Effect of Inorganic Additives on a Conventional Anionic–Nonionic Mixed Surfactants System in Aqueous Solution

The interaction between an anionic surfactant (sodium dodecyl sulfate) and a nonionic surfactant [polyoxyethylene (9.5) octyl phenyl ether] in aqueous salt solution was investigated using the surface tension method. The critical micelle concentration values were determined for the individual surfactants and their corresponding mixtures. The interaction parameter between the surfactants in the mixed micelles, the activity and activity coefficients in the mixed micelles, and the thermodynamic parameters were calculated using various approaches, viz., Clint, Rubingh, and Maeda models. It was observed that the critical micelle concentration of the mixed surfactants system reveals little deviation from ideality.     

Micellar and Interfacial Behavior of Mixed Systems Containing Glycoside‐Based Surfactant and Cationic Didecyldimethylammonium Chloride

The behavior of binary mixtures of glycoside‐based surfactants in combination with didecyldimethylammonium chloride (DDAC) has been studied using surface tension measurements. The three glycoside‐based surfactants are nonionic decyl glycoside (APG), nonionic dodecyl ethoxy glycoside (AEG) and anionic disodium dodecyl ethoxy glycoside citrate (AEG‐EC). Lower critical micelle concentrations (CMC) and minimum molecular area (A_min) values were obtained for all the mixed systems. The pC₂₀ values of APG/DDAC and AEG‐EC/DDAC mixtures are larger than pure surfactants, while the values of AEG/DDAC are between those of AEG and DDAC. Interactions between the monomers have also been investigated by determining the interaction parameters. Negative β_m and β_s values indicate synergistic effects in both the mixed micelle and monolayer formation. For different mixed systems, interaction in the mixed micelle formation becomes stronger in the order: AEG/DDAC < AEG‐EC/DDAC < APG/DDAC. The degree of synergism in the mixed monolayer formation follows the order: AEG/DDAC < APG/DDAC < AEG‐EC/DDAC.     

Comparative study on foaming and foam stability of multiple mixed systems of fluorocarbon,hydrocarbon, and amino acid surfactants

This study focuses on the effect of amino acid surfactant (sodium lauroyl glutamate [SLG]) on foam properties of a mixture of fluorocarbon (FS-50) and hydrocarbon (APG0810) surfactants. The molecular interactions, foamability, and foam stability of the surfactant solutions are systematically studied. The results show that SLG has stronger ability to lower surface tension of water compared to APG0810, but worse that than FS-50, and to adsorb onto gas/liquid interface in mixed solutions with FS-50 compared to APG0810. The addition of SLG increased foamability of APG0810/FS-50 mixed solution, and decelerated foam drainage and coarsening of individual APG0810, individual FS-50, and mixture of APG0810/FS-50 solutions. The mixture of SLG/FS-50 exhibited the higher foamability and foam stability than the frequently used critical component of the new developed AFFF, the mixture of APG0810/FS-50. This study can provide guidance for the scientific application of amino acid surfactants in the development of environmentally friendly firefighting foams.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Solubilization and adsolubilization of styrene and ethylcyclohexane

Mixtures of anionic and cationic surfactants with single and twin head groups were used to solubilized styrene and ethylcyclohexane into mixed micelles and adsolubilize them into mixed admicelles on silica and alumina surfaces. Two combinations of anionic and cationic surfactants were studied: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), with a single-head cationic surfactant, dodecylpyridinium chloride (DPCl). Mixtures of SDS/PODD showed solubilization synergism (increased oil solubilization capacity) when mixed at a molar ratio of 1∶3; however, the SHD-PDS/DPCl mixture at a ratio of 3∶1 did not show solubilization enhancement over SHDPDS alone. Adsolubilization studies of SDS/PODD (enriched in PODD) adsorbed on negatively charged silica and SHDPDS/DPCl adsorbed on positively charged alumina showed that while mixtures of anionic and cationic surfactants had little effect on the adsolubilization of styrene, the adsolubilization of ethylcyclohexane was greater in mixed SHPDS/DPCl systems than for SHDPDS alone. Finally, it was concluded that whereas mixing anionic and cationic surfactants with single and double head groups can improve the solubilization capacity of micelles or admicelles, the magnitude of the solubilization enhancement depends on the molecular structure of the surfactant and the ratio of anionic surfactant to cationic surfactant in the micelle or admicelle.     

Synthesis and Surface Active Properties of Gemini Cationic Surfactants and Interaction with Anionic Azo Dye (AR52)

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, ¹H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.     

