高亲水性纳米二氧化硅颗粒稳定Pickering乳液

用未修饰的高亲水性纳米二氧化硅颗粒(SiO2 NPs)在其等电点附近制备Pickering乳液。结果表明,等电点(pH 2.7)条件下SiO2 NPs借助高能均质与油水界面剧烈混合,并在范德华引力的驱动下以弱吸附的状态在界面处负载,从而稳定得到O/W型Pickering乳液。增加SiO2 NPs的浓度或减小油相体积分数可提高单位油滴界面的颗粒负载率,增大连续相黏度并促进乳液液滴之间形成三维网络结构从而提高乳液稳定性。通过调节连续相的pH以促进SiO2 NPs表面的硅烷醇发生质子化与去质子化的转变,实现乳液多次pH响应循环。     

Core-shell-structured silica/polyacrylate particles prepared by Pickering emulsion: influence of the nucleation model on particle interfacial organization and emulsion stability

This work reports a new evidence of the versatility of silica sol as a stabilizer for Pickering emulsions. The organization of silica particles at the oil-water interface is a function of the nucleation model. The present results show that nucleation model, together with monomer hydrophobicity, can be used as a trigger to modify the packing density of silica particles at the oil-water interface: Less hydrophobic methylmethacrylate, more wettable with silica particles, favors the formation of core-shell-structured composite when the composite particles are prepared by miniemulsion polymerization in which monomers are fed in batch (droplet nucleation). By contrast, hydrophobic butylacrylate promotes the encapsulating efficiency of silica when monomers are fed dropwise (homogeneous nucleation). The morphologies of polyacrylate-nano-SiO₂ composites prepared from different feed ratio of methylmethacrylate/butylacrylate (with different hydrophobicity) and by different feed processes are characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques. The results from SEM and TEM show that the morphologies of the as-prepared polyacrylate/nano-SiO₂ composite can be a core-shell structure or a bare acrylic sphere. The stability of resulting emulsions composed of these composite particles is strongly dependent on the surface coverage of silica particles. The emulsion stability is improved by densely silica-packed composite particles.     

SiO2改性聚丙烯纤维棉对油水乳状液的高效分离

近年来,基于特殊润湿性理论制备表面具有微纳米粗糙结构的多孔材料成为油水分离领域研究的重点。为了满足不同环境下对不同形式油-水乳状液高效高通量分离的需求,该研究利用纳米SiO2颗粒对聚丙烯（PP）纤维棉有针对性地亲（疏）水改性,构建了系列不同润湿性和粗糙度的PP纤维棉,探究了不同孔隙度和表面能的PP纤维棉对W/O及O/W型乳状液的分离性能,结果表明,经过亲（疏）水改性后的PP纤维棉对水/正己烷和水/甲苯乳状液的分离效率都高于99.5%,通量高于700 L/(m2·h),并针对不同形式油-水乳状液阐释其相应的分离机制,为后续油-水乳状液分离材料的科学设计和可控制备提供了理论依据。     

pH值对原油乳状液稳定性的影响

研究了pH值对原油乳状液稳定性的影响, 测定了胶质和沥青质在油水界面上的聚集和铺张情况, 不同pH值下油水界面张力以及胶质和沥青质模拟乳状液的稳定性变化, 并且完成了不同pH值下的乳状液化学破乳以及电场破乳实验。沥青质相对胶质更易在界面上聚集和铺展, 形成高黏弹性的界面膜。pH值为酸性或碱性时都能有效降低油水界面张力, 增加乳状液稳定性, 使其化学破乳脱水困难, 而破乳实验也验证了这一观点。随着pH值从2增加到10, 胶质模拟乳状液和沥青质模拟乳状液稳定性变化大, 变化趋势则刚好相反, 胶质模拟乳状液稳定性增加, 油水分离速度减慢;沥青质模拟乳状液稳定性减弱, 体系电导率0.21～1.8mS/cm。因此pH<7时, 沥青质稳定能力强, 而胶质稳定能力弱, 电脱水过程中电脱装置正常工作;pH>7时, 结果相反, 表明电脱装置短路现象与沥青质、胶质稳定能力变化相关。     

