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China Surfactant Detergent & Cosmetics ›› 2024, Vol. 54 ›› Issue (1): 1-15.doi: 10.3969/j.issn.2097-2806.2024.01.001
• Basic research • Next Articles
Pei Liu1,2,Ting Pan1,Xiaomei Pei1,*(
),Binglei Song1,Jianzhong Jiang1,Zhenggang Cui1,*(),Bernard P. Binks3,*()
Received:2023-08-25
Revised:2023-12-02
Online:2024-01-22
Published:2024-01-26
Contact:
*Tel.: +86-13382888025, E-mail: pxmxiaomei@163.com（Xiaomei Pei）; cuizhenggang@hotmail.com（Zhenggang Cui）; b.p.binks@hull.ac.uk（Bernard P. Binks）.
CLC Number:
Pei Liu, Ting Pan, Xiaomei Pei, Binglei Song, Jianzhong Jiang, Zhenggang Cui, Bernard P. Binks. Dual-responsive oil-in-water emulsions co-stabilized by a nonionic-anionic Bola surfactant and silica nanoparticles[J].China Surfactant Detergent & Cosmetics, 2024, 54(1): 1-15.
Scheme 1
Synthetic route of CH3O（EO） 5-R11-COOH"
Fig. 1
ESI-MS spectrum of the synthesized surfactant CH3O（EO） 5-R11-COOH"
Fig. 2
1H-NMR spectrum of the synthesized surfactant CH3O（EO） 5-R11-COOH"
Fig. 3
13C-NMR spectrum of the synthesized surfactant CH3O（EO） 5-R11-COOH"
Fig. 4
FT-IR spectrum of the synthesized surfactant CH3O（EO） 5-R11-COOH"
Tab. 1
Surface activity parameters of CH3O（EO）5-R11-COOH at different pH and comparison with that of C12EO5 at 25 ℃"
| Surfactant | cmc/（mmol/L） | γcmc/（mN/m） | Γmax/（10-10 mol/cm2） | Amin/（nm2/molec） |
|---|---|---|---|---|
| CH3O（EO） 5-R11-COOH （pH=3.0） | 0.032 | 41.4 | 2.65 | 0.63 |
| CH3O（EO） 5-R11-COONa （pH=7.3） | 0.075 | 42.0 | 2.25 | 0.74 |
| CH3O（EO） 5-R11-COONa （pH=12.0） | 0.350 | 41.5 | 1.70 | 1.01 |
| C12EO5[ | 0.060 | 30.4 | 3.42 | 0.49 |
Fig. 5
Plots of surface tension as a function of concentration for CH3O（EO） 5-R11-COOH at different pH and comparison with that of C12EO5 at 25 ℃"
Fig. 6
（A） Photos of conventional emulsions of n-decane-in-water stabilized by 0.1 mmol/L CH3O（EO） 5-R11-COOH alone at different pH taken 24 h after preparation at 25 ℃. （B and C） Photos and optical micrographs of conventional emulsions of n-decane-in-water （7 mL/7 mL） stabilized solely by CH3O（EO） 5-R11-COONa at pH of 10.9 at different concentrations （given in mmol/L） taken one month after preparation at 25 ℃"
Fig. 7
pH-Responsiveness of conventional emulsions of n-decane-in-water stabilized by （A） 1 mmol/L CH3O（EO） 5-R11-COOH alone and （B） 3 mmol/L R11-COONa alone after addition of 0.2 mol/L HCl （“Off （1）”） or 0.2 mol/L NaOH （“On （1）”） at 25 ℃. After demulsification the separated oil was removed and fresh oil was added before re-homogenization （H）"
Fig. 8
（A） Photos and （B） optical micrographs of n-decane-in-water （7 mL/7 mL） emulsions co-stabilized by 0.1 mmol/L CH3O（EO）5-R11-COOH and 0.1 wt.% silica nanoparticles at different pH taken 24 h after preparation at 25 ℃. The first six are Pickering emulsions, and the last three are oil-in-dispersion emulsions"
Fig. 9
