Influence of nonionic surfactant additive on the properties of ionic surfactant solutions

The interaction of sodium dodecyl sulfate with a nonionic surfactant (a block copolymer of ethylene oxide and propylene oxide) has been investigated by the measurement of conductivity, surface tension and viscosity. The break point on the equivalent conductivity-square root of concentration diagram which gives the critical micelle concentration (cmc) of sodium dodecyl sulfate became less definite by the addition of the nonionic surfactant, because of the decrease in conductivity below the cmc and increase above the cmc. The steep decrease in reduced viscosity took place in dilute concentration of sodium dodecyl sulfate solutions. In the surface tension vs. concentration diagram, the concentration at which the two linear portions of the curve intersect represents the cmc. The addition of nonionic surfactant decreases this crossed point of sodium dodecyl sulfate and finally obscures the crossed point. These reults are interpreted in terms of an interaction between sodium dodecyl sulfate and nonionic surfactant.     

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.     

温度及无机盐对LMEE和SDS混合溶液表面张力的影响

通过表面张力的测定,研究了温度和不同无机盐对月桂酸甲酯乙氧基化物(laurylmethylesterethoxylate,简称LMEE)与十二烷基硫酸钠(SDS)复配物表面张力及临界胶束浓度(CMC)的影响。研究表明:混合体系的CMC在很宽的复配比例内出现最低值,25℃、未加无机盐时可使CMC最低降至3 8×10-5mol/L;温度对复配体系表面张力的影响较小,温度上升复配物的CMC略有降低。3种价态无机盐的加入均可使复配物的CMC有所降低,但与单一表面活性剂相比,温度和无机盐对复配物的CMC影响均不大,说明复配体系的抗温变及抗盐能力均有增强。     

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。     

Surfactant precipitation in aqueous solutions containing mixtures of anionic and nonionic surfactants

The salinity tolerance (precipitation phase boundary) is measured for a mixed anionic/nonionic surfactant system above the CMC. For any total surfactant concentration, the salinity tolerance is shown to increase as the percentage of nonionic surfactant in the system is increased. A model is developed which can predict the phase boundaries for the mixed surfactant system from the pure anionic surfactant phase boundary and information about mixed micelle formation. In the model, precipitation is viewed as a solubility product relationship between the anionic surfactant monomer and the total unassociated counterion. The reason that salinity tolerance (or counterion concentration necessary to cause precipitation) increases with addition of nonionic surfactant is that mixed micelle formation reduces the anionic surfactant monomer concentration. For the experimental studies, sodium dodecyl sulfate is the anionic surfactant, a polyethoxylated nonylphenol is the nonionic surfactant, and sodium chloride is the added salt.     

Lipase-mediated synthesis of alkyl ricinoleates and 12-hydroxy stearates and evaluation of the surfactant properties of their sulfated sodium salts

An efficient and simple lipase-mediated synthesis of alkyl ricinoleates and 12-hydroxy stearates was performed by transesterification of methyl ricinoleate/12-hydroxy stearate and various alcohols in a solvent-free system without estolide formation. The reaction conditions were optimized by varying the temperature, pressure, and dosage of lipase. Sulfates of alkyl ricinoleates/12-hydroxy stearates were evaluated for surfactant properties such as surface tension, critical micelle concentration, emulsifying properties, foaming power, and calcium tolerance. The surfactant properties of sulfated alkyl ricinoleates were found to be superior to the sulfated alkyl 12-hydroxy series. The surfactant properties of the above two series of compounds were then compared with sodium dodecyl sulfate, and the properties of sulfated dodecyl ricinoleate and sulfated dodecyl 12-hydroxy stearate were found to be comparable with sodium dodecyl sulfate.     

