Destabilization‐Enhanced Centrifugation of Metalworking Oil‐in‐Water Emulsions: Effect of Demulsifying Agents

The effect of a commercial flocculant (Alpacon® WS009) and two coagulant salts (CaCl₂ and AlCl₃) on the stability of metalworking oil‐in‐water (O/W) emulsions was examined. Two O/W emulsions were tested: a fresh emulsion, prepared in the laboratory from a commercial concentrate, and a waste metalworking emulsion, provided by a local waste management company, with initial oil concentrations of 32900 and 16900 mg/L, respectively. The emulsion stability was studied at different demulsifier concentrations, temperatures and pH through centrifugation tests, zeta potential and multiple light scattering measurements. Emulsion breakdown is explained by electrostatic repulsion of oil droplets and steric interactions. The former was observed for the laboratory emulsion, while the latter was observed for the waste emulsion. Aluminum chloride was the only effective agent for demulsifying both emulsions.     

Preparation and Properties of Siloxane-Modified Styrene-Acrylate Latex Particles with Core-Shell Structure

Siloxane-modified styrene-acrylate latex particles with core-shell structure were prepared by two-stage semicontinuous emulsion polymerization using a reactive surfactant. Effects of catalyst dosage, weight ratio of γ-methacryloxypropyltrimethoxysilane (MAPS) to hydroxyl silicone oil (HSO) and siloxane content on the grafting degree of siloxane were studied. The chemical components of the copolymer were characterized by Fourier transform infrared spectra. The micromorphology of latex particles was observed by transmission electron microscopy. The stability properties of emulsion were tested by Ca²⁺, centrifugal, and mechanical stability test. The latex film was studied by water contact angle, water absorption ratio and thermal gravimetric analysis. The results show that siloxane-modified styrene-acrylate latex with core-shell structure can be synthesized using reactive surfactant and the prepared emulsion presents excellent stability. By using hydroxyl silicone oil (HSO) to react with silane coupling agent MAPS during emulsion polymerization, HSO can be located in the side chain of the polymer and endow the latex film with excellent stabilities.     

Effects of Curcumin on the Oxidative Stability of Oils Depending on Type of Matrix,Photosensitizers, and Temperature

The photosensitizing activity of curcumin was tested in corn oil and oil‐in‐water (O/W) emulsion systems under visible light irradiation. In addition, the antioxidative/prooxidative properties of curcumin were evaluated in corn oil at 100 °C and in O/W emulsion at room temperature under riboflavin photosensitization or at 60 °C in the dark. Curcumin acted as a photosensitizer in corn oil and O/W emulsions . The oxidative stability of corn oil samples containing curcumin (0–5.0 mmol/kg oil) were not significantly different (p > 0.05) at 100 °C, implying curcumin did not act as an antioxidant nor a prooxidant in corn oil. However, curcumin inhibited lipid oxidation in O/W emulsions under riboflavin photosensitization at room temperature and 60 °C in the dark. The photosensitization and antioxidant abilities of curcumin were greatly influenced by matrix types and presence of riboflavin. Therefore, antioxidative or prooxidative characteristics of curcumin should be evaluated considering matrix type including bulk oil or O/W emulsions and presence of visible light irradiation.     

Effect of oil type on stability of high internal phase water-in-oil emulsions with super-cooled internal phase

This study considered the stability and rheology of a type of high internal phase water-in-oil emulsions (W/O) emulsion. The aqueous phase of the emulsions is a super-cooled inorganic salt solution. The oil phase is a mixture of industrial grade oils and stabilizer. Instability of these systems manifests as crystallization of the metastable dispersed droplets with time. This work focused on the effects of oil polarity and oil viscosity on the stability of these emulsions. Ten types of industrial oils, covering the viscosity range 1.4–53.2?cP, and with varying polarity, were used in combination with polymeric poly(isobutylene) succinic anhydride (PIBSA) and sorbitan monooleate (SMO)-based surfactants. The effect of oil relative polarity on rheological parameters of the emulsion was evident mainly in the emulsions stabilized using polymeric surfactant, whereas the oil viscosity did not show any significant effect. The optimum stability of the emulsions stabilized with SMO was achieved using high polar oils with a viscosity of 3?±?0.5?cP. However, when using the PIBSA surfactant, the best emulsion stability was achieved with low polar, high viscosity oils.     

