Pickering emulsion polymerization of graphene oxide-stabilized styrene

Polystyrene (PS) particles were prepared via Pickering emulsion polymerization using graphene oxide (GO) as the stabilizer. The results show that pH is an important factor in the stability of Pickering emulsions. The effects of two different phase initiators, the water phase initiator potassium persulfate and the oil phase initiator azobisisobutyronitrile, on the morphology of PS particles in Pickering emulsion polymerization had been investigated in detail. Wrinkled particles were prepared using the water phase initiator, and spherical particles were prepared using the oil phase initiator. In addition, hexadecane was used as the auxiliary stabilizer in the polymerization, which narrowed the diameter distribution of the PS spheres, and the hollow PS spheres were fabricated. The size of the GO particles also influenced the final morphology of the particles. Nano-sized polymer particles were grafted onto the surface of micro-sized GO. Small GO particles were suitable for Pickering emulsion polymerization to prepare the composite particles. The thermogravimetric analysis of the prepared particles confirmed that they were PS/GO composite particles, which could have a wide range of potential applications, such as in catalysts, sensors, environmental remediation, and energy storage.     

Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization

Poly(styrene-co-methacrylic acid) (PS-co-MAA) particles were synthesized via surfactant-free emulsion polymerization and then used as particulate emulsifiers for preparation of Pickering emulsions. Our results showed that adjusting the solution pH can tune the wettability of PS-co-MAA particles to stabilize either water-in-oil (W/O) or oil-in-water (O/W) Pickering emulsions. Stable W/O emulsions were obtained with PS-co-MAA particles at low pH values due to their better affinity to the dispersed oil phase. In contrast, increasing the pH value significantly changed the stabilizing behavior of the PS-co-MAA particles, leading to the phase inversion and formation of stable O/W emulsions. We found that the oil/water ratio had a significant influence on pH value of the phase inversion. It decreased with decreasing the oil/water ratio, and no phase inversion occurred when the styrene volume fraction reduced to 10 %. Additionally, macroporous polystyrene (PS) foam and PS microspheres were obtained via polymerization of Pickering high internal phase emulsion (Pickering HIPE) and O/W Pickering emulsion, respectively.     

改性氧化石墨烯稳定Pickering乳液法制备高导热相变整体材料

采用表面引发原子转移自由基聚合法(SI-ATRP)改性氧化石墨烯(GO), 并用其稳定Pickering高内相乳液, 一步成型制得高导热氧化石墨烯/石蜡复合整体相变材料. 通过SI-ATRP方法, 在氧化石墨烯表面引入分子刷, 提高GO的分散性, 实现了低GO含量下优异的导热强化效果. 当GO添加量仅为相变复合材料整体的0.4%(质量分数)时, 其热导率(3.968 W?m^-1?K^-1)比纯石蜡的热导率(0.608 W?m^-1?K^-1)有较大提升. 通过测试发现, 在1000次循环后相变材料的泄漏率仅为1.1%~1.3%, 表现出良好的形状稳定性和热可靠性. 制备的新型形状稳定相变材料在温控、 储能应用中具有潜在的用途.     

Formation of Pickering emulsion by use of PCM and SiC and application to preparation of hybrid microcapsules with interfacial polycondensation reaction

It was tried to form Pickering emulsion by use of paraffin wax as a phase change material (PCM) and SiC as solid powder and to apply to the preparation of the hybrid microcapsules with the interfacial polycondensation reaction. Pickering emulsion could be formed by stirring PCM and SiC in the continuous water phase. The mean diameter of PCM droplets in the (O/W) emulsion decreased with the added amount of SiC. The SiC weight adhered on the surface of PCM droplets become the maximum in the continuous phase with pH 6.8. The hybrid microcapsules with the shell made of SiC and polyurea resin film could be prepared by using Pickering emulsion. There was a critical adhesion weight of SiC, above which the hybrid microcapsules could not be formed. Thermal conductivity of hybrid microcapsules could be improved as compared with the PCM microcapsules. Copyright © 2015 John Wiley & Sons, Ltd.     