二元表面活性剂体系微乳液的相行为及热力学研究

用表面张力法研究了苯乙烯基酚聚氧乙烯聚氧丙烯醚嵌段型非离子表面活性剂(PEP)分别与十二烷基硫酸钠(SDS)、十二烷基三甲基溴化铵(CTAB)复配体系分子间的相互作用,并根据测定的临界胶束浓度(CMC)及正规溶液理论计算了复配体系分子间相互作用参数及分子交换能,考察了表面活性剂、助表面活性剂、温度等因素对复配表面活性剂体系微乳液形成过程的相行为及热力学性质的影响。结果表明,二元组分(PEP+SDS)及(PEP+CTAB)复配体系在胶束中和表面吸附层中的都存在较强的增效作用,体系的能量降低,且前者的增效作用大于后者。(PEP+SDS)/正己醇/正庚烷/水微乳液的W/O微乳区域面积最大,温度对该微乳液的相行为影响很小。在此微乳液形成的过程中,助表面活性剂醇从连续油相进入微乳液界面层的标准自由能变化ΔGs0;标准焓变-ΔHs=0,为无热效应过程,ΔGs是由醇分子的混乱度熵变ΔSs决定的。     

Composition of mixed anionic/nonionic surfactant micelles

A proposed method of determining the composition of mixed micelles in equilibrium with monomer of known composition is described. The systems were sodium dodecyl sulfate-polyoxyethylene 23 lauryl ether (Brij 35) in water and in 0.1 M sodium chloride solution at 25°C. This technique applies the Gibbs-Duhem equation to the mixed micelle, which is treated as a pseudophase. This proposed methodology which needs only critical micelle concentration data as a function of monomer composition, is applied to an anionic/nonionic surfactant pair. The calculated monomer-micelle equilibrium is found to be very similar to the much-used regular solution for nonideal systems.     

Influence of sodium dodecyl sulfate on the characteristics of bovine serum albumin solutions and foams

Results from surface tension measurements on mixed solutions of the protein bovine serum alburnin (BSA) and an anionic surfactant (SDS: sodium dodecyl sulfate) suggested that at an air-liquid interface, adsorption was affected by the protein-surfactant interaction and by the relative concentration of each component in solution. Two plateaus corresponding to the critical aggregation concentration (CAC) and the critical micelle concentration (CMC) of SDS, respectively, were observed in the surface tension isotherms of SDS in the presence of BSA. The CAC and CMC depended on the concentration of BSA. Effects of SDS concentration on the conformational changes of BSA were investigated by Fourier transform-Raman spectroscopy. The results showed that the contents of α-helix decreased while the contents of random coil increased. The presence of the anionic surfactant SDS had a negative influence on the way that proteins adsorb at an air-liquid interface, leading to the change of behavior of protein-stabilized film.     

一种含氟烷基磷酸酯类氟碳表面活性剂的复配研究

研究了含氟烷基磷酸单酯类表面活性剂[分子式为H(CF2)6CH2OPO(ONa)2,记为DFH-PS]与无机盐和普通碳氢表面活性剂的复配性能,研究结果表明,DFH-PS水溶液最低表面张力为23.73 mN/m;当NaCl浓度为0.2 mol/L时,可使DFH-PS水溶液最低表面张力下降到21.62 mN/m;阴离子碳氢表面活性剂十二烷基硫酸钠(SDS)对该含氟表面活性剂影响显著,当n(DFH-PS)∶n(SDS)=5∶1时,可使水溶液表面张力在很低浓度时降至22.22 mN/m;与非离子表面活性剂辛基酚聚氧乙烯(10)醚(OP-10)混合,当n(DFH-PS)∶n(OP-10)=8∶1时,可使水溶液表面张力降至27.0 mN/m。     

两性/阴离子表面活性剂复配体系性能研究

采用环氧氯丙烷与磷酸二氢钠反应制备中间体,再与十二叔胺反应,制备甜菜碱型磷酸酯两性表面活性剂,并与十二烷基苯磺酸钠(SDBS)进行复配。测定复配前后产品的表面张力、临界胶束浓度、泡沫稳定性和乳化能力等性能。结果表明,在最佳合成工艺条件下,甜菜碱型磷酸酯两性表面活性剂的表面张力为30 mN/m,临界胶束浓度为7.98 g/L。对于复配体系,当甜菜碱型磷酸酯表面活性剂与SDBS以质量比6∶4进行复配时增效作用最好,其表面张力为23 mN/m,临界胶束浓度为4.84 g/L,对松节油的乳化性能较好。     

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.     

