FORMATION OF MULTIPLE EMULSIONS IN A FOUR-COMPONENT SYSTEM CONTAINING NONIONIC SURFACTANTS

ABSTRACT

W/O/W and O/W/O multiple emulsions have been found in systems consisting of water, light mineral oil, and two nonionic surfactants (Span 80 and Tween 20).No specific order of addition of the components or pre-mixing was followed. Following gentle agitation at 25°, 35° and 45° for 48?hours, W/O/W emulsions were found at water contents above 30%, while 0/W/O emulsions generally appeared below 60% water.W/0 and 0/W emulsions, micellar phases and liquid crystalline phases were also observed at various compositions. The multiple emulsion regions decreased in size as temperature increased and the areas and positions of the other phases were also temperature dependent.     

MICELLE FORMATION BY ANIONIC AND CATIONIC SURFACTANTS IN AQUEOUS 18-CROWN-6 ETHER,P-CYCLODEXTRIN,AND 1,10-PHENANTHROLINE SOLUTIONS AT DIFFERENT TEMPERATURES

The conductances of sodium perfluorooctanoate (SPFO), sodium dodecylsulphate (SDS), dodecyltrimethylammonium bromide (DTAB), and tetradecyltrimethylammonium bromide (TTAB) in 18-crown-6 ether + water (CR+W), p-cyclodextrin + water (CY+W), and 1,10-phenanthroIine + water (Phen+W) mixtures with fixed 4 mM of each additive were determined over the temperature range of 5-55 °C. The conductivity plots for all the surfactants showed single break from which the critical micellization concentration (cmc) and degree of micelle ionization (x) were computed. From the pre and the post micellar slopes of the conductivity curves, the equivalent conductivities of the monomeric (Aass) and the micellar states (Amjc), respectively, were calculated and discussed with respect to the surfactant-additive complexation. It was observed that the micelle formation of all the ionic surfactants irrespective of the nature of their head groups were delayed in CYC+W in comparison to that in CR+W and Phen+W systems over the temperature range studied. The micelle formation of SPFO and SDS in CR+W and Phen+W systems showed stabilization of the respective micelles due to the adsorption of Na⁺-CR and Na+-Phen complexes at the micelle solution interface in comparison to that of DTAB and TTAB.     

ADSORPTION AND ASSOCIATION IN BINARY MIXTURES OF CATIONIC SURFACTANTS

The adsorption and solution properties of cationic surfactants dodecylammonium chloride, tetradecylammonium chloride, and hexadecylammonium chloride, as well as hexadecyltrimtehylammonium bromide in pure and mixed states, were studied by surface tension and conductance measurements. The surfactants mixed non-ideally in both mixed monolayer and in the mixed micelles. The regular solution theory was used for evaluating the non-ideal interactions between molecules in adsorbed and micellar states. Similar values of the mixed monolayer and mixed micelle molecular interaction parameters in a mixture imply the molecules at the interface and in the mixed micelle have similar interactions. No synergism in surface tension effectiveness was observed. The adsorbed film at the air/water interface and mixed micelles were richer in more surface-active component.     

PHASE AND INTERFACIAL TENSION BEHAVIOR OF NONIONIC SURFACTANTS

It is verified that a 1:1 correspondence exists between the sizes of a stable emulsion droplet prior to and subsequent to solidification through a chemical reaction.     

烷基磷（膦）酸萃取剂钠盐与非离子表面活性剂AEO_9混合体系胶团的形成和分子间的相互作用

本文研究了烷基磷（膦）酸萃取剂钠盐ＮａＥＨＥＨＰ，ＮａＤＴＭＰＰ，Ｎａ_２（ＭＥＨＰ）与非离子表面活性剂ＡＥＯ_９以不同比例复配后水溶液胶团的形成及分子间的相互作用，结果表明混合胶团的形成使ＣＭＣ大大降低。分子间在胶团中的相互作用强弱为：Ｎａ_２（ＭＥＨＰ）体系＞ＮａＤＴＭＰＰ体系＞ＮａＥＨＥＨＰ体系，分子间在表面层的吸引作用小于同体系分子间在胶团中的相互作用，这一结果有利于混合胶团的形成。     

正离子表面活性剂与负离子表面活性剂在水溶液中的相互作用

本工作研究了碳氢链较短的溴化辛基三甲铵(简写为C₈NMe₃Br)及辛基硫酸钠(简写为C₈SNa)混合水溶液的一些表面化学性质:在表面及“油-水”界面上的混合吸附、在表面上的气泡寿命和在界面上的液滴寿命以及溶液在石蜡表面上的润湿性能.从这些性质了解正、负离子表面活性剂的相互作用.结果表明:(1)混合表面活性剂有很高的表面活性.1:1C₈NMe₃Br-C₈SNa混合物的临界胶团浓度(cmc)为～7.5×10^-3m,远小于单一表面活性剂.在此浓度时,表面张力低达～23达因/厘米;溶液-正庚烷的界面张力更低,达～0.2达因/厘米,亦远低于单一表面活性剂;(2)混合表面活性剂溶液有很高的气泡寿命及液滴寿命,亦即有较大的表面膜及界面膜强度;(3)混合溶液比单一表面活性剂的润湿性能好;(4)不同比例的C₈NMe₃Br-C₈SNa混合溶液的表(界)面总吸附量与1:1混合溶液的相近,当浓度较大时,吸附层中两者比例大多接近1:1,且表(界)面张力亦甚低:(5)与一般离子型表面活性剂的情形完全不同,无机盐对1:1混合溶液的表(界)面张力影响很小.计算吸附量时,Gibbs公式应取1RT形式,而不采用对一般离子型表面活性剂适用的2RT形式.由此得出的最小平均“分子”面积为27～29Ų,表明吸附层中表面活性离子排列紧密,膜凝聚性强.上述结果充分说明正、负离子表面活性剂在水溶液中有强烈的相互作用,其本质主要在于附加的正、负电荷的库仑引力,由此导致正、负离子表面活性剂混合溶液的一系列表面化学特性.     

夜蓝与阴离子表面活性剂在水溶液中显色反应——吸光光度法测定环境水样中阴离子表面活性剂

在聚乙烯醇存在的1.8mol/L磷酸溶液中,夜蓝与阴离子表面活性剂形成离子缔合物。溶液由绿色变为蓝色,可用于水相直接光度测定阴离子表面活性剂。最大吸收波长555nm,摩尔吸光系数分别为5.72×10~4L·mol~(-1)·cm~(-1)(十二烷基苯磺酸钠),5.77×10~4 L·mol~(-1)·cm~(-1)(十二烷基硫酸钠),4.36×10~4 L·mol~(-1)·cm~(-1)(十二烷基磺酸钠)。方法简便、快速,具有良好的选择性。可用于河水和生活废水中10~(-6)—10~(-7)mol/L阴离子表面活性剂的测定。     

ADSORPTION OF NONIONIC SURFACTANTS ON LATEXES

Adsorption isotherms of ethoxylated nonylphenols on poly(styrene) and poly(vinyl chloride) latexes have been measured. The isotherms all reach a limiting adsorption at concentrations somewhat higher than the critical micellar concentrations of the surfactants. The relative affinity of the surfactants to the latex surfaces was found to decrease with increased ethylene oxide chain length. Analysis of the isotherms indicates some affinity of the ethylene oxide chain to the latex surface. This affinity may possibly be attributed to the presence of surface carboxylic groups

Some of the isotherms were obtained using the serum replacement technique developed by S.M. Ahmed et. al. (S.M. Ahmed, M.S. El-Aasser, G.H. Pauli, G.W. Poehlein and J.W. Vanderhoff, J. Coll. Interface Sci., 73 388 (1980). In the application of this technique to the adsorption of nonionic surfactants it was found that polydispersity of the surfactant plays an important role since surfactant species with high affinity to the latex surface will continuously replace other species with lower affinity.     

光度法研究染料与非离子表面活性剂的相互作用

染料与表面活性剂的相互作用对纺织品的染色有重要影叫,一直是广泛研究的课题.近年来由于胶束增溶光度法的发展,它又引起了分析化学家的注意.但是现有的研究多集中于染料与电性相反的离子型表面活性剂的相互作用,且缺乏深入的定量研究.本文研究一种阴离子染料——漂蓝6B与非离子表面活性剂Triton X-100间的相互作用,用光度法定量地确定了二者的结合比,并进而研究了阴离子表面活性剂SDS对此种相互作用的影响.     

SYNTHESIS AND PROPERTIES OF ASYMMETRICAL NONIONIC DOUBLE CHAIN SURFACTANTS FROM LYSINE

New monodisperse nonionic surfactant molecules based on lysine with two different fatty acid chains in the hydrophobic part and one or two polyoxyethylene methoxy capped chain s (EOn-Me) in the hydrophilic head group were synthesized and their physicochemical and toxicity properties were compared to the symmetrical homologs with the same number of methylene groups in the acyl fatty chains. Our findings indicate that the asymmetry studied results in higher surface active properties and in a greater capacity for micellization when compared with their symmetrical analogs, albeit with a slight increase in toxicity.     

pH DEPENDENCE OF SENSITIZED PHOTOOXIDATION IN MICELLAR ANIONIC AND CATIONIC SURFACTANTS, USING THIAZINES DYES

Abstract— Our study of the kinetics of sensitized photooxidation, as a function of pH in anionic micellar systems using cationic dyes as sensitizers, shows that adsorption of the dye slows the protonation step of his triplet state. This observation has important implicaticins in interpretation of results in the so-called photodynamic effect in biological systems: using cationic dyes as sensitizers the rate of photooxidation for the same pH is different depending whether or not the medium allows adsorption of the dye.     

全氟辛酸与十二烷基硫酸钠混合溶液中的胶团形成

用表面张力法、电导法,pH测定法研究全氟辛酸-十二烷基硫酸钠混合水溶液的胶团形成及全氟辛酸胶团的特性.结果表明:(1)电导法与pH测定法弥补了表面张力法的不足,进一步证明在碳氟链表面活性剂与碳氢链表面活性剂混合水溶液中形成两种胶团.(2)全氟辛酸与十二烷基硫酸钠混合水溶液中所形成的两种胶团,分别基本上由全氟辛酸和十二烷基硫酸钠组成.十二烷基硫酸钠的存在对全氟辛酸胶团的形成不显示影响.全氟辛酸的氢离子对十二烷基硫酸钠胶团显示反离子效应.(3)全氟辛酸是典型的离子型表面活性剂,由于它对氢离子的结合力特别强,其胶团几乎是电中性的.这一特性可以解释全氟辛酸-十二皖基硫酸钠混合溶液胶团形成的机制.     

非离子胶束对竹红菌乙素及其溴代物基态和激发态的保护作用

本文用Triton X-100非离子型胶束增溶竹红菌乙素(HB)及其两种溴代物(5-Br-HB,5,8-diBr-H8),发现该胶束对HB的基态和激发态都有保护作用:(1)HB基态的ρK_a值升高;(2)荧光量子产率增大。这使其光敏反应产生的活性中间体¹O₂和·OH的产额增加,从而增强了其光敏活性,实验还发现,这种胶束对HB的两种溴代物的激发态亦有保护作用,且强于HB,这导致它们O₂和·OH的产额显著高于HB.¹O₂和·OH产额的提高,在光敏损伤作用中具有重要的生物学意义。     

SOLUBILIZATION IN MIXED REVERSE MICELLAR SYSTEMS OF AOT/NONIONIC SURFACTANTS/n-HEPTANE

Solubilization of water and aqueous NaCl solutions in mixed reverse micellar systems of anionic surfactant AOT and nonionic surfactants in n-heptane was studied. It was found that the maximum solubilization capacity of water was higher in the presence of certain concentrations of NaCl electrolyte, and these concentrations increased with the increase of nonionic surfactant content and their EO chain length. Soluibilization capacity was enhanced by mixing AOT with nonionic surfactants. The observed phenomena were interpreted in terms of the stability of the interfacial film of reverse micellar microdroplet and the packing parameter of the surfactant that formed mixed reverse micelles.     

罗丹明B共振光散射法测定阴离子表面活性剂

在B-R缓冲溶液中,基于罗丹明B与阴离子表面活性剂(ASF)产生强烈共振光散射增强效应,建立了一种测定阴离子表面活性剂(SDS和SDBS)的方法。试验发现对于SDS和SDBS,最大共振光散射峰位于518和373 nm处。方法具有高的灵敏度,检出限分别为0.023 mg.L-1(SDS)和0.038 mg.L-1(SDBS),用于合成样和环境水样中阴离子表面活性剂含量的测定,回收率为94.0%~105.0%之间,并与亚甲蓝光度法相比,结果满意,可用于环境水样中阴离子表面活性剂的测定。     

STRUCTURE AMD VISCDMETRIC BEHAVIOR OF GEL PHASES IN QUATERNARY SYSTEMS CONTAINING ANIONIC SURFACTANTS

The homogeneous viscous phases which form by mixing sodium dodecylsulphate, butanol, toluene and water in different proportions have been characterized through viscometric measurements and optical techniques. Abrupt increases in viscosity observed in some regions of the phase diagram have been correlated to the formation of birefringent phases which exhibit non-newtonian behavior. These highly swollen mesophases are shown to be of the lamellar type by the characteristic optical textures displayed under polarizing microscope. An addition of NaCl salt to the systems, upon decreasing the solubility of the surfactant in water, tends to destroy the organized structure and give rise to a diphasic system (Winsor II). Similarly, a rise in temperature increases the relative affinity of the tensio-active agent for water, producing a transition from the lamellar phase to an isotropic newtonian phase through a two-phase coexistence region.     

INTERACTIONS BETWEEN CATIONIC STARCH AND ANIONIC SURFACTANTS III RHEOLOGY AND STRUCTURE OF THE COMPLEX PHASE

This paper reports on studies of the rheological properties of cationic starch (CS)/ surfactant systems. The degree of substitution of the CS was 0.1 - 0.8. Surfactants investigated were sodium dodecyl sulfate (SDS), potassium octanoate (KOct), sodium decanoate (NaDe)potassium dodecanoate (KDod), sodium oleate (NaOl) and sodium erucate (NaEr). Aggregation of surfactant micelles with the polymer produces a hydrophobic and pseudoplastic gel-like complex phase with low water content and high viscosity. The rheological behavior of the gels is described by the Herschel-Bulkley model. In dilute aqueous solution the CS/surfactant aggregate structure resembles a randomly coiled polymer network, in which polymer molecules are linked by micelles. The rheological data for the gel are compatible with the assumption that the surfactants form liquid crystalline structures with the polymer anchored to the surfactant aggregates, as recently suggested for analogous systems. However, this conjecture needs to be corroborated by more direct determinations of the structure.     

全（多）氟烷基非离子型表面活性剂的合成

通过Ｏ－烯丙基化，全氟烷基化和还原３步过程在聚乙二醇分子中引入了全（多）氟烷基，合成了１０多种全（多）氟烷基非离子型表面活性剂。     

THE EFFECT OF CATIONIC,ANIONIC, AND NONIONIC SURFACTANT MICELLES ON THE ALKALINE HYDROLYSIS OF ESTERS

The alkaline hydrolysis of aromatic and normal aliphatic acid esters has been studied at 25°C in micellar solutions of surfactants (DTAB, TTAB, CTAB, SDS, Brij 35 and Triton X—100) with UV spectrophotometry and the method of thermokinetics in this paper. The rate constants of the alkaline hydrolysis of esters in micellar pseudophase, k_1m and K_2m have been calculated, respectively. The ratios of k_2m to k_2w or k_1w to k_1w indicate that the alkaline hydrolysis of esters arc inhibited by all of the surfactants investigated. It was supposed that such inhibition is mostly in relation to the micropolarity of micellar surface. The critical micellar concentrations of the corresponding systems have also been measured with the conductivity method and UV spectrophometry in this paper.