Adsorption and desorption kinetics of CmE8 on impulsively expanded or compressed air–water interfaces

The adsorption kinetics of C_mE₈ (m=10, 12, and 14) at an air–water interface are investigated. A pendant bubble is formed in aqueous surfactant solution and allowed to attain equilibrium. The bubble is then impulsively expanded or compressed with some change of area large enough to appreciably deplete or enrich the surface concentration and change the surface tension. The surfactant is then allowed to re-equilibrate. The surface tension evolution during this process is measured using video images of the pendant drop. The surface tension evolution is compared to mass transfer arguments. First, the re-equilibration of interfaces laden with C₁₄E₈ are studied. For compressed interfaces, surfactant must desorb to restore equilibrium. The surface tension rises more slowly than predicted by a diffusion-controlled evolution, implying that the re-equilibration is mixed diffusive-kinetic controlled. By analyzing the surface tension evolution in terms of a mixed kinetic-diffusive model, values for the kinetic constants for adsorption and desorption are found. These results are compared to those obtained previously for C_mE₈ (m=10 and 12). For all of these molecules, the adsorption rate constant is similar (β₁=5.6±1.0×10⁻⁶ cm³ (mol s)⁻¹). However, the desorption rate constant (₁) varies strongly. Increasing m by 2 lowers the desorption rate constant ₁ by nearly a factor of 15. This is consistent with an increased resistance to re-immersion into water with the length of a hydrocarbon chain.     

Gemini表面活性剂/C12En混合体系的界面吸附、扩张粘弹与泡沫稳定性

用表面张力法研究了阳离子gemini表面活性剂乙基-1, 2-双(十二烷基二甲基溴化铵)(简写为12-2-12)和非离子表面活性剂十二烷基聚氧乙烯醚(C₁₂E_n,其中n = 4, 10, 23)混合体系在气液界面上的吸附行为;用扩张流变技术研究了吸附膜的扩张粘弹行为,实验数据用Lucassen-van den Tempel (LVT)模型进行拟合并根据模型得到了极限弹性值.最后研究了混合体系的泡沫行为,用泡沫塌陷到初始高度一半所对应的时间(t_1/2)来表征泡沫的稳定性.结果表明,所有的非离子表面活性剂C₁₂E_n均与12-2-12产生了吸引作用.在12-2-12浓度相同的情况下,混合吸附层中吸附分子的最小分子占据面积的顺序为12-2-12/C₁₂E₂₃ > 12-2-12/C₁₂E₁₀ > 12-2-12/C₁₂E₄,而极限弹性的顺序为ε_{0, fit}(12-2-12/C₁₂E₄) > ε_{0, fit}(12-2-12/C₁₂E₁₀) > ε_{0, fit}(12-2-12/C₁₂E₂₃).与单组分12-2-12形成的吸附膜相比,只有12-2-12/C₁₂E₄形成更加紧密的结构.具有较小亲水头基的非离子表面活性剂C₁₂E₄的加入,可增强12-2-12吸附膜的弹性,进而增强了对应体系泡沫的稳定性.     

Solution behavior of a surfactant aldehyde–the oxidation product of an alcohol ethoxylate

It has previously been shown that alcohol ethoxylates readily undergo autoxidation and that one of the major oxidation products is the surfactant aldehyde, i.e. an ethoxylate carrying a –CH₂CHO group at the terminal end of the polyoxyethylene chain. In this work the cloud point, phase behavior and aggregation characteristics of the surfactant aldehyde produced by oxidation of C₁₂H₂₅(OCH₂CH₂)₅OH (C₁₂E₅) are determined and compared with the values obtained with the parent surfactant. It was found that the physico–chemical behavior of the two species was very similar, which indicates that a considerable portion of the aldehyde group is in hydrated state, i.e. the surfactant aldehyde consists of a mixture of aldehyde in carbonyl form and the corresponding geminal diol. The cloud point of the surfactant aldehyde decreased rapidly with time, even when it was stored at low temperature. Also the parent surfactant and its homologue C₁₂E₆ exhibited a decrease in cloud point during storage. For instance, a 1% aqueous solution of C₁₂E₆ showed a cloud point decrease from 62 to 32°C after 4 months storage at 40°C. Such a change in solution behavior can have important practical implications.     

