Eudragit®-PEG Nanoparticles: Physicochemical Characterization and Interfacial Tension Measurements

The objectives of this study are to understand the mechanisms involved in the stabilization of water/oil interfaces by polymeric nanoparticles (NPs) (Eudragit®). Eudragit L100 NPs of various sizes and Zeta potentials were studied and compared at a water/cyclohexane model interface using a droplet tensiometer (Tracker Teclis, Longessaigne, France). The progressive interfacial adsorption of the NPs in the aqueous phase was monitored by tensiometry. The model interface was maintained and observed in a drop tensiometer, analyzed via axisymmetric drop shape analysis (ADSA), to determine the interfacial properties. Given the direct relationship between the stability of Pickering emulsions (emulsions stabilized by solid nanoparticles) and the interfacial properties of these layers, different nanoparticle systems were compared. Specifically, Eudragit NPs of different sizes were examined. Moreover, the reduction of the Zeta potential with PEG-6000 induces partial aggregation of the NPs (referred to as NP flocs), significantly impacting the stability of the interfacial layer. Dynamic surface tension measurements indicate a significant decrease in interfacial tension with Eudragit® nanoparticles (NPs). This reduction correlates with the size of the NPs, highlighting that this parameter does not operate in isolation. Other factors, such as the contact angle and wettability of the nanoparticles, also play a critical role. Notably, larger NPs further diminished the interfacial tension. This study enhances our understanding of the stability of Pickering emulsions stabilized by Eudragit® L100 polymeric nanoparticles.

Effect of active species in crude oil on the interfacial tension behavior of alkali/synthetic surfactants/crude oil systems

The effect of active species present in crude oil on the interfacial tension （IFT） behavior of alkali/synthetic surfactants/crude oil systems was studied. The system consisted of heavy alkyl benzene sulfonate, sodium chloride, sodium hydrate and Daqing crude oil. Experimental results indicated that active species would diffuse from oil/aqueous interface to aqueous phase and finally an equilibrium could be reached in the system with increasing contact time. Moreover, the minimum IFT and equilibrium IFT values increased with increasing contact time and a linear relationship existed between dynamic IFT and f^-1/2 when IFT value approaching the minimum and after the minimum IFT was reached. This indicated that the dynamic IFT-time behavior was diffusion controlled. The oil and aqueous phases were analyzed by infrared （IR） spectroscopy. IR spectra of oil and aqueous phases illustrated that the content of active species in the oil phase decreased, but the content of active species in the aqueous phase increased after alkali reacted with crude oil. This indicated that the active species present in oil played an important role in reducing IFT.

Molecular design and applications of a nanostructure green Tripodal surface active ionic liquid in enhanced oil recovery: Interfacial tension reduction, wettability alteration, and emulsification

Surface active ionic liquids (SAILs) are considered as prominent materials in enhanced oil recovery thanks to their high interfacial activity. This study reports the preparation and applications of a nanostructure Tripodal imidazolium SAIL as an environmentally-friendly substitute to the conventional surfactants. The product has a star-like molecular structure centered by a triazine spacer, namely [(C_(4)im)_(3)TA][Cl_(3)], prepared by a one-step synthesis method and characterized with FT-IR, NMR, XRD, and SEM analysis methods. The interfacial tension of the system was decreased to about 78% at critical micelle concentration of less than 0.08 mol·dm^(−3). Increasing temperature, from 298.2 to 323.2 K, improved this capability. The solid surface wettability was changed from oil-wet to water-wet and 80% and 77% stable emulsions of crude oil–aqueous solutions were created after one day and one week, respectively. Compared to the Gemini kind homologous SAILs, the superior effects of the Tripodal SAIL were revealed and attributed to the strong hydrophobic branches in the molecule. The Frumkin adsorption isotherm precisely reproduced the generated IFT data, and accordingly, the adsorption and thermodynamic parameters were determined.