Synergistic Behavior Between Zwitterionic Surfactant α-Decylbetaine and Anionic Surfactant Sodium Dodecyl Sulfate

Here, we present experimental surface tension isotherms of mixed solutions of a zwitterionic surfactant α-decylbetaine (DB) and an anionic surfactant sodium dodecyl sulfate (SDS) in different molar ratios. These mixed solutions show a composition dependency with respect to both surface tension effectiveness and critical micelle concentration. The pseudo-regular solution theory has been used to evaluate the interaction parameters in the micelle, β ^m and at the surface, β ^s. The results revealed that the mixed solutions of DB/SDS behave synergistically in both surface tension reduction effectiveness and mixed micelle formation at all mole fractions investigated. The values of adsorption area per surfactant molecule at air/solution interface were estimated, which provides some useful information on evaluating the interaction between DB and SDS in mixed adsorbed monolayers. The solubilization behaviors of toluene in DB/SDS mixed solutions were also investigated to help in understanding the structure of mixed micelles of DB and SDS.     

不同NaCl浓度下十二烷基硫酸钠的理化参数和热力学行为

为了更好地研究不同NaCl浓度对阴离子表面活性剂胶束理化性质和结构稳定性的影响,以阴离子表面活性剂十二烷基硫酸钠（C₁₂H₂₅SO₄Na）在不同温度下的临界胶束浓度为基础,分别测试并得出了不同NaCl浓度与不同温度作用下溶液的表面张力、泡沫半衰期和黏度变化规律。在此基础上通过分析得出NaCl作用下溶液的黏度活化能、标准熵变、标准焓变等热力学参数及变化规律。结果表明：C₁₂H₂₅SO₄Na降低表面张力的效率由温度效应和盐效应共同控制,随着温度的升高,温度效应发挥的作用越来越大;黏度最大值所对应的表面活性剂浓度为该温度和NaCl浓度下的临界胶束浓度;C₁₂H₂₅SO₄Na胶束化过程的影响随着温度的升高由熵驱动逐渐转化为焓驱动,这种转化过程随着NaCl浓度的升高越来越提前。掌握温度和NaCl浓度的耦合作用对C₁₂H₂₅SO₄Na理化性质的影响,以期为进一步研究其热力学行为奠定基础。     

Solution properties of mixed surfactant system sodium dodecyl sulfate and alkyl polyoxyethylene ether system

The effect of oxyethylene groups in a nonionic surfactant on the solution properties of anionicnonionic systems is described; these systems are sodium dodecyl sulfate (SDS)—hexadecyl polyoxyethylene ethers (C₁₆POE_n, where n=10, 20, 30 and 40). The degree of ionic dissociation of the mixed micelles decreases with increasing numbers of oxyethylene groups in the nonionic surfactant. As polyoxyethylene chain lengths increase, the electrical conductivities of the mixed surfactant solutions decrease, in spite of the decrease in activation energy for conduction. The radius of the mixed micelle with the electric double layer is larger for a nonionic surfactant having a shorter polyoxyethylene chain length than for one having a long polyoxyethylene chain. This may be attributed to the fact that the mixed micelle is formed more easily by a nonionic surfactant with a shorter polyoxyethylene chain length than by one with a longer chain.     

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.     

