Dilational Rheology of Extended Surfactants at the Air/Water and Oil/Water Interfaces: Effect of Propylene Oxide Group Numbers.

In this paper, the interfacial properties of extended surfactants with different oxypropylene (PO) groups were comprehensively investigated by using interfacial dilational rheology. The differences in molecular orientation, spatial configuration, and relaxation process were compared at the gas-water interface and oil-water interface. The influences of the PO groups on the interface viscoelasticity were analyzed, providing important theoretical support for the wide application of extended surfactants. Experimental results show that the lower number of PO groups in extended surfactants does not cause differences in their presence states on the interface; however, once it increases, the longer PO segment will spiral up in the direction perpendicular to the interface, forming a spatial configuration like a thin cylinder. Compared with air, the PO group has better solubility in the oil phase. The chain segment can still maintain a helical extension from the beginning to the end as a result. However, the upper layer of the thin cylinder will collapse to a certain extent at the surface. Moreover, the orientation of the hydrophobic side has a dynamic process of "tilting to upright" with the increase of adsorption amount or in response to interfacial dilation and compression. The increase of PO number or the insertion of oil molecules has little effect on dilational modulus, and the interfacial film strength is generally relatively low. That is to say, the better emulsifying and solubilizing ability of PO-containing extended surfactants may be more attributed to the matching steric effect at interface or better packing action in bulk phase than to higher film strength.

The Interfacial Dilational Rheology Properties of Betaine Solutions: Effect of Anionic Surfactant and Polymer.

Interfacial dilational rheology is one of the important means to explore the interfacial properties of adsorption films. In this paper, the interfacial rheological properties of the mixed system of sulfobetaine ASB with a linear alkyl group and two anionic surfactants, petroleum sulfonate (PS) and alkyl polyoxyethylene carboxylate (AEC), were investigated by interfacial dilational rheology. The effect of the introduction of polymer hydrophobically modified polyacrylamide (HMPAM) on the interfacial properties of the mixed system was analyzed. In this experiment, the surfactant solution was used as the external phase and n-decane was used as the internal phase. A periodic sinusoidal disturbance of 0.1 Hz was applied to the n-decane droplets, and the changes of parameters such as droplet interfacial tension and interfacial area were monitored in real time with the help of a computer. The results show that the betaine ASB molecule responds to the dilation and compression of the interface through the change of ion head orientation, while the feedback behavior of petroleum sulfonate PS and AEC molecules embedded with oxygen vinyl groups in the molecule is diffusion and exchange between the interface and the bulk phase. Therefore, the interface film formed by ASB alone is higher, and the film formed by PS and AEC molecules alone is relatively lower. After adding two kinds of anionic surfactants to the betaine system, the ionic head of PS or AEC molecules will be attached to the positive center of the hydrophilic group of ASB molecules by electrostatic attraction and no longer adsorb and desorb with the interface deformation. The interfacial rheological properties of the compound system are still dominated by betaine, with higher dilational modulus and lower phase angle. When a small amount of HMPAM is added, or the content of hydrophobic monomer AMPS in the bulk phase is low, the intermolecular interaction at the interface is enhanced, the slow relaxation process is intensified, and the interfacial film strength is increased. As the content of AMPS further increases, hydrophobic blocks and surfactant molecules will form interfacial aggregates similar to mixed micelles at the oil-water interface, which will regulate the properties of the film by affecting the adsorption of surfactants at the interface. As long as the interfacial tension is the same, the properties of the interfacial film are the same. Based on the colloid interface science and the background of enhanced oil recovery, this study provides a reference for the field application of chemical flooding formulations.

Confined Structures and Selective Mass Transport of Organic Liquids in Graphene Nanochannels.

