吸附与润湿 Ⅱ.Triton X-100和Triton X-305在炭黑/水和炭黑/环己烷界面上的吸附层结构

(1)测定了15℃和30℃时炭黑自水和环己烷中吸附非离子型表面活性剂Triton X-100和Triton X-305的等温线;(2)计算了吸附过程的标准热力学函数△G~0、AH~0和△S~0;(3)测定了石墨/水/环己烷和石墨/水/空气的接触角与表面活性剂浓度的关系.分析所得结果,可得结论:在炭黑/水或石墨/水界面上,Triton型表面活性分子形成单分子吸附层,分子以憎水的iso-C_8H_(17)C_6H_4基团附着在表面,而以亲水的聚氧乙烯链伸入水相的方式取向;在炭黑/环己烷或石墨/环己烷界面上,分子是通过聚氧乙烯链吸附到表面上的,当浓度增加时分子在表面上可能通过聚氧乙烯链间的相互作用而发生聚集,即可能形成表面反式胶团.     

吸附与润湿I非离子表面活性剂在SiO2/水和SiO2/环己烷界面的吸附层结构

根据Triton X-100在硅胶/水和硅胶/环己烷界面以及Triton x-305在硅胶/水界面的吸附结果,提出了两种简单的吸附模型,在硅胶/环己烷界面上形成的是单分子吸附层,吸附质分子以乙氧基链躺在硅胶表面上而以碳氢链伸入环己烷的方式取向.在硅胶/水界面上形成的是双分子吸附层,第一层中的分子以乙氧基链躺在硅胶表面上而以碳氢链朝外;第二层中的分子取向相反,即以碳氢链朝向第一层分子形成的碳氢链层,而以乙氧基链伸进水中,对石英玻璃-水-环己烷的接触角(θ水)的测定结果表明,θ水随水相中表面活性剂浓度的增加先升后降,进一步支持了上述吸附模型。     

吸附与涧湿 Ⅰ.非离子表面活性剂在SiO_2/水和SiO_2/环已烷界面的吸附层结构

根据Triton X-100在硅胶/水和硅胶/环已烷界面以及TritonX-305在硅胶/水界面的吸附结果,提出了两种简单的吸附模型。在硅胶/环己烷界面上形成的是单分子吸附层,吸附质分子以乙氧基链躺在硅胶表面上而以碳氢链伸入环己烷的方式取向。在硅胶/水界面上形成的是双分子吸附层,第一层中的分子以乙氧基链躺在硅胶表面上而以碳氢链朝外;第二层中的分子取向相反,即以碳氢链朝向第一层分子形成的碳氢链层,而以乙氧基链伸进水中。对石英玻璃-水-环己烷的接触角(θ_水)的测定结果表明,θ_水随水相中表面活性剂浓度的增加先升后降,进一步支持了上述吸附模型。     

自溶液中的吸附 ⅩⅢ.硅胶自环己烷-正脂肪醇和水-正脂肪醇中吸附Triton X-100

测定了硅胶和活性炭自水、环己烷和正丁醇中吸附Triton X-100的等温线。提出了TritonX-100在硅胶-环己烷界面上形成单分子层,在硅胶-水界面上形成双分子层的吸附模型。测定了硅胶自环己烷-正脂肪醇(C_2,C_4,C_8和C_(12))和水-正脂肪醇(C_2和C_4)混合溶剂中吸附Triton X-100的等温线。自环己烷-正脂肪醇中吸附时,醇的烃链越短,浓度越大,降低Triton X-100的吸附作用越显著。自水-正脂肪醇中吸附时,正丁醇降低Triton X-100的吸附作用比乙醇时更显著。但当Triton X-100的浓度较低时,正丁醇(0.5 mol·din~(-3))的存在却使TritonX-100的吸附有所增加。     

