Search Results (15)

Janus nanoparticles (JNPs) extend the concept of amphiphilicity beyond classical molecular surfactants into the nanoscale. Amphiphilic behavior is defined by the presence of hydrophobic and hydrophilic moieties within a single molecular structure. Traditionally, such molecular structures are known as surfactants or amphiphiles and are capable of reducing interfacial tension, adsorbing spontaneously at interfaces, stabilizing emulsions and foams, and forming micelles, bilayers, or vesicles. Recent experimental, theoretical, and computational studies demonstrate that these behaviors are scalable to nanostructured colloids such as JNPs. Amphiphilic JNPs, defined by anisotropic surface chemistry on distinct hemispheres, display interfacial activity driven by directional wetting, variable interfacial immersion depth, and strong interfacial anchoring. They can stabilize liquid/liquid and liquid/gas interfaces, and enable templated or spontaneous self-assembly into supra-structures, such as monolayer sheets, vesicles, capsules, etc., both in bulk and at interfaces. Their behavior mimics the “soft” molecular amphiphiles but also includes additional particularities given by their “hard” structure, as well as contributions from capillary, van der Waals, hydrophobic, and shape-dependent forces. This review focuses on compiling the evidence supporting amphiphilicity as a scalable property, discussing how JNPs function as colloidal amphiphiles and how geometry, polarity contrast, interfacial interactions, and environmental parameters influence their behavior. By comparing surfactant behavior and JNP assembly, this work aims to clarify the transferable principles, the knowledge gap, as well as the emergent properties associated with amphiphilic Janus colloids. Full article

Several traditional methods for producing polymer microparticle adsorbents for metal ions exist, such as bulk polymerization followed by milling and crushing the material to micron-size particles, precipitation from organic solvents, and suspension polymerization utilizing surfactants. Alternative methods that are easily scalable and are environmentally friendly are in high demand. This study employs Pickering Emulsion Polymerization Technology (PEmPTech) to synthesize nanostructured polymer microspheres that incorporate Schiff-base ligands, which can be utilized for metal ion adsorption, and specifically Cu(II) ions. Our innovative approach makes use of nanoparticle-stabilized, surfactant-free emulsions/suspensions, enabling the straightforward production of ligand-bearing microspheres while allowing for the precise modulation of the polymer matrix chemistry to maximize adsorption capacities. Through this method, we demonstrate notable enhancements in Cu(II) ion adsorption, which correlates with both the polarity of the monomers used and the concentration of Schiff-base ligands within the microspheres. Notably, our results offer insights into the structure–activity relationships essential for designing tailored adsorbents. This work provides a scalable method to produce high-performance adsorbents and also contributes to sustainable methodologies by excluding harmful surfactants and solvents. Full article

In this study, chitosan-based surfactants were synthesized by epoxy–amine chemistry to stabilize concentrated O/W emulsions at pH7. Chitosan was first depolymerized by nitrous deamination to obtain chitooligosaccharides (COS) with degrees of polymerization of 10 (DP10) and 20 (DP20). Then, three different epoxidized fatty chains, i.e., octyl/decyl glycidyl ether (C9), hexadecyl glycidyl ether (C16) and epoxidized cardanol (card), were grafted onto the amine groups of chitosan to form six amphiphilic structures. NMR measurements revealed grafting efficiencies ranging from 1 to 30% while HLB values ranged from 13 to 20. The relationships between these surfactant structures and their adsorption properties were investigated by tensiometric measurements, highlighting the need for a short hydrophilic moiety and high grafting efficiency to obtain the best adsorption. Subsequently, concentrated O/W emulsions (66% of oil) at pH7 were produced using COS-based surfactants and the impact of stirring time and speed during the emulsification process was described through rheological, droplet size and microscopy measurements. Finally, emulsions were stored over 2 months in order to study the destabilization phenomenon into the mixture, i.e., coalescence and creaming, by using laser granulometry and Turbiscan. Results demonstrated that stability could be enhanced by increasing emulsion viscosity, reducing droplet size or optimizing the adsorption layer at the O/W interfaces. Full article

