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1.
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   

2.
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   

3.
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   

4.
The evolution of monomer droplets and latex particles of methyl methacrylate miniemulsions, initiated by an oil‐phase initiator, stabilized by a cationic surfactant mixture, and costabilized by different amounts of hexadecane, was investigated. With an increasing hexadecane concentration, the ultrasonication time required for the miniemulsions to reach a critically stabilized state was reduced, and a unimodal size distribution of the droplets with a decreasing average diameter was obtained. For lower hexadecane concentrations, a bimodal size distribution of the latex particles, with a significant increase in the volume fraction of the smaller latex particles, was achieved after the polymerization. The enhanced growth of the volume fraction of the smaller latex particles came from both nucleation of the shrinking droplets due to Ostwald ripening and homogeneous and/or micellar nucleation, if micelles existed, triggered by radicals in the aqueous phase. For high hexadecane concentrations, Ostwald ripening was effectively retarded, and the miniemulsions were sufficiently stabilized against the degradation of molecular diffusion. The size distributions of the droplets and latex particles were almost identical. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4603–4610, 2006  相似文献   

5.
Impact of oil type on nanoemulsion formation and Ostwald ripening stability   总被引:5,自引:0,他引:5  
The formation of stable transparent nanoemulsions poses two challenges: the ability to initially create an emulsion where the entire droplet size distribution is below 80 nm, and the subsequent stabilization of this emulsion against Ostwald ripening. The physical properties of the oil phase and the nature of the surfactant layer were found to have a considerable impact on nanoemulsion formation and stabilization. Nanoemulsions made with high viscosity oils, such as long chain triglycerides (LCT), were considerably larger ( D = 120 nm) than nanoemulsions prepared with low viscosity oils such as hexadecane ( D = 80 nm). The optimization of surfactant architecture, and differential viscosity eta D/eta C, has led to the formation of remarkably small nanoemulsions. With average sizes below 40 nm they are some of the smallest homogenized emulsions ever reported. What is more remarkable is that LCT nanoemulsions do not undergo Ostwald ripening and are physically stable for over 3 months. Ostwald ripening is prevented by the large molar volume of long chain triglyceride oils, which makes them insoluble in water thus providing a kinetic barrier to Ostwald ripening. Examination of the Ostwald ripening of mixed oil nanoemulsions found that the entropy gain associated with oil demixing provided a thermodynamic barrier to Ostwald ripening. Not only are the nanoemulsions created in this work some of the smallest reported, but they are also thermodynamically stable to Ostwald ripening when at least 50% of the oil phase is an insoluble triglyceride.  相似文献   

6.
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   

7.
Controlling stability and aging of emulsions is important from commercial and scientific perspectives. Achieving such control comes through gaining an understanding of the relationship between emulsion constituents and microstructure and how these influence the kinetics and mechanism of destabilisation. We present here an investigation determining the rate of destabilisation as a function of time for a series of water/n-alkane/Triton X-100 oil-in-water emulsions. The time dependence of the emulsions was investigated using static light scattering, PFG-NMR and measurement of gross phase separation. By changing the chain length of the oil from hexane to tetradecane, an almost five orders of magnitude variation in emulsion lifetime could be achieved, while maintaining most of the other chemical and physical characteristics of the emulsions. Further, we show that while Ostwald ripening is the dominant destabilisation mechanism, two distinct regimes are evident. Initially, we observed an enhanced Ostwald ripening regime due to the presence of oil-swollen micelles in the aqueous continuum, that is a depletion flocculation mechanism is followed. The presence of oil-swollen micelles was confirmed using PFG-NMR. The micelles aid the gross oil transport between the discrete oil domains. Upon phase separation the oil-swollen micelles are predominantly removed from the emulsion along with the excess water resulting in a concomitant reduction in the ripening rate, producing the more general Ostwald ripening cubic dependence of droplet radius as a function of time for the lower molecular weight oils. The oils with higher molecular weight (decane and above), however, were observed to switch over to destabilisation via creaming. PFG-NMR was shown to be a powerful technique to fully probe emulsion microstructure as a function of time with droplet size and spacing being directly obtained from the data.  相似文献   

8.
We describe results from systematic measurements of the rate of bubble Ostwald ripening in foams with air volume fraction of 90%. Several surfactant systems, with high and low surface modulus, were used to clarify the effect of the surfactant adsorption layer on the gas permeability across the foam films. In one series of experiments, glycerol was added to the foaming solutions to clarify how changes in the composition of the aqueous phase affect the rate of bubble coarsening. The experimental results are interpreted by a new theoretical model, which allowed us to determine the overall gas permeability of the foam films in the systems studied, and to decompose the film permeability into contributions coming from the surfactant adsorption layers and from the aqueous core of the films. For verification of the theoretical model, the gas permeability determined from the experiments with bulk foams are compared with values, determined in an independent set of measurements with the diminishing bubble method (single bubble attached at large air-water interface) and reasonably good agreement between the results obtained by the two methods is found. The analysis of the experimental data showed that the rate of bubble Ostwald ripening in the studied foams depends on (1) type of used surfactant-surfactants with high surface modulus lead to much slower rate of Ostwald ripening, which is explained by the reduced gas permeability of the adsorption layers in these systems; (2) presence of glycerol which reduces the gas solubility and diffusivity in the aqueous core of the foam film (without affecting the permeability of the adsorption layers), thus also leading to slower Ostwald ripening. Direct measurements showed that the foam films in the studied systems had very similar thicknesses, thus ruling out the possible explanation that the observed differences in the Ostwald ripening are due to different film thicknesses. Experiments with the Langmuir trough were used to demonstrate that the possible differences in the surface tensions of the shrinking and expanding bubbles in a given foam are too small to strongly affect the rate of Ostwald ripening in the specific systems studied here, despite the fact that some of the surfactant solutions have rather high surface modulus. The main reason for the latter observation is that the rate of surface deformation of the coarsening bubbles is extremely low, on the order of 10(-4) s(-1), so that the relaxation of the surface tension (though also slow for the high surface modulus systems) is still able to reduce the surface tension variations down to several mN/m. Thus, we conclude that the main reason for the reduced rate of bubble Ostwald ripening in the systems with high surface modulus is the low solubility and diffusivity of the gas molecules in the respective condensed adsorption layers (which have solid rather than fluid molecular packing).  相似文献   

9.
Liquid nanodroplets within a size range of 50 to 500 nm can easily be prepared by shearing a system containing oil, water and a surfactant. The growth of the nanodroplets can effectively be suppressed by using a strong hydrophobe as an additivie to the oil and an effective surfactant. The hydrophobe acts as an osmotic agent which stabilizes the system against Ostwald ripening. The growth of the droplets by collision is controlled by the density of the surfactant layer. Freshly prepared miniemulsions are “critically stabilized” and show a slow, but pronounced growth, whereas a miniemulsion in “equilibrium” exhibits constant droplet size on longer time scales. Polymerization of the oil droplets of such miniemulsions turns out to be very promising and extends the possibilities of classical emulsion polymerization. Since each droplet can be considered a small reactor in which polymerization reactions take place, the process allows one to create new particle structures, e.g. polyaddition reactions can take advantage of unusual monomers, the incorporation of materials which are not soluble in the continuous phase, and the formation of nanocapsules.  相似文献   

10.
The aim of this study is to determine the effects of oil solutes and alcohol cosolvents on the structure of oil-in-water microemulsions stabilized by poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers. The systems investigated involved the solubilization of 1,3,5-trimethylbenzene or 1,2-dichlorobenzene by P123 (EO(20)-PO(70)-EO(20)) pluronic surfactant micelles in water and water + ethanol solvents. The structures of these swollen micelles were determined by small-angle neutron scattering (SANS). A thermodynamic model was employed to interpret the characterization data. The results of the thermodynamic model for micellization agreed well with the SANS data from samples of micelles swollen by both oils. The model predicted the size of the micelles within 5% accuracy using only one fitting parameter, the micelle polydispersity. Ethanol had significantly different effects on the polymer micelles that contained solubilized oil compared to pure polymer micelles. For pure polymer micelles, the addition of ethanol increased the solubility of the polymer and, therefore, decreased the total volume fraction of micelles, while for polymer-oil aggregates, ethanol tended to have a positive effect on the volume fraction of micelles. SANS results showed that the greatest divergence from pure aqueous solvent results occurred at oil concentrations above the microemulsion stability limit.  相似文献   

11.
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   

12.
Previously available data on solubilization kinetics of two oils in a micellar solution of sodium dodecyl sulfate, have been plotted with the data for one more oil provided here. These rates show that they reach saturation values with increasing micellar concentrations. These saturation values are then shown to be linearly dependent on the solubilities of oil, in keeping with the theory that the mechanism for solubilization of soluble oils by an ionic surfactant is chiefly molecular dissolution of the oil followed by a quick uptake by the micelles.  相似文献   

13.
Oil-in-water nanoemulsions are finding increasing use as delivery systems to encapsulate lipophilic bioactive components in personal care and pharmaceutical. The aim of this study was to optimize the composition and stability of ceramide-2 nanoemulsions. The nanoemulsions were prepared by high pressure homogenizer emulsification method using sodium dilauramidoglutamide lysine (DLGL) as surfactant. Results showed that the oil type and concentration had an appreciable impact on the particle size and stability of the ceramide-2 enriched nanoemulsions. The presence of the aliphatic alcohol altered the curvature of the surfactant molecular and increased the stability of nanoemulsions. The zeta potential of nanoemulsions decreased with the addition of cetyl trimethyl ammonium chloride (1631), which weakens the electrostatic interactions between droplets and lowers the stability of the nanoemulsions. The particle size decreased with increasing concentrations of both sodium dodecyl sulfate (SDS) and cocoamidopropyl betaine (CAB). The variation of zeta potential with SDS and CAB was insignificant, which was attributed to the high zeta potential value resulted from anionic gemini surfactant DLGL. The instability mechanism of nanoemulsions was the Ostwald ripening. This study demonstrated that the addition of aliphatic alcohol, SDS, or CAB was beneficial to the stability of ceramide-2 nanoemulsions and decreased the Ostwald ripening rate.  相似文献   

14.
We have performed sudden composition changes on a (surfactant + oil + water) system by adding water to a (surfactant + oil) solution. This composition change quenches the system into a metastable oil-in-water emulsion with a population in the 100 nm range. The conditions for a successful quench are as follows: the initial water content should be below a boundary called the "clearing boundary" (CB), the final water content should be sufficiently beyond CB, and the quench should be fast. We have used high purity components to avoid the complex phase separation patterns that occur with low purity ingredients: the surfactant is octaethylenehexadecyl ether (C(16)E(8)) and the oil is hexadecane (C(16)). Under these conditions, we show that the pathway for this type of quench proceeds through the swelling of the reverse micellar phase by the added water and the formation of a sponge phase. Then, further water addition causes the nucleation of oil droplets in this sponge phase, with a size that matches the spontaneous curvature of the sponge phase. Part of the surfactant remains adsorbed on these droplets, and the rest is expelled as micelles that coexist with the droplets. It is concluded that a PIC emulsification will always lead to a bimodal size distribution with surfactant "wasted" in small micelles. This is in contrast with the more efficient PIT emulsification.  相似文献   

15.
Paraffin oil-in-water nano-emulsions stabilized by Tween 80/Span 80 were prepared using the emulsion inversion point method at different emulsification temperatures. Nano-emulsions with droplet size below 200 nm were formed above a critical surfactant-to-oil ratio of 0.20 at 50 degrees C. The main destabilization mechanism of the systems was found to be Ostwald ripening. An interesting phenomenon was that the Ostwald ripening rate declined as the surfactant concentration rose. Furthermore, flocculation was also found to contribute to the instability of the nano-emulsions, especially for those with low surfactant concentrations. Study on the electrophoretic properties of emulsion droplets revealed a negative value of the zeta potential, which was strongly dependent on the pH of the systems.  相似文献   

16.
We observed the diminishing of single microscopic oil drops to study the kinetics of solubilization of n-decane and benzene by micellar solutions of sodium dodecyl sulfate (SDS). Each drop is located in a horizontal glass capillary of inner diameter 0.06 cm filled with a thermostated surfactant solution; the small vertical dimension of the cell prevents the appearance of uncontrollable thermal convections. The experiments show that the radius of an n-decane drop decreases linearly with time, whereas for benzene this dependence is nonlinear. To interpret the data, a kinetic model of solubilization is developed. It accounts for the diffusion and capturing of dissolved oil molecules by the surfactant micelles, as well as for the finite rate of oil dissolution at the oil-water interface. By processing the data, we determined the rate constant of solubilization for a given oil and surfactant. It turns out that the elementary act of catching a dissolved oil molecule by a surfactant micelle occurs under a barrier (rather than diffusion) control. The effective rate of solubilization is greater for the oil, which exhibits a higher equilibrium solubility in pure water (benzene), despite the lower value of the solubilization rate constant for this oil.  相似文献   

17.
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   

18.
We provide an overview of the most recent advances in the field of surfactant and polymer-stabilized emulsions. The article is focused on inter-droplet forces, monolayer adhesion, aggregation of emulsion droplets, emulsion gels and finally destruction through coalescence and Ostwald ripening.  相似文献   

19.
The solubilization of triglycerides [1,2,3-tributanoylglycerol (TBG) and 1,2,3-trihexanoylglycerol (THG)] in water/octa(oxyethylene) dodecyl ether (C(12)EO(8)) systems has been investigated. Oil-induced changes in the structure of liquid crystals in water/C(12)EO(8) system have been studied by optical observation and small-angle X-ray scattering (SAXS) measurements. In the water/C(12)EO(8)/oil systems, solubilization of THG and TBG induces a transition between H(1) (hexagonal) and L(alpha) (lamellar) liquid crystals at high C(12)EO(8) concentrations, whereas at low surfactant concentrations a H(1)-I(1) (discontinuous micellar cubic phase) transition occurs. This anomalous behavior is attributed to the partitioning of solubilized oil in the micelles. At low surfactant concentrations THG is mainly solubilized into the hydrophobic cores of the surfactant micelles, indicating high swelling or low penetration tendency, resulting in a steep increase in the radius of the aggregates (r(H)), thereby inducing a rod-sphere transition. At high surfactant concentrations, THG is not mainly solubilized into the core but distributed between the palisade layer and the core of the aggregates. The TBG is considerably solubilized into the surfactant palisade layer, indicating a high penetration tendency, resulting in an increase in the effective cross-sectional area per surfactant molecule, a(s). The thermal stability of the I(1) phase increases with the solubilization of THG into the aggregate cores. The percentage deviation of the experimental interlayer spacings (P(d)) from complete swelling was also evaluated for different triglycerides in the H(1) and L(alpha) phases or different surfactant concentrations. It is found that the penetration tendency of triglycerides could be used as a tuning parameter for I(1) phase formation depending on the surfactant concentration and the molecular weight of the oil.  相似文献   

20.
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   

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