支链化甜菜碱和阳离子表面活性剂在聚甲基丙烯酸甲酯表面的吸附及其润湿性质

利用座滴法研究了两性离子表面活性剂支链十六烷基(聚氧乙烯)_n醚羟丙基羧酸甜菜碱(n = 0, 3)和阳离子表面活性剂支链十六烷基(聚氧乙烯)_n醚羟丙基季铵盐溶液在聚甲基丙烯酸甲酯(PMMA)表面上的润湿性质,考察了表面活性剂类型、结构及浓度对接触角的影响趋势。研究发现,表面活性剂浓度低于临界胶束浓度(cmc)时,分子通过氢键以平躺的方式吸附到PMMA界面,亲水基团靠近固体界面, PMMA表面被轻微疏水化;表面张力和粘附张力同时降低,导致此阶段接触角随浓度变化不大。浓度高于cmc时,表面活性剂通过疏水作用吸附,亲水基团在外, PMMA表面被明显亲水改性,接触角随浓度升高显著降低。由于具有相同的支链烷基,表面活性剂类型变化和聚氧乙烯基团的引入对接触角影响不大。     

自溶液中的吸附——XIV.硅胶自Triton X—100和几种烷基硫酸钠的混合水溶液中的吸附

本文测定了硅胶自水中对Triton X-100的吸附,其吸附等温线呈不平常的S型,极限吸附量相当于1.00nm~2/分子,约比气液界面上的大一倍。加入0.1M的NaCl和改变pH对吸附无可察觉的影响。硅胶基本不吸附烷基硫酸钠。当Triton X-100的浓度低于其在混合溶液中的CMC时,烷基硫酸钠的存在对Triton X-100的吸附无影响;但其极限吸附量则随烷基硫酸钠浓度的增大而降低;烷基硫酸钠的碳氢链越长,这种效应就越显著。根据相分离模型,以及只有分子状态的Triton X-100被吸附而胶团不被吸附的假设,可以解释所得结果。     

不对称Gemini表面活性剂在气/液界面的吸附动力学

合成出由1个亚甲基联接羟基和季铵基头基, 且带两根不同长度烷烃链的不对称Gemini表面活性剂CmH2m+1OCH2CH(OH)CH2N+(CH3)2C8H17Br(记为CmOhpNC8, m=10, 12, 14). 用最大泡压法研究了浓度低于临界胶团浓度时, CmOhpNC8在气/液界面上的吸附动力学. 结果表明, CmOhpNC8表现出很明显的吸附动力学效应. CmOhpNC8向新鲜气/液界面吸附时由扩散过程控制; 当界面上已具有一定吸附量时, 显示出吸附能垒Ea. 随着烷烃链的增长而明显降低, 表明长烷烃链的分子到达亚层后更容易插入表面层,这被归结为分子烷烃链间的疏水相互作用随着链增长而增强所致.     

亚砜类非离子型表面活性剂在固/液界面上的吸附——Ⅰ.硅胶/水溶液界面上的吸附

表面活性剂在固/液界面上的吸附在多种应用中起重要作用,因而引起了广泛的兴趣.就已有的工作来看,对非离子型表面活性剂在固/液界面吸附的研究比对离子型表面活性剂所作的同类研究要少.其中绝大部分研究的是聚氧乙烯型表面活性剂,并且多数是用工业产品.它实际上是具有不同乙氧基聚合度或不同大小疏水基的混合物.这使得说明固/液界面吸附规律和机制更为困难.再者,聚氧乙烯型表面活性剂虽有应用广泛的优点,但因聚氧乙烯链可能采取伸展或不同程度卷曲的构型,也给理论研究带来附加的复杂因素.此外,对同一种结构确定的非离子型表面活性剂在各种吸附剂上吸附的系统研究还很少见.所以,我们选择亲水基和疏水基的组成和结构都确定的亚砜类化合物作一系列吸附研究.     