Stability of Emulsions Containing Interesterified Fats Based on Mutton Tallow and Walnut Oil

In this work, modified fats were produced by enzymatic interesterification of mutton tallow with walnut oil. As a result of forcing the fat hydrolysis process by addition of water to the enzymatic preparation (11.5, 13.0, 14.5, 16.0 wt %), additional levels of polar fractions (MAGs, DAGs, and FFAs) were observed. The aim of this work was to evaluate the stability of emulsions of modified fats containing natural emulsifiers resulting from enzymatic interesterification of mutton tallow with walnut oil. The physical‐chemical parameters of obtained fats were determined in this study. Using several methods, the stability of the formed emulsions was also evaluated. The results showed that the fats resulting from interesterification in the presence of Lipozyme RM IM (immobilized lipase from Rhizomucor miehei, Novozymes Bagsvaerd, Denmark) with 13.0, 14.5, and 16.0 wt % of water in the enzymatic preparation could form stable emulsion systems. On the other hand, the emulsion of the interesterification system where the amount of water in the enzymatic preparation was 11.5 % showed very low stability. The number of natural emulsifiers (MAGs and DAGs) that arose after interesterification was insufficient to stabilize the emulsion system. The work has shown the possibility of using interesterified fats as the fat phase. Emulsions formed on the basis of interesterified fats without any additional emulsifiers such as sunflower lecithin had properties comparable to emulsions containing mixed non‐interesterified fat containing additional emulsifier. The natural emulsifiers formed as part of enzymatic interesterification allow formation of stable emulsion systems.     

石油醚W/O乳状液及其液膜稳定性

以破乳率为衡量标准,借助显微镜直接观察,探讨了乳状液含水量、表面活性剂用量、乳化时间、乳化强度等因素对石油醚W/O型乳状液体系稳定性的影响。在实验范围内,乳状液含水量的提高及表面活性剂用量的增加,有利于乳状液的稳定;存在较优的乳化时间20min和乳化强度4000rmin-1。选取脂肪烃、芳香烃、混合烃共6种不同油相制备乳状液,对比其稳定性的差异。此外,还初步考察了石油醚W/O/W液膜溶胀和泄漏问题,结果表明该乳状液膜泄漏率低于3.5%,表观溶胀率约为20%。     

In situ surfactant generation as a means of miniemulsification?

In situ emulsification, where the surfactant is synthesized spontaneously at the oil/water interface, has been put forth as a simpler method for the preparation of miniemulsions‐like systems. Miniemulsions are relatively stable oil‐(e.g., monomer)‐in‐water emulsions having droplet sizes anywhere in the range of 50–500 nm, and are typically created with high shear and stabilized by the combination a surfactant and a costabilizer. Using the in situ method of preparation, emulsion stability and droplet and particle sizes were monitored and compared with conventional emulsions and miniemulsions. Styrene emulsions prepared by the in situ method do not demonstrate the stability of a comparable miniemulsion. Upon polymerization, the final particle size generated from the in situ emulsion did not differ significantly from the comparable conventional emulsion polymerization; the reaction mechanism for in situ emulsions is more like conventional emulsion polymerization rather than miniemulsion polymerization. Similar results were found when the in situ method was applied to controlled free radical polymerizations (CFRP), which have been advanced as a potential application of the method. Molecular weight control was found to be achieved via diffusion of the CFRP agents through the aqueous phase owing to limited water solubilities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of Tocopherol/Sesamol on the Physical Stability and Bioactivity of Oil-in-Water Emulsions of Different Oil Types

