Search Results (27)

CO₂-responsive worm-like micelles (WLMs) are considered promising for applications in smart materials, enhanced oil recovery, and drug delivery because of their reversible and tunable properties. This study presents a novel system of CO₂-responsive WLMs, which is constructed using a double-tailed surfactant (DTS). When exposed to CO₂, the DTS molecules undergo protonation, resulting in the formation of ultra-long-chain cationic surfactants that self-assemble into worm-like micelles. The zero-shear viscosity of the DTS–CO₂ solution achieves approximately 300,000 mPa·s, which is 300,000 times higher than that of pure water. In contrast, the DTS–air solution exhibits a viscosity of only 2 mPa·s. The system retains a viscosity above 100,000 mPa·s across a temperature range of 25–120 °C under a CO₂ atmosphere. Moreover, it demonstrates reversible transitions between high- and low-viscosity states without any loss of responsiveness, even after multiple cycles. The critical overlap concentration of the DTS–CO₂ micellar system is determined to be 80 mM. This research offers valuable insights into the development of CO₂-responsive surfactants, highlighting their potential for designing advanced functional materials. Full article

To increase the interaction between a catalyst and large pollutant molecules in industrial wastewater, this study employed worm-like micelles created by surfactants as soft templates for synthesizing structured hydrotalcites with high specific surface areas and diverse pore sizes. Following this, the integration of these hydrotalcites with AgBr yielded supported, structured hydrotalcites that exhibited enhanced redox properties. Characterization techniques, including XRD, FT-IR, SEM, and EDS, validated the successful incorporation of AgBr into the structured hydrotalcites. Furthermore, UV–Vis DRS and electrochemical analyses revealed that the integration with AgBr narrowed the band gap of the hydrotalcites, thereby expanding their light absorption range. At 25 °C with an initial solution pH of 5 and an adsorbent dosage of 0.5 g/L, the efficiency of methyl orange removal by the composite material reached 97.69% after 60 min of dark adsorption. EPR and reactive species-trapping experiments revealed that the high-efficiency degradation of methyl orange was primarily attributed to the combined action of highly active h⁺, •O₂₋, and ¹O₂ species. Full article

Dual networks formed by entangled polymer chains and wormlike surfactant micelles have attracted increasing interest in their application as thickeners in various fields since they combine the advantages of both polymer- and surfactant-based fluids. In particular, such polymer-surfactant mixtures are of great interest as novel hydraulic fracturing fluids with enhanced properties. In this study, we demonstrated the effect of the chemical composition of an uncharged polymer poly(vinyl alcohol) (PVA) and pH on the rheological properties and structure of its mixtures with a cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride already exploited in fracturing operations. Using a combination of several complementary techniques (rheometry, cryo-transmission electron microscopy, small-angle neutron scattering, and nuclear magnetic resonance spectroscopy), we showed that a small number of residual acetate groups (2–12.7 mol%) in PVA could significantly reduce the viscosity of the mixed system. This result was attributed to the incorporation of acetate groups in the corona of the micellar aggregates, decreasing the molecular packing parameter and thereby inducing the shortening of worm-like micelles. When these groups are removed by hydrolysis at a pH higher than 7, viscosity increases by five orders of magnitude due to the growth of worm-like micelles in length. The findings of this study create pathways for the development of dual semi-interpenetrating polymer-micellar networks, which are highly desired by the petroleum industry. Full article

We report on the effect of a hydrocarbon (n-dodecane) on the rheological properties and shapes of the hybrid wormlike micelles (WLMs) of a surfactant potassium oleate with an embedded polymer poly(4-vinylpyridine). With and without hydrocarbon solutions, the hybrid micelles exhibit the same values of viscosity at shear rates typical for hydraulic fracturing (HF) tests, as solutions of polymer-free WLMs. Therefore, similar to WLMs of surfactants, they could be applied as thickeners in HF fluids without breakers. At the same time, in the presence of n-dodecane, the hybrid micelles have much higher drag-reducing efficiency compared to microemulsions formed in polymer-free systems since they form “beads-on-string” structures according to results obtained using cryo-transmission electron microscopy (cryo-TEM), dynamic-light scattering (DLS), and small-angle X-ray scattering (SAXS). Consequently, they could also act as drag-reducing agents in the pipeline transport of recovered oil. Such a unique multi-functional additive to a fracturing fluid, which permits its concurrent use in oil production and oil transportation, has not been proposed before. Full article