阳离子和两性表面活性剂在聚甲基丙烯酸甲酯表面的吸附行为

利用座滴法研究了阳离子表面活性剂十六烷基醚羟丙基季铵盐(C₁₆PC)、十六烷基聚氧乙烯醚羟丙基季铵盐(C₁₆(EO)₃PC)和两性离子表面活性剂十六烷基醚羟丙基羧酸甜菜碱(C₁₆PB)、十六烷基聚氧乙烯醚羟丙基羧酸甜菜碱(C₁₆(EO)₃PB)溶液在聚甲基丙烯酸甲酯(PMMA)表面上的润湿性质, 考察了表面活性剂类型及浓度对接触角的影响趋势. 研究发现: 低浓度条件下表面活性剂分子可能以平躺的方式吸附到固体界面, 且亲水基团靠近固体界面, PMMA表面被轻微疏水化; 在高浓度时则通过Lifshitz-van der Waals 作用吸附, 亲水基团在外, PMMA表面被亲水改性. 聚氧乙烯基团(EO基团)的引入对阳离子表面活性剂的接触角影响不大; 而含有聚氧乙烯基团的两性离子表面活性剂在PMMA界面上以类似半胶束的聚集体吸附, 大幅度降低接触角.     

非离子表面活性剂Triton X-100溶液在不同生长期小麦叶片表面的润湿行为

选择不同生长期小麦叶片,利用座滴法研究了非离子表面活性剂Triton X-100在小麦叶片表面接触角,考察浓度对接触角、粘附张力、固-液界面张力及润湿状态的影响。研究表明,在低浓度下,表面活性剂分子在气-液界面吸附量(ΓLV)和固-液界面吸附量(Γ'SL)相似,但吸附量较少形成了不饱和吸附层,接触角保持不变,其润湿状态为Cassie-Baxter状态;当浓度进一步增加,液滴突破叶片表面三维立体结构中存在的钉扎效应,取代空气层而处于Wenzel状态,接触角陡降,同时Γ'SL/ΓLV远大于1;当浓度超过临界胶束浓度(CMC)时,表面活性剂分子在气-液界面和固-液界面形成饱和吸附层,并产生毛细管效应,使溶液在小麦叶片三维立体结构中产生半渗透过程,此时接触角保持不变。     

Wetting and adsorption: II. Adsorption of Triton X-100 and Triton X-305 onto carbon black from water and cyclohexane solutions

The adsorption isotherms of nonionic surfactants Triton X-100 and Triton X-305 from water and cyclohexane on carbon black have been determined at 15 and 30°C. The Langmuir-type and BET-type isotherms are obtained for adsorption of Triton X-100 and Triton X-305 from water and cyclohexane respectively. Both the contact angles of water for graphite/water/air and graphite/water/cyclohexane decrease monotonously with increasing surfactant concentration. From these results, it is proposed that the adsorption of Triton X-100 and Triton X-305 on carbon black or graphite from water is monolayer. For the adsorption from cyclohexane solutions, the ethyleneoxide group of the surfactant molecules may be adsorbed onto the polar spot at the surface of carbon black, and the hydrophobic group of adsorbed molecules may direct toward the liquid phase or attaches to the nonpolar surface region around the polar spot. As the concentration increases, the ethylene oxide groups of the adsorbed molecules can be aggregated with each other via polar interactions to form hemi-reversed micelle.     

Adsorption Kinetics of Some Polyethylene Glycol Octylphenyl Ethers Studied by the Fast Formed Drop Technique

The adsorption kinetics of Triton X-100 and Triton X-405 at solution/air and solution/hexane interfaces is studied by the recently developed fast formed drop technique. The dynamic interfacial tension of Triton X-100 and Triton X-405 solutions against hexane has been measured without preequilibration of the water and oil phases. It is found that the dynamic interfacial tension of Triton X-100 solutions passes through a minimum. This strange behavior is attributed to partial solubility of the surfactant in hexane. Such minima of the dynamic interfacial tension of Triton X-405 solutions have not been observed, which correlates well with the solubilities of both surfactants in hexane reported in the literature. The dynamic surface tension of solutions of both surfactants and the dynamic interfacial tension of Triton X-405 solutions are interpreted by the Ward and Tordai model for diffusion controlled adsorption. It is shown that proper interpretation of the experimental data depends on the type of isotherm used. More consistent results are obtained when the Temkin isotherm is used instead of the Langmuir isotherm. The results obtained with Triton X-100 at the solution/air interface confirm that the adsorption of this surfactant occurs under diffusion control. The adsorption of Triton X-405 at solution/air and at solution/hexane interfaces seems to occur under diffusion control at short periods of time, but under mixed (diffusion-kinetic) control at long periods of time. A hypothesis is drawn to explain this phenomenon by changes in the shape of the large hydrophilic heads of Triton X-405 molecules. Copyright 2000 Academic Press.     

