Investigation of Oil–Asphaltene Slurry Rheological Behavior

The presence of asphaltene means additional difficulties related to transport and processing due to the increased crude oil viscosity caused by the asphaltene. For a better knowledge of the flow properties of asphaltene containing crude oils, it is necessary to understand how asphaltene affects the rheological properties. The aim of this article is to provide information on such rheological properties of oil–asphaltene slurry systems. The results of rheological experiments show that the non-Newtonian flow curves can be approximated by the Bingham plastic model to determine the apparent viscosity and the yield stress as a function of asphaltene concentration and temperature. An explanation is also provided for the observed behavior.     

Thickening properties and emulsification mechanisms of new derivatives of polysaccharides in aqueous solution

The thickening properties of aqueous solutions of HHM-HEC (hydrophobically-hydrophilically modified hydroxyethylcellulose) and the emulsification mechanisms of HHM-HEC/water/oil systems were investigated. A dramatic increase in viscosity was observed with increased HHM-HEC concentration in water, caused by aggregation of hydrophobic alkyl chains. At higher concentrations of HHM-HEC (above 0.6 wt%) in water, it forms an elastic gel, which has good thixotropic properties and a high yield value. O/W (oil-in-water) type emulsions were obtained using HHM-HEC, which can emulsify various kinds of oil, including hydrocarbon, silicone, and perfluoropolymethylisopropyl ether. The viscosity of these emulsions depends only upon the oil volume fraction, not on the kind of oil. In addition, the oil particle size in the emulsions remained constant after a certain period because HHM-HEC formed a strong gel network structure and a protective layer, which prevented the emulsion from coalescing. Measurements of interfacial tension revealed that the alkyl chains in HHM-HEC did not significantly lower the interfacial tension at the water/oil interface when 0.5 wt% of HHM-HEC was added to water. Steady flow and oscillatory experimental results show that the rheological behavior of HHM-HEC/water/oil emulsions was similar to that of aqueous solutions of HHM-HEC. In the HHM-HEC/water/oil emulsion system, oil droplets were dispersed and kept stable in the strong gel structure of HHM-HEC. The aqueous solution of HHM-HEC showed salt resistance. It is thought to be due to sulfonic acid groups in HHM-HEC. The stability of the emulsion using HHM-HEC is based on both protective colloidal effects and associative thickening caused by alkyl chains in HHM-HEC.     

Lyotropic Liquid Crystal Formed in Oleyl Polyoxyethylene Solutions by Adding Different Additives: NaDC,Tween 80, Alkyl Esters

Lyotropic liquid crystalline of oleylpolyoxyethylene(20)(AEO₂₀)/oil/water system was investigated at 25°C. The phase behavior, microstructure, and rheological properties of liquid crystalline were investigated by rheological techniques and polarizingoptical microscopy in the presence of various additives including Tween 80, sodium deoxycholate (NaDC), isoamylacetate, butyl acetate, isopropyl myristate. Diagrams show that cubic phase transforms to hexagonal phase when a shorter chain length oil is applied or NaDC or Tween 80 is added to the system.Flow experiments indicate the shear-thinning properties and a plastic behavior. The turning points of flow curves of the system AEO₂₀ and system AEO₂₀/NaDC were found. The dynamic modulus increase with increase in water content however the tendency is weaken by adding NaDC. Frequency dependence of experimental G ′ and G ′ were fitted using the multiple Maxwell model the cubic LLCs described by three relaxation times while hexagonal LLCs described by 5–8 elements. When AEO₂₀ mixes with Tween 80, the hexagonal have a monotonic decrease distribution of relaxation times without valleys.     

Interfacial shear rheology of protein-surfactant layers

The shear rheology of adsorbed or spread layers at air/liquid and liquid/liquid phase boundaries is relevant in a wide range of technical applications such as mass transfer, monolayers, foaming, emulsification, oil recovery, or high speed coating. Interfacial shear rheological properties can provide important information about interactions and molecular structure in the interfacial layer. A variety of measuring techniques have been proposed in the literature to measure interfacial shear rheological properties and have been applied to pure protein or mixed protein adsorption layers at air/water or oil/water interfaces. Such systems play for example an important role as stabilizers in foams and emulsions. The aim of this contribution is to give a literature overview of interfacial shear rheological studies of pure protein and protein/surfactant mixtures at liquid interfaces measured with different techniques. Techniques which utilize the damping of waves, spectroscopic or AFM techniques and all micro-rheological techniques will not discuss here.     

Application of Modified Natural Oils as Reactive Diluents for Epoxy Resins

Bisphenol A based low-molecular-weight epoxy resin was modified with epoxidized soybean oil, which exhibit viscosity reducing ability comparable to commercial grade active diluents. The studied compositions showed a non-Newtonian rheological behavior, typical for Bingham liquids. The values of the flow index (n) and the consistency index (k) for the compositions tested in the temperature range 25–65 °C were calculated from the Ostwald-de Waele rheological model and were used to calculate the flow-activation energy (E_a) using the Arhenius equation. Studies of co-crosslinking of mixed oil-resin compositions using isophorone diamine showed essential decrease of the reaction heat and peak maximum temperature. Mechanical properties, thermal stability, water absorption and chemical resistance of the epoxy resin modified with natural oil, were also investigated. Compositions of epoxy resin Ruetapox 0162, modified with the oil diluent, preserved very good mechanical properties of the epoxy resins and demonstrated relatively low water absorption as well as high chemical resistance. The compositions displayed even higher impact strength than pure epoxy resin due to plasticizing effect of the built-in oil. Compositions with the high contents (up to 60 weight %) of the oil were flexible materials with fast elastic recovery.     

Investigations into the electrical and coalescence behaviour of water-in-crude oil emulsions in high voltage gradients

The stability of water-in-crude oil emulsions when subjected to high voltage electric fields depends on the nature of the crude oil and the presence of chemical additives. Optical microscopy, conductivity and coalescence measurements have revealed two distinct types of behaviour, designated type I and type II. These are shown to be related to the crude oil/water interfacial rheological properties. For incompressible crude oil/water films, droplet—droplet coalescence is hindered and chains of water droplets are established. These increase the electrical conductivity of the emulsion (type I behaviour). On the other hand, efficient droplet—droplet coalescence accompanied by minimal conduction occurs in electric fields if the interfacial film is compressible (type II).     

Materials based on solid-stabilized emulsions

Solid-stabilized emulsions are obtained by shearing a mixture of oil, water, and solid colloidal particles. In this article, we present a large variety of materials, resulting from a limited coalescence process. Direct (o/w), inverse (w/o), and multiple (w/o/w) emulsions that are surfactant-free and monodisperse were produced in a very wide droplet size range, from micrometers to centimeters. These materials exhibit original properties compared with surfactant-stabilized emulsions: outstanding stability with respect to coalescence and unusual rheological behavior. For such systems, the elastic storage modulus G' is not controlled by interfacial tension but by the interfacial elasticity resulting from the strong adhesion between the solid particles adsorbed at the oil-water interface. Due to the wide accessible droplet size range, concentrated emulsions can be extremely fluid while emulsions with low droplet volume fraction can behave as solids.     

Enthalpy-entropy compensation of micellization of ethoxylated nonyl-phenols

The thermodynamics of micellization of non-ionic surfactants (ethoxylated nonyl-phenols with different chain length) was studied as a function of ethoxy group number, electrolyte concentration and type, and concentration of short-chain alcohols at different temperature. On the basis of the thermodynamic data the enthalpy/entropy correlation and the H/S compensation temperature were calculated to characterize the solvent-solute and solute-solute interaction. The experimental results have definitely proved that a well-defined correlation exists for all investigated systems and the compensation temperature is independent of the ethoxy group number and the presence of alcohols. The inorganic electrolytes, however, decrease theT _c compared to both alcohol-free and alcohol-containing systems, indicating the change in the mechanism of the micellization process. The new theoretical results significantly contribute to confirmation of the earlier conclusion concerning the stability and the structure of non-ionic surfactant solutions.     

界面扩张流变法研究C12mimBr对Gemini12-2-12在空气/水界面聚集行为的影响

采用界面扩张流变技术研究了季铵盐偶联表面活性剂C₁₂-(CH₂)₂-C₁₂·2Br (Gemini12-2-12)及其与离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C₁₂mimBr)复配体系的动态界面张力、扩张流变性质和界面弛豫过程等, 探讨了C₁₂mimBr 对C₁₂mimBr/Gemini12-2-12 混合体系界面性质的影响及C₁₂mimBr 对Gemini12-2-12界面聚集行为影响的机制. 结果表明, 随着离子液体表面活性剂的不断引入, 体系界面吸附达到平衡所需的时间逐渐缩短, 扩张模量和相角明显降低, 界面吸附膜由粘弹性膜转变为近似纯弹性膜; 同时, 界面及其附近的弛豫过程也发生显著变化, 慢弛豫过程消失, 快弛豫过程占主导地位, 且离子液体浓度越高, 快弛豫的贡献越大. 这些界面性质的变化主要归因于离子液体表面活性剂C₁₂mimBr参与界面形成及两表面活性剂在界面竞争吸附的结果. 少量离子液体表面活性剂C₁₂mimBr 的加入可以填补疏松的Gemini12-2-12 界面上的空位, 形成混合界面吸附膜. 随着C₁₂mimBr 含量的增加, 嵌入界面的C₁₂mimBr 分子数不断增多, 导致界面上相互缠绕的Gemini12-2-12烷基链“解缠”, 在体相和界面分子扩散交换的过程中“解缠”的Gemini12-2-12分子从界面上解吸回到体相, 与此同时, C₁₂mimBr 分子相对较小的空间位阻及较强的疏水作用促使其优先扩散至界面进而取代Gemini12-2-12分子, 最终界面几乎完全被C₁₂mimBr分子所占据.     

Effect of Oil/Water Ratios on the Phase Behavior and the Solubilization Ability of Microemulsion Systems Containing Sodium Dodecyl Sulfate

An α–ε–β fish-like phase diagram of three phase microemulsions was proposed and used to investigate the phase behavior of the microemulsion systems sodium dodecyl sulfate (SDS)/alcohol/oil/water at various oil/water ratios. Related physicochemical properties of the microemulsion systems were calculated. As the oil/water mass ratio increases, the solubility (ε _B) of the alcohol increases, while both the mass fraction of alcohol in the interfacial layer (A ^S) and the solubilization ability (SP ^∗) decrease. The effect of oils on the properties of the microemulsion systems was investigated.     

Studies in the phase behavior of the microemulsions formed by mixed cationic and nonionic surfactants

The middle-phase behavior for the systems of cetyltrimethylammonium bromide (CTAB)/poly-ethyleneglycol-9-monododecyl ether (AEO₉)/alcohol/oil/brine and CTAB/octylphenolpolyoxyethylene-10-ether (Triton X-100)/alcohol/oil/brine have been studied with ɛ-β fishlike phase diagram method. The interfacial layer composition was determined, and some significant physicochemical parameters are derived from the hydrophilic-lipophilic balance plane equation. The effects of different alcohols, oils, temperature and inorganic salt (NaCl) on the middle-phase behavior of microemulsion formed by composite CTAB/AEO₉ systems were also investigated systematically. The effects of different factors on the phase behavior of microemulsions formed by CTAB/AEO₉ and CTAB/TX-100 systems were compared. The results suggest that the solubilization of CTAB/AEO₉ microemulsion is higher than that of CTAB/TX-100 system under the same conditions.     

Interfacial tension of alkylglucosides in different APG/oil/water systems

The interfacial performance of pure alkylglucosides (C₈G₁, C₁₀G₁ and C₁₂G₁) and of technical grade alkylpolyglucoside (APG) surfactants was investigated in three different water/oil systems (decane, isopropylmyristate and 2-octyldodecanol). From the dependence of the interfacial tension on the surfactant concentration below the CMC the cross-sectional area of the molecules at the decane/water interface was estimated. The plateau values of the interfacial tension at the CMC _c are independent of temperature and almost independent of added electrolyte in the decane/water system. The ability of the surfactants to lower the oil/water interfacial tension is most pronounced for the nonpolar oil. The partition coefficient of the surfactant between oil and water phase (k _c) was estimated from the CMC and the observed break point of the interfacial tension after equilibration of the two phases. In decane/water,k _c is nearly zero for all surfactants studied. For the polar oils,k _c increases with the chain length of the surfactant up tok _c10 for C₁₂G₁ in octyldodecanol/water. The values of _c in the different oil/water systems appear to be correlated withk _c and exhibit a minimum neark _c=1.     

Physicochemical Properties of a Ternary System Based on Medium Chain Triglycerides/Water/Mixed Nonionic Sugar-Based Surfactants

Equal ratios of medium chainlength triglycerides and water were emulsified with 5% w/w of mixed nonionic surfactants with various hydrophilic-lipophilic balance (HLB) values. The HLB numbers ranged from 15 to 6.6. Emulsifiers with HLB numbers 15, 14.2, 13.3, and 12.5 produced low viscosity milk-like liquid, 11.6, 10.8, 10, and 9.1 produced cream, 8.3 and 7.4 produced paste like consistency, and 6.6 produced a coarse emulsion. The effects of HLB on stability, particle size, and rheological properties were studied. Emulsifiers with intermediate HLB numbers produced emulsions that are stable for 30 days at room temperature but a thin layer of oil on top of the emulsion was observed at 45°C. The thin oil layer can be redispersed with mild agitation without loss of stability. Emulsifiers with high and low HLB number (15, 14.2, 13.3, 6.6) produced emulsions that were unstable at both storage conditions. The stability of the emulsions correlate well with the particle size. The curve flow plot for most of the emulsions fit the Herschel Bulkley model. They exhibit a pseudoplastic type behavior. Emulsifiers with different HLB numbers also affect the shear stress at zero shear, τ₀, and the yield value, τ.     