Lipid-based delivery systems are widely used to incorporate chemicals with poor solubility. The influence of tocopherol and sesamol on emulsion delivery systems, including their bioactivity, is not well-known. Herein, the overall aim of this study is to understand the effect of tocopherol and sesamol on the physical stability and bioactivity of various emulsions comprised of oil (medium chain triglyceride, coconut oil, palm oil) with different carbon chain lengths using the C. elegans model. All emulsions show good physical stability; droplet size, polydispersity index, zeta potential, and microstructure are relatively constant over the incubation time. Tocopherol and sesamol show the greatest bioactivity (greater lipid-lowering effect and in vivo antioxidant activity) in emulsions fabricated with palm oil. Knowledge on emulsion stability and bioactivity is important for delivery systems in the food industry involving tocopherol, sesamol, and other related bioactive compounds.     

基于纤维素纳米晶稳定的亚微米Pickering乳液制备

与传统表面活性剂稳定的乳液相比,固体纳米颗粒稳定的Pickering乳液具有较强的界面稳定性、多功能性、低毒性等优势,在生物医药领域具有较大的应用潜力。而相较于尺寸较大的微米级Pickering乳液,亚微米Pickering乳液具有更大的比表面积、更有效的递送效率,有望进一步拓展Pickering乳液在生物医药领域的应用。但由于Pickering乳液的制备影响因素众多,且相互制约,刚性的固体颗粒难以在较小的有限油水界面排布,增加了亚微米Pickering乳液的制备难度。本工作以制备稳定的亚微米Pickering乳液为研究目标,采用具有良好生物相容性的天然多糖–纤维素纳米晶(CNCs)为颗粒乳化剂,角鲨烯作为油相,考察了颗粒浓度、油水比例、水相成分、超声时间及频率对Pickering乳液粒径分布及稳定性的影响,最终得到了具有良好的储存稳定性和抗离心稳定性的粒径为638.7?8.40 nm的亚微米Pickering乳液(CNCs-PE)。通过激光共聚焦显微镜证实了CNCs吸附在油水界面,形成了Pickering乳液结构。利用CCK-8法评价了CNCs和CNCs-PE的细胞毒性,结果表明,两者都具有良好的细胞安全性。此外,将其用于吸附模型抗原OVA,吸附率达到约80%,且肌肉注射部位的切片结果也表明其注射安全性良好。此结果为亚微米Pickering乳液进一步研究提供了参考,并有望拓展CNCs稳定的亚微米Pickering乳液在生物医药领域的应用。     

The effect of monoethylene glycol on the stability of water-in-oil emulsions

It is important from both a strategic and economic standpoint to study the mechanism of formation of water/oil emulsions, to predict their increase of viscosity with respect to that of the crude oil, and to obtain information about the stability vs separation of these substances (since their presence can impair oil processing and distribution). The objective of this work was to ascertain the influence of monoethylene glycol (MEG) on these parameters and its action mechanism. The addition of MEG in different proportions in the oil emulsions significantly changed the flow curve of the emulsion, passing from a quasi-Newtonian one to a shear thinning behaviour. Besides this, when MEG was present at low concentrations, the demulsification process was slow and an increase in concentration made the emulsions more stable than samples containing the same aqueous phase proportion. Under the conditions studied, the addition of MEG did not reduce the quantity of the aqueous phase separated compared to the emulsions free of MEG, but significantly delayed the demulsification process. Rheology provided important information regarding the phase separation process of the aqueous phase in oil phase emulsions, and dynamic testing suggested that the most relevant effect of the addition of MEG is an increase of the emulsion elasticity that can be correlated with the increase in the emulsion stability observed by bottle test and Turbiscan.     