The structures and properties of hydrophobic association polymers can be controlled using micelles. In this work, we synthesize a reactive hydrophobic surfactant monomer, KS-3, from oleic acid, N,N-dimethylpropylenediamine, and allyl chloride. A strong synergistic effect between KS-3 and cocamidopropyl betaine in aqueous solution enhances the hydrophilic dispersibility of KS-3, thereby transforming spherical micelles into cylindrical micelles. KS-3 was grafted onto a polyacrylamide chain via aqueous free-radical polymerization to obtain RES, a hydrophobic association polymer. Structural analysis revealed that the RES polymers assembled in wormlike micelles were more tightly arranged than those assembled in spherical micelles, resulting in a compact network structure in water, smooth surface, and high thermal stability. Rheological tests revealed that the synthesized polymers with wormlike and spherical micelles exhibited shear-thinning properties along with different structural strengths and viscoelasticities. Therefore, controlling the micellar state can effectively regulate the polymer properties. The polymers obtained through wormlike micelle polymerization have potential applications in fields with high demands, such as drug release, water purification, and oilfield development. Full article

In this paper, a series of porous hierarchical Mg/Al layered double hydroxides (named as LDH, TTAC-MgAl-LDH, CTAC-MgAl-LDH, and OTAC-MgAl-LDH) was synthesized by a simple green hydrothermal method using wormlike micelles formed by salicylic acid and surfactants with different carbon chain lengths (0, 14, 16, and 18) as soft templates. BET, XRD, FTIR, TG, and SEM characterizations were carried out in order to investigate the structure and properties of the prepared materials. The results showed that the porous hierarchical CTAC-MgAl-LDH had a large specific surface area and multiple pore size distributions which could effectively increase the reaction area and allow better absorption capability. Benefiting from the unique architecture, CTAC-MgAl-LDH exhibited a large adsorption capacity for sulfonated lignite (231.70 mg/g) at 25 °C and a pH of 7, which outperformed the traditional LDH (86.05 mg/g), TTAC-MgAl-LDH (108.15 mg/g), and OTAC-MgAl-LDH (110.51 mg/g). The adsorption process of sulfonated lignite followed the pseudo-second-order kinetics model and conformed the Freundlich isotherm model with spontaneous heat absorption, which revealed that electrostatic adsorption and ion exchange were the main mechanisms of action for the adsorption. In addition, CTAC-MgAl-LDH showed a satisfactory long-time stability and its adsorption capacities were still as high as 198.64 mg/g after two adsorption cycles. Full article

pH-responsive viscoelastic fluids are often achieved by adding hydrotropes into surfactant solutions. However, the use of metal salts to prepare pH-responsive viscoelastic fluids has been less documented. Herein, a pH-responsive viscoelastic fluid was developed by blending an ultra-long-chain tertiary amine, N-erucamidopropyl-N, N-dimethylamine (UC₂₂AMPM), with metal salts (i.e., AlCl₃, CrCl₃, and FeCl₃). The effects of the surfactant/metal salt mixing ratio and the type of metal ions on the viscoelasticity and phase behavior of fluids were systematically examined by appearance observation and rheometry. To elucidate the role of metal ions, the rheological properties between AlCl₃− and HCl−UC₂₂AMPM systems were compared. Results showed the above metal salt evoked the low-viscosity UC₂₂AMPM dispersions to form viscoelastic solutions. Similar to HCl, AlCl₃ could also protonate the UC₂₂AMPM into a cationic surfactant, forming wormlike micelles (WLMs). Notably, much stronger viscoelastic behavior was evidenced in the UC₂₂AMPM−AlCl₃ systems because the Al³⁺ as metal chelators coordinated with WLMs, promoting the increment of viscosity. By tuning the pH, the macroscopic appearance of the UC₂₂AMPM−AlCl₃ system switched between transparent solutions and milky dispersion, concomitant with a viscosity variation of one order of magnitude. Importantly, the UC₂₂AMPM−AlCl₃ systems showed a constant viscosity of 40 mPa·s at 80 °C and 170 s⁻¹ for 120 min, indicative of good heat and shear resistances. The metal-containing viscoelastic fluids are expected to be good candidates for high-temperature reservoir hydraulic fracturing. Full article

Coarse-grained molecular dynamics simulations that incorporate explicit water-mediated hydrophilic/hydrophobic interactions are employed to track spatiotemporal evolution of diblock copolymer aggregation in initially homogeneous solutions. A phase portrait of the observed morphologies and their quantitative geometric features such as aggregation numbers, packing parameters, and radial distribution functions of solvent/monomers are presented. Energetic and entropic measures relevant to self-assembly such as specific solvent accessible surface area (SASA) and probability distribution functions (pdfs) of segmental stretch of copolymer chains are analyzed. The simulations qualitatively capture experimentally observed morphological diversity in diblock copolymer solutions. Topologically simpler structures predicted include spherical micelles, vesicles (polymersomes), lamellae (bilayers), linear wormlike micelles, and tori. More complex morphologies observed for larger chain lengths and nearly symmetric copolymer compositions include branched wormlike micelles with Y-shaped junctions and cylindrical micelle networks. For larger concentrations, vesicle strands, held together by hydrogen bonds, and “giant” composite aggregates that consist of lamellar, mixed hydrophobic/hydrophilic regions and percolating water cores are predicted. All structures are dynamic and exhibit diffuse domain boundaries. Morphology transitions across topologically simpler structures can be rationalized based on specific SASA measurements. PDFs of segmental stretch within vesicular assemblies appear to follow a log-normal distribution conducive for maximizing configuration entropy. Full article

