Citation: Shuo Lu, Dong-jie Yang, Yuan-yuan Li, Zhi-xian Li, Xue-qing Qiu. Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles[J]. Acta Polymerica Sinica, ;2019, 50(2): 160-169. doi: 10.11777/j.issn1000-3304.2018.18211 shu

Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles

1.
State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640
2.
College of Pharmacy, Henan University of Chinese Medicine, Zhengzhou 450046

Corresponding author: Xue-qing Qiu, cexqqiu@scut.edu.cn
Received Date: 5 October 2018
Revised Date: 25 October 2018
Available Online: 27 November 2018

pH-Responsive oil-in-water Pickering emulsions using n-decane as oil phase were prepared by mixing quaternized lignin (QAL) and titanium dioxide (TiO₂) nanoparticles as emulsifiers. The emulsions stabilized by 0.5 wt% TiO₂ neat nanoparticles are extremely unstable due to the strong hydrophilic properties of the nanoparticles. However, when TiO₂ nanoparticles are dispersed in neutral solution containing 0.1 wt% QAL, all the emulsifier particles can be applied onto the n-decane/water interface, which greatly improves the stability of the emulsions and the droplet size ranges from 20 μm to 60 μm. Meanwhile, emulsions stabilized by QAL and TiO₂ nanoparticles show outstanding pH-responsive properties, which are stable in the range of 6.0 < pH < 7.0 while unstable under the acidic and basic conditions. The synergistic stabilization mechanism of QAL and TiO ₂ nanoparticles was studied with zeta potential, adsorption kinetics, and three-phase contact angle. QAL pertains to amphoteric surfactants whose isoelectric point is 7.5. When 6.0 < pH < 7.0, QAL molecules are negatively charged, allowing them to combine with TiO ₂ nanoparticles via electrostatic interactions. The hydrophobic phenylpropane skeleton of QAL molecule reduces the hydrophilicity of TiO₂ nanoparticles thereby enhances their surface activity to form stable emulsions. However, under the acidic and alkaline conditions, QAL molecules turn into the same charge with TiO₂ nanoparticles. Thus, QAL molecules significantly desorb from TiO₂ nanoparticles surface due to electrostatic repulsion. TiO₂ nanoparticles become intensely hydrophilic again and unable to stay on the oil/water interface, which makes the emulsions unstable as a result. Therefore, the adsorption behaviour between QAL and TiO₂ nanoparticles endows Pickering emulsions with double pH-responsive characteristics. With the alternative pH of aqueous phase by adding aqueous HCl and aqueous NaOH, the emulsion system can be recycled many times between emulsification and demulsification while the average droplet size has no obvious change due to its excellent salt tolerance.
- Quaternized lignin,
- TiO₂,
- pH Responsive,
- Pickering emulsions,
- Adsorption
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沈阳化工大学材料科学与工程学院沈阳 110142