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。     

Dynamically Reconfigurable,Multifunctional Emulsions with Controllable Structure and Movement

Dynamically reconfigurable oil‐in‐water (o/w) Pickering emulsions are developed, wherein the assembly of particles (i.e., platinum‐on‐carbon and iron‐on‐carbon particles) can be actively controlled by adjusting interfacial tensions. A balanced adsorption of particles and surfactants at the o/w interface allows for the creation of inhomogeneity of the particle distribution on the emulsion surface. Complex Pickering emulsions with highly controllable and reconfigurable morphologies are produced in a single step by exploiting the temperature‐sensitive miscibility of hydrocarbon and fluorocarbon liquids. Dynamic adsorption/desorption of (polymer) surfactants afford both shape and configuration transitions of multiple Pickering emulsions and encapsulated core/shell structured can be transformed into a Janus configuration. Finally, to demonstrate the intrinsic catalytic or magnetic properties of the particles provided by carbon bound Pt and Fe nanoparticles, two different systems are investigated. Specifically, the creation of a bimetallic microcapsule with controlled payload release and precise modulation of translational and rotational motions of magnetic emulsions are demonstrated, suggesting potential applications for sensing and smart payload delivery.     

Investigation on the mechanical strength of magnetic hollow silica prepared from Pickering emulsion route

In this paper, a one-pot sol–gel method was used to synthesize magnetic hollow silica through Pickering emulsion route. The mechanical strength of as-prepared magnetic hollow silica was adjusted and investigated. It was found that the emulsion droplet in Pickering emulsion was solely stabilized by cetrltrimethylammionium bromide (CTAB)-modified Fe₃O₄ particles while the silica source originally dispersed in oil phase was hydrolyzed at the emulsion droplet interface. This led to the formation of silica that then coated on the interface of the emulsion droplet to create magnetic hollow silica after being washed and dried. Controlling the hydrolyzing rate and degree of silica source and enhancing the binding force between silica and Fe₃O₄ nano particles can improve the mechanical strength of magnetic hollow silica.     

Formation of Janus TiO2 nanoparticles by a pickering emulsion approach applying phosphonate coupling agents

Anisotropic surface modification of TiO2 nanoparticles was achieved applying a Pickering emulsion approach. TiO2 nanoparticles were prepared by sol-gel routes which allowed an excellent control over their size and morphology. The obtained colloids were further used as stabilizers in the formation of oil-in-water Pickering emulsion. For reasons of comparison, also commercially available titanium dioxide nanoparticles (Evonik AEROXIDE TiO2 P25) were used in the functionalization experiments. An organophosphorus coupling agent present in the oil phase coordinated to the surface of the anatase nanoparticles. In such a way an anisotropic surface modification of the particles was achieved which increased the stability of the Pickering emulsion. Spectroscopic studies revealed the presence of organophosphorus coupling agents which exhibited a covalent bonding to the surface of the particles. Thermogravimetric analyses confirmed a lower surface coverage of the particles modified in emulsion compared to those modified in suspension. Reactions of organophosphorus coupling agents containing an additional methacrylate group applying an organic monomer (methyl methacrylate) as the oil phase of the Pickering emulsion resulted in hybrid TiO2@polymer spheres. Spectroscopic characterization of the resulting particles revealed that the phosphonates were coordinated to the TiO2 surface and at the same time copolymerized with the MMA within the oil droplet. Morphological investigations of the isolated final product showed that the material was composed of polymer spheres with the stabilizing TiO2 nanoparticles on their surface.     

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.     

Nanocellulose-stabilized Pickering emulsions and their applications

Abstract

Pickering emulsion, which is an emulsion stabilized by solid particles, offers a wide range of potential applications because it generally provides a more stable system than surfactant-stabilized emulsion. Among various solid stabilizers, nanocellulose may open up new opportunities for future Pickering emulsions owing to its unique nanosizes, amphiphilicity, and other favorable properties (e.g. chemical stability, biodegradability, biocompatibility, and renewability). In this review, the preparation and properties of nanocellulose-stabilized Pickering emulsions are summarized. We also provide future perspectives on their applications, such as drug delivery, food, and composite materials.     

Synthesis of Janus composite particles by the template of dumbbell-like silica/polystyrene

Janus particles possess promising performances. It is challenging to develop new methods to control composition and microstructure of the particles. In this report, we describe a general template synthesis of several non-spherical Janus composite particles by the template of dumbbell-like silica/polystyrene (PS) Janus particles. Both PS and silica can be modified to introduce desired functional groups respectively, or induce crystallization of other materials on the particle surface. Especially, by favorable growth of materials within the sulfonated PS gel forming the core–shell structure at the polymer part, several new Janus hollow particles are obtained after removal of the PS core.     