Synthesis of Petroleum Sulfonate Surfactant with Ultra-Low Interfacial Tension in Rotating Packed Bed Reactor

Petroleum sulfonate is one of the most important surfactants used in surfactant flooding for enhanced oil recovery, which is mainly obtained by treating high-boiling petroleum fractions in a stirred tank reactor(STR) or in a fallingfilm reactor(FFR). The synthesis of petroleum sulfonate with ultra-low interfacial tension from viscous petroleum fractions was carried out in a rotating packed bed(RPB) reactor using dilute liquid sulfur trioxide as the sulfonating agent in this study. The effects of various experimental conditions on components content and oil-water interfacial tension(IFT) were investigated. Under the optimum conditions, the active matter content could reach up to 50.3% and the IFT could be equal to 4.7×10-3 m N/m. Compared with the traditional reactor, the active matter content is by 14.12% higher in the RPB as compared to that obtained in the STR. The uneven change of the test oil droplets during the IFT measurement was also discussed. The increase of heavy components content not only can eliminate the contraction phenomenon, but also can reduce the IFT to a minimum. This can be conducive to explaining the reason for producing IFT and the preparation of proper formulations for practical application.

Synthesis and Interfacial Properties of Bio-Based Zwitterionic Surfactants Derived from Different Fatty Acids in Non-Edible Vegetable Oils

Waste cooking oils and non-edible vegetable oils are abundant and renewable resources for bio-based materials which have showed great potential applications in many industries.In this study,five fatty acids commonly found in non-edible vegetable oils,including palmitic acid,stearic acid,linoleic acid,linolenic acid,ricinoleic acid,and their mixtures,were used to produce bio-based zwitterionic surfactants through a facile and high-yield chemical modification.These surfactants demonstrated excellent surface/interfacial properties with the minimum surface tensions ranging from 28.4 mN/m to 32.8 mN/m in aqueous solutions.The interfacial tensions between crude oil and surfactant solutions were remarkably reduced to lower values ranging from 0.0028 mN/m to 0.1983 mN/m without the aid of extra alkali,which particularly implied a great potential application in enhanced oil recovery.Meanwhile,these bio-based surfactants also showed good wetting properties(contact angles of~51°comparing with that of double distilled water,92.04°)and appropriate predicted biodegradability(degradation order of“weeks”for bio-based surfactants synthesized from saturated fatty acids,and“months”for those synthesized from unsaturated fatty acids).Bio-based surfactants synthesized from unsaturated fatty acids showed better interfacial properties in reducing interfacial tension between crude oil and formation water.The bio-based surfactants presented in this study are alternative substitutes for traditional petroleum-based surfactants in various surfactant application fields.

Prediction of surface and interfacial tension based on thermodynamic data and CALPHAD approach

In this article, following a brief introduction concerning experimental measurements of surface and interfacial tensions, methods for calculating surface tension and surface segregation for binary, ternary, and multicomponent high-temperature melts based on Bulter＇s original treatment [ 1] and on available physical properties and thermodynamic data, especially excess Gibbs free energies of bulk phase and surface phase versus temperature obtained from thermodynamic databases using the calculation of phase diagram （CALPHAD） approach, with special attention to the model parameter β, have been described. In addition, the geometric models can be extended to predict surface tensions of multicom- ponent systems from those of sub-binary systems. For illustration, some calculated examples, including Pb-free soldering systems and phase-diagram evaluation of binary alloys in nanoparticle systems are given. On the basis of surface tensions of high-temperature melts, interracial tensions between liquid alloy and molten slag as well as molten slag and molten matter can be calculated using the Girifalco-Good equation [2]. Modifications are suggested in the Nishizawa＇s model [3] for estimation of interracial tension in liquid metal （A）/ceramics （MX） systems so that the calculations can be carried out based on the sublattice model and thermodynamic data, without deliberately differentiating the phase of MX at high temperature. Finally, the derivation of an approximate expression for predicting interfacial tension between the high-temperature multicomponent melts, employing Becker＇s model [4] in conjunction with Bulter＇s equation and inteffacial tension data of the simple systems is described, and some examples concerning pyrometallurgical systems are given for better understanding.