Recently, considerable attention has been given to using magnetic nanoparticles (MNPs) for capturing oil from oil-in-water (O/W) emulsions, despite MNPs’ inherent instability and agglomeration. Their stabilization through changing surface chemistry is required to increase dispersivity. In this research, we use cetyltrimethylammonium bromide (CTAB) as a cationic surfactant to increase the positive surface charge of the particles, resulting in a better stability in the aqueous solution because of increased repulsive forces. The functionalized MNPs are characterized using transmission electron microscopy (TEM), zeta potential, and contact angle (CA) measurements. The aim of this study is to investigate the oil separation efficiency (SE) and equilibrium oil adsorption capacity of the synthesized particles, which are determined using gas chromatography analysis. We also study the adsorption behavior using isotherm and kinetic models. The SE values indicate the superior performance of MNP@CTAB for oil adsorption from dodecane-in-water nanoemulsion (SE = 99.80%) compared to the bare MNPs with SE of approximately 57.46%. These findings are attributed to the stronger electrostatic attraction between the MNP@CTAB having high positive charge and negatively charged oil droplets. The adsorption isotherm results using both linear and non-linear regression methods show that the Freundlich isotherm is the best fit to the experimental equilibrium data (with calculated R² > 0.97), verifying a multilayer heterogeneous adsorption. Moreover, the pseudo-first-order kinetic model describes the experimental equilibrium data in a greater congruence (R² = 0.99), suggesting physical adsorption of oil onto MNPs through van der Waals and physical bonding, which is also confirmed through zeta potential measurements. Full article

Emulsions that mix two or more immiscible phases are broadly applied in pharmaceutics, chemistry, and industries. The phase inversion temperature (PIT) method is an emulsifying approach to preparing an emulsion with low energy consumption and cheap equipment. The effects of surfactant characteristics and processes of cooling or heating on the fuel properties of emulsions composed of silicone oil by the emulsifying method, such as mean droplet sizes of the de-ionized water phase, were considered herein. The application of the silicone oil emulsion as engine fuel was first evaluated. The results show that the emulsions added with the polyol surfactant mixture appeared to have a larger mean water-droplet size, a larger number of dispersed water droplets, a wider range of dispersed-water sizes, and lower kinematic viscosity than those with Brij 30 surfactant. Increasing the surfactant concentration of either Tween 20 mixed with Span 80 or Brij 30 surfactant increased kinematic viscosity and the number of dispersed droplets while decreasing mean droplet sizes. After being subjected to fast heating and then fast cooling, the silicone oil emulsion appeared to form many smaller dispersed droplets than those being proceeded with slow cooling. The emulsion of silicone oil was found to have adequate engine fuel properties. Full article

The use of lignin, an abundant phenolic bio-polymer, allows us to transform our fossil-based economy into a sustainable and bio-based economy. The transformation of bulk lignin into colloidal lignin particles (CLPs) with well-defined surface chemistry and morphology is a possible way to cope with the heterogeneity of lignin and use it for material applications. These CLPs can be used as emulsifiers in so-called Pickering emulsions, where solid particles stabilise the emulsion instead of environmentally harmful synthetic surfactants. This work investigates the application of CLPs produced from various bulk lignins as a stabiliser in o/w Pickering emulsions with two different oil phases (solid and liquid state). The CLPs had a primary particle size of 28 to 55 nm. They were successful in stabilising oil-in-water Pickering emulsions with high resistance to coalescence and a strong gel-like network. This enables novel applications for CLPs in the chemical and cosmetic industries, and can replace fossil-based and synthetic ingredients. Full article

Formulation is an ancient concept, although the word has been used only recently. The first formulations made our civilization advance by inventing bronze, steel, and gunpowder; then, it was used in medieval alchemy. When chemistry became a science and with the golden age of organic synthesis, the second formulation period began. This made it possible to create new chemical species and new combinations “à la carte.” However, the research and developments were still carried out by trial and error. Finally, the third period of formulation history began after World War II, when the properties of a system were associated with its ingredients and the way they were assembled or combined. Therefore, the formulation and the systems’ phenomenology were related to the generation of some synergy to obtain a commercial product. Winsor’s formulation studies in the 1950s were enlightening for academy and industries that were studying empirically surfactant-oil-water (SOW) systems. One of its key characteristics was how the interfacial interaction of the adsorbed surfactant with oil and water phases could be equal by varying the physicochemical formulation of the system. Then, Hansen’s solubility parameter in the 1960s helped to reach a further understanding of the affinity of some substances to make them suitable to oil and water phases. In the 1970s, researchers such as Shinoda and Kunieda, and different groups working in Enhanced Oil Recovery (EOR), among them Schechter and Wade’s group at the University of Texas, made formulation become a science by using semiempirical correlations to attain specific characteristics in a system (e.g., low oil-water interfacial tension, formulation of a stable O/W or W/O emulsion, or high-performance solubilization in a bicontinuous microemulsion system at the so-called optimum formulation). Nowadays, over 40 years of studies with the hydrophilic-lipophilic deviation equation (HLD) have made it feasible for formulators to improve products in many different applications using surfactants to attain a target system using HLD in its original or its normalized form, i.e., HLD_N. Thus, it can be said that there is still current progress being made towards an interdisciplinary applied science with numerical guidelines. In the present work, the state-of-the-art of formulation in multiphase systems containing two immiscible phases like oil and water, and therefore systems with heterogeneous or micro-heterogeneous interfaces, is discussed. Surfactants, from simple to complex or polymeric, are generally present in such systems to solve a wide variety of problems in many areas. Some significant cases are presented here as examples dealing with petroleum, foods, pharmaceutics, cosmetics, detergency, and other products occurring as dispersions, emulsions, or foams that we find in our everyday lives. Full article