分子氧化及光电催化氧化对石油Pickering乳液的破乳研究进展

石油开采、集输、加工过程中会面临复杂的工况条件,原油中的天然表面活性剂与人工添加乳化剂以及纳微米固体颗粒共同形成石油Pickering乳液,使得油水体系呈稳定的水包油（O/W）、油包水（W/O）或多重乳化状态。油水乳状液作为注水采油的主要产物,其高效破乳是石油工业链条中的普遍需求。目前对于石油Pickering的破乳仍然借鉴普通油水乳液的方法,而对于成因复杂的油水乳状液,以去除成膜乳化剂为目标的氧化破乳法比传统破乳法的效果更佳。为此,本文基于高效的氧化破乳机制,介绍了石油Pickering乳液的特点及危害,与非氧化反应类型的传统化学破乳法进行对比,综述了分子氧化、光催化氧化、电化学氧化三类技术对于不同来源及特征的油水乳状液的破乳进展。通过对每种方法的机理过程、应用实例、优缺点等方面详细分析,总结了分子氧化、光催化氧化、电化学氧化在石油Pickering乳液破乳中的局限性,并对今后如何实现石油Pickering乳液精准破乳提出展望。     

油水乳液分离吸附材料的分离原理、构建方法和分离性能

采用吸附材料进行油水分离是经济且非常有效的方法。吸附材料主要有无机材料、合成高分子材料和天然有机纤维材料等。相比较而言，天然有机纤维材料为可再生生物质资源，来源广泛、生物降解性好，可有效防止二次污染，具有良好的发展潜力，备受关注。本文首先简要介绍了油水乳液稳定性的影响因素，然后综述了油水分离材料的分离原理、构建方法和分离性能等研究进展，并总结了油水乳液分离材料的表征及其分离性能的评价指标。特别地，重点总结了天然有机纤维基吸附材料分离油水乳液的研究进展。最后指出研究智能响应型天然有机纤维基油水乳液分离吸附材料是重要的发展方向。     

Influence of Nanoparticles and Drop Size Distributions on the Rheology of w/o Pickering Emulsions

The rheological behavior of particle/oil suspensions and w/o Pickering emulsions consisting of water, 1‐dodecene and different fumed silica nanoparticles was investigated. The particles varied in hydrophobicity and specific surface area. The influence of particle concentration and water content on rheology was determined and the emulsion drop size distributions were examined. Emulsions with different drop sizes were created by either varying the particle concentration or the water content. It was found that the particles in the continuous oil phase and not the drop size distribution seem to be the major influencing factor on the Pickering emulsion rheology.     

Comparison of the effects of three different phosphatidylcholines on casein-stabilized oil-in-water emulsions

Soy oil-in-water emulsions, stabilized by casein, but incorporating one of three different phosphatidylcholines (PC), namely egg-PC, di-palmitoyl phosphatidylcholine (DPPC) and di-oleyl phosphatidylcholine (DOPC), have been studied by photon correlation spectroscopy, light scattering, fast protein liquid chromatography, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). Egg-PC enhanced the stability of emulsions made with low casein concentration, and it competed for space with casein at the oil-water interface during the emulsification process, but no further displacement of protein was found. DPPC had little effect on emulsion stability nor did it show a detectable competition at the interface with casein during or after emulsification. DOPC, however, not only competed with casein at the interface during emulsification, it also removed casein from the interface during storage of the emulsion. The displacement of casein caused instability of the emulsions. Adding DOPC to emulsions also led to displacement of casein from the interface and caused instability of the emulsion, but the process was much slower and occurred to a smaller extent compared to emulsions prepared with DOPC. The different behavior of egg-PC, DPPC, and DOPC on the oil-water interface was in good agreement with their relative solubility in the oil phase as measured by spectrophotometry. All three lipids modified the hydrodynamic thickness of the adsorbed casein layer corresponding to their modification of the surface concentration of casein.     

