Cryo-electron tomography study of the evolution of wormlike micelles to saturated networks and perforated vesicles.

HYPOTHESIS: The formation of micellar aggregates and the changes in their morphology are crucial for numerous practical applications of surfactants. However, a proper structural characterization of complicated micellar nanostructures remains a challenge. This paper demonstrates the advances of cryo-electron tomography (cryo-ET) in revealing the structural characteristics that accompany the evolution of surfactant aggregates. EXPERIMENTS: By using cryo-ET in combination with cryo-transmission electron microscopy (cryo-TEM), small-angle neutron scattering (SANS), and rheometry, studies were carried out on a model system composed of zwitterionic and nonionic surfactants. In this system, the molecular packing parameter was increased gradually by increasing the molar fraction of nonionic surfactant. FINDINGS: A series of structural transformations was observed: linear wormlike micelles (WLMs) â†’ branched WLMs â†’ saturated network of multiconnected WLMs â†’ perforated vesicles (stomatosomes). The transformations occur through an increase in the number of branches at the expense of cylindrical subchains and semispherical endcaps. Exponential distribution of subchains length was confirmed experimentally for multiconnected saturated networks. The stomatosomes were formed when the length of subchains becomes much shorter than the persistence length, causing the three-dimensional (3D) structure to transform into a two-dimensional (2D) membrane. This work identifies the mechanism of the structural changes, which can be further used to design various surfactant self-assemblies.

Hybrid Polymer-Surfactant Wormlike Micelles for Concurrent Use for Oil Recovery and Drag Reduction.

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.

Salt-Induced Transformations of Hybrid Micelles Formed by Anionic Surfactant and Poly(4-vinylpyridine).

Salt-induced structural transformation of charged hybrid surfactant/polymer micelles formed by potassium oleate and poly(4-vinylpyridine) was investigated by cryo-TEM, SANS with contrast variation, DLS, and 2D NOESY. Cryo-TEM data show, that at small salt concentration beads-on-string aggregates on polymer chains are formed. KCl induces the transformation of those aggregates into rods, which is due to the screening of the electrostatic repulsion between similarly charged beads by added salt. In a certain range of salt concentration, the beads-on-string aggregates coexist with the rodlike ones. In the presence of polymer, the sphere-to-rod transition occurs at higher salt concentration than in pure surfactant system indicating that hydrophobic polymer favors the spherical packing of potassium oleate molecules. The size of micelles was estimated by DLS. The rods that are formed in the hybrid system are much shorter than those in polymer-free surfactant solution suggesting the stabilization of the semi-spherical endcaps of the rods by embedded polymer. 2D NOESY data evidence that in the spherical aggregates the polymer penetrates deep into the core, whereas in tighter packed rodlike aggregates it is located mainly at core/corona interface. According to SANS with contrast variation, inside the rodlike aggregates the polymer adopts more compact coil conformation than in the beads-on-string aggregates. Such adaptive self-assembled polymer-surfactant nanoparticles with water-insoluble polymer are very promising for various applications including drag reduction at transportation of fluids.

Modeling Micellar Growth and Branching in Mixtures of Zwitterionic with Ionic Surfactants.

Zwitterionic surfactants are widely applied as drag-reducing or thickening agents because their aggregation patterns may drastically change in response to variations of the system composition or external stimuli, which provides controllable viscoelasticity. For predicting aggregation behavior of surfactant mixtures, classical molecular thermodynamic models have been widely used. Particularly, the results of modeling have been reported for zwitterionic/ionic surfactant mixtures. However, for solutions containing a zwitterionic surfactant, no molecular thermodynamic model has been proposed for a micellar branch. In this work we extend the classical molecular thermodynamic aggregation model to describe aggregation in the aqueous mixtures that contain a zwitterionic and an ionic surfactant. We derive analytical expressions (1) for the contribution of dipoles to the electrostatic term of the standard free energy of aggregation into micellar branches and (2) for the dipolar contribution to the persistence length of wormlike micelles. The dependence of micellar branching on the surfactant concentration is taken into account by including the population of micellar branches in the material balance equations. This model is applied to predict aggregation equilibrium in aqueous salt solutions of betaine (oleoylamidopropyl-N,N-dimethylbetaine) mixed with sodium dodecyl sulfate (SDS) and the longer tail sodium n-alkyl sulfates. We discuss the predicted properties of the aggregates and micellar networks and compare our predictions with available experimental data.

Antiseptic Polymer-Surfactant Complexes with Long-Lasting Activity against SARS-CoV-2.

