Tan Shuwen, Xu Xiaojia, Zhang Ting, Li Min, Liu Xiaoyan, Claesson Per M, Fang Yu
Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, P R China.
Department of Chemistry, Division of Surface and Corrosion Science, KTH Royal Institute of Technology, Teknikringen 29, Stockholm SE-100 44, Sweden.
Langmuir. 2024 Aug 13;40(32):16946-16958. doi: 10.1021/acs.langmuir.4c01743. Epub 2024 Jul 30.
Microgels have been widely used for stabilizing emulsions due to their softness and stimulus responsiveness. Although ultrastable emulsions have been prepared by microgel nanoparticles, the role of electrostatic interactions on emulsion stability is still a controversial topic and further investigation of the effect of microgel deformability is required. In the present study, neutral poly(-vinylcaprolactam) (PVCL) and charged poly(-vinylcaprolactam)methacrylic acid (P(VCLMAA)) microgels were synthesized and further used as emulsifiers to stabilizing emulsion. The P(VCLMAA) microgel has a swelling ratio larger than that of the PVCL microgel in water. The nanomechanical properties of the microgels in water were characterized by atomic force microscopy with using the tip of different radii. The result reveals that the P(VCLMAA) microgel is more deformable than the PVCL counterpart. Stability tests of the emulsions showed that below the volume phase transition temperature (VPTT) of the microgels, both microgel types can stabilize the emulsions under various conditions. Unexpectedly, most of the emulsions still remain stable above the VPTT. Further increasing the temperature to 60 °C, P(VCLMAA) microgel emulsions remained stable at a pH value above the p of MAA while the emulsion was unstable below the p. However, phase separation occurs in PVCL microgel-stabilized emulsions at 60 °C. These results demonstrate that electrostatic repulsion and deformability of the microgels can enhance the emulsion stability, providing insights into the rational design and preparation of ultrastable Pickering emulsions.
微凝胶由于其柔软性和刺激响应性已被广泛用于稳定乳液。尽管通过微凝胶纳米颗粒制备了超稳定乳液,但静电相互作用对乳液稳定性的作用仍然是一个有争议的话题,需要进一步研究微凝胶可变形性的影响。在本研究中,合成了中性聚(乙烯基己内酰胺)(PVCL)和带电聚(乙烯基己内酰胺)甲基丙烯酸(P(VCLMAA))微凝胶,并进一步用作乳化剂来稳定乳液。P(VCLMAA)微凝胶在水中的溶胀率大于PVCL微凝胶。使用不同半径的尖端通过原子力显微镜对水中微凝胶的纳米力学性能进行了表征。结果表明,P(VCLMAA)微凝胶比PVCL微凝胶更易变形。乳液的稳定性测试表明,在微凝胶的体积相变温度(VPTT)以下,两种类型的微凝胶都可以在各种条件下稳定乳液。出乎意料的是,大多数乳液在VPTT以上仍保持稳定。进一步将温度提高到60°C,当pH值高于MAA的pKa时,P(VCLMAA)微凝胶乳液保持稳定,而在pKa以下乳液不稳定。然而,在60°C时,PVCL微凝胶稳定的乳液会发生相分离。这些结果表明,微凝胶的静电排斥和可变形性可以提高乳液稳定性,为超稳定Pickering乳液的合理设计和制备提供了见解。