Formation of Pickering emulsions stabilized via interaction between nanoparticles dispersed in aqueous phase and polymer end groups dissolved in oil phase

The influence of end groups of a polymer dissolved in an oil phase on the formation of a Pickering-type hydroxyapatite (HAp) nanoparticle-stabilized emulsion and on the morphology of HAp nanoparticle-coated microspheres prepared by evaporating solvent from the emulsion was investigated. Polystyrene (PS) molecules with varying end groups and molecular weights were used as model polymers. Although HAp nanoparticles alone could not function as a particulate emulsifier for stabilizing dichloromethane (oil) droplets, oil droplets could be stabilized with the aid of carboxyl end groups of the polymers dissolved in the oil phase. Lower-molecular-weight PS molecules containing carboxyl end groups formed small droplets and deflated microspheres, due to the higher concentration of carboxyl groups on the droplet/microsphere surface and hence stronger adsorption of the nanoparticles at the water/oil interface. In addition, Pickering-type suspension polymerization of styrene droplets stabilized by PS molecules containing carboxyl end groups successfully led to the formation of spherical HAp-coated microspheres.     

SANS and SAXS analysis of charged nanoparticle adsorption at oil-water interfaces

A systematic study of the adsorption of charged nanoparticles at dispersed oil-in-water emulsion interfaces is presented. The interaction potentials for negatively charged hexadecane droplets with anionic polystyrene latex particles or cationic gold particles are calculated using DLVO theory. Calculations demonstrate that increased ionic strength decreases the decay length of the electrostatic repulsion leading to enhanced particle adsorption. For the case of anionic PS latex particles, the energy barrier for particle adsorption is also reduced when the surface charge is neutralized through changes in pH. Complementary small-angle scattering experiments show that the highest particle adsorption for PS latex occurs at moderate ionic strength and low pH. For cationic gold particles, simple DLVO calculations also explain scattering results showing that the highest particle adsorption occurs at neutral pH due to the electrostatic attraction between oppositely charged surfaces. This work demonstrates that surface charges of particles and oil droplets are critical parameters to consider when engineering particle-stabilized emulsions.     

New Pickering emulsions stabilized by bacterial cellulose nanocrystals

We studied oil in water Pickering emulsions stabilized by cellulose nanocrystals obtained by hydrochloric acid hydrolysis of bacterial cellulose. The resulting solid particles, called bacterial cellulose nanocrystals (BCNs), present an elongated shape and low surface charge density, forming a colloidal suspension in water. The BCNs produced proved to stabilize the hexadecane/water interface, promoting monodispersed oil in water droplets around 4 μm in diameter stable for several months. We characterized the emulsion and visualized the particles at the surface of the droplets by scanning electron microscopy (SEM) and calculated the droplet coverage by varying the BCN concentration in the aqueous phase. A 60% coverage limit has been defined, above which very stable, deformable droplets are obtained. The high stability of the more covered droplets was attributed to the particle irreversible adsorption associated with the formation of a 2D network. Due to the sustainability and low environmental impact of cellulose, the BCN based emulsions open opportunities for the development of environmentally friendly new materials.     

PS colloidal particles stabilized by graphene oxide

Exfoliated graphene oxide (GO) sheets with hydrophilic functional groups on the surface were prepared by the oxidation of graphite. Because of the hydrophilic groups on the sheets and the hydrophobic carbon surface, GO sheets were located at the oil-water interface and could be used as a stabilizer in Pickering emulsions. After the Pickering emulsion polymerization of styrene, PS colloidal particles with GO sheets on the surface were prepared. The size of the GO sheets exerts an important influence on the preparation of PS colloidal particles. Small GO sheets located at the liquid-liquid interface and GO-stabilized PS colloidal particles were prepared; however, for large GO sheets, smaller PS colloidal particles prepared on the GO surface were observed. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and morphology of the colloidal particles. TEM, SEM, and XPS results all suggest the successful preparation of GO-stabilized PS colloidal particles.     

