Control of Particle Adsorption for Stability of Pickering Emulsions in Microfluidics

Studying the stability of Pickering emulsion is of great interest for applications including catalysis, oil recovery, and cosmetics. Conventional methods emphasize the overall behavior of bulk emulsions and neglect the influence of particle adsorbing dynamics, leading to discrepancies in predicting the shelf‐life of Pickering emulsion–based products. By employing a microfluidic method, the particle adsorption is controlled and the stability of the Pickering emulsions is consequently examined. This approach enables us to elucidate the relationship between the particle adsorption dynamics and the stability of Pickering emulsions on droplet‐level quantitatively. Using oil/water emulsions stabilized by polystyrene nanoparticles as an example, the diffusion‐limited particle adsorption is demonstrated and investigated the stability criteria with respect to particle size, particle concentration, surface chemistry, and ionic strength. This approach offers important insights for application involving Pickering emulsions and provides guidelines to formulate and quantify the Pickering emulsion–based products.     

Graphitic Carbon Nitride Stabilizers Meet Microfluidics: From Stable Emulsions to Photoinduced Synthesis of Hollow Polymer Spheres

Graphitic carbon nitride (g‐CN) has been utilized as a heterogeneous catalyst, but is usually not very well dispersible. The amphiphilic character of g‐CN can be altered by surface modifications of g‐CN nanopowders. Introducing hydrophilicity or hydrophobicity is a promising avenue for producing advanced emulsion systems. In this study, a special surface‐modified g‐CN is used to form stable Pickering emulsions. Using a PDMS‐based microfluidic device designed for stable production of both single and double emulsions, it is shown that surface‐modified g‐CNs allow the manufacture of unconventionally stable and precise Pickering emulsions. Shell thickness of the double emulsions is varied to emphasize the robustness of the device and also to demonstrate the extraordinary stabilization brought by the surface‐modified carbon nitride used in this study. Due to the electrostatic stabilization also in the oil phase, double emulsions are centered. Finally, when produced from polymerizable styrene, hollow polymer microparticles are formed with precise and tunable sizes, where g‐CN is utilized as the only stabilizer and photoinitiator.     

Current Trends in Pickering Emulsions: Particle Morphology and Applications

In recent years, Pickering emulsions and their applications have attracted a great deal of attention due to their special features, which include easy preparation and enhanced stability. In contrast to classical emulsions, in Pickering emulsions, solid microparticles or nanoparticles that localize at the interface between liquids are used as stabilizers, instead of surfactants, to enhance the droplet lifetime. Furthermore, Pickering emulsions show higher stability, lower toxicity, and stimuli-responsiveness, compared with emulsions that are stabilized by surfactants. Therefore, they can be considered attractive components for various uses, such as photocatalysis and the preparation of new materials. Moreover, the nanoparticle morphology strongly influences Pickering emulsion stability as well as the potential utilization of such emulsions. Here, we review recent findings concerning Pickering emulsions, with a particular focus on how the nanoparticles morphology (i.e., cube, ellipsoid, nanosheet, sphere, cylinder, rod, peanut) influences the type and stability of such emulsions, and their current applications in different fields such as antibacterial activity, protein recognition, catalysis, photocatalysis, and water purification.     

Water-in-Water Emulsions Stabilized by Silica Janus Nanosheets

Water-in-water (w/w) emulsions have been recognized for their broad applications in foods, cosmetics, and biomedical engineering. In this work, silica Janus nanosheets (JNs) with polyacrylic acid (PAA) chains grafted on one surface via crushing functional silica foams, and used silica JNs as Pickering stabilizer to produce stable water-in-water (w/w) emulsions from the aqueous two-phase system (ATPS) containing methacrylic acid (MAA) and NaCl are prepared. The interfacial area of w/w emulsions increases linearly with the concentration of silica JNs, and the interfacial coverage of nanosheets is calculated to be about 98%. After polymerizing w/w emulsions prepared from MAA/NaCl ATPS, it is found that silica JNs are entrapped at the interface of w/w emulsions with the smooth PAA-grafted surface located toward MAA-rich phase due to their specific interaction. These results show that functional silica JNs can be used as a promising amphiphilic Pickering stabilizer to produce well-defined w/w emulsions for numerous application fields.     