Surface chemicals concepts of flotation de-inking

This review outlines the important parameters, which influence the flotation de-inking and discusses the surface chemical aspects of the process. Although, it has been established increasing temperature and pH facilitate the release of ink particles from the fibre during pulping (prior to flotation), it has not yet been completely established to what extent these parameters increase or decrease the efficiency of the primary flotation step. In fact, increasing temperature appears to decrease the flotation rate and also an increase in pH can retard the flotation due to a reduction in capture efficiency between the air bubbles and the ink particles decreasing the flotation in the cell. In addition, the size, shape and roughness of the ink particles influence this bubble/particle capture mechanism. Bubble frequency and bubble size is influenced by surface tension (type and concentration of frother) but X-ray studies also indicate that the fibre consistency can influence the bubble shape and flow patterns causing channelling and re-circulation of bubble flow in the cell. Tests with different gases (oxygen and nitrogen instead of air) show no significant gains in optical and mechanical properties of the fibre. Fatty acids with higher chain length and lower degree of saturation are less soluble and ensure lower carry-over but less foaming and also less fibre recovery. The primary mechanisms of fatty acid flotation involves precipitation of calcium soap, followed by micro-encapsulation of ink through a hetero-coagulation mechanism, followed by the bubble/ink particle capture step. In the use of nonionic surfactant, cloud point and HLB are important parameters, which influence brightness, washing and flotation efficiency. Optimum flotation occurs with slight excess of fatty acid to reduce surface tension and optimum calcium levels ensuring that most of the calcium is removed in the process. A lower calcium level gives lower stock loss but a high calcium has a detrimental effect, causing scaling and deposition. A critical nonionic/fatty acid balance is needed to minimize stock loss during the flotation. New chemicals need to be developed to increase selectivity, reduce entrainment and increase the process efficiency. Also, the underlying knowledge linking structural/function relationship for de-inking chemicals in relationship to the heterogenity at the pulps needs to be established. Further progress could help in the treatment of higher fibre content pulps, reducing water and chemical consumption and reducing redeposition of the ink on the fibre.     

Modification of ilmenite surface chemistry for enhancing surfactants adsorption and bubble attachment

In this study, microwave irradiation is used to modify ilmenite surface chemistry to enhance the adsorption of surfactants and the air bubble attachment. The results indicate that microwave irradiation can increase ilmenite flotation recovery by 20%. A positron emission particle tracking technique is used to study the dynamic behaviour of ilmenite particles in a Denver cell. The data shows that the poor flotation recovery of ilmenite is not only due to the reduce probability of ilmenite being captured by air bubbles, but also the short residence time of the particles remaining in the froth phase. The ilmenite particles can be frequently captured by air bubbles, but dropped to the bulk liquid from the froth phase, normally over 15 s. Microwave irradiation changes the ilmenite flow pattern in the Denver cell. The average time of ilmenite remaining in froth phase is increased from 11.5 to 29.1 s.     

氯化铅纳米线的胶束模板诱导合成及其机理研究

一维纳米材料由于在光学、磁学、微电子学等领域中具有广阔的应用前景而引起了科技工作者的广泛兴趣 .目前 ,研究得最多的一维纳米材料为碳纳米管 [1,2 ] ,它的某些性质已得到实际应用 .而纳米线 (纳米丝、纳米纤维 )的研究尚处于初始阶段 ,至今已合成或制备出的纳米线只有硫化钼、硫化镉、氮化镓、砷化铟、硫酸钙、碳酸钡、碳化硼、锡 -铅、金、银、铋等十余种 [3～ 16 ] ,尚未见有氯化铅纳米线的报道 .氯化铅晶体通常呈九配位三帽三方柱层状结构 ,具有方向上的电性差异 .当进入纳米尺寸时 ,可能产生奇异的理化现象 .本文用反相胶团或 W/ …     

Influence of NaCl on the behavior of PEO-PPO-PEO triblock copolymers in solution, at interfaces, and in asymmetric liquid films

The solution behavior of the polymeric surfactant Pluronic F127 (PEO(99)PPO(65)PEO(99)) and its adsorption behavior on aqueous-silica and aqueous-air interfaces, as well as the disjoining pressure isotherms of asymmetric films (silica/aqueous film/air) containing F127, are studied. The interfacial properties of adsorbed F127 layers (the adsorbed amount Gamma and the thickness h) as well as the aqueous wetting film properties [film thickness (h) and refractive indexes] were studied via ellipsometry. The solution properties of F127 were investigated using surface tensiometry and light scattering. The interactions between the air-water and silica-water interfaces were measured with a thin film pressure balance technique (TFB) and interpreted in terms of disjoining pressure as a function of the film thickness. The relations between the behaviors of the asymmetric films, adsorption at aqueous air, and aqueous silica interfaces and the solution behavior of the polymeric surfactant are discussed. Special attention is paid to the influence of the concentrations of F127 and NaCl. Addition of electrolyte lowers the critical micelle concentration, diminishes adsorption on silica, and increases the thickness of the asymmetric film.     