Adsorption Behavior and Mechanisms of Surfactants by Farmland Soils in Northeast China

The adsorption of two nonionic surfactants polyethylene glycol tert-octylphenyl ether Triton X-100 (TX-100), polyoxyethylene lauryl ether(Brij35) and an anionic surfactant sodium dodecyl benzene sulfonate(SDBS) by two soils(S1, S2) of different natures and their respective organic-matter-extracted samples(S3, S4) were investigated. These adsorption isotherms show different adsorption stages of different types of surfactants by soils. The data fitted Langmuir equation very well. The adsorption maximum capaci...     

亚砜类非离子型表面活性剂在固/液界面上的吸附(III)碳黑/水溶液界面上的吸附

研究了癸基甲基亚砜在水溶液/炭黑界面上的吸附及温度、加盐(Nacl)、加酸(HCl)对吸附的影响.吸附等温线呈完整的双平台形式. 第一平台吸附量～6 μmol·m~(-2); 第二平台吸附量,即极限吸附量, 为42—48 μmol·m~(-2). 随着吸附增加, 炭黑/水溶液接触角下降, 润湿性, 悬浮性改善.应用两阶段吸附模型和吸附等温线通用公式可以对实验结果作定性和定量的解释. 提供了吸附热力学数据. 指示吸附第二阶段是与体相中表面活性剂胶团化作用相似的熵驱动过程。     

Wetting and adsorption: I. The structure of adsorbed layer of nonionic surfactants at SiO2/water and SiO2/cyclohexane interface

Based on the adsorption of Triton X-100 on silica/water and silica/cyclohexane interfaces and the adsorption of Triton X-305 on silica/water interface, two adsorption models have been proposed. On silica/cyclohexane interface, the adsorption of Triton X-100 is monomolecular layer. The molecules in the monolayer are presumed to be attached to the silica surface by their EO chain such that their hydrocarbon chain are exposed to the cyclohexane phase. On silica/water interface, the adsorption of Triton X-100 or Triton X-305 is bimolecular layer. The surfactant molecules orientated in the first layer are similar with that on the silica/cyclohexane interface. The molecules in the second layer are postulated to adsorb on those of the first in the opposite orientation, with EO chain directed toward the adsorption medium. The contact angle of quartz-water-cyclohexane (θ_W) as a function of the concentration of Triton X-100 and Triton X-305 in water has been measured with quartz plate employing the captive drop (cyclohexane) technique. The observed θ_W (measured through water) rose from < 10° to a maximum of about 120° for Triton X-100 and of about 40° for Triton X-305 as the concentration of surfactant in water increased, and then fell, as the concentration increased further. The results are consistent with the proposed adsorption models.     

Adsorption of cationic and nonionic surfactants on a SiO<Subscript>2</Subscript> surface from aqueous solutions: 1. Adsorption of dodecylpyridinium bromide and Triton X-100 from individual solutions

Adsorption of cationic surfactant dodecylpyridinium bromide and nonionic surfactant Triton X-100 from aqueous solutions on the surface of SiO₂ particles is studied at various pH values (3.6, 6.5, and 10). The data on the adsorption are compared with the data on the wetting of quartz plates by solutions of these surfactants. Adsorption of both studied surfactants on the SiO₂ surface is greatly dependent on solution pH. The mechanism of adsorption of the cationic surfactant is shown to be changed when passing to the alkaline pH region. Triton X-100 does not demonstrate a substantial change in the adsorption mechanism in the pH range from 3.6 to 10.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 274–280.Original Russian Text Copyright © 2005 by Kharitonova, Ivanova, Summ.     

