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.     

纳米纤维素凝胶微粒及其在Pickering泡沫中的应用

目的研究氧化纳米纤维素/乳酸链球菌素(TONCC/nisin)凝胶粒子的性质及其在环保抗菌泡沫中的应用。方法利用TONCC的表面羧基基团与nisin的表面阳离子的吸附耦合作用,制备TONCC/nisin水凝胶和微凝胶,以微凝胶作为稳定粒子,环氧大豆油丙烯酸酯(AESO)为油相,制备TONCC/nisin/AESO Pickering乳液,对水凝胶、微凝胶、乳液的稳定性进行研究;通过热固化乳液得到环保抗菌的泡沫材料,并对泡沫材料的结构和抗菌效果进行表征。结果水凝胶的结构随着在水中浸泡时长的增加而发生变化,宏观表现为坍塌变形,nisin逐渐析出,微凝胶随着静置时间的延长其粒径变化不大;以微凝胶作为界面稳定剂的AESO乳液的热稳定性较好,在90℃下加热30 min乳液液滴并未发生聚并现象,该乳液固化后形成的多孔泡沫材料对李斯特菌的抑制作用明显,当泡沫中nisin含量为2μg/g时,其抑菌率为43%。结论TONCC和nisin形成的微凝胶粒子在水中稳定性较好,可以用于乳化AESO制备Pickering泡沫,同时赋予泡沫多孔性和抗菌性,在制备环保抗菌泡沫方面有很大的应用潜力。     

Crab Chitin‐Based 2D Soft Nanomaterials for Fully Biobased Electric Devices

2D nanomaterials have various size/morphology‐dependent properties applicable in electronics, optics, sensing, and actuating. However, intensively studied inorganic 2D nanomaterials are frequently hindered to apply in some particular and industrial fields, owing to harsh synthesis, high‐cost, cytotoxicity, and nondegradability. Endeavor has been made to search for biobased 2D nanomaterials with biocompatibility, sustainability, and biodegradability. A method of hydrophobization‐induced interfacial‐assembly is reported to produce an unprecedented type of nanosheets from marine chitin. During this process, two layers of chitin aggregations assemble into nanosheets with high aspect ratio. With super stability and amphiphilicity, these nanosheets have super ability in creating highly stable Pickering emulsions with internal phase up to 83.4% and droplet size up to 140 μm, in analogue to graphene oxide. Combining emulsifying and carbonization can further convert these 2D precursors to carbon nanosheets with thickness as low as ≈3.8 nm. Having biologic origin, conductivity, and dispersibility in various solvents, resultant carbon nanosheets start a new scenario of exploiting marine resources for fully biobased electric devices with sustainability and biodegradability, e.g., supercapacitor, flexible circuits, and electronic sensors. Hybrid films of chitin and carbon nanosheets also offer low‐cost and environment‐friendly alternative of conductive components desirable in green electronics, wearable electronics, biodegradable circuits, and biologic devices.     

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.     

无皂硅丙胶乳表面施胶剂的制备及对纸张的增强作用

以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH570)作自交联单体,聚乙烯醇(PVA)为高分子胶体稳定剂,苯乙烯(St)、丙烯酸丁酯(BA)、甲基丙烯酸(MAA)为单体采用无皂种子聚合制备了稳定性好、性能优异的无皂硅丙乳液表面施胶剂,并优化了合成工艺条件。结果表明,当w(MAA)=2%~3%,软硬单体比例n(BA)/n(St)=2~2.5,w(PVA)=10%~15%,w(KH570)=5%时,无皂硅丙乳液表面施胶剂具有优异的施胶效果;以质量分数为1.0%的聚合物乳液进行表面施胶时,纸张施胶度可达14.5 s,表面强度达3.69 m/s,耐折度3300次。     

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.     

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.     

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.     

Hollow polymer microspheres containing a gold nanocolloid core adsorbed on the inner surface as a catalytic microreactor

Hollow polymer microspheres with different polarity and functional group for the shell layer containing gold nanocolloid cores adsorbed on the inner surface were prepared by selective removal of sandwiched silica layer from the corresponding gold/silica/polydivinylbenzene (Au/SiO₂/PDVB), Au/SiO₂/poly(ethyleneglycol dimethacrylate) (Au/SiO₂/PEGDMA), and Au/SiO₂/poly(ethyleneglycol dimethacrylate-co-methacrylic acid) (Au/SiO₂/P(EGDMA-co-MAA) tri-layer microspheres, respectively. The tri-layer microspheres were synthesized by distillation precipitation polymerizations of divinylbenzene (DVB), ethyleneglycol dimethacrylate (EGDMA), EGDMA together with methacrylic acid (MAA) in presence of 3-(methacryloxy)propyltrimethoxysilane (MPS)-modified gold/silica (Au/SiO₂) core–shell particles as seeds, which were prepared by coating of a layer of silica onto the surface of Au nanocolloids with the aid of polyvinylpyrrolidone (PVP) via a modified Stöber method. The catalytic property and stability as a microreactor of the hollow polymer microspheres with Au nanocolloid cores adsorbed on the inner surface were studied by the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AnP) with sodium borohydride (NaBH₄) as reductant. Transmission electron microscopy (TEM) and Fourier transform infrared spectra (FT-IR) were used for characterizing the morphology and structure of the resultant microspheres.     