Self‐Assembly of Graphene Oxide at Interfaces

Due to its amphiphilic property, graphene oxide (GO) can achieve a variety of nanostructures with different morphologies (for example membranes, hydrogel, crumpled particles, hollow spheres, sack‐cargo particles, Pickering emulsions, and so on) by self‐assembly. The self‐assembly is mostly derived from the self‐concentration of GO sheets at various interfaces, including liquid‐air, liquid‐liquid and liquid‐solid interfaces. This paper gives a comprehensive review of these assembly phenomena of GO at the three types of interfaces, the derived interfacial self‐assembly techniques, and the as‐obtained assembled materials and their properties. The interfacial self‐assembly of GO, enabled by its fantastic features including the amphiphilicity, the negatively charged nature, abundant oxygen‐containing groups and two‐dimensional flexibility, is highlighted as an easy and well‐controlled strategy for the design and preparation of functionalized carbon materials, and the use of self‐assembly for uniform hybridization is addressed for preparing hybrid carbon materials with various functions. A number of new exciting and potential applications are also presented for the assembled GO‐based materials. This contribution concludes with some personal perspectives on future challenges before interfacial self‐assembly may become a major strategy for the application‐targeted design and preparation of functionalized carbon materials.     

Interparticle photo-cross-linkable Pickering emulsions for rapid manufacturing of complex-structured porous ceramic materials

A new series of Pickering emulsions that can be photo-cured by interparticle photo-cross-linking reactions using small amounts of multifunctional acrylate (MA) monomers is proposed to rapidly manufacture complex-structured porous ceramic materials. In our new process, water in oil (w/o) Pickering emulsion was designed by vigorous mixing of water and polyethyleneimine partially complexed with oleic acid (PEI–OA)-stabilized SiO₂/toluene suspension containing small amounts of MA and a photo-radical initiator. Ultraviolet light irradiation to this w/o Pickering emulsion induced the formation of interparticle photo-crosslinks, which resulted in successful photocuring by photo-radical polymerization of MA and the Michael addition reaction between the polymerized MA and PEI–OA on the particles in the oil phase. We further applied the newly designed photo-curable Pickering emulsion and demonstrated that SiO₂ components with pores related to the dispersed aqueous phase and complexed outer structures could be shaped via silicone molding or a hybridized approach of photocuring and green machining. Because of the reduced amounts of MA used, the porous SiO₂ green components could be heat-treated using rapid heating profiles without any structural collapse for dewaxing and partial sintering.     

Microfluidic Generation of All‐Aqueous Double and Triple Emulsions

Higher order emulsions are used in a variety of different applications in biomedicine, biological studies, cosmetics, and the food industry. Conventional droplet generation platforms for making higher order emulsions use organic solvents as the continuous phase, which is not biocompatible and as a result, further washing steps are required to remove the toxic continuous phase. Recently, droplet generation based on aqueous two‐phase systems (ATPS) has emerged in the field of droplet microfluidics due to their intrinsic biocompatibility. Here, a platform to generate all‐aqueous double and triple emulsions by introducing pressure‐driven flows inside a microfluidic hybrid device is presented. This system uses a conventional microfluidic flow‐focusing geometry coupled with a coaxial microneedle and a glass capillary embedded in flow‐focusing junctions. The configuration of the hybrid device enables the focusing of two coaxial two‐phase streams, which helps to avoid commonly observed channel‐wetting problems. It is shown that this approach achieves the fabrication of higher‐order emulsions in a poly(dimethylsiloxane)‐based microfluidic device, and controls the structure of the all‐aqueous emulsions. This hybrid microfluidic approach allows for facile higher‐order biocompatible emulsion formation, and it is anticipated that this platform will find utility for generating biocompatible materials for various biotechnological applications.     

Drying oil-in-water Pickering emulsions to make redispersible powders

We report on the formation of powder by drying oil-in-water emulsions stabilized by silanised silica nanoparticles. Drying was achieved by spraying fine droplets (up to a hundred micrometres in diameter) of the emulsions into a chamber of hot, flowing air. We show that the surfaces of droplets of the emulsions become enriched with nanoparticles as the water evaporates in the drying chamber. Controlling the relative amounts of oil and particles in the droplets being dried is the key to encapsulating the oil drops within the powder. Dried Pickering emulsions containing up to 40 wt% encapsulated oil that could be dispersed in water as drops of the same size as in the original emulsion were produced.     