Kinetics of CO2 nanobubble formation at the solid/water interface

The kinetics of adsorption of CO(2) molecules dissolved in aqueous solution onto a hydrophobised silica surface were investigated using a quartz crystal microbalance (QCM). The results of this investigation were compared with those obtained earlier from tapping mode atomic force microscopy (TMAFM) under the same experimental conditions (J. Yang, J. Duan, D. Fornasiero, J. Ralston, J. Phys. Chem. B., 2003, 107(25), 6139-6147; ref. 1). The QCM results represent the early stage of CO(2) gas adsorption (<20 min), before CO(2) gas bubbles adsorbed on the surface can be directly observed by TMAFM. The QCM results confirmed our observation from TMAFM imaging: that CO(2) gas molecules present in solution only adsorb on silica when its surface is hydrophobic. More importantly, the results showed that gas adsorption/bubble growth undergoes two consecutive kinetic processes: a slow and a fast adsorption process.     

Frother/collector interactions in thin froth films and flotation

Aqueous thin film studies and surface tension measurements on a mixed surfactant system consisting of poly(ethylene oxide) (PEO), which was chosen as a model flotation frother, and potassium ethyl xanthate, which was chosen as a model flotation collector, enable the interaction between the two surfactants at the air/solution interface to be elucidated.

For the film containing the non-ionic frother, the interface was charged and addition of low concentrations of xanthate acted as a common electrolyte and reduced the thickness of the film, inducing rupture. However, at high xanthate collector concentrations, the negatively charged xanthate was found to interact with the non-ionic PEO causing an accumulation of negative charge at the air/solution interface. Higher frother concentrations were necessary to produce non-rupturing thin films upon increasing the xanthate concentration.     

How does a non-ionic hydrophobically modified telechelic polymer interact with a non-ionic vesicle? Rheological aspects

The association between hydrophobically modified polyethylene glycol, HM-PEG, and non-ionic vesicles of tetraethylene glycol monododecyl ether, C₁₂E₄, was investigated. HM-PEG is in a triblock form, with an alkyl chain attached to each hydrophilic polymer-end. Such polymer structure is denoted as telechelic. The vesicle average radius was measured by self-diffusion measurements. The system exhibits both a monophasic gel and biphasic regions. The monophasic region was characterized from a rheological point of view. We argue that the gel formation is due to the presence of polymer crosslinks between different surfactant aggregates, once the polymer's hydrophobic moieties may adsorb into the vesicle bilayer. This association is strongly concentration dependent which is reflected in the monotonic increase of the storage modulus, relaxation time and shear viscosity with the addition of surfactant and/or polymer.     

Micellization and interaction of anionic and nonionic mixed surfactant systems in water

Interaction between binary surfactant mixtures containing anionic surfactants viz. sodium dodecyl sulphates (NaDS) and magnesium dodecyl sulphates (Mg(DS)₂) and a nonionic surfactants viz. dodecyl dodecapolyethylene glycol ether (C₁₂E₁₂) and dodecyl pentadecapolyethylene glycol ether (C₁₂E₁₅) in water at different mole fractions (0–1) were studied by surface tension, viscometry and dynamic light scattering (DLS) methods. The composition of mixed micelles and the interaction parameter, β evaluated from the CMC data obtained by surface tension for different systems using Rubingh's theory were discussed. Activity coefficient (f₁ and f₂) of metal dodecyl sulphates (MDS)/C₁₂E_m (m = 12, 15) mixed surfactant systems were evaluated, which shows extent of ideality of individual surfactant in mixed system. The estimated interaction parameter indicates an overall attractive interaction in the mixed micelles, which is predominant for NaDS as compared to Mg(DS)₂. Counter ion valency has specific effect on the mixed micelles, as Mg(DS)₂ has less interaction with nonionic surfactants in comparison to NaDS due to strong condensation of counter ion. The stability factors for mixed micelles were also discussed by Maeda's approach, which was justified on the basis of steric factor due to difference in head group of nonionic surfactant. DLS measurements and viscosity data reveals the synergism in mixed micelles, showing typical viscosity trends and linearity in sizes were observed.     