Hierarchical porous cellulose/activated carbon composite monolith for efficient adsorption of dyes

Cheap and efficient adsorbents to remove contaminants of toxic dye molecules from wastewater are strongly in demand for environmental reasons. This study provides a novel design of a monolithic adsorbent from abundant materials via a facile synthetic procedure, which can greatly reduce the problems of the tedious separation of adsorbents from treated wastes. A hierarchically porous cellulose/activated carbon (cellulose/AC) composite monolith was prepared by thermally-induced phase separation of cellulose acetate in the presence of AC, using a mixture of DMF and 1-hexanol, followed by alkaline hydrolysis. The composite monolith had alarge specific surface area with mesopore distribution. It not only showed high uptake capacity towards methylene blue (MB) or rhodamine B (RhB) but could also simultaneously adsorb MB and RhB from their mixture, in which the adsorption of one dye was not influenced by the other one. Remarkable effects of solution pH, initial concentration of dye (C ₀), contact time, adsorbent dosage and temperature on the adsorption of MB and RhB onto the composite monolith were demonstrated. The binding data for MB and RhB adsorption on the composite monolith fitted the Freundlich model well, suggesting a heterogeneous surface of the composite monolith. The monolith could retain around 90% of its adsorption capacity after 8 times reuse. These data demonstrate that the cellulose/AC composite monolith has a large potential as a promising adsorbent of low cost and convenient separation for dye in wastewater.     

SiO2纳米颗粒与聚氧乙烯对Pickering乳液的协同稳定作用简

研究了聚氧乙烯(PEO)与SiO2纳米颗粒对水/二甲苯体系Pickering乳液的协同稳定作用. 实验发现,PEO的存在减小了乳液液滴的平均直径,抑制了乳液的相反转,有效阻止了乳液的熟化,使乳液具有更好的稳定性. 进一步对纳米颗粒膜的流变性质进行研究,结果表明,PEO高分子促进了纳米颗粒形成更大尺寸的聚集结构,提高了其在界面上的吸附性,增强了颗粒膜的力学性能,在较小颗粒用量条件下使得Gibbs稳定性判据得到满足.     

Particle self-assembly in oil-in-ionic liquid Pickering emulsions

We have studied polydimethylsiloxane (PDMS)-in-1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) Pickering emulsions stabilized by polystyrene microparticles with different surface chemistry. Surprisingly, in contrast to the consensus originating from oil/water Pickering emulsions in which the solid particles equilibrate at the oil-water droplet interfaces and provide effective stabilization, here the polystyrene microparticles treated with sulfate, aldehyde sulfate, or carboxylate dissociable groups mostly formed monolayer bridges among the oil droplets rather than residing at the oil-ionic liquid interfaces. The bridge formation inhibited individual droplet-droplet coalescence; however, due to low density and large volume (thus the buoyant effect), the aggregated oil droplets actually promoted oil/ionic liquid phase separation and distressed emulsion stability. Systems with binary heterogeneous polystyrene microparticles exhibited similar, even enhanced (in terms of surface chemistry dependence), bridging phenomenon in the PDMS-in-[BMIM][PF(6)] Pickering emulsions.     