双子表面活性剂的综述

双子表面活性剂是一类新型的表面活性剂,它是由联结基团通过化学键将两个或多个单体表面活性剂连接在一起形成的表面活性剂。由于其优异的性质越来越受到国内外学者的重视。与传统表面活性剂相比较,双子表面活性剂在降低表面张力、聚集生成胶团、Krafft点和临界胶束浓度(CMC)等性能上都明显更加的优异。文章就它的性能和应用等方面进行介绍。     

十二烷基硫酸钠对非离子表面活性剂CM101浊点的影响

研究了阴离子表面活性剂十二烷基硫酸钠(SDS)对非离子表面活性剂CM101浊点的影响。结果表明:当SDS加入量为2%时,CM101的浊点提高到59.6℃,达到农药制剂热稳定性的要求。同时,该混合体系满足非理想二元表面活性剂复配增效的条件,表面张力和临界胶束浓度都有明显降低。     

磺酸盐型双基表面活性剂的合成与表面性能

以壬基酚和甲醛为原料,合成了一种新型的磺酸盐型双基表面活性剂(Gemini-A)。利用元素分析、红外光谱确定了Gemini-A的结构。研究了Gemini-A水溶液的润湿性,比较了Gemini-A与传统表面活性剂的增溶能力。试验结果表明,Gemini-A水溶液具有较低的表面张力(33.51 mN/m)和临界胶束浓度(0.141 mmol/L)及良好的润湿性,显示出了较好的表面性能,具有很强的增溶能力,是符合3次采油要求的表面活性剂。     

非离子型Gemini表面活性剂的性质

Gemini表面活性剂具有的优良表面活性,使之有望作为三次采油用的表面活性剂。用界面张力仪及HAAKERS600流变仪研究了非离子型Gemini表面活性剂的表面活性及流变特性。结果表明,25℃下,氧乙基数(EO数)分别为8,10,12的3种非离子型Gemini表面活性剂8-NP-8、10-NP-10及12-NP-12的临界胶束浓度(cmc)值分别为:0.99,0.15和0.032 mmol/L;非离子型Gemini表面活性剂的表面活性及cmc值受电解质的影响较小;氧乙基数为12的非离子型Gemini表面活性剂可以使亲水及亲油固体表面的接触角明显降低,水润湿性增强;非离子型Gemini表面活性剂溶液的粘度随剪切速率增加基本保持不变,呈现出牛顿流体的特性。     

Surface adsorption in the mixtures of sodium dodecylsulphate and oxyethylenated nonylphenol with different oxyethylenation degrees

The effectiveness of surface adsorption in an aqueous solution of mixtures of surfactants composed of an anionic surfactant, sodium dodecylsulphate, mixed with a nonionic one, polyoxyethylenated nonylphenol, was studied. Their behavior was compared separately. This surface adsorption was characterized by the values of the surface tension at 25°C of the total concentrations below, but near to the critical micelle concentration (CMC) in the mixtures mentioned. These were obtained as a function of different proportions of surfactants in the mixture and different chain lengths of nonionic polyoxyethylenated surfactant. The total surface excess concentrations of the surfactant mixtures and the average of molecular area per surfactant species at the aqueous solution/air interface were calculated. Finally, the values were analyzed vs the above parameters. Presented at the XDCth Meetings of CED/AID, Granada, Spain, March, 1988.     

Wettability alteration and reducing water blockage in tight gas sandstone reservoirs using mixed cationic Gemini/nonionic fluorosurfactant mixtures

The unrecovered hydraulic fracturing fluid will invade the matrix and induce water blockage, creating formation damage and hindering the oil or gas production rate. First, the synergistic effect of cationic Gemini surfactant (MQAS) and nonionic fluorosurfactant (N-2821) mixtures on reducing the surface tension and wettability alteration was investigated in this paper. The critical micelle concentration (CMC) of the surfactant mixture is one or two orders of magnitude lower than that of N-2821 and MQAS, indicating that the MQAS/N-2821 mixtures exhibit an apparent synergistic effect in reducing surface tension. Moreover, the maximal contact angle of MQAS/N-2821 mixtures reached 83.55° at α_N-2821 = 0.5, and the total surfactant concentration of 1 × 10⁻⁴ mol/L due to the adsorption of surfactant. The adsorption mechanism of surfactants on the surface of quartz sand was then examined. The adsorption kinetics is consistent with the pseudo-second-order model at different surfactant concentrations, while the Freundlich model is suitable for describing the adsorption behavior of surfactants on the sandstone surface. This finding indicates that surfactant adsorption is multilayered. The MQAS/N-2821 surfactant mixtures have excellent surfactant activity due to the relationship of the capillary pressure to the surface tension, pore radius, and contact angle; thus, the addition of surfactant mixtures can reduce the liquid saturation effectively. Furthermore, the sequential imbibition experiments indicate that MQAS/N-2821 mixtures alter the wettability of the core plug, which results from the adsorption of surfactants. Compared with brine water, the MQAS/N-2821 mixtures decreased the liquid saturation and increased the permeability recovery ratios of the core plug.     

