Adsorption kinetics in micellar solutions of nonionic surfactants

Standard models of the adsorption kinetics of surfactants at the air-water surface assume that micelles break down into monomers in the bulk solution and that only monomers adsorb. We show here that micelles of the nonionic surfactant C14E8 adsorb to the surface of a liquid jet at a diffusion-controlled rate. Micellar adsorption can be switched off by incorporation of a small amount of ionic surfactant into the micelle and switched on again by addition of salt. More sophisticated models of adsorption processes in micellar solutions are required that permit a kinetic flux of micelles to the air-water interface.     

表面活性剂对气-液界面纳米颗粒吸附规律的影响

通过测定及分析纳米颗粒和表面活性剂-纳米颗粒复配体系在自由吸附过程与动态收缩过程中表面张力的变化,总结了纳米颗粒在气-液界面的吸附排布规律以及表面活性剂对其吸附规律的影响.实验结果表明,自由吸附过程中,随矿化度增加、阳离子活性剂浓度增加,平衡表面张力降低,这与颗粒吸附密度增加及颗粒润湿性改变有关.浓度低于临界胶束浓度(CMC)时,阳离子活性剂体系与混合体系的表面张力差异证明了阳离子活性剂可以通过静电作用吸附于纳米颗粒表面,进而部分溶解于水相;而阴离子活性剂与纳米颗粒相互作用力较弱,对表面张力影响较小.纳米颗粒体系在液滴收缩过程中,表面张力从自由吸附平衡态进一步降低大约9 m N/m,说明自由吸附过程中纳米颗粒不能达到紧密排布;同时表面张力呈现为缓慢降低、快速降低和达到平衡三部分,表面压缩模量可达70 m N/m,满足了液膜Gibbs稳定准则,这将有助于提高泡沫或者乳液稳定性.纳米颗粒-表面活性剂体系在液滴收缩过程中表面张力降低值随活性剂浓度增加而减小;表面压缩模量由高到低依次为:纳米颗粒>阳离子活性剂-纳米颗粒>阴离子-纳米颗粒>表面活性剂.     

Surface tension of an electrolyte-air interface: a Monte Carlo study

We present a new method for calculating the surface tension of an electrolyte-air interface using Monte Carlo (MC) simulations with an implicit solvent in a spherical drop geometry. The boundary conditions for the electric field at the interface are accounted for using image and counter-image charges. The density profiles obtained from the simulations are used to calculate the excess surface tension of the electrolyte-air interface using the Gibbs adsorption isotherm equation. The results are found to be in good agreement with experiments and the earlier theoretical calculations.     

季铵盐型双子表面活性剂在空气-水界面的单分子膜

利用Langmuir膜天平测定不对称双子表面活性剂12-2-16和对称双子表面活性剂12-2-12在空气-水界面上形成单分子膜的表面压,通过单分子膜的π-A等温线、微分等温线和静态弹性,分析其相转变和成膜特性.结果表明,与传统阳离子表面活性剂DTAB比较,12-2-16、12-2-12比DTAB单分子膜的分子极限面积大,崩溃压高,并有较高的静态弹性,因而具有较高的凝聚性和稳定性,其中12-2-16单分子膜的凝聚性和稳定性最高.     

Phase-field modeling droplet dynamics with soluble surfactants

Using lattice Boltzmann approach, a phase-field model is proposed for simulating droplet motion with soluble surfactants. The model can recover the Langmuir and Frumkin adsorption isotherms in equilibrium. From the equilibrium equation of state, we can determine the interfacial tension lowering scale according to the interface surfactant concentration. The model is able to capture short-time and long-time adsorption dynamics of surfactants. We apply the model to examine the effect of soluble surfactants on droplet deformation, breakup and coalescence. The increase of surfactant concentration and attractive lateral interaction can enhance droplet deformation, promote droplet breakup, and inhibit droplet coalescence. We also demonstrate that the Marangoni stresses can reduce the interface mobility and slow down the film drainage process, thus acting as an additional repulsive force to prevent the droplet coalescence.     

