Droplet composition affects the rate of oxidation of emulsified ethyl linoleate

Our objective was to study the influence of droplet composition on the rate of lipid oxidation in emulsions. A series of oil-in-water emulsions stabilized by a nonionic surfactant (Tween 20) was studied. These emulsions had the same total oil concentration (5 wt%) and initial droplet diameter (0.3 μm), but contained droplets with different ratios of ethyl linoleate (substrate) andn-tetradecane (inert diluent). Lipid oxidation was measured as a function of time by three different methods: gas-chromatographic determination of residual substrate; ultraviolet-visible spectrophotometric determination of conjugated dienes; and measurement of aqueous thiobarbituric acid-reactive substances. All three methods showed similar trends for emulsions of similar composition. The progress of lipid oxidation in the emulsions was dependent on the concentration of ethyl linoleate in the emulsion droplets. At low concentrations (1% oil as substrate), oxidation proceeded at a relatively slow and constant rate. At intermediate concentrations (20%), the oxidation rate was rapid initially and then slowed down with time. At high concentrations (100%), the oxidation rate was slow at first, and then increased with time. An explanation of our results is proposed in terms of the distribution of substrate molecules between the droplet interior and interface, and the ingress of aqueous radicals into the emulsion droplets.     

Surface Melting in Alkane Emulsion Droplets as Affected by Surfactant Type

The influence of surfactant type (Tween 20, Tween 40, Tween 60, Tween 80, Brij 58, Triton X-100, SDS, STS) on the crystallization and melting characteristics of emulsified (mean droplet diameter 0.52 μm) n-octadecane and n-eicosane were studied using microcalorimetry. The melting point (~37 °C) of the eicosane droplets was higher than the crystallization point (~24 °C) and was not affected by the surfactant selected. There was a similar separation between the crystallization (~14 °C) and melting (~28 °C) point of the emulsified octadecane however the details of the transitions was affected by the surfactant selected. For Tween 40 and Brij 58-stabilized droplets there was a split peak on crystallization which we attribute to a surface heterogeneous nucleation mechanism. Only these surfactant-alkane combinations had a split peak on melting. The size of the lower temperature fraction decreased with droplet size suggesting another surface effect. However, the size of the surface layer was calculated to be many times the length of the surfactant tail suggesting the crystal structure was modified by the nucleation mechanism.     

Continuous-phase fat crystals strongly influence water-in-oil emulsion stability

To elucidate the role of continuous-phase fat crystals on emulsion destabilization, water-in-canola oil emulsions prepared with 0–2% (w/w) added solid fat (hydrogenated canola stearine or hydrogenated cottonseed stearine) were examined using pulsed NMR droplet-size analysis, sedimentation, and microscopy. Droplet-size analysis showed that addition of either fat prior to emulsification (precrystallized fat) or fat quench-crystallized in situ following emulsification (postcrystallized fat) decreased the degree of droplet coalescence, based on volume-weighted (d ₃₃) mean droplet diameters, with postcrystallized emulsions being more stable against coalescence. Sedimentation studies corroborated these results, with greatly enhanced stability against sedimentation in postcrystallized emulsions. Precrystallized fat had very little effect on emulsion sedimentation at levels as high as 2% (w/w). Postcrystallized cottonseed stearine produced slightly less resistant emulsions than did canola stearine, even if both were in the β-form. Surface energetics revealed that canola stearine had greater affinity for the oil/water interface and hence a greater displacement energy. The presence of micronsized (Pickering) crystals located directly at the droplet interface, resulting from in situ crystallization or generated by the shearing of precrystallized fats, provided enhanced stability vis-à-vis preformed crystals. These stabilized emulsions via the formation of crystal networks that partially immobilized droplets.     

Solid Lipid Nanoparticles: Effect of Carrier Oil and Emulsifier Type on Phase Behavior and Physical Stability

The impact of surfactant type and carrier oil type on the phase behavior and physical stability of emulsified tripalmitin was investigated. Solid lipid nanoparticles (SLNs) were prepared by homogenizing lipid and aqueous phases at a temperature (≈80 °C) above the melting point of tripalmitin, and then cooling the resulting oil-in-water emulsion to induce lipid droplet crystallization. When stored at 37 °C, tripalmitin particles had good long-term stability (d < 150 nm) when coated with Tween 20, but were prone to aggregation and gelation when coated with modified starch (MS). Conversely, when stored at ≤20 °C tripalmitin particles coated by MS were more stable to aggregation/gelation than those coated by Tween 20. Blending tripalmitin with low melting point lipids (either medium chain triglycerides or orange oil) prior to homogenization led to a considerable alteration in the SLN phase behavior and stability. DSC measurements indicated that the presence of the carrier oils reduced the crystallization temperature, melting temperature, and melting enthalpy of tripalmitin. In addition, the carrier oils improved the stability of SLNs to particle aggregation and gelation, although some particle coalescence still occurred. These results have important implications for formulating colloidal delivery systems for utilization within the food and other industries.     