玉米油W1/O/W2型多重乳状液稳定性的研究

高脂食品严重危害着人类健康,这引起人们对低脂食品的的不断追求,因此脂肪替代品的开发越来越受到人们重视。本试验以玉米油和生物高聚物为主要原料通过两步乳化法制备W1/O/W2多重乳状液作为脂肪替代品(FS),以离心稳定性为衡量标准,用显微镜直接观察,探讨了初复乳乳化工艺、各相相对体积比对玉米油W1/O/W2型多重乳状液体系稳定性的影响。结果表明:1.影响玉米油多重乳状液稳定性的主要因素有:复乳的乳化工艺,内水相与油相体积之比等。2.两步乳化工艺中第二步乳化工艺对复乳稳定性影响较大,其规律是随着乳化强度的提高,粒径减小,稳定性呈上升趋势,适宜的乳化条件为7200 r.min.1,13 min,而第一步乳化工艺对复乳稳定性几乎没有影响。3.内水相与油相、初乳与外水相均是影响复乳稳定性的主要因素,前者主要是依靠改变初乳黏度来影响复乳稳定性,后者主要是乳滴间范德华力与电排斥力共同作用的结果,适宜的体积比分别为1:4和1:1。     

Application of magnetic nanoparticles as demulsifiers for surfactant-enhanced oil recovery

Nonionic surfactants are increasingly being applied in oil recovery processes due to their stability and low adsorption onto mineral surfaces. However, these surfactants lead to the production of emulsified oil that is extremely stable and difficult to separate by conventional methods. This research characterizes the stability of crude oil mixed with a nonionic surfactant, L24–22, in a brine solution. When subjected to gravity separation, a middle oil-rich and bottom water-rich emulsion are generated for various water–oil ratios. Thermal treatments can effectively break oil-rich emulsions, but the bottom water layer remains contaminated with micron-sized crude oil droplets. A magnetic nanoparticle treatment is shown to demulsify the crude oil emulsions, dropping the total organic carbon (TOC) in the water layer from 1470 to 30 ppm.     

Stability Assessment of Virgin Coconut Oil‐Based Emulsion Products

In recent years, there has been dramatic growth in the market for virgin coconut oil (VCO). VCO, a promising functional food oil, has gained popularity and captured public attention worldwide. Two VCO‐based emulsion products were developed as a new nutritional food supplement with the aim of increasing the consumption of VCO. The stability of VCO‐based emulsion products was assessed during a storage period of 3 months to gauge the quality of the optimized VCO‐based emulsions. The particle‐size distributions of the VCO‐based emulsions remained stable throughout the 3‐month storage period at 25 and at 50°C. However, a slight increase in the particle sizes was observed in the VCO‐based emulsions samples after 2 months of storage at 4 °C. Nevertheless, phase separation did not occur in either of the VCO‐based emulsions products throughout the storage‐stability assessment period. No signs of microbial growth were detected in the emulsion products during the storage period. Furthermore, no significant changes in the free fatty acid contents of the emulsion products were observed during storage at 4 or 25°C throughout the storage period. The VCO‐based emulsion products possessed sufficient emulsion stability to withstand changes at different storage temperatures.     

Rheology and stability of phospholipid-stabilized emulsions

Lecithin in cosmetic emulsions produces a unique “skin feel,” which can be related to its rheological properties. In this study, water-in-oil (w/o) and oil-in-water (o/w) emulsions were made from a cosmetic-grade caprylic/capric triglyceride with deoiled lecithin and hydroxylated lecithin. Synthetic surfactants commonly used in commercial cosmetic products were used as controls. Optical light microscope investigation showed significant differences in the structures of the w/o and o/w emulsions made with the lecithins. Freeze/thaw tests were conducted to evaluate emulsion stability. The o/w emulsion (oil/water = 20:80) was stable with 3% hydroxylated lecithin at room temperature. However, 4% hydroxylated lecithin was needed for stabilizing the emulsion with an oil-to-water ratio of 20:80 or 30:70 through the freeze/thaw treatments. With 4% deoiled lecithin, the w/o emulsion showed a water-holding capacity up to 80%, which was also stable through two freeze/thaw cycles. All emulsions in this study exhibited pseudoplastic flow, in which a minimum shearing stress, a yield value, was required before flow became linear. In general, the emulsion viscosity increased as lecithin content increased. Changing the oil-to-water ratio also affected the emulsion viscosity. The deoiled lecithin-based w/o emulsions had higher yield values than hydroxylated lecithin-based o/w emulsions. Therefore, more force was needed to spread the w/o emulsions. In addition, because w/o emulsions had more viscous continuous phases and a greater volume of internal phases, the w/o emulsions were more viscous than the o/w emulsions.     