A conservative SPH method for surfactant dynamics

In this paper, a Lagrangian particle method is proposed for the simulation of multiphase flows with surfactant. The model is based on the multiphase smoothed particle hydrodynamics (SPH) framework of Hu and Adams (2006) [1]. Surface-active agents (surfactants) are incorporated into our method by a scalar quantity describing the local concentration of molecules in the bulk phase and on the interface. The surfactant dynamics are written in conservative form, thus global mass of surfactant is conserved exactly. The transport model of the surfactant accounts for advection and diffusion. Within our method, we can simulate insoluble surfactant on an arbitrary interface geometry as well as interfacial transport such as adsorption or desorption. The flow-field dynamics and the surfactant dynamics are coupled through a constitutive equation, which relates the local surfactant concentration to the local surface-tension coefficient. Hence, the surface-tension model includes capillary and Marangoni-forces. The present numerical method is validated by comparison with analytic solutions for diffusion and for surfactant dynamics. More complex simulations of an oscillating bubble, the bubble deformation in a shear flow, and of a Marangoni-force driven bubble show the capabilities of our method to simulate interfacial flows with surfactants.     

表面活性剂浓度对球形气泡界面和尾流的影响

发展了一种研究气泡界面污染程度的数值模型,并用其对流场中不同表面活性剂浓度下、上浮气泡的界面参量和周围流场进行了模拟研究。该模型假设吸附于气泡界面的表面活性剂分布在毗邻气液界面的薄吸附层中,且气泡界面上表面活性剂的吸附与解吸过程也发生于此;界面切应力为界面浓度的函数。研究发现:气泡界面的流动性会因表面活性剂的吸附而降低,该现象会增大气泡周围流域中切向速度在界面法向上的变化量,从而对界面性质和周围流场产生影响;由于对流的作用和吸附-解吸动态平衡的存在,气泡前部界面不完全干净,且受污染界面的流动性也不完全为零。     

Lattice-Boltzmann simulations of dynamic interfacial tension due to soluble amphiphilic surfactant

An amphiphilic Lattice-Boltzmann approach is adopted to model dynamic interfacial tension due to non-ionic surfactant. In the current system, the surfactant adsorption kinetics is diffusion dominated and the interface separates two immiscible fluids. A rotational relaxation time and a diffusive/viscous relaxation time are associated with the surfactant. The model results are compared with experimental data for the dynamic interfacial tension of a pendant oil droplet in water, with oil soluble surfactant. We demonstrate how to adapt and calibrate the model to capture the adsorption timescale of the surfactant and the magnitude of interfacial tension reduction due to surfactant. A scheme to overcome numerical instabilities due to the relatively low surfactant concentration, is devised. We are able to qualitatively match the Frumkin equation of state for the interfacial tension.     

氟苯-水体系界面不稳定现象

以乙醇、正丁醇和聚乙烯醇为水相表面活性剂,采用悬滴法测定了氟苯-水溶液体系的界面张力,观测了氟苯-水溶液体系的界面。实验结果表明:氟苯和去离子水相互饱和,氟苯-水体系界面清晰,氟苯液滴的形态和大小不发生变化;体系中界面张力与溶液中表面活性剂浓度间的关系遵守Langmuir-Szyszkowski方程;Sternling和Scriven的界面稳定性判据适用于实验中的氟苯-水体系的界面稳定性判定。     

SANS structural determination of a nonionic surfactant layer adsorbed on clay particles

We study adsorption of two nonionic surfactants (C₁₂E₅ and C₁₂E₈) on a dispersed suspension of negatively charged laponite particles. First, we quantify adsorption, i.e. the amount of adsorbed molecules per gram of dried solid. Then, we show that contrast variation experiments under controlled conditions along the adsorption isotherm of the surfactant on dispersed laponite particles allow to determine the average thickness of a nonionic surfactant layer adsorbed on a solid anisotropic particle. Received 4 August 1998     

Critical assessment of effective interfacial potentials based on a density functional theory for wetting phenomena on curved substrates

In this Letter we examine an effective interfacial Hamiltonian approach for wetting phenomena based on two different density approximations in the framework of a density functional theory. The system under consideration is an attractive spherical wall subject to adsorption by a metastable liquid. We argue that, contrary to a planar geometry, in the spherical case the popular sharp-kink approximation leads to a considerable disagreement for the film thickness with numerical results obtained from density functional theory. We show that the deviation originates from the inaccuracy of the predicted liquid-gas surface tension. We further demonstrate that the prediction can be substantially improved when a soft-interface approximation is adopted, such that the liquid-gas interface is approximated by a smooth monotonic function.     

