As a complex component of crude oil, asphaltenes determine the stability of emulsion . However, the mechanism of asphaltenes stabilize emulsion is still insufficient recognition due to the complexity of the molecular structure of asphaltenes. In this paper, the experiments and dissipative particle dynamics simulations were used to study the interfacial properties of asphaltenes. The adsorption of asphaltenes at the oil–water interface was studied by interfacial tension (IFT) experiments. A realistic molecular structure of asphaltene was constructed on the results of the characterization of the asphaltenes. The effects of asphaltenes concentration, temperature, and shear on the formation and stability of emulsion based on this molecular structure were investigated by simulations. The results show that the IFT decreases as asphaltenes concentration increases, while the droplet size of the emulsion decreases and becomes more uniformly distributed. Increasing the temperature enhances the interfacial activity of the asphaltenes, but also promotes its dissolution in the oil phase, which has a negative effect on reducing the IFT value and the stability of the emulsion. As the shear rate increases , the configuration of the emulsion changes from droplets to ellipsoids and rods, and the structure of the interfacial film is disrupted. This work provides useful insights into the mechanisms of asphaltenes concentration, temperature, and shear on the stability of the emulsion.
Xiao-Qian Wei,Wan-Ju Zhang,Lu Lai,Ping Mei,Li-Mei Wu,Yan-Qun Wang
The effects of cationic surfactants on the properties of Pickering emulsions stabilized by silica nanoparticles (nano-SiO 2 ) were investigated. The zeta potential , three-phase contact angle ( θ ), and dynamic interfacial tension (DIT) were measured to analyze the interaction between hydrophilic nano-SiO 2 and four different cationic surfactants (i.e., dodecyltrimethylammonium bromide [DTAB], bis-quaternary ammonium salts [BQAS-12], multiple quaternary ammonium salts [MQAS-12], and dimethyldioctadecylammonium bromide [DDAB-18]). All these surfactants can naturally improve the stability of Pickering emulsions induced by hydrophilic nano-SiO 2 . The nano-SiO 2 /MQAS-12 mixtures exhibited the best ability to stabilize the O/W emulsions, followed by nano-SiO 2 /BQAS-12 mixtures. The nano-SiO 2 /DDAB-18 mixtures can induce emulsion inversion from O/W to W/O. All emulsions exhibited excellent salt tolerance and acid-base resistance properties. Determining the zeta potential showed that nano-SiO 2 had the highest negative charge at the pH of 9.5. Thus, the surfactant molecules can be adsorbed remarkably on the nano-SiO 2 surface. Modification with different cationic surfactants can significantly increase the θ value of nano-SiO 2 , but the bilayers for DTAB-12, BQAS-12, and MQAS-12, except for DDAB-18, were adsorbed. DIT curves indicated that competitive adsorption of the surfactants occurred between the oil/water interface and nano-SiO 2 surface. The competitive adsorption of MQAS-12 was stronger than those of BQAS-12 and DTAB-12. The nano-SiO 2 /DDAB-18 mixture had an apparent induction region and required a considerable amount of time to reach equilibrium. The modified nano-SiO 2 was also not adsorbed in the oil/water interface spontaneously, which may be due to the large size of particles compared with small surfactant molecules.
The oil polarity was hypothesized to significantly influence the microscopic conformation of interfacial myofibrillar protein (MP) and thus the mesoscopic interfacial rheology of MP film , which ultimately tuned the macroscopic stability of MP-stabilized emulsions. In this research, the inner mechanism was revealed hierarchically based on emulsions multi-scale properties, by a combination of in vitro interfacial concentration measurement, dynamic interfacial tension measurement and interfacial dilatational rheology (highlighting Lissajous plots). Then, the above conclusion was verified through in silico molecular dynamic simulation. At macroscopic level, the light scattering results showed that emulsion prepared with higher polarity oil exhibited higher physical stability. This could be explained from the mesoscopic perspective that: (1) the adsorption dynamics of MP was faster (though lower diffusion rate, but higher penetration and rearrangement rate) on the higher polarity interface, which decreased interfacial tension more efficiently; (2) adsorption ratio, surface load and desorption ratio indicated that ‘multilayer interfacial film’ was formed by loosely-bound MP on the lower polarity interface, which decreased the effective interfacial coverage to impair emulsions stability; (3) Lissajous plots showed that interfacial structure with higher stability against large deformation was formed on the higher polarity oil interface. Finally, the microscopic molecular mechanism for explaining the above findings was revealed by in silico molecular dynamic simulation: though MP was less unfolded on the higher polarity interface leading to weaker intermolecular hydrophobic interactions, this compact molecular structure with stronger intramolecular rigidity predominantly contributed to steadier interfacial film structure. This multi-scale study provides a deep insight into the inner relationship between oil polarity and emulsions stability.
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