Mechanistic investigation on the formation of epoxy resin multi‐hollow spheres prepared by a phase inversion emulsification technique

Micrometer sized multi‐hollow spheres of epoxy resin were prepared by a physical method so‐called phase inversion emulsification technique. The formation mechanism of the titled spheres was studied by incomplete phase inversion. The requisite for the formation of multi‐hollow spheres was that irreversible coalescence among the water droplets under shear action before the phase inversion point existed. This process could be facilitated by a lower emulsifier concentration and a higher emulsification temperature. Moreover, a theoretical explanation of the formation of the titled spheres was presented.     

Polyurea nanocapsules obtained from nano‐emulsions prepared by the phase inversion temperature method

We describe here a new and simple method for preparation of polyurea nanocapsules from nanodroplets that were obtained by the phase inversion temperature (PIT) method. In the first stage, a nano‐emulsion was prepared, by a heating–cooling cycle, in which the oil phase contained an oil soluble monomer (toluene 2 , 4 ‐diisocyanate (TDI)). In the second stage, a water‐soluble monomer and crosslinker (diethylenetriamine (DETA)) was added, leading to formation of a polymeric shell by an interfacial polycondensation reaction. The new method was demonstrated for obtaining nanocapsules of about 100 nm, in which hexadecane, dodecane, or decane were the core materials, without using any special equipment. The morphology and structure of the nanocapsules were evaluated by attenuated total reflection Fourier transform infrared (ATR‐FTIR) measurements and electron microscopy. The thermal behavior of the nanocapsules containing hexadecane was studied by Differential Scanning Calorimetry (DSC) measurements, indicating that such nanocapsules can be utilized in thermal energy storage. Copyright © 2010 John Wiley & Sons, Ltd.     

Nanoemulsion formation by phase inversion emulsification: on the nature of inversion

Emulsification processes are usually characterized by the way they allow the surfactants, as well as the dispersed phase, to be incorporated into emulsions. A model cyclohexane-in-water emulsion using a pair of polyoxyethylene nonylphenyl ether surfactants, one oil-soluble and one water-soluble, was considered. Two surfactant mixing approaches consisting of mixed surfactants (agent-in-oil and agent-in-water) and segregated surfactants (agent in corresponding oil and water phases) were used to produce the model emulsion. Formation of oil-in-water nanodroplets could be only achieved if emulsification was associated with the formation of a three-phase microemulsion structure (transitional phase inversion) across the path. This occurred only if segregated surfactants were used in a process in which water was added to oil. With decreasing surfactant concentration, a point was reached below which the inversion mechanism transformed from transitional to catastrophic, leading to the formation of large droplets. The transformation was also accompanied by a shift in the evolution of the drop size. Drop size variations showed a minimum at the inversion point for the transitional phase inversion, whereas they showed a maximum for the catastrophic phase inversion. The agent-in-oil technique followed a catastrophic phase inversion mechanism and ranked second in terms of drop size.     

Hydroxyapatite nanoparticle prepared by controlled precipitation from aqueous phase

Hydroxyapatite nanoparticles (NPs) were prepared by controlled precipitation in the presence of stabilizers that confined growth and inhibited the aggregation of nanoparticles. Electrostatically stabilized NPs were prepared in the presence of sodium citrate; Tween 80 was used for steric stabilization. At low stabilizer concentrations, nanorods were formed of grown together, spheroidal hydroxyapatite NPs of ~20 nm in diameter. The rod length decreased as ether sodium citrate or Tween 80 concentration increased. When Cit^3–/Ca²⁺ = 3mol/mol, platelike NPs were formed 20–45 nm long and ~10 nm wide; for Cit^3–/Ca²⁺ = 4 mol/mol, NPs had sizes of 10–15 nm. At relatively high Tween 80 concentrations (>0.05 mol/L), foamlike structures were obtained.     

The influence of internal phase viscosity on the viscosity of concentrated water-in-oil emulsions

Summary The influence of the viscosity of the internal phase on the viscosity of concentrated water-in-oil emulsions has been investigated and found to be negligible. It is indicated that thechemical nature of the dispersed medium may be of importance, however, with particular reference to its relationship to the stabilising agent, and an example of this is given. In liquid suspensions the ratio of the viscosities of the two phases is of importance in the transmission of viscous effects from the continuous to the disperse medium. This is not found to be the case for the emulsions examined, and the significance of the rigid structure of the interfacial film in this respect is discussed.

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Zusammenfassung Der Einflu? der Viskosit?t der inneren Phase auf die Viskosit?t von konzentriertem Wasser-in-?lemulsion wurde untersucht. Er ist vernachl?ssigbar. Dagegen ist die chemische Struktur des dispergierten Mediums wichtig, besonders im Zusammenhang mit dem Stabilisator, wie ein Beispiel zeigt. Da in flüssigen Suspensionen das Verh?ltnis der Viskosit?ten der beiden Phasen für die Berechnung der Viskosit?t der Dispersion aus denen der beiden Medien eine Rolle spielen sollte und dies bei den untersuchten Emulsionen nicht der Fall war, wird eine Wirkung von festen Grenzfl?chenfilmen für eine Erkl?rung diskutiert.

     

磺化聚苯乙烯离聚体水基微乳液乳化过程中相反转机理的研究

将聚苯乙烯改性制成磺化聚苯乙烯离聚体，溶解在甲苯／甲醇混合溶剂中，缓慢加水将聚苯乙烯乳化成稳定的水包油的水基微乳液。本文通过研究在乳化过程中体系粘度和导电性的变化，研究了聚苯乙烯离聚体溶液乳化过程的相反转机理和离子含量对乳化过程和相反转机理的影响。     

Compartmentalization and separation of aqueous reagents in the water droplets of water-in-oil high internal phase emulsions

We have compartmentalized aqueous reagents and indicator species within the micrometer-sized water droplets of mixed high internal phase emulsions (HIPEs). Mass transport of the reagents across the micrometer-thickness oil films separating the water droplets followed by reaction with the indicator species produces a visible color change which provides a simple method to measure the trapping times of the reagents. Trapping times have been measured for an uncharged reagent (hydrogen peroxide) and charged reagents (HCl and NaClO) in different HIPEs. The trapping times are discussed in terms of a model in which the transferring species partitions from the water to the oil film followed by a rate-determining step of diffusion across the oil film. Rather surprisingly, it is found that trapping times are of similar orders of magnitude for both uncharged and charged aqueous species transferring across liquid oil films.     

Curing of neat ED-20 epoxy resin and of its aqueous emulsions

The behavior of neat ED-20 epoxy resin and of its aqueous emulsions in the course of heating in the temperature interval 20–500°С in the presence of cross-linking agents of different structures (NC-558, polyethylenepolyamine, Telalit 180, Epilink 701) was studied. The water absorption, hardness, and microstructure of coatings prepared from these epoxy systems were examined.     

Characterization of DNA-loaded porous polyethersulfone particles prepared by phase inversion technique

In this study, DNA-loaded polyethersulfone (PES) porous particles were prepared by means of a liquid-liquid phase separation technique. The porous structure parameters and the diameter of the particles were then determined. It was found that the PES concentration strongly affects the porous structure and the specific surface area of the particles. By manipulating the preparation conditions, it is possible to control the structure of the particles. The DNA-loaded PES microspheres prepared using the phase inversion method are stable in water and an aqueous NaCl solution, while the DNA is hydrolyzed under acidic conditions. The DNA-loaded PES microspheres effectively accumulate harmful DNA-intercalating pollutants and endocrine disruptors, such as ethidium bromide and acridine orange, and have the potential to be used in environmental applications.__________From Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 167–172.Original English Text Copyright © 2005 by Changsheng Zhao, Kaiguang Yang, Xuesong Zhou, Yi Lei, Gang Yang, Yong Lei, Norio Nishi.This article was submitted by the authors in English.     

Wet-spun porous fibers from high internal phase emulsions: Continuous preparation and high stretchability

Although high internal phase emulsion (HIPE)-templating is promising to prepare macroporous materials (polyHIPEs) with controllable shapes and tuneable property, fibrous polyHIPEs with stretchability and their continuous preparation are still challenging. Here, we report the fabrication of polyHIPE fibers in a continuous manner through wet spinning of HIPEs. The successful fabrication of polyHIPE fibers depends on HIPE dispersed phase fractions, ammonia-catalyzed interfacial reaction and wet spinning. Dry polyHIPE fibers exhibit tunable diameters, hierarchically porous structures, high stability to temperature and to various solutions, and high stretchability (with a high tensile strain of 155%), which is hard to achieve for polyHIPEs. The polyHIPE fibers show enhanced uptakes to both water (14.4 ml g⁻¹) and organic solvents (up to 26.3 ml g⁻¹), and the amphiphilic swelling is rare for polyHIPEs. Moreover, the dry polyHIPE fibers show good thermal insulation, similar to that of cotton. Simple wet spinning, combining with HIPEs with tuneable composition, is promising for preparing various polyHIPE fibers for various potential applications.     

Hydrophilic polymer foams with well‐defined open‐cell structure prepared from pickering high internal phase emulsions

Open‐cell hydrophilic polymer foams are prepared through oil‐in‐water Pickering high internal phase emulsions (HIPEs). The Pickering HIPEs are stabilized by commercial titania (TiO₂) nanoparticles with adding small amounts of non‐ionic surfactant Tween85. The morphologies, such as average void diameter and interconnectivity, of the foams can be tailored easily by varying the TiO₂ nanoparticles and Tween85 concentrations. Further, investigation of the HIPE stability, emulsion structure and the location of TiO₂ nanoparticles in resulting foams shows that the surfactant tends to occupy the oil‐water interface at the contact point of adjacent droplets, where the interconnecting pores are hence likely to be formed after the consolidation of the continuous phase. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

On the thermodynamics of particle-stabilized emulsions: curvature effects and catastrophic phase inversion

The flexural properties of a particle adsorption monolayer are investigated theoretically. If the particles are not densely packed, the interfacial bending moment and the spontaneous curvature (due to the particles) are equal to zero. The situation changes if the particles are closely packed. Then the particle adsorption monolayer possesses a significant bending moment, and the interfacial energies of bending and dilatation become comparable. In this case, the bending energy can either stabilize or destabilize the Pickering emulsion, depending on whether the particle contact angle is smaller or greater than 90 degrees . Theoretical expressions are derived for the bending moment, for the curvature elastic modulus, and for the work of interfacial deformation and emulsification. The latter is dominated by the work for creation of a new oil-water interface and by the work for particle adsorption. The curvature effects give a contribution of second order, which is significant only for emulsification at 50:50 water/oil volume fractions. A thermodynamic criterion for the type of the formed emulsion is proposed. It predicts the existence of a catastrophic phase inversion in particle-stabilized emulsions, in agreement with the experimental observations. The derived theoretical expressions could find application for interpretation of experimental data on production and stability of Pickering emulsions.     

Composite materials prepared by phase inversion deposition of polyacrylonitrile onto porous polyethylene films

Composite ultrafiltration membanes were prepared by deposition of polyacrylonitrile onto a porous polyethylene support by the phase inversion procedure. The supports were hydrophilized by treatment in a barrier discharge argon plasma. Methods were suggested for controlling the pore size in the polyacrylonitrile layer. The filtration characteristics of the membranes and their mechanical properties were determined.     

Tough interconnected polymerized medium and high internal phase emulsions reinforced by silica particles

Emulsion templating using high internal phase emulsions is an effective route to prepare low density and high porosity macroporous polymers known as polymerized high internal phase emulsions (polyHIPEs). Conventional polyHIPEs, synthesized from surfactant stabilized w/o emulsions have low permeabilities and poor mechanical properties. We present interconnected open macroporous low density nanocomposites produced by polymerizing the continuous phase of emulsion templates, which contained styrene, polyethyleneglycoldimethacrylate, and silylated silica particles. Polyethyleneglycoldimethacrylate and the silylated silica particles acted as crosslinker. The functionalized silica particles were incorporated into the polymer, which resulted in a significant improvement of the mechanical properties of the polyHIPEs without affecting the interconnected and permeable pore structures. The polyHIPEs contained up to 60 wt % silylated silica particles. Young's modulus of the reinforced macroporous polymers increased up to 600% compared with nonreinforced macroporous polymers. The mechanical performance was further increased by increasing the foam density of the macroporous nanocomposites from around 200 to 370 g/cm³ by raising the organic phase volume of the emulsion templates from 20 to 40 vol %. The macroporous polymers synthesized from less concentrated emulsions also possessed interconnected open porous although less permeable structures. The polyHIPE nanocomposites have a permeability of about 200 mD, whereas the polyMIPE nanocomposites still have permeabilities of around 50 mD. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1979–1989, 2010     

Phase behavior and rheology of oil-swollen micellar cubic phase and gel emulsions in nonionic surfactant systems

We have studied the phase behavior and rheological property of the cubic phase and related gel emulsions in water/nonionic/dodecane systems. In the phase behavior study, it is pointed out that the formation of the discontinuous cubic phase (I₁) is not common in all nonionic surfactant systems; however, a cubic phase (I₁) with oil-swollen micelles or a cubic phase microemulsion is found in the water/C₁₆EO₆/dodecane system, which can solubilize large amount of oil. It was also observed that water/C₁₆EO₆/dodecane system forms stable gel emulsion. In the rheological study we have found an anomalous behavior of the I₁ phase in the water/C₁₂EO₆/dodecane and the water/C₁₆EO₆/dodecane systems. In the water/C₁₂EO₆/dodecane system, the viscoelastic nature of the I₁ phase has been observed, which is shifted to the elastic nature with the addition of dodecane, whereas, highly elastic nature was observed in the water/C₁₆EO₆/dodecane system. In both the cases shear-thinning behavior were seen. The elastic modulus, G′ and complex viscosity, |η1| of the I₁ phase increase with the dodecane concentration in the water/C₁₂EO₆/dodecane system, whereas, decreasing trend have been observed in the water/C₁₆EO₆/dodecane system. This anomalous behavior is suggested due to the nonspherical shape of micelles or polydispersity of the micelles in the water/C₁₆EO₆/dodecane system. The rheological behavior of the O/I₁ gel emulsion was also studied in both the systems.     

Study on thermal induced phase inversion of concentratedO/W emulsions stabilized by various tween emulsifiers

Summary Thermal induced phase inversion of concentrated oil-in-water emulsions stabilized by various fatty acid polyoxyethylene esters of sorbitan (Tween 21, Tween 61, Tween 65, Tween 80 and Tween 81) has been studied. Phase inversion temperature (PIT) was determined by differential thermal analysis and the changes in internal structure of emulsions caused by heating were followed microscopically. The PITS obtained were dependent on the kind of Tween. When the emulsions were stabilized by Tween 65, the PIT also depended on whether the emulsifier was dissolved in water or in oil phase or in the both. Microscopic examination of the emulsions during heating showed that the appearance of water droplets within the oil drops, i.e. the development of a multiphase (W/O/W) emulsion structure precedes phase inversion.

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Zusammenfassung Die thermische Phaseninversion konzentrierter Öl-in-Wasser-Emulsionen (durch verschiedene Emulgatoren des Tween-Typs stabilisiert) wurde untersucht und die Phasen-inversionstemperatur durch Differentialthermoanalyse bestimmt.Die Phaseninversionstemperatur hängt von der Tweenart ab. Mit Tween 65 ist die Phaseninversionstemperatur auch davon abhängig, ob der Emulgator in Wasser, in Öl oder in beiden Phasen gelöst wird. Mikroskopische Untersuchungen haben gezeigt, daß Wassertröpfchen innerhalb der Öltropfen entstehen, d. h., daß die Entwicklung einer mehrphasigen Wasser-Ö1-Wasser-Struktur der Phaseninversion vorangeht.

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With 5 figures     

Complex layering observed in high internal phase emulsions at a silicon surface by neutron reflectometry

The neutron reflectivity profiles from the interface between silicon and aqueous phase-in-oil high internal phase emulsions of steadily increasing surfactant hydrophilicity, are reported for two isotopic contrasts for each surfactant. Layered models are required to fit the structured reflectivity profiles that demonstrate that the oxidised top layer of the silicon is always covered by a surfactant monolayer. Interposed between the surfactant monolayer and the bulk emulsion is a layer of oil--a geometric effect caused by reorganisation of the aqueous droplets. As the surfactant hydrophilicity increases, alternating aqueous and oil+surfactant layers are inserted between this topmost oil layer and the oxide attached surfactant monolayer. The resulting structures have compositions and layer spacings suggestive of sections from lamellar phases. This increase in layer ordering with increasing surfactant hydrophilicity is expected. The bulk emulsions are observed to exhibit lamellar or sponge phases increasingly as surfactant hydrophilicity increases.     

Impact of oil composition on formation and stability of emulsions produced by spontaneous emulsification

In this study, triglycerides of different chain lengths were mixed with paraffin oil, and their effectiveness in forming emulsions produced by spontaneous emulsification upon the addition of water was investigated. The emulsion droplet size exhibited a similar trend as a function of the triglyceride/paraffin oil composition for medium-chain (MCTs) (C8–C10) and long-chain (C18) triglycerides (LCTs). However, emulsions formulated with MCTs and LCTs have a much smaller droplet size (about 50?nm) than emulsions based upon short-chain (C4) triglycerides (SCTs). The addition of SCTs resulted in droplet sizes around 800?nm and the emulsions formed were very unstable. The droplet size, polydispersity index, zeta potential, and emulsion stability of these systems will be described as a function of the oil phase composition.