SEM images of n-decane-in-water （7 mL/7 mL） emulsions co-stabilized by 0.1 mmol/L CH3O（EO） 5-R11-COOH and 0.1 wt.% silica nanoparticles at two pH values taken 24 h after preparation at 25 ℃. （A） Pickering emulsion at pH of 4.6; （B） oil-in-dispersion emulsion at pH of 9.4"
Fig. 10
（A, B） Digital photos and （C） micrographs of n-decane-in-water （7 mL/7 mL） Pickering emulsions co-stabilized by 0.1 wt.% silica nanoparticles and CH3O（EO）5-R11-COOH of different concentration （shown in mmol/L） at pH of 3, taken （A） 24 h and （B, C） 7 days after preparation at 25 ℃"
Fig. 11
（A, B） Digital photos and （C） micrographs of n-decane-in-water （7 mL/7 mL） oil-in-dispersion emulsions co-stabilized by CH3O（EO） 5-R11-COONa of different concentration （shown in mmol/L） and 0.1 wt.% silica nanoparticles at pH of 9.0, taken （A） 24 h and （B, C） 7 days after preparation at 25 ℃"
Fig. 12
（A） Photos and （B） optical micrographs of n-decane-in-water （7 mL/7 mL） Pickering emulsions co-stabilized by 0.1 wt.% silica nanoparticles and 0.1 mmol/L CH3（EO） 5-R11-COOH at pH of 3 undergoing switching off/on cycles induced by heating and cooling, taken 12 h after operation"
Fig. 13
（A） Photos and （B） optical micrographs of n-decane-in-water （7 mL/7 mL） Pickering emulsions co-stabilized by 0.1 wt.% silica nanoparticles and 0.1 mmol/L CH3（EO） 5-R11-COOH at pH of 3 undergoing switching off/on cycles induced by heating and cooling, taken 12 h after operation. After each demulsification the separated oil was removed and fresh oil was added for the next re-homogenization"
Fig. 14
Plot of the time required for demulsification vs heating temperature for Pickering emulsions co-stabilized by 0.1 wt.% silica nanoparticles and 0.1 mmol/L CH3O（EO） 5-R11-COOH at pH of 3"
Fig. 15
Appearance and micrograph of an oil-in-dispersion emulsion co-stabilized by 0.1 mmol/L CH3O（EO） 5-R11-COOH and 0.1 wt.% silica nanoparticles at pH of 9.1, which remains stable to heating"
Fig. 16
Photos and micrographs of emulsions （O/W Pickering at pH of 3.0; oil-in-dispersion at pH of 9.5） co-stabilized by 0.1 mmol/L CH3O（EO） 5-R11-COOH and 0.1 wt.% silica nanoparticles following alternation of pH at 25 ℃"
Fig. 17
Digital photos of n-decane-in-water （7 mL/7 mL） emulsions co-stabilized by 0.1 wt.% silica nanoparticles and 0.1 mmol/L R11-COONa, 0.1 mmol/L C12EO4 or 0.1 mmol/L C12EO5 at different pH, taken 24 h after preparation at 25 ℃"
Fig. 18
Schematic illustration of the interactions between CH3O（EO） 5-R11-COOH and silica nanoparticles and the transition of the microstructure of emulsions they co-stabilize triggered by pH and temperature"
Fig. 19
Dynamic interfacial tension between n-decane and water measured by the drop shape method at 25 ℃. The equilibrium interfacial tension between fresh oil and pure water is 50.1 mN/m, but that between pure water and the oil separated from the equivolumetric mixture of oil and an aqueous solution of 1 mmol/L CH3O（EO） 5-R11-COONa at pH of 10.9 is much lower, suggesting the transfer of surfactant to the oil phase"
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