Synergistic Effect of Mixed Surfactant Systems on Foam Behavior and Surface Tension

Foam and surface tension behaviors of different ionic/nonionic surfactant solutions along with their different combinations have been investigated. Among different surfactants, sodium dodecyl sulfate showed the highest foamability over other surfactants. Mixed surfactant systems were always found to have higher foamability than the individual surfactant. It was also noticeable that nonionic surfactants show good foamability when they combine with anionic and cationic surfactants. In the case of mixed surfactant systems, nonionic/cationic surfactant mixtures showed lower surface tension than nonionic/anionic surfactant mixture due to a synergistic effect.     

Interaction Between Nonionic and Gemini (Cationic) Surfactants: Effect of Spacer Chain Length

The interaction between mixtures of nonionic surfactant polyethylene glycol p-(1,1,3,3-tetramethyl butyl)-phenyl ether and cationic gemini surfactants alkanediyl-α,ω-bis(dimethyldodecylammonium bromide) (12-s-12, where s = 2, 4 and 6) was studied using surface tension and small-angle neutron scattering measurements. Marked interaction was observed for the investigated surfactants mixtures which depend upon the hydrophobic spacer length of the gemini surfactant and also on the fraction of nonionic surfactant in the mixed systems. The results are discussed in terms of interaction parameters calculated according to the theory of regular solutions which uses the critical micelle concentration determined tensiometrically to calculate the molecular interaction parameter and the mole fractions of the two components in the mixed micelles. A relatively high negative molecular interaction parameter value (up to −3.40) obtained for mixtures of nonionic and cationic gemini surfactant indicates a presence of strong attractive interaction in the mixed system that increases with the spacer length of the gemini surfactant. Micellar parameters deduced from small-angle neutron scattering measurements also compliment the surface tension results.     

Effects of surface activity on aquatic toxicity of binary surfactant mixtures

The purpose of this study was to discuss the effects of surface activity on the aquatic toxicity of binary surfactant mixtures comprising anionic, nonionic, and cationic surfactants. Surface tension was measured to determine the cmc (critical micelle concentration), and acute aquatic toxicity tests were conducted on Daphnia magna to obtain 24h-EC(50) (24h 50% effective concentration). TU (toxic unit) was calculated to evaluate the toxicity of the mixture. Most of the surfactant mixtures showed no synergistic increase in the aquatic toxicity. The mixture of anionic/nonionic surfactants showed synergistic interfacial activity with decreasing cmc, but the toxicity did not increase. The surface tension of the mixture at 24h-EC(50) (γ(tox)), which was used as an indicator of the toxic concentration, decreased considerably and TU was >1, indicating decreased toxicity. γ(tox) of the anionic/anionic surfactant mixture decreased when tested with hard water (hardness of 625 ppm). γ(tox) could not be used as a toxic indicator for the anionic/cationic surfactant mixtures because they showed aquatic toxicity before their surface tension began to decrease.     

PEG-Gemini型非离子表面活性剂的合成及应用

以1,12-十二醇、油酸、聚乙二醇（300，400，600，800，1000）为原料合成一系列Gemini型非离子表面活性剂，并采用IR，NMR对产物进行了结构确证。为了评估Gemini型非离子表面活性剂作为注射用增溶辅料的有效性，在表面张力、增溶性以及溶血活性等方面与Tween 80进行了比较。结果表明：二-9(8)PEG1000, 二-8(9)-羟基-十八烷酸十二烷基二醇二酯（PODD-1000）的安全有效指数是Tween-80的13倍，更适用于作为注射剂的增溶辅料。     

Monomer-micelle equilibrium in the diffusion of surfactants in binary systems through collagen films

Three different binary systems (two anionic/nonionic and one anionic/amphoteric) were selected to study the behavior of these mixtures in their diffusion through a collagen film and the formation of micelle aggregates in such systems. The inhibition observed in the surfactant diffusion of anionic/nonionic and anionic/amphoteric binary mixtures through a collagen film, in comparison with that of single surfactants, has been related to the behavior of these binary systems in the micellization process. The surfactant flux in these systems is mainly determined by the monomeric species. The modification of the equilibrium monomers-micelle aggregates shown by these surfactant binary systems could be also associated with the reduction of the irritancy power for such binary systems.     