核壳硅丙共聚物/硅溶胶杂化液表面施胶剂的制备及应用

以马来酸酐聚氧乙烯酯(MT)为可聚合乳化剂,采用种子聚合制备了核壳硅丙共聚物,并与硅溶胶形成杂化液,制得反应性表面施胶剂,讨论了其合成影响因素,并优化了合成工艺条件;用IR对马来酸酐聚氧乙烯酯乳化剂、核壳硅丙共聚物、硅溶胶进行了表征。研究表明,当w(MT)≥2%时核壳硅丙共聚物乳液具有良好稳定性,当w(KH570)=2%,w(硅溶胶)=6%时,核壳硅丙共聚物/水溶胶杂化液表面施胶剂具有良好的施胶效果。     

Nanocomposite nanofibers of poly(d, l-lactic-co-glycolic acid) and graphene oxide nanosheets

Significant improvements in the thermomechanical and surface chemical properties of nanocomposite nanofibers of poly(d, l-lactic-co-glycolic acid) (PLGA) were achieved by adding 2-dimensional nanoscale fillers of graphene oxide (GO) nanosheets to PLGA nanofibers. The significant enhancement of storage and loss moduli of the PLGA/GO (2 wt.%.) nanocomposite nanofibers were presumably caused by enhanced chemical bonding between the oxygenated functional groups of the highly dispersible GO nanosheets and the hydroxyl groups of the polymer chains in the PLGA matrix, resulting in strong interfacial interactions between the nanofiller and polymer matrix. Enhanced hydrophilicity of nanocomposite nanofibers caused by embedded GO nanosheets also allowed for good biocompatibility of neuronal cells, resulting in enhanced cell proliferation and viability. Our findings indicate that nanocomposite biopolymer nanofibers embedded with GO nanosheets are attractive candidates for use in biomedical applications such as scaffolds.     

硅溶胶改性碳纤维对碳纤维/环氧树脂复合材料界面性能影响

以硅烷偶联剂和正硅酸乙酯(TEOS)为前躯体, 以固体酸-对甲苯磺酸为催化剂制备硅溶胶, 利用硅溶胶对碳纤维进行表面改性后, 以环氧树脂为基体, 制备碳纤维增强环氧树脂复合材料。利用SEM、 TEM、 万能试验机、 偏光显微镜等对表面改性前后的碳纤维形态、 力学性能及碳纤维/环氧树脂复合材料的界面性能进行表征, 研究了硅溶胶改性碳纤维对其复合材料界面性能影响。结果表明, 硅溶胶处理碳纤维后, 在碳纤维表面原位生成具有膜-粒结构的表面层, 改性后碳纤维的强度由2.41 GPa提高到3.00 GPa, 界面性能也得到了明显改善, 界面剪切强度(IFSS)提高了51.41%。     

Multi-functional hybrid coatings containing silica nanoparticles and anti-corrosive acrylate monomer for scratch and corrosion resistance

Multi-functional hybrid coatings having both anti-corrosion and scratch resistance were prepared from modified silica nanoparticles and functional acrylates. To improve the dispersion properties of silica nanoparticles in the organic/inorganic hybrid coatings, the surface of the nanoparticles was modified with γ-methacryloxypropyltrimethoxysilane. The coating solution could be prepared by mixing modified silica nanoparticles, tetrasiloxane acrylate, di-acrylate monomer containing an anti-corrosion functional group, acrylic acid, and an initiator in a solvent. The mixture was then dip-coated on iron substrates and finally polymerized by ultraviolet (UV) irradiation. Corrosion and scratch resistance of the coated iron was evaluated by electrochemical impedance spectroscopy (EIS) and a pencil hardness test, respectively. From the EIS results, the coatings with tetrasiloxane acrylate and di-acrylate did not show any decrease in impedance or phase angle, even after 50 days' exposure to 0.1 M NaCl electrolyte, whereas the conventional acrylate coatings started to fail after only 24 h. A hybrid coating containing the amine-quinone functional group exhibited excellent corrosion protection properties with 4-5H pencil hardness.     

