The Effects of Alcohol with Different Chain Length on the Phase Equilibria of Nonionic Surfactant System

Addition of alcohol with longer chain length (C₆H₁₃OH, C₈H₁₇OH, and C₁₂H₂₁OH) caused a reduction the cloud point of a commercial nonionic surfactant, Tesgitol (T_15-s-9). The formation of lamellar liquid crystal (LLC) was favored so that isotropic liquid (L₁)-LLC two-phase region became wider with increasing temperature at an appropriate weight ratio of surfactant to alcohol. The isotropic liquid phase/liquid two phase transformation was replaced by a two-phase transformation to isotropic liquid/lamellar liquid crystal at the cloud point for the system without alcohol.     

Geranyl Acetate Emulsions: Surfactant Association Structures and Stability

The phase diagram of fragrance oil, geranyl acetate, water, and a surfactant, Laureth 4, was used to calculate the surfactant association structures present in emulsions with constant O/W ratio for increased fractions of surfactant. The liquid crystal appeared in the emulsion at a critical value of the surfactant fraction and additional surfactant caused an approximately linear increase of it, while the fraction of the aqueous phase experienced a corresponding reduction. The result of the calculations was confirmed by optical microscopy observation with the samples between crossed polarizers. The calculations revealed the formation of vesicles from the liquid crystal to result in a drastic reduction of the “free” aqueous phase, due to the amount of the aqueous liquid forming the core of the vesicle.     

MICROEMULSION SYSTEMS WITH A NONIONIC COSURFACTANT

The conditions to obtain W/0 microemulsions using ionic surfactants and a nonionic cosurfactant, a polyoxyethylene alkyl ether, were investigated. The length of the polyoxyethylene chain was critical to obtain the typical water solubilization maximum

The variation of the W/0 microemulsion region with hydrocarbon content was different from that of the usual type of microemulsions having a medium chain length alcohol as cosurfactant. In the present systems the W/0 microemulsion region was not a direct continuation of the inverse micellar area at zero content of hydrocarbon. Addition of hydrocarbon was necessary for the formation of inverse micelles

The microemulsion regions were sensitive to the kind of hydrocarbon used; a sign of the importance of the nonionic surfactant for the stability of this kind of microemulsions.     

POLYMERIC SURFACTANTS BASED ON OLEIC ACID III. Copolymerization of Sodium Acrylamidostearate and Oleic Acid in a Lamellar Liquid Crystal

Copolymerization of sodium acrylamidostearate (NaAAS) and oleic acid was performed in the lamellar liquid crystal (LLC) formed by NaAAS, oleic acid and water, in the absence of N.N’-methylenebisacrylamide (MBAA) and in the presence of MBAA, respectively. In the absence of MBAA, after the polymerization the lamellar structure remained, and the disorder of the lamellar liquid crystal was, to some extent, enhanced. Surface tension, small-angle X-ray diffraction, viscosity, and fluorescence methods were used to study the properties of the linear copolymer. The linear polymeric surfactant behaves like     

Influence of Charge Density of Anionic Polyelectrolytes on Structure Formation in Liquid Crystalline Systems

The influence of different amounts of anionic copolymers of N-Methyl N-vinyl acetamide (NMVA) and acrylic acid with various charge densities on the formation of the lamellar liquid crystal formed by sodium dodecyl sulfate (SDS)/decanol/water was investigated by means of polarization microscopy, small angle x-ray scattering (SAXS), transmission electron microscopy and rheology. On the contrary to the incorporation of poly(acrylic acid)     

Swelling of Water/Nonionic Surfactant Lamellar Liquid Crystals: A Model

A model is presented to provide quantitative measures to estimate the trends of the change in the penetration of the added component into the polar part of the amphiphile layer in lamellar liquid crystals of water and ethoxylated surfactants with added water (or polar solvents). The total thickness of the bi‐layer is treated as composed of an aqueous layer, of a layer of the polar groups from the surfactant and of the hydrocarbon chains of the latter. A fraction α of the added water is assumed penetrating the polar group layer leading to its expansion. The evaluation is built on the fact that experimental determinations of the interlayer spacing in the overwhelming majority of cases show a first order linear dependence on the ratio of added water. In the model this linearity is obtained by variation of the degree of penetration of water. The model indicated a reduction in the degree of penetration with added water, which is a rational trend. The model demonstrates the earlier interpretation of a structure, whose interlayer spacing is invariant with water contents as nonswelling; for example, in which all added water penetrates the amhiphile layer, is not appropriate. The model demonstrates the constancy of the interlayer spacing to be a consequence of a balance between the expansion of the amphiphile layer and the increase of a “free water” layer.     

HYDROTROPES

The structure and action of hydrotropes are discussed using surfactant association structures as a model.

The main action of a hydrotrope is to prevent phase separation from an aqueous solution; either by disordering of a lamellar liquid crystal or by preventing the formation of well defined normal and inverse micelles.     

Some experiments on complex spontaneous emulsification in the system water–benzene–ethanol

The system water–benzene–ethanol was used to illustrate the complexity of spontaneous emulsification, when water-poor emulsions are brought in contact with water. In the first case, an O/W emulsion located close to the plait point in the system was used. The aqueous phase in the emulsion was incompatible with water, and a strong spontaneous emulsification to an O/W between the two liquids took place in the water layer close to the interface between layers. In the second case, a W/O emulsion, also close to the plait point, was brought in contact with water. Now, the spontaneous emulsification between the water and the oil phase of the original emulsion to an O/W emulsion also took place in the water layer forming a distinct emulsion layer beneath the interface.     

Minimum Evaporation Model of Dermatological Delivery Systems. Lamellar Liquid Crystal Formulations Containing Brazilian Nut (Bertholletia excelsa HBK) Vegetable Oil and Guarana Glycolic Extract

Formulations with lyotropic liquid crystals were prepared from a Brazilian nut vegetable oil, guarana extract and combination of sorbitan monooleate (Span 80) and sorbitan monolaurate ethoxylate EO 20 (Tween 20) in the ratio 1:3 (surfactant component) and their physical–chemical aspects and rheological properties were determined. Compositions with liquid crystals were found in the pseudoternary diagram in a surfactant range of 70–90% and polarized light microscopy, small-angle x-ray scattering (SAXS) showed them to be lamellar. The preparations were furthermore characterized rheologically by shear stress shear rate sweeps finding plastic and pseudoplastic behavior without thixotropy. Electric conductivity and pH measurements demonstrated a potential for future application as dermatological delivery system of the active compounds in the Bertholletia excelsa and Paullinia cupana.      

Destabilization of a dual emulsion to form a Janus emulsion

A vegetable oil (VO) was added to an emulsion of silicone oil in water (SO/W) with mixing limited to once turning the test tube upside down. Initially, the VO was dispersed into virtually centimeter-sized drops and the emulsion contained effectively no Janus drops, while after 1 h of agitation at a low level to prevent creaming, drops of 50–100-μm size of the two oils were observed: in addition to an insignificant number of Janus drops. The topology of the latter showed them to emanate from flocculated individual drops of the two oils, but with no discernible effect by the interfacial tension equilibrium on the drop topology. Continued gentle mixing gave increasing fraction of Janus drops of increased size with a topology gradually approaching the one expected from the interfacial equilibrium at the contact line. The spontaneous formation of Janus drops indicated a reduction of the interfacial free energy in the process and the interfacial energy difference between separate and Janus drops was calculated for an appropriate range of interfacial tensions and for all oil fractions. The calculations enabled a distinction of the decrease due to interfacial area changes from the reduction of interfacial tensions per se, with the latter only a minor fraction. Figure

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