Interfacial composition, structural parameters and thermodynamic properties of water-in-oil microemulsions

The formation and structural characteristics of water-in-oil microemulsions comprising hexadecylpyridinium chloride (CPC), alkanols (C₄–C₆) and alkanes (C₅, C₈–C₁₀) have been investigated by the method of dilution. The compositions of the surfactant and the cosurfactant in the interfacial region (interphase) of the microemulsion droplets have been determined. The thermodynamics of transfer of the cosurfactants (alkanols) from the continuous oil (alkane) phase to the interface have been evaluated from dilution measurements at different temperatures. The structural parameters, radii of the droplet and the waterpool, aggregation numbers of CPC and the alkanols in the interphase of a droplet, and the nanoparticle density of solution have been estimated assuming monodispersity of the droplets. The thermodynamics and structural parameters have been examined in terms of the chain lengths of the alkanols and alkanes. Received: 12 September 2000 Accepted: 27 October 2000     

Effects of polymer addition on the rheology of o/w microemulsions

Microemulsions are profitably employed in the pharmaceutical field to prepare drug delivery systems release for guest drugs sparingly soluble in water. In particular, they can be used for topical and transdermal administration in place of ointments or creams, on condition that their rheological properties are properly modulated. The present work concerns the analysis of the rheological effects produced by the addition of different amounts of Carbopol 940, a polymer widely used for topical applications, to an O/W microemulsion containing a lipophilic phase (Labrafac Hydro, 21 wt%) and stabilized by the surfactant (Cremophor RH40)/co-surfactant (Transcutol) couple. The contribution of the disperse phase is evaluated by comparing the linear and nonlinear properties of the Carbopol/microemulsion system (CM) with those of the corresponding aqueous Carbopol systems with co-surfactant (CWT) and without co-surfactant (CW). Four polymer concentrations (0.25%, 0.5%, 1%, and 2%) are taken into consideration. The linear viscoelastic properties of the microemulsions essentially mirror those of the corresponding aqueous Carbopol systems when the polymer concentration is sufficiently high (1–2%). In these conditions the oil phase is reasonably hosted within the meshes of the three-dimensional polymeric gel network and gives only a slight contribution to the connectivity of the whole system. Similar considerations can be drawn from the flow behavior of the systems examined in the low shear region. Received: 6 February 2000 Accepted: 13 November 2000     

光散射技术在研究高分子溶液和凝胶方面的应用

从溶液中的高分子、凝胶粒子及微乳胶粒子形态结构的表征和凝胶化过程、微乳液聚合及大分子缔合等动态过程的跟踪等方面的研究综述了近十几年来光散射技术在高分子溶液和凝胶领域的应用,并简单介绍了光散射技术的基本原理、发展简史和仪器及使用方法。     

Polymerisation of vinyl acetate in microemulsions with methanol

 The homogeneity domains for the system vinyl acetate – methanol – monomaleate of nonylphenol ethoxylated with 25 mol ethylene oxide as an aqueous solution (MEMNPEO25) (33%) have been studied; it has been shown that, due to the shorter chain of methanol, these domains are more reduced than in the case of ethanol. The changes in refractive indexes and electrical conductivities have shown the formation of microemulsions with different structures (water-in-oil, bicontinuous or oil-in-water). Ammonium persulphate is soluble only in oil-in-water or in bicontinuous microemulsions. The initial polymerisation rates as well as the decomposition rates for the initiator are apparently affected when the microemulsion structure is modified. The polymerisation rate of vinyl acetate is higher in the presence of methanol than in the presence of ethanol for similar compositions; this fact may be attributed to a higher degree of ionisation of the initiator in the presence of methanol. Also, in polymerisations initiated by benzoyl peroxide, the conversions are influenced by the microstructure; thus, the maximum corresponds to water-in-oil microemulsions. By measuring the amount of unreacted MEMNPEO25 (gel permeation chromatography) we were able to show that the copolymer formed consisted of vinyl acetate and reactive surfactant. Received: 9 March 1999/Accepted: 13 March 2000     

Estimation of the aggregation number and core radius of microemulsions

Summary A simple working method for the estimation of the aggregation numbers and core radii from weight measurements of sodium bis-2-ethylhexylsulphosuccinate (aerosol-OT orAOT)/decane/water microemulsions of several compositions is proposed.Starting out from the hypotheses that (i) the density of the water inside the droplets is the same as that of free water, (ii) all the surfactant is localized as interface, and (iii) the penetration of the organic phase into the interface is negligible, values for the aggregation number and core radii comparable to those determined using more sophisticated methods were obtained.The results/methodological simplicity ratio may be of great advantage in kinetic work on reaction mechanisms in microemulsions.

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Abschätzung von Aggregationszahl und Radius von Mikroemulsionen

Zusammenfassung Es wird eine einfache Methode zur Abschätzung von Aggregationszahl und Core-Radius von Mikroemulsionen aus Gewichtsmessungen von Natriumbis-2-ethylhexylsulphosuccinat (aerosol-OT oderAOT)/Decan/Wasser-Mikroemulsionen verschiedener Zusammensetzung vorgeschlagen. Unter den Annahmen, daß (i) die Dichte von Wasser innerhalb der Aggregationen die gleiche als bei freiem Wasser ist, (ii) das ganze Emulsionsmittel in der Grenzfläche vorliegt und (iii) das Eindringen der organischen Phase in die Grenzfläche vernachlässigbar ist, können Werte für Aggregationszahlen und Core-Radien erhalten werden, die durchaus mit entsprechenden Werten aus aufwendigeren Methoden vergleichbar sind. Das Leistungsverhältnis (Ergebnisse/geringer Aufwand) ist sehr vorteilhaft und macht die Methode für kinetische Arbeiten zur Bestimmung von Reaktionsmechanismen in Mikroemulsionen interessant.

     

Rheological analysis of triblock copolymer-microemulsion networks

The rheological properties of microemulsion-triblock copolymer [poly(oxyethylene)-b-polyisoprene-b-poly(oxyethylene)] networks were studied by oscillatory shear measurements. The principal viscoelastic pattern of our systems stays the same whether the surfactant is ionic or nonionic. A closer examination shows, however, the enormous influence of the respective phase behavior of the underlying microemulsions. Also, specific interactions between the surfactants and the hydrophilic poly(oxyethylene) blocks lead to a significant effect on the formation of network structures.Characteristic rheological data such as plateau moduli and relaxation times for a series of different samples were derived differing in polymer or droplet concentrations, apart from the molecular weights of the poly-(oxyethylene) and the polyisoprene blocks. Finally, we could construct polymer and droplet concentration invariant master — mastercurves using the temperature invariant mastercurves.     

The self-organization properties of <Emphasis Type="Italic">n</Emphasis>-dodecylammonium α-glutamate/<Emphasis Type="Italic">n</Emphasis>-C<Subscript>5</Subscript>H<Subscript>11</Subscript>OH/water system

A biocompatible surfactant-n-dodecylammonium α-glutamate (GDA) with biodegradable and biocompatible properties was synthesized, and the phase behavior and the structural properties of GDA/n-pentanol/water system was studied by small-angle X-ray diffraction, electron spin resonance, and freeze-fracture transmission electron microscopy (FF-TEM). In the ternary phase diagram of GDA/n-pentanol/water system, there exist three isotropic regions—O/W, bicontinuous, and W/O structures, and two anisotropic regions—hexagonal liquid crystal (HEX), and lamellar liquid crystal (LLC) regions. UV irradiation causes the decrease in the interlayer space, d, of lamellar liquid crystal and in the radius, r, of column aggregates of hexagonal liquid crystal, but it has little effect on the structure of O/W and W/O microemulsions.     

载药微乳液相行为的研究

提出了一种基于相图研究实现纳米药物载体可控制备的方法.采用微乳液控温相图绘制装置绘制了硬脂酸聚烃氧(40)酯(S-40)/聚氧乙烯聚氧丙烯醚嵌段共聚物(F-68)/单硬脂酸甘油酯(GMS)/水体系的拟三元相图,基于电导率测定值确定了微乳液的结构(W/O、双连续相和O/W),该体系同时存在液晶区域.乳化剂S-40/F-68的质量比为7:3.研究了脂溶性药物维甲酸(RA)对微乳液相行为的影响，结果表明RA的加入对微乳液的相行为影响较小.基于相图研究结果制备了维甲酸固体脂质纳米粒(RA-SLN),亚微米粒度分析仪(PCS)测定的平均粒径和透射电镜测试都表明RA-SLN为10 nm左右的球状粒子.     

The use of microemulsion for determination of sodium and potassium in biodiesel by flame atomic absorption spectrometry

A new method for F AAS determination of sodium and potassium in biodiesel using water-in-oil microemulsion as sample preparation is proposed. The method was investigated for biodiesel produced from different sources, as soybean, castor and sunflower oil and animal fat and was also applied for vegetable oils. The optimized condition for microemulsion formation was 57.6% (w/w) of n-pentanol, 20% (w/w) of biodiesel or vegetable oil, 14.4% (w/w) of Triton X-100 and 8% (w/w) of water (aqueous standard of KCl or NaCl in/or diluted HNO₃). The optimized instrumental parameters were: aspiration rate of 2 mL min⁻¹ and the flame composition of 0.131 of C₂H₂/air ratio. For comparison purpose, the determination of sodium and potassium were also carried out according to European norms (EN 14108 and EN 14109, respectively). These norms are applied for determination of sodium and potassium in fatty acid methylic ester samples and consist in the sample dilution using organic solvent and determination by F AAS. The stability of microemulsified aqueous standards and samples was investigated and it was found to be stable for at least 3 days while the organic standard diluted with xylene showed a decrease around of 15% in the analytical signal in 1 h. The limits of detection were 0.1 μg g⁻¹ and 0.06 μg g⁻¹ and the obtained characteristic concentrations were 25 μg L⁻¹ and 28 μg L⁻¹ for sodium and potassium, respectively. The proposed method presented two times better limits of detection and better precision (0.4–1.0%) when compared with the dilution technique (1.5–4.5%). The accuracy of the method was evaluated through recovery tests and comparison with the results obtained by dilution technique. The recoveries ranged from 95% to 115% for biodiesel and 90% to 115% for vegetable oil samples. Comparison between the results obtained for biodiesel by both methods showed no significant differences at the 95% confidence level according to a Student's t-test. This study shows that the proposed method based on microemulsion as sample preparation can be applied as an efficient alternative for sodium and potassium determination in biodiesel samples.