驱油剂对三元复合驱含油污水中油滴稳定性的影响

三元复合驱技术已在大庆油田成功进行工业化应用。三元复合驱含油污水中由于含有残余的化学药剂，导致其很难处理，从而限制了三元复合驱技术的推广。本文首先采用室内实验制备模拟三元复合驱含油污水，然后通过沉降实验研究驱油剂对油滴稳定性的影响，最后结合驱油剂对油水界面张力、油滴Zeta电位、油滴粒径大小的影响来阐释驱油剂对油滴稳定性的作用机制。结果表明：油滴的稳定性随着NaOH浓度的增大先增大后减小，当NaOH浓度由0增大到400mg/L时，NaOH与原油中的酸性物质反应生成表面活性剂增强油滴的稳定性；当NaOH浓度大于400mg/L时，NaOH本身作为电解质压缩双电层，使油滴的稳定性减小。油滴的稳定性随着表面活性剂浓度的增大而增大，这是因为表面活性剂可以吸附在油滴表面，使油水界面张力减小，同时增大油滴表面的Zeta电位，从而使油滴的稳定性增强。油滴的稳定性随着聚合物浓度的增大先减小后增大，当聚合物的浓度小于300mg/L时，聚合物的桥接、絮凝作用起主导作用，聚合物分子可以吸附到油滴表面，将油滴连接到一起，同时聚合物分子可以压缩液滴表面的双电层，从而有利于油滴的聚结；当聚合物的浓度大于300mg/L时，体系的黏度增大，油滴的运动速度减小，此时聚合物分子占满油滴表面，表现出空间位阻作用，从而使油滴的稳定性增强，不利于油滴的聚结。     

Influence of the plate-type continuous micro-separator dimensions on the efficiency of demulsification of oil-in-water emulsion

The objective of this article is to find the optimal dimensions of rectangular plate-type micro-separators in order to enhance the continuous separation of immiscible liquids. The main structure of the separators contains two plates: a hydrophobic (PTFE) upper plate and a hydrophilic (stainless steel) bottom plate which formed the contact surfaces for the fluids in the channel. The devices have two outlets, one for the aqueous phase and the other for the organic phase enabling the continuous separation and withdrawal of the separated phases. Demulsification has been carried out using Shellsol/water emulsion in the presence of a non-ionic surfactant (Tween 80). The separation efficiency is investigated as a function of micro-separator sizes, channel depths, flow rates and plate configurations. The major parameter that controls the destabilization mechanism is the ratio between the droplet size and the channel depth. When the size of the dispersed droplets remains smaller than the height of the separator (channel depths: 25–100 μm), creaming is the main demulsification mechanism. Creaming refers to the migration of the dispersed phase of an emulsion, under the influence of buoyancy. The particles float upwards and rise to the top due to the difference in the densities of the particles and the medium. The separation efficiency depends mainly on the residence time of the liquid/liquid mixture in the device regardless of the separator dimensions and channel heights. The separation rate is limited by the removal of the cream layer, formed at the top of the upper plate, from the separator. When the size of the dispersed droplets is larger than the depth of the separator (channel height of 9 μm), the separation performance and mechanism become different. The coalescence of the dispersed droplets occurs by passing through the device. The comparison of the data corresponding to creaming and coalescence phenomena emphasizes that the coalescence greatly enhance and accelerate the separation action. The phase separation in the micro-coalescer takes place considerably faster than in the micro-separators.     

Poly(methyl methacrylate) multihollow particles by water in oil in water emulsion polymerization

Multihollow‐structured poly(methyl methacrylate) (PMMA) particles were produced employing the water in oil in water (W/O/W) emulsion polymerization technique where sorbitan monooleate was used as a primary surfactant and sodium laurylsulfate and Glucopen, a polypeptide derivative, were used as secondary surfactants. Vinyl acetate was copolymerized to improve the wettability of the particles. The agitation speed and concentration of the urethane acrylate employed as a reactive viscosity enhancer played a crucial role in determining the morphology and average size of the PMMA multihollow particles. In high agitation speed the multihollow particles displayed a small size and narrow size distribution resulting from efficient droplet breakup. Especially when the urethane acrylate was incorporated, PMMA multihollow particles with a smooth and clear surface were achieved. This was believed to be because the urethane acrylate increased the viscosity of the monomer mixture and helped to form the stable W/O/W emulsion droplets that restricted droplet coalescence during polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 38–44, 2000     