Plasmonic Janus Microspheres Created from Pickering Emulsion Drops

Metal nanostructures have been created in a film format to develop unique plasmonic properties. Here, well-defined metal nanostructures are designed on the surface of microspheres to provide plasmonic microgranules. As conventional techniques are inadequate for nanofabrication on spherical surfaces, photocurable emulsion drops with a regular array of silica particles are employed at the interface to create periodic nanostructures. The silica particles, originating from the dispersed phase, fully cover the interface by forming a non-close-packed hexagonal array after drop generation, and slowly protrude to the continuous phase during aging while their interparticle separation decreases. Therefore, hexagonal arrays of spherical dimples with controlled geometry and separation are created on the surface of microspheres by photocuring the drops and removing the particles. Directional deposition of either aluminum or gold results in a continuous film with a hexagonal array of holes on the outermost surface and isolated curved disks in dimples, which renders the hemisphere of microspheres plasmonically colored. The resonant wavelength is controlled by adjusting the aging time, metal thickness, and size of silica particles, providing various plasmonic colors. This granular format of the plasmonic Janus microspheres will open a new avenue of optical applications including active color pixels, optical barcodes, and microsensors.     

Pickering乳液聚合制备草莓型PSt/SiO2有机-无机复合微球

在纳米硅溶胶分散介质中,以苯乙烯(St)为单体,偶氮二异丁脒盐酸盐(AIBA)为引发剂,不添加任何辅助单体,通过Pickering乳液聚合,成功制备了PSt/SiO2有机-无机复合微球,透射电镜研究显示,复合微球具有草莓型形态。所得复合微球粒径在190 nm-300 nm之间,二氧化硅吸附量介于28%-44%之间。研究了初始硅溶胶用量、AIBA用量和反应温度等因素对复合微球粒子粒径和二氧化硅吸附量的影响。结果发现,初始硅溶胶用量增大,复合微球粒径减小、二氧化硅吸附量增大;引发剂用量增加,二氧化硅吸附量增大;反应温度升高,复合微球粒径增大,但对二氧化硅吸附量影响较小。     

Fabrication of Janus particles via a “photografting-from” method and gold photoreduction

Faster and simpler methods for the fabrication of Janus particles are of tremendous importance for a real implementation of these particles. By combining thiol-modified silica particles (SMPs) with the use of UV light, it is possible to rapidly fabricate Janus particles coated with polymer brushes and gold nanoparticles via photochemical emulsion-assisted route. From the silica particle surface, polymeric brushes of polyethylene(glycol), PEG, were grafted via a photografting-from method on one hemisphere by using the thiol groups as photoinitiator of the polymerization. The other hemisphere was coated with gold nanoparticles (AuNPs) generated in situ via photoreduction of chloroauric acid promoted by Norrish type I photoinitiator. PEG/AuNPs@SMPs coated with Au nanoparticles with average diameter of 12.7 or 22.5 nm were obtained by playing on the mass ratio between thiol-modified silica particles and gold precursor. The Janus PEG/AuNPs@SMPs were fully characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and UV–Vis spectroscopy. This strategy merges the advantages of emulsion-based selective masking and UV-induced reactions, and it is proved to be a feasible and fast route (reactions are completed in dozens of minutes) for Janus particles fabrication.     

Pickering乳液聚合制备聚苯乙烯/纳米SiO2复合微球与其性质

以两亲性纳米SiO2为稳定剂构筑Pickering乳液,分别采用偶氮二异丁腈(AIBN)及过硫酸铵(APS)作为引发剂引发苯乙烯单体聚合,制得了不同尺寸及形貌的聚苯乙烯/纳米SiO2(PS/SiO2)复合微球,并分析了Pickering乳液聚合的机理。通过傅里叶变换红外光谱仪(FT-IR)、凝胶渗透色谱-多角度激光光散射联用仪(GPC-MALLS)、热失重分析(TGA)及差示扫描量热仪(DSC)对产物进行了表征,结果表明,AIBN引发所得复合微球为微米级(0.5μm~2.0μm),而APS引发产物为亚微米级(0.1μm~0.5μm),两者引发所得聚合物重均分子量(-Mw)分别为4.780×104g/mol及3.411×105g/mol;复合微球的热性能因纳米SiO2的存在而得到增强。     

Preparation of silica nanoparticle-armored polyaniline microspheres in a Pickering emulsion

Silica nanoparticle-armored polyaniline microspheres (SNAPMs) were synthesized in a Pickering emulsion for the first time. The products were characterized by SEM, XRD and FTIR. The FTIR results showed that the silica nanoparticles were attached to the surfaces of the polyaniline microspheres by a hydrogen bonding action. The SEM results showed that the amount of the silica nanoparticles added in the emulsion had a distinct effect on the morphology and size of the SNAPMs. A mechanism for the formation of the SNAPMs was discussed. The route reported here may be used for the preparation of other composite nanostructures.     