A front-tracking method for computation of interfacial flows with soluble surfactants

A finite-difference/front-tracking method is developed for computations of interfacial flows with soluble surfactants. The method is designed to solve the evolution equations of the interfacial and bulk surfactant concentrations together with the incompressible Navier–Stokes equations using a non-linear equation of state that relates interfacial surface tension to surfactant concentration at the interface. The method is validated for simple test cases and the computational results are found to be in a good agreement with the analytical solutions. The method is then applied to study the cleavage of drop by surfactant—a problem proposed as a model for cytokinesis [H.P. Greenspan, On the dynamics of cell cleavage, J. Theor. Biol. 65(1) (1977) 79; H.P. Greenspan, On fluid-mechanical simulations of cell division and movement, J. Theor. Biol., 70(1) (1978) 125]. Finally the method is used to model the effects of soluble surfactants on the motion of buoyancy-driven bubbles in a circular tube and the results are found to be in a good agreement with available experimental data.     

Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface

The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75?nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from ?79.8 to 15.3?mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and water/decane interface.     

A diffuse-interface method for two-phase flows with soluble surfactants

A method is presented to solve two-phase problems involving soluble surfactants. The incompressible Navier-Stokes equations are solved along with equations for the bulk and interfacial surfactant concentrations. A non-linear equation of state is used to relate the surface tension to the interfacial surfactant concentration. The method is based on the use of a diffuse interface, which allows a simple implementation using standard finite difference or finite element techniques. Here, finite difference methods on a block-structured adaptive grid are used, and the resulting equations are solved using a non-linear multigrid method. Results are presented for a drop in shear flow in both 2D and 3D, and the effect of solubility is discussed.     

A molecular dynamics study on interfacial heat transport of alkanethiol surfactant coated nanofluids-effect of chain length and stiffness

The thermal transport across the alkanethiol surfactant layer at the nanoparticle/base fluid interface in nanofluids was investigated by molecular dynamics simulation, with consideration of the conformation of the surfactant layer with different surfactant chain lengths and backbone stiffness. The variation of temperature drop at nanoparticle-surfactant interface reveals that the interfacial thermal conductance was mediated by the chain length, possibly due to the difference in the adsorption density of surfactant on the surface of the nanoparticles, because of the blocking effect from the bending of the long alkyl chains. The intrinsic thermal conductivity of the surfactant layer increased with decreasing chain length and increasing chain stiffness because of the phonon scattering effect from the bending and cross-linking of the alkyl chains. We quantified the modes of heat flow across the surfactant layer and found that the contribution of intramolecular bonded interaction was much higher than that of atomic translation and nonbonded interaction separately. By analysing the variation of bonded interaction contrition with chain length and stiffness, it is demonstrated that the increased thermal conductivities benefited from the enhanced thermal transfer through the covalent bonds of surfactant molecules. The results can provide insights into the design of thermally conductive surfactants.     

Premicellar and micelle formation behavior of aqueous anionic surfactants in the presence of triphenylmethane dyes: protonation of dye in ion pair micelles

The premicellar and micelle formation behaviors of four cationic triphenylmethane dyes, viz, Pararosaniline (RN), Crystal violet (CV), Ethyl violet (EV), and Malachite green (MG), in aqueous anionic surfactant solutions of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dodecyl sulfonate (SDSN) have been studied by spectral and surface tension measurements. The study was carried out within a pH range where the dyes are stable in their quinoid forms. The dyes have been found to form dye–surfactant ion pairs (DSIPs) with the surfactants, at the surfactant concentrations well below their critical micelle concentration, CMC*. The DSIPs behave like nonionic surfactants and form an air–water interfacial monolayer. The DSIPs have a lower critical micelle concentration (CMC_IP), greater efficiency, and lower effectiveness than the corresponding pure surfactants. As the surfactant concentration is increased below the CMC*, the DSIPs start forming micelles of their own where the dye gets protonated and exists as a protonated dye–surfactant ion pair (PDSIP) in the ion pair micelles. As the concentration of the surfactant exceeds the CMC* of the pure surfactant, the protonation reverses gradually with the dye remaining in the micelles in solubilized form and the DSIPs in the air–water interfacial monolayer are replaced by pure surfactants. The distorted helical isomeric form (isomer B) of the dyes is favored in the PDSIPs. Copyright © 2009 John Wiley & Sons, Ltd.     