Synergistic solubilization of decafluorobiphenyl by micelles of fluorocarbon surfactants

Solubilization of decafluorobiphenyl (FBIP) by surfactants in aqueous solution was examined to investigate the properties of micelles composed of surfactants having a per-fluorocarbon chain. Fluorocarbon surfactants solubilize FBIP better than hydrocarbon surfactants. Significant solubilization by fluorocarbon surfactants was observed upon addition of salt. Highly synergistic solubilization of FBIP using surfactant mixtures was also observed for fluorocarbon and hydrocarbon surfactants in the presence of salt. The high solubilization ability of surfactants can be attributed to micelle growth. A simple geometrical consideration of molecular packing in micelles revealed that the characteristic micelle is composed of bulky fluorocarbon chains. The solubilization behavior accompanied by micelle growth would be closely associated with a change in interfacial contact area between the micelle core and bulk water. The behavior of fluorescence intensity of micelle-solubilized FBIP also indicated a change in micropolarity of fluorocarbon micelles accompanied by micelle growth.     

Mixed Micellar and Interfacial Interactions of a Triblock Polymer (EO37PO56EO37) with a Series of Monomeric and Dimeric Surfactants

The mixed micellar and interfacial properties of mixtures of triblock polymer (TBP) with a series of monomeric (dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and cetyltrimethylammonium bromide, and dimeric (dimethylene bis[alkyldimethylammonium bromide], m-2-m, where m = 10, 12, and 14) cationic surfactants were investigated using surface tension and viscosity measurements in aqueous solutions at different temperatures. Various physicochemical properties such as critical micelle concentration, mixed micellar mole fraction, interaction parameter, interfacial, and thermodynamic parameters were evaluated. All the binary mixtures exhibit synergistic interactions which increase with temperature and pass through a minimum with the increase in hydrophobic chain length of the cationic surfactants. The contribution of TBP in mixed micelle formation also increases with the hydrophobic chain length of the surfactants. The interfacial and thermodynamic parameters reveal that the adsorption of the surfactant mixtures at the air–solution interface is more favorable than that of micelle formation and the unfavorable enthalpy changes are overwhelmed by favorable entropy changes. Further, the mixtures of TBP with smaller chain length surfactants show a sharp rise in relative viscosity at higher mole fractions of these surfactants.     

硫酸酯盐双子表面活性剂的合成和界面张力的研究

实验室条件下,以长链羧酸(月桂酸)、聚乙二醇等为主要原料,通过赫尔-乌尔哈-泽林斯基反应等和酯化反应,用醚键加入方式加入联接基团,用浓硫酸加成反应加入硫酸酯键,从而在实验室条件下合成具有特殊结构的双子表面活性剂-GA12-S-12.通过用旋转液滴法测合成的硫酸酯盐阴离子双子表面活性剂的表面张力,测得其临界胶束浓度(CMC)为438 mg/L,临界胶束浓度下表面张力为30.9 mN/m,并对比十二烷基硫酸钠水溶液表面张力,显示GA12-S-12[低聚二醇(α-硫酸酯钠)月桂酸双酯阴离子双子表面活性剂]具有更优的表面活性.进一步配制不同浓度的GA12-S-12表面活性剂溶液,测定它们与长庆五里湾原油的界面张力,效果显示其适用于五里湾区原油采收率的提高.     

GSS362/TX-100复配体系在水中的溶液行为研究

研究了1,3-丙二醇双子琥珀酸二异辛酯磺酸钠(GSS362)和辛基酚聚氧乙烯醚(TX-100)复配物在水中的表面性质和胶束化行为,并对理想混合临界胶束浓度以及混合体系中各组分在表面吸附层和胶束中的组成、相互作用参数和热力学参数进行分析计算。结果表明,复配物在水溶液中不存在协同效应,但是TX-100的加入明显降低了GSS362的临界胶束浓度,混合胶束的形成为自发过程,胶束中GSS362与TX-100分子具有较弱的相互作用,胶束中富含非离子表面活性剂TX-100。