A Statistical Thermodynamic Model of Vapor-Liquid Interfacial Tension for Liquid Mixtures at High Pressure

1 INTRODUCTIONInterfacial tension of pure fluids and their mixtures is an important property for the development,design and simulation of many chemical processes.The interfacial behavior has important prac-tical applications in material science,environment science and chemical engineering separationprocesses as well as in secondary or tertiary recovery of petroleum.Although interfacial phenom-ena are rather complicated,interfacial tension of free vapor-liquid interface is considered as a firstand fundamental step of the study.For example,enhanced carbon dioxide“flooding”

Interactions of ferro-nanoparticles(hematite and magnetite) with reservoir sandstone: implications for surface adsorption and interfacial tension reduction

There are a few studies on the use of ferro-nanofluids for enhanced oil recovery,despite their magnetic properties;hence,it is needed to study the adsorption of iron oxide(Fe2 O3 and Fe3 O4) nanoparticles(NPs) on rock surfaces.This is important as the colloidal transport of NPs through the reservoir is subject to particle adsorption on the rock surface.Molecular dynamics simulation was used to determine the interfacial energy(strength) and adsorption of Fe2 O3 and Fe3 O4 nanofluids infused in reservoir sandstones.Fourier transform infrared spectroscopy and X-ray photon spectroscopy(XPS) were used to monitor interaction of silicate species with Fe2 O3 and Fe3 O4.The spectral changes show the variation of dominating silicate anions in the solution.Also,the XPS peaks for Si,C and Fe at 190,285 and 700 eV,respectively,are less distinct in the spectra of sandstone aged in the Fe3 O4 nanofluid,suggesting the intense adsorption of the Fe3 O4 with the crude oil.The measured IFT for brine/oil,Fe2 O3/oil and Fe3 O4/oil are 40,36.17 and 31 mN/m,respectively.Fe3 O4 infused with reservoir sandstone exhibits a higher silicate sorption capacity than Fe2 O3,due to their larger number of active surface sites and saturation magnetization,which accounts for the effectiveness of Fe3 O4 in reducing IFT.

Study of Oil/Water Interfacial Tension of Vacuum Residual Fractions from Iranian Light Crude Oil

The vacuum residual from Iranian Light crude oil are separated into a series of 16 narrow fractions according to the molecular weight by the supercritical fluid extraction and fractional (SFEF) technology. The chemical element and the UV spectrum of each fraction are analyzed. The effects of several factors on the interfacial tension are investigated, which are the fraction concentration in oil phase, the ratio of oil component, the salts dissolved in the water phase and the pH value. The interfacial tension decreases rapidly as the concentration of the residual fraction in the oil increases, showing a higher interfacial activity of the fraction. The interfacial tension changes, as the amount of absorption or the state of the fractions in the interface changes resulting from different ratios of oil, different kinds or concentrations of salts in water, and different pH values. It is concluded that the interfacial tension changes regularly, corresponding to the regular molecular parameters of the vacuum residual fractions.

PREPARATION,IDENTIFICATION AND INTERFACIAL ACTIVITIES OF PETROLEUM CARBOXYLATE AS SURFACTANT FOR CHEMICAL FLOODING

Petroleum carboxylate that may be suitable for tertiary oil recovery have been produced inexpensively from the fractions of Daqing crude oil by a two step process.The feed stock was first oxidized in the vapor phase,followed by reaction of the oxidized products with sodium hydroxide.Dilute solutions of sodium carboxylates were produced and show ultralow(10^(-2)mN/m)interfacial tensions(IFTs)against a variety of hydrocarbons with a wide range of ACN(Alkane Carbon Number).Infrared spectroscopy was used to identify the functional groups in the oxidized and the saponified products.

The axisymmetric long-wave interfacial stability of core-annular flow of power-law fluid with surfactant

The long wave stability of core-annular flow of power-law fluids with an axial pressure gradient is investigated at low Reynolds number. The interface between the two fluids is populated with an insoluble surfactant. The analytic solution for the growth rate of perturbation is obtained with long wave approximation. We are mainly concerned with the effects of shear-thinning/thickening property and interfacial surfactant on the flow stability. The results show that the influence of shear-thinning/thickening property accounts to the change of the capillary number. For a clean interface, the shear-thinning property enhances the capillary instability when the interface is close to the pipe wall. The converse is true when the interface is close to the pipe centerline. For shear-thickening fluids, the situation is reversed. When the interface is close to the pipe centerline, the capillary instability can be restrained due to the influence of surfactant. A parameter set can be found under which the flow is linearly stable.

