Cunchuan Zheng

CO2/N2-switchable viscoelastic fluids based on a pseudogemini surfactant system

ABSTRACT We prepared a CO2/N2-switchable pseudogemini surfactant system composed of sodium oleate (NaOA) and N, N, N’, N’-tetramethyl-1, 6-hexanediamine (TMHDA) at a mole ratio of 2:1. The two tertiary amine groups of the TMHDA can be protonated into quaternary ammonium salt when the system was bubbled with CO2, which can ‘‘bridge’’ two NaOA molecules via electrostatic attraction to form a pseudogemini surfactant. The formed pseudogemini surfactant can further self-assemble to wormlike micelles, causing a sharp increase in viscosity. The viscoelastic property and structure transitions of the pseudogemini surfactant system were investigated before and after bubbling of CO2. The pseudogemini surfactant system transformed from water-like to gel-like fluid with the bubbling of CO2, followed by white precipitate. The cryo-transmission electron microscope (cryo-TEM) characterization and rheological measurements exhibited that the sol–gel transition was attributed to a spherical-wormlike micelle transition. Moreover, this transition was switchable at least in three cycles. Finally, a reasonable mechanism of aggregate behavior transition was proposed from the viewpoint of the molecular states, micelle structures, and intermolecular interactions. GRAPHICAL ABSTRACT

pH and temperature-responsive wormlike micelles formed by single amine oxide surfactant

ABSTRACT In this paper, a novel type of pH- and temperature-responsive smart wormlike micelles based on (Z)-N,N-dimethyl-3-(octadec-9-enamido) propan-1-amine oxide (OAPAO) synthesized was studied. The structure of OAPAO was characterized by 1H NMR and FTIR. The micellization and aggregation properties of the OAPAO surfactant in aqueous solution at different pH values were studied using equilibrium surface tension. The OAPAO solution exhibited pH-regulated surface activity at the air–water interface by assessing relevant parameters such as cmc, γcmc, Гmax, and Amin at pH = 2.10, 6.80, and 11.90. The viscosity and rheological measurements demonstrated the pH-sensitive flowing behavior and property, which was attributed to the interactions transition between the OAPAO head groups. Moreover, the system could be promptly switched between low viscous fluid and highly viscoelastic fluid by alternatively adjusting the pH between 2.05 and 6.82. Combining the distribution state of OAPAO, a mechanism for the different intermolecular forces at different pH regions was proposed. Furthermore, the OAPAO solution exhibited an evident temperature-responsiveness at pH = 6.82 and 11.88 in a certain temperature range (25–65°C) resulting from the effect of temperature on the hydrophobic effect and the intermicellar branching junctions. GRAPHICAL ABSTRACT

CO2-Responsive wormlike micelles based on sodium oleate and hydrophobic tertiary amines

ABSTRACT We reported two simple and novel CO2-responsive surfactant wormlike micellar systems consisting of commercial anionic surfactant sodium oleate (NaOA) and common hydrophobic tertiary amine N,N-dimethylcyclohexylamine (DMCHA), N,N-dimethylbenzylamine (DMBA). The conductivity, pH, and rheological measurements demonstrated the CO2-sensitive flowing behavior and property, which were attributed to the spherical-wormlike micelles transition, verified by cryogenic transmission electron microscopy (Cryo-TEM) and dynamic laser light scattering (DLS) measurements. Moreover, the transition can be easily cycled more than three times without deterioration of viscosity. Combined with the species distribution curve and 1H NMR spectra, a mechanism of the intermolecular electrostatic interaction and hydrophobic effects was proposed. GRAPHICAL ABSTRACT

The pH and temperature dual-responsive micelle transition in the mixture of hydrotrope potassium phthalic acid and quaternary ammonium surfactants cetyltrimethylammonium bromide

ABSTRACT A facile and effective route to prepare a pH and temperature dual-responsive surfactant micelle has been introduced based on hydrotrope potassium phthalic acid (PPA) and quaternary ammonium surfactants cetyltrimethylammonium bromide (CTAB). The system can be switched between viscoelastic solution and water-like fluid by adjusting pH values. In this paper, different binding abilities between the hydrotrope and surfactants have been demonstrated during the process of adjusting pH because the hydrotrope has different ionization degrees with the pH variation. And with the aid of rheological measurements and cryo-TEM observation, we discussed the different effects of the hydrotrope on surfactants at various pH values in detail and analyzed the possible aggregate transition mechanism of CTAB–PPA system induced by pH. Besides, this CTAB–PPA system has temperature-responsive property when pH < 2.50. The temperature sensitivity and reversible control of rheological properties may greatly facilitate practical applications of such responsive viscoelastic solution. GRAPHICAL ABSTRACT

Preparation of CO2 responsive wormlike micelles and the effect of hydrogen bond on the strength of the network

ABSTRACT We first prepared two types of CO2-responsive wormlike micelles based on N-butyldiethanolamine–sodium oleate (BDEA–NaOA) and N,N-diethyl butylamine–sodium oleate (DEBA–NaOA), respectively. And then, we compared the two different systems to investigate the effect of hydrogen bond on the properties of wormlike systems. The results of the pH and conductivity variation show that tertiary amine groups on BDEA and DEBA were ionized to quaternary ammonium salts after bubbling of CO2 into the systems, which work with OA− to form wormlike micelles based on electrostatic interaction. The results of rheological measurements exhibit that the viscosity and viscoelastic of the BDEA–NaOA were obviously superior to DEBA–NaOA. The dramatically difference of the two kind of wormlike micelles was due to the strong intermolecular hydrogen bond between the BDEA and NaOA. This indicates that the hydrogen bond could show great effect on the properties of the wormlike micelles. Finally, a reasonable mechanism was proposed based on the molecular structure, micelles assembly, and the intermolecular interactions. GRAPHICAL ABSTRACT

CO2 responsive wormlike micelles based on sodium oleate, potassium chloride and N,N-dimethylethanolamine

ABSTRACT The anionic surfactant sodium oleate (NaOA) can self-assemble in aqueous solution in the presence of counter-ion inorganic salts to form wormlike micelles (WLMs), which exhibited viscoelastic behavior. In this paper, KCl was used to induce the formation of wormlike micelles with sodium oleate. In this process, we found that the addition of N, N-dimethylethanolamine (DMEA) can destroy the structure of WLMs leading significant decrease of viscosity. However, after introducing CO2 into the ternary solution (KCl-NaOA-DMEA), the WLMs can be regenerated due to the electrostatic interaction between the protonated DMEA and the anionic surfactants. The addition of sodium hydroxide (NaOH) causes the electrostatic interaction between OA- and DMEAH+ be destroyed, which results in the wormlike micelles becoming spherical micelles of lower viscosity. The transition of WLMs with high viscosity and low viscosity spherical micelles can be repeated several times by using CO2 and NaOH. GRAPHICAL ABSTRACT