Copolymerization of unsaturated polyester with styrene in inverted emulsion

Copolymerization of unsaturated polyester with styrene in water-in-oil (W/O) type emulsion was carried out with the use of various basic compounds as emulsifiers. It was found that a stable, gellike W/O type emulsion of unsaturated polyester resin is formed only when pK_a's of the bases are above 6 and their concentrations are higher than some critical value. In these conditions, water can be dispersed in emulsion up to 900% to the resin. By polymerization, the stable W/O type emulsion is transformed to a white solid copolymer which is dry to the touch and which contains 90–95% of initially added water. It was confirmed that the basic compounds react with the carboxylic group of the polyester to form at the water-resin interface polyester salts, which act as true emulsifying agents. The stabilization mechanism of the emulsion at various concentrations of the polyester salt was investigated, mainly by microscopic observations, and an interpretation of the critical value of emulsifier concentration is proposed.     

Emulsification characteristics of three- and two-phase emulsions prepared by the ultrasonic emulsification method

Diesel engines exhausting gaseous emission and particulate matter have long been regarded as one of the major air pollution sources, particularly in metropolitan areas, and have been a source of serious public concern for a long time. The emulsification method is one of the potentially effective techniques to reduce emission pollution from diesel engines. Ultrasonic waves are a kind of sound waves with a frequency larger than 20 kHz, and they cannot be detected by the human ear. The phenomena of cavitation and hot spots produced by the rather violent action of ultrasonic waves can cause rapid chemical and physical reactions. This allows immiscible liquids to be well stirred with each other by means of ultrasonics. An ultrasonically vibrating machine that provides ultrasonic waves of a 40-kHz frequency was employed to prepare two- and three- phase emulsions in this experimental study. The fuel properties and the emulsion stability of the diesel emulsions were measured and analyzed. Experimental results show that the ultrasonic emulsification method successfully prepared two- and three-phase emulsions with tiny dispersed-phase droplets that are very evenly distributed in the outer oil or water phase. The ultrasonic processing time, quantity and HLB of the emulsifying agent were noted to have determinative influences on the formation of the emulsion and the fuel properties. A longer ultrasonic processing time caused less un-emulsified diesel fuel, smaller sizes and a more even distribution of dispersed-phase droplets in the outer oil phase and larger emulsion viscosity. However, a longer ultrasonic processing time also produced a larger temperature rise in the emulsion, leading to the deterioration of the emulsion stability. The O/W emulsion was found to have the lowest percentage of separation and thus the highest emulsion stability among the O/W/O, O/W and W/O emulsions. In addition, in comparison with the W/O emulsion, the O/W emulsion was shown to have a smaller size and a more even distribution of the dispersed-phase droplets. It also had a lesser rise in emulsion temperature when the ultrasonic processing time increased. The control of the ultrasonic processing time is important to successfully prepare the three-phase O/W/O emulsion. Too long a vibration time at the second-stage of emulsification is shown to cause the dispersed-phase pellets to contract and congregate with the inner-phase droplets. The three-phase emulsion structure then finally disappears and transforms into a two-phase emulsion. The addition of 2% by volume of the emulsifier mixture of Span80 and Tween80 with a HLB = 8, as suggested by this study for the preparation of stable two- and three-phase emulsions, were observed to have the lowest percentage of separation of the W/O and O/W/O emulsions. For preparing a stable O/W emulsion, the proportion of the emulsifier could be as low as 1.5% by volume. The percentage of separation of the O/W/O emulsion was lower and less influenced by the change in emulsion temperature than was the W/O emulsion with the same water content. However, the O/W/O emulsion was found to have a larger viscosity and a more significant variation of its viscosity, depending on the ultrasonic processing time, than the W/O emulsion.     

