Co-adsorption of surfactants and propyl gallate on the hydrophilic oxide surfaces

Propyl gallate (PG) adsolubilisation in the cationic, anionic and nonionic surfactant micelles formed in the bulk solution and at the silica/solution interface has been investigated. It was found that in the absence of surfactant, propyl gallate does not adsorb on the silica surface from aqueous solution. However, in the presence of hexyltrimethylammonium bromide (CTAB), its uptake by silica significantly increases. Alumina is quite an effective adsorbent for SDS and propyl gallate and does not adsorb nonionic TX-100. The addition of PG promotes adsorption of SDS and TX-100.     

Novel surface tension isotherm for surfactants based on local density functional theory

In this Letter we report a new general method for calculating of surface tension isotherms in the presence of surfactants, based on a local density functional. We illustrate this method by deriving the interfacial tension isotherm for nonionic surfactants at an air-water or oil-water interface by using the self-consistent field theory of polymer brushes. We consider a particular case of local density functional to calculate explicitly how the interfacial tension and the surfactant adsorption depend on the surfactant bulk concentration. Experimental data for the surface tension and the surfactant adsorption isotherm for nonionic surfactants were interpreted with the help of the new isotherm. Very good agreement between the adsorption of n-dodecyl pentaoxyethylene glycol ether (C12E5) at an air-water interface, calculated from the surface tension isotherm and small-angle neutron-scattering is obtained.     

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.     

Enrichment of surfactant from its aqueous solution using ultrasonic atomization

Dilute aqueous solutions of dodecyl-benzenesulfonic acid sodium salt (DBS-Na) and polyoxyethylenenonylphenyl ethers (PONPEs) were ultrasonically atomized. The surfactants were concentrated in collected mist droplets. The enrichment ratio increased with decreasing surfactant concentration. Depending on the surfactant’s molecular weight and affinity to water, different enrichment ratio was observed in the range of low feed concentrations. For anionic surfactant, DBS-Na, the enrichment ratio was significantly improved by KCl addition and a peak appeared on the plot of the ratio against KCl concentration. Addition of NaCl or CaCl₂ · 2H₂O to the surfactant solution also enhanced the enrichment ratio; however, the effect was relatively small. Such behaviors of the ratio were interpreted as enhanced interfacial adsorption of the surfactant and a lack of supply of surfactant monomers from liquid bulk because of slow breaking of surfactant micelles. Time required for collecting an amount of mist was also observed. Among the three salt systems, the time for KCl system was twice as long as others. This fact suggested that the formation of smaller droplets in KCl system.     

AFM studies on Langmuir-Blodgett films of cholesterol

The Langmuir monolayer of cholesterol at the air-water interface exhibits a condensed phase in which the cholesterol molecules are aligned normal to the water surface. We have transferred the monolayer from water surface to different substrates by Langmuir-Blodgett (LB) technique and have studied their assembly by atomic force microscope (AFM). Our studies reveal that the aggregation of cholesterol molecules on hydrophobic surfaces leads to interesting structures. The cholesterol molecules assemble into a uniform film, elongated domains and uniformly distributed torus-shaped domains (doughnuts) for one, two and four cycles of deposition, respectively. Beyond four cycles, the molecules adsorb and desorb by an equal amount resulting in no further deposition. The formation of uniformly distributed doughnuts can be attributed to the hydrophobic interaction and reorganization of the molecules due to successive adsorption and desorption during deposition cycles. Our studies on hydrophilic surfaces show that cholesterol cannot form more than one layer of deposition.PACS: 68.47.Pe Langmuir-Blodgett films on solids; polymers on surfaces; biological molecules on surfaces - 68.37.Ps Atomic force microscopy (AFM) - 68.43.Mn Adsorption/desorption kinetics     

Simulation of the Critical Adsorption of Semi-Flexible Polymers

The critical adsorption of semi-flexible pol.ymer chains on attractive surfaces is studied using Monte Carlo simulations.The results reveal that the critical adsorption point of a free polymer chain is the same as that of an end-grafted one.For the end-grafted polymer,we find that the finite-size scaling relation and the maximum fluctuation of adsorbed monomers are equivalent in estimating the critical adsorption point.The effect of chain stiffness on the critical adsorption is also investigated.The surface attraction strength for the critical adsorption of semi-flexible polymer chain decreases exponentially with an increase in the chain stiffness;In other words,lower adsorption energy is needed to adsorb a stiffer polymer chain.The result is explained from the viewpoint of the free energy profile for the adsorption.     

Hydrodynamic boundary conditions and dynamic forces between bubbles and surfaces

Dynamic forces between a 50 microm radius bubble driven towards and from a mica plate using an atomic force microscope in electrolyte and in surfactant exhibit different hydrodynamic boundary conditions at the bubble surface. In added surfactant, the forces are consistent with the no-slip boundary condition at the mica and bubble surfaces. With no surfactant, a new boundary condition that accounts for the transport of trace surface impurities explains variations of dynamic forces at different speeds and provides a direct connection between dynamic forces and surface transport effects at the air-water interface.     

表面活性剂添加对水平管内气液两相流含液率的影响

应用电导断层测量技术研究表面活性剂添加对水平管内气液两相流含液率的影响,实验工质为空气/水、空气/100 mg/kg十二烷基硫酸钠(SDS)水溶液。结果表明,空气/水气液两相流动在光滑分层流型区,表面活性剂添加对平均截面含液率基本没有影响。随着液体流速的增加,空气/水气液两相流动进入波状分层流型区域,添加表面活性剂可以抑制或消除界面波动,增大平均截面含液率。表面活性剂的添加使弹状流含液率下降,气液流速较低时这一现象尤为明显。     

An isothermal titration calorimetry study of the interactions between an oxyphenylethylene/oxyethylene diblock copolymer and sodium dodecyl sulfate

Interactions between the diblock copolymer S₁₅E₆₃ and the surfactant sodium dodecyl sulfate (SDS) have been investigated by isothermal titration calorimetry (ITC) in the temperature range 10–40°C. At 20°C, the block copolymer is associated into micelles with a hydrodynamic radius of 11.6?nm, which is composed of a hydrophobic styrene oxide (S) core and a water-swollen oxypolyethylene (PEO) corona. The copolymer/surfactant system has been studied at a constant copolymer concentration of 0.25?wt% and over a wide range of surfactant concentration, from 7.5?×?10^?6 up to 0.3?M. The titration calorimetric data for SDS in the temperature range 10–20°C presents a first endothermic increase indicating the formation of mixed copolymer rich-surfactant micelles. From that point, important differences in the ITC plots for surfactant titrations in the presence and in the absence of the copolymer are present. A shallow second endothermic peak is assigned to the interaction between SDS molecules and copolymer molecules resulting from the beginning of micelle disruption. An exothermic peak indicates the end of this disruption where only SDS micelles attached to single copolymer monomers are present, as shown by DLS in a previous paper. At higher temperatures in the range 25–40°C, the first endothermic maximum is not totally shown because interactions between surfactant and block copolymer start at very low SDS concentrations. Moreover, the second endothermic peak is absent and the exothermic minimum is less pronounced as a consequence of the increased micellization of the block copolymer.     

The adsorption of fluor-carbon complexes on GaAs(110) studied by electron energy loss spectroscopy

The room temperature adsorption of CF₃COOH, CH₃COOH and CO on cleaved GaAs(110) surfaces has been studied by vibrational electron energy loss spectroscopy (HRELS), second derivative electron energy spectroscopy (ELS) and electron diffraction (LEED). CO does not adsorb on the GaAs surfaces in measurable quantities. Acetic acid CH₃COOH is dissociatively adsorbed as an acetate bonded to Ga surface atoms with the split-off hydrogen on As surface atoms. The fluorated acid CF₃COOH decomposes via an acetate intermediate CF₃COO into active CF₃ groups which adsorb on Ga surface atoms. The split-off hydrogen sticks to surface As atoms while the generated CO₂ desorbs. The adsorption models are consistent with the LEED c(2×2) superstructure observed after saturated adsorption of both acids.     

Investigation of dodecylammonium adsorption on mica,albite and quartz surfaces by QM/MM simulation

The absorption mechanisms of collector and mineral surface structures play important roles in studies of lepidolite flotation. In this work, quantum mechanics (QM) and hybrid quantum mechanics/molecular mechanics (MM) methods were implemented to investigate the flotation mechanisms of lepidolite from muscovite, quartz and albite. The crystal structures, electron density distributions, bonds and the densities of states of lepidolite were calculated and compared with those of muscovite. The adsorption structures and energies of monomer dodecylammonium (DDA) on the three different minerals were also calculated. The headgroup of the DDA cation was found to adsorb on the surface of minerals, with its hydrophobic tail stretching into the vacuum slab, approximately perpendicular to the surface. Simulation results indicate that the purity of fine lepidolite is limited by the existence of muscovite, due to their similarities in surficial structure and properties. Other gangues were found to be removed efficiently with the use of acidic conditions. The results are in good agreement with other experiments. Compared with simple MM simulations, the use of the QM/MM methods to investigate the adsorption on minerals without specific forcefield parameters was concluded to be a more accurate method to attain monomer surfactant–mineral adsorption energies.     