Influence of clay addition on the properties of olive oil in water emulsions

The behaviour of olive oil-in-water emulsions (O/W) was studied in the presence of smectite particles. The distribution of these particles in the emulsions and the effect of their interaction with the surfactant on the stability of the emulsions were investigated. Whereas the variation of surfactant and/or clay content did not seem to affect the nature of the emulsion, it had a significant influence on emulsion stability. This observation led to two main assumptions on the distribution of clay particles within the emulsion, either exclusively in the continuous phase, or also at the oil-water interface.In the absence of clay, the variation of surfactant concentration (from 0 to 17% (w/w)) allowed to distinguish 3 domains. In the first concentration domain (0–4.2%) emulsions stability increased with the content of surfactant. Within the second domain (4.2–8.5% (w/w)), a slight decrease in stability was observed due to flocculation by depletion. For surfactant concentrations equal or higher than 8.5% (3rd domain), emulsion stability increased sharply, probably due to the development of interactions between surfactant molecules as they came closer to their gelling concentration. The effect of clay addition to the aqueous phase (up to 10% (w/w)) on the physicochemical properties of the studied emulsions was assessed from stability, drop size, interfacial tension, rheological and acido-basic analyses. A model based on the location of clay particles either in the bulk or at the interface could be proposed, in which clay particles would interact with surfactant molecules in the bulk phase, and form a mechanical barrier around the oil droplets, thus increasing emulsion stability.     

Fabrication of magnetically responsive anti-fouling and easy-cleaning nanofiber membrane and its application for efficient oil-water emulsion separation

The magnetically responsive anti-fouling nanofiber membrane(MRANM) was fabricated for efficient oilwater emulsion separation,which could be cleaned using oscillating magnetic field.MRANM was prepared by grafting superparamagnetic Fe₃O₄ nanoparticles onto the surface of electrospun polyacrylonitrile nanofiber membrane(PANM),Compared with PANM,the water contact angle of MRANM decreased from 104° to 0°,indicating that the hydrophilicity of the membrane was significantly improv...     

The Influence of Secondary Emulsifiers on Lipid Oxidation within Sodium Caseinate-Stabilized Oil-in-Water Emulsions

The effect of protein displacement at the interface by a secondary emulsifier on the oxidative stability of sodium caseinate-stabilized tuna oil-in-water emulsion systems was determined. Emulsions were prepared with a selection of anionic and non-ionic emulsifiers and stored at both 25 and 50 °C with no added prooxidant, and at 4 °C in the presence of ferrous sulfate. The progress of oxidation during storage was monitored through solid phase microextraction headspace analysis. Metal ion catalyzed oxidation was enhanced for the emulsions stabilized with an anionic emulsifier in comparison to emulsion systems stabilized with non-ionic emulsifiers and sodium caseinate alone. The increased oxidation observed for the emulsion with the anionic surfactant is due to electrostatic interactions between divalent metal ions and the negatively charged surfactant at the oil-water interface. The sodium caseinate interfacial layer had little prooxidant effect at the droplet surface, most likely due to the ability of free protein molecules in solution to sequester metal ions, which may have provided some protection against oxidative deterioration.     

绿色纤维素基水凝胶的制备及油水分离性能

为研发绿色环保的水凝胶膜用于油水分离,本研究从废弃杨木中提取纤维素,并采用协同组装策略构建了一种绿色纤维素基水凝胶（CLH）膜,用于油水分离。将氯化锂（LiCl）作为活性吸水单元引入纤维素骨架中,然后利用聚乙烯醇（PVA）将LiCl颗粒包裹在纤维素骨架上制备CLH水凝胶膜。制备过程绿色环保,操作简单。制备的CLH水凝胶膜具有层状结构,可以克服传统水凝胶不可压缩的缺陷。在重力作用下,CLH水凝胶膜可以实现油水混合物和水包油乳液的高效分离。同时,CLH水凝胶膜油水分离过程中表现出良好的稳定性、耐久性和循环稳定性。因此,本文研发的协同组装策略不仅可以有效解决因废弃木材的产生造成的纤维素资源浪费问题,还可以为油水分离提供一种新的方法。     

