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
1. [1]
  Binks B P. Curr Opin Colloid Interface Sci, 2002, 7: 21 − 41 doi: 10.1016/S1359-0294(02)00008-0
2. [2]
  Chevalier Y, Bolzinger M A. Colloid Surf, A, 2013, 439: 23 − 34 doi: 10.1016/j.colsurfa.2013.02.054
3. [3]
  Aveyard R, Binks B P, Clint J H. Adv Colloid Interface, 2003, 100-102: 503 − 546 doi: 10.1016/S0001-8686(02)00069-6
4. [4]
  Tang J, Quinlan PJ, Tam KC. Soft Matter, 2015, 11(18): 3512 − 3529 doi: 10.1039/C5SM00247H
5. [5]
  Zhu Y, Jiang J, Liu K, Cui Z, Binks B P. Langmuir, 2015, 31(11): 3301 − 3307 doi: 10.1021/acs.langmuir.5b00295
6. [6]
  Liu H, Wei Z, Hu M, Deng Y, Tong Z, Wang C. RSC Adv, 2014, 4(55): 29344 − 29351 doi: 10.1039/C4RA01660B
7. [7]
  Fujii S, Read ES, Binks B P, Armes S P. Adv Mater, 2005, 17(8): 1014 − 1018 doi: 10.1002/(ISSN)1521-4095
8. [8]
  Cui Z G, Cui C F, Zhu Y, Binks B P. Langmuir, 2012, 28(1): 314 − 320 doi: 10.1021/la204021v
9. [9]
  Zhu Y, Pei X, Jiang J, Cui Z, Binks B P. Langmuir, 2015, 31(47): 12937 − 12943 doi: 10.1021/acs.langmuir.5b03681
10. [10]
  Tang J, Lee M F, Zhang W, Zhao B, Berry R M, Tam K C. Biomacromolecules, 2014, 15(8): 3052 − 3060 doi: 10.1021/bm500663w
11. [11]
  Morse A J, Armes S P, Thompson K L, Dupin D, Fielding L A, Mills P, Swart R. Langmuir, 2013, 29(18): 5466 − 5475 doi: 10.1021/la400786a
12. [12]
  Nguyen B T, Wang W, Saunders B R, Benyahia L, Nicolai T. Langmuir, 2015, 31(12): 3605 − 3611 doi: 10.1021/la5049024
13. [13]
  Liu H, Wang C, Zou S, Wei Z, Tong Z. Langmuir, 2012, 28(30): 11017 − 11024 doi: 10.1021/la3021113
14. [14]
  Gao Z, Zhao J, Huang Y, Yao X, Zhang K, Fang Y, Nishinari K, Phillips G O, Jiang F, Yang H. LWT-Food Sci Technol, 2017, 76: 1 − 8 doi: 10.1016/j.lwt.2016.10.038
15. [15]
  Pang K, Ding B, Liu X, Wu H, Duan Y, Zhang J. Green Chem, 2017, 19(15): 3665 − 3670 doi: 10.1039/C7GC01592E
16. [16]
  Doherty W O S, Mousavioun P, Fellows CM. Ind Crop Prod, 2011, 33(2): 259 − 276 doi: 10.1016/j.indcrop.2010.10.022
17. [17]
  Stewart D. Ind Crop Prod, 2008, 27(2): 202 − 207 doi: 10.1016/j.indcrop.2007.07.008
18. [18]
  Figueiredo P, Lintinen K, Hirvonen J T, Kostiainen MA, Santos H A. Prog Mater Sci, 2018, 93: 233 − 269 doi: 10.1016/j.pmatsci.2017.12.001
19. [19]
  Lora J H, Glasser W G. J Polym Environ, 2002, 10(1-2): 39 − 48
20. [20]
  Ye X X, Luo W, Lin L, Zhang Y Q, Liu M H. J Disper Sci Technol, 2016, 38(6): 852 − 859
21. [21]
22. [22]
  Li S, Li Z, Zhang Y, Liu C, Yu G, Li B, Mu X, Peng H. ACS Sustain Chem Eng, 2017, 5(5): 4214 − 4222 doi: 10.1021/acssuschemeng.7b00194
23. [23]
24. [24]
  Yi H, Yang Y, Gu X, Huang J, Wang C. J Mater Chem A, 2015, 3(26): 13749 − 13757 doi: 10.1039/C5TA02288F
25. [25]
  Silmore K S, Gupta C, Washburn N R. J Colloid Interface Sci, 2016, 466: 91 − 100 doi: 10.1016/j.jcis.2015.11.042
26. [26]
  Wei Z, Yang Y, Yang R, Wang C. Green Chem, 2012, 14(11): 3230 − 3236 doi: 10.1039/c2gc36278c
27. [27]
  Qian Y, Zhang Q, Qiu X, Zhu S. Green Chem, 2014, 16(12): 4963 − 4968 doi: 10.1039/C4GC01242A
28. [28]
29. [29]
  Li Y, Qiu X, Qian Y, Xiong W, Yang D. Chem Eng J, 2017, 327: 1176 − 1183 doi: 10.1016/j.cej.2017.07.022
30. [30]
  Cai C, Zhan X, Zeng M, Lou H, Pang Y, Yang J, Yang D, Qiu X. Green Chem, 2017, 19(22): 5479 − 5487 doi: 10.1039/C7GC02571H
31. [31]
  Ye F, Miao M, Jiang B, Campanella O H, Jin Z, Zhang T. Food Chem, 2017, 229: 152 − 8 doi: 10.1016/j.foodchem.2017.02.062
32. [32]
  Lu J, Zhou W, Chen J, Jin Y, Walters K B, Ding S. RSC Adv, 2015, 5(13): 9416 − 9424 doi: 10.1039/C4RA14109A
33. [33]
  Yi C, Yang Y, Zhu Y, Liu N, Liu X, Luo J, Jiang M. Langmuir, 2012, 28(25): 9211 − 9222 doi: 10.1021/la301605a
34. [34]
  Low L E, Tey B T, Ong B H, Chan E S, Tang S Y. Carbohyd Polym, 2017, 155: 391 − 399 doi: 10.1016/j.carbpol.2016.08.091
35. [35]
  Zhao X, Yu G, Li J, Feng Y, Zhang L, Peng Y, Tang Y, Wang L. ACS Sustain Chem Eng, 2018, 6(3): 4105 − 4114 doi: 10.1021/acssuschemeng.7b04508
36. [36]
  Nowotny M K, Sheppard L R, Bak T, Nowotny J. J Phys Chem C, 2008, 112(14): 5275 − 5300 doi: 10.1021/jp077275m
37. [37]
  González E, Bonnefond A, Barrado M, Casado Barrasa A M, Asua J M, Leiza J R. Chem Eng J, 2015, 281: 209 − 217 doi: 10.1016/j.cej.2015.06.074
38. [38]
  Zhang S, Li L, Liu Y, Zhang Q. Chinese J Chem Eng, 2017, 25(2): 223 − 231 doi: 10.1016/j.cjche.2016.08.003
39. [39]
  Hao Y, Liu Y, Yang R, Zhang X, Liu J, Yang H. Chinese Chem Lett, 2018, 29(6): 778 − 782 doi: 10.1016/j.cclet.2018.01.010
40. [40]
  Chen Y, Li W, Zhang X. Colloid J, 2011, 73(2): 267 − 274 doi: 10.1134/S1061933X11020189
41. [41]
42. [42]
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沈阳化工大学材料科学与工程学院沈阳 110142