聚(苯胺-含硅丙烯酸酯)乳胶膜的防腐蚀性能

为了提高丙烯酸酯乳液的防腐蚀性能和聚苯胺的成膜性能,以乙烯基三甲氧基硅烷(VTMS)为功能单体合成了含硅丙烯酸酯乳液,并以此乳液为种子合成了聚(苯胺-含硅丙烯酸酯)乳液,研究了软硬单体比、甲基丙烯酸(MAA)含量和VTMS含量对共聚乳胶膜性能的影响。结果表明:当软硬单体质量比为1∶1,MAA质量分数为4%,VTMS质量分数为6%时,制备的乳胶膜具有较好成膜性、疏水性(接触角89.3°,吸水率8.1%)、弯曲性和附着力,在3.5%NaCl溶液中的腐蚀速率为2.75×10~(-4)mm/a。     

Design of microencapsulated phase change material by one-step swelling polymerization in Pickering emulsion

Microencapsulated phase change materials (MePCMs) based on swelling polymerization in Pickering emulsion were demonstrated. Monodisperse poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) P(GMA-co-HEMA) particles were prepared by dispersion polymerization. The introduction of hydrophilic monomer HEMA endowed the obtained particles with suitable surface hydrophilicity for stabilizing Pickering emulsion. MePCMs with PGMA–polystyrene interpenetrating composite shell were formed when non-crosslinked particles were employed as stabilizer, while MePCMs with particles-embedded shell were prepared with crosslinked particles as Pickering stabilizer. Phase change property, thermal stability and thermal reliability of two kinds of MePCMs were investigated by TGA, FT-IR, DSC and cycling test. The temperature of 10% weight loss of MePCMs with interpenetrating shell was 11 °C higher than that of MePCMs with particles-embedded shell. After cycling test, the percentage of leached core materials from MePCMs with interpenetrating shell was approximately one-third of that from MePCMs with particles-embedded shell. The results showed that MePCMs with an integral shell presented better thermal stability, tightness and thermal reliability than MePCMs with particles-embedded shell. The research developed a simple process for MePCMs with excellent performance.     

Evaluation of the emulsifying properties of some cationic starches

Different cationic potato, maize, and waxy maize starches were evaluated for their emulsifying properties. Emulsions were prepared using 20% (w/w) arachidic oil and 80% (w/w) water. Emulsions with the cationic starches as emulsifier in a concentration ranging from 1% to 5% (w/w) were prepared and characterized by droplet size and viscosity measurements, and the stability was evaluated visually and by electrical conductance measurements. None of the cationic potato, waxy maize starches, and maize starches with a low degree of substitution (DS) showed adequate emulsifying properties. Emulsions prepared using non-pregelatinized (C ☆ bond 05914, 2% and 5% w/w; C ☆ bond 05907, 5% w/w) and pregelatinized (C ☆ bond 12504, 5% w/w) cationic maize starches with high-DS were visually stable. The initial mean droplet volume diameter of the emulsions prepared with these cationic starches in a 5% (w/w) concentration was similar and ranged from 2.40 to 2.84 μm however, there was an important difference in droplet size distribution. The droplet size distribution of the emulsions prepared using the non-pregelatinized high-DS cationic starches was markedly narrower than in the case of the emulsions prepared using the pregelatinized high-DS cationic starches. The droplet size of the emulsions remained almost constant during 120 days of storage. Visual inspection and electrical conductance measurements showed that these emulsions were stable for at least 120 days.     

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.     

助溶剂驱使溶胶-凝胶化SiO_2/聚丙烯酸酯复合涂层

采用助溶剂和硅烷偶联剂(Z-6040)对碱性硅溶胶进行复合改性后添加到聚丙烯酸酯乳液中制备SiO2/聚丙烯酸酯杂合乳液(Si/PAE),分别考查助溶剂的种类和用量对硅溶胶的溶胶-凝胶化(sol-gel)反应及复合涂层综合性能的影响,结果发现:异丙醇是合适的助溶剂,其最佳添加量为硅溶胶质量的10%。TEM测试和纳米粒径分析发现:助溶剂可以提高无机硅颗粒在杂合乳液中的分散能力,降低Si/PAE的平均粒径。傅里叶红外光谱(FT-IR)和原子力显微镜(AFM)分析说明:Si/PAE乳液在成膜过程中,助溶剂可驱使硅溶胶发生sol-gel反应,并在涂层表面富集含硅聚合物,Si/PAE的涂层结构平整且致密。TGA分析发现:Si/PAE涂层具有较好的热稳定性。     

P(St-EA-MAA)模板法制备中空二氧化硅微球

以种子乳液聚合制得的P(St-EA-MAA)共聚物微球为模板,γ-氨丙基三甲氧基硅烷(APS)为助结构导向剂,正硅酸四乙酯(TEOS)为硅源,制备了P(St-EA-MAA)/SiO2复合微球,经高温煅烧除去聚合物模板,得到了中空二氧化硅微球。热重分析(TGA)表明模板剂的最佳脱除温度为600℃。高分辨透射电镜(HRTEM)观察显示所制得的二氧化硅微球具有典型的中空结构和良好的单分散性,其尺寸主要取决于共聚物微球的大小,通过调节微球模板的尺寸可以有效控制中空微球的大小。N2吸附-脱附曲线显示二氧化硅壁具有丰富的微孔,比表面积、平均孔径和孔容分别为117.87m2/g、1.98nm和0.21cm3/g。在制备复合微球的过程中加入一定量的CTAB可以调整中空微球的壁厚和壁的孔结构,使其比表面积、平均孔径和孔容增加到219.79m2/g、3.89nm和0.25cm3/g。     

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。