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1.
The influence of the nature of the interfacial membrane on the kinetics of droplet growth in hydrocarbon oil-in-water emulsions was investigated. Droplet growth rates were determined by measuring changes in the droplet size distribution of 1 wt % n-tetradecane or n-octadecane oil-in-water emulsions using laser diffraction. The interfacial properties of the droplets were manipulated by coating them with either an SDS layer or with an SDS-chitosan layer using an electrostatic deposition method. The emulsion containing SDS-coated octadecane droplets did not exhibit droplet growth during storage for 400 h, which showed that it was stable to Ostwald ripening because of this oils extremely low water-solubility. The emulsion containing SDS-coated n-tetradecane droplets showed a considerable increase in mean droplet size with time, which was attributed to Ostwald ripening associated with this oils appreciable water-solubility. On the other hand, an emulsion containing SDS-chitosan coated n-tetradecane droplets was stable to droplet growth, which was attributed to the ability of the interfacial membrane to resist deformation because of its elastic modulus and thickness. This study shows that the stability of emulsion droplets to Ostwald ripening can be improved by using an electrostatic deposition method to form thick elastic membranes around the droplets.  相似文献   

2.
The well-known alcoholic beverage Pastis becomes turbid when mixed with water due to the poor solubility of trans-anethol, the anise-flavored component of Pastis in the water solution formed. This destabilization appears as the formation of micrometer-sized droplets that only very slowly grow in size, thus expanding the life of the anise-flavored beverage. The slow growth has been attributed to an extremely low interfacial tension of the droplets. Fitting experimental droplet growth rates to an Ostwald ripening model, interfacial tensions were deduced in the past. Direct determination of the interfacial tensions was not yet reported on these systems. We have measured the interfacial tensions and used these data to predict droplet growth rates using an Ostwald ripening model and a model for creaming of the droplets. The interfacial tension was measured to be about 11 mN/m for a 30/70 w/w % ethanol/water mixture, and it decreases slightly to a value of 1.4 mN/m in the case of a 70/30 w/w % ethanol/water mixture. These values are not as low as those deduced in the past. The theoretical predictions for both the Ostwald ripening rates and the creaming rates, using the directly measured interfacial tensions, are found to contradict with the experimental results on Ostwald ripening and creaming. While the experiments on Ostwald ripening show an increase in stability with increasing ethanol concentration, the results based on our interfacial tension measurements in combination with the same Ostwald ripening model show a decrease in stability with an increase in ethanol concentration. Further research is needed to understand fully which parameters play a role in both droplet growth and the stability of these three-component emulsions to elucidate the current discrepancy between model and experiment. This could be useful for a better control of "spontaneous emulsification" processes.  相似文献   

3.
The influence of oil type (n-hexadecane, 1-decanol, n-decane), droplet composition (hexadecane:decanol), and emulsifier type (Tween 20, gum arabic) on droplet growth in oil-in-water emulsions was studied. Droplet size distributions of emulsions were measured over time (0-120 h) by laser diffraction and ultrasonic spectroscopy. Emulsions containing oil molecules of low polarity and low water solubility (hexadecane) were stable to droplet growth, irrespective of the emulsifier used to stabilize the droplets. Emulsions containing oil molecules of low polarity and relatively high water solubility (decane) were stable to coalescence, but unstable to Ostwald ripening, irrespective of emulsifier. Droplet growth in emulsions containing oil molecules of relatively high polarity and high water solubility (decanol) depended on emulsifier type. Decanol droplets stabilized by Tween 20 were stable to droplet growth in concentrated emulsions but unstable when the emulsions were diluted. Decanol droplets stabilized by gum arabic exhibited rapid and extensive droplet growth, probably due to a combination of Ostwald ripening and coalescence. We proposed that coalescence was caused by the relatively low interfacial tension at the decanol-water boundary, which meant that the gum arabic did not absorb strongly to the droplet surfaces and therefore did not prevent the droplets from coming into close proximity.  相似文献   

4.
Formation of water-in-diesel oil (w/o) nano-emulsion has been achieved by a low-energy emulsification method by stabilizing a new combination of nonionic sorbitan esters surfactants, that is PEG20-sorbitan monostearate and sorbitan monooleate in mixed proportions. Different combinations of the surfactants (T6?+?S8) have been tested and the best possible combination of mixed surfactants is found at a surfactants ratio of 35:65 (wt/wt) for T6:S8 at hydrophile–lipophile balance (HLB)?=?8.01, which resulted in smaller droplet size of 44.87?nm. A phase diagram study is performed to identify the zones of formation of transparent, translucent, and opaque emulsions (44?nm??27?m3?·?s?1. Comparison of Ostwald ripening rate with other sets of surfactants obtained by different authors showed the lowest rate among them, indicative of enhanced stability. A rheological study of the tested set of nano-emulsions depicts the Newtonian behavior (1.0371?≤?n?≤?1.0826) over a wider range of shear rates (10–1000?s?1) at different temperatures (25–40°C).  相似文献   

5.
Two coarsening mechanisms of emulsions are well established: droplet coalescence (fusion of two droplets) and Ostwald ripening (molecular exchange through the continuous phase). Here a third mechanism is identified, contact ripening, which operates through molecular exchange upon droplets collisions. A contrast manipulated small‐angle neutron scattering experiment was performed to isolate contact ripening from coalescence and Ostwald ripening. A kinetic study was conducted, using dynamic light scattering and monodisperse nanoemulsions, to obtain the exchange key parameters. Decreasing the concentration or adding ionic repulsions between droplets hinders contact ripening by decreasing the collision frequency. Using long surfactant chains and well‐hydrated heads inhibits contact ripening by hindering fluctuations in the film. Contact ripening can be controlled by these parameters, which is essential for both emulsion formulation and delivery of hydrophobic ingredients.  相似文献   

6.
The purposes of this study are to determine Ostwald ripening rates in water-in-oil (W/O) emulsions and evaluate the potential application of the LSW theory to W/O emulsions. Water-in-oil emulsions were prepared by mixing water and hydrocarbon phases containing Span 83 and homogenizing. n-Heptane, n-decane, n-dodecane, and n-tetradecane were used to obtain a range of solubilities. A linear increase in the cube of the droplet size with time was observed (within the initial period of 1-2 h after emulsion preparation), supporting the LSW theory. Based on this linear relationship, Ostwald ripening rates were determined to be 3.0 x 10(-24), 2.3 x 10(-24), 1.8 x 10(-24), and 5.8 x 10(-25) m3 s(-1) for water-in-heptane, water-in-decane, water-in-dodecane, and water-in-tetradecane emulsions, respectively. These values are in agreement with theoretical predictions calculated using the LSW equation. It was observed that the ripening process gradually slowed, resulting in deviations from the LSW theory. This was attributed to the effect of the interfacial surfactant film through which the dispersed material has to diffuse during Ostwald ripening. This effect is not taken into consideration by the LSW theory. The results showed that Ostwald ripening of W/O emulsions was less sensitive to the nature of oil used and slower compared to O/W emulsions consisting of the same hydrocarbons.  相似文献   

7.
The kinetics of droplet growth in the metastable region were investigated in cellulose acetate/acetone/nonsolvent system. The results obtained by the dynamic light scattering apparatus indicated that the droplet diameter d increased with time t in the relation of d3t in all cases. From the detailed consideration on the slope values in these relations, it was concluded that the droplet growth mechanism in this system was coalescence mechanism rather than Ostwald ripening mechanism. The direct observation of the freeze-dried polymer solution by SEM was not contradictory to this conclusion. The initial stage of droplet growth was investigated by the stopped-flow apparatus. The experimental results on the turbidities showed that the droplets grew in the relation of d3t as well as the results by the light scattering.  相似文献   

8.
Ostwald ripening in n-alkane oil-in-water emulsions stabilized by sodium caseinate at neutral pH has been studied by monitoring time-dependent changes in the number-average droplet diameter and the droplet-size distribution. In qualitative agreement with theory, the destabilization rate has been shown to increase with reduction of the n-alkane chain length and on addition of ethanol to the aqueous phase. Replacement of caseinate by β-lactoglobulin also leads to improved stability, but addition of calcium ions does not. The potential use of transglutaminase-induced crosslinking of adsorbed protein as a way of inhibiting the Ostwald ripening of caseinate-stabilized emulsions has been examined. It is shown that enzymic crosslinking before emulsification can lead to a modest reduction in the coarsening rate at long storage times. Crosslinking of caseinate after emulsification produces enhanced stability at short times, but there is a catastrophic loss of stability at long times due to droplet coalescence.  相似文献   

9.
The transient hot-wire method has been used to measure the thermal conductivity κ and heat capacity per unit volume ρcp of untreated (virgin) and crosslinked cis-1,4-poly(isoprene) (PI) in the temperature range 160-513 K for pressures p up to 0.75 GPa. The results show that the crosslinking rate of the polymer chains becomes significant at ∼513 K on isobaric heating at 0.5 GPa changing PI into an elastomeric state within 4 h without the use of crosslinking agents. The crosslinked PI and untreated PI have about the same κ = 0.145 Wm−1 K−1 and cp = 1.81 kJ kg−1 K−1 at 295 K and 20 MPa, but different relaxation behaviours. Two relaxation processes, corresponding to the segmental and normal modes, could be observed in both PI and crosslinked PI but these have a larger distribution of relaxation times and become arrested at higher temperatures (∼10 K) in the latter case. The arrest temperature for the segmental relaxation of untreated and crosslinked PI, for a relaxation time of ∼1 s, are described well by the empirical relations: T(p) = 209.4 (1 + 4.02 p)0.31 and T(p) = 221.3 (1 + 2.33 p)0.40 (p in GPa and T in K), respectively, which thus also reflects the pressure variations of the glass transition temperatures.  相似文献   

10.
The infinite dilution diffusion coefficients of n-hexane, n-heptane and n-decane in crosslinked silicone rubber with different crosslinking agent concentrations were measured in the temperature range of 348.15 K-368.15 K by inverse gas chromatography. The crosslinked silicone rubber was obtained by dissolving PDMS prepolymer, crosslinking agent and catalyst in n-heptane solvent and characterized by FTIR spectra. The Van Deemter equation was used to determine diffusion coefficients from the variation in chromatographic peak width with carrier gas flow rate. The good linear relation indicated the Van Deemter equation used in this work was reliable. The influences of small molecule solvent, crosslinking agent concentration and temperature on the infinite dilution diffusion coefficient were investigated. The results showed that the infinite dilution diffusion coefficient decreased with an increasing number of CH2 group in the alkane series. The increase in crosslinking agent concentration resulted in decrease of the infinite dilution diffusion coefficient. The infinite dilution diffusion coefficient increased with the rising of temperature. The interdependence on the infinite dilution diffusion coefficient and temperature accorded with Arrhenius equation well. Diffusion constant and activation energy obtained from the Arrhenius equation provided straight lines with the specific critical volume and crosslinking agent concentration.  相似文献   

11.
Water Transport by Nanodispersion Droplets in a Water-in-Oil Emulsion   总被引:1,自引:0,他引:1  
The mechanisms of water transport through an organic dispersion medium are considered for an emulsion during Ostwald ripening and for a three-phase system upon a contact of a water-in-oil emulsion with an external aqueous phase. Electron microscopy shows a formation of nanodispersion droplets during the diffusion of water through the organic phase of water-in-oil emulsions. The experimental water diffusion coefficient during Ostwald ripening in emulsions is 40 times smaller than the calculated molecular diffusion coefficient. The experimental diffusion coefficients are determined for rhodamine C, which solubilizes in the surfactant micelles, and for ethyl alcohol, a cosurfactant, which reduces the interfacial tension in the emulsion and promotes the formation of nanodispersion droplets. The experimental diffusion coefficients of rhodamine C and ethanol are three orders of magnitude smaller than the calculated values. The ratio between the numbers of rhodamine C and water molecules diffusing through the organic phase is 1 : 10000. The nanodispersion droplets are shown to make the main contribution to the water transport in the organic dispersion medium of the emulsions. Water can also be transported by single surfactant molecules, but this mechanism is not the predominant one.  相似文献   

12.
The time dependence of the dynamic mobility and the ultrasonic attenuation of octane and decane oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) was measured. The emulsions grew to larger droplets due to Ostwald ripening. The growth rate measured by attenuation depends on the surfactant concentration and the polydispersity of the emulsion. At surfactant concentrations below the critical micelle concentration (cmc) of SDS, the growth was linear with time and the rate was dependent on the polydispersity of the drops; the rate was several times faster than that predicted on the basis of a diffusion growth mechanism. Above the cmc, however, as the droplets grew in size there was a point at which the rate of growth increased, which corresponds to the droplet size at which depletion forces due to the surfactant micelles become significant. Under these conditions both the electroacoustic dynamic mobility and the acoustic attenuation spectra displayed characteristics of flocs: a large decrease in the phase lag at higher frequencies in the dynamic mobility spectrum and a decrease in the attenuation coefficient at low-megahertz frequencies with an increase at higher frequencies. This depletion flocculation enhancement in ripening rates in the presence of SDS micelles provides another, alternative, and self-consistent mechanism for the effect of surfactant micelles on Ostwald ripening.  相似文献   

13.
Oil-in-water emulsions of slightly soluble oils such as tetralin prepared by high-pressure homogenization and stabilized by sodium dodecyl sulfate undergo depletion flocculation induced by an initially polydisperse droplet size distribution. The smaller droplets flocculate the larger ones; the flocculation can be reversed by gentle sonication. After aging, the flocs disappear because the smaller droplets dissolve through Ostwald ripening. These effects were observed by electroacoustic measurements, supplemented by light scattering.  相似文献   

14.
Degradation of kinetically-stable o/w emulsions   总被引:3,自引:0,他引:3  
This article summarizes the studies on the degradation of the thermodynamically unstable o/w (nano)emulsion--a dispersion of one liquid in another, where each liquid is immiscible, or poorly miscible in the other. Emulsions are unstable exhibiting flocculation, coalescence, creaming and degradation. The physical degradation of emulsions is due to the spontaneous trend toward a minimal interfacial area between the dispersed phase and the dispersion medium. Minimizing the interfacial area is mainly achieved by two mechanisms: first coagulation possibly followed by coalescence and second by Ostwald ripening. Coalescence is often considered as the most important destabilization mechanism leading to coursing of dispersions and can be prevented by a careful choice of stabilizers. The molecular diffusion of solubilizate (Ostwald ripening), however, will continuously occur as soon as curved interfaces are present. Mass transfers in emulsion may be driven not only by differences in droplet curvatures, but also by differences in their compositions. This is observed when two or more chemically different oils are emulsified separately and the resulting emulsions are mixed. Compositional ripening involves the exchange of oil molecules between emulsion droplets with different compositions. The stability of the electrostatically- and sterically-stabilized dispersions can be controlled by the charge of the electrical double layer and the thickness of the droplet surface layer formed by non-ionic emulsifier. In spite of the similarities between electrostatically- and sterically-stabilized emulsions, there are large differences in the partitioning of molecules of ionic and non-ionic emulsifiers between the oil and water phases and the thickness of the interfacial layers at the droplet surface. The thin interfacial layer (the electrical double layer) at the surface of electrostatically stabilized droplets does not create any steric barrier for mass transfer. This may not be true for the thick interfacial layer formed by non-ionic emulsifier. The interactive sterically-stabilized oil droplets, however, can favor the transfer of materials within the intermediate agglomerates. The stability of electrosterically-stabilized emulsion is controlled by the ratio of the thickness of the non-ionic emulsifier adsorption layer (delta) to the thickness of the electrical double layer (kappa(-1)) around the oil droplets (delta/(kappa(-1))) = (deltakappa). The monomer droplet degradation can be somewhat depressed by transformation of coarse emulsions to nano-emulsion (miniemulsion) by intensive homogenization and by the addition of a surface active agent (coemulsifier) or/and a water-insoluble compound (hydrophobe). The addition of hydrophobe (hexadecane) to the dispersed phase significantly retards the rate of ripening. A long chain alcohol (coemulsifier) resulted in a marked improvement in stability, as well, which was attributed to a specific interaction between alcohol and emulsifier and to the alcohols tendency to concentrate at the o/w interface to form stronger interfacial film. The rate of ripening, according to the Lifshitz-Slyozov-Wagner (LSW) model, is directly proportional to the solubility of the dispersed phase in the dispersion medium. The increased polarity of the dispersed phase (oil) decreases the stability of the emulsion. The molar volume of solubilizate is a further parameter, which influences the stability of emulsion or the transfer of materials through the aqueous phase. The interparticle interaction is expected to favor the transfer of solubilizate located at the interfacial layer. The kinetics of solubilization of non-polar oils by ionic micelles is strongly related to the aqueous solubility of the oil phase (the diffusion approach), whilst their solubilization into non-ionic micelles can be contributed by interparticle collisions.  相似文献   

15.
The layer-by-layer electrostatic deposition method is a novel technique to precisely control the interfacial properties of multilayered films such as charge, thickness, permeability, and composition. The formation and stability of multilayered emulsions is however often plagued by extensive droplet flocculation and aggregation even at ideal polyelectrolyte concentrations where saturation should occur. Addition of salts may reduce the degree of attractive interactions ions and thus improve deposition. To test this hypothesis, the influence of different Hofmeister salts (KCl, NaCl, LiCl, and NH4Cl) at various salt concentrations (0–2500 mM) on the aggregation behavior of multilayered emulsions was investigated. A simple coating process of fish gelatin interfacial membranes with sugar beet pectin was used. Our results show that mean particle diameter and particle size distribution of emulsions initially decreased from 600 nm to 328 nm with increasing salt concentrations up to 250 mM. Above a critical level (>500 mM), heavy aggregation of emulsions at the presence of chaotropic salts occurred whereas kosmotropes reduced flocculation and creaming. Microscopic images and isothermal titration calorimetry confirmed particle size measurements. Results thus suggest that addition of salts may be an extremely useful tool to modulate and improve depositioning of alternatingly charged polymers on surfaces.   相似文献   

16.
Premix membrane emulsification is a promising method for the production of colloidal oil-in-water emulsions as drug carrier systems for intravenous administration. The present study investigated the possibility of preparing medium-chain triglyceride emulsions with a mean particle size below 100 nm and a narrow particle size distribution using sucrose laurate as an emulsifier. To manufacture the emulsions, a coarse pre-emulsion was repeatedly extruded through alumina membranes (Anodisc) of 200 nm, 100 nm and 20 nm nominal pore size. When Anodisc membranes with 20 nm pore size were employed, nanoemulsions with z-average diameters of about 50 nm to 90 nm and polydispersity indices smaller than 0.08 could be obtained. Particle growth due to Ostwald ripening was observed over 18 weeks of storage. The Ostwald ripening rate linearly depended on the emulsifier concentration and the concentration of free emulsifier, indicating that micelles in the aqueous phase accelerated the Ostwald ripening process. Long-term stability of the nanoemulsions could be achieved by using a minimised emulsifier concentration or by osmotic stabilisation with soybean oil added in a mass ratio of 1:1 to the lipid phase.  相似文献   

17.
The present study was conducted to enhance the peel of Citrus sinensis (sweet orange) by using their essential oils (EOs) as a potential source of natural bioactive molecules. EOs were obtained by hydrodistillation and their chemical profile was determined through GC-MS analysis. O/W EO emulsions were prepared using pectin as biopolymer emulsifier at different proportions, including different amounts of ascorbic acid (0, 0.5, and 1% w/w). The effect of pectin and ascorbic acid concentrations on the stability and rheological behavior of emulsions was investigated. It was found that adding ascorbic acid to the appropriate concentration of pectin enhances the interfacial membranes surrounding the oil droplets and decreases the droplet sizes. As a result both the viscoelastic modules and the resulting viscosity of emulsions increase leading to an improvement of their stability. Antioxidant activity of orange EO emulsion in combination with ascorbic acid was found significantly higher than that without ascorbic acid, and higher than that of individual components. Overall, this study would be helpful in developing more effectives systems with promising physical and antioxidant characteristics for the preservation of foods.  相似文献   

18.
Fluorinated copolymers are well known for their large range of applications. These applications can be improved by grafting or crosslinking of several agents. The mechanism of crosslinking of hexamethylene diamine and 2,4,4-trimethyl-1,6-hexanediamine is well known and occurs in four different steps. To elaborate a film of commercially available poly(VDF-co-HFP) copolymer crosslinked by 2,4,4-trimethyl-1,6-hexanediamine, a step of press cure under air is necessary. Temperature, time and pressure were optimised by regarding the solubility of the press cured films, the mechanical properties, the swelling rate in methyl ethyl ketone, and the degradation of the films. The best temperature, time and pressure for press cure were 150 °C, from 15 to 30 min, and 20 bars, respectively. Other properties of crosslinked poly(VDF-co-HFP) copolymers containing 10 mol.% and 20 mol.% of HFP were characterized. First, all films were insoluble in concentrated HCl. Secondly, swelling rates of different amounts of diamine crosslinked copolymers were measured in ethylene carbonate/dimethyl carbonate and in methyl ethyl ketone; it was proved that the higher the molar percentage of diamine, the higher the crosslinking density, so the lower the swelling rate. Concerning thermal properties, glass transition temperature mainly increased when the amount of diamine increased. Thermal stability measurements showed a higher decomposition temperature when the percentage of diamine was very low (5 mol.%). Finally, mechanical properties were measured by dynamic mechanical analysis; the storage tensile modulus (E′) of a diamine crosslinked Kynar® copolymer versus temperature exhibited a high drop because Kynar® was a highly amorphous copolymer. Moreover, the higher the amount of diamine, the higher the rubbery modulus.  相似文献   

19.
The influence of environmental conditions (pH, NaCl, CaCl2, and temperature) on the properties and stability of oil-in-water (O/W) emulsions containing oil droplets surrounded by one-, two-, or three-layer interfacial membranes has been investigated. Three oil-in-water emulsions were prepared with the same droplet concentration and buffer (5 wt % corn oil, 5 mM phosphate buffer, pH 6) but with different biopolymers: (i) primary emulsion: 0.5 wt % beta-Lg; (ii) secondary emulsion: 0.5 wt % beta-Lg, 0.1 wt % iota-carrageenan; (iii) tertiary emulsion: 0.5 wt % beta-Lg, 0.1 wt % iota-carrageenan, 0-2 wt % gelatin. The secondary and tertiary emulsions were prepared by electrostatic deposition of the charged biopolymers onto the surfaces of the oil droplets so as to form two- and three-layer interfacial membranes, respectively. The stability of the emulsions to pH (3-8), sodium chloride (0-500 mM), calcium chloride (0-12 mM), and thermal processing (30-90 degrees C) was determined. We found that multilayer emulsions had better stability to droplet aggregation than single-layer emulsions under certain environmental conditions and that one or more of the biopolymer layers could be made to desorb from the droplet surfaces in response to specific environmental changes (e.g., high salt or high temperature). These results suggest that the interfacial engineering technology used in this study could lead to the creation of food emulsions with improved stability to environmental stresses or to emulsions with triggered release characteristics.  相似文献   

20.
We studied the spontaneous emulsification and droplet growth mechanism in trans-anethol/water/ethanol solutions, also known as the beverage ouzo, using dynamic light scattering spectroscopy. This simple ternary mixture is a generic example of a system that forms microemulsions spontaneously when brought into the two-phase region. The volume fraction of the dispersed phase was found to profoundly affect the growth rates of the droplets, which is a new finding that has not been predicted by the Lifshitz-Slyozov-Wagner theory. Time-dependent measurements show that the droplet growth is governed by Ostwald ripening (OR), and no coalescence was observed. Furthermore, the OR rates increase with increasing oil concentration at low alcohol content. We attribute this behavior to enhanced droplet-droplet interactions. At high ethanol concentrations, we found that the measured rates decreased as the oil concentration increased. The OR growth mechanism completely correlates with changes in droplet size. The kinetics of droplet growth shows that the ripening has a saturation limit at a droplet radius of about 1.5 mum. Thus, formed emulsions remain stable for months.  相似文献   

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