Research advances of preparation of Pickering emulsions and their stability

doi:10.16085/j.issn.1000-6613.2023-0528

Abstract

Abstract:

Pickering emulsion refers to an emulsion which is stabilized by ultrafine solid particles or solid colloidal particles instead of traditional surfactants. It is widely applied in many fields involving petroleum, water treatment, cosmetics, food, pharmacy and materials industries due to its advantages such as excellent stability, convenient regulation, environment protection and low cost. In view of preparation and stability of Pickering emulsions, the preparation methods of Pickering emulsions were reviewed systematically. Then, the pattern and research progress of solid emulsifier particles were sketched. Besides, the stability mechanism of Pickering emulsions were revealed. Furthermore, the influencing factors on stability of Pickering emulsions were analyzed. And then, the existing problems of Pickering emulsions were discussed. Finally, the development trends of Pickering emulsions were outlooked. In future, the progress of Pickering emulsion were mainly shown in the following three aspects. ① The cheap, environment-friendly and reused Pickering emulsions with unmodified or modified natural solid nanoparticles were realized. ② The intelligent responsive Pickering emulsions (temperature, pH, magnetic and other response types) were applied in preparation of materials, slowly release or recovery of substance, catalytic reaction and so on. ③ The structure of solid emulsifier particles and emulsions were accurately controlled, and the systemized theory of emulsions preparation was established through deeply investigating the stability mechanism of Pickering emulsions.

Key words: Pickering emulsions, particles, preparation, stability, mechanism, influencing factors

摘要：

Pickering乳液是一类以超细固体颗粒或固态胶体颗粒代替传统表面活性剂作乳化剂而制备的新型乳液，其具有稳定性好、易调控、环境友好、成本低等优点，在石油、水处理、化妆品、食品、医药、材料制备等多个领域得到了广泛应用。基于Pickering乳液的制备和稳定性，本文简述了Pickering乳液的制备方法，介绍了固体乳化剂粒子的类型和研究进展，阐述了Pickering乳液的稳定机制，解析了Pickering乳液稳定性的影响因素，分析了Pickering乳液存在的问题，展望了Pickering乳液的发展方向。未来Pickering乳液的发展主要集中在以下三个方面：①以天然固体纳米粒子或经过各种改性修饰后的天然固体纳米粒子为乳化剂，制备价格低廉、绿色环保、可重复使用的Pickering乳液；②制备智能响应型（温度、pH、磁场等响应型）Pickering乳液，用于材料制备、物质缓释或回收、催化反应等过程；③深入研究不同固体粒子稳定Pickering乳液的机制，精确调控固体乳化剂粒子和乳液的结构，建立Pickering乳液系统制备理论。

关键词: Pickering乳液, 粒子, 制备, 稳定性, 机制, 影响因素

CLC Number:

TQ028.8

QI Yabing, WU Zibo, YANG Qingcui. Research advances of preparation of Pickering emulsions and their stability[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2017-2030.

齐亚兵, 吴子波, 杨清翠. Pickering乳液制备及稳定性研究进展[J]. 化工进展, 2024, 43(4): 2017-2030.

Figures/Tables 11

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乳化法分类	优点	缺点	应用情况
转子-定子匀浆法	操作简单、成本低、乳液制备速度快、易于放大	乳液温度升高多，不适用于热敏型乳液制备；剪切力大、固体粒子破碎多；液滴尺寸大且分布范围广	广泛应用于工业规模乳液的制备
超声乳化法	设备简单，能耗低，制乳速度快，可以制备较小尺寸的乳液	固体粒子破碎多，超声探头会污染料液，液滴尺寸分布范围广，液滴包封效果差、液滴呈多分散性；料液温升高，降低了热敏性粒子或乳液的稳定性；工业放大困难	在乳液制备领域有一定的工业规模应用
高压匀浆法	占地面积小、效率高、能量大、制乳速率快、制乳过程可连续操作、所得乳液液滴尺寸小	能耗高、操作费用较高、制乳器清洗困难、高压操作容易损坏固体乳化剂粒子	在乳液制备领域有一定的工业规模应用
微流控乳化法	乳化过程中对固体乳化剂粒子无明显的破碎作用；可精确控制乳液滴的尺寸；过程可视化；液滴高度分散；能量消耗低，制乳成本低；乳化过程中无热量产生，有利于乳液的稳定	操作复杂、制乳效率低，液滴粒径较大；乳液与微通道之间有可能发生反应，在使用前一般需对微通道作表面处理；仅适用于低黏度流体的制乳，不适合高黏度流体制乳	目前微流控制乳技术还处于实验室研究阶段，未见大规模的工业应用
膜乳化法	操作简单、能耗低、表面活性剂用量少、操作成本低，剪切力小、固体粒子破碎风险小，能制备尺寸小、分布均一的乳液，制备过程中无热量产生，可降低热敏型乳液不稳定的风险	乳液制备时间较长、产率低，膜孔易污染、清洗困难，乳液滴单分散性差，仅适用于低黏度乳液的制备	目前其仅处于实验室研究阶段，还不适合工业规模的放大

乳化法分类	优点	缺点	应用情况
转子-定子匀浆法	操作简单、成本低、乳液制备速度快、易于放大	乳液温度升高多，不适用于热敏型乳液制备；剪切力大、固体粒子破碎多；液滴尺寸大且分布范围广	广泛应用于工业规模乳液的制备
超声乳化法	设备简单，能耗低，制乳速度快，可以制备较小尺寸的乳液	固体粒子破碎多，超声探头会污染料液，液滴尺寸分布范围广，液滴包封效果差、液滴呈多分散性；料液温升高，降低了热敏性粒子或乳液的稳定性；工业放大困难	在乳液制备领域有一定的工业规模应用
高压匀浆法	占地面积小、效率高、能量大、制乳速率快、制乳过程可连续操作、所得乳液液滴尺寸小	能耗高、操作费用较高、制乳器清洗困难、高压操作容易损坏固体乳化剂粒子	在乳液制备领域有一定的工业规模应用
微流控乳化法	乳化过程中对固体乳化剂粒子无明显的破碎作用；可精确控制乳液滴的尺寸；过程可视化；液滴高度分散；能量消耗低，制乳成本低；乳化过程中无热量产生，有利于乳液的稳定	操作复杂、制乳效率低，液滴粒径较大；乳液与微通道之间有可能发生反应，在使用前一般需对微通道作表面处理；仅适用于低黏度流体的制乳，不适合高黏度流体制乳	目前微流控制乳技术还处于实验室研究阶段，未见大规模的工业应用
膜乳化法	操作简单、能耗低、表面活性剂用量少、操作成本低，剪切力小、固体粒子破碎风险小，能制备尺寸小、分布均一的乳液，制备过程中无热量产生，可降低热敏型乳液不稳定的风险	乳液制备时间较长、产率低，膜孔易污染、清洗困难，乳液滴单分散性差，仅适用于低黏度乳液的制备	目前其仅处于实验室研究阶段，还不适合工业规模的放大

乳化剂粒子类型	优点	缺点
无机固体粒子	来源广泛，制备过程较简单，应用范围广	无机固体粒子难以降解，对环境具有一定影响
有机固体粒子	材料来源较广，所制备乳液的稳定性好，易于制备智能响应性Pickering乳液	制备过程较复杂，技术成熟度不高
有机-无机复合固体粒子	乳液稳定性好，易于精确调控乳液性能，可实现物质精准输送或传递	制备过程较复杂，制备成本较高，复合固体粒子稳定性有待提高
Janus粒子	粒子分散性好，稳定性高，易于操控	制备过程较复杂，不能精确控制Janus粒子的形状，生产成本较高，难以实现规模化制备

乳化剂粒子类型	优点	缺点
无机固体粒子	来源广泛，制备过程较简单，应用范围广	无机固体粒子难以降解，对环境具有一定影响
有机固体粒子	材料来源较广，所制备乳液的稳定性好，易于制备智能响应性Pickering乳液	制备过程较复杂，技术成熟度不高
有机-无机复合固体粒子	乳液稳定性好，易于精确调控乳液性能，可实现物质精准输送或传递	制备过程较复杂，制备成本较高，复合固体粒子稳定性有待提高
Janus粒子	粒子分散性好，稳定性高，易于操控	制备过程较复杂，不能精确控制Janus粒子的形状，生产成本较高，难以实现规模化制备

固体乳化剂	Pickering乳液					用途	参考文献
固体乳化剂	制乳方式	水相	油相	类型	特征	用途	参考文献
水杨酸改性纳米TiO₂	匀浆法	杀虫剂NH水溶液	CH₂Cl₂	—	乳液粒径0.58~1.43μm	制备防蚊微胶囊	[23]
纳米Fe₃O₄	匀浆法	水	十八烯基琥珀酸酐	O/W	乳液粒径445.5~8027nm	制备施胶乳液	[24]
球磨重质碳酸钙粒子	匀浆法	超纯水	大豆油	O/W	乳液粒径(17.7±1.6)~(172.4±11.7)μm；乳析指数9.5%~76.5%	制备食品级碳酸钙乳液	[25]
十六烷基三甲基溴化铵改性坡缕石粒子	匀浆法	水	正十四烷、甲苯、煤油、柴油或原油	O/W	乳液粒径约30μm，改性后的坡缕石粒子油水界面张力降低，粒子表面特征改变，且在连续相中形成了三维网络结构，有助于提高乳液的稳定性	制备Pickering乳液凝胶	[26]
六甲基二硅氮烷改性介孔中空SiO₂微球	超声乳化法	去离子水	甲基丙烯酸甲酯和丙烯酸丁酯	—	小尺寸、小壳壁厚度微球，较大微球浓度，中等疏水性和适宜油水比有利于提高Pickering乳液的稳定性	—	[27]
氧化石墨烯	匀浆法	去离子水	石蜡	—	此氧化石墨烯Pickering相变材料乳液具有高导热性和高稳定性	制备氧化石墨烯 Pickering相变材料乳液	[28]
月桂酸改性纳米ZnO	匀浆法	水	液体石蜡	—	调节月桂酸用量可改变纳米氧化锌颗粒表面的亲疏水性，部分亲水的纳米氧化锌颗粒（三相接触角40°~60°）具有最小乳液滴尺寸和最优稳定性	制备表面负载氧化锌纳米颗粒的有机硅弹性微球	[29]
改性硅藻土粒子	匀浆法	—	—	—	—	制备复合物微球、两亲性凝胶、絮凝材料	[30]
蒙脱土、海藻酸钠	匀浆法	水	液体石蜡	O/W	海藻酸钠不仅使连续相变黏稠，在液滴周围形成凝胶状环境；还可以修饰蒙脱土表面，协同增强液滴的静电力。通过pH和盐的各种刺激，可调节蒙脱土/海藻酸钠稳定乳液的流变性质	制备具有生物相容性、多重刺激可调流变性Pickering乳液	[31]
碳纳米管/MgO复合粒子	超声乳化法	—	—	—	以碳纳米管/MgO复合物制备的Pickering乳液在高温、高盐条件下可稳定存在。此纳米复合物的加入显著降低了油水界面张力，并可改变多孔介质的润湿性由油润湿变为水润湿	此复合物粒子用于多孔介质内的驱油	[32]