.3 for the PDEA stabilizer chains. Stable liquid marbles were also successfully prepared from aqueous Gellan gum solution and glycerol.