Properties of aqueous solution of sodium cyclododecyl sulfate

Sodium cyclododecyl sulfate was prepared from cyclododecyl alcohol and chlorosulfonic acid to investigate the physical and surface active properties of the surfactant. Its Krafft point, critical micelle concentration (CMC), surface tension, emulsifying power, wetting time and dispersing power were examined and compared with those of sodium dodecyl sulfate which has a linear structure and contains the same number of carbon atoms in the hydrophobic portion. The sodium cyclododecyl sulfate, in contrast to the sodium dodecyl sulfate, had a higher (about two times) Krafft point, much larger (about 10 times) CMC, showed the same excellent wetting property, but exhibited lower emulsifying power. Also the sodium cyclododecyl sulfate is more insoluble (as shown by the Krafft point) than the sodium dodecyl sulfate, while calcium ion stability of the cyclododecyl sulfate surfactant is greater than that of the linear anionic surfactant.     

Physicochemical Properties of Novel Phosphobetaine Zwitterionic Surfactants and Mixed Systems with an Anionic Surfactant

A series of novel zwitterionic phosphobetaine (PPBT) surfactants were synthesized using long chain fatty alcohol, epichlorohydrin, dimethylamine and sodium dihydrogen phosphate as raw materials. The physicochemical properties of the phosphobetaine surfactants such as isoelectric point, foaming, surface tension, critical micelle concentration (CMC) and Krafft point were measured. Low CMC and surface tension values indicated the surface activities of the phosphobetaine surfactants were quite excellent. The CMC and surface tension values of PPBT/SDS mixed systems were determined. It was found both of CMC and surface tension values decreased compared with single surfactant system because of the association between dodecyl sulfate anions and cationic groups in phosphobetaine by electrostatic attraction.     

Contact angle of surfactant solutions on precipitated surfactant surfaces. II. Effects of surfactant structure,presence of a subsaturated surfactant,pH, and counterion/surfactant ratio

The contact angle of a saturated aqueous surfactant solution on the precipitate of that surfactant was measured by using the sessile drop method. The sodium and calcium salts of alkyl sulfates (C₁₂, C₁₄, and C₁₈) had advancing contact angles higher than those of alkyl trimethylammonium bromides (C₁₄, C₁₆, and C₁₈). The measured advancing contact angles for several surfactant solutions did not substantially change with varying surfactant/counterion ratios; therefore, the precipitating counterion concentration (e.g., water hardness) had little effect on the wettability. The contact angles of fatty acid (C₁₂ and C₁₆) solutions did not show any dependence on pH between a pH of 4 and 10. The contact angles of saturated calcium dodecanoate (CaC₁₂) solutions containing a second subsaturated surfactant (sodium dodecyl sulfate: NaDS) decreased with increasing NaDS concentrations until reaching the critical micelle concentration of the surfactant mixture. These results show that the second suractant can act as a wetting agent in this saturated surfactant system. Application of Young’s equation to contact angles showed that the solid/liquid surface tension can change substantially with surfactant concentration and be important in addition to the liquid/vapor surface tension in reducing contact angles. Application of the Zisman equation results in a “critical” surface tension for the CaC₁₂ or soap scum of 25.5 mN/m, which is comparable to difluoroethene.     

一种全氟辛基两性磷酸酯氟碳表面活性剂的复配研究

对一种全氟辛基两性磷酸酯氟碳表面活性剂协同作用进行了研究,考察了该表面活性剂与无机盐、阴离子碳氢表面活性剂、阴离子氟碳表面活性剂和非离子氟碳表面活性剂的复配性能,并对结果进行了讨论。研究表明:该两性磷酸酯氟碳表面活性剂自身表面张力为24.0 mN/m;电解质氯化钠对该两性磷酸酯氟碳表面活性剂影响显著,可使表面张力下降到22.4 mN/m;阴离子碳氢表面活性剂十二烷基硫酸钠(SDS)可使表面张力降至21.4 mN/m;阴离子氟碳表面活性剂全氟丁基磺酸钾和四乙基全氟辛基磺酸铵分别使表面张力降至20.9 mN/m和20.2 mN/m;而非离子氟碳表面活性剂N-乙基-N-聚氧乙烯(9)醚-全氟辛基磺酰胺能使表面张力降至20.9 mN/m。