烷基芳基磺酸盐结构对微乳液相行为的影响

用Winsor相图法研究了自制的6种不同结构的烷基芳基磺酸盐/不同醇/正癸烷/NaCl/水体系在不同温度下所形成的微乳液。 探讨了烷基芳基磺酸盐结构对微乳液相行为的影响。 同时考察了温度和醇对微乳液相行为的影响。 结果表明,随着烷基芳基磺酸盐长烷基链的增长,中相形成盐度S1、中相消失盐度S2、中相盐宽ΔS和最佳盐浓度S*值均减小,最佳中相体积V*M和最佳增容量σ*值均增大;随着烷基芳基磺酸盐分子的芳环向长烷基链中间位置移动,S1、S2、ΔS、S*值均减小,V*M和σ*值均增大;随着温度升高,V*M和σ*值均减小,S1、S2、ΔS、S*值均增大,在25 ℃时,体系无中相微乳液形成;随着正构醇碳原子数的增加,V*M和σ*值均增大,S1、S2、ΔS、S*值均减小。     

助表面活性剂对阴/阳离子表面活性剂复配形成微乳液的影响

中相微乳液;盐度扫描;助表面活性剂对阴/阳离子表面活性剂复配形成微乳液的影响     

Phase Behavior of Microemulsions Formulated with Sodium Alkyl Polypropylene Oxide Sulfate and a Cationic Hydrotrope

The partial ternary phase diagram of anionic extended surfactant of alkyl polypropylene oxide sulfate C₁₂(PO)₄SO₄ alone and combined with the cationic hydrotrope, tetrabutyl ammonium bromide with water and decane were determined under ambient conditions. Middle phase microemulsion was formulated using salinity scans in the dilute region of surfactant/brine/decane. Visual inspection as well as cross polarizer and optical microscopy were used to detect anisotropy. Spinning drop tensiometer was used to measure interfacial tension (IFT). The first ternary phase diagram using the extended surfactant alone showed three one phase regions, the anisotropic lamellar liquid crystalline phase, L _α and the isotropic L₁ micellar liquid and L₃ sponge phase. In the second ternary phase diagram using the extended surfactant combined with tetra butyl ammonium bromide, an isotropic micellar region, L ₁, appeared in the diluted area of the phase diagram. Meanwhile the L _α phase disappeared completely and the three phase region has a bluish transparent middle phase. Interfacial tension measurements between middle phase and brine, and between decane and brine yielded ultra low values. Calculated IFT values using the characteristic length obtained using De Gennes approximation gave almost half the measured values. The interfacial rigidity was also calculated and compared to values obtained from the literature.     

醇对高效氯氟氰菊酯微乳液相图的影响

通过电导率的测定研究了高效氯氟氰菊酯微乳液的结构结构及结构转变。在表面活性剂、高效氯氟氰菊酯环己酮溶液、醇相对含量一定的情况下,当醇为乙醇时,微乳液经历了由W/O到双连续最后到O/W型的变化;当醇为正辛醇时,微乳液经历了由W/O到液晶、双连续最后到O/W型的变化。绘制了不同条件下高效氯氟氰菊酯微乳体系的拟三元相图,讨论了醇种类、醇含量对各类型微乳区形成的影响。结果表明,随着醇碳链的增大,微乳区面积先增大后减小;醇(正辛醇)固定时,随着醇含量增加,微乳区面积先减小后增大。     

新型农药丙酯草醚对微乳液体系相行为的影响

表面活性剂;微乳液;“鱼形”相图;丙酯草醚     

Phase diagrams of surfactant/water/synthetic perfume ternary systems

The phase diagrams of hexadecyl polyoxyethylene ether (C₁₆POE₁₀)/water/synthetic perfume, and sodium dodecyl sulfate (SDS)/water/synthetic perfume ternary systems were prepared. The synthetic perfumes used are, d-limonene, -hexylcinnamaldehyde, -ionone, benzyl acetate, linalool, and eugenol. In a series of C₁₆POE₁₀/water/synthetic perfume ternary systems, as the hydrophilicity of synthetic perfume increases, the regions of normal and inverse micellar solution phases were found to be extended, while that of the lamellar liquid crystal phase was reduced. Moreover, every region of normal micellar solutions, inverse micellar solutions, and lamellar liquid crystal phases in SDS/water/synthetic perfume ternary systems was found to be smaller than those in C₁₆POE₁₀/water/synthetic perfume systems.     

SDS/正戊醇-二甲苯-水(盐水)拟三元体系相图和电导研究及纳米ZnO的制备

实验绘制了十二烷基硫酸钠(SDS)/正戊醇(n-C₅H₁₀OH)-二甲苯[C₆H₄(CH₃)₂]-水[或Zn(NO₃)₂溶液]四组分微乳液体系在不同温度时的拟三元相图. 测定了电导率随水(或盐溶液)含量变化的规律, 电导的规律与相图吻合. 依据电解质理论探讨了微乳液的微观结构, 研究表明, 温度对油包水(W/O)反相微乳液区域影响不大, 电解质的加入对油包水(W/O)反相微乳液区域影响较大. 通过SDS/正戊醇-二甲苯-H₂O及SDS/正戊醇-二甲苯-盐水的拟三元体系的相图观察及实验研究, 选择乳化剂(SDS/正戊醇)与二甲苯质量比为4:6的微乳液作为最佳条件, 制备出了ZnO纳米粒子.     

Phase behavior studies of quaternary systems containing N-lauroyl-N-methylglucamide/alcohol/alkane/water

The three-phase behavior of quaternary systems comprising N-lauroyl-N-methylglucamide (MEGA-12)/alcohol/alkane/water has been studied using epsilon-beta fishlike phase diagrams. From the epsilon-beta fishlike phase diagrams a series of phase inversions Winsor I (2) --> III (3) --> II (2) were observed, and the hydrophilic-lipophilic balanced (HLB) plane equation for the quaternary system was deduced. Some physicochemical parameters, such as the mass fraction of alcohol in the HLB interfacial layer, A S, the coordinates of the start (beta B, epsilon B) and end points (beta E, epsilon E) of the middle-phase microemulsion, the mass fractions of MEGA-12 and alcohol in the total system (C S and C A), and the solubilities of MEGA-12 and alcohol in oil phase (S O and A O), were calculated. The effects of different alcohols, alkanes, and NaCl concentrations in the aqueous phase on the phase behavior and solubilization capacity were investigated, which indicates that alcohol with longer and alkane with shorter hydrocarbon chains have a larger solubilization capacity. NaCl concentration has little influence on the phase behavior.     

Studies on Phase Behavior of Alkyl Polyglucoside Based on Microemulsions with Modified Fishlike Phase Diagram

The three-phase behavior in the quaternary system of an alkyl (C8/10^- or C12/14^-)polyglucoside / 1-butanol / n-octane / water has been studied at 40℃ with the modified fishlike phase diagram, which is presented by us for the first time. The mass fraction of 1-butanol in the hydrophile-lipophile balanced interfacial layer, A^S, the coordinates of the start point B and the end point E of the phase diagram, and the solubilities of alkyl polyglucoside and 1-butanol in n-octane phase were calculated. The solubilization of the microemulsion was also discussed.     

磁场对复配乳化剂/苯胺微乳液聚合体系相行为的影响

首次在酸性条件下, 以十二烷基苯磺酸钠(SDBS)和聚乙二醇辛基苯基醚(TX-100)为复配乳化剂, 制备SDBS/TX-100/正丁醇(nBA)/苯胺(An)/盐酸(HCl)微乳液体系, 并通过该体系的拟三元相图, 考察了恒定磁场(0.4 T)、助表面活性剂(nBA)与复配乳化剂的质量比(K_m＝m_nBA/m_SDBS/TX-100)及SDBS与TX-100的质量比(S_m＝m_SDBS/m_TX-100)对复配乳化剂/苯胺微乳液聚合体系相行为和电导行为的影响. 结果表明: 随着K_m的增加, 微乳区面积先增大后减小, 当K_m＝1.0时, 形成的微乳区面积最大|随着S_m的减少, 微乳区面积逐渐增大|外加磁场可以增大微乳区面积, 且随着S_m的减小, 磁场对微乳液体系的作用逐渐减弱. 循环伏安的测试结果表明, 复合乳化剂微乳液法制备的聚苯胺, 其循环伏安性能优于单组分乳化剂(SDBS或TX-100)微乳液法制备的聚苯胺.     

Effect of Addition of Cosurfactant on the Phase Behaviour of Oil-in-water Aminosilicone Oil Microemulsion

Stable and transparent aminosilicone oil microemulsion of the average particle size below 0.05 micron was prepared. The interaction of the aminosilicone oil, water, complex surfactants and cosurfactant was studied by part pseudotemary phase diagram. The effect of cosurfactants (such as alcohol) and the mechanism of its effect on the phase behaviour of the pseudotemary system were investigated.     

非离子表面活性剂TWeen80相图的研究

本文研究了醇类（正丁醇、正戊醇、正辛醇和正癸醇）、油类（正十八烷、正十六烷、正十四烷、正十烷、正癸烷和正辛烷）、正十八烷含量以及NaCl浓度对Tween80／醇／油／水体系相图的影响。结果表明，NaCl浓度对Tween80／正辛醇／正十八烷／水体系相图的影响不明显；醇类随着炭原子数目的增加，O／W微乳液区面积增大，W／O微乳液区面积减小，微乳液区总面积增大；不同的油类形成的微乳液区面积由大到小的顺序是：正十六烷≈正十四烷＞正十二烷＞正癸烷＞正十八烷＞正辛烷；随着正十八烷含量的增加，微乳区面积减小。用2277热活性检测系统测定了石油菌B－2分别在非微乳液和助表面活性剂分别是正戊醇、正辛醇，油是正十八烷所形成的微乳液中生长的功率－时间曲线。结果表明微乳液培养基更适用于B－2利用高碳烷烃进行生长；正辛醇作助表面活性剂形成的微乳液培养基比正戊醇作助表面活性剂形成的微乳液培养更为有利；O／W型微乳液比W／O型微乳液对B－2的生长更为有利。     

Phase behavior in mixtures of cationic and anionic surfactants in aqueous solutions

Phase behavior of cationic/anionic surfactant mixtures of the same chain length (n=10, 12 or 14) strongly depends on the molar ratio and actual concentration of the surfactants. Precipitation of catanionic surfactant and mixed micelles formation are observed over the concentration range investigated. Coacervate and liquid crystals are found to coexist in the transition region from crystalline catanionic surfactant to mixed micelles.The addition of oppositely charged surfactant diminishes the surface charge density at the mixed micelle/solution interface and enhances the apparent degree of counterion dissociation from mixed micelles. Cationic surfactants have a greater tendency to be incorporated in mixed micelles than anionic ones.     

Evaluation and Optimization of Water-in-Oil Microemulsion Using Ternary Phase Diagram and Central Composite Design

In the present study, water-in-oil (w/o) microemulsions were prepared, evaluated, and optimized using pseudoternary phase diagram and central composite design (CCD). Ternary phase diagrams were designed to determine the microemulsion region whereas face-centered CCD helped in the determination of the effect of variables like oil type and surfactant ratio on globule size and viscosity of w/o microemulsion. The design exhibited that the factors have statistically significant effects (p < 0.0001) on the selected responses. The actual responses showed excellent agreement with the predicted values as suggested by the CCD with lower residual standard error. Similarly, the optimized values were found within the range as predicted by the model. Furthermore, other characteristics of microemulsions like pH, conductivity, refractive index, and transmittance were also analyzed. Overall, the primary objective of the research was to fabricate water-in-oil microemulsions which could facilitate effective delivery of hydrophilic molecules and drugs.     

溶剂性质对DBS/C~1~0H~2~1OH/溶剂体系的相行为 与结构的影响

在DBS/C~1~0H~2~1OH/溶剂体系中,以甲酰胺、水或甘油为溶剂时,在一定浓度范围内能生成O/W,W/O微乳液和层状液晶。C~1~0H~2~1OH在各种溶剂的DBS胶束中的分配系数K均很高。以甲酰胺、水为溶剂时,DBS能在一定浓度范围内生成层状液晶,但以甘油为溶剂时,则不能生成层状液晶。C~1~0H~2~1OH的加入有助于层状液晶的生成,但过量的C~1~0H~2~1OH却使层状液晶失稳。在相同质量比C~1~0H~2~1OH/DBS下,按顺序H~2O,FA,Gly,层状液晶中溶剂的渗透率α降低,d~0值亦降低;以FA为溶剂时,表示其表观有序度的Δν值却较高;以水为溶剂时,Δν值却较低;以Gly为溶剂时,Δν具有中等值。不同溶剂层状液晶两亲双层内的分子取向与溶剂性质对层状液晶稳定性的影响相一致。     

Physicochemistry of Mixed Systems of Water/AOT (Surfactant)/Alkanol (Cosurfactant)/Cycloalkanone (Oil): A Detailed Study of Phase Behavior,Salt Effect,and Conductance Properties

Water in oil microemulsion (μE) systems comprising water/AOT ± alkanol (n-butanol to n-dodecanol)/cycloalkanone (cyclopentanone to cycloheptanone, CA5, CA6, and CA7) were physicochemically studied with respect to phase and conductance behaviors. In absence of alkanols, AOT produced large clear zone with the cycloalkanones, compared to linear alkanes. Clear zone was comprised of gel, viscous, and clear fluid. Alkanols increased the fluidity of μE while its clarity was reduced. A maximum two-phase region was observed for n-heptanol (also for formulations with n-octanol). Salts, which reduced the clarity of the μE, followed the order of effectivity: Na⁺ < Mg²⁺ < Al³⁺. A correlation between clarity and turbidity was found irrespective of molecular size of oil, cosurfactant and salt. The influence of water and temperature on the conductance behavior of W/O formulations was studied. The studied systems were found to be less conducting than those with linear alkanes. Energetics and other structural parameters of the studied systems were evaluated from conductance behavior and the use of scaling equations.     

Phase behavior of ethylene oxide-dimethylsiloxane PEO-PDMS-PEO triblock copolymers with water

Linear ethylene oxide-dimethylsiloxane PEO-PDMS-PEO triblock copolymers have been synthesized by hydrosilation of ,-dihydropoly(dimethylsiloxane) ) and -methyl--propargylpoly(ethylene oxide) . Studies by optical microscopy, complementary small-angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) have shown that the copolymers mixed with water are characterized by lyotropic liquid crystalline phases according to composition and temperature. The binary phase diagrams with varying copolymer composition are reported.     

辛烷基酚聚氧乙烯醚反相微乳体系的相行为及纳米复合碳酸盐的制备

绘制了一系列辛烷基酚聚氧乙烯醚(OP-10)+正辛醇+环己烷+水(或CaCl₂水溶液)拟三元体系相图,分别研究了助表面活性剂正辛醇的添加比例和CaCl₂水溶液的浓度对微乳区域的影响,发现在OP-10+正辛醇+环己烷+水拟三元体系相图中,随着正辛醇/OP-10的质量比逐渐增大,微乳区的面积逐渐增大,当正辛醇/OP-10质量比为1:2.5时微乳区的面积最大,之后微乳区面积随着其质量比的增大而减小,表明适量地加入助表面活性剂正辛醇有利于微乳区的形成;但过多地增加正辛醇的量反而不利于微乳相的形成。 确定正辛醇/OP-10的质量比为1:2.5,改变CaCl₂的浓度,发现OP-10+正辛醇+环己烷+CaCl₂水溶液拟三元体系相图中,CaCl₂浓度为0.1 mol/L时微乳区面积最大。分别配制总浓度为0.1 mol/L的5种不同摩尔比的Ca²⁺/Ba²⁺微乳液,并与等摩尔的碳酸钠水溶液反应制备共沉淀碳酸盐,使用扫描电子显微镜(SEM)对所制备样品进行表征分析,发现当微乳液为钙离子盐时,主要形成大的立方形颗粒;掺入钡离子,Ca²⁺和Ba²⁺摩尔比为3:1、1:1和1:3时,形成的沉淀分别为四棱锥形、球形和玉米棒形;当微乳液为钡离子盐时,沉淀主要为不规则多面体。     

环境因素对正负表面活性剂体系相行为的影响

在1:1正负离子表面活性剂混合体系(十二烷基硫酸钠/辛基三甲基溴化铵 SDS-C8NM3Br; 十二烷基硫酸钠/十二烷基三甲基溴化铵,SDS-C12NM3Br)中加入短链脂肪醇 (乙醇,正丙醇,正丁醇),正负离子表面活性剂沉淀溶解,出现表面活性剂双水相.上相有液晶存在,下相有囊泡自发形成.折光率数据和电镜结果表明:上相为表面活性剂富集相,下相表面活性剂浓度较低.混合体系中,出现表面活性剂双水相所需短链脂肪醇的体积百分数,随短链脂肪醇的链长增加而降低.温度升高,出现表面活性剂双水相所需短链脂肪醇的体积百分数降低.对SDS/C8NM3Br/H2O体系的研究结果表明:超声处理,可使混合体系中沉淀向囊泡转化,与短链脂肪醇的加入后的作用类似.     

卵磷脂/正丙醇/肉豆蔻酸异丙酯/水微乳体系的相结构研究

以卵磷脂为表面活性剂,正丙醇为助表面活性剂,肉豆蔻酸异丙酯(IPM)为油相,配制成W/O型微乳。并通过浊点法、电导法、动态光散射法(DLS)以及差示扫描量热法(DSC)研究了微乳相结构随含水量的变化。对于选定配比微乳,浊点法在含水量超过10.71%时变浑浊;电导率在含水量达到3.85%之前增长缓慢,之后快速增大,含水量超过10.71%时电导率下降;DLS显示微乳粒径随含水量先减小后增大,其转折点在5.66%,而含水量超过10.71%后粒径突增3个数量级;DSC曲线在含水量超过3.85%后出现水的结晶峰,且随含水量的增大峰位往高温方向平移,同时峰面积增大。当含水量达到11.5%时出现两水峰叠加。研究表明含水量在3.85%~5.66%范围内属于W/O向双连续相转变的过程,而含水量10.71%则是体系发生相分离的临界点。