Selective transport of liquids is an important process in the energy and environment industry. The increased energy consumption and the demands of clean water and fossil fuels have urged the development of high-performance membrane technologies. Nanoscale channels with the critical size for molecular sieving and atomistically smooth walls for significant boundary slippage are highly promising to balance the tradeoff between permeability and selectivity. In this work, we explore the molecular structures and dynamics of organic solvents and water, which are confined within nanoscale two-dimensional galleries between graphene or graphene oxide sheets. Molecular dynamics simulation results show that the layered order and significant interfacial slippage are universal for all molecular liquids, leading to notable flow enhancement for channels with a width of few nanometers, in the order of ethylene glycol > butanol > ethanol > hexane > toluene > water > acetone. The extracted dependence of permeability, selectivity on the channel width, and properties of molecular liquids clarify the underlying mechanisms of selective mass transport in nanofluidics, which help to understand and control the filtration and separation processes of molecular liquids. The performance of graphene oxide membranes for permeation and filtration is finally discussed based on the calculated flow resistance for pressure-driven flow or molecular diffusivity for diffusive flow, as well as the solubility and wettability of membranes.

Interfacial rheological behaviors of inclusion complexes of cyclodextrin and alkanes.

The transformation of cyclodextrins (CDs) and alkanes from separated monomers to inclusion complexes at the interface is illustrated by analyzing the evolution of interfacial tension along with the variation of interfacial area for an oscillating drop. Amphiphilic intermediates are formed by threading one CD molecule on one alkane molecule at the oil/aqueous interface. After that, the amphiphilic intermediates transform into non-amphiphilic supramolecules which further assemble through hydrogen bonding at the oil/aqueous interface to generate a rigid network. With the accumulation of supramolecules at the interface, microcrystals are formed at the interface. The supramolecules of dodecane@2α-CD grow into microrods which form an unconsolidated shell and gradually cover the drop. However, the microcrystals of dodecane@2ß-CD are significantly smaller which fabricate into skin-like films at the interface. The amphiphilic intermediates during the transformation increase the feasibility of self-emulsification and the skin-like films enhance the stability of the emulsion. With these unique properties, CDs can be promising for application in hydrophobic drug delivery, food industry and enhanced oil recovery.

Structure-behavior-property relationship study of surfactants as foam stabilizers explored by experimental and molecular simulation approaches.

A multiscale stability study of foams stabilized by sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), and sodium polyoxyethylene alkylether sulfate (AES) was conducted, to investigate the relationship of surfactant molecular behavior and interfacial monolayer configuration of foam film to the foam film properties. Molecular dynamic (MD) simulations using a full-atom model was utilized to explore the microscopic features of the air/liquid interface layer. Several parameters such as the distribution of surfactant head groups and the order degree of surfactant hydrophobic tails were used to describe the molecular adsorption behavior. The effect of molecular structure on the nature of the foam film and the impact on the dynamic stability of wet foam is discussed. In the experimental evaluation, the SDBS foam films manifest strong stiffness and low viscoelasticity as shown by the interfacial shear rheology determination as well as texture analyzer (TA) measurement results, which agree very well with the array behavior of SDBS molecules at the air/water interface as described by the simulation results and is identified to be the reason for the poor dynamic stability. Comparing the molecular structure of SDS, SDBS, and AES, the special contributions of the linking groups such as the O atom, the phenyl group, and the EO (oxyethyl) chain to the interfacial array behavior of surfactants were characterized. It is concluded that microhardness of the foam film enhanced by rigid linking groups favors static foam stability but decreases the dynamic foam stability, while viscoelasticity of the foam film enhanced by soft linking groups increases the dynamic foam stability.

Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids.

A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates.

Effect of divalent cationic ions on the adsorption behavior of zwitterionic surfactant at silica/solution interface.