Ice-templated porous polymer/UiO-66 monolith for Congo Red adsorptive removal

Chitosan/MOF composite porous monolith used in water remediation as adsorbent can realize high-efficient removal of pollutant in water and facile recycling from water. However, dissolution of chitosan (without crosslinking) in acidic aqueous solution will cause breakage of composite monolith. Herein, we report a chitosan/UiO-66 monolith prepared by ice-templating method. Specially, a pre-crosslinking treatment (by glutaraldehyde) is employed before the monolith formation, which obviously boosts its stability in aqueous solution. The composite monolith is evaluated by SEM, N₂ adsorption, XRD, and batch adsorption tests for Congo Red (CR). The results show that the composite monolith possesses a typical ice-templating structure with hierarchical (mirco- / meso- and macro-) pores. UiO-66 particles are embedded on the surface of chitosan matrix, and the crystal structure of UiO-66 is not changed obviously by the crosslinking and freezing process. The composite monolith exhibits high adsorption efficiency (90% of CR was removed from its aqueous solution in 60 min) and the maximum adsorption capacity of 246.21 mg/g (derived from Langmuir model) can be reached. After adsorption, the monolith is collected by a facile procedure and recovered using ethanol for evaluating its reusability. After 4 cycles, the CR removal efficiency of the composite monolith still remains ~90% of the initial efficiency. This work demonstrates that the simple crosslinking procedure before monolith formation can ensure the intact shape of the chitosan/MOF monolith during adsorption.     

Can polymersomes form colloidosomes?

Hydroxy-functionalized polymersomes (or block copolymer vesicles) were prepared via a facile one-pot RAFT aqueous dispersion polymerization protocol and evaluated as Pickering emulsifiers for the stabilization of emulsions of n-dodecane emulsion droplets in water. Linear polymersomes produced polydisperse oil droplets with diameters of ～50 μm regardless of the polymersome concentration in the aqueous phase. Introducing an oil-soluble polymeric diisocyanate cross-linker into the oil phase prior to homogenization led to block copolymer microcapsules, as expected. However, TEM inspection of these microcapsules after an alcohol challenge revealed no evidence for polymersomes, suggesting these delicate nanostructures do not survive the high-shear emulsification process. Thus the emulsion droplets are stabilized by individual diblock copolymer chains, rather than polymersomes. Cross-linked polymersomes (prepared by the addition of ethylene glycol dimethacrylate as a third comonomer) also formed stable n-dodecane-in-water Pickering emulsions, as judged by optical and fluorescence microscopy. However, in this case the droplet diameter varied from 50 to 250 μm depending on the aqueous polymersome concentration. Moreover, diisocyanate cross-linking at the oil/water interface led to the formation of well-defined colloidosomes, as judged by TEM studies. Thus polymersomes can indeed stabilize colloidosomes, provided that they are sufficiently cross-linked to survive emulsification.     

Selective separation of lambdacyhalothrin by porous/magnetic molecularly imprinted polymers prepared by Pickering emulsion polymerization

Porous/magnetic molecularly imprinted polymers (PM‐MIPs) were prepared by Pickering emulsion polymerization. The reaction was carried out in an oil/water emulsion using magnetic halloysite nanotubes as the stabilizer instead of a toxic surfactant. In the oil phase, the imprinting process was conducted by radical polymerization of functional and cross‐linked monomers, and porogen chloroform generated steam under the high reaction temperature, which resulted in some pores decorated with easily accessible molecular binding sites within the as‐made PM‐MIPs. The characterization demonstrated that the PM‐MIPs were porous and magnetic inorganic–polymer composite microparticles with magnetic sensitivity (M_s = 0.7448 emu/g), thermal stability (below 473 K) and magnetic stability (over the pH range of 2.0–8.0). The PM‐MIPs were used as a sorbent for the selective binding of lambdacyhalothrin (LC) and rapidly separated under an external magnetic field. The Freundlich isotherm model gave a good fit to the experimental data. The adsorption kinetics of the PM‐MIPs was well described by pseudo‐second‐order kinetics, indicating that the chemical process could be the rate‐limiting step in the adsorption of LC. The selective recognition experiments exhibited the outstanding selective adsorption effect of the PM‐MIPs for target LC. Moreover, the PM‐MIPs regeneration without significant loss in adsorption capacity was demonstrated by at least four repeated cycles.     