The fuel properties of three-phase emulsions as an alternative fuel for diesel engines

Diesel engines are employed as the major propulsion power for in-land and marine transportation vehicles primarily because of their rigid structure, low breakdown rate, high thermal efficiency and high fuel economy. It is expected that diesel engines will be widely used in the foreseeable future. However, the pollutants emitted from diesel engines (in particular nitrogen oxides and particulate matter) are detrimental to the health of living beings and ecological environment have been recognized as the major air pollution source in metropolitan areas and have thus attracted much research interest. Although diesel oil emulsion has been considered as a possible approach to reduce diesel engine pollutants, previous relevant applications were restricted to two-phase emulsions. Three-phase emulsions such as oil-in-water-in-oil briefly denoted as O/W/O emulsions and water-in-oil-in-water, denoted as W/O/W, have not been used as an alternative fuel for any combustion equipment. Studies on the properties of three-phase emulsion as fuel have not been found in the literatures. The emulsification properties of an O/W/O three-phase diesel fuel emulsion were investigated in this experimental study. The results show that the mean drop size of the O/W/O emulsion was reduced significantly with increasing homogenizing machine revolution speed. An increase in inner phase proportion of the O/W/O emulsion resulted in increasing the emulsion viscosity. The viscosity of O/W/O emulsion is greater than that for water-in-oil (denoted briefly as W/O emulsion) for the same water content. More stable emulsion turbidity appeared for three-phase O/W/O diesel emulsions added with emulsifier with HLB values ranging from 6 to 8. In addition, three-phase O/W/O emulsions with greater water content will form a larger number of liquid droplets, leading to a faster formation rate and greater emulsion turbidity at the beginning but a faster descending rate of emulsion turbidity afterwards. The potential for using O/W/O emulsions as an alternative fuel for diesel engines was also evaluated.     

Properties of Emulsions Formed In Situ In a Heavy‐Oil Reservoir during Water Flooding: Effects of Salinity and pH

Differing from conventional emulsions, water‐in‐oil (W/O) emulsions are produced with no additional surfactants in this study. The testing results show that both interfacial tension (IFT) and dilational modulus at all salinities and pH are much higher than those of normal emulsions. A high IFT is not good for making emulsions, but a higher dilational modulus will contribute to more stable emulsions. Emulsion stability declines slightly as salinity increases and the most unstable W/O emulsion appears at pH = 7. To deeply understand the effects of salinity and pH on emulsion stability, petroleum acid is extracted and characterized using Fourier transform ion cyclotron resonance mass spectrometry.     

聚酯磺酸盐的合成及其乳液的研究(Ⅱ)

２．４聚酯磺酸盐乳液的制备２．４．１聚酯磺酸盐的种类对乳液稳定性的影响乳液的制备方法、乳液类型的确定（润湿滤纸法）、稳定期的测定一参考文献［１２］。配比：聚酯磺酸盐／通用不饱和聚酯／苯乙烯／水＝１／１／１／３,所得乳液稳定性见表７和表８。２．４．２聚酯磺酸盐含量对乳液稳定性的影响配比：聚酯（包括聚酯磺酸盐）／苯乙烯／水＝２／１／３。聚酯磺酸盐含量指占聚酯重量百分率。所得结果见表９和表１０。２．４．３不同含水量对乳液稳定性的影响配比：聚酯磺酸盐／苯乙烯＝２／１,含水量指水占乳液重量百分率。用聚酯磺…     

Erdöl-Emulsionen — Eigenschaften,Stabilität und Spaltung

Petroleum emulsions — Properties, stability, and demulsification . Petroleum always occurs together with brine and is often recovered as an water-in-oil emulsion. Emulsions containing more than 90 percent of water are known; they are often very stable. The viscosity of the emulsions rises at a faster rate than the water content and is always significantly higher than that calculated according to the Einstein equation. Petroleum emulsions are stabilized by adsorption of the asphaltenes and petroleum resins colloidally dispersed in the petroleum. These components form mechanically stable films at the water/oil interface. The films contain several anionic, cationic, and amphoteric interfacially active substances, which are associated to form micelles, and which are adsorbed at the oil/water interface as a result of their interfacial activity. The adsorption films are wetted by the oil phase. The emulsions are stable towards coalescence, but not towards flocculation. Demulsifying agents displace the stabilizers from the interface or change their wettability.     

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.     

Comparison of fuel properties and emission characteristics of two- and three-phase emulsions prepared by ultrasonically vibrating and mechanically homogenizing emulsification methods

Emulsions have long been considered as an alternative fuel for combustion equipment in order to achieve better fuel economy and pollution reduction. While a mechanical homogenizing method is frequently used to prepare emulsions, the use of an ultrasonic emulsification method to do so is still rather limited, and is mostly applied to two-phase emulsions only. Hence, two-phase W/O and three-phase O/W/O emulsions, prepared by a mechanical homogenizer and an ultrasonic vibrator, respectively, were prepared and used as engine fuel. The emulsion properties, engine performance, and engine emission characteristics between these two emulsification methods were measured and compared. The potential of the ultrasonic emulsification method was also evaluated. The experimental results show that the emulsions prepared by the ultrasonic vibrator appeared to have more favorable emulsification characteristics such as smaller dispersed water droplets that were distributed more uniformly in the continuous oil phase, lower separation rate of water droplets from the continuous phase of diesel fuel and thus a lower separating rate of the dispersed water droplets from the emulsion, larger emulsion stability, and larger emulsion viscosity than the emulsions produced using a mechanical homogenizer. In addition, a larger content of water was emulsified when the emulsion was prepared using the ultrasonic vibrator than the mechanical homogenizer. The emulsions prepared by the ultrasonic vibrator also had a lower fuel consumption rate, lower bsfc, and significantly lower CO emission while at the same time having a larger black smoke opacity. When comparing the two-phase W/O and the three-phase O/W/O emulsions prepared by either the ultrasonic vibrator or the mechanical homogenizer, the two-phase W/O emulsions appeared to have a lower fuel consumption rate, bsfc, CO, and a lower black smoke opacity than the three-phase O/W/O emulsions, regardless of whether they were prepared by ultrasonic vibrator or mechanical homogenizer.     

Characteristics of water-absorbent polymer emulsions

Water-in-Oil (W/O) and Oil-in-Water (O/W) type water absorbent polymer emulsions were studied using two different polymerization methods. W/O type water absorbent polymer emulsions were prepared by the inverse emulsion polymerization of ammonium acrylate (AA), the quaternized salt of dimethyl-aminoethyl methacrylate (DMQ) and acrylamide (AM) with N,N-methylene-bisacrylamide (MBA) as a crosslinker. A pH sensitive water absorbent polymer emulsion was prepared by the conventional emulsion polymerization of diethyl-aminoethyl methacrylate (DEAEMA) with ethylene glycol dimethacrylate (EGDMA) as a crosslinker. It was confirmed that the water absorption capacity of crosslinked polymers in inverse emulsion was controlled by crosslink density and dissociative charge density, and the crosslinked polyDEAEMA particles had a phase transition property of swelling and shrinking with pH. The dispersions of these water swollen crosslinked polymer particles exhibited an increase in viscosity and thixotropic fluidity.     

Mass transfer studies on multiple emulsion as a controlled mass release system

A novel type of multiple emulsions which contain a microemulsion in macrodroplets, was prepared by a two-step emulsification procedure. Mineral oil was used as the oil phase with a mixture of Aerosol OT and Span 20 as primary emulsifiers. A water-in-oil microemulsion was prepared by gradual addition of water in oil containing both these emulsifiers. This microemulsion system, when dispersed in an aqueous solution containing secondary emulsifier, produces water-in-oil-in-water (W/O/W) multiple emulsions. The release rate of solute dissolved in the internal aqueous phase was measured using the dialysis technique. A theoretical model describing the diffusion of a multiple emulsion system was developed, which predicts the half-life for 50% of the internal solute to diffuse to the external phase. Experimental results showed the stability of multiple emulsions improved significantly upon using a thermodynamically stable microemulsion as a primary emulsion and a polymeric surfactant as a secondary emulsifier. As a resull, half-life of these multiple emulsions is greater than that of conventional multiple emulsions.     

Hydrodynamic cavitation as an efficient method for the formation of sub-100 nm O/W emulsions with high stability

Hydrodynamic cavitation, a newly developed process intensification technique, has demonstrated immense po-tential for intensifying diverse physical and chemical processes. In this study, hydrodynamic cavitation was ex-plored as an efficient method for the formation of sub-100 nm oil-in-water (O/W) emulsions with high stability. O/W emulsion with an average droplet size of 27 nm was successful y prepared. The average droplet size of O/W emulsions decreased with the increase of the inlet pressure, number of cavitation passes and surfac-tant concentration. The formed emulsion exhibited admirable physical stability during 8 months. Moreover, the hydrodynamic cavitation method can be generalized to fabricate large varieties of O/W emulsions, which showed great potential for large-scale formation of O/W emulsions with lower energy consumption.     

Stability of vitamin A in oil-in-water-in-oil-type multiple emulsions

The stabilityof vitamin A was studied in thee different emulsions: oil-in-water (O/W), water-in-oil (W/O), and oil-in-water-in-oil (O/W/O). The stability of retinol (vitamin A alcohol) in the O/W/O emulsion was the highest among the thee types of emulsions; remaining percentages at 50°C after 4 wk in the O/W/O, W/O, and O/W emulsions were 56.9, 45.7, and 32.3, respectively. With increasing peroxide value of O/W and W/O emulsifiers, the remaining percentage of vitamin A palmitate and retinol in the emulsions decreased significantly, indicating that peroxides in the formulae accelerate the decomposition of vitamin A. Organophilic clay mineral (an oil gelling agent and a W/O emulsifier) also affected the stability of retinol; synthesized saponite was better than naturally occurring bentonite for retinol stability. The stability of retinol in the O/W/O emulsion increased with increasing inner oil phase ratio (φ_i), whereas in O/W it was unaffected by φ_i. Encapsulation percent of retinol in the O/W/O emulsion, the ratio of retinol in the inner oil phase to the total amount in the emulsion, increased with increasing φ_i. The remaining percent of retinol in the O/W/O emulsion was in excellent agreement with encapsulation percent, suggesting that retinol in the inner oil phase is more stable than that in the outer oil phase. Addition of antioxidants (tert-butylhydroxytoluene, sodium ascorbate, and EDTA) to the O/W/O emulsion improved the stability of retinol up to 77.1% at 50°C after 4 wk. We conclude that the O/W/O emulsion is a useful formula to stabilize vitamin A.     

Effects of molecular weight distribution of nonionic surfactants on stability of O/W emulsions

From the relationship between the distribution width of oxyethylene (OE) or alkyl chains and O/W emulsions stability, it became evident that even with the same average OE or alkyl chain lengths, the phase-inversion temperature (PIT) and O/W emulsion stability depend on width. However, emulsification at the PIT invariably results in a very stable O/W emulsion. Emulsifiers with a large distribution width of OE or alkyl chains were also found to improve O/W emulsion stability.     

Hydrate formation from high water content-crude oil emulsions

Methane hydrate formation and dissociation studies from high water content ( water) - crude oil emulsions were performed. The hydrate and emulsion system was characterized using two particle size analyzers and conductivity measurements. It was observed that hydrate formation and dissociation from water-in-oil (W/O) emulsions destabilized the emulsion, with the final emulsion formulation favoring a water continuous state following re-emulsification. Hence, following dissociation, the W/O emulsion formed a multiple o/W/O emulsion (60 vol% water) or inverted at even higher water cuts, forming an oil-in-water (O/W) emulsion (68 vol% water). In contrast, hydrate formation and dissociation from O/W emulsions ( water) stabilized the O/W emulsion.     

A novel method for preparing oil-in-water-in-oil type multiple emulsions using organophilic montmorillonite clay mineral

A stable formula using oil-in-water-in-oil (O/W/O) type multiple emulsions was investigated. The components consisted of hydrophilic nonionic surfactant (HCO-60), organophilic montmorillonite, and lipophilic nonionic surfactant (DIS-14). O/W/O emulsions were prepared by a double-step procedure in which an O/W emulsion was prepared in the first step, and then the O/W emulsion was “re-emulsified” in an oil phase with organophilic montmorillonite. The diameter of the innermost oil droplets decreased with increasing HCO-60 content (0.1–3%), while the viscosity showed a maximum at 1% of HCO-60, indicating that the yiel of re-emulsification is highest at this condition. Viscosity of the O/W/O emulsion increased with increasing organophilic montmorillonite and DIS-14. According to the results of a phase ratio study, viscosity and stability of the O/W/O emulsion decreased at high weight fraction of inner oil phase (0.4–0.5), indicating that the excess amount of inner oil phase is absorbed by the outer oil phase. These results revealed that the weight fraction of inner oil phase should be kept below 0.3 for a stable O/W/O emulsion. A similar study on the weight fraction of O/W phase [фO/W)/O] suggested that the O/W/O emulsion is stable at ϕ(O/W)/O=0.65–0.70.     

Characterization of a double emulsion system (oil-in-water-in-oil emulsion) with low solid fats: Microstructure

A double emulsion system [oil-in-water-in-oil (O/W/O)] with 16.3% (w/w) water and 83% (w/w) oil was prepared and stabilized using a novel method of mixing two oil-in-water (O/W) emulsions together. The first emulsion consisted of 85% (w/w) liquid canola oil, 14.4%(w/w) water, 0.5% (w/w) sodium caseinate, and 0.1% (w/w) lecithin and the second emulsion contained 73% (w/w) canola oil, 8% (w/w) palm-cotton stearin (50∶50), 0.2% (w/w) lecithin, 18.2% (w/w) water, and 0.6% (w/w) sodium caseinate. Mixing the two emulsions (50∶50) by weight produced a product with 79% (w/w) liquid canola oil and 4% (w/w) palm-cotton stearin. The two O/W emulsions were prepared separately at 50°C, mixed together at 45°C for 2–5 min, and then supercooled in a −5°C ice/salt bath while mixing at low shear rates (2,000–3,000 rpm). Under supercooling conditions the fat globules in the second emulsion (containing liquid oil and stearin) began to break down as a result of fat crystal growth and shearing action and release plastic fat. During this stage, the continuous aqueous phase underwent a phase transition and the emulsion viscosity dropped from 37,000–50,000 to 250 cP. The released plastic fat continued to harden as the temperature dropped and stabilized the first O/W emulsion (containing only liquid oil). The low shear rate mixing was stopped when the temperature dropped below 15°C and before the O/W/O emulsion hardens. Microstructural analysis of the first emulsion before and after supercooling showed essentially intact fat globules. The microstructure of the second emulsion before supercooling showed the same intact globules as the first emulsion, but after supercooling, an amorphous mass with only a few intact globules was seen. By mixing the two emulsions together and supercooling, a stable O/W/O emulsion was formed with plastic fat as the continuous phase and the first O/W emulsion as the dispersed phase.     

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.     

Thixotropic Behavior of Oil‐in‐Water Emulsions Stabilized with Ethoxylated Amines at Low Shear Rates

Oil‐in‐water (O/W) emulsification is a lubricating pipeline method based on the reduction of the energy frictional loss produced during viscous flow. The flow behavior of heavy O/W emulsions formulated with nonionic surfactants is described. The effects of pH and salinity of the aqueous phase on droplet diameter, stability, and apparent viscosity of O/W emulsions were evaluated. The low‐shear Couette flow of O/W emulsions displayed intense shear‐thinning and thixotropic behavior. Thixotropy was associated to the droplet deformation energy caused by shear rate changes. The droplet deformation and alignment led to the apparent viscosity reduction compared to the fluid at rest. Thixotropic behavior is supposed to balance between the breakdown and recovery of droplet ordered structures. Emulsion formulation parameters were influenced by the aqueous phase pH, enabling to manage the emulsion properties. The droplet mean diameter of < 18 µm resulted in very stable emulsions.     

聚合物3530S对坨一原油各组分油水界面性质及乳状液稳定性影响

用界面张力仪、表面粘弹性仪和Zeta电位仪研究了聚合物3530S对胜利坨一原油各组分模型油与模拟水间的界面特性及乳状液稳定性的影响规律。结果表明,沥青质及胶质模型油与模拟水间的界面张力低于蜡组分模型油,原油中的界面活性组分主要为沥青质和胶质。聚合物加入模拟水后,含有聚合物的模拟水与沥青质、胶质及蜡组分模型油之间的界面剪切粘度与界面张力均上升,油滴表面的Zeta电位降低。沥青质和胶质模型油与含聚合物3530S的模拟水所形成的W/O乳状液较蜡组分模型油所形成的W/O乳状液更稳定。     

三元复合驱中原油乳化作用研究

通过乳状液稳定实验考察了大庆油田碱-表面活性剂-聚合物三元复合驱过程乳状液的形成机理、乳状液类型及稳定性。结果表明,大庆原油与碱反应1d时,测得其浓相体积分数为25%,所形成的乳状液为O/W型乳状液,而随着原油与碱作用时间的增加,其浓相体积分数达到40%以上,形成W/O型乳状液,且乳状液稳定性随作用时间增加而增强。大庆原油与水溶性表面活性剂ORS-41溶液作用时,所形成的乳状液为O/W型,且乳状液的稳定性与原油和ORS-41作用时间的长短关系较小。原油与NaOH和ORS-41混合溶液作用时,形成上层为W/O型乳状液,下层为O/W型乳状液的混合体系。