N-甲基咪唑与2,2'-联吡啶在铜表面共吸附的SERS研究

采用电化学现场表面增强拉曼光谱(SERS)分别研究了非水体系中N-甲基咪唑(NMIM),2,2’-联吡啶(2,2-’bipy)在铜电极表面的吸附行为以及两者的共吸附行为。结果表明在非水体系中,NMIM可在很宽的电位区间内稳定地吸附在金属表面,而2,2-’bipy在一个相对较窄的电位区间内能稳定地吸附在金属表面。当两者共存时存在竞争吸附和共吸附行为,较负的电位下主要以NMIM吸附为主,在略偏负的电位区间内以2,2-’bipy吸附为主,而正电位区间两者在金属表面共吸附,NMIM倾斜吸附在金属表面,而2,2’-bipy以顺式结构垂直吸附在金属表面。     

Controlling adsorption status of individual fullerene at room-temperature

The influence of Ag atoms on the adsorption statuses of individual fullerene molecules on Si surface at room temperature has been investigated by scanning tunneling microscopy. For a fullerene molecule, its adsorption status can be switched from one initial state into multiple final states by attaching Ag atoms onto various parts of the molecule. Once silver atoms are removed from the adsorption sites by a STM tip, the adsorption statuses of the fullerene molecules are recovered as that for fullerene molecules on a bare Si surface.     

Wetting transitions of simple liquid films adsorbed on self-assembled monolayer substrates: an ellipsometric study

We report on an ellipsometric experimental study designed to explore the relevance of the wetting phase diagram predicted by liquid state physics of basic models, to the wide class of simple organic liquid films that adsorb from saturated vapour onto planar substrates at room temperature. The wetting properties are explored by measuring adsorption isotherms in the approach to saturation, in particular, for adsorption of n-hexane on a variety of specially constructed substrates (self-assembled monolayers) spanning a wide range of surface energy, and by carrying out the microscopic equivalent of contact angle experiments at saturation. We locate a wetting transition, which in our case is continuous, and then study its properties in detail. The general prediction of the wetting phase diagram, that wetting transitions should be ubiquitous in nature and readily located via control over the substrate field, is supported by our data, but the quantitative nature of the thick film adsorption regime is not in agreement with Lifshitz theory. This conclusion supports the work of a variety of earlier related studies, but contrasts with recent results for adsorption onto the surface of water. In addition, the correlation length determined from our complete wetting adsorption isotherms is mesoscopic, suggesting that equilibrium statistical mechanics of simple models of inhomogeneous fluids cannot explain the data.     

Structure of polymer micelles close to the solid interface

Block copolymers are widely used in industry. For scientific interests their aqueous solutions offer a model system for the investigation of crystallisation as the macromolecules agglomerate for elevated concentrations into micelles, which crystallise when a critical volume fraction is reached. We report on grazing incidence small angle neutron scattering (GISANS) or near surface small angle neutron scattering (NS-SANS) as an experimental tool to investigate the micelle crystallisation close to interfaces with different chemical termination. We find that in general crystallization is suppressed at a repulsive surface and favoured at an attractive one. Furthermore we show that the crystallization close the interface can be controlled by the micelle stability, resulting from the different composition and length of the monomers. The effect of the interface is found more important for a high micelle stability, whereas for a low stability it is shadowed by adsorbed monomers.     

Adsorption of benzene on the fresh steel surface formed by cutting under high vacuum

The adsorption of benzene on a fresh steel surface was carried out in high vacuum at room temperature. The fresh surface was formed by cutting in a high vacuum chamber, and benzene was allowed to adsorb on the surface during cutting. The adsorption and the surface reaction of benzene was monitored with a quadrupole mass spectrometer. It was found that the cut surface was so active that the catalytic decomposition of benzene occured even at room temperature. The adsorption rate and the sticking probability of benzene were estimated. The adsorption rate linearly increased with cutting speed, that is, the formation rate of the fresh steel surface. It was found that the adsorbed amount was under the monolayer level, and that the adsorption activity of toluene on the fresh surface was about two times larger than that of benzene.     

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.     

The structure of oxygen on W(001) by low energy ion scattering

The adsorption of oxygen on the W(001) surface has been studied by LEED, AES, and low energy alkali ion scattering in order to obtain a more detailed understanding of the short-range surface structure. Exposure at room temperature results in oxygen adsorption near bridge sites for all coverages below 0.6 ML as determined by the ion scattering incidence angle dependence. Above 0.6 ML, the oxygen adsorbs in four-fold hollow sites. When the oxygen-covered surface is annealed to 950 K, the surface reconstructs, leaving vacancies in the W lattice. This is confirmed by the observation of ions scattered from second layer W, through the vacancies, at relatively low angles of incidence. The oxygen atoms do not adsorb in the position vacated by the missing W atoms but instead adsorb atop the second W layer.     

脂肪醇聚氧乙烯醚在空气-水界面上铺展单分子膜的脱附性质

采用Wilhelmy法测定脂肪醇聚氧乙烯醚在空气-水界面上铺展单分子膜的动态表面压,并由此计算动态脱附动力学参数.实验结果表明,样品铺展膜的脱附初期扩散系数约10-3～10- 4cm2/sec,远远大于溶液表面吸附的扩散系数,铺展膜的初始表面浓度越大,其初期脱附扩散系数也越大.但是从脱附整个过程看,铺展膜的初始表面浓度越大,其平均脱附速率常数越小,脱附过程是属于扩散控制和表面能垒控制共同作用的混合模式.