SCL@SiO_2纳米颗粒的制备及其稳定的Pickering乳液

用共轭亚油酸钠(SCL)在SiO_2纳米颗粒表面吸附,得到表面改性的SiO_2纳米颗粒,然后在80℃下通过热聚合引发SCL分子自交联,从而稳定SCL@SiO2纳米颗粒的SCL层并改善其表面润湿性。通过Zeta电位、FTIR、DLS、TG和DTG对材料进行了表征。结果显示:SCL物理吸附在SiO_2纳米颗粒表面。以SCL@SiO2纳米颗粒作为单一乳化剂制备液体石蜡的Pickering乳液,结果表明:该Pickering乳液在制备一个月后外观基本不发生变化,而传统乳液出现明显破乳现象。热重分析结果显示:SCL@SiO2纳米颗粒的SCL层比简单吸附脂肪酸的SiO_2改性颗粒更稳定,且粒径会随着pH的减小而增大(11～16 nm),因此,由SCL@SiO2纳米颗粒稳定的Pickering乳液粒径(15～29μm)也具有一定的pH响应性。     

海藻酸辛酰胺协同纳米二氧化硅稳定Pickering乳液

采用辛胺疏水改性海藻酸钠合成了具有两亲性的高分子表面活性剂海藻酸辛酰胺(OAAD),并将其与SiO2纳米颗粒协同制备了稳定的Pickering乳液。通过FTIR、1HNMR、表面张力、荧光光谱、动态光散射、接触角测量、光学显微镜分别对OAAD、OAAD/SiO2纳米颗粒水分散体系和Pickering乳状液的性能进行了表征。结果表明,辛胺氨基成功接枝到海藻酸钠(SA)分子链上,OAAD界面张力较SA降低、临界聚集质量浓度为0.60 g/L,表现出良好的两亲性。将OAAD吸附在SiO2纳米颗粒表面形成的水分散体系用于稳定Pickering乳液时,发现随着OAAD质量浓度增加,SiO2纳米颗粒润湿性增加,Zeta电位减少,粒径增加;而乳液的粒径则逐渐减少,稳定性增强,其机理经初步分析为,当一定浓度的OAAD吸附在SiO2纳米颗粒表面,可导致颗粒间絮凝,从而在油水界面形成网络结构式界面膜,有利于提高Pickering乳液的稳定性。     

纳米二氧化硅的疏水改性及其对Pickering乳液的稳定作用

为了探究固体粒子对乳液的稳定作用,采用L-赖氨酸作为催化剂合成纳米SiO2粒子,并用六甲基二硅胺烷(HMDS)对纳米SiO2粒子进行表面疏水改性,将经过HMDS改性后的纳米SiO2粒子作为稳定剂制备出Pickering乳液。通过粒径分析仪、场发射透射电子显微镜、FTIR、TG-DSC、接触角测量仪、光学显微镜、电导率仪分别对纳米SiO2的制备、表面改性和Pickering乳液的性能进行了表征。结果表明,成功合成出粒径小且形貌均一的硅球,具有疏水性的三甲基硅基成功接枝到纳米SiO2的表面;不同纳米SiO2浓度制备的Pickering乳液,发现随着SiO2浓度的增大,乳液的稳定性逐渐增强,乳液液滴直径呈现减小的趋势;不同油水比制备的Pickering乳液,发现随着油相体积的增大,乳液的稳定性呈现增大的趋势。     

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。     

共轭亚油酸钠修饰TiO2纳米片稳定双水相Pickering乳液

采用水热法制备超薄TiO₂纳米片(TiO₂ NSs),以共轭亚油酸钠(SCL)在TiO₂ NSs表面吸附并引发SCL自交联制备共轭亚油酸钠修饰的TiO₂纳米片SCL@TiO₂ NSs,用紫外、红外、热重等手段证实SCL双层吸附在TiO₂ NSs表面上。以SCL@TiO₂ NSs稳定聚乙二醇20000(PEG 20000)-葡聚糖500000(DEX 500000)双水相Pickering乳液,结果表明,以0.5%(质量分数)的SCL@TiO₂ NSs即可稳定乳液,当控制乳化剂浓度不变时,改变两相比例可以使乳液发生相反转。该双水相Pickering乳液具有pH响应性。     

纳米纤维素用于稳定两相界面的研究进展

综述了纳米纤维素稳定Pickering乳液和泡沫的机理,比较了纳米纤维素和纳米颗粒稳定界面的异同,分析了不同纳米纤维素种类、纵横比、盐度、表面改性、表面活性剂等因素对Pickering乳液和泡沫流体性能的影响。为促进纳米纤维素稳定界面的研究和应用,提出了目前存在的问题并展望了今后的研究方向。     

月桂酸改性氧化锌纳米颗粒的Pickering乳化性能研究

研究了不同程度月桂酸表面改性氧化锌纳米颗粒的Pickering乳化性能。通过调节月桂酸用量来改变氧化锌纳米颗粒表面亲疏水性(接触角θ),并探讨了不同接触角氧化锌纳米颗粒稳定的Pickering乳液的乳滴粒径、相转变及稳定性变化规律。结果表明,部分亲水的氧化锌纳米颗粒稳定(三相接触角40°～60°)的O/W型乳液具有最小的液滴尺寸和最优的稳定性。在最优条件下利用Pickering乳液聚合法制备了表面负载氧化锌纳米颗粒的有机硅弹性微球,粒径为5～20μm。     

TiO2纳米颗粒稳定的Pickering乳液用作防晒乳成分研究

采用烷基化改性的TiO_2纳米颗粒为稳定剂,化妆品级白油为油相,黄芪水溶液为水相,制备了一种载药Pickering乳液。利用TEM、接触角测试仪和光学显微镜对TiO_2纳米颗粒及载药Pickering乳液进行了表征。结果表明,该纳米颗粒分散性良好、尺寸均匀,具备良好的稳定乳液能力;通过紫外吸收测试,控制释放药物和清洗对照实验,表明该载药Pickering乳液具有较高的防晒效果和随光照时间控制释放药物以及易于从皮肤表面清洗的特性。     

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。     

双季铵盐改性纳米SiO_2的乳化性能研究

用双季铵盐BQAS-16对纳米SiO_2进行表面改性,并以改性后的纳米SiO_2为乳化剂,制备了Pickering乳液。探究了改性比例、pH、盐的加入和油水体积比对Pickering乳液稳定性的影响。结果表明,与纳米SiO_2相比,BQAS-16改性后的纳米SiO_2具有更优异的乳化性能。随着BQAS-16用量的增加,乳液的稳定性增加。随着pH的增大,乳液的稳定性基本不变;但当pH增至13时,乳液的稳定性显著降低。随着NaCl浓度的增加,乳液的稳定性基本不变。当油水体积比为1∶1时,乳液的稳定性最好。     

海藻酸辛酰胺的制备及其协同氨基SiO2纳米粒稳定液体石蜡/水乳液的研究

以辛胺为疏水改性剂,采用酰化法制得具有两亲性的海藻酸辛酰胺(ACA)。将ACA与采用修正Stber法制备的氨基二氧化硅(SiO_2-NH_2)纳米粒混合,在超声的作用下制得O/W型Pickering乳液。通过FT-IR,~1H NMR和荧光光谱对ACA的结构和性能进行表征。并采用激光粒度和Zeta电位分析仪、接触角测量仪和光学显微镜探究了ACA,SiO_2-NH_2及其协同水分散体系的胶体性能和相应的Pickering乳液的形貌。结果表明:ACA的取代度为0.29,在0.15 mol/L Na Cl水溶液中的临界聚集浓度(cac)为0.42 g/L,表现出较强的两亲性能。ACA通过静电作用力成功地吸附于SiO_2-NH_2纳米粒上,使水动力学粒径只有155 nm的SiO_2-NH_2纳米粒增长至386 nm,Zeta电位由+22.2 mV转变为-30.7 mV,在水溶液中能够表现出良好的稳定性。吸附于SiO_2-NH_2纳米粒表面的ACA可以抑制无机纳米粒的聚沉,而游离的ACA形成的胶束结构的疏水内腔能够增溶油滴,减少小油滴的聚并。光学显微镜中出现了粒径较大的Pickering乳液液滴和粒径较小的传统乳液液滴共存的现象,当ACA质量浓度在0.5 cac~1.0 cac时,2种乳液共存现象最为显著。     

基于纳米氢氧化铝颗粒的Pickering乳液制备

以异丙醇铝为原料,采用醇盐水解?水热法制备勃姆石型纳米氢氧化铝颗粒,优化制备条件;以所制颗粒为稳定剂、角鲨烯为油相,通过超声破碎法制备Pickering乳液,考察了颗粒浓度、水相成分、超声时间及功率对Pickering乳液粒径及稳定性的影响。结果表明,水热温度200℃、水热时间2 h条件下,可制得结晶度高且均一的勃姆石型纳米氢氧化铝颗粒,平均粒径为55.70?9.20 nm,多分散性指数(PDI)为0.187?0.011;所制Pickering乳液平均粒径为1870?55 nm,PDI=0.120?0.010,可在室温下稳定储存120 d以上,且生物相容性良好,有望应用于生物医药领域。     

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。     

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。     

The construction of pseudo-Janus silica/surfactant assembly and their application to stabilize Pickering emulsions and enhance oil recovery

Nanoparticles with high surface energy and chemical activity have drawn substantial attention in petroleum industry. Recently, Janus nanoparticles exhibited tremendous potential in enhanced oil recovery (EOR) due to their asymmetric structures and properties. In this study, a series of amphiphilic pseudo-Janus@OTAB (PJ@C18) nanoparticles with different concentrations of stearyltrimethylammoium bromide (OTAB) were successfully fabricated. The structures and properties of PJ@C18 were characterized by Fourier transform infrared spectroscopy and ζ-potential measurements. Based on the emulsification experimental results, the interaction models and the self-assembly behavior between hydrophilic nanoparticles (SiO₂@NH₂) and OTAB molecules at the oil/water interface were proposed, which was further confirmed via the measurements of the contact angle and dynamic interfacial tension. Interestingly, it was found that the change of pH value from 7.5 to 4.0 caused the type reversal of the PJ@C18-1000 stabilized Pickering emulsions. Furthermore, the PJ@C18-1000 stabilized Pickering emulsion system with excellent salt and temperature tolerances (10000 mg∙L^–1, 90 °C) significantly improved the oil recovery in the single-tube (more than 17%) and double-tube (more than 25%) sand pack model flooding tests. The findings of this study could help to better understand the construction mechanism of pseudo-Janus silica/surfactant assembly and the potential application of PJ@C18-1000 stabilized Pickering emulsions for EOR.     

掺氮TiO_2纳米颗粒稳定的Pickering乳液制备及其触发酶反应

利用烷基硅烷接枝的掺氮TiO_2纳米颗粒稳定W/O型Pickering乳液,研究了TiO_2掺氮量对成乳的影响以及乳液的可见光响应性能,并将其作为微反应器应用于触发脲酶催化尿素生成碳酸铵的反应中。结果表明:在可见光照射下,烷基硅烷接枝的掺氮TiO_2纳米颗粒表面由疏水变为亲水,可引发乳液液滴聚并以及液滴内酶促反应发生。     

Suspension polymerization based on inverse Pickering emulsion droplets for thermo-sensitive hybrid microcapsules with tunable supracolloidal structures

Polymerization using Pickering emulsion droplets as reaction vessels is being developed to become a powerful tool for fabrication of hybrid polymer particles with supracolloidal structures. In this paper, two kinds of thermo-sensitive hybrid poly(N-isopropylacrylamide) (PNIPAm) microcapsules with supracolloidal structures were successfully prepared from suspension polymerization stabilized by SiO₂ nanoparticles based on inverse Pickering emulsion droplets. SiO₂ nanoparticles could self-assemble at liquid-liquid interfaces to form stable water-in-oil inverse Pickering emulsion. NIPAm monomers dissolving in suspended aqueous droplets were subsequently polymerized at different temperatures. The hollow microcapsules with SiO₂/PNIPAm nanocomposite shells were obtained when the reaction temperature was above the lower critical solution temperature (LCST) of PNIPAm. While the core-shell microcapsules with SiO₂ nanoparticles' shells and PNIPAm gel cores were produced when the polymerization was conducted at the temperature lower than LCST using UV light radiation. The supracolloidal structures with different cores could be tuned by simply changing reaction temperature, which was confirmed by confocal laser scanning microscopy and scanning electron microscopy. The interesting properties of both microcapsules were their ability of reversibly swelling during drying/wetting cycles and responsive to temperature stimulus. Such functional microcapsules may find applications in double control release system due to the presence of the supracolloidal structures and thermo-sensitivity.     

Synthesis of Polystyrene/Hydrophobic SiO2 Composite Particles via Oil‐in‐Water Pickering Emulsion Polymerization

The aim of this work is to present a facile Pickering emulsion polymerization method for the synthesis of submicron polystyrene/SiO₂ core/shell composite particles. The commercial hydrophobic SiO₂ nanoparticles were used as stabilizing agent for creating a stable oil‐in‐water emulsion. Although the adsorption of hydrophobic SiO₂ nanoparticles in the emulsion system was unfavorable in terms of thermodynamics, by ultrasound treatment, self‐assembly of hydrophobic SiO₂ nanoparticles effectively stabilized oil‐in‐water Pickering emulsions during polymerization. Using 3 wt.% SiO₂ nanoparticles (based on styrene monomer) and 1:10 volume ratio of styrene monomer:water, the composite particles having average size of 790 nm and relatively narrow particles distribution were produced. With decreasing the volume ratio, smaller composite particles were created. Results from scanning electron microscope revealed that SiO₂ nanoparticles were located exclusively at the surface of the polystyrene latex particles. The SiO₂ content, determined by thermogravimetric analysis, was 12.6 wt.% in the composite particles. The route reported here may be used for the preparation of other composite nanostructures. POLYM. ENG. SCI., 59:E195–E199, 2019. © 2018 Society of Plastics Engineers