Wormlike surfactant micelles are widely used in various applications including fracturing technology in oil industry, template synthesis of different nanoobjects, micellar copolymerization of hydrophilic and hydrophobic monomers, and so forth. Most of those applications suggest the solubilization of different additives in the micelles. The present paper is aimed at the comparative study of the effect of the solubilization of hydrophobic (n-decane and 1-phenylhexane) and hydrophilic (N-isopropylacrylamide and acrylamide) substances on the rheological properties and structure of the micelles using several complementary techniques including rheometry, small angle neutron scattering, dynamic light scattering, and diffusion ordered NMR spectroscopy. For these studies, mixed micelles of potassium oleate and n-octyltrimethylammonium bromide containing the excess of either anionic or cationic surfactants were used. It was shown that hydrophobic additives are completely solubilized inside the micelles being localized deep in the core (n-decane, 1-phenylhexane) or near the core/corona interface (1-phenylhexane). At the same time, only a small fraction of hydrophilic additives (14% of N-isopropylacrylamide and 4% of acrylamide) penetrate the micelles being localized at the corona area. Despite different localization of the additives inside the micelles, all of them induce the breaking of wormlike micelles with the formation of either ellipsoidal microemulsion droplets (in the case of hydrophobic additives) or ellipsoidal surfactant micelles (in the case of hydrophilic additives). The breaking of micelles results in the drop of viscosity of the solution up to water value. The main result of this paper consists in the observation of the fact that for all the additives under study, the dependences of the viscosity on the volume fraction of additive lie on the same master curve being shifted along the volume fraction axis by a certain factor depending on the hydrophobicity of the added species. Those data are quite useful for various applications of wormlike surfactant micelles suggesting the solubilization of different additives inside them. Full article

Wormlike micelles, which are linear aggregates created by the self-assembly of surfactants, may entangle to form dynamic three-dimensional network-like structures, endowing solutions with considerable macroscopic viscoelasticity. Recently, a pressing need has arisen to research a novel stimuli-responsive worm-like micelle that is efficient and environmentally friendly. CO₂ is an inexpensive, abundant, non-toxic, biocompatible, and non-combustible gas, and it is anticipated that CO₂ may serve as the trigger for stimuli-responsive worm-like micelles. In this paper, the formation of CO₂-switchable pseudo-tetrameric surfactants, which subsequently self-assemble into CO₂-switched wormlike micelles, is accomplished using a simple mixing of two commercial reagents, such as stearic acids and cyclen. The rheological characteristics switched by the use of CO₂ are cycled between that of a low-viscosity (1.2 mPa·s) fluid and a viscoelastic fluid (worm-like micelles, 3000 mPa·s). This article expands the field of study on stimuli-responsive worm-like micelles. Full article

In recent years, there has been increasing interest in daily-use chemical products providing a pleasant scent. The added fragrance molecules may induce microstructural transitions of surfactant aggregates, which further affect the physical and chemical properties of the products. Here, the effects of four types of aromatic alcohols (cinnamyl alcohol, phenyl ethanol, phenyl methanol and anisyl alcohol) on cetyltrimethylammonium bromide (CTAB)/KBr aggregates were studied. The combined results from rheology, dynamic light scattering, and transmission electron microscopy measurements showed that cinnamyl alcohol induced significant micellar growth, while increases in micellar growth were less obvious for the other aromatic alcohols. The changes in the interfacial molarities of water, aromatic alcohol, and bromide ions during such transitions were studied using the chemical trapping method. Transitions resulting from added cinnamyl alcohol were accompanied by significant declines in interfacial water and bromide ion molarities, and a rise in interfacial alcohol molarity. The marked decrease in interfacial water molarity was not observed in previous studies of the octanol induced formation of wormlike micelles and vesicles, indicating that a different mechanism was presented in the current system. Nuclear magnetic resonance investigation showed that π–π stacking between cinnamyl alcohols, but not cation–π interactions between alcohols and CTAB headgroups, facilitated the tight packing of alcohol molecules in CTAB aggregates and the repulsion of water from the interfacial region. The current study may provide a theoretical basis for the morphological regulation of surfactant aggregates in the presence of additives. Full article