The adsorption behavior of zwitterionic surfactant dodecyl sulfobetaine (DBS) on a silica/solution interface with Ca(2+), Mg(2+) existing in aqueous solution is explored by atomistic molecular simulations. The interaction energy contribution of van der Waals and electrostatic potentials in the surfactants/water/silica system are respectively calculated, from which the electrical interaction can be found to play a decisive role in the adsorption tendency of DBS on the silica surface with or without inorganic ions, despite different mechanisms. The distinct decrease of energy has been found to be derived from electrical interaction when DBS adsorb on the silica surface covered by Ca(2+) or Mg(2+). Therefore, it can be predicted that the cationic ions combined on the negatively charged silica surface in a mineral water medium might decrease the adsorption trend of DBS on the silica surface, which has been experimentally proven by TOC measurement. Structural information of the close interface layer and the distribution of water molecules are analyzed after the complete molecular dynamics simulation using a ternary model. Ca(2+) and Mg(2+) combined on the silica surface can reduce the adsorption amount of DBS by preventing the direct interaction between DBS and surface, and bringing about the orientation reversal of DBS molecules to break the order of adsorption interface layer. Furthermore, changes in the status of the water spreading on the silica surface caused by the complexation of cations are also an important reason in the adsorption reduction.

Molecular behavior and synergistic effects between sodium dodecylbenzene sulfonate and Triton X-100 at oil/water interface.

Significant synergistic effects between sodium dodecylbenzene sulfonate (SDBS) and nonionic nonylphenol polyethylene oxyether, Triton X-100 (TX-100), at the oil/water interface have been investigated by experimental methods and computer simulation. The influences of surfactant concentration, salinity, and the ratio of the two surfactants on the interfacial tension were investigated by conventional interfacial tension methods. A dissipative particle dynamics (DPD) method was used to simulate the adsorption properties of SDBS and TX-100 at the oil/water interface. The experiment and simulation results indicate that ultralow (lower than 10(-3) mN m(-1)) interfacial tension can be obtained at high salinity and very low surfactant concentration. Different distributions of surfactants in the interface and the bulk solution corresponding to the change of salinity have been demonstrated by simulation. Also by computer simulation, we have observed that either SDBS or TX-100 is not distributed uniformly over the interface. Rather, the interfacial layer contains large cavities between SDBS clusters filled with TX-100 clusters. This inhomogeneous distribution helps to enhancing our understanding of the synergistic interaction of the different surfactants. The simulation conclusions are consistent with the experimental results.

The array and interfacial activity of sodium dodecyl benzene sulfonate and sodium oleate at the oil/water interface.

There is a close correlation between the interfacial activity and the adsorption of the surfactant at the interface, but the detailed molecular standard information was scarce. The interfacial activity of two traditional anionic surfactants sodium dodecyl benzene sulfonate (SDBS) and sodium oleate (OAS) were studied by experimental and computer simulation methods. With the spinning drop method and the suspension drop method, the interfacial tension of oil/aqueous surfactant systems was measured, and the influence of surfactant concentration and salinity on the interfacial tension was investigated. The dissipative particle dynamics (DPD) method was used to simulate the adsorption of SDBS and OAS at the oil/water interface. It was shown that it is beneficial to decrease interfacial tension if the hydrophobic chains of the surfactant and the oil have similar structure. The accession of inorganic salts causes surfactant molecules to form more compact and ordered arrangements and helps to decrease the interfacial tension. There is an osculation relation between interfacial density and interfacial activity. The interfacial density calculated by molecular simulation is an effective parameter to exhibit the interfacial activity.

A study of dilational rheological properties of polymers at interfaces.

Viscoelastic properties of two polymers, partially hydrolyzed polyacrylamide and partially hydrolyzed modified polyacrylamide, widely used in chemical flooding in the petroleum industry, were investigated at three interfaces, water-air, water-dodecane, and water-crude oil, by means of a dilational method provided by I.T. Concept, France, at 85 degrees C. Polymer solutions were prepared in brine with 10,000 mg/l sodium chloride and 2000 mg/l calcium chloride. It has been shown that the viscoelastic modulus increases with the increment of polymer concentration in the range of 0-1500 mg/l at the water-air interface. Each polymer shows different viscoelatic behavior at different interfaces. Generally speaking, values of the viscoelastic modulus (E), the real part (E'), and the imaginary part (E") at the crude oil-water interface for each polymer are lower than at the air-water or water-dodecane interface. The two polymers display different interfacial properties at the same interface. Polymer No. 2 gives more viscous interfaces than polymer No. 1. All the information obtained from this paper will be helpful in understanding the interfacial rheology of ultra-high-molecular-weight polymer solutions.