Interfacial Tension of CO_2 and Organic Liquid under High Pressure and Temperature

In order to investigate the effect of organic liquid molecular structure and the intermolecular force operating with CO2 molecules and organic liquid molecules on interfacial tension(IFT) between CO2 and organic liquid at the first contact, the interfacial tension between CO2 and hexane, octane, ethanol and cyclohexane at different temperatures and pressures is measured by using the pendant drop method and the axisymmetric drop shape analysis(ADSA). The results show that the interfacial tension between CO2 and organic liquids is affected by the polarity and the structure of the organic liquid molecule obviously. The intermolecular force operating within CO2 molecules or organic liquid, and that between CO2 and organic liquids molecules play a dominate role on the interfacial tension between CO2 and the organic liquids.

The role of CO2 and ion type in the dynamic interfacial tension of acidic crude oil/carbonated brine

The e ects of CO2 and salt type on the interfacial tension(IFT) between crude oil and carbonated brine(CB) have not been fully understood. This study focuses on measuring the dynamic IFT between acidic crude oil with a total acid number of 1.5 mg KOH/g and fully CO2-saturated aqueous solutions consisting of 15,000 ppm of KCl, NaCl, CaCl2 and MgCl2 at 30 °C and a wide range of pressures(500–4000 psi). The results of IFT measurements showed that solvation of CO2 into all the studied aqueous solutions led to an increase in IFT of acidic crude oil(i.e., comparison of IFT of crude oil/CB and crude oil/brine), while no significant e ect was observed for pressure. In contrast, the obtained results of studied salts indicated a positive e ect on the IFT reduction of acidic crude oil/carbonated water(CW)(i.e., comparison of IFT of crude oil/CB and crude oil/CW).

INTERFACIAL TENSIONS OF SOLID COPPER/LIQUID LEAD AND SOLID COPPER/LIQUID BISMUTH

The solid-liquid interfacial tensions of Cu(solid)-Pb(liquid)andCu(solid)-Bi(liquid)binary systems have been determined by the dihedral angle method.The results show that at 850℃ the interfacial tensions are 368±55mN/m for Cu-Pb sys-tem and 336±35mN/m for Cu-Bi systa,respectively,the error ranges of which aremore narrow than those found in some papers published abroad.In addition,there is nodetective segregation of other solute atoms or compounds in the vicinity of the tip of cop-per grain boundary where dihedral angles formed.

Highly efficient [C8mim][Cl] ionic liquid accompanied with magnetite nanoparticles and different salts for interfacial tension reduction

The 1-octyl-3-methylimidazolium chloride, [C8 mim][Cl] ionic liquid(IL) was used as a novel surfactant in n-heptane/water system. The interfacial tensions(IFT) were measured and corresponding variations were investigated. An IFT reduction of 80.8% was appropriate under the IL CMC of about 0.1 mol·L^-1 and stronger effects were achieved when magnetite nanoparticles and salts were present profoundly under alkaline p Hs.The equilibrium IFT data were accurately simulated with the Frumkin adsorption model. Hereafter, the saturated surface concentration, equilibrium constant and interaction parameter were obtained and their variations were demonstrated. Further, emulsion stability and contact angle of oil/water interface over quartz surface were studied. The oil/water emulsion stability was hardly changed with nanoparticles;however, the stability of oil/water + IL emulsions was significantly improved. It was also revealed that the presence of sodium and calcium chloride electrolytes fortifies the IL impact, whereas sodium sulfate weakens. From dynamic IFT data and fitting with kinetic models, it was found that the IL migration toward interface follows the mixed diffusion–kinetic control model. Consequently, the IL diffusion coefficient and the appropriate activation energy were determined.

INTERFACIAL TENSION BETWEEN SLAG AND COPPER MATTE

The interfacial tension between FeO-CaO-SiO_2-MgO system slag and Cu-Fe-S system matte was determinated by the X-ray radiograph sessile drop method.The effects of FeO/SiO_2 ratio in the slag,contents of CaO,FeO,ZnO and CaF_2 in the slag on interracial tension and the relation of inter facial tension with the grade of matte and temperature have been studied.The floatation coefficient and film coefficient of slag-matte system has been calculated and the mechanism of the transition of iron and oxygen from slag to matte has also been discussed.

Quantitative Structure-Property Relationship on Prediction of Surface Tension of Nonionic Surfactants

A quantitative structure-property relationship (QSPR) study has been made for the prediction of the surface tension of nonionic surfactants in aqueous solution. The regressed model includes a topological descriptor, the Kier & Hall index of zero order (KH0) of the hydrophobic segment of surfactant and a quantum chemical one, the heat of formation (fHD) of surfactant molecules. The established general QSPR between the surface tension and the descriptors produces a correlation coefficient of multiple determination, 2r=0.9877, for 30 studied nonionic surfactants.

Substrate elastic deformation due to vertical component of liquid-vapor interfacial tension

Young＇s equation is a fundamental equation in capillarity and wetting, which reflects the balance of the horizontal components of the three interracial tensions with the contact angle （CA）. However, it does not consider the vertical component of the liquid-vapor interracial tension （VCLVIT）. It is now well understood that the VCLVIT causes the elastic deformation of the solid substrate, which plays a significant role in the fabrication of the microfluidic devices because of the wide use of the soft materials. In this paper, the theoretical, experimental, and numerical aspects of the problem are reviewed. The effects of the VCLVIT-induced surface deformation on the wetting and spreading, the deflection of the microcantilever, and the elasto.capillarity and electro- elasto.capillarity are discussed. Besides a brief review on the historical development and the recent advances, some suggestions on the future research are also provided. Key words

Determination of interfacial tension and viscosity under dripping flow in a step T-junction microdevice

Microfluidic approaches for the determination of interfacial tension and viscosity of liquid-liquid systems still face some challenges.One of them is liquid-liquid systems with low interfacial and high viscosity,because dripping flow in normal microdevices can’t be easily realized for the systems.In this work,we designed a capillary embedded step T-junction microdevice to develop a modified microfluidic approach to determine the interfacial tension of several systems,specially,for the systems with low interfacial tension and high viscosity.This method combines a classical T-junction geometry with a step to strengthen the shear force further to form monodispersed water/oil(w/o)or aqueous two-phase(ATP)droplet under dripping flow.For systems with low interfacial tension and high viscosity,the operating range for dripping flow is relative narrow whereas a wider dripping flow operating range can be realized in this step Tjunction microdevice when the capillary number of the continuous phase is in the range of 0.01 to 0.7.Additionally,the viscosity of the continuous phase was also measured in the same microdevice.Several different systems with an interfacial tension from 1.0 to 8.0 m N·m^(-1) and a viscosity from 0.9 to 10 m Pa·s were measured accurately.The experimental results are in good agreement with the data obtained from a commercial interfacial tensiometer and a spinning digital viscometer.This work could extend the application of microfluidic flows.

Toward accurate density and interfacial tension modeling for carbon dioxide/water mixtures

Phase behavior of carbon dioxide/water binary mixtures plays an important role in various CO2-based industry processes. This work aims to screen a thermodynamic model out of a number of promising candidate models to capture the vapor–liquid equilibria, liquid–liquid equilibria, and phase densities of CO2/H2O mixtures. A comprehensive analysis reveals that Peng–Robinson equation of state (PR EOS) (Peng and Robinson 1976), Twu α function (Twu et al. 1991), Huron–Vidal mixing rule (Huron and Vidal 1979), and Abudour et al. (2013) volume translation model (Abudour et al. 2013) is the best model among the ones examined;it yields average absolute percentage errors of 5.49% and 2.90% in reproducing the experimental phase composition data and density data collected in the literature. After achieving the reliable modeling of phase compositions and densities, a new IFT correlation based on the aforementioned PR EOS model is proposed through a nonlinear regression of the measured IFT data collected from the literature over 278.15–477.59 K and 1.00–1200.96 bar. Although the newly proposed IFT correlation only slightly improves the prediction accuracy yielded by the refitted Chen and Yang (2019)’s correlation (Chen and Yang 2019), the proposed correlation avoids the inconsistent predictions present in Chen and Yang (2019)’s correlation and yields smooth IFT predictions.