智能响应型Pickering乳液的制备及在物质分离中的应用进展

Pickering乳液是指由微纳米固体粒子代替传统表面活性剂作为乳化剂而稳定的乳液,具有较强的稳定性和超高油/水界面,能够为多相界面反应和物质传输提供高效稳定的场所。Pickering乳液的乳滴结构和性质与固体颗粒的尺寸形貌及表面性质密不可分,通过调控固体颗粒本身或表面的性质可以赋予Pickering乳液特定的响应性功能,拓宽其应用领域。本文对近年来不同响应型（磁性、CO₂、pH、光、温度等响应型）的Pickering乳液的主要研究成果进行了综述,重点介绍了Pickering乳液的稳定性原理、响应型Pickering乳液的制备方法和结构调控策略,以及近年来Pickering乳液在物质分离提取中的应用研究进展,最后对智能响应型Pickering乳液应用研究的发展趋势进行了展望。     

Preparation and power consumption of surfactant-fuel oil-water emulsions using axial, radial, and mixed flow impellers

Surfactant-oil-water emulsions could have applications in enhanced oil recovery and the bio-desulfurization process applied to crude oil and some fractions. A simple way to prepare oil in water (O/W) emulsions is using a tank and an agitation device. The aim of this work is to propose a technology to prepare surfactant-fuel oil-water emulsions by means of a system involving a tank equipped with baffles, and an agitation device. The employed fuel oil was a high-viscosity fraction, which makes it difficult to handle. Axial, radial, and mixed flow impellers were assessed in the preparation of O/W emulsions, with and without the presence of baffles. Sixteen commercial surfactants were evaluated on the O/W emulsion formation. The effect of the storage temperature on the emulsions stability was assessed. The presence of salt on the surfactant-fuel oil-water emulsion was also investigated. Power vs. Reynolds numbers, extremely important data for the scaling up of the process, were calculated in basis of the power drawn when preparing the emulsions. Total consumption energy applied to the system, as well as pumping capacity were measured and related to the quality of the O/W emulsions obtained.     

非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控

用具有氧化还原活性分子乙酰基二茂铁吖嗪(Fc⁺A)对磁性纳米颗粒Fe₃O₄@SiO₂进行非共价疏水改性,将改性颗粒作为乳化剂制备Pickering乳液。通过TEM、SEM、FTIR、XRD、接触角测量、光学显微镜等对纳米颗粒及Pickering乳液的结构、形貌和性能进行表征。结果表明：制备的核壳结构纳米颗粒粒径为150 nm左右,分散均匀;Fc⁺A成功修饰到纳米颗粒表面,且随Fc⁺A浓度的增加,改性颗粒的接触角明显增大;Fc⁺A浓度为12.5 mmol/L,乳化剂浓度为0.3%(质量),油水比为4∶6,搅拌速率为10000 r/min,得到的Pickering乳液具有良好的稳定性。而且,所得乳液具双重响应性,通过氧化还原和磁场可实现对乳液稳定性的可逆调控。     

The viscoplastic properties of crude oil-water interfaces

The breaking of water-in-crude oil emulsions is a major challenge in the conventional petroleum industry, while oil-in-water emulsions present similar issues in commercial oilsands extraction processes. The stability of these emulsions can be attributed to complex rheological properties of the crude oil-water interface. Novel micromechanical techniques are developed that allow direct measurements of interfacial behaviour of emulsion drops. In these techniques, individual emulsion drops are elongated using micropipettes, where one micropipette is shaped into a cantilever for force measurements. As such, the surface behaviour of a drop is recorded in stress-strain experiments. In an alternative technique, the extended drop is released from a micropipette, and its natural, tension-driven relaxation is observed.The surface behaviour of bitumen (a heavy crude oil) emulsion drops in aqueous environments, that include dissolved calcium ions and suspended montmorillonite clays, is studied. The plasticity and other surface properties of these bitumen drops are discussed. A simple, lumped-parameter model is developed to describe the recovery of a bitumen drops to their final non-spherical shapes.     

Safety investigations of trinitrotoluene/water emulsions

In the disposal of explosives, preparation of the dismantled material is necessary before subjecting it to a breakdown process. Knowledge of the material properties and determination of safety-related parameters are major prerequirements when designing a disposal facility and increasing handling safety. When TNT is treated using emulsion processing, a desensitization of the TNT melt via the aqueous phase is obtained, in addition to increasing the surface area of the TNT phase. During the entire process of TNT treatment, the system is exposed to a wide range of different stresses as a result of the mechanical energy applied. This study presents the results of an investigation on the sensitivity of pure TNT melts and TNT/water emulsions at different concentrations on exposure to the applied impact or shock energies. It is found that the impact sensitivity of a TNT/water emulsion is lower by a factor of 4 when the TNT concentration has been reduced from 50 wt % to 30 wt %. On exposure to stress from a detonation shock wave, a desensitization of the system due to the aqueous phase is also found, so that the safety of the TNT treatment process can be increased by using a TNT/water emulsion when applying mechanical breakdown methods.     