Electrokinetic characterization of polystyrene–non-ionic surfactant complexes

An experimental study on the electrophoretic mobility (μ_e) of polystyrene particles after the adsorption of non-ionic surfactants with different chain lengths is described. Two sulphate latexes with relatively low surface charge densities (3.2 and 4.8 μC cm⁻²) were used as solid substrate for the adsorption of four non-ionic surfactants, Triton X-100, Triton X-165, Triton X-305 and Triton X-405, each one with 9–10, 16, 30 and 40 molecules of ethylene oxide (EO), respectively. The electrophoretic mobility of the polystyrene–non-ionic surfactant complexes was studied versus the amount of adsorbed surfactant (Γ). The presence of non-ionic surfactant onto particles surface seems to produce a slight shifting of the slipping plane because the mobilities of the different complexes display a very small decreasing. The increase in the number of EO chains in the surfactant molecule seems to operate as a steric impediment which decreases the number of adsorbed large surfactant molecules. The electrophoretic mobilities of the latex–surfactant complexes with maximum adsorption were measured versus the pH and ionic strength of the dispersion. While the different complexes showed a similar qualitative behaviour compared with that of the bare latex against the pH, the adsorption of the surfactant reduces the typical maximum in the μ_e−log[electrolyte].     

烷基聚葡糖苷溶液的表面吸附平衡与动力学

用吊片法和气泡最大压力法分别测定了烷基聚葡糖苷(APG)C₉.₆G_1.3水溶液的平衡和动态表面张力,研究了APG水溶液表面的吸附平衡、动力学及其影响因素.测得其cmc(临界胶束浓度)为0.032g/L.吸附过程由初始的扩散控制转变到势垒控制,吸附势垒为4～7kJ/mol.温度升高,平衡和动态表面张力均减小,吸附量增加;加入无机盐,平衡和动态表面张力增大,吸附量亦增加;醇类的吸附使动态表面张力下降速率加快,表明APG与醇分子间有协同吸附作用.     

Behaviors of sodium glycochenodeoxycholate and sodium glycoursodeoxycholate in binary mixed micelles of bile salt and nonionic surfactant

The behavior of sodium glycochenodeoxycholate (NaGCDC) and sodium glycoursodeoxycholate (NaGUDC) in binary mixed micelles consisting of bile salt and octaoxyethylene glycol mono n-decyl ether (C₁₀E₈) has been studied on the basis of micellar compositions, polarities of the interior of intramicelles, mean aggregation numbers and ¹H NMR measurements. Micellar compositions for both NaGCDC---C₁₀E₈ and NaGUDC---C₁₀E₈ systems showed a tendency to change from C₁₀E₈-rich micelles to bile-salt-rich micelles with an increase on the mole fraction of bile salts from the results of both theoretical calculations using the critical micelle concentration and the micellar polarity. The microenvironment of intramicelles for the NaGCDC---C₁₀E₈ system was found to be more hydrophobic than that for the NaGUDC---C₁₀E₈ system. Mean aggregation numbers of mixed micelles for both systems decreased abruptly with an increase in the mole fraction of bile salts in the range of low mole fraction, but those for NaGCDC were larger than those for NaGUDC. Furthermore, from the results of ¹H NMR measurements, the motions of the methyl group protons in the 18 position of the molecular structure of NaGCDC were slightly restricted with an increase in the mole fraction of NaGCDC. In contrast, the methyl group protons in the 18 and 19 positions of the molecular structure of NaGUDC became freer with an increase in the mole fraction of NaGUDC.     

Desorption kinetics of surfactants at fluid interfaces by novel coaxial capillary pendant drop experiments

Surfactants appear in multiphase fluid systems in which the interface and the adjacent bulk phase have been removed from equilibrium. Here, a new method is described for the measurement of rate constants of desorption of surface-active materials from fluid/fluid interfaces and the extent to which adsorption is reversible: the coaxial capillary pendant drop experimental technique.

Kinetic constants are determined by desorption experiments in pendant drops in which the interface adjacent to a surfactant solution is removed from equilibrium by replacing the subphase of the drop with pure water. Further, we demonstrate that although the rate of subphase exchange is comparatively slow with respect to the desorption timescale, it is possible to resolve desorption processes which occur under local equilibrium with the adjacent bulk phase from those that are determined in part by sorption kinetics. Experiments which measure the desorption kinetic coefficient, , using a homologous series of n-alkyl (C₈, C₁₀, C₁₂, C₁₄) dimethyl phosphine oxides are presented.     