Tailoring the interfacial assembly of colloidal particles by engineering the mechanical properties of the interface

Fluid interfaces can be used as a platform for promoting the direct and spontaneous self-assembly of colloidal particles, where the driving force is the reduction in interfacial energy. In addition, fluid interfaces allow fine-tuning of the particles ensemble by an external force, such as the presence of an imposed interfacial flow, or by engineering the interparticle interactions dictated by the interplay of interfacial forces. As a consequence, a wide-ranging set of interfacial structures can be achieved from liquid-like layers, which can flow under stress, to amorphous solids that are able to sustain static stress. Here, far from a comprehensive overview of the interfacial assembly of colloidal particles, different ways of tailoring it by rationally designing the rheological properties of the interface are provided, with a focus on experimental and theoretical methods and model systems that have been recently exploited. In particular, ligand-coated nanoparticles, with a strong emphasis on the effect of the ligands on the interfacial structure and the rheological properties, and soft nanogel particles, in which an environmental factor, such as the temperature, drives to different interfacial structures and mechanical responses will be further discussed.     

Physical and Rheological Characteristics of Emulsion Model Structures Containing Iranian Tragacanth Gum and Oleic Acid

The physical and rheological properties of oil in water model emulsion systems containing Iranian tragacanth gum (TG) (0.5, 1 g/100 ml emulsions), whey protein isolate (WPI) (2, 4 g/100 ml emulsions), and oleic acid (5, 10 ml/100 ml emulsions) were investigated for droplet-size distribution, creaming index, and rheological properties of emulsions. The shear-thinning behavior of all dispersions was modeled using power law, Cross, and Ellis models. The power law model described the flow behavior of dispersions for its lowest standard error (0.29) and highest determination coefficient (R²) (0.99). Rheological investigation showed that both loss (G″) and storage (G′) modules increased as gum and oil content increased. Delta degree was 0.1 and increased as frequency increased, indicating that liquid-like viscose behavior dominated solid-like elastic behavior. Droplet-size distribution was measured by light scattering and microscopic observations revealed a flocculated system. Gum, WPI, and oil contents decreased the emulsion creaming index with gum concentration having the greatest effect.     

胶质液体泡沫的流变性

应用RV-30旋转粘度计和锥板式RS300应力控制流变仪, 采用稳态剪切方法和小振幅振荡剪切对胶质液体泡沫(CLA)体系的流变特性进行了系统分析, 讨论了温度、 相体积比(油相与水相体积比, PVR)和剪切速率对体系流变性质的影响. 稳态剪切实验结果表明, CLA体系表现出非牛顿流体特征, 其流变行为符合Herschel-Bulkley流变模式. 同时, CLA体系表现出剪切稀释特性, 不具有触变性. 粘弹性实验结果表明, 在低PVR(PVR=2~4)条件下, CLA无线性粘弹性区; 当PVR=8时, 表现出一定程度的粘弹性; 温度对体系的流变行为和粘弹性的影响不显著. 通过与高内相乳状液(HIPRE)体系比较, 发现CLA与HIPRE具有相似的流变特性, 这也说明两者在微观结构上具有一定的相似性.     

Effect of alkaline materials on interfacial rheological properties of oil-water systems

Interfacial rheological properties of a model crude oil-water system were studied in the presence of sodium hydroxide. The interfacial viscosity, the non-Newtonian flow behavior and the activation energy of viscous flow were determined as a function of shear rate, alkali concentration and aging time. The fundamental conclusion of the experimental results is that the interfacial viscosity drastically decreases in the presence of alkaline materials and the change under favorable conditions may exceed 3 or 4 orders of magnitude. Simultaneously, the sodium hydroxide effectively suppresses the non-Newtonian flow behavior of the interfacial layer. The experimental observations are explained by simultaneous chemical processes taking place in the boundary layer. The present data may help to elucidate the formation, stability and breaking of alkali-containing oil-water emulsions and they provide additional information for better understanding of the displacement mechanism and for the formulation of alkaline flooding as a potential chemically enhanced oil-recovery method. Received: 6 April 1998 Accepted: 18 August 1998     

Physicochemical Studies on an All-Purpose Pesticide Spray Adjuvant-(APSA-80)

APSA-80, an useful pesticide spray adjuvant is a mixture of 2-[2-(4-nonylphenoxy) ethoxy] ethanol, 1-butanol and tall oil fatty acids. It is strongly surface active and can decrease the surface tension of water to ～20 mNm^?1 at its critical micelle concentration (CMC) of 0.006 g%. APSA-80 itself and its binary mixtures, (APSA-80 + water) and (APSA-80 + isopropylmyristate [IPM]) and ternary mixtures (APSA-80 + water +IPM) can undergo a number of physical changes with rise in temperature; the main changes are in color, turbidity and phases. The ternary mixtures of APSA-80/water/IPM with changing compositions can form mono-, bi-, and triphasic solutions as well as gels and viscous solutions. The gel and viscous phases show characteristic rheological properties of both shear thinning and thickening types. They also show permeation of hydrophilic and oleophilic dyes through them. SEM and optical microscopic measurements have shown interesting surface morphologies of the gels and their vertical projections in three-dimensional pictorial mode. Salts like LiCl, NaCl, KCl, CsCl, MgSO₄, and Al₂(SO₄)₃ can have both minor and major effects on the gel consistencies. The alkanols like ethanol, propanol, and isopropanol are also mild to fairly large gel influencing co solvents. The antibacterial properties of APSA-80 have been studied with two Gram positive bacteria and a yeast; the activities found were moderate.     

Thermodynamic study of interfacial tension between oil and aqueous phases composed of ionic liquids and brine

The first fundamental step in determining the physicochemical properties of an equilibrium system is to determine the activity coefficient of electrolyte and non-electrolyte ions. Based on understanding the importance of activity coefficient in thermodynamic systems in this study, in order to predict interfacial tension between oil and aqueous phases composed of ionic liquids and brine, a modified thermodynamic equation based on concentration and coefficient of activity of ionic liquids is defined. For this study, the Extended UNIQUAC model is desired and its adjustable parameters are optimized with Genetic + PSO algorithm. The modified model has practical features such as investigating the effect of concentrations of salts in the water of oil fields formation on the interfacial tension of the system, investigating the effect of concentrations of various organic compounds such as ionic liquids on the interfacial tension of the system and investigating the interaction energy between organic and inorganic ions. In this study, the optimization of the modified thermodynamic equation to predict the interfacial tension of solutions containing [C₈Py][Cl], [C₁₈Py][Cl], [C₁₂mim][Cl] and [C₁₈mim][Cl] with the presence of brine and distilled water is investigated. Also, the effect of ionic strength of the solution in 32 equilibrium systems on interfacial tension is investigated. According to the optimization results of this study, the design of a computer program can be considered to predict the interfacial tension with the presence of ionic liquids and salts.     

Stability of emulsions of water in mineral oils containing asphaltenes

Emulsions of water in mineral oils are stable if the oil phase contains asphaltenes which are near the condition of incipient flocculation. This condition is determined by the composition of the oil phase and by the nature of the asphaltenes. High aromaticity of the oil phase and the presence of deflocculants prevent flocculation of asphaltenes; the deflocculants may be interfacially active agents or asphaltene-like compounds with better solubility in the oil phase. Conditions of incipient flocculation of asphaltenes correlate very well with a considerable increase of rheological resistance of the interface between the oil phase and distilled water, determined according to the torsion oscillation method. Stabilization of the water-in-oil emulsions is therefore caused by the build-up of a coherent layer of asphaltenes in the water-oil interface in these cases. Deflocculants of asphaltenes in the oil phase destroy their stabilizing effect; however, the deflocculants themselves may stabilize the water-in-oil emulsions by adsorption on the water-oil interface and then the correlation between the condition of asphaltenes and emulsion stability does not hold, nor is the interfacial viscosity perceptibly increased. Under borderline conditions of emulsion stability a few percent of sodium chloride in the water phase counteracts the build-up of a stabilizing layer of asphaltenes in the water-oil interface and so do higher p_H values of a buffered water phase. At low p_H-values emulsion stability does not correlate with interfacial resistance. It can be concluded that asphaltenes stabilize water-in-oil emulsions if they accumulate on the water-oil interface. This interfacial layer may show a coherence, which is an indication of the presence of asphaltenes rather than a condition for stability of the emulsions.