Synthesis of ZnO/polystyrene composites particles by Pickering emulsion polymerization

ZnO/polystyrene composite particles were synthesized by Pickering emulsion polymerization. ZnO nanoparticles were first prepared by reaction of zinc acetate and sodium hydroxide in ethanol medium. Then different amount of styrene monomer was emulsified in water in the presence of ZnO nanoparticles either by mechanical stirring or by sonication, followed by polymerization of styrene. Two kinds of initiators were used to start the polymerization, azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). The X-ray diffraction pattern verified the crystal structure of ZnO and FT-IR spectra evidenced the existence of ZnO and polystyrene (PS) in ZnO/polystyrene composite particles. Different morphologies were observed for the composite particles when using different initiators. From TEM photographs, AIBN-initiated system produced mainly core-shell composite particles with PS as core and ZnO as shell, while KPS-initiated system showed both composite particles and pure PS particles. Two schemes of reaction mechanism were proposed to explain the morphologies accordingly. Both systems of composite particles showed good pH adjusting ability.     

Phase inversion of the Pickering emulsions stabilized by plate-shaped clay particles

We investigated the phase inversion of Pickering emulsions stabilized by plate-shaped clay particles. Addition of water induced a phase inversion from a water-in-oil (W/O) emulsion to an oil-in-water (O/W) emulsion when the amount of the oil phase exceeded a limiting amount of oil absorption to solid particles. On the other hand, a phase inversion from a powdery state to an O/W emulsion state through an oil-separated state is observed when the amount of an oil phase is less than the limiting amount of the oil absorption. Interestingly, the oil separated is re-dispersed as emulsion droplets into the O/W emulsion phase. This type of phase inversion, which is a feature of the Pickering emulsions stabilized by the clay particles, is caused by a change in the aggregate structures of particles.     

Sulfonated graphene oxide: the new and effective material for synthesis of polystyrene-based nanocomposites

The new sulfonated graphene oxide (S-GO) was prepared and firstly used as effective materials for the synthesis of polystyrene/graphene nanocomposites via Pickering emulsion polymerization. The functionalized, chemically modified GO nanosheets were obtained via facile covalent functionalization with a reactive surfactant, sulfanilic acid. It was found that Pickering emulsion could be formed by simple self-assembly method using the S-GO as a stabilizer (just need 1 wt% relative to the oil phase), which could be adsorbed at the oil–water interface to stabilize the emulsion effectively. After the Pickering emulsion polymerization of styrene, the polystyrene/S-GO nanocomposites were prepared successfully. It is noteworthy that the S-GO not only could be used as a highly effective surfactant for styrene monomers but also could be homogeneously dispersed and incorporated into the polymeric matrix.     

膜乳化-液中干燥法制备单分散高分子微球

粒径可控的单分散高分子微球,在分析化学中可用作高效液相色谱填料^[1,2];在化学工业中可用作催化剂载体;在生物领域中用于药物释放、癌症与肝炎等临床诊断、细胞标记与识别等^[3].高分子微球的制备方法大致可分为两类,一是利用由单体出发的聚合反应或缩聚反应形成微球,二是高分子溶液经物理或物理化学手段处理后形成微球^[4]     

Study of emulsion polymerization stabilized by amphiphilic polymer nanoparticles

Submicron-sized polystyrene (PS) microspheres with a relatively narrow particle size distribution can be easily produced through emulsion polymerization induced by γ-ray at room temperature using a new type of amphiphilic cross-linked poly(stearyl methacrylate-co-acrylamide-co-acrylic acid) particles as stabilizer. The properties of these amphiphilic particles were described, including morphology, size, ζ potential, and contact angles. The effect of the pH value and the content of amphiphilic particles on the formation and stability of emulsions were also investigated. Meanwhile, the obtained PS microspheres were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. In addition, through observing the morphology and size of emulsion droplets at different times under an optical microscope, we found it is interesting that Pickering emulsions formed initially disappeared gradually, which is different from the common Pickering emulsions stabilized by inorganic particles. Thus, the mechanism was further discussed.     

Particle self-assembly at ionic liquid-based interfaces

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid–water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid–water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water–ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated.