Simulation of phase separation with large component ratio for oil-in-water emulsion in ultrasound field

This paper presents an exploration for separation of oil-in-water and coalescence of oil droplets in ultrasound field via lattice Boltzmann method. Simulations were conducted by the ultrasound traveling and standing waves to enhance oil separation and trap oil droplets. The focus was to the effect of ultrasound irradiation on oil-in-water emulsion properties in the standing wave field, such as oil drop radius, morphology and growth kinetics of phase separation. Ultrasound fields were applied to irradiate the oil-in-water emulsion for getting flocculation of the oil droplets in 420 kHz case, and larger dispersed oil droplets and continuous phases in 2 MHz and 10 MHz cases, respectively. The separated phases started to rise along the direction of sound propagation after several periods. The rising rate of the flocks was significantly greater in ultrasound case than that of oil droplets in the original emulsion, indicating that ultrasound irradiation caused a rapid increase of oil droplet quantity in the progress of the separation. The separation degree was also significantly improved with increasing frequency or irradiation time. The dataset was rearranged for growth kinetics of ultrasonic phase separation in a plot by spherically averaged structure factor and the ratio of oil and emulsion phases. The analyses recovered the two different temporal regimes: the spinodal decomposition and domain growth stages, which further quantified the morphology results. These numerical results provide guidance for setting the optimum condition for the separation of oil-in-water emulsion in the ultrasound field.     

Droplets banding characteristics of water-in-oil emulsion under ultrasonic standing waves

Droplets banding is critical to emulsion separation under ultrasonic irradiation as it can greatly improve the separation efficiency. In this paper, the formation process of droplets banding under ultrasonic standing waves was precisely captured by high-speed microscopic photography; by processing the images, the droplets banding characteristics, including the banding formation time and banding interval, were extracted. Then the effects of acoustic intensity, frequency, droplet size, and physical properties of oil and water on the droplets banding characteristics were discussed in details. The results show that the range of acoustic intensities, within which the droplets banding can form, increases with the increase of the frequency; a maximum allowable acoustic intensity exists for banding formation, which also increases with the frequency. The banding formation time, which increases with increasing oil viscosity but decreases with droplet size, is found to be hardly affected by the oil-water interfacial tension. In addition, the banding interval is only related to the frequency, which closely corresponds to the half wavelength.     

Physical and chemical characteristics of ultrasonically-prepared water-in-diesel fuel: Effects of ultrasonic horn position and water content

An ultrasonic technique was applied to preparation of two-phase water-in-oil (W/O) emulsified fuel of water/diesel oil/surfactant. In this study, an ultrasonic apparatus with a 28 kHz rod horn was used. The influence of the horn tip position during ultrasonic treatment, sonication time and water content (5 or 10 vol%) on the emulsion stability, viscosity, water droplet size and water surface area of emulsion fuels prepared by ultrasonication was investigated. The emulsion stability of ultrasonically-prepared fuel significantly depended on the horn tip position during ultrasonic irradiation. It was found that the change in the stability with the horn tip position was partly related to that in the ultrasonic power estimated by calorimetry. Emulsion stability, viscosity and sum of water droplets surface area increased and water droplet size decreased with an increase in sonication time, and they approached each limiting value in the longer time. The maximum values of the viscosity and water surface area increased with water content, while the limiting values of the emulsion stability and water droplet size were almost independent of water content. During ultrasonication of water/diesel oil mixture, the hydrogen and methane were identified and the cracking of hydrocarbon components in the diesel oil occurred. The combustion characteristics of ultrasonically-prepared emulsion fuel were studied and compared with those of diesel oil. The soot and NOx emissions during combustion of the emulsified fuel with higher water contents were significantly reduced compared with those during combustion of diesel oil.     

Ultrasound-assisted desalination of crude oil: The influence of mixing extent,crude oil species,chemical demulsifier and operation variables

Coalescence of water droplets in crude oil has been effectively promoted by chemical demulsifiers integrated with ultrasound. Temporary images of water droplets in W/O emulsions were directly monitored using a metallurgical microscope. Water droplets achieved expansion of 118% at 40 min ultrasonic irradiation time under well mixing conditions. However, water droplets in heavy crude oil undergo less aggregation than those in light crude oil, due to resistance of mobility in highly viscous fluid. In the absence of chemical demulsifiers, water droplets enveloped by native surfactants appeared to aggregate arduously because of occurrence of interfacial tension gradients. Influential significance analyses have been executed by a factorial design method on operation variables, including acoustic power intensity, operation temperature, ultrasonic irradiation time and chemical demulsifier dosages. In this work, the outcomes indicate that the optimal operating conditions for desalination of crude oil assisted by ultrasound were as follows: acoustic power intensity = 300 W, operation temperature = 90℃, ultrasonic irradiation time = 75 min and chemical demulsifier dosages = 54 mg/L. Besides, it was found that the most influential importance of operation parameter was temperature, followed with acoustic power intensity, ultrasonic irradiation time and chemical demulsifier dosages.     

Physicochemical characterization of black seed oil-milk emulsions through ultrasonication

The ultrasonic formation of stable emulsions of a bioactive material, black seed oil, in skim milk was investigated. The incorporation of 7% of black seed oil in pasteurised homogenized skim milk (PHSM) using 20 kHz high intensity ultrasound was successfully achieved. The effect of sonication time and acoustic power on the emulsion stability was studied. A minimum process time of 8 min at an applied acoustic power of 100 W was sufficient to produce emulsion droplets stable for at least 8 days upon storage at 4 ± 2 °C, which was confirmed through creaming stability, particle size, rheology and color analysis. Partially denatured whey proteins may provide stability to the emulsion droplets and in addition to the cavitation effects of ultrasound are responsible for the production of smaller sized emulsion droplets.     

Ultrasound emulsification: effect of ultrasonic and physicochemical properties on dispersed phase volume and droplet size

Ultrasonic emulsification of oil and water was carried out and the effect of irradiation time, irradiation power and physicochemical properties of oil on the dispersed phase volume and dispersed phase droplet size has been studied. The increase in the irradiation time increases the dispersed phase volume while decreases the dispersed phase droplets size. With an increase in the ultrasonic irradiation power, there is an increase in the fraction of volume of the dispersed phase while the droplet size of the dispersed phase decreases. The fractional volume of the dispersed phase increases for the case of groundnut oil-water system while it is low for paraffin (heavy) oil-water system. The droplet size of soyabean oil dispersed in water is found to be small while that of paraffin (heavy) oil is found to be large. These variations could be explained on the basis of varying physicochemical properties of the system, i.e., viscosity of oil and the interfacial tension. During the ultrasonic emulsification, coalescence phenomenon which is only marginal, has been observed, which can be attributed to the collision of small droplets when the droplet concentration increases beyond a certain number and the acoustic streaming strength increases.     

Ultrasonic initiation of polystyrene latex synthesis

Polystyrene latex samples have been synthesised from an oil-in-water (o/w) emulsion of the monomer using ultrasonic irradiation as the initiation source. No added chemical initiators were used in any of the reactions. The free radicals formed from the cavitation process under the action of the ultrasound are sufficient to initiate the polymerisation. In the current study, the effects of varying the input intensity of the ultrasound were investigated. A marked increase in the monomer conversion rate as a function of time was seen as the power was increased. Despite this increase in conversion rate, the increasing intensity did not affect the resultant latex particle sizes. In all cases, the particle diameters at the conclusion of a polymerisation were seen to be in the range of 40 to 50 nm. The effects of changing the concentration of surfactant in the polymerisation medium and of changing the temperature were also probed. Increases in both were seen to lead to an increased rate of conversion at a fixed input intensity. Again, the particle diameters were invariant as a function of changing conditions. The small particle sizes and high conversion rates are thought to be due to a continuous nucleation process that is caused by the scavenging of free radicals throughout the polymerisation by freshly formed small oil droplets.     

Sustained release formulations of citronella oil nanoemulsion using cavitational techniques

Nanoemulsion synthesis has proven to be an effective way for transportation of immobile, insoluble bioactive compounds. Citronella Oil (lemongrass oil), a natural plant extract, can be used as a mosquito repellent and has less harmful effects compared to its available market counterpart DEET (N, N-Diethyl-meta-toluamide). Nanoemulsion of citronella oil in water was prepared using cavitation-assisted techniques while investigating the effect of system parameters like HLB (Hydrophilic Lipophilic Balance), surfactant concentration, input energy density and mode of power input on emulsion quality. The present work also examines the effect of emulsification on release rate to understand the relationship between droplet size and the release rate. Minimum droplet size (60 nm) of the emulsion was obtained at HLB of 14, S/O¹ ratio of 1.0, ultrasound amplitude of 50% and irradiation time of 5 min. This study revealed that hydrodynamic cavitation-assisted emulsification is more energy efficient compared to ultrasonic emulsification. It was also found that the release rate of nanoemulsion enhanced as the droplet size of emulsion reduced.     

Total Integration of the Sample Injection,Microdroplet Reaction,Phase Separation,Real-Time Optical Detection,and Recovery of Diverse Silver–Gold Bimetallic Nanoalloys in a Continuous Process

Microfluidic droplet generators have garnered great attention due to the uniformity, high-throughput capability, and facile experimental setup. To maximize the potentials of droplet technology as a chemical/biological nanoliter-scale reactor, the downstream processes such as separation of the aqueous and oil phase, real-time monitoring of the products formed in droplets, and the final product recovery from the droplets is necessary. In this study, the droplet is utilized as a chemical reactor to synthesize a variety of Ag and Au bimetallic nanoalloys in a fully integrated microsystem including sample injection, a T-junction droplet generator, droplet reaction, water–oil phase separation, real-time UV–vis absorbance detection, and product recovery. The flow rate of the Ag nanoparticle (NP) solution and the HAuCl₄ solution was tuned to generate different molar ratios of Ag and Au components. The in-line UV–vis absorbance spectrometer displays a peak shift of the Ag/Au bimetallic alloys depending on the molar ratio of Ag/Au in the continuous process, enabling to judge the kind of the Ag/Au alloys in situ and collect a variety of Ag/Au nanoalloys. Thus, the desired nanomaterials can be obtained with minimal trial and error, saving time and cost.     

Nano-emulsification of oriental lacquer sap by ultrasonic wave propagation: Improvement of thin-film characteristics as a natural resin

Lacquer sap has received much attention as a traditional natural resin because it is a renewable and eco-friendly biopolymer resource unlike artificial coating materials. However, strict drying conditions and long drying times of lacquer sap should be modified to expand its applications. This study presents the first attempt to investigate the effect of different amplitudes of ultrasonic waves on the lacquer sap composed of water-in-oil (W/O) emulsion droplets and the mechanical properties of the resultant film by solvent evaporation. Acoustically induced cavitation via batch ultrasonication facilitates the generation of submicron-sized W/O emulsion. The drying time of sonicated lacquer sap was noticeably shortened as the amplitude of acoustic power increased. Interestingly, the transparency of the film cast from lacquer sap consisting of the smallest emulsion droplets increased significantly, weakening the degree of colour change from caramel-like yellow to dark brown as polymerisation progressed. These are attributed to the effective and frequent contact of laccase enzyme with urushiol at the increased interfacial area of nano-emulsified W/O droplets pulverised by ultrasonic waves. The quinone radical-generation in the interface layer and its transfer to the urushiol oil phase through water-insoluble glycoprotein emulsifier are greatly promoted, resulting in highly cross-linked, dense three-dimensional polymer networks, which also increased the lacquer film hardness after drying. As the emulsion droplet size decreased, the mutual interaction between the catechol moiety of urushiol and the substrates increased, resulting in improved adhesion. The nano-emulsification of the lacquer sap by ultrasonic waves can be used in a simple, effective, and eco-friendly way to shorten the drying time and improve the film characteristics of natural resins. This approach could pave the way for its wide range of applications in industrial fields, taking into account green and sustainable chemistry.     

基于兰姆波在倾斜镜子基板上的油水微分离实验*

该文提出利用兰姆波在倾斜的镜子基板上推动油水混合液滴,实现油水的微分离。实验主要研究了油水混合液滴在分离过程中的运动位移特性关系。运用Navier-Stokes、声流力等方程进行理论分析,发现混合液滴在分离过程中水滴所受到的驱动力大于油滴。通过对实验多变量的控制、单一变量的研究、建立油水混合液滴在倾斜镜子基板上受力平衡方程,发现激发电压、油水混合比例、基板倾角三个因素对油水微分离位移实验有着重要的影响。结果表明:当基板倾角和油水混合比例一定时,油水分离位移随着激发电压的增大而减小;在激发电压和基板倾角不变时,油水分离位移随着油水混合比例的减小而减小;当激发电压和油水混合比例不变时,油水分离位移随着基板倾角的增大而减小。该油水分离方法可以被应用到其他非压电基板上,为获得其他两种不相溶混合液滴的分离提供技术支持。     

Theoretical and experimental investigation of desalting and dehydration of crude oil by assistance of ultrasonic irradiation

In this paper desalting/dehydration process of crude oil by ultrasonic irradiation in a novel batch standing-wave resonator reactor is studied both theoretically and experimentally. The effect of main parameters including ultrasonic irradiation parameters, namely irradiation input power and irradiation time, and also operating parameters, such as temperature and injected water, on the removal efficiencies of salt and water is examined. The obtained results demonstrate that finding the optimum values of the above mentioned parameters is important to prevent a significant decrease in the removal efficiencies of water and especially salt. Thus, crude oil was subjected to optimal ultrasonic irradiation with an input power of 57.7 W, and irradiation time of 6.2 min at temperature of 100 °C. The injected water to dissolve the salt of crude oil was 7 vol.%. Also, the applied settling time and dosage of chemical demulsifier were 60 min and 2 ppm, respectively. Under these optimum conditions the removal efficiencies of the desalting/dehydration process were 84% and 99.8%, respectively, which are suitable for refineries.Also, based on the optimal experimental data, two inferential estimators are developed to obtain the relationships between the salt and water removal efficiencies, and input energy density. These empirical relationships can offer a proper estimation for the salt and water removal efficiencies with irradiation input energy.     

A study on the emulsification of oil by power ultrasound

A commercial ultrasonic probe was used to study emulsification of an o/w system (5 wt% soybean oil stabilised with 1 wt% Tween 80 in water). Two different sets of experiments were performed.

Firstly, we investigated the effect of power, duty cycle and ultrasound time on the production of an oil-in-water emulsion from a coarse pre-emulsion mix. The droplets reached a stable size (0.7 μm) within 5 min independent of the power and duty cycle used.

Secondly, the mechanism of emulsification was studied by observing the emulsification process at an oil–water interface (no pre-mix) with a high-speed camera. Transient cavitation is thought to be responsible for acoustic emulsification; however there have been no measurements to relate the transient cavitation zone to the production of an emulsion. It has already been shown that the transient cavitation in probe systems is directly under the probe tip. High-speed observations showed that an emulsion could only be obtained if the interface was within a few millimetres of the probe tip. These results strongly suggest that the transient cavitation zone is responsible for the acoustic emulsification of oil.     

Effect of ultrasound on the preparation of soy protein isolate-maltodextrin embedded hemp seed oil microcapsules and the establishment of oxidation kinetics models

In this study, microcapsules were prepared by spray drying and embedding hemp seed oil (HSO) with soy protein isolate (SPI) and maltodextrin (MD) as wall materials. The effect of ultrasonic power on the microstructure and characteristics of the composite emulsion and microcapsules was studied. Studies have shown that ultrasonic power has a significant impact on the stability of composite emulsions. The particle size of the composite emulsion after 450 W ultrasonic treatment was significantly lower than the particle size of the emulsion without the ultrasonic treatment. Through fluorescence microscopy observation, HSO was found to be successfully embedded in the wall materials to form an oil/water (O/W) composite emulsion. The spray-dried microcapsules showed a smooth spherical structure through scanning electron microscopy (SEM), and the particle size was 10.7 μm at 450 W. Fourier transform infrared (FTIR) spectroscopy analysis found that ultrasonic treatment would increase the degree of covalent bonding of the SPI-MD complex to a certain extent, thereby improving the stability and embedding effect of the microcapsules. Finally, oxidation kinetics models of HSO and HSO microcapsules were constructed and verified. The zero-order model of HSO microcapsules was found to have a higher degree of fit; after verification, the model can better reflect the quality changes of HSO microcapsules during storage.     

Pulsed ultrasound assisted dehydration of waste oil

A method to aid the separation of the oil phase from waste oil emulsion of refineries had been developed by using a pulsed ultrasonic irradiation technology. Compared with conventional continuous ultrasonic irradiation, it is found that pulsed ultrasonic irradiation is much better to make water drop coalescence and hence dehydration of waste oil. The effects of ultrasonic irradiation parameters on waste oil dehydration are further discussed. The orthogonal experiment is also designed to investigate the degrees of influence of ultrasonic parameters and the optimal technological conditions. Under the optimal experimental conditions, the water content of waste oil is decreased from 65% to 8%, which thereby satisfies the requirements of refineries on the water content of waste oil after treatment (<10%).     

Process optimization of ultrasound-assisted curcumin nanoemulsions stabilized by OSA-modified starch

This study reports on the process optimization of ultrasound-assisted, food-grade oil–water nanoemulsions stabilized by modified starches. In this work, effects of major emulsification process variables including applied power in terms of power density and sonication time, and formulation parameters, that is, surfactant type and concentration, bioactive concentration and dispersed-phase volume fraction were investigated on the mean droplet diameter, polydispersity index and charge on the emulsion droplets. Emulsifying properties of octenyl succinic anhydride modified starches, that is, Purity Gum 2000, Hi-Cap 100 and Purity Gum Ultra, and the size stability of corresponding emulsion droplets during the 1 month storage period were also investigated. Results revealed that the smallest and more stable nanoemulsion droplets were obtained when coarse emulsions treated at 40% of applied power (power density: 1.36 W/mL) for 7 min, stabilized by 1.5% (w/v) Purity Gum Ultra. Optimum volume fraction of oil (medium chain triglycerides) and the concentration of bioactive compound (curcumin) dispersed were 0.05 and 6 mg/mL oil, respectively. These results indicated that the ultrasound-assisted emulsification could be successfully used for the preparation of starch-stabilized nanoemulsions at lower temperatures (40–45 °C) and reduced energy consumption.     

Emulsification by high frequency ultrasound using piezoelectric transducer: Formation and stability of emulsifier free emulsion

Emulsifier free emulsion was developed with a new patented technique for food and cosmetic applications. This emulsification process dispersed oil droplets in water without any emulsifier. Emulsions were prepared with different vegetable oil ratios 5%, 10% and 15% (v/v) using high frequency ultrasounds generated by piezoelectric ceramic transducer vibrating at 1.7 MHz. The emulsion was prepared with various emulsification times between 0 and 10 h. Oil droplets size was measured by laser granulometry. The pH variation was monitored; electrophoretic mobility and conductivity variation were measured using Zêtasizer equipment during emulsification process. The results revealed that oil droplets average size decreased significantly (p < 0.05) during the first 6 h of emulsification process and that from 160 to 1 μm for emulsions with 5%, 10% and from 400 to 29 μm for emulsion with 15% of initial oil ratio.For all tested oil ratios, pH measurement showed significant decrease and negative electrophoretic mobility showed the accumulation of OH⁻ at oil/water interface leading to droplets stability in the emulsion. The conductivity of emulsions showed a decrease of the ions quantity in solution, which indicated formation of positive charge layer around OH⁻ structure. They constitute a double ionic layer around oil particles providing emulsion stability. This study showed a strong correlation between turbidity measurement and proportion of emulsified oil.     

Ultrasonic assisted water-in-oil emulsions encapsulating macro-molecular polysaccharide chitosan: Influence of molecular properties,emulsion viscosity and their stability

An ultrasonic technique was applied to formulation of two-phase water-in-paraffin oil emulsions loading a high-molecular polysaccharide chitosan (CS) and stabilized by an oil-soluble surfactant (Span80) at different operational conditions. The influence of chitosan molecular properties, phase volume ratio (φ_w), Span80 volume fraction (φ_s) and ultrasonic processing parameters were systemically investigated on the basis of mean droplet diameter (MDD) and polydispersity index (PDI) of emulsions. It was observed that the molecular weight (M_w) of CS was an important influential factor to MDD due to the non-Newtonian properties of CS solution varying with M_w. The minimum MDD of 198.5 nm with PDI of 0.326 was obtained with ultrasonic amplitude of 32% for 15 min at an optimum φ_w of 35%, φ_s of 8%, probe position of 2.2 cm to the top of emulsion, while CS with M_w of 400 kDa and deacetylation degree of 84.6% was used. The rise of emulsion viscosity and the reduction of negative zeta potential at φ_w increasing from 5% to 35% were beneficial to obtain finer droplets and more uniform distribution of emulsions, and emulsion viscosity could be represented as a monotonically-decreasing power function of MDD at the same φ_w. FTIR analysis indicated that the molecular structure of paraffin oil was unaffected during ultrasonication. Moreover, the emulsions exhibited a good stability at 4 °C with a slight phase separation at 25 °C after 24 h of storage. By analyzing the evolution of MDD, PDI and sedimentation index (SI) with time, coalescence model showed better fitting results as comparison to Ostwald ripening model, which demonstrated that the coalescence or flocculation was the dominant destabilizing mechanism for such W/O emulsions encapsulating CS. This study may provide a valuable contribution for the application of a non-Newtonian macromolecule solution as dispersed phase to generate nano-size W/O emulsions via ultrasound, and widen knowledge and interest of such emulsions in the functional biomaterial field.     

Effect of slit dual-frequency ultrasonic emulsification technology on the stability of walnut emulsions

A highly hygienic walnut emulsion beverage was prepared by using a slit dual-frequency emulsification technique. The optimal ultrasonic parameters were studied as a model system: the ultrasonic time of 50 min, the ultrasonic power density of 260 W/L, and a dual-frequency ultrasonic combination of 28/68 kHz. Walnut emulsion with an average mean volume diameter of 2.05 µm, a Zeta potential absolute value of 40 mV was obtained after ultrasonic treatment, and the emulsion stability could be maintained for more than 14 days without phase separation. At the lowest ultrasonic energy input, the vibrating emulsion could promote droplet aggregation. However, excessive energy input could result in sample overtreatment and reduced emulsion activity. The laser scanning confocal microscope (LSCM) and transmission electron microscope (TEM) confirmed that walnut emulsion processed by slit dual-frequency ultrasonic had pretty high stability. Therefore, the slit dual-frequency ultrasonic emulsification technique was found to be well suited for the preparation of complex and fine oil-in-water food emulsions.     

Pickering emulsion prepared by nano-silica particles – A comparative study for exploring the effect of various mechanical methods

Pickering emulsions are eco-friendly, stabilized by solid particles, and have an essential role in leading industries. Although Pickering emulations have found several applications, surprisingly few investigations have attempted to explore the effectiveness of various mechanical processes for its production. To fill these gaps, the present investigation comprehensively examined the application of various Pickering emulsion preparation processes such as rotor-stator homogenization emulsification (R-SH), ultrasonic emulsification, and their combined processes by using nano-silica particles. The influences of emulsification time and intensity on emulsion droplets' distribution were analyzed as indicative factors. The kerosene/water nano-silica Pickering emulsion was utilized for all assessments. The obtained results demonstrated that the main distribution peak of the emulsion prepared by R-SH occurred where the chord length was greater than 40 μm. Micro-scale nano-silica-aggregates generated large droplets, while the fine-emulsion fraction was significantly increased after ultrasonic treatment. The experimental results showed that the emulsion prepared only by ultrasound needed substantial power to form a Pickering emulsion since the oil phase was difficult to disperse in the water phase. Finally, it was concluded that preprocessing by R-SH could form a stable and uniform emulsion speedily, which is essential for ultrasound emulsion preparation.