ABA low molar mass triblock copolymers in reverse emulsions: A rheological study

The effect of blocks length and molar mass of ABA triblock copolymers on the rheological behavior of water in oil (w/o) emulsions was investigated. Emulsion parameters such as water droplet concentration (and droplet size) of a series of inverted emulsion systems were evaluated. All copolymer/emulsion systems studied showed a non-Newtonian behavior, and the presence of the copolymer in the emulsion system led to an increase of the low shear viscosity when the size of the midblock of the copolymer was in a specific size range. This suggests the formation of a transient network through the interconnection, by the copolymer, of the smaller water droplets present in the emulsion. Consequently, the systems behave as w/o emulsions containing reversibly crosslinked oil-soluble polymers in the continuous phase, resulting in a pronounced shear thinning behavior. For the different emulsions studied, the relative viscosity increased, with few exceptions, with increasing droplet concentration. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and Characterization of Virgin Olive Oil‐Beeswax Oleogel Emulsion Products

Virgin olive oil and beeswax were used to prepare four oleogel emulsions (EM1–EM4) through simultaneous oleogelation emulsification, and these oleogels were compared with breakfast margarine (BM). The melting temperatures of the oleogel emulsions ranged from 52.29 to 57.52 °C, while it was 40.36 °C for the BM sample. Similarly, the solid fat content (SFC) of the oleogel emulsions was between 3.57 and 3.68 % at 20 °C, and that of BM was 7.70 %. Except the EM3 sample, all oleogel emulsions exhibited mechanical stability. The firmness and stickiness values of the oleogel emulsion samples were lower than those of the BM sample, but they remained almost constant through 90 days of storage. Furthermore, the fine water droplets and needle‐like beeswax crystals within the continuous oil phase were stable during the storage. The X‐ray diffraction patterns of the samples revealed that the oleogel emulsions contain crystals similar to β′ polymorphs, characterized by a homogenous, smooth and fine texture. The presence of inter and intramolecular hydrogen bonds was proved by Fourier Transform Infrared (FT‐IR) measurements. The developed oleogel emulsions were found to be stable in terms of texture, color and oxidation during 90 days of storage. In conclusion, these oleogel emulsion products can be used as margarine/spread stocks.     

Stabilization of liquid water-in-oil emulsions by modifying the interfacial interaction of glycerol monooleate with aqueous phase ingredients

Glycerol monooleate (GMO)-stabilized liquid water-in-vegetable oil emulsions are difficult to stabilize due to the desorption of GMO from the water-vegetable oil interface toward the oil phase. This work improved the stability of GMO-stabilized liquid 20 wt% water-in-canola oil (W/CO) emulsion by modifying the dispersed aqueous phase composition with hydrogen bond-forming agents. As a control, 20 wt% water-in-mineral oil (W/MO) emulsion was also utilized. Different concentrations of hydrogen bond-forming agents (citric acid (CA), ascorbic acid (AA), low methoxyl pectin (LMP)) with and without salts (sodium chloride (S) or calcium chloride (Ca)) were added to the aqueous phase before emulsification, which enhanced emulsifier binding to the water–oil interface. W/CO emulsion without any aqueous phase additive destabilized instantly, whereas W/MO emulsion stayed stable during the week-long observation. The addition of hydrogen bond-forming agents and salts significantly improved emulsion stability. LMP, with many hydrogen bond-forming groups, was able to provide the highest emulsion stability after 7 days in both oils compared to AA, CA and their mixtures with S. Emulsions with both oils formed weak gels due to the formation of an extensive network of water droplet aggregates. Overall, the hydrogen bond-forming agents interacted with GMO at the interface, thereby favoring their presence at the water droplet surface and significantly improving the stability of liquid W/CO emulsions. The knowledge developed in this research can be useful in utilizing GMO to stabilize liquid water-in-oil emulsions without using any fat crystal network.     