纳米粒子对表面活性剂乳液稳定性的影响

制备了由三种不同类型的表面活性剂稳定的乳状液,考察了纳米粒子对表面活性剂乳液稳定性的影响作用,结果表明,ZnO纳米粒子SDBS、Oπ-10和CTAB稳定的乳液均具有破乳作用;MgO纳米粒子对SDBS稳定的乳液具有破乳作用;Fe2O3纳米粒子对三种表面活性剂乳液的稳定性没有显著影响。     

Nanoparticle cages for enzyme catalysis in organic media

Encapsulation of enzymes in Pickering emulsions results in a large interfacial area of the enzyme-containing aqueous phase for biocatalysis in organic media. This immobilization technique minimizes enzyme inactivation through stabilizing immiscible liquids by particles, facilitates separation processes, and significantly increases catalytic performance of both stable and vulnerable enzymes. Thus, a broad technical applicability can be envisioned.     

The Horizon of the Emulsion Particulate Strategy: Engineering Hollow Particles for Biomedical Applications

With their hierarchical structures and the substantial surface areas, hollow particles have gained immense research interest in biomedical applications. For scalable fabrications, emulsion‐based approaches have emerged as facile and versatile strategies. Here, the recent achievements in this field are unfolded via an “emulsion particulate strategy,” which addresses the inherent relationship between the process control and the bioactive structures. As such, the interior architectures are manipulated by harnessing the intermediate state during the emulsion revolution (intrinsic strategy), whereas the external structures are dictated by tailoring the building blocks and solidification procedures of the Pickering emulsion (extrinsic strategy). Through integration of the intrinsic and extrinsic emulsion particulate strategy, multifunctional hollow particles demonstrate marked momentum for label‐free multiplex detections, stimuli‐responsive therapies, and stem cell therapies.     

液膜用高分子表面活性剂性能研究

本文介绍液膜用高分子表面活性剂PSN_(-89414)的性能,通过界面张力测定,用表面活性剂分子在界面上吸附理论导出公式求得Span80,PS_(-89414)的界面吸附平衡常数K_(?)及S_(af)的数值,结果表明,K_(?)、S_(af)数值愈大的表面活性剂制得乳状液愈稳定,液膜溶胀愈小。PSN_(-89414)的W/O/W乳状液体系用于稀土分离,速度快,从浓度1.2g/L的稀土溶液浓集到103g/L。     

Selectively Permeable Double Emulsions

Natural organisms are made of different types of microcompartments, many of which are enclosed by cell membranes. For these organisms to display a proper function, the microcompartments must be selectively permeable. For example, cell membranes are typically permeable toward small, uncharged molecules such as water, selected nutrients, and cell signaling molecules, but impermeable toward many larger biomolecules. Here, it is reported for the first time dynamic compartments, namely surfactant‐stabilized double emulsions, that display selective and tunable permeability. Selective permeability is imparted to double emulsions by stabilizing them with catechol‐functionalized surfactants that transport molecules across the oil shell of double emulsions only if they electrostatically or hydrophobically attract encapsulants. These double emulsions are employed as semipermeable picoliter‐sized vessels to controllably perform complexation reactions inside picoliter‐sized aqueous cores. This thus far unmet level of control over the transport of reagents across oil phases opens up new possibilities to use double emulsion drops as dynamic and selectively permeable microcompartments to initiate and maintain chemical and biochemical reactions in picoliter‐sized cell‐mimetic compartments.     

The effect of additives on the treatment of oil-in-water emulsions by vacuum evaporation

A simple batch vacuum evaporation process for the treatment of several oil-in-water (O/W) emulsions is reported. The experiments were carried out with waste emulsions from an industrial copper rolling process and with model emulsions prepared in the laboratory. No detailed information on the formulation of the industrial waste O/W emulsions was available. Several model emulsions were formulated using the same base oil (an 85–15% (w/w) mixture of a synthetic poly-α-olefin and a trimethylol propane trioleate ester, respectively) and one of the three following surfactants: Brij-76 (polyethylene glycol octadecyl ether, non-ionic), CTAB (hexadecyltrimethyl ammonium bromide, cationic), and Oleth-10 (glycolic acid ethoxylate oleyl ether, anionic). Experimental results show a strong influence of operating conditions, such as pressure or bath temperature, on the evaporation performance. As a general trend, the higher the values of these parameters, the higher the pollutant content in the obtained aqueous effluent. The presence of surfactants increase the evaporation rate, especially at low operating vacuum pressures, the solubility of oil molecules in water and the evaporation temperature of model O/W emulsions. Furthermore, COD reductions higher than 99.5% for the treated waste O/W emulsions were achieved.     

Direct Synthesis of MOF‐Derived Nanoporous Carbon with Magnetic Co Nanoparticles toward Efficient Water Treatment

Nanoporous carbon particles with magnetic Co nanoparticles (Co/NPC particles) are synthesized by one‐step carbonization of zeolitic imidazolate framework‐67 (ZIF‐67) crystals. After the carbonization, the original ZIF‐67 shapes are preserved well. Fine magnetic Co nanoparticles are well dispersed in the nanoporous carbon matrix, with the result that the Co/NPC particles show a strong magnetic response. The obtained nanoporous carbons show a high surface area and well‐developed graphitized wall, thereby realizing fast molecular diffusion of methylene blue (MB) molecules with excellent adsorption performance. The Co/NPC possesses an impressive saturation capacity for MB dye compared with the commercial activated carbon. Also, the dispersed magnetic Co nanoparticles facilitate easy magnetic separation.     

Stability of orange oil/water nanoemulsions prepared by the PIT method

This article reports the preparation and characterization of orange oil/water nanoemulsions stabilized by commercial nonionic surfactants based on ethoxylated lauryl ether (Ultrol line), by the phase inversion temperature (PIT) method. The orange oil/surfactant/water dispersions were prepared at different HLB values, by varying the concentrations of the surfactants as well as the concentration of the oil phase. The stability of the o/w nanoemulsions and the size distribution of the dispersed particles in these systems in general depended on the concentration of the oil phase used: the emulsions prepared with an oil phase of 14 wt% had smaller droplet size in the dispersed phase than the emulsions prepared in the presence of oil phases of 20 and 30 wt%. The nanoemulsions prepared with pure surfactants were more stable in the presence of Ultrol L60, but the surfactants' cloud point had a strong influence on the stability of the emulsions formed when this was very near room temperature. Because of this, we prepared systems containing mixtures of surfactants. Among these systems, the most stable nanoemulsions were those prepared with a Ultrol L100/Ultrol L20 mixture with HLB of 12.40. This behavior can be attributed to the complete solubilization in mixed micelles of the more hydrophobic surfactant.     

One-pot fabrication of magnetic nanocomposite microcapsules

Fe₂O₃ nanoparticles can self-assembly at liquid-liquid interfaces to form stable water-in-oil Pickering emulsions. Novel magnetic and thermo-sensitive microcapsules were one-pot fabricated by radical polymerization of N-isopropylacrylamide (NIPAm) at the aqueous phases of Pickering emulsions at 60 °C. The obtained PNIPAm was deposited from the water phases onto the interfaces of water-in-oil Pickering emulsions to form Fe₂O₃/PNIPAm nanocomposite shells because of its hydrophobicity at this reaction temperature. Pickering emulsion polymerization opens up a new route to fabricate a variety of hollow and hybrid microcapsules.     

纳微米颗粒的表面改性及其在Pickering乳液中的应用进展

以固体粒子替代表面活性剂稳定的Pickering乳液,不仅可以赋予乳液许多特殊的性能(电磁和温度感应性能等),还可消除由添加表面活性剂所带来的副作用(过敏性和毒性等),这使得Pickering乳液可以应用到对表面活性物质具有很大限制的生物材料领域。系统综述了常见Pickering乳液用固体粒子,以及为了获得不同类型的乳液而对固体粒子进行表面改性的主要方法,着重归纳了表面改性前亲水性羟基磷灰石(HAp)和改性后疏水性HAp作为颗粒乳化剂稳定的Pickering乳液的类型及其进一步合成的产物。     

Formation and Stability Studies of Multiple (w/o/w) Emulsions Prepared with Newly Synthesized Rosin-Based Polymeric Surfactants

The multiple (water-in-oil-in-water, w/o/w) emulsions were prepared using newly synthesized rosin-based polymeric surfactants. The oil phase used was liquid paraffin. These emulsions were evaluated for stability by various methods: conductivity, viscosity, particle size, and visual inspection. The stability studies were carried out at 37°C and 4°C for 1 month. The multiple emulsion prepared with polymer 7 was found to be more stable compared to the emulsions prepared with polymer 2.     

Formation and stability studies of multiple (w/o/w) emulsions prepared with newly synthesized rosin-based polymeric surfactants

The multiple (water-in-oil-in-water, w/o/w) emulsions were prepared using newly synthesized rosin-based polymeric surfactants. The oil phase used was liquid paraffin. These emulsions were evaluated for stability by various methods: conductivity, viscosity, particle size, and visual inspection. The stability studies were carried out at 37°C and 4°C for 1 month. The multiple emulsion prepared with polymer 7 was found to be more stable compared to the emulsions prepared with polymer 2.