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1.
Formation of a normal (not temporary) W/O/W multiple emulsion via the one-step method as a result of the simultaneous occurrence of catastrophic and transitional phase inversion processes has been recently reported. Critical features of this process include the emulsification temperature (corresponding to the ultralow surface tension point), the use of a specific nonionic surfactant blend and the surfactant blend/oil phase ratio, and the addition of the surfactant blend to the oil phase. The purpose of this study was to investigate physicochemical properties in an effort to gain a mechanistic understanding of the formation of these emulsions. Bulk, surface, and interfacial rheological properties of adsorbed nonionic surfactant (CremophorRH40 and Span80) films were investigated under conditions known to affect W/O/W emulsion formation. Bulk viscosity results demonstrated that CremophorRH40 has a higher mobility in oil compared than in water, explaining the significance of the solvent phase. In addition, the bulk viscosity profile of aqueous solutions containing CremophorRH40 indicated a phase transition at around 78 ± 2 °C, which is in agreement with cubic phase formation in the Winsor III region. The similarity in the interfacial elasticity values of CremophorRH40 and Span80 indicated that canola oil has a major effect on surface activity, showing the significance of vegetable oil. The highest interfacial shear elasticity and viscosity were observed when both surfactants were added to the oil phase, indicating the importance of the microstructural arrangement. CremophorRH40/Span80 complexes tended to desorb from the solution/solution interface with increasing temperature, indicating surfactant phase formation as is theoretically predicted in the Winsor III region. Together these interfacial and bulk rheology data demonstrate that one-step W/O/W emulsions form as a result of the simultaneous occurrence of phase-transition processes in the Winsor III region and explain the critical formulation and processing parameters necessary to achieve the formation of these normal W/O/W emulsions.  相似文献   

2.
Mixtures of polyols (glycerol, propylene glycol, glucose) and water were emulsified in oil (isopropyl myristate (IPM), medium chain triglycerides (MCT), long chain triglycerides (LCT), and d-limonene) under elevated pressures and homogenization, in the presence of polyglycerol polyricinoleate (PGPR), glycerol monooleate (GMO), and their mixture as emulsifiers to form water-in-oil emulsions. High pressures was applied to: a) the emulsion, b) the aqueous phase and c) the oil phase in the presence of the emulsifiers (PGPR and GMO). Under optimal pressure (2000 atms) applied to the ready-made emulsion or to the aqueous phase prior to its emulsification, and with optimal composition (30wt% polyol in the aqueous phase and MCT as the oil phase), the aqueous droplets were stable for months and submicron in size (0.1 μm). Moreover, due to equalization of the oil and the aqueous phases refractive indices, the emulsions were almost transparent. Pressure and polyols have synergistic effects on the emulsions stability. During preparation, surface tensions and interfacial tensions were dramatically reduced until an optimal water/polyols ratio was achieved, which allows rupturing of the droplets to submicronal size (0.1 μm) without recoalescence and fast diffusion to the interface. These unique W/O emulsions are suitable for preparing W/O/W double emulsions for sustained release of active materials for food applications.  相似文献   

3.
We studied spontaneous emulsification (SE) at Water/Oil (W/O) interfaces, using several types of aqueous reservoirs immersed in dodecane plus Span80 surfactant. Above a threshold surfactant concentration C(SE), aqueous satellite droplets are formed at the W/O interface. Varying the aqueous reservoir size, from below 100 microm (droplets) to centimeters (macroscopic phases), allowed investigating SE with complementary techniques. Release (rates) and size distributions for SE droplets were measured with microscopy. For gelled aqueous phases, water expulsion due to SE was quantified. Values for C(SE) were measured and were found to be higher for aqueous phases containing gelatin and/or NaCl. We also studied water exudation during network building and syneresis in aqueous gelatin gels immersed in dodecane/Span80. Below C(SE) (i.e., in the absence of SE) this process is still responsible for significant physico-chemical changes at the W/O interface. To study these in more detail, we performed atomic force microscopy experiments (in force-distance mode) on macroscopic gels. Both changes in the local elastic response and in the wettability of the AFM tip were detected. Together they suggest the formation of "water pockets" after prolonged (gel) setting times, along with a densification of the interfacial gelatin network.  相似文献   

4.
The in situ surface activation of raw CaCO(3) nanoparticles by interaction with a series of sodium carboxylates of chain length between 6 and 12 as well as sodium 2-ethylhexylsulfosuccinate (AOT) was studied, and the impact of this on the stabilization and phase inversion of toluene-water emulsions was assessed. By using complementary experiments including measurement of particle zeta potentials, adsorption isotherms of amphiphile, and relevant contact angles, the mechanism of this activation was revealed. The results show that hydrophilic CaCO(3) nanoparticles can be surface activated by interaction with sodium carboxylates and AOT even if they are not surface-active themselves. Both the electrostatic interaction between the positive charges on particle surfaces and the negative charges of anionic amphiphile headgroups and the chain-chain interactions of the amphiphile result in monolayer adsorption of the amphiphile at the particle-water interface. This transforms the particles from hydrophilic to partially hydrophobic such that they become surface-active and stabilize oil-in-water O/W(1) emulsions and induce O/W(1) → water-in-oil W/O phase inversion, depending on the chain length of the carboxylate molecules. At high amphiphile concentration, bilayer or hemimicelle adsorption may occur at the particle-water surface, rendering particles hydrophilic again and causing their desorption from the oil-water interface. A second phase inversion, W/O → O/W(2), may occur depending on the surface activity of the amphiphile. CaCO(3) nanoparticles can therefore be made good stabilizers of both O/W and W/O emulsions once surface activated by mixing with traces of suitable anionic amphiphile.  相似文献   

5.
The objective of this study was to investigate the significance of inner and outer phase pressure, as well as interfacial film strength on W/O/W multiple emulsion stability using microscopy and long-term stability tests. It was observed that immediately upon applying a coverslip to samples the multiple droplets deformed and there was coalescence of the inner aqueous droplets. Under certain conditions (such as lipophilic surfactant concentration and internal phase osmotic pressure) the destabilized multiple emulsions formed unique metastable structures that had a "dimpled" appearance. The formation of these metastable structures correlated with the real-time instability of the W/O/W multiple emulsions investigated. Multiple emulsion stability also correlated with the interfacial film strength (measured by interfacial elasticity) of the hydrophobic surfactant at the mineral oil/external continuous aqueous phase interface. The formation of the metastable dimpled structures and the long-term stability of the multiple emulsions were dependent on the osmotic pressure of the inner droplets and the Laplace curvature pressure as described by the Walstra Equation (P. Walstra, "Encyclopedia of Emulsion Technology" (P. Becher, Ed.), Vol. 4. Dekker, New York, 1996). It appears that the effect of coverslip pressure on multiple emulsions may be useful as an accelerated stability testing method or for initial formulation screening.  相似文献   

6.
The formation of a so-called water/oil (W/O)-microemulsion (AOT/isooctane/water) was followed by light scattering and ultracentrifuge measurements. With increasing weighed-in water concentrations the microemulsion is stabilized by repeated aggregational processes of micelles containing water due to a decrease of the free interfacial enthalpy. This process conforms very satisfactorily to a model describing an adsorption of surfactants at the water/hydrocarbon interface resulting from dipole-image dipole interactions.  相似文献   

7.
The mechanism of the solvent extraction of cytochrome c (Cyt c) via reverse micelle formation was studied from an electrochemical point of view. Potentiometric measurements showed that the Galvani potential difference of the oil/water (O/W) interface played a crucial role in the spontaneous extraction of Cyt c with bis(2-ethylhexyl)sulfosuccinate (AOT). However, the dependence of the extraction efficiency on the concentration of an aqueous electrolyte (KCl) could be explained not by the effect of the interfacial potential, but by the change in the interfacial tension (gamma). Electrocapillary measurements showed that the adsorption of AOT anions to the O/W interface resulted in a significant decrease of gamma in a higher potential range, where reverse micelles were formed. The bottom level of gamma in the higher potential range was increased with [KCl]. The lower extraction efficiency for higher [KCl]'s was elucidated by a "size exclusion effect". This was also supported by water-content measurements by the Karl Fisher method.  相似文献   

8.
研究了3种不同结构的水溶性阳离子表面活性剂对纳米二氧化硅颗粒的原位表面活性化作用, 它们分别是单头单尾的十六烷基三甲基溴化铵(CTAB)、单头双尾的双十二烷基二甲基溴化铵(di-C12DMAB)和双头双尾的Gemini型阳离子三亚甲基-二(十四酰氧乙基溴化铵)(II-14-3), 并通过测定Zeta电位、吸附等温线及接触角等参数对相关机理进行了阐述. 结果表明, 阳离子表面活性剂吸附到颗粒/水界面形成以疏水基朝向水的单分子层, 从而增强了颗粒表面的疏水性是原位表面活性化的基础. 通过吸附CTAB和II-14-3, 颗粒的疏水性适当增强, 能吸附到正辛烷/水界面稳定O/W(1)型乳状液; 而通过吸附di-C12DMAB所形成的单分子层更加致密, 颗粒的疏水性进一步增强, 进而使乳状液从O/W(1)型转变为W/O型; 当表面活性剂浓度较高时, 由于链-链相互作用, 表面活性剂分子将在颗粒/水界面形成双层吸附, 使颗粒表面变得亲水而失去活性, 但此时体系中游离表面活性剂的浓度已增加到足以单独稳定O/W(2)型乳状液的程度. 因此当采用纳米二氧化硅和di-C12DMAB的混合物作乳化剂时, 通过增加di-C12DMAB的浓度即可诱导乳状液发生O/W(1)→W/O→O/W(2)双重相转变.  相似文献   

9.
Nanoemulsions were formed spontaneously by diluting water-in-oil (W/O) or brine-in-oil (B/O) microemulsions of a hydrocarbon (octane), anionic surfactant (Aerosol-OT or AOT) and water or NaCl brine in varying levels of excess brine. The water-continuous nanoemulsions were characterized by interfacial tension, dynamic light scattering, electrophoresis, optical microscopy and phase-behavior studies. The mechanism of emulsification was local supersaturation and resulting nucleation of oil during inversion. For nanoemulsions formed at low salinities with Winsor I phase behavior, octane drops grew from initial diameters of 150-250nm to 480-1000nm over 24h, depending on salinity. Growth was caused by mass transfer but seemed to approach the asymptotic stage of Ostwald ripening described by the Lifshitz-Slyozov-Wagner (LSW) theory only for dilution with salt-free water. Near the higher cross-over salinity (Winsor III), the nanoemulsions showed much slower growth with droplet size consistently remaining below 200nm over 24h and reaching 250nm after 1week. Birefringence indicated the presence of liquid crystal for these conditions, which could have contributed to the slow growth rate. At even higher salinity levels in the Winsor II domain, W/O/W multiple emulsions having drops greater than 1μm in diameter were consistently recorded for the first 5-7h, after which size decreased to values below 1μm. The number and size of internal water droplets in multiple emulsion drops was found to decrease over time, suggesting coalescence of internal droplets with the continuous water phase and mass transfer of water from internal droplets to continuous phase as possible mechanisms of the observed drop shrinkage. Electrophoresis studies showed the nanoemulsions to be highly negatively charged (zeta potentials of -60mV to -120mV). The high charge on octane droplets helped assure stability to flocculation and coalescence, thereby allowing mass transfer to control growth in the Winsor I and III regions.  相似文献   

10.
A one-step double emulsification protocol using one surfactant was developed for oil-in-water-in-oil (O(1)/W/O(2)) double emulsions. Two n-alkane oils and three different surfactants were studied, with focus placed on a formulation containing mineral oil, glycerol monoleate (GMO) and deionized water. Phenomenologically, double emulsion formation and stability originate from the combined actions of phase inversion and interfacial charging of the oil/water interface during high shear homogenization. Based on the extent of double emulsion formation and stability, a critical emulsification zone dependent on the weight ratios of GMO to water was identified. Within this critical zone, enhanced O(1)/W/O(2) emulsion formation occurred at higher pH and lower salt concentrations, demonstrating the key role of interfacial charging on double emulsification. Overall, this novel approach provides a novel platform for the development of double emulsions with simple compositions and processing requirements.  相似文献   

11.
The emulsification processes, during which acylglycerols/zinc stearate emulsifier, water, and oil phase formed ternary systems, such as water-in-oil (W/O) emulsions, oil-in-water (O/W) dispersions, and unstable oil-water mixtures, were investigated in order to characterize the progressive transformations of the dispersed systems. The type, structure, and phase transitions of the systems were found to be determined by temperature and water phase content. Crystallization of the emulsifier caused the destabilization and subsequent phase inversion of the emulsions studied, at a temperature of 60-61 degrees C. The observed destabilization was temporary and led, at lower temperature, to W/O emulsions, "O/W + O" systems, or O/W dispersions, depending on the water content. Simultaneous emulsification and cooling of 20-50 wt % water systems resulted in the formation of stable W/O emulsions that contained a number of large water droplets with dispersed oil globules inside them ("W/O + O/W/O"). In water-rich systems (60-80 wt % of water), crystallization of the emulsifier was found to influence the formation of crystalline vesicle structures that coexisted, in the external water phase, with globules of crystallized oil phase. Results of calorimetric, rheological, and light scattering experiments, for the O/W dispersions obtained, indicate the possible transition of a monostearoylglycerol-based alpha-crystalline gel phase to a coagel state, in these multicomponent systems.  相似文献   

12.
Water transportation through the oil phase in W/O emulsions and in W1/O/W2 systems (W/O emulsion in contact with water) was examined. Substance diffusion through interfaces led to interface instability and spontaneous emulsification which caused nanodispersion formation. The photomicrographs of Pt/C replicas of emulsions showed the presence in the continuous oil phase a lot of nanodispersion droplets with a diameter in the range 17-25 nm. Diffusion coefficient (D) of water calculated on the base of Lifshiz-Slezov-Wagner (LSW) equation was about 15 times lower than the coefficients of molecular diffusion. Since such emulsions were extremely unstable toward coalescence, the growth of water droplets took place through as Ostwald ripening as coalescence. In three-phase W1/O/W2 systems diffusion of water, Rhodamine C, and ethanol was studied. D calculated on the base of the equation of nonstationary diffusion were approximately 1000 times lower than molecular ones. It was assumed, that nanodispersion droplets were more likely water carriers in investigated W/O emulsions stabilized by sorbitan monooleate.  相似文献   

13.
Abstract

The aim of this work was to study the encapsulation properties of polyols-in-oil-in-water (P/O/W) multiple emulsions for Vitamin C (Vc). The influence of formulation factors, including the concentration of lipophilic emulsifier, hydrophilic emulsifier, salt and glycerol had been investigated. The results indicated that the encapsulation stability could be improved by increasing the lipophilic emulsifier concentration which could strengthen the interfacial film. In contrast, the excess of hydrophilic emulsifier destabilized the emulsion. The presence of glycerol in the outer aqueous phase accelerated the phase transfer, thus reduced the encapsulation rate. The addition of salt in inner polyols phase had little effect on encapsulation rate while markedly affected the morphology and stability of this system. P/O/W multiple emulsions showed better encapsulation stability than the W/O/W multiple emulsions as the former’s encapsulation rate could remain more than 75% after 2?weeks while the latter only remained less than 60%. Meanwhile, the P/O/W emulsions exhibited higher storage modulus (G’), bigger loss modulus (G’’) and broaden linear viscoelastic regions than W/O/W emulsions.  相似文献   

14.
Selecting effective antioxidants is challenging since their efficiency in inhibiting lipid oxidation depends on the rate constants of the chemical reactions involved and their concentration at the reaction site, i.e., at the interfacial region. Accumulation of antioxidants at the interface of emulsions is key to modulate their efficiency in inhibiting lipid oxidation but its control was not well understood, especially in emulsions. It can be optimized by modifying the physicochemical properties of antioxidants or the environmental conditions. In this work, we analyze the effects of surfactant concentration, droplet size, and oil to water ratio on the effective interfacial concentration of a set of chlorogenic acid (CGA) esters in fish oil-in-water (O/W) emulsions and nanoemulsions and on their antioxidant efficiency. A well-established pseudophase kinetic model is used to determine in the intact emulsified systems the effective concentrations of the antioxidants (AOs). The relative oxidative stability of the emulsions is assessed by monitoring the formation of primary oxidation products with time. Results show that the concentration of all AOs at the interfacial region is much higher (20–90 fold) than the stoichiometric one but is much lower than those of other phenolipid series such as caffeic or hydroxytyrosol derivatives. The main parameter controlling the interfacial concentration of antioxidants is the surfactant volume fraction, ΦI, followed by the O/W ratio. Changes in the droplet sizes (emulsions and nanoemulsions) have no influence on the interfacial concentrations. Despite the high radical scavenging capacity of CGA derivatives and their being concentrated at the interfacial region, the investigated AOs do not show a significant effect in inhibiting lipid oxidation in contrast with what is observed using other series of homologous antioxidants with similar reactivity. Results are tentatively interpreted in terms of the relatively low interfacial concentrations of the antioxidants, which may not be high enough to make the rate of the inhibition reaction faster than the rate of radical propagation.  相似文献   

15.
Emulsions were prepared using poly(N-isopropylacrylamide) microgels as thermoresponsive stabilizers. The latter are well-known for their sensitivity to temperature: they are swollen by water below the so-called volume phase transition temperature (VPTT = 33 °C) and shrink when heated above it. Most of the studies reported in the literature reveal that the corresponding emulsions are of the oil-in-water type (O/W) and undergo fast destabilization upon warming above the VPTT. In the present study, whereas O/W emulsions were obtained with a wide panel of oils of variable polarity and were all thermoresponsive, water-in-oil (W/O) emulsions were found only in the presence of fatty alcohols and did not exhibit any thermal sensitivity. To understand the peculiar behavior of emulsions based on fatty alcohols, we investigated the organization of microgels at the oil-water interface and we studied the interactions of pNIPAM microgels with octanol. By combining several microscopy methods and by exploiting the limited coalescence process, we provided evidence that W/O emulsions are stabilized by multilayers of nondeformed microgels located inside the aqueous drops. Such behavior is in contradiction with the empirical Finkle rule stating that the continuous phase of the preferred emulsion is the one in which the stabilizer is preferentially dispersed. The study of microgels in nonemulsified binary water/octanol systems revealed that octanol diffused through the aqueous phase and was incorporated in the microgels. Thus, W/O emulsions were stabilized by microgels whose properties were substantially different from the native ones. In particular, after octanol uptake, they were no longer thermoresponsive, which explained the loss of responsiveness of the corresponding W/O emulsions. Finally, we showed that the incorporation of octanol modified the interfacial properties of the microgels: the higher the octanol uptake before emulsification, the lower the amount of particles in direct contact with the interface. The multilayer arrangement was thus necessary to ensure efficient stabilization against coalescence, as it increased interface cohesiveness. We discussed the origin of this counterexample of the Finkle's rule.  相似文献   

16.
The development of lipid oxidation in oil-in-water (O/W) emulsions is widely influenced by the properties of the interfacial layer, which separates the oil and water phases. In this work, the effect of the structure of the interface on the oxidative stability of surfactant stabilized O/W emulsions was investigated. Emulsions were prepared with either single Tween 20 or Tween 20/co-surfactant mixtures in limiting amounts. The co-surfactants, Span 20 and monolauroyl glycerol have the same hydrophobic tail as Tween 20 but differ by the size and composition of their polar headgroup. Metal-initiated lipid oxidation, monitored through the measurement of oxygen uptake, formation of conjugated dienes and volatile compounds, developed more rapidly in the emulsions stabilized by the surfactant mixture than in the single Tween 20-stabilized emulsion. The reconstitution of Tween 20/co-surfactant films at the air-water interface and their surface-pressure isotherms highlighted that, contrary to single Tween 20 molecules, Tween 20/co-surfactant mixtures exhibited an heterogeneous distribution within the interfacial layer, offering probably easier access of water-soluble pro-oxidants to the oil phase. These observations provide direct information about the link between the homogeneity of the interface layer and the oxidative stability of emulsions.  相似文献   

17.
The ternary phase diagram for N-[3-lauryloxy-2-hydroxypropyl]-L-arginine L-glutamate (C12HEA-Glu), a new amino acid-type surfactant, /oleic acid (OA)/water system was established. The liquid crystal and gel complex formations between C12HEA-Glu and OA were applied to a preparation of water-in-oil (W/O) emulsions. Stable W/O emulsions containing liquid paraffin (LP) as the oil and a mixture of C12HEA-Glu and OA as the emulsifier were formed. The preparation of stable W/O emulsions containing 85 wt% water phase was also possible, in which water droplets would be polygonally transformed and closely packed, since the maximum percentage of inner phase is 74% assuming uniformly spherical droplets. Water droplets would be taken into the liquid crystalline phase (or the gel complex) and the immovable water droplets would stabilize the W/O emulsion system. The viscosity of emulsions abruptly increased above the 75 wt% water phase (dispersed phase). The stability of W/O emulsions with a lower weight ratio of OA to C12HEA-Glu and a higher ratio of water phase was greater. This unusual phenomenon may be related to the formation of a liquid crystalline phase between C12HEA-Glu and OA, and the stability of the liquid crystal at a lower ratio of oil (continuous phase). W/O and oil-in-water (O/W) emulsions containing LP were selectively prepared using a mixture of C12HEA-Glu and OA since the desirable hydrophile-lipophile balance (HLB) number for the emulsification was obtainable by mixing the two emulsifiers.  相似文献   

18.
《Chemical physics letters》1987,141(4):357-360
Two-phase systems consisting of water-in-oil (W/O) microemulsions in equilibrium with excess water and oil-in-water (O/W) microemulsions in equilibrium with excess oil have been prepared using the surfactant sodium bis (2-ethylhexyl)sulphosuccinate (AOT) without cosurfactant. The interfacial tension of the planar interface separating the phases for the W/O case is only weakly dependent upon the volume fraction of droplets in the microemulsion phase whereas for the O/W case, the microemulsion droplet size increases and the tension drops as the dispersed volume fraction is increased.  相似文献   

19.
We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W1/O/W2) consist of water droplets (W1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W1 in oil globules) and the inverse emulsion (oil globules in W2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.  相似文献   

20.
Microchannel (MC) emulsification is a novel technique for preparing monodispersed emulsions. This study demonstrates preparing water-in-oil-in-water (W/O/W) emulsions using MC emulsification. The W/O/W emulsions were prepared by a two-step emulsification process employing MC emulsification as the second step. We investigated the behavior of internal water droplets penetrating the MCs. Using decane, ethyl oleate, and medium-chain triglyceride (MCT) as oil phases, we observed successful MC emulsification and prepared monodispersed oil droplets that contained small water droplets. MC emulsification was possible using triolein as the oil phase, but polydispersed oil droplets were formed from some of the channels. No leakage of the internal water phase was observed during the MC emulsification process. The internal water droplets penetrated the MC without disruption, even though the internal water droplets were larger than the resulting W/O/W emulsion droplets. The W/O/W emulsion entrapment yield was measured fluorometrically and found to be 91%. The mild action of droplet formation based on spontaneous transformation led to a high entrapment yield during MC emulsification.  相似文献   

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