Adsorption and Micellization in Solutions of Dodecylpyridinium Bromide–Nonionic Surfactant Mixtures

Dependences of the surface tension of aqueous solutions of cationic (dodecylpyridinium bromide) and nonionic (Tween 80, Triton X-100) surfactants and their mixtures on total surfactant concentration and solution composition were studied. The values of critical micellization concentration (CMC) and excess free energy of adsorption were determined from tensiometric measurements. Based on Rubingh–Rosen model (approximation of the theory of regular solutions), the compositions of micelles and adsorption layers at the solution–air interface as well as parameters of interaction between the molecules of cationic and nonionic surfactants were calculated for the systems indicated above. It was established that, in the case of surfactant mixtures with considerable difference in the CMCs, the micelles of individual surfactant with lower CMC value are formed. The effect of negative deviation from the ideality during the adsorption of surfactants from mixed solutions at the solution–air interface was disclosed. It was shown that the interaction energy depends significantly on the composition of mixed systems.     

Adsorption of nonionic surfactant triton X-100 on solids from aqueous and nonaqueous solutions

The adsorption of nonionic surfactant Triton X-100 on quartz sand and methylated quartz sand from water and toluene was investigated by means of spectrophotometry, the radiotracer technique, and wetting angle measurements.     

Experimental observations on the scaling of adsorption isotherms for nonionic surfactants at a hydrophobic solid-water interface

The self-assembly of nonionic surfactants in bulk solution and on hydrophobic surfaces is driven by the same intermolecular interactions, yet their relationship is not clear. While there are abundant experimental and theoretical studies for self-assembly in bulk solution and at the air-water interface, there are only few systematic studies for hydrophobic solid-water interfaces. In this work, we have used optical reflectometry to measure adsorption isotherms of seven different nonionic alkyl polyethoxylate surfactants (CH3(CH2)I-1(OCH2CH2)JOH, referred to as CIEJ surfactants, with I = 10-14 and J = 3-8), on hydrophobic, chemically homogeneous self-assembled monolayers of octadecyltrichlorosilane. Systematic changes in the adsorption isotherms are observed for variations in the surfactant molecular structure. The maximum surface excess concentration decreases (and minimum area/molecule increases) with the square root of the number of ethoxylate units in the surfactant (J). The adsorption isotherms of all surfactants collapse onto the same curve when the bulk and surface excess concentrations are rescaled by the bulk critical aggregation concentration (CAC) and the maximum surface excess concentration. In an accompanying paper we compare these experimental results with the predictions of a unified model developed for self-assembly of nonionic surfactants in bulk solution and on interfaces.     

Dynamic Interfacial Tension of Surfactant Mixtures at Liquid-Liquid Interfaces

Dynamic interfacial tensions for surfactant mixtures at liquid-liquid interfaces were obtained with a drop volume tensiometer. The surfactants tested were Triton X-100, palmitic acid, and Span 80 at both the water-hexadecane and water-mineral oil interfaces. Two-surfactant mixtures were examined with the surfactants initially dissolved in different phases to minimize bulk-phase interactions. For concentrations below the CMC, it was found that the adsorption kinetics of palmitic acid and Triton X-100 mixtures were dominated by the latter surfactant. Apparent diffusion coefficients were obtained for Triton X-100 both in the absence and in the presence of palmitic acid. These values were largely insensitive to the presence of palmitic acid. For mixtures of Span 80 and Triton X-100, the adsorption kinetics were found to be influenced significantly by both surfactants. In this case, relative changes in surfactant concentrations affected the dynamic interfacial tension of the mixed system. A previously proposed multicomponent adsorption model described the dynamic interfacial tension adequately at low concentrations of Triton X-100, when desorption could be neglected. At higher concentrations, modifications were needed to account for solubilization into the oil phase. These corrections allowed the model to describe the long time adsorption quite well. However, predicted values of short time interfacial tensions were overestimated, likely due to a synergistic interaction of the two surfactants. Copyright 1999 Academic Press.