结合图像数字化技术用悬滴法测动态界面张力——动态界面张力与表面活性剂浓度的关系

引　言从微观机理上讲 ,能否制得稳定乳状液与乳化剂扩散速度、界面层吸附速度和成膜分子间协同作用等因素有关 ,而这些信息可以通过测动态界面张力反映出来 ,因此测动态界面张力是研究乳状液稳定性微观机理的一条重要途径 .测动态界面张力的方法[1] 很多 ,其中悬滴法 (滴外形法的一种 )有独特的优点[1] .目前 ,在国外已利用该法展开了许多卓有成效的研究工作[2～ 6 ] ;国内李佟茗[7] 等已报道采用计算机图像采集技术实时记录气泡长大过程测动态表面张力的工作 ;田宜灵[8] 等则报道了用数字化摄像仪拍摄悬滴 ,以选面法[9] 计算静态界面张力…     

非离子表面活性剂乳液体系抗聚并稳定性的实验与分析

实验考察了非离子表面活性剂TX和AEO乳化白油所得乳液体系抗聚并稳定性随电解质浓度和表面活性剂HLB值的变化规律 .针对上述体系建立了两液珠间的静态力学模型 .利用模型考察了界面电位和电解质浓度对两液珠间作用力的影响 .通过分析上述模型模拟结果和实验现象之间的矛盾 ,指出在液珠的碰撞过程中 ,表面活性剂分子在界面静电排斥力的作用下 ,存在着被挤入到分散相液珠内的趋势 ,从而导致了界面的变形和表面活性剂空穴区的形成 ,阐述了乳液珠滴发生聚并的一种微观机制     

Movement of dispersed droplets of W/O emulsion in a uniform DC electrostatic field:Simulation on droplet coalescence☆

Considering the droplet coalescence, the motion of a group of dispersed droplets in W/O emulsion in a DC electric field is simulated. The simulation demonstrates the evolutions of droplet number, size as wel as its distribution, local concentration distribution and droplet size-velocity relation with the applied time of electric field. The sim-ulated average droplet size is roughly consistent with the experimental value. The simulated variation of droplet number with time under several applied voltages shows that increasing voltage is more effective for raising the rate of droplet coalescence than extending exerting time. However, with the further raise of applied voltage, the improvement in droplet coalescence rate becomes less significant. The evolution of simulated droplet size–velocity relationship with time shows that the inter-droplet electric repulsion force is very strong due to larger electric charge on the droplet under higher applied voltage, so that the magnitude and the direction of droplet velocity become more random, which looks helpful to droplet coalescence.     

Destabilization of the Emulsion Formed during Aqueous Extraction of Soybean Oil

Characterization and destabilization of the emulsion formed during aqueous extraction of oil from soybean flour were investigated. This emulsion was collected as a cream layer and was subjected to various single and combined treatments, including thermal treatments and enzymatic treatments, aimed at recovery of free oil. The soybean oil emulsion formed during the aqueous extraction processing of full fat flour contains high molecular weight glycinin and β-conglycinin proteins and smaller oleosin proteins, which form a multilayer interface. Heat treatment alone did not modify the free oil recovery but freeze–thaw treatment increased the oil yield from 3 to 22%. After enzymatic treatment of the emulsion, its mean droplet size changed from 5 to 14 μm and the oil recovery increased to 23%. This increase could be attributed to the removal (due to enzymatic hydrolysis) of large molecular weight polypeptides from the emulsion interface, resulting in partial emulsion destabilization. When enzymatic treatment was followed by a freeze–thaw step, the oil recovery increased to 46%. This result can be attributed to the thinner interfacial membrane after enzymatic hydrolysis, partial coalescence during freeze–thaw, and coalescence during centrifugation. Despite the reduction in emulsion stability achieved, additional demulsification approaches need to be pursued to obtain an acceptably high conversion to free oil.     

Drop mixing in suspension polymerisation

In suspension polymerisation, monomer is suspended as liquid droplets in a continuous water phase by means of strong agitation and the presence of a suspending agent. As the suspension polymerisation proceeds, the viscosity of a monomer-polymer droplet increases with conversion. Hence, the physical behaviour of the droplet changes during the process. When new dispersible material is added to the existing suspension drops, the new material and existing drops can remain segregated for significant amounts of time. The aim of this project was to study the behaviour of drop mixing when new material is added to the existing suspension polymerisation. This study concentrated on the effect of the dispersed phase viscosity on drop mixing. The results show that viscosity affects drop size and that may then affect the rate of coalescence between drops. A critical drop size exists which determines the coalescence efficiency effect. Above the critical drop size, mixing rate increases as the drop viscosity decreases. While below the critical drop size, drop size of the dispersion determines the coalescence rate; as the drop size increases, coalescence rate also increases. The investigation of the effect of suspending agent shows that Tween 20 is more efficient in stabilising and protecting the drops, based on a weight basis, than PVA as the coalescence rate is lower with Tween 20.     

Influence of soybean protein isolates-phosphatidycholine interaction on the stability on oil-in-water emulsions

Soybean protein isolates and phospholipids present specific surface properties with synergistic or antagonistic effects on emulsion stability. Oil-in-water emulsions (25∶75 w/w) were prepared using native and denatured soybean isolates (NSI and DSI, respectively) with the addition of phosphatidylcholine (PC) (protein/PC ratio 100∶1 to 10∶1). The effect of ionic strength was also studied by adding sodium chloride (0–100 mM) to the aqueous phase. Analysis of NSI/PC and DSI/PC emulsions showed that the creaming rate diminished upon addition of PC, with the creamed phase showing more stability than those of the control systems. In DSI/PC systems, the coalescence process was partially controlled, as evidenced by a decrease in the size of oil droplets. Both systems were altered by the presence of sodium chloride, with an increase in the creaming rate attributable to flocculation and the coalescence of droplets. Under these conditions, DSI/PC emulsions exhibited a stronger protein-phospholipid interaction than those of NSI/PC.     

Water-in-triglyceride oil emulsions. Effect of fat crystals on stability

The influence of low concentrations (0.1-5%) of fat crystals on the stability of water-in-soybean oil emulsions was examined by light scattering and sedimentation experiments. Both the initial flocculation/coalescence rate and long-term stability against water separation were determined. The initial flocculation/coalescence rate increased upon addition of small amounts of fat crystals. When the crystal concentration was increased above a critical concentration (specific to a system), a decrease in the flocculation/coalescence rate occurred. The increased flocculation/coalescence rate is likely the effect of bridging of water droplets by fat crystals. Fat crystal wetting by water is an important criterion for this phenomenon to occur. Emulsion stabilization for crystal concentrations above critical is caused by a mechanical screening of water droplets. The presence of considerable amounts of crystals in oil also lowered the density difference between droplet and medium, and enhanced viscosity. The degree of increase in viscosity depended upon the emulsifier. Both a decrease in density difference and an increase in viscosity play a role in hindering flocculation/coalescence of droplets. In long-term studies of water separation, all concentrations of fat crystals stabilized the water-in-oil emulsions. The droplet size of these emulsions increased until the critical droplet size was approached where the screening effect of crystals on the droplets no longer stabilized the emulsions. The stabilizing effect for emulsions with monoolein was continuously improved by increasing the amount of crystals up to 5%. For lecithin-stabilized emulsions, an optimal effect was achieved for fact crystal concentrations of 1–2%.     

N,N-二甲基甲酰胺/液体石蜡非水乳液体系的稳定性研究

将Tween 80,PluronicL64和聚醚胺JEFFAMINE M-2070(M-2070)分别与Span 85复配制得了N,N-二甲基甲酰胺(DMF)/液体石蜡非水乳液体系,从亲水亲油平衡值(HLB)、液滴粒径和稳定时间等方面研究了二元表面活性剂复配对非水乳液稳定性的影响;在Tween 80和Span 85复配基础上,将十二烷基苯磺酸钠(SDBS)、十六烷基三甲基溴化铵(CTAB)和聚乙烯吡咯烷酮(PVP)分别添加到非水乳液体系中,从粒径和乳液稳定时间2个方面考察了三元表面活性剂复配对乳液稳定性的影响。结果表明,Tween 80和Span 85复配可得到较稳定的非水乳液;添加CTAB后,非水乳液的稳定性反而降低;添加PVP后,非水乳液的稳定性有一定程度地加强;而添加SDBS后,乳液的稳定性大大增强。     

Prediction of average droplet size in flowing immiscible polymer blends

The paper is focused on calculation of the average droplet size in immiscible blends during their steady flow. Available theoretical and experimental results of studies of the droplet breakup and coalescence are utilized to derive the equations describing dynamic equilibrium between the droplet breakup and coalescence. New expression for the coalescence efficiency, reliably reflecting recent theoretical results, is proposed. The equation for the average steady droplet size, controlled by the stepwise breakup mechanism and coalescence of droplets with not very different sizes, is derived for blends containing up to 10–20 vol % of the droplets. For blends with above approximate 20 vol % of the droplets, the breakup by the Tomotika mechanism and coalescence in highly polydisperse system is modeled. Results of the derived equations are compared with experimental data; qualitative agreement is found for the dependence of the droplet size on the amount of the dispersed phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45250.     