Emulsifying and self‐emulsified properties of siloxane polymer grafted with easy hydrophile

A series of siloxane polymers (SHE) with varying weight percents of simple nonionic hydrophilic groups have been synthesized and characterized by FTIR and ¹³C‐NMR. Emulsions have been made by self‐emulsification of those polymers in pure water and also by emulsifying silicone oil using those polymers as oil‐in‐water type emulsifiers. The stability of those emulsions have been examined apparently from the phase separation and also from the particle size increase on storage by Transmission Electron Microscopy (TEM) and photo microscopy. The results reviled that SHE 40, having 40 wt % grafted hydrophile, formed the most stable self‐emulsified emulsion, and SHE30 and SHE40 could be used as effective emulsifiers for silicone oil emulsification. The possible use of those emulsions as a defoamer for water‐borne systems has also been investigated by measuring the reduction of foam height of a strongly foamed aqueous solution of sodium lauryl sulfate (SLS). The defoaming ability decreases with the increase in hydrophile wt % in the polymer backbone; however, it increases with the emulsion (defoamer) concentrations. When compared with respect to the total wt % of hydrophobe contents in the emulsion defomer, the self‐emulsified emulsion has shown better defoaming than the silicone oil emulsion, and the results are well in accord with the difference in size of the respective emulsion particles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2408–2415, 2002     

Influence of oil phase concentration on droplet size distribution and stability of oil‐in‐water emulsions

The objective of this study was to investigate the effect of oil phase concentration, at different emulsification conditions concerning homogenization time and emulsifier content, on droplet size distribution and stability of corn oil‐in‐water emulsions. Emulsions were prepared with 3, 5, 10, and 20% w/w triethanolamine oleate (calculated on oil amount), 0.53% w/w carboxymethylcellulose (calculated on water amount), and 5, 10, 20, 30, or 40% w/w oil, and homogenized 5, 10, 20, and 60 min. It was found that increase in oil phase concentration led to decrease in specific surface area and increase in polydispersity of emulsion at lower emulsifier concentration and less intense homogenization. At emulsifier concentrations ≤10% and homogenization time ranges of 20–60 min the non‐monotonous variation in droplet size parameters with oil concentration was observed, as a result of the interaction between triethanolamine oleate and carboxymethylcellulose, which were confirmed by viscosity measurements. However, at emulsifier concentration of 20% an increase in specific surface area and decrease in polydispersity with the increase in oil concentration occurred due to an increase in equilibrium concentration of emulsifier in the continuous phase. Further, influence of oil concentration on emulsion creaming stability was found to be independent on emulsifier concentration and homogenization time. Therefore, a decrease in creaming with increase in oil concentration was observed in all the examined triethanolamine oleate (TEAO) concentration and homogenization time ranges. Practical applications: Emulsions are colloidal systems which can be encountered in different industrial sectors, such as food, pharmaceutical, cosmetics, oil industry, etc. Determination of the droplet size of emulsion is probably the most important way of their characterization, since it influences the properties of emulsion such as rheology, texture, shelf life stability, appearance, taste, etc. The size of the droplets depends on a wide range of parameters. One of them is certainly the concentration of the oil phase. However, since the impact of one parameter is often influenced with the intensity of the other variable involved in the emulsion generation, the aim of the present work was to examine the effect of corn oil concentration on droplet size parameters and stability of oil‐in‐water emulsions at different emulsification conditions. Therefore a step toward creation of emulsions with desired final properties was made.     

农药水乳剂物理稳定性的研究进展

简要介绍了乳状液形成与稳定机理,重点综述了相关理论和方法在农药水乳剂物理稳定性中的研究与应用现状,分析了当前农药新剂型加工理论研究不足以及乳化剂环保性能有待提高等具体问题。