Interfacial Rheology Measured with a Spinning Drop Interfacial Rheometer: Particularities in More Realistic Surfactant–Oil–Water Systems Close to Optimum Formulation at HLDN = 0

Three different cases were selected to study the effect of physicochemical formulation on interfacial rheology properties of surfactant–oil–water (SOW) systems by increasing the complexity of the system from a basic case. This was performed by changing the normalized hydrophilic–lipophilic deviation (HLD_N) to attain the optimum formulation at HLD_N = 0. Two types of SOW systems were studied: the first one used an ionic surfactant with a salinity scan, and the second one a mixture of two nonionic surfactants in a formulation scan produced by changing their proportion. Both of them contained cyclohexane as a pure oil phase, without alcohol. Sec-butanol was then added as a co-surfactant with hardly any formulation influence on HLD_N. The complexity in interfacial rheology was then increased by changing the oil to a light crude with low asphaltene content. The interfacial rheology is also reported for a realistic system with a high asphaltene content comprised of crude oil diluted in cyclohexane with a conventional surfactant and a commercial demulsifier. The findings confirm that at optimum formulation and whatever the scanning variable (salinity, average ethylene oxide number in the nonionic surfactant mixture, or surfactant/demulsifier concentration), the interfacial tension, and interfacial elastic moduli E, E′, and E″ exhibit a deep minimum. These observations are related to the acceleration of the surfactant exchanges between the interface, oil, and water, near the optimum formulation. Several arguments are put forward to explain how these findings could contribute to the decrease in emulsion stability at HLD_N = 0.     

Trends to Attain a Lower Interfacial Tension in a Revisited Pure Alkyl Polyethyleneglycol Surfactant–Alkane–Water Ternary System. Basic Concepts and Straightforward Guidelines for Improving Performance in Enhanced Oil Recovery Formulations

Surfactant–oil–water systems exhibit a low interfacial tension minimum when the interactions between the adsorbed surfactant with water exactly coincide with its interactions with oil. This occurrence takes place at the so‐called optimum formulation, which was conceptually derived by Winsor in the 1950s and rendered by numerical correlations for enhanced oil recovery in the 1970s. The actual low value of the interfacial tension minimum has been found to increase or decrease with formulation variables and though some hints are available, no general relationship has been reported up to now, probably because too many variables are involved in complex interactions. It is shown in the present article that a linear relationship between low‐tension performance and formulation variables can be found for very simple ternary systems containing a pure ethoxylated alcohol, n‐alkane and water at variable temperature, i.e., when there are only four degrees of freedom. In such a case the iso‐performance contours studied in bi‐dimensional spaces are reported to be almost straight lines and as a consequence the path to lower the tension through formulation adjustments is easy to find as being perpendicular as possible to the contours. On the other hand, it is shown that displacing the limit of restrictions like the surfactant precipitation boundary is a priority issue, thus justifying many trends which have been proposed on empirical grounds in the past years. The reported simple guidelines for a simple surfactant–oil–water ternary is likely to considerably facilitate the formulator's work in a real system with a score of formulation variables.     

New Interfacial Rheology Characteristics Measured Using a Spinning Drop Rheometer at the Optimum Formulation. Part 2. Surfactant–Oil–Water Systems with a High Volume of Middle-Phase Microemulsion

This article is a continuation of our first study on dilational interfacial rheology properties at optimum formulation for surfactant-oil–water systems at low surfactant concentration just above the cμc. Here, we have investigated a high content of middle-phase microemulsion with an optimum WIII phase behavior for a system containing sodium dodecyl sulfate, n-pentanol, and kerosene. A new oscillating spinning drop interfacial rheometer was used to measure the interfacial properties. The very low dilational elasticity moduli and phase angle found at or near hydrophilic–lipophilic deviation (HLD) = 0 are related to the presence of the bicontinuous phase microemulsion and to the fast surfactant exchanges between the bulk and the interface, regardless of the phases involved in the measurement using the spinning drop apparatus, i.e., the two-phase excess oil and excess water (O-W) or the bicontinuous microemulsion and excess water (M-W). We show that at or near optimum formulation, the interfacial tension and the dilational modulus for the M-W case almost instantly reach equilibrium, because of the high surfactant content in the microemulsion and the fast exchanges between the bulk and the interface. In contrast, when both excess phases (O-W) are measured, the changes in these properties are slower, due to the scarce presence of surfactants in both phases. The possibility of having almost all the surfactants trapped in the middle-phase bicontinuous microemulsion could explain the emulsion instability in all the WIII range. This is behaving as if there were no surfactant available in the oil and water phases to stabilize the oil or water droplets thus formed.     

A Normalized Hydrophilic–Lipophilic Deviation Expression HLDN Is Necessary to Avoid Confusion Close to the Optimum Formulation of Surfactant-Oil–Water Systems

The physicochemical conditions to attain a minimum interfacial tension between oil and water were intensively studied in the 1970s when the chemical-enhanced oil recovery became an emergency with the increase in petroleum cost. Correlations between the formulation variables (salinity, oil nature, surfactant and co-surfactant nature, temperature, and pressure) required to attain a minimum interfacial tension or a three-phase behavior, so-called optimum formulation, were related to the chemical potential concept in the late 1970s. They were then transformed in a generalized hydrophilic–lipophilic deviation (HLD) expression in 2000. Some confusion in the ranking and classification of the surfactant parameters with different scales has occurred in recent years. The aim here is to propose a normalized HLD_N expression with the alkane carbon number (ACN) variable scale to clear up the current misunderstanding in the use of different HLD expressions. The use of a single HLD_N expression for all systems improves the prediction of formulation effects, but does not eliminate the limitations due to the partitioning of species in surfactant mixtures.     

Preparation and Performance Evaluation of Fatty Amine Polyoxyethylene Ether Diethyl Disulfonate for Enhanced Oil Recovery in High‐Temperature and High‐Salinity Reservoirs

To enhance oil recovery in high‐temperature and high‐salinity reservoirs, a novel fatty amine polyoxyethylene ether diethyl disulfonate (FPDD) surfactant with excellent interfacial properties was synthesized. The interfacial tension (IFT) and contact angle at high temperature and high salinity were systematically investigated using an interface tension meter and a contact angle meter. According to the experimental results, the IFT between crude oil and high‐salinity brine water could reach an ultra‐low value of 10^?3 mN m^?1 without the aid of extra alkali at 90°C after aging. The FPDD surfactant has strong wettability alternation ability that shifts wettability from oil‐wet to water‐wet. The FPDD surfactant with a high concentration also has good emulsion ability under high‐temperature and high‐salinity conditions. Through this research work, we expect to fill the lack of surfactants for high‐temperature and high‐salinity reservoirs and broaden its great potential application area in enhanced oil recovery.     

How the Influence of Different Salts on Interfacial Properties of Surfactant–Oil–Water Systems at Optimum Formulation Matches the Hofmeister Series Ranking

In this work, we present the effects of salts on sodium dodecyl benzene sulfonate micellization and on the interfacial performance of a sodium dodecyl benzene sulfonate–heptane–brine system at optimum formulation, i.e., hydrophilic–lipophilic deviation (HLD) = 0. In order to do that, interfacial tension and dilational interfacial rheology properties of surfactant–heptane–water systems at optimum formulation are measured using an interfacial spinning drop tensiometer with an oscillating velocity, which can accurately measure interfacial rheology properties at both low and ultralow interfacial tensions. The brines used contain one of the following salts: MgCl₂, CaCl₂, NaCl, NH₄Cl, NaNO₃, CH₃COONa, or Na₂SO₄. We performed a one-dimensional salinity scan with each of these salts to achieve an optimum formulation. In relation to the Hofmeister series, we found that, at optimum formulation, systems with chaotropic ions (NH₄⁺, NO₃⁻) present interfaces with ultralow interfacial tensions, very low dilational modulus, and a low phase angle, whereas kosmotropic ions (Mg²⁺, Ca²⁺, SO₄⁻²) generate high interfacial tension and high rigidity monolayers. Intermediate ions in the Hofmeister series (Na⁺, CH₃COO⁻, Cl⁻) present interfaces with intermediate properties. Furthermore, according to the Hofmeister series, interfaces can be respectively ordered from higher to lower rigidity for surfactant counterions Mg²⁺ > Ca²⁺ > Na⁺ > NH₄⁺ and coions SO₄²⁻ > CH₃COO^– > Cl⁻ > NO₃⁻, which correspond to a salting-out (highest rigidity) and salting-in (lowest rigidity) effect. We observed that counterions have a more significant effect on surfactant–oil–water system properties than those that act as coions.     

Relationship between the interfacial tension and compatibility of polycarbonate and poly(acrylonitrile–butadiene–styrene) blends with reactive compatibilizers

We studied the morphological, mechanical, and rheological properties of polycarbonate (PC) and poly(acrylonitrile–butadiene–styrene) (PolyABS) blends with different types of compatibilizer. Styrene–acrylonitrile–maleic anhydride terpolymer (SAM) was used as a compatibilizer of the blends. For comparison, styrene–acrylonitrile–glycidyl methacrylate terpolymer (SAG) was also used as a compatibilizer. For the PC–PolyABS (70/30 wt %) blends with SAM, the mechanical strength and complex viscosity reached a maximum when the SAM concentration was 5 phr. The mechanical and rheological results of the blend were consistent with the morphological result that the PolyABS domain size reached a minimum when the SAM content was 5 phr. The interfacial tension (α) of the blend was compared with the compatibilizer type and content, which were calculated by the Palierne emulsion model with the relaxation time of the PC–PolyABS blend. The α is consistent with the morphological and mechanical properties of the PC–PolyABS blend. The results of the morphological, mechanical, and rheological properties of the blend suggest that SAM was a more effective compatibilizer than SAG, and the optimum compatibilizer content of SAM was 5 phr. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46418.     

Phase inversion of polyacrylamide based inverse‐emulsions: Effect of the surfactant and monomer on postinversion equilibrium properties

The influence of the interfacial chemistry on the phase inversion of polymerized water‐in‐oil emulsions has been investigated. For copolymerizations of acrylamide with cationic monomers, the effect of substituting of fatty acid esters and ethoxylated fatty acid esters with ABA block type stabilizers, on the kinetics and extent of phase inversion, were examined. It was determined that the solution viscosity was a valid metric to identify the mechanism by which inversion occurs, while conductivity provided a means to quantify inversion efficiency, Therefore, the interfacial chemistry was found to influence not only the plateau value of the viscosity of the polymer solution but also its kinetics. The most suitable inversion was observed with a polymer emulsion stabilized with low block copolymer stabilizer levels in the blend (8 wt %), relative to traditional fatty acid esters and ethoxylated fatty acid esters. This provided an ultimate solution viscosity 30% higher than for a polymer synthesized under identical conditions though with higher levels of the ABA block stabilizer. Overall, the optimal formulation (8% ABA) was found to liberate 88% of the latent viscosity. Given that the options in regards to inverting surfactants can be, legislatively, limited, the present work makes a case for the selection of the interfacial composition not only for its stability during reaction, and the molecular weight of the synthesized polymer, but also for the extent and rapidity of inversion. The formulation‐composition map approach provided an understanding of phase inversion applied to polymer emulsion and was a useful fingerprint to qualitatively describe the catastrophic mechanism of inversion. The surfactant affinity difference applied to a blend of surfactant was found to be a convenient formulation parameter which allowed us to locate the representative point on the map of the polymer emulsion stabilized with different surfactant blend composition. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

How to Attain an Ultralow Interfacial Tension and a Three-Phase Behavior with a Surfactant Formulation for Enhanced Oil Recovery: A Review. Part 2. Performance Improvement Trends from Winsor’s Premise to Currently Proposed Inter- and Intra-Molecular Mixtures

The minimum interfacial tension occurrence along a formulation scan at the so-called optimum formulation is discussed to be related to the interfacial curvature. The attained minimum tension is inversely proportional to the domain size of the bicontinuous microemulsion and to the interfacial layer rigidity, but no accurate prediction is available. The data from a very simple ternary system made of pure products accurately follows the correlation for optimum formulation, and exhibit a linear relationship between the performance index as the logarithm of the minimum tension at optimum, and the formulation variables. This relation is probably too simple when the number of variables is increased as in practical cases. The review of published data for more realistic systems proposed for enhanced oil recovery over the past 30 years indicates a general guidelines following Winsor’s basic studies concerning the surfactant–oil–water interfacial interactions. It is well known that the major performance benefits are achieved by blending amphiphilic species at the interface as intermolecular or intramolecular mixtures, sometimes in extremely complex formulations. The complexity is such that a good knowledge of the possible trends and an experienced practical know-how to avoid trial and error are important for the practitioner in enhanced oil recovery.     

Novel fluorinated surfactants for enhanced oil recovery in carbonate reservoirs

Novel surfactant‐polymer (SP) formulations containing fluorinated amphoteric surfactant (surfactant‐A) and fluorinated anionic surfactant (surfactant‐B) with partially hydrolyzed polyacrylamide (HPAM) were evaluated for enhanced oil recovery applications in carbonate reservoirs. Thermal stability, rheological properties, interfacial tension, and adsorption on the mineral surface were measured. The effects of the surfactant type, surfactant concentration, temperature, and salinity on the rheological properties of the SP systems were examined. Both surfactants were found to be thermally stable at a high temperature (90 °C). Surfactant‐B decreased the viscosity and the storage modulus of the HPAM. Surfactant‐A had no influence on the rheological properties of the HPAM. Surfactant‐A showed complete solubility and thermal stability in seawater at 90 °C. Only surfactant‐A was used in adsorption, interfacial tension, and core flooding experiments, since surfactant‐B was not completely soluble in seawater and therefore was limited to deionized water. A decrease in oil/water interfacial tension (IFT) of almost one order of magnitude was observed when adding surfactant‐A. However, betaine‐based co‐surfactant reduced the IFT to 10^?3 mN/m. An adsorption isotherm showed that the maximum adsorption of surfactant‐A was 1 mg per g of rock. Core flooding experiments showed 42 % additional oil recovery using 2.5 g/L (2500 ppm) HPAM and 0.001 g/g (0.1 mass%) amphoteric surfactant at 90 °C.     

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.     

Viscoelastic Surfactants with High Salt Tolerance,Fast‐Dissolving Property,and Ultralow Interfacial Tension for Chemical Flooding in Offshore Oilfields

Injected chemical flooding systems with high salinity tolerance and fast‐dissolving performance are specially required for enhancing oil recovery in offshore oilfields. In this work, a new type of viscoelastic‐surfactant (VES) solution, which meets these criteria, was prepared by simply mixing the zwitterionic surfactant N‐hexadecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (HDPS) or N‐octyldecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (ODPS) with anionic surfactants such as sodium dodecyl sulfate (SDS). Various properties of the surfactant system, including viscoelasticity, dissolution properties, reduction of oil/water interfacial tension (IFT), and oil‐displacement efficiency of the mixed surfactant system, have been studied systematically. A rheology study proves that at high salinity, 0.73 wt.% HDPS/SDS‐ and 0.39 wt.% ODPS/SDS‐mixed surfactant systems formed worm‐like micelles with viscosity reaching 42.3 and 23.8 mPa s at a shear rate of 6 s^?1, respectively. Additionally, the HDPS/SDS and ODPS/SDS surfactant mixtures also exhibit a fast‐dissolving property (dissolution time <25 min) in brine. More importantly, those surfactant mixtures can significantly reduce the IFT of oil–water interfaces. As an example, the minimum of dynamic‐IFT (IFT_min) could reach 1.17 × 10^?2 mN m^?1 between the Bohai Oilfield crude oil and 0.39 wt.% ODPS/SDS solution. Another interesting finding is that polyelectrolytes such as sodium of polyepoxysuccinic acid can be used as a regulator for adjusting IFT_min to an ultralow level (<10^?2 mN m^?1). Taking advantage of the mobility control and reducing the oil/water IFT of those surfactant mixtures, the VES flooding demonstrates excellent oil‐displacement efficiency, which is close to that of polymer/surfactant flooding or polymer/surfactant/alkali flooding. Our work provides a new type of VES flooding system with excellent performances for chemical flooding in offshore oilfields.     

Phase inversion of polyacrylamide‐based inverse‐emulsions: Influence of inverting‐surfactant type and concentration

The phase inversion of polymeric water‐in‐oil emulsions has been systematically studied by employing nonylphenol and alcohol ethoxylates with various chemistries as well as physical chemical characteristics. A combination of thermodynamics, phase diagrams, and rheometry were used to investigate the behavior of the inverting surfactants as well as the inverted, acrylamide‐based, cationic emulsions. Polymeric inverse‐emulsions containing the inverting surfactant showed no evidence of low‐shear thinning, though they did thin as hydrodynamic forces increased (0.01 to 100 s^?1) prior to reaching a chemistry‐ and concentration‐independent plateau, as is typical for emulsions. The viscosity of emulsions containing inverting surfactants reached a minimum at 1.2% of the “emulsion breaker”. The efficiency of inversion was optimized at 2 wt % of nonylphenols, expressed as a percentage of the total emulsion mass, and increased with the degree of ethoxylation. Interestingly, the viscosity of the polymer inverted in water was maximized at an inverting‐surfactant level corresponding to the CMC of the pure surfactant in water. The alcohol ethoxylates required a higher concentration for inversion (3 wt %), though they provided a higher ultimate inverse viscosity of the polymeric emulsion in water. Therefore, while the inversion process was less efficient with alcohol ethoxylates, the ultimate dilution solution properties of the polyelectrolytes liberated were improved relative to the nonylphenols. Overall, the process of adding a water‐in‐oil emulsion, containing an emulsion breaker, to an excess of water involves a catastrophic inversion mechanism. To be effective under such circumstances, an inverting surfactant should have a partition coefficient between the aqueous an organic phases greatly exceeding unity as well as a hydrophilic–lipophilic balance (HLB) above 12. Effectiveness increases linearly with the partition coefficient. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3567–3584, 2007     

Anionic and Cationic Surfactant Synergism: Minimizing Precipitation,Microemulsion Formation,and Enhanced Solubilization and Surface Modification

Anionic–cationic surfactant mixtures are known to exhibit synergistic effects (e.g., low critical micelle concentration, ultralow interfacial tension, middle phase microemulsion formulation, and increased solubilization and adsolubilization). However, the anionic–cationic surfactant mixtures are also prone to form other unique phases such as precipitates, gels, and coacervates in place of middle-phase microemulsions. Research summarized in this article demonstrates that asymmetric anionic–cationic surfactant mixtures have been shown to promote middle-phase microemulsions instead of these other phases, albeit with a slight decrease in synergism when using these asymmetric mixtures. The use of anionic–cationic surfactant mixtures also is shown to enhance or decrease surfactant adsorption depending on anionic–cationic surfactant ratios. Middle-phase microemulsion formation is demonstrated using anionic-rich or cationic-rich alcohol-free microemulsions by anionic–cationic ratio scans while also reducing or eliminating electrolyte requirement. Solubilization and adsolubilization are shown to increase for mixed anionic–cationic surfactant systems, especially for hydrophobic solutes. Thus, by exploiting these synergisms while avoiding phase separation, properly designed anionic–cationic surfactant mixtures can be advantageous for a wide range of applications.     

Rheology and morphology of polytrimethylene terephthalate/ethylene propylene diene monomer blends in the presence and absence of a reactive compatibilizer

The dynamic rheological behavior and phase morphology of Polytrimethylene terephthalate (PTT) and ethylene propylene diene monomer (EPDM) uncompatibilized blends and those compatibilized with maleic anhydride grafted EPM (EPM‐g‐MA) were investigated. Effects of blend ratio and reactive compatibilization on the morphology and rheological properties of compatibilized and uncompatibilized blends have been analyzed. The viscosity ratio between the polymers was found to be sensitive to frequency which gave an indirect idea about the unstable morphology. The complex viscosity and dynamic modulus increased with increase in compatibilizer addition up to critical micelle concentration. Palierne and Choi‐Schowalter models were used to calculate the interfacial tension between the polymers. The interfacial tension decreased with the addition of compatibilizer up to CMC. It was also found that the minimum value of interfacial tension was found at CMC beyond that a levelling off is observed. The rheological properties of both compatibilized and uncompatibilized blends are found to be closely related to their phase morphology. POLYM. ENG. SCI., 50:1945–1955, 2010. © 2010 Society of Plastics Engineers     

Effect of Nanoparticles on Viscosity and Interfacial Tension of Aqueous Surfactant Solutions at High Salinity and High Temperature

Surfactant flooding has widely been used as one of the chemically enhanced oil recovery (EOR) techniques. Surfactants majorly influence the interfacial tension, γ, between oil and brine phase and control capillary number and relative permeability behavior and, thus, influence ultimate recovery. Additives, such as nanoparticles, are known to affect surfactant properties and are regarded as promising EOR agents. However, their detailed interactions with surfactants are not well understood. Thus, in this work, we examined the influence of silica nanoparticles on the ability of surfactants to lower γ and to increase viscosity at various temperatures and salinities. Results show that the presence of nanoparticles decreased γ between n-decane and various surfactant formulations by up to 20%. It was found that γ of nanoparticles–surfactant solutions passed through a minimum at 35 °C when salt was added. Furthermore, the viscosity of cationic surfactant solutions increased at specific salt (1.5 wt.%) and nanoparticle (0.05 wt.%) concentrations. Results illustrate that selected nanoparticles–surfactant formulations appear very promising for EOR as they can lower brine/n-decane interfacial tension and act as viscosity modifiers of the injected fluids.     

Carbon dioxide‐in‐water foams stabilized with nanoparticles and surfactant acting in synergy

Synergistic interactions at the interface of nanoparticles (bare colloidal silica) and surfactant (caprylamidopropyl betaine) led to the generation of viscous and stable CO₂‐in‐water (C/W) foams with fine texture at 19.4 MPa and 50°C. Interestingly, neither species generated C/W foams alone. The surfactant became cationic in the presence of CO₂ and adsorbed on the hydrophilic silica nanoparticle surfaces resulting in an increase in the carbon dioxide/water/nanoparticle contact angle. The surfactant also adsorbed at the CO₂–water interface, reducing interfacial tension to allow formation of finer bubbles. The foams were generated in a beadpack and characterized by apparent viscosity measurements both in the beadpack and in a capillary tube viscometer. In addition, the macroscopic foam stability was observed visually. The foam texture and viscosity were tunable by controlling the aqueous phase composition. Foam stability is discussed in terms of lamella drainage, disjoining pressure, interfacial viscosity, and hole formation. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3490–3501, 2013     

Synthesis and characterization of fluorine‐containing polyurethane–acrylate core–shell emulsion

Fluorinated polyurethane–acrylate (FPUA) hybrid emulsion was prepared by copolymerization of polyurethane, methyl methacrylate, and 1H,1H,2H,2H‐heptadecafluorooctyl acrylate (FA) via emulsion polymerization in the presence of a perfluoronated reactive surfactant. The polyurethane was synthesized from isophorone diisocyanate, poly(propylene glycol)‐1000, dimethylolpropionic acid, 1,4‐butanediol, and 2‐hydroxyethyl methylacrylate. The influence of the monomer on the surface properties, wetting behaviors, particle size, and viscosity of the emulsion was investigated. The mechanical properties of FPUA latex films were improved, and water absorption and contact angle were improved with the addition of methyl methacrylate and FA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43357.     

Interfacial Rheology of Mixed Surfactants at the Oil/Water Interface

The interfacial rheology of surfactant mixtures (SBT and Tween^® 80) at the oil/water interface is investigated using toluene as a model oil. The surfactant ratio in the mixed system has an important impact on the interfacial properties. After adding Tween^® 80, the interfacial tension and modulus of SBT show remarkable changes. Compared with the individual SBT or Tween^® 80 systems, the interfacial properties of the mixed surfactant system improve, especially at a 1:1 ratio. At the optimum ratio, synergistic adsorption takes place resulting in improved asphalt emulsion stability.     

The tough microcapsules of acrylic acid–styrene–isoprene–styrene quadrablock copolymer shell via Pickering emulsion technique

Pickering emulsion technique has been demonstrated a simple method to fabricate the microcapsules. However, the resulted microcapsules are often fragile. This limits their applications. Here, we report that the microcapsules with the nanostructured shell of poly(acrylic acid‐b‐styrene‐b‐isoprene‐b‐styrene) (ASIS), which is of high toughness and elasticity, could be fabricated via Pickering emulsions using ASIS nanoparticles as stabilizing particles. The surfactant‐free ASIS latex (with theoretical molecular weight for each block: 1.5k–15k–55k–10k) was synthesized by reversible additional fragmentation transfer (RAFT) emulsion polymerization using amphiphilic macro‐RAFT agent [poly(acrylic acid)₂₀‐b‐polystyrene₅ trithiocarbonate] as both reactive surfactant and polymerization mediator. It was found that the ASIS nanoparticles were able to self‐assemble on oil/water interface to stabilize Pickering emulsion of hexadecane in the pH range from 8 to 12. The droplet diameter was finely tuned from 17 to 5 µm by increasing the ASIS particle levels from 0.13 to 12 wt % based on the mass of the ASIS aqueous dispersions. With toluene as a coalescing aid, the capsules with a coherent and nonporous shell were obtained with the dispersed phase volume percentage as high as 50%. The toluene treated capsules were so mechanically strong to survive the utrasonic treatment. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46700.