Nanoscale organofunctional silanes have been developed, tested and successfully applied to protect stone buildings in Europe against climatic effects since the 1860s. The same nanotechnologies can also be used in pavement engineering to create strong chemical bonds between a stabilising agent and granular material. The attachment of the organofunctional silane to a material also changes the surface of the material to become hydrophobic, thereby considerably reducing future chemical weathering. These properties allow naturally available materials to be used in any pavement layer at a low risk. In the built environment, scientists soon determined that the successful use of an organo-silane depends on the type and condition of the stone to be treated. The same principles apply to the implementation of applicable nanotechnologies in pavement engineering. Understanding the basic chemistry, determining the properties of the stabilising agent and the organofunctional modifying agent and the chemical interaction with the primary and secondary minerals of the material are essential for the successful application of these technologies in pavement engineering. This paper explains some basic chemistry, which fundamentally influences engineering outputs that can be achieved using New-age (Nano) Modified Emulsions (NME) stabilising agents with naturally available granular materials in all road pavement layers below the surfacing. Full article

Biodegradable polymeric microparticles are widely used in drug delivery systems with prolonged-release profiles and/or cell microcarriers. Their fabrication via the oil/water emulsion solvent evaporation technique has normally required emulsifiers in the aqueous phase. The present work aims to evaluate the effectiveness of various polysaccharides, such as chitosan, hyaluronic acid, cellulose, arabinogalactan, guar and their derivatives, as an alternative to synthetic surfactants for polylactide microparticle stabilization during their fabrication. Targeted modification of the biopolymer’s chemical structure was also tested as a tool to enhance polysaccharides’ emulsifying ability. The transformation of biomacromolecules into a form of nanoparticle via bottom-up or top-down methods and their subsequent application for microparticle fabrication via the Pickering emulsion solvent evaporation technique was useful as a one-step approach towards the preparation of core/shell microparticles. The effect of polysaccharides’ chemical structure and the form of their application on the polylactide microparticles’ total yield, size distribution and morphology was evaluated. The application of polysaccharides has great potential in terms of the development of green chemistry and the biocompatibility of the formed microparticles, which is especially important in biomedicine application. Full article

Polymerization of high internal phase emulsions (polyHIPEs) is a well-established method for the production of high porosity foams. Researchers are often regulated to using a time-intensive trial and error approach to achieve target pore architectures. In this work, we performed a systematic study to identify the relative effects of common emulsion parameters on pore architecture (mixing speed, surfactant concentration, organic phase viscosity, molecular hydrophobicity). Across different macromer chemistries, the largest magnitude of change in pore size was observed across surfactant concentration (~6 fold, 5–20 wt%), whereas changing mixing speeds (~4 fold, 500–2000 RPM) displayed a reduced effect. Furthermore, it was observed that organic phase viscosity had a marked effect on pore size (~4 fold, 6–170 cP) with no clear trend observed with molecular hydrophobicity in this range (logP = 1.9–4.4). The efficacy of 1,4-butanedithiol as a reactive diluent was demonstrated and provides a means to reduce organic phase viscosity and increase pore size without affecting polymer fraction of the resulting foam. Overall, this systematic study of the microarchitectural effects of these macromers and processing variables provides a framework for the rational design of polyHIPE architectures that can be used to accelerate design and meet application needs across many sectors. Full article

Nanoparticles (NPs) have been proposed for enhanced oil recovery (EOR). The research has demonstrated marvelous effort to realize the mechanisms of nanoparticles EOR. Nevertheless, gaps still exist in terms of understanding the nanoparticles-driven interactions occurring at fluids and fluid–rock interfaces. Surface-active polymers or other surface additive materials (e.g., surfactants) have shown to be effective in aiding the dispersion stability of NPs, stabilizing emulsions, and reducing the trapping or retention of NPs in porous media. These pre-requisites, together with the interfacial chemistry between the NPs and the reservoir and its constituents, can result in an improved sweep efficiency. This paper investigates four types of polymer-coated silica NPs for the recovery of oil from water-wet Berea sandstones. A series of flooding experiments was carried out with NPs dispersed at 0.1 wt.% in seawater in secondary and tertiary oil recovery modes at ambient conditions. The dynamic interactions of fluids, fluid–rock, and the transport behavior of injected fluid in the presence of NPs were, respectively, studied by interfacial tension (IFT), spontaneous imbibition tests, and a differential pressure analysis. Core flooding results showed an increase in oil recovery up to 14.8% with secondary nanofluid injection compared to 39.7% of the original oil in place (OOIP) from the conventional waterflood. In tertiary mode, nanofluids increased oil recovery up to 9.2% of the OOIP. It was found that no single mechanism could account for the EOR effect with the application of nanoparticles. Instead, the mobilization of oil seemed to occur through a combination of reduced oil/water IFT, change in the rock surface roughness and wettability, and microscopic flow diversion due to clogging of the pores. Full article