Antiseptic polymer gel-surfactant complexes were prepared by incorporating the low-molecular-weight cationic disinfectant cetylpyridinium chloride into the oppositely charged, slightly cross-linked polymer matrices. Three types of polymers were used: copolymers of acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate; copolymers of acrylamide and sodium methacrylate; copolymers of vinylpyrrolidone and sodium methacrylate. It was shown that the rate of the release of the cationic disinfectant from the oppositely charged polymer gels could be tuned in a fairly broad range by varying the concentration of the disinfectant, the degree of swelling, and degree of cross-linking of the gel and the content/type of anionic repeat units in the polymer matrix. Polymer-surfactant complexes were demonstrated to reduce SARS-CoV-2 titer by seven orders of magnitude in as little as 5 s. The complexes retained strong virucidal activity against SARS-CoV-2 for at least one week.

Cationic Surfactants as Disinfectants against SARS-CoV-2.

The virucidal activity of a series of cationic surfactants differing in the length and number of hydrophobic tails (at the same hydrophilic head) and the structure of the hydrophilic head (at the same length of the hydrophobic n-alkyl tail) was compared. It was shown that an increase in the length and number of hydrophobic tails, as well as the presence of a benzene ring in the surfactant molecule, enhance the virucidal activity of the surfactant against SARS-CoV-2. This may be due to the more pronounced ability of such surfactants to penetrate and destroy the phospholipid membrane of the virus. Among the cationic surfactants studied, didodecyldimethylammonium bromide was shown to be the most efficient as a disinfectant, its 50% effective concentration (EC50) being equal to 0.016 mM. Two surfactants (didodecyldimethylammonium bromide and benzalkonium chloride) can deactivate SARS-CoV-2 in as little as 5 s.

Green nanocomposite gels based on binary network of sodium alginate and percolating halloysite clay nanotubes for 3D printing.

Alginate hydrogels with embedded rigid percolating network of halloysite clay nanotubes were evaluated as a novel ink for 3D printing. Hydrophilic alginate macromolecules adsorbing on halloysite stabilize the network of the nanotubes and form their own network of interlaced polymer chains. The effect of halloysite content on the structure and properties of the hydrogels was studied by rheometry, thermogravimetric analysis, FTIR-spectroscopy, dynamic light scattering, transmission electron microscopy, and 3D cryo-electron microscopy. Hydrogels demonstrate a very pronounced shear-thinning at extrusion and rather quick viscosity recovery after extrusion assigned to rapid rearrangement of the network structure promoted by mobile alginate chains. Even at low volume fractions (up to 0.054) the nanotubes reinforce the hydrogel increasing its storage modulus up to 650 Pa and inducing the appearance of yield stress. These properties make the alginate/halloysite hydrogels promising for the application in 3D printing for fabrication of green and sustainable nanocomposite materials made from natural components.

Printable Alginate Hydrogels with Embedded Network of Halloysite Nanotubes: Effect of Polymer Cross-Linking on Rheological Properties and Microstructure.

Rapidly growing 3D printing of hydrogels requires network materials which combine enhanced mechanical properties and printability. One of the most promising approaches to strengthen the hydrogels consists of the incorporation of inorganic fillers. In this paper, the rheological properties important for 3D printability were studied for nanocomposite hydrogels based on a rigid network of percolating halloysite nanotubes embedded in a soft alginate network cross-linked by calcium ions. Particular attention was paid to the effect of polymer cross-linking on these properties. It was revealed that the system possessed a pronounced shear-thinning behavior accompanied by a viscosity drop of 4-5 orders of magnitude. The polymer cross-links enhanced the shear-thinning properties and accelerated the viscosity recovery at rest so that the system could regain 96% of viscosity in only 18 s. Increasing the cross-linking of the soft network also enhanced the storage modulus of the nanocomposite system by up to 2 kPa. Through SAXS data, it was shown that at cross-linking, the junction zones consisting of fragments of two laterally aligned polymer chains were formed, which should have provided additional strength to the hydrogel. At the same time, the cross-linking of the soft network only slightly affected the yield stress, which seemed to be mainly determined by the rigid percolation network of nanotubes and reached 327 Pa. These properties make the alginate/halloysite hydrogels very promising for 3D printing, in particular, for biomedical purposes taking into account the natural origin, low toxicity, and good biocompatibility of both components.

Unmodified Silica Nanoparticles Enhance Mechanical Properties and Welding Ability of Epoxy Thermosets with Tