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     

微乳液相行为和微观结构的研究

用正交试验法求得阳离子表面活性剂双十八烷基二甲基氯化铵(DOD-MAC)/阴离子表面活性剂十二烷基硫酸钠(SDS)/正丁醇/正庚烷/盐水体系中相微乳液形成的最佳配方:W_(DODMAC):W_(SDS)=1:4～1:5;C_(n-butanol)%=11.0～12.0;C_(NaCl)%=3.25附近.研究了盐浓度、DODMAC和SDS复配比例、正丁醇浓度(1.0%～14.0)%以及酸种类(正丙醇、正丁醇和正戊醇)对微乳液相态、超低界面张力(γ_(mo),γ_(mw))、最佳含盐度(S)和盐宽(△S)的影响,得到了微乳液相行为的一些规律.并用FT-IR,ESR和冷冻蚀刻方法研究了中相微乳液微观结构,3种方法均表明中相微乳液随着含盐度增加,微观结构经历o/w型到B.C.再到w/o型转变.中相微乳液分子组织形态的有序分布规律,有助于构作微乳液体系的模型,有助于对中相微乳液微观结构认识及阐明微乳液微观结构与宏观特性之间关系.     

碳氟表面活性剂复配体系的中相微乳液研究

全氟辛酸钠(OBS)/十六烷基三甲基溴化铵(CTAB)-正丁醇/正丙醇-油-盐水体系能形成多相微乳液, 本文应用正交试验设计寻找了最佳中相微乳液体系组成, 然后系统地研究了含盐量、表面活性剂总浓度, 醇总浓度, 油的种类对该体系中相微乳液的形成, 相态和其特性参数的影响。并且应用红外光谱对微乳液的微观结构进行了测定。最后还对碳氢表面活性剂和碳氢/碳氟表面活性剂复配体系进行了比较。本文结果对三次采油和日用化工等领域的应用以及对理论研究都具有重要的意义。     

苄泽类非离子表面活性剂与离子型表面活性剂复配性质研究

通过测定苄泽类非离子型表面活性剂Brij58、Brij76、Brij78与阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)复配体系的表面张力,研究了复配体系的形成胶束能力、降低表面张力效率、降低表面张力能力3种增效作用,并结合复配体系中表面活性剂分子间的相互作用参数进行了深入的讨论。研究结果表明,与阳离子表面活性剂复配时,Brij76/CTAB体系增效作用最强;与阴离子表面活性剂复配时,Brij58/SDS复配体系增效作用最强,而且苄泽类非离子型表面活性剂与阴离子表面活性剂复配增效作用更加显著。     

阴阳离子表面活性剂体系超低油水界面张力的应用

通过阴阳离子表面活性剂复配,在实际油水体系中获得了超低界面张力.通过在阴离子表面活性剂分子结构中加入乙氧基(EO)链段,以及采用阴阳离子加非离子型表面活性剂的三组分策略,有效解决了混合表面活性剂在水溶液中溶解度问题.进而研究了阳离子表面活性剂结构、非离子表面活性剂结构、三者组分配比、表面活性剂总浓度等因素对油水界面张力的影响,从而在胜利油田多个实际油水体系中获得了较大比例范围和较低浓度区域的油水超低界面张力,部分体系甚至达到了10-4 mN·m-1.由于阴阳离子表面活性剂间强烈的静电吸引作用,相关体系具有很好的抗吸附能力.经过石英砂48 h吸附后,体系仍然具有很好的超低界面张力.     

无表面活性剂微乳液体系：N,N－二甲基甲酰胺/呋喃甲醛/水

通常微乳液一般由四个组分构成：水相、油相、表面活性剂和助表面活性剂。本文报道了一种不含表面活性剂的微乳液体系(简称SFME),由呋喃甲醛(油相),水和N,N－二甲基甲酰胺(DMF)三组分构成,不含传统的表面活性剂。对其相行为进行了研究,发现存在一个单相微乳液区和一个两相平衡区。采用电导率法和冷冻蚀刻电镜(FF-TEM)考察了单相区域中微乳液的微结构,结果表明可分为油包水(O/W)、双连续(BC)和水包油(W/O)三个区域。液滴直径介于40-70nm。     

阴离子型微乳液的电导行为及其溶液结构

根据电导测量,研究了属于W/O→双连续→O/W一类微乳液的十二烷基硫酸钠(SDS)/正丁醇/辛烷/水体系的溶液结构.并探讨了表面活性剂离子对微乳液导电行为的贡献,以及表面活性剂与助表面活性剂含量、油含量对微乳液溶液结构的影响.微乳液的导电行为在W/O子区域中主要是由于SDS阴离子和在O/W子区域中是由于Na离子的影响.在双连续区(IZ)中SDS阴离子和Na阳离子都能影响导电行为增加表面活性剂含量有助于形成O/W微乳液,而助表面活性剂和油含量都增加有助于于形成W/O微乳液.     

阴、阳离子表面活性剂混合体系在硅胶/水及硅胶/矿化水界面上的吸附

研究阴、阳离子表面活性剂混合体系(十二烷基氯代吡啶,辛基磺酸钠,辛基三乙基溴化铵/十二烷基苯磺酸钠)在硅胶,纯水和硅胶,矿化水界面上的吸附作用,探讨阴(阳)离子表面活性剂的存在对阳(阴)离子表面活性剂吸附作用的影响．结果表明,阴离子表面活性剂的存在基本不影响阳离子表面活性剂在带负电固体表面的吸附;而阳离子表面活性剂的存在却使本来吸附量就不大的阴离子表面活性剂在带负电的固体表面上不再吸附．在矿化水中阳离子表面活性剂的吸附量比在纯水中明显降低．从硅胶表面吸附机制解释了所得结果．     

新型无表面活性剂微乳液体系：乙醇/呋喃甲醛/水

通常, 微乳液一般由四个组分构成：水相、油相、表面活性剂和助表面活性剂。本文报道了一种不含表面活性剂的微乳液体系(简称SFME),由呋喃甲醛(油相),水和乙醇三组分构成,不含传统的表面活性剂。对其相行为进行了研究,发现存在一个单相微乳液区和一个两相平衡区。采用电导率法和冷冻蚀刻电镜(FF-TEM)考察了单相区域中微乳液的微结构,结果表明可分为油包水(O/W)、双连续(BC)和水包油(W/O)三个区域。液滴直径介于30~80nm。     

N-烷基-N-(2-羟乙基)-N,N-二甲基溴化铵与十二烷基硫酸钠复配系统的双水相

合成了N-十二烷基-N-(2-羟乙基)-N,N-二甲基溴化铵、N-十四烷基-N-(2-羟乙基)-N,N-二甲基溴化铵和N-十六烷基-N-(2-羟乙基)-N,N-二甲基溴化铵等3个季铵盐阳离子表面活性剂. 研究了它们以及N-十六烷基-N,N,N-三甲基溴化铵(CTAB)与阴离子表面活性剂十二烷基硫酸钠(SDS)复配系统在313.15 K时的双水相行为. 复配系统在两个非常狭窄的区域能形成双水相, 两相区近似以等摩尔线为中心对称分布, 随着阳离子表面活性剂碳链长度的增长, 富含阳离子表面活性剂的双水相区向阴阳离子表面活性剂摩尔比减小的方向稍有移动.     

反相微乳液中苯酚硝化反应选择性的研究

采用气相色谱内标法研究了苯酚在AOT/异辛烷/水、CTAB/正癸醇/异辛烷/水、DBSA/异辛烷/水3种反相微乳液中进行硝化反应的选择性;考察了表面活性剂种类、反应时间、反应温度以及反相微乳液的含水量等因素对反应选择性的影响.研究结果表明,苯酚在微乳液体系中的硝化反应具有明显的邻位选择性,阴离子表面活性剂DB-SA体系的邻位选择性最高,这与它同时具有微乳催化和酸催化作用有关.     

Extraction of cobalt by the AOT microemulsion system

The extraction of cobalt by Winsor II microemulsion system was studied. In the bis (2-ethylhexyl) sulfosuccinate sodium salt (AOT)/n-pentanol/n-heptane/NaCl system, AOT was used as a anionic surfactant to form microemulsion in n-heptane, n-pentanol was injected in the microemulsion as a cosurfactant. Co(II) was found to be extracted into the microemulsion phase due to ion pair formation such as Co²⁺(R–SO₃ ⁻)Cl. The influence of different parameters such as the volume ratio of aqueous phase to microemulsion, surfactant concentration, pH of the feed solutions, cosurfactant concentration as well as temperature on the extraction yield (E%) were investigated. The results showed that it was possible to extract 95% of cobalt by the AOT Winsor II microemulsion.     

Physicochemical investigations of microemulsification of eucalyptus oil and water using mixed surfactants (AOT+Brij-35) and butanol

Microemulsification of a vegetable oil (eucalyptus) with single and mixed surfactants (AOT and Brij-35), cosurfactant of different lipophilicities (isomers of butanol), and water were studied at different surfactant and cosurfactant mixing ratios. The phase diagrams of the quaternary systems were constructed using unfolded and folded tetrahedron, wherein the phase characteristics of different ternary systems can be underlined. The microemulsion zone was found to be dependent upon the mixing ratios of surfactant and cosurfactant; the largest microemulsion zone was formed with 1:1 (w/w) S:CS. The effects of temperature and additives (NaCl, urea, glucose, and bile salts of different concentrations) on the phase behavior were examined. The mixed microemulsion system showed temperature insensitivity, whereas the Brij-35 (single) stabilized system exhibited a smaller microemulsion zone at elevated temperature. NaCl and glucose increased the microemulsion zone up to a certain concentration, beyond which the microemulsion zones were decreased. These additives decreased the microemulsion zones as temperature was increased. The effect of urea on microemulsion zone was found to be insignificant even at the concentration 3.0 mol dm(-3). Little effect on microemulsion zone was shown by NaC (sodium cholate) at 0.25 and 0.5 mol dm(-3) at different temperatures. The conductance of the single (AOT) and mixed microemulsion system (AOT+Brij-35) depends upon the water content and mixing ratios of the surfactants, and a steep rise in conductance was observed at equal weight percentages of oil and water. Viscosities for both single (AOT) and mixed (AOT+Brij-35) surfactant systems passed through maxima at equal oil and water regions showing structural transition. The viscosities for microemulsion systems increased with increasing Brij-35 content in the AOT+Brij-35 blend. Conductances and viscosities of different monophasic compositions in the absence and presence of additives (NaCl and NaC) were measured at different temperatures. The activation energy of conduction (DeltaE(cond)( *)) and the activation enthalpy for viscous flow (DeltaH(vis)( *)) were evaluated. It was found that both DeltaE(cond)( *) and DeltaH(vis)( *) were a function of the nature of the dispersion medium. Considering the phase separation point of maximum solubility, the free energy of dissolution of water or oil (DeltaG(s)(0)) at the microdispersed state in amphiphile medium was estimated and found to be a function of surfactant composition.     

Effects of salinity on the viscosity and birefringence of a microemulsion system

Oil/water/surfactant systems form complex equilibrium phases which are sensitive to a number of parameters, including amount and concentration of cosurfactant (often an alcohol), salinity, and temperature. If one of these variables is changed systematically as, for example, the salinity, an interesting transition may be observed in which at low salinities a microemulsion is in equilibrium with an excess oil phase, at moderate salinities a middle phase microemulsion is in equilibrium with both excess oil and excess water phases, and at higher salinities brine is in equilibrium with a microemulsion phase. To help elucidate the structure of the microemulsion, studies of viscoelasticity and streaming birefringence in oscillatory shear flow have been conducted of a middle phase-forming system as a function of salinity. It is found that the viscoelastic properties of the microemulsions are unchanged for shear rates varying from 0.1 to 100 sec⁻¹. Both the birefringence and the viscosity maximize near the salinity marking the transition from lower phase to middle phase microemulsion. Further inflections in these properties occur at a salinity marking the midrange of the middle phase microemulsion. For all cases the dominent relaxation time is near 3 to 5 msec while the birefringence changes by two orders of magnitude. The birefringence is a sensitive indicator of the elastic structure of the microemulsion.     

影响反相微乳液导电性能的因素

分别以聚乙二醇辛基苯基醚(Triton X-100)或十六烷基三甲基溴化铵(CTAB)为表面活性剂, 与正己烷、正己醇和水构成反相微乳液. 研究了水相H+浓度、表面活性剂、助表面活性剂等对微乳液导电性能的影响. 结果表明, 增加水相H+浓度可大幅度提高反相微乳液的导电能力, 当H+浓度由1.0 mol•L-1增加到10 mol•L-1时, 微乳液的电导率可提高1~2个数量级. 当水相H+浓度为10 mol•L-1时, 微乳液的电导率随溶水量的增大而增大, 水油体积比为3:10时, 两种体系的电导率均达到3200 μS•cm-1. Triton X-100浓度对微乳液的电导率影响较大, 电导率随其浓度增加而增大；而CTAB浓度对微乳液电导率的影响较小, 电导率随其浓度增加略有减小；助表面活性剂正己醇使非离子型反相微乳液的电导率下降, 而使阳离子型反相微乳液的电导率先增大, 然后减小, 呈骆峰状变化.     

Effect of alpha-lactalbumin on the phase behavior of AOT-brine-isooctane mixtures: role of charge interactions

We have found that both electrostatic and hydrophobic interactions are involved in the ability of the protein alpha-lactalbumin (alpha-LA) to affect the self-assembly of the anionic surfactant sodium bis(ethylhexyl) sulfosuccinate (AOT, 3.5 wt %) in equivolume mixtures of organic and aqueous solutions. The composition and size of AOT phase structures that form in the presence of 0.35 wt % protein were evaluated as a function of pH and ionic strength. In the absence of protein, AOT forms water-in-oil microemulsion droplets for all pH and salt concentrations studied here. The presence of the protein in the water-in-oil microemulsion phase boosts water solubilization and droplet size, as the spontaneous curvature of the surfactant interface becomes less negative. Aggregates of protein, surfactant, and oil also form in the water-continuous phase. The size and composition of structures in both phases can be tuned in the presence of protein by varying the pH and ionic strength. alpha-LA induces the appearance of an anisotropic surfactant phase at pH <5.8. At intermediate salt concentrations, a third isotropic, viscous aqueous phase appears that contains 55-60% of the protein, 10-14% of the surfactant, and significant amounts of oil. Circular dichroism and fluorescence spectroscopy indicate that the protein contains enhanced alpha-helical secondary structure when self-assembling with surfactant, and has a loosened tertiary structure. The protein does not interact with the surfactant as an unfolded random coil. Although the conformation of alpha-LA in aqueous salt solutions is known to depend on pH, when self-assembling with AOT the protein adopts a structure whose features are quite pH insensitive, and likely reflect an intrinsic interaction with the interface.     

The effect of different polymer length on water droplets of reverse AOT microemulsion

We study the effect of polyethylene glycol (PEG) on the dynamic and structure of water droplets at the reverse sodium bis-(2-ethylhexyl) sulfosuccinate (AOT) microemulsion. The mixture of water and oil with anionic surfactant AOT can form microemulsion. The dynamic of microemulsion in the presence of PEG is investigated by photon correlation spectroscopy technique. We mainly focus on the variation of the translational diffusion behaviour as a function of the polymer concentration and polymer length scale. By increasing the content of the lowest PEG length scale (M_n = 285), the dynamic of microemulsion slows down. In addition, one relaxation process is distinguished for all polymer concentration. However, for the two higher polymer length scale (M_n = 2200 and 6000), two relaxations are observed and the dynamic of microemulsion speeds up. We used the small angle X-ray scattering technique to monitor the size and the polydispersity of the mixture system (AOT microemulsion/PEG).     

Tailoring of horseradish peroxidase activity in cationic water-in-oil microemulsions

Horseradish peroxidase (HRP) in cationic water-in-oil (W/O) microemulsions has always been ignored in reverse micellar enzymology, mainly because cationic surfactants are inhibitors of enzyme peroxidase. In the present study, for the first time, we have successfully introduced the cationic W/O microemulsion as an attractive host for efficient HRP activity. To this notion, much improved activity of HRP was observed in the W/O microemulsion of cetyltrimethylammonium bromide (CTAB) with an increase in n-hexanol concentration and W0 ([water]/[surfactant]), presumably due to the increased interfacial area of the microemulsions. In support of our above observation, six surfactants were synthesized with an increased headgroup size where the methyl groups of CTAB were subsequently replaced by the n-propyl and 2-hydroxyethyl groups, respectively, to prepare mono-, di-, and tripropylated/hydroxyethylated n-hexadecylammonium bromide. The peroxidase activity enhanced with headgroup size and also followed an overall trend similar to that found in the case of CTAB. Possibly, the reduced positive charge density at the augmented interfacial area by means of increase, either in headgroup size, cosurfactant concentration, and/or W0, is not capable of inactivating HRP. Also, the larger space at the interface may facilitate easier solubilization of the enzyme and increase the local concentration of enzyme and substrate, leading to the higher activity of HRP. The best activity was obtained with surfactant N-hexadecyl-N,N,N-tripropylammonium bromide, the highest ever found in any cationic W/O microemulsions, being almost 3 times higher than that found in water. Strikingly, this observed highest activity is comparable with that observed in an anionic bis(2-ethylhexyl)sulfosuccinate sodium salt (AOT)-based system, the best W/O microemulsions used for HRP.