The most complex components in heavy crude oils tend to form aggregates that constitute the dispersed phase in these fluids, showing the high viscosity values that characterize them. Water-in-oil (W/O) emulsions are affected by the presence and concentration of this phase in crude oil. In this paper, a theoretical study based on computational chemistry was carried out to determine the molecular interaction energies between paraffin–asphaltenes–water and four surfactant molecules to predict their effect in W/O emulsions and the theoretical influence on the pressure drop behavior for fluids that move through porous media. The mathematical model determined a typical behavior of the fluid when the parameters of the system are changed (pore size, particle size, dispersed phase fraction in the fluid, and stratified fluid) and the viscosity model determined that two of the surfactant molecules are suitable for applications in the destabilization of W/O emulsions. Therefore, an experimental study must be set to determine the feasibility of the methodology and mathematical model displayed in this work. Full article

Owing to a decrease in mineral oil resources, it is crucial to develop packaging materials based on renewable resources. Hence, a water vapor-barrier coating is developed as a natural wax-based dispersion. This dispersion should be stable over the storage time. In this study, the physical stability of a wax-based melt dispersion was analyzed (24 h and 21 days after production), and instability phenomena such as agglomeration, coalescence, and flotation were identified. Furthermore, the inter-correlations among the particle size, viscosity of the continuous phase, physical stability, surfactant chemistry, and hydrophilic–lipophilic balance value were characterized. Particle sizes were described by volume/surface mean d_3,2, volume moment mean d_4,3, and number mean d_1,0 diameter, as well as the span of the volume and number distribution. Stability was characterized by the flotation rate, emulsion stability index, and Turbiscan stability index. Coalescence and agglomeration were not observed after the solidification of the wax particles. A significant correlation was observed for the emulsion stability index, with d_3,2, and for flotation rate, with d_1,0, d_4,3, and viscosity as well, with d_1,0, d_3,2. Surfactants with hydrophilic–lipophilic balance values of 11–13.5 seem to be the most suitable for stabilizing candelilla wax-in-water suspensions. Particles were smaller, and wax suspensions were better stabilized using Tween 20 and Span 20, compared with Tween 80 and Span 80. Full article

Water management is becoming increasingly challenging and several technologies, including membrane distillation (MD) are emerging. This technology is less affected by salinity compared to reverse osmosis and is able to treat brines up to saturation. The focus of MD research recently shifted from seawater desalination to industrial applications out of the scope of reverse osmosis. In many of these applications, surfactants or oil traces are present in the feed stream, lowering the surface tension and increasing the risk for membrane wetting. In this study, the technological boundaries of MD in the presence of surfactants are investigated using surface tension, contact angle and liquid entry pressure measurements together with lab-scale MD experiments to predict the wetting resistance of different membranes. Synthetic NaCl solutions mixed with sodium dodecyl sulfate (SDS) were used as feed solution. The limiting surfactant concentration was found to be dependent on the surface chemistry of the membrane, and increased with increasing hydrophobicity and oleophobicity. Additionally, a hexadecane/SDS emulsion was prepared with a composition simulating produced water, a waste stream in the oil and gas sector. When hexadecane is present in the emulsion, oleophobic membranes are able to resist wetting, whereas polytetrafluoretheen (PTFE) is gradually wetted by the feed liquid. Full article

Several researchers have proposed that mobility control mechanisms can positively contribute to oil recovery in the case of emulsions generated in Enhanced-Oil Recovery (EOR) operations. Chemical EOR techniques that use alkaline components or/and surfactants are known to produce undesirable emulsions that create operational problems and are difficult to break. Other water-based methods have been less studied in this sense. EOR processes such as polymer flooding and LoSal^TM injection require adjustments of water chemistry, mainly by lowering the ionic strength of the solution or by decreasing hardness. The decreased ionic strength of EOR solutions can give rise to more stable water-in-oil emulsions, which are speculated to improve mobility ratio between the injectant and the displaced oil. The first step toward understanding the connection between the emulsions and EOR mechanisms is to show that EOR conditions, such as salinity and hardness requirements, among others, are conducive to stabilizing emulsions. In order to do this, adequate stability proxies are required. This paper reviews commonly used emulsion stability proxies and explains the advantages and disadvantage of methods reviewed. This paper also reviews aqueous-based EOR processes with focus on heavy oil to contextualize in-situ emulsion stabilization conditions. This context sets the basis for comparison of emulsion stability proxies. Full article