Use of Nanoindentation,Finite Element Simulations,and a Combined Experimental/Numerical Approach to Characterize Elastic Moduli of Individual Porous Silica Particles

This article describes the use of a combination of experimental nanoindentation and finite element numerical simulations to indirectly determine the elastic modulus of individual porous, micron-sized silica (SiO₂) particles. Two independent nanoindentation experiments on individual silica particles were employed, one with a Berkovich pyramidal nanoindenter tip, the other with a flat punch nanoindenter tip. In both cases, 3D finite element simulations were used to generate nanoindenter load–displacement curves for comparison with the corresponding experimental data, using the elastic modulus of the particle as a curve-fitting parameter. The resulting indirectly determined modulus values from the two independent experiments were found to be in good agreement, and were considerably lower than the published values for bulk or particulate solid silica. The results are also consistent with previously reported modulus values for nanoindentation of porous thin film SiO₂. Based on a review of the literature, the authors believe that this is the first article to report on the use of nanoindentation and numerical simulations in a combined experimental/numerical approach to determine the elastic modulus of individual porous silica particles.     

硅溶胶存在下的聚丙烯酸酯无皂乳液聚合

采用无皂乳液聚合法合成了粒径分布单一的硅溶胶/聚丙烯酸酯复合乳液。讨论了硅溶胶对无皂乳液聚合成核过程、乳胶粒粒径及其分布、乳液稳定性的影响。结果表明,硅溶胶的加入减小了乳胶粒粒径,并且对乳液有稳定作用。通过透射电镜(TEM)对复合乳胶粒结构进行观察,表明乳胶粒具有两相复合结构。结合实验结果,提出了该体系无机有机两相复合机理,即无皂乳液聚合初期的聚丙烯酸酯初始微粒不稳定,易与硅溶胶粒子聚并。     

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.     

Fabrication and characterization of asymmetric Janus and ternary particles

Asymmetric Janus and ternary silica particles with an average diameter of 450 nm were fabricated by sequentially arranged particle-embedding and surface-modification processes. Thermally induced embedding of particles into polymer-fiber substrates allowed for precise control of the degree of particle submergence and the subsequent chemical modification of the hemispherical exposed particle surfaces. In addition to Janus particles with the desired surface-functionality ratios of 1:2, 1:1, and 2:1, this unique fabrication approach was also used to produce complicated and well-defined heterogeneous materials, including bifunctionalized Janus and ternary particles. The bifunctionalized Janus particles were produced with two hemispherical surfaces alternately labeled with gold and iron oxide nanoparticles, which simultaneously enabled anisotropic surface-plasmon resonance and a magnetic response. Ternary particles were also constructed, yielding submicrometer spheres with functionalized equatorial belts. The surface distributions of functional components in these spherical materials were carefully examined for uniformities in particle embedding. Statistical analyses revealed that the functional components were distributed with a uniformity of over 80% for all of the asymmetric Janus and ternary particles.     

改性硅气凝胶/聚甲基丙烯酸甲酯乳液的制备与性能研究

采用HMDS(六甲基二硅氮烷)改性硅气凝胶,通过乳液聚合法,将改性硅气凝胶与甲基丙烯酸甲酯(MMA)进行聚合,制得改性硅气凝胶/聚甲基丙烯酸甲酯复合乳液,并且讨论了硅气凝胶的表面状态,以及改性气凝胶质量分数对复合乳液性能的影响。结果表明:HMDS可成功修饰于硅气凝胶表面,将改性硅气凝胶与PMMA乳液体系复合,乳液综合性能呈现较为显著的变化。HMDS修饰的硅气凝胶有助于降低乳液的导热系数,加入3%HMDS修饰的硅气凝胶可以使成膜后的乳液具有较低的导热系数。     

细乳液聚合制备纳米二氧化硅-丙烯酸酯复合乳液的研究

采用硅溶胶和丙烯酸酯单体通过细乳液聚合制备纳米二氧化硅/丙烯酸酯复合高分子乳液。考察了聚合过程中硅溶胶量对于单体转化率和聚合物粒子粒径的影响,并用GPC、XPS表征所得的复合乳液。实验结果表明:二氧化硅的引入提高了聚合反应速率,增加聚合物的分子量并使分子量分布变窄;在复合乳液粒子中,二氧化硅主要以分散相分布在连续的丙烯酸酯相内部;复合乳液的力学性能明显优于不含二氧化硅的纯丙烯酸酯聚合物乳液。     

硅溶胶中二氧化硅粒径及比表面积测定

硅溶胶中二氧化硅粒度大小与尺寸分布对其性能有重大影响，为此提出了二氧化硅粒径与比表面积应成为交的重要性能指标，并对二氧化硅粒径比表面积的测定方法做了讨论。     

Preparation of a silica nano–composite emulsion resin and study of properties and behaviors

Nano‐composite particles were prepared by different methods and we used emulsion co‐polymerization of methyl methacrylate/butyl acrylate monomers mixture in the presence of well‐dispersed silica nano particles to improve physical properties of the base polymers or add proper functions to them. The size distribution and morphology of composite latex particles characterized by dynamic laserlight scattering, Transmission Electron Microscopy and Solid Electron Microscopy. The nano‐composites formed by using two nonionic and anionic surfactants and caused to making two acrylic resins which we studied the adhesion, surface hardness, flammability, gloss brightness and organic solvent resistance of samples. This nano‐composite acrylic resins were specially improved in the flame and solvent resistance. In our test results, we found that by increasing the silica content of nano‐composites, the properties consist of adhesion and gloss decreased, if solvent and flame resistance improved properly.