There are economic and technical challenges to overcome when increasing resource recovery from low permeability reservoirs. For such reservoirs, the hydraulic fracturing plan with the development of clean and less expensive fracturing fluid plays a vital aspect in meeting the energy supply chain. Numerous recent published studies have indicated that research on worm-like micelles (WLMs) based on viscoelastic surfactant (VES) fluid has progressed substantially. This study looks at the development of CO₂-sensitive viscoelastic fracturing fluid (CO₂-SVFF), its applications, benefits, limitations, and drawbacks of conventional fracturing fluids. The switchable viscoelasticity of CO₂-SVFF system signifies how reusing of this fluid is attained. Compared to conventional surfactants, the CO₂-SVFF system can be switched to high viscosity (to fracture formation and transporting proppants) and low viscosity (easy removal after causing fracture). The effect of pH, conductivity, temperature, and rheological behaviors of CO₂-SVFFs are also highlighted. Further, the aid of Gemini surfactants and nanoparticles (NPs) with low concentrations in CO₂-SVFF can improve viscoelasticity and extended stability to withstand high shear rates and temperatures during the fracturing process. These studies provide insight into future knowledge that might lead to a more environmentally friendly and successful CO₂-SVFFs in low-permeability reservoirs. Despite the increased application of CO₂-SVFFs, there are still several challenges (i.e., formation with high-temperature range, pressure, and salinity). Full article

Fe₃O₄@ZnO nanocomposites (NCs) were synthesized to improve the stability of the wormlike micelle (WLM) network structure of viscoelastic surfactant (VES) fracturing fluid and were characterized by Fourier transform infrared spectrometry (FT-IR), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). Then, an NC-enhanced viscoelastic surfactant solution as a fracturing fluid (NC-VES) was prepared, and its properties, including settlement stability, interactions between NCs and WLMs, proppant-transporting performance and gel-breaking properties, were systematically studied. More importantly, the influences of the NC concentration, shear rate, temperature and pH level on the stability of NC-VES were systematically investigated. The experimental results show that the NC-VES with a suitable content of NCs (0.1 wt.%) shows superior stability at 95 °C or at a high shear rate. Meanwhile, the NC-VES has an acceptable wide pH stability range of 6–9. In addition, the NC-VES possesses good sand-carrying performance and gel-breaking properties, while the NCs can be easily separated and recycled by applying a magnetic field. The temperature-resistant, stable and environmentally friendly fracturing fluid opens an opportunity for the future hydraulic fracturing of unconventional reservoirs. Full article

The viscoelastic properties and structure parameters have been investigated for aqueous solutions of wormlike micelles of cationic surfactant erucyl bis(hydroxyethyl) methylammonium chloride with long C22 tail in the presence inorganic salt KCl. The salt content has been varied to estimate linear to branched transition conditions due to screening of the electrostatic interaction in the networks. The local cylindrical structure and low electrostatic repulsion was obtained by SANS data. The drastic power law dependencies of rheological properties on surfactant concentrations were obtained at intermediate salt content. Two power law regions of viscosity dependence were detected in semi-dilute solutions related to “unbreakable” and “living” micellar chains. The fast contour length growth with surfactant concentration demonstrated that is in good agreement with theoretical predictions. Full article

Viscoelastic surfactants (VES) are amphiphilic molecules which self-assemble into long polymer-like aggregates—wormlike micelles. Such micellar chains form an entangled network, imparting high viscosity and viscoelasticity to aqueous solutions. VES are currently attracting great attention as the main components of clean hydraulic fracturing fluids used for enhanced oil recovery (EOR). Fracturing fluids consist of proppant particles suspended in a viscoelastic medium. They are pumped into a wellbore under high pressure to create fractures, through which the oil can flow into the well. Polymer gels have been used most often for fracturing operations; however, VES solutions are advantageous as they usually require no breakers other than reservoir hydrocarbons to be cleaned from the well. Many attempts have recently been made to improve the viscoelastic properties, temperature, and salt resistance of VES fluids to make them a cost-effective alternative to polymer gels. This review aims at describing the novel concepts and advancements in the fundamental science of VES-based fracturing fluids reported in the last few years, which have not yet been widely industrially implemented, but are significant for prospective future applications. Recent achievements, reviewed in this paper, include the use of oligomeric surfactants, surfactant mixtures, hybrid nanoparticle/VES, or polymer/VES fluids. The advantages and limitations of the different VES fluids are discussed. The fundamental reasons for the different ways of improvement of VES performance for fracturing are described. Full article