Adsorption Isotherms of Cetylpyridinium Chloride with Iron III Salts at Air/Water and Silica/Water Interfaces

The interaction of iron III salts and cetylpyridinium chloride (CPC) has been studied at the air/water and silica/water interfaces. The surface tension of cetylpyridinium chloride has been determined in aqueous solutions in the presence of iron III chloride and iron III nitrate at two constant pH values, namely, 3.5 and 1.2. It is shown that the surface tension of the cationic surfactant depends upon the ionic strength of the solution through the pH adjustment in the presence of the former salt but not in the presence of the latter. The effect of iron III nitrate on the surface tension of CPC is similar to that of potassium nitrate, indicating that the iron III various-hydrolyzed species do not interfere with the composition of the air/water interface. The competitive adsorption of iron III nitrate salt and the cationic surfactant at a silica/water interface was next investigated. The adsorption isotherms were determined at pH 3.5. It is shown that although the iron III ions, which were added to the silica dispersion in the presence of the cetylpyridinium ions, were strongly bound to the anionic surface sites, the surfactant ions are not salted out in the solution but remain in close vicinity of the silica surface. Conversely as the cationic surfactant is added first to the silica dispersion in the presence of the adsorbed iron III ions, the metal ions and the surfactant ions are both coadsorbed onto the silica surface. It is suggested that iron III hydrolyzed or free cations and the cationic surfactant molecules may not compete for the same adsorption sites onto the silica surface.     

界面扩张流变法研究C_(12)mimBr对Gemini12-2-12在空气/水界面聚集行为的影响

采用界面扩张流变技术研究了季铵盐偶联表面活性剂C12-(CH2)2-C12·2Br(Gemini12-2-12)及其与离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C12mim Br)复配体系的动态界面张力、扩张流变性质和界面弛豫过程等,探讨了C12mim Br对C12mim Br/Gemini12-2-12混合体系界面性质的影响及C12mim Br对Gemini12-2-12界面聚集行为影响的机制.结果表明,随着离子液体表面活性剂的不断引入,体系界面吸附达到平衡所需的时间逐渐缩短,扩张模量和相角明显降低,界面吸附膜由粘弹性膜转变为近似纯弹性膜;同时,界面及其附近的弛豫过程也发生显著变化,慢弛豫过程消失,快弛豫过程占主导地位,且离子液体浓度越高,快弛豫的贡献越大.这些界面性质的变化主要归因于离子液体表面活性剂C12mim Br参与界面形成及两表面活性剂在界面竞争吸附的结果.少量离子液体表面活性剂C12mim Br的加入可以填补疏松的Gemini12-2-12界面上的空位,形成混合界面吸附膜.随着C12mim Br含量的增加,嵌入界面的C12mim Br分子数不断增多,导致界面上相互缠绕的Gemini12-2-12烷基链"解缠",在体相和界面分子扩散交换的过程中"解缠"的Gemini12-2-12分子从界面上解吸回到体相,与此同时,C12mim Br分子相对较小的空间位阻及较强的疏水作用促使其优先扩散至界面进而取代Gemini12-2-12分子,最终界面几乎完全被C12mim Br分子所占据.     

气相二氧化硅/季铵Gemini表面活性剂稳定的泡沫体系

以zeta电位法研究了季铵Gemini表面活性剂亚甲基-α, ω-双(十二烷基二甲基溴化铵) (12-s-12, s=2, 6)在水溶液中修饰气相二氧化硅(F-SiO₂)粒子。这些粒子随表面活性剂浓度C增加经历了表面从原先的亲水到疏水再重新亲水的改变,其中疏水粒子可以自发吸附在气泡液膜中,从而很好地稳定泡沫。重新亲水的粒子脱附出液膜,仅留下表面活性剂稳定气泡。强的液膜弹性对应于稳定的泡沫。联接链长度影响了Gemini在F-SiO₂粒子表面的吸附,因而也影响了液膜的弹性和对泡沫的稳定。超短s=2联接链的12-2-12由于反离子解离不完全而带有较少的正电荷,在粒子表面的初始吸附弱于12-6-12,但因此减少了吸附分子头基间的静电排斥,可以形成更致密的吸附层。由于12-2-12本身比12-6-12具有更强的界面吸附能力,F-SiO₂粒子和12-2-12的协同作用可以更好地稳定泡沫体系。