聚苯乙烯-丙烯腈/蒙脱土纳米复合材料的制备和结构

引 言 近年来,聚合物/蒙脱土纳米复合材料已成为材料科学界的一个研究热点,各种高分子材料均被尝试用来制备此类纳米复合材料以提高聚合物的力学性能、热性能和阻隔性能[1-4].对聚合物/蒙脱土纳米复合材料的研究主要集中在制备方法、结构和性能表征方面,如何利用蒙脱土片层的特性来探索简单易行、成本较低且能够使蒙脱土充分剥离分散的方法一直是此方面的研究焦点.     

Surface composition regulates clearance from plasma and triolein lipolysis of lipid emulsions

Sphingomyelin (SM) and cholesterol (Chol) are major surface lipid constituents of plasma lipoproteins. We investigated the effects of SM and Chol on the plasma clearance of lipid emulsions as a model for lipoprotein particles in rats. The presence of Chol facilitated the removal of emulsion particles from plasma, whereas SM delayed particle removal. Preinjection of lactoferrin, an inhibitor of the apolipoprotein E (apoE) receptor, revaled that the differences in clearance of emulsions were due to the differences in affinity for the apoE receptor. Measurement of apolipoprotein binding suggested that the balance of apoE and apoC (apoC-II and apoC-III) bound to emulsions caused the difference in plasma clearance of emulsion particles. That is to say, SM in the emulsion surface decreased binding of apoE, which led to a longer circulation of emulsion particles in plasma. Chol, on the other hand, decreased the ratio of apoC to apoE, which may have promoted emulsion uptake through the apoE receptor. We also examined in vitro lipolysis using immobilized lipoprotein lipase (LPL) in a heparin affinity column. Lipolysis rates were significantly reduced by the incorporation of SM into the emulsion surface, but not by the incorporation of Chol, indicating that SM in the lipoprotein surface is an important lipid component regulating LPL-mediated lipolysis. Our results suggest that the presence of SM and Chol in the lipoprotein surface plays an important role in the circulation behavior and LPL-mediated lipolysis of lipid emulsions through their effect on the selectivity of plasma protein binding.     

基于纤维素纳米晶稳定的亚微米Pickering乳液制备

与传统表面活性剂稳定的乳液相比,固体纳米颗粒稳定的Pickering乳液具有较强的界面稳定性、多功能性、低毒性等优势,在生物医药领域具有较大的应用潜力。而相较于尺寸较大的微米级Pickering乳液,亚微米Pickering乳液具有更大的比表面积、更有效的递送效率,有望进一步拓展Pickering乳液在生物医药领域的应用。但由于Pickering乳液的制备影响因素众多,且相互制约,刚性的固体颗粒难以在较小的有限油水界面排布,增加了亚微米Pickering乳液的制备难度。本工作以制备稳定的亚微米Pickering乳液为研究目标,采用具有良好生物相容性的天然多糖–纤维素纳米晶(CNCs)为颗粒乳化剂,角鲨烯作为油相,考察了颗粒浓度、油水比例、水相成分、超声时间及频率对Pickering乳液粒径分布及稳定性的影响,最终得到了具有良好的储存稳定性和抗离心稳定性的粒径为638.7?8.40 nm的亚微米Pickering乳液(CNCs-PE)。通过激光共聚焦显微镜证实了CNCs吸附在油水界面,形成了Pickering乳液结构。利用CCK-8法评价了CNCs和CNCs-PE的细胞毒性,结果表明,两者都具有良好的细胞安全性。此外,将其用于吸附模型抗原OVA,吸附率达到约80%,且肌肉注射部位的切片结果也表明其注射安全性良好。此结果为亚微米Pickering乳液进一步研究提供了参考,并有望拓展CNCs稳定的亚微米Pickering乳液在生物医药领域的应用。