Sonochemical degradation of surfactants with different charge types: Effect of the critical micelle concentration in the interfacial region of the cavity

Ionic surfactants tend to accumulate in the interfacial region of ultrasonic cavitation bubbles (cavities) because of their surface active properties and because they are difficult to evaporate in cavitation bubbles owing to their extremely low volatilities. Hence, sonolysis of ionic surfactants is expected to occur in the interfacial region of the cavity. In this study, we performed sonochemical degradation of surfactants with different charge types: anionic, cationic, zwitterionic, and nonionic. We then estimated the degradation rates of the surfactants to clarify the surfactant behavior in the interfacial region of cavitation bubbles. For all of the surfactants investigated, the degradation rate increased with increasing initial bulk concentration and reached a maximum value. The initial bulk concentration to obtain the maximum degradation rate had a positive correlation with the critical micelle concentration (cmc). The initial bulk concentrations of the anionic surfactants were lower than their cmcs, while those of the cationic surfactants were higher than their cmcs. These results can be explained by the negatively charged cavity surface and the effect of the coexisting counterions of the surfactants.     

The effect of ionisation of silica nanoparticles on their binding to nonionic surfactants in oil–water system: an atomistic molecular dynamic study

ABSTRACT

In this study, the adsorption of nonionic surfactant, triethylene glycol monododecyl ether (C₁₂E₃), on a surface of silica nanoparticle (NP) has been studied with variation in the degree of ionisation (DI) of silica NP using all-atom molecular dynamic simulations in hexadecane–water system. Hydrogen bonding is found to be responsible for the adsorption of C₁₂E₃ on NP, particularly at low DI. We observe that with increasing DI of NP, the amount of adsorption of C₁₂E₃ on NP reduces, which is negligible beyond DI ～ 0.5. The decrease in the adsorption with increasing DI is due to the decrease in the number of hydrogen bonds formed by the silica NP with surfactant molecules. Potential of mean force (PMF) profiles indicate attractive interactions between NP and C₁₂E₃ for DI < 0.5, and for larger DI depletion effect is observed. This work explains the unusual effect of nonionic surfactant on interfacial tension in the presence of silica particles as observed in recent experiments.     

Synthesis and surface activity properties of alkylphenol polyoxyethylene nonionic trimeric surfactants

A series of trimeric n-alkylphenol polyoxyethylene surfactants (TAP) were successfully synthesized and the molecular structure were confirmed by NMR, FTIR spectrum and elemental analysis. Using the same synthesis route, the trimeric nonylphenol polyoxyethylene surfactant (TNP) was synthesized using industrial product nonylphenol and paraformaldehyde, and its molecular structure was characterized by ¹HNMR, FTIR spectrum and elemental analysis. The optimal reaction conditions were established. The surface activity properties of TAP and TNP (such as the critical micelle concentration (cmc), the values of surface tension at the cmc (γ_cmc), the maximum surface excess concentration (Γ_cmc), and the minimum surface area per surfactant molecule (A_cmc)), were determined by means of Wilhelmy plate method and steady-state fluorescence probe method, respectively. The experimental results show that the lengths of the hydrophilic group oxyethylene (EO) chains and hydrophobic group methylene chains have an influence on the cmc, γ_cmc, Γ_cmc, and A_cmc of series of surfactants. Furthermore, TAP are arranged to staggered three-dimensional array mode at the air-water interface, which has exhibited better surface properties, such as low cmc values, strong adsorption affinities and wet abilities.     

Monolayers of diblock copolymer at the air-water interface: the attractive monomer-surface case

We have studied both experimentally and theoretically the surface pressure isotherms of copolymers of polystyrene-polyethyleneoxide (PS-PEO) at the air-water interface. The SCMF (single chain mean-field) theory provides a very good agreement with the experiments for the entire range of surface densities and is consistent with the experiments if an adsorption energy per PEO monomer at the air-water interface of about one k_{B T} is taken. In addition, the chain density profile has been calculated for a variety of surface densities, from the dilute to the very dense ones. The SCMF approach has been complemented by a mean-field approach in the low density regime, where the PEO chains act as a two-dimensional layer. Both theoretical calculations agree with the experiments in this region. Received: 19 June 1997 / Revised: 2 February 1998 / Accepted: 11 February 1998