直流脉冲电场下液滴-界面聚并行为

为了深入探究直流脉冲电场下液滴-界面聚并行为,针对去离子水作为分散相、葵花油作为连续相的体系,分别改变电场参数（电场强度、频率、波形）和物性参数（界面张力、电导率、液滴粒径、固体颗粒）进行显微实验研究,得到了液滴-界面聚并机制及各参数的影响规律。实验结果表明,液滴-界面存在完全聚并和不完全聚并两种机制,决定因素是泵吸和颈缩过程的相互作用。电场强度增大,不完全聚并程度增大,而电场频率的作用则相反,这与电场力大小和液滴稳定程度有关。随表面活性剂浓度增大,二次液滴急剧增大,超过临界胶束浓度后,小幅减小。随电导率和SiO₂浓度增大,不完全聚并程度均先增大后减小,而随液滴粒径增大,不完全聚并程度持续增大。大部分工况下,液滴在直流稳恒电场下不完全聚并程度高于直流脉冲电场。为脉冲静电破乳机理的深入探讨及高效紧凑脉冲电脱盐脱水设备的研发奠定了理论基础。     

Development of Nanoemulsion of Silicone Oil and Pine Oil Using Binary Surfactant System for Textile Finishing

Nanoemulsions of silicone oil and pine oil using a binary surfactant system were prepared. Silicone oil and pine oil were used to achieve softness and mosquito repellency and antibacterial activity respectively when the nanoemulsion was applied on the fabric. A silicone surfactant (AG-pt) and a hydrocarbon surfactant (TDA-6) were used in different proportions to obtain stable nanoemulsions at the lowest possible droplet size. The various emulsification process variables such as ratio of hydrocarbon to silicone surfactant, surfactant concentration, ratio of silicone oil to pine oil, oil weight fraction and sonication time have been studied. The optimal variables include the ratio of hydrocarbon to silicone surfactant of 80:20, surfactant concentration of 8%, ratio of silicone oil to pine oil of 80:20, oil weight fraction of 20% and 15 min of sonication time at 40% of the applied power. Nanoemulsions were found to be very stable with emulsion droplet size around 41 nm. In order to compare different emulsification techniques, emulsions were also prepared using the conventional method. Emulsions analyzed using SEM showed spherical droplets ranging from 40 to 120 nm. Atomic force microscopy was used to evaluate the bounciness, fluffiness and softness of fabric. From this study, it was found that stable nanoemulsion with a lowest possible droplet size of silicone and pine oil could be prepared by ultrasonic emulsification technique in order to deliver multiple properties when applied to fabric.     

Coalescence of Water Droplets in Crude Oil Emulsions: Analytical Solution

In petroleum refineries, water is used in desalting units to remove the salt contained in crude oil. Typically, 7 % of the volume of hot crude oil is water, forming a water‐and‐oil emulsion. The emulsion flows between two electrodes and is subjected to an electric field. The electrical forces promote the coalescence of small droplets of water dispersed in crude oil, and these form bigger droplets. This paper calculates the forces acting on the droplets, highlighting particularly the mechanisms proposed for droplet–droplet coalescence under the influence of an applied electric field. Moreover, a model is developed in order to calculate the displacement speed of the droplets and the time between droplet collisions. Thus, it is possible to simulate and optimize the process by changing the operational variables (temperature, electrical field, and water quantity). The main advantage of this study is to show that it is feasible to increase the volume of water recycled in desalting processes, thus reducing the use of freshwater and the generation of liquid effluents in refineries.     

Significance of polymer on emulsion stability in surfactant‐polymer flooding

The influence of polymer on stability and shear rate on droplet size of emulsion is evaluated in the laboratory, microstructure of the emulsion is observed under a microscope, and the pore distribution of the cores is analyzed through mercury injection experiments. In the process of surfactant‐polymer (SP) flooding, the thickness of polymer absorbed on the surface of the rock is calculated by a mathematical model. The experiments show that the polymer is good for the stability of emulsion, with the increase of shear rate, stability becomes better, and droplet size gets smaller. Due to the adsorption of polymer, the pore throat turns narrow, seepage velocity is increasing, and also the emulsion becomes more stable with the smaller‐size droplets. During the single emulsifier flooding, the emulsion is easy to coalescence for its instability, and the seepage channel can be easily blocked, which leads to the high injection pressure. Consequently, the polymer plays an important role on emulsion stability in SP flooding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42171.