Styrene and methylmethacrylate oil-in-water microemulsions

 A simple procedure for the preparation of styrene-in-water and methylmethacrylate (o/w) micro-emulsions was established. This consisted of the preparation of a w/o emulsion using a low HLB number surfactant (Synperonic NP4, nonyl phenyl with 4 mol ethylene oxide) and a small amount of an anionic surfactant (Aerosol OT, diethyl hexyl sulphosuccinate, or sodium dodecyl benzene sulphonate). The w/o emulsion was then titrated with an aqueous solution of a high HLB number surfactant (Synperonic NP15, nonyl phenyl with 15 mol ethylene oxide). The droplet size and poly-dispersity were determined using photon correlation spectroscopy (PCS). The temperature range within which a microemulsion remained stable decreased with increase in the concentration of styrene or methylmethacrylate and this could be explained in terms of the phase diagram of the microemulsion system. Conductivity measurements as a function of temperature showed that the systems are oil-in-water microemulsions. Received: 20 December 1996 Accepted: 5 March 1997     

Phase behaviour and microstructures of microemulsions(Ⅰ)

By the orthogonal design,the optimal formation conditions for the middle-phase microemulsions in the system dioctadeeyldimethylammornum chloride (DODMAC)/ sodium dodecyl sulfate (SDS)/n-butanol/n-hep-ane/brine were obtained as follows.Investigations have been made on the effects of the concentrations of NaCl and n-butanol(1.0%-14.0%),the rantos of W to Wshs and the kinds of alcohols (n-propanol,n-butanol,and n-pentanol) on the formation,the phase behavtour,the ultralow interfacial tensions,the optimal salinity (S*),and the length of salinity (S).Some rules and data were worked out about the formation and characteristics of the middle-phase microemulsions.The mi-crostruenres of the middle-phase microemulsions were also studied by using FT-IR,ESR,and freeze fracture electron microscopy techmques The results from the three methods show that the microstructures of the middle-phase mi-croemnlsions undergo the change from O/W to bicontinuous(B C.) and to W/O.The distribution rule of the orga-mzed molecule ass     

Synthesis and Characterization of Zirconia Nanocrystallites by Cationic Surfactant and Anionic Surfactant

1 INTRODUCTION Zirconia is a kind of metallic oxide with high mel- ting point. It is highly corrosion-resistant for acid fu- sant and neutral fusant, thus it can be used as refrac- tory material, and it can also be utilized as acid acy- loxy bi-functional catalystic material owing to hav- ing both acid and alkali surface centers[1]. Moreover, zirconia has superior ion-exchange capacity as well as chemical and mechanical stability, therefore, it can also be applied as a catalyst carrier. …     

可聚合囊泡体系(烯丙基-二甲基-十二烷基溴化胺和十二烷基硫酸钠)在溶液中的盐效应

高稳定的囊泡广泛用于制作生物模型、药物输送以及合成纳米材料的模板。获得高稳定囊泡结构的重要方法之一是用聚合反应固定囊泡结构。作为可聚合囊泡制备的前期基础工作,研究了一种可聚合的囊泡体系：1-丙烯基－2,2,二甲基－十二烷基溴化胺（ADDB）和ADDB与十二烷基磺酸钠（SDS）的等摩尔比混合体系。该囊泡体系即使在高浓度盐水中也能够自发地形成均相的囊泡溶液。在聚合之前,采用动态激光光散射（DLS）、冷冻蚀刻透射电镜（FF-TEM）技术研究了可聚合囊泡的盐效应。DLS测试发现没有盐存在时,囊泡大小为83 nm,盐的浓度增加到250 mmol/L时,囊泡尺寸增大到250 nm。然而继续增大盐浓度到1000 mmol/L, 囊泡尺寸减小到180nm. FF-TEM结果发现盐浓度小于150 mM时, 单个囊泡为70 nm左右,然而明显存在囊泡的絮凝与融合;当盐浓度增加到400 mM时,单个囊泡尺寸减小到20 nm. 因此DLS 观测到囊泡尺寸增大的原因是由于囊泡的絮凝与融合;而尺寸减小的原因是由于在高盐浓度下,盐屏蔽了带电颗粒之间的静电相互作用,在熵增的驱使下,大囊泡变成小囊泡。     

高浓度区正负离子表面活性剂混合胶团的形状与大小变化

本文研究高浓度区正、负离子表面活性混合胶团的形态及大小随浓度的变化规律。根据正、负离子表面活性剂混合体系的相行为,胶团溶液的光散射以及流变性质测量,提出了混合胶团的棒-球转变模型。认为在较高浓度,随浓度增大,混合胶团经历了一个长棒变短,短棒变为球状的转变过程。     

Phase behaviour and physicochemical properties of microemulsions with a non-ionic surfactant (IGEPAL)

The non-ionic surfactant pentaethylenglycol-4-octylphenyl ether (igepal CA-520) represents a good industrial alternative to the long-tail members of the C_iE_j family. In this paper, the phase behaviour of the microemulsion system igepal CA-520/n-decane/brine is studied in detail. An isotropic phase was found, as well as liquid crystalline and cream-like structures, depending on composition and temperature. Such structures can either form single-phase homogeneous mixtures, or coexist with other structures when phase separation takes place. Below surfactant concentration of about 20%, more complicated phase equilibria develop as temperature changes. The presence of different additives shifts the temperature ranges where the different phases exist, while keeping the general shape of the phase diagram, which agrees with the general rules for non-ionic surfactants. Complementary rheology experiments reveal a change from non-Newtonian to Newtonian behaviour during the phase transition from a lamellar phase to the isotropic microemulsion. A structure of water droplets associated in clusters can be proposed from SANS and electrical conductivity.     

正负离子表面活性剂混合体系中高稳定性囊泡的形成

对总浓度为0.01 mol/L，摩尔比为2：1的十二烷基硫酸钠/溴化十二烷基三乙 铵的正负离子表面活性剂混合体系形成的囊泡的稳定性进行了研究。发现这一体系 形成的囊泡在长放置（5个月）后依然存在。在加入较大量的无机盐（0.15 mol/L NaBr）、较大幅度pH变化（pH = 2～12）、温度变化（从80 ℃到-22 ℃）情况下 体系中的囊泡依然呈现出优异的稳定性。在非水溶剂乙醇（100%）中这类正负离子 表面活性剂仍然可以形成囊泡。     

阴离子Gemini表面活性剂和阳离子传统表面活性剂混合体系双水相中囊泡形貌的转变

通过电子显微镜观察了阴离子gemini表面活性剂C₁₁- p-PhCNa和阳离子传统表面活性剂DTAB混合体系双水相中囊泡形貌随体系组成和浓度的转变。结果表明,双水相较浓的一相中形成了多层囊泡,囊泡的大小和壁厚随相的组成和浓度而改变,两组分等电荷混合有利于形成较大且壁较厚的囊泡。分析表明, gemini表面活性剂在聚集体中采取的反式构象可能是其容易形成厚壁多层囊泡的重要原因,C₁₁- p-PhCNa联接链上的苯氧基与DTA⁺之间的p-阳离子相互作用以及两组分相反电性头基之间的静电吸引使囊泡壁的多层结构更加稳定。     

Soy Oil Microemulsions Made of Anionic Surfactant,Oleic Acid,Diethyleneglycol Ethyl Ether,and Water: Optimized Systems

Soy oil microemulsions has been optimized for systems made of phosphated oleyl ether 3EO as surfactant, oleic acid, diethyleneglycol monoethyl ether, and water. The soy oil solubilization has been estimated as a function of different ratios between surfactant/oleic acid (5/95, 10/90, 15/85, and 20/80) and water/glycol (4/1, 2/1, 1/1, 1/2, and 1/4). The maximum simultaneous solubilization of soy oil and hydrophilic phase (water plus glycol) in ratios 3/1, 1/1, and 1/3 (besides the 1/0 and 0/1) was considered. In order to display the widest microemulsion area, the better ratios surfactant/oleic acid were 10/90, 15/85, and 20/80 when water and glycol ratios were 1/2 and 1/4. For these systems, the transition between W/O, bicontinuous and O/W microemulsions were followed through electrical conductivity changes.     

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.     

Design of bicontinuous polymeric microemulsions

Recent experiments suggest that thermodynamically stable, bicontinuous microemulsions can be achieved in symmetric ternary blends of two homopolymers and a diblock copolymer by formulating alloys with compositions near mean-field isotropic Lifshitz points. We argue that practical application of this design criterion may require use of homopolymers of unequal molecular weights and block copolymers of different architecture. We demonstrate the existence of, and explicitly locate, mean-field isotropic Lifshitz points in ternary blends with homopolymer molecular weight asymmetry and either AB diblock or ABA triblock copolymer architectures. These calculations considerably expand the parameter space for observing bicontinuous microemulsions and allow for more flexibility in tailoring melt rheological properties and solid-state mechanical properties. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2775–2786, 1997     

碳氟-碳氢表面活性剂混合水溶液在油面上铺展

本文研究RfCONH(CH2)3N(C2H5)2CH3I/CnH2n 1,COONa及RfCOONa/CmH2m 1N(CH3)3Br(Rf=F[CF(CF3)CF2O]2CF(CF3);n=7,8.11,13;m=8,10,12)两类正，负离子碳氟－碳氢表面活性剂混合水溶液在油面上的铺展及对油面的密封性能。研究表明在碳氟表面活性剂中加入异电性碳氢表面活性剂可大大降低碳氟表面活性剂水溶液的铺展浓度，也可使一些因素表面张力较高而不能铺展的碳氟表面活性剂水溶液在油面上铺展。在碳氟表面活性剂中加入异电性碳氢表面活性剂可提高水膜对油面的密封性。若在混合表面活性剂中加入黄原胶，水膜的密封性能更好。     

阴离子、阳离子和非离子表面活性剂在纳/微米草酸钙晶体上的吸附差异

研究了尺寸分别为50 nm和3μm的一水草酸钙(COM)和二水草酸钙(COD)晶体对不同电荷表面活性剂的吸附差异,包括阴离子型表面活性剂磺基琥珀酸钠二辛酯(AOT)、阳离子型表面活性剂十六烷基三甲基溴化铵(CTAB)和非离子型表面活性剂壬基酚聚氧乙烯醚(NP-40),探究了尿液中带不同电荷的分子对纳米、微米尿微晶的影响。结果表明,表面活性剂的吸附量大小为AOTCTABNP-40,即阴离子型表面活性剂的吸附量最大,非离子型表面活性剂的吸附量最小;晶体尺寸相同时,COM的吸附能力稍大于COD;吸附表面活性剂后,晶体表面的ζ电位绝对值都增大,有利于抑制晶体的团聚和沉降。提出了晶体吸附不同表面活性剂的分子模型。不同电荷表面活性剂与纳/微米COM、COD晶体之间存在不同的相互作用。表面活性剂吸附量越大,沉降越慢,对晶体悬浮液的稳定效果越明显。     

阴离子、阳离子和非离子表面活性剂在纳/微米草酸钙晶体上的吸附差异

目的：研究尺寸分别为50 nm和3 μm的一水草酸钙（COM）和二水草酸钙（COD）晶体对不同电荷表面活性剂的吸附差异,包括阴离子型表面活性剂磺基琥珀酸钠二辛酯（AOT）、阳离子型表面活性剂十六烷基三甲基溴化铵（CTAB）和非离子型表面活性剂壬基酚聚氧乙烯醚（NP-40）,探究尿液中带不同电荷的分子对纳米、微米尿微晶的影响。方法：测定不同表面活性剂在纳/微米COM、COD晶体上的吸附量;采用ζ电位仪测定吸附不同表面活性剂后晶体表面的ζ电位;检测加入不同表面活性剂后悬浮液的沉降系数。结果：表面活性剂的吸附量大小为AOT > CTAB > NP-40,即阴离子型表面活性剂的吸附量最大,非离子型表面活性剂的吸附量最小;晶体尺寸相同时,COM的吸附能力稍大于COD;吸附表面活性剂后,晶体的ζ电位绝对值都增大,有利于抑制晶体的团聚和沉降。提出了晶体吸附不同表面活性剂的分子模型。结论：不同电荷表面活性剂与纳/微米COM、COD晶体之间存在不同的相互作用。表面活性剂吸附量越大,沉降越慢,对晶体悬浮液的稳定效果越明显。     

Sub-zero temperature behaviour of non-ionic microemulsions in the presence of propylene glycol by DSC

The five-component system is quite unique since it allows formation of reverse micelles with hydrophilic ethoxylated alcohol in the presence of ethanol and it facilitates dilution by water/propylene glycol (1,2-propanediol, PG) aqueous phase, all the way from a water-in-oil (W/O) microemulsion via a bicontinuous phase to an oil-in-water (O/W) microemulsion.The surfactant/alcohol/PG can strongly bound water in the inner phase so that it freezes below –10°C and acts in part as bound water and in part as non-freezable water. Upon dilution to >30 mass% aqueous phase (water/PG at constant mass ratio of 1/1) the system becomes bicontinuous and the aqueous layers are composed again from bound water. Even after complete inversion to O/W microemulsions the water in the continuous phase is strongly interacting with the PG/surfactant and remains bound or non-freezable. Water/PG/ethanol have a strong effect on the head groups (freezing below -10°C) and also on the hydrophobic tails (recrystallizing and melting) at lower temperature when dilution exceeds 45 mass% water/PG (1/1).No free water was detected neither in the W/O microemulsion's inner droplet domains nor when the microemulsion was either bicontinuous or when it was inversed to O/W. Continuous phase of resulting O/W microemulsion apparently is based on water/PG at a mass ratio of 1/1.This revised version was published online in November 2005 with corrections to the Cover Date.     

SDS及其与十二烷基三乙基溴化铵混合体系在矿化水中的表面活性

测定了十二烷基硫酸钠(SDS)、十二烷基三乙基溴化铵(DTEAB)单一体系及不同摩尔比的混合体系在矿化水溶液中的表面活性,并与在纯水和NaCl水溶液中的表面活性作了比较．所得结果表明：(1)阴离子表面活性剂SDS在含Ca^2 ,Mg^2 等的矿化水中有比在纯水和NaCl水溶液中更好的表面活性．这一方面是由于矿化水中的Ca^2 ,Mg^2 对负电胶团和表面吸附层的强烈电性作用,另一方面在大量Na^ 存在时,钠钙盐混合表面活性剂Krafft点提高不多;(2)SDS和DTEAB混合物在矿化水中具有很强的增效作用,其表面活性的变化规律与在纯水和NaCl水溶液中基本相同,表明阴阳离子表面活性剂混合体系具有优异的抗矿化水性能．这些结果可用阴、阳表面活性离子的电性作用解释．     

Organic reactions and nanoparticle preparation in CO(2)-induced water/P104/p-xylene microemulsions

Nanometer-sized gold particles are synthesized by the reduction of HAuCl(4) with KBH(4) in the CO(2)-induced microemulsion of (EO)(27)(PO)(61)(EO)(27) (P104; EO=ethylene oxide, PO=propylene oxide)/p-xylene/CO(2)/H(2)O. The recovery of gold particles from the microemulsion can be easily accomplished by the venting of CO(2), while the surfactant remains in the organic phase. The effect of the molar ratio of the reductant to HAuCl(4), the concentration of the reactants, and the molar ratio of water to EO segments (W(0)) in the reverse micelles on the size of the gold particles is studied. The hydrolysis of benzoyl chloride (BzCl) and p-nitrophenyl chloroformate (NPhCl) has also been carried out in the microemulsion. The results show that the observed rate constants k(obs) of both substrates increase significantly with W(0), and that W(0) has a larger influence on the hydrolysis of BzCl. The different extents of the influence of W(0) on the two reactions can be ascribed to the different reaction mechanisms and the expected changes in nucleophilicity and polarity of water in the reverse micelles.     

DSC spectra as thermal fingerprints of percolative microemulsions

Three component percolative W/O microemulsions were studied by differential scanning calorimetry. Water-AOT-Decane, D₂O-AOT-Decane, Water-AOT-Isooctane and Water-Ca(AOT)₂-Decane systems were analyzed. Thus by changing, in the order, the dispersed phase, the dispersing medium, and by modifying the interphase region. The thermal history of the samples was monitored by a suitable thermal program. Following the latter, first order phase transitions associated with the freezing and/or melting of the two massive phases were obtained, as well as the higher order phase transition associated with the percolation process. From the melting spectra an estimate of the amount of water bound to the hydrophilic groups of the AOT as well as of that of oil bound to the hydrophobic surfactant tails was obtained. The latter result shows a difference in the behaviour of the continuous oily phase at the O/W interphase. From the freezing spectra, the percolative character of the microemulsion was evidenced by the exotherms associated with the freezing of the water phase. This work was supported by M.U.R.S. T. and I.N.F.M.     

Vesicle formation of 1:1 cationic and anionic surfactant mixtures in nonaqueous polar solvents

The vesicle formations of 1:1 cationic-anionic surfactants in various nonaqueous polar solvents and their aqueous mixtures were investigated. Outstanding vesicle-forming capability and stability of cationic and anionic surfactants were found in nonaqueous polar solvents and their aqueous mixtures except for in formamide. A small amount of formamide destroys the vesicles formed by cationic-anionic surfactants in aqueous solutions. These results could be very well explained based on the effect of the medium dielectric constant. Received: 26 May 1998 Accepted in revised form: 24 November 1998     

盐对正负离子表面活性剂双水相性质的影响

主要研究了盐对SDS/CTAB/H₂O混合系统双水相相行为的影响, 并对双水相上相的液晶性质进行了初步的探索. 结果表明: 盐能促使阴离子双水相区和阳离子双水相区分别向SDS和CTAB方向移动, 并使双水相区加宽. 反离子扩散双电层中盐的离子半径越大, 其对ATPS区的位置及相区宽度的影响程度越大. 盐的浓度达到一定值时, 它对双水相的影响可以达到饱和状态. ATPS_a区的饱和盐浓度值大于ATPS_c区的饱和盐浓度值. 异号盐离子对反离子层的限制作用与其离子半径有关.