Tunable Viscoelastic Properties of Sodium Polyacrylate Solution via CO2-Responsive Switchable Water.

Upon stimulus by CO2, CO2-switchable viscoelastic fluids experience a deliberate transition between non-viscous and highly viscous solution states. Despite attracting considerable recent attention, most such fluids have not been applied at a large- scale due to their high costs and/or complex synthesis processes. Here, we report the development of CO2-switchable viscoelastic fluids using commercially available sodium polyacrylate (NaPAA) and N,N-dimethyl ethanol amine (DMEA)-based switchable water. Upon bubbling CO2, into the solutions under study, DMEA molecules are protonated to generate quaternary ammonium salts, resulting in pronounced decreases in solutions viscosity and elasticity due to the influence of increased ionic strength on NaPAA molecular conformations. Upon removal of CO2 via introduction of N2, quaternary salts are deprotonated to tertiary amines, allowing recovery of fluid viscosity and elasticity to near the initial state. This work provides a simple approach to fabricating CO2-switchable viscoelastic fluids, widening the potential use of CO2 in stimuli-responsive applications.

Double Z-scheme system of silver bromide@bismuth tungstate/tungsten trioxide ternary heterojunction with enhanced visible-light photocatalytic activity.

The ternary heterojunction of silver bromide@bismuth tungstate/tungsten trioxide (AgBr@Bi2WO6/WO3) was designed and synthesised by hydrothermal and deposition-precipitation approaches. The composites were characterised by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS). The photoabsorption range and bandgaps of the photocatalysts were analysed by ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS). Compared with Bi2WO6/WO3 or AgBr alone, the AgBr@Bi2WO6/WO3 composites displayed higher visible-light photocatalytic performance for degrading rhodamine B (RhB). AgBr@Bi2WO6/WO3 with 40% AgBr concentration was optimum for photocatalytic activity. Radical-trapping experiments revealed that superoxide anion radicals (O2-) and holes (h+) were the active species during photocatalytic degradation and that O2- was the dominant active species. Therefore, the increased photocatalytic activity of AgBr@Bi2WO6/WO3 was attributed to the atypical double Z-scheme system, which effectively improved the transfer and separation of electron-hole pairs in ternary heterojunction structures.

Effects of Calcium Ions on the Solubility and Rheological Behavior of a C22-Tailed Hydroxyl Sulfobetaine Surfactant in Aqueous Solution.

Effects of calcium ions (Ca2+) on the solubility, aggregate structure, and rheological behavior of a C22-tailed zwitterionic surfactant, erucyl dimethyl amidopropyl hydroxyl sulfobetaine (EHSB), have been investigated in aqueous solution. In comparison with sodium ions (Na+), Ca2+ ions exhibit a much higher efficiency in decreasing the Krafft temperature (TK) of EHSB. Specifically, contrary to Na+ ions which have no obvious effect on the rheological properties of the EHSB solution, Ca2+ ions increase the viscosity of the EHSB solution at lower EHSB concentration, and enhance its elasticity at higher EHSB concentration. Moreover, Ca2+ ions raise the temperature needed for the elastic-to-viscous transition of the EHSB solution at higher concentration. At lower EHSB concentration, the hydrophobic interaction between the ultralong hydrocarbon chains induces a tighter packing of the hydrophobic chains by forming a more stretched configuration, while at higher EHSB concentration, the electrostatic attraction between Ca2+ ions and the sulfonate groups of EHSB induces a tighter packing of the headgroups by forming Ca2+-mediated bridges among the EHSB headgroups. Besides, the above interactions may strengthen the hydrogen bonding of OH groups and/or of C═O amide groups, which in turn facilitates the compact packing of the surfactant molecules in aggregates and promotes the growth and entanglement of wormlike micelles. Thus, the EHSB solution shows Ca2+-dependent rheological behaviors. The solubility and rheological properties of the ultralong chain surfactant solution can be simultaneously improved with the addition of divalent Ca2+ ions.

Systematic evaluation of petroleum sulfonate: polarity separation and the relationship between its structure and oil recovery properties.

Petroleum sulfonate is one of the most important surfactants in the tertiary oil recovery process. However, its complex composition significantly impedes its evaluation, and the relationship between its structure and oil recovery properties is still unclear. In this study, the actives of petroleum sulfonate are subdivided into seven components, a-g, with different polarities via column chromatography. The structural information of each component is fully characterized. Moreover, the relationship between the oil recovery properties and the structure of the separated components is systematically studied. The results reveal the average relative molecular mass in the range of 560-626, average alkyl side chain containing 36-40 carbon atoms and alkyl chain containing an average of 6 branched chains is the ideal structure for enhancing oil recovery properties. Furthermore, this study provides a reliable evaluation method and reveals the relationship between the structure and oil recovery properties of petroleum sulfonate.

A systematic approach to measure the contents of mono- and di-sulfonates in petroleum sulfonates by the novel method of acid-base titration coupled with traditional two-phase titration.

Petroleum sulfonates are broadly employed to increase the oil recovery efficiency in tertiary recovery, while the content of di-sulfonates in petroleum sulfonates is a critical factor in the flushing efficiency, because it adversely impacts the decrease of oil-water interfacial tension. Thus far, no methods have been considered convenient and reliable to determine the contents of mono- and di-sulfonates besides the traditional extraction method. This study established a simple and practical approach of acid-base titration coupled with traditional two-phase titration to measure the contents of mono- and di-sulfonates in petroleum sulfonates. To judge the reliability of the approach, the actives of petroleum sulfonates were separated into mono- and di-sulfonates using the traditional extraction method, the separation effect of which was confirmed using infrared spectroscopy and main elemental analysis. As the results demonstrated, all the contents of di-sulfonates in four petroleum sulfonates measured by the acid-base titration method are similar to those found by the extraction method. The contents of di-sulfonates (%) in four petroleum sulfonate samples were measured by comparing acid-base titration with the extraction method; respectively they were 8.57/8.19, 5.67/5.98, 5.61/5.35 and 2.37/2.15; the relative error of the measured di-sulfonates is about 6%, which satisfies the titration accuracy of petroleum sulfonates. In parallel experiments, the results of five acid-base titrations are very close, and the precision of the acid-base titration method was about 3%. Accordingly, this systematic approach by combining the new acid-base titration and traditional two-phase titration is of great significance to develop the evaluation system of petroleum sulfonates.

Slow dynamics of water confined in Newton black films.

Slowdown of translational and reorientational dynamics of water confined in Newton black films (NBFs) is revealed by molecular dynamics simulations. As a film becomes thinner, both translational and reorientational dynamics become slower. The polarization of water molecules in the macroscopic electrostatic field across the NBF and the coordination of Na(+) ions and surfactant anionic groups around water molecules concertedly lead to slowdown of water dynamics. The polarization effect is obvious for water not coordinated by Na(+) ions, which exhibits reorientational dynamics depending on initial dipole orientations. Na(+) ions and surfactant anionic groups retard dynamics of surrounding water by decreasing the hydrogen bond exchange probability and increasing the viscosity of water. The dependences of translational and reorientational dynamics on coordination environments of water are similar. Dynamics of water in positions close to the interfaces of NBFs are mainly retarded by Na(+) ions and surfactant anionic groups, while the macroscopic polarization effect plays the main role in influencing water dynamics in positions far from the interfaces. This study sheds light on the improvement of knowledge about the water dynamics slowdown mechanism in similar environments like reverse micelles and lamellar structures.

Temperature-dependent phase transition and desorption free energy of sodium dodecyl sulfate at the water/vapor interface: approaches from molecular dynamics simulations.

Adsorption of surfactants at the water/vapor interface depends upon their chemical potential at the interface, which is generally temperature-dependent. Molecular dynamics simulations have been performed to reveal temperature influences on the microstructure of sodium dodecyl sulfate (SDS) molecule adsorption layer. At room temperature, SDS molecules aggregate at the interface, being in a liquid-expanded phase, whereas they tend to spread out and probably transit to a gaseous phase as the temperature increases to above 318 K. This phase transition has been confirmed by the temperature-dependent changes in two-dimensional array, tilt angles, and immersion depths to the aqueous phase of SDS molecules. The aggregation of SDS molecules accompanies with larger immersion depths, more coordination of Na(+) ions, and less coordination of water. Desorption free energy profiles show that higher desorption free energy appears for SDS molecules at the aggregate state at low temperatures, but no energy barrier is observed. The shapes of desorption free energy profiles depend upon the distribution of SDS at the interface, which, in turn, is related to the phase state of SDS. Our study sheds light on the development of adsorption thermodynamics and kinetics theories.

Ultralow interfacial tension for enhanced oil recovery at very low surfactant concentrations.

The interfacial tension (IFT) between alkanes and several individual surfactants and their mixtures has been investigated, using three kinds of alkyl hydrocarbons: decane, dodecane, and tetradecane. For individual and mixed surfactant systems, critical micelle concentrations and areas per molecule at the hydrocarbon-aqueous solution interface were calculated; for the mixed surfactant systems, betasigma(LL), the molecular interaction parameter at the hydrocarbon-aqueous solution interface, and beta(M), the molecular interaction parameter in mixed micelle formation, were calculated. It was found that IFT in the 10(-3) mN/m (ultralow) range can be obtained at surfactant concentrations below 0.05 wt % and even at concentrations below 0.01 wt %, when mixtures of certain surfactants are used at the proper ratio. Surfactants with branched-chain alkyl groups show a much better IFT reduction effectiveness than those with straight-chain alkyl groups. Contrary to what has been observed at the air-aqueous solution surface, mixtures of two homologues with two hydrophobic groups show significant molecular interactions, with both betasigma(LL) and beta(M) having negative values in the 4-5 range in some cases, with the betasigma(LL) value more negative than beta(M). The relationship between micellar shape and ultralow IFT was investigated by calculating the critical packing parameter of the surfactants. It was found that ultralow IFT between the surfactant mixtures and the three hydrocarbons investigated could reach ultralow (<10(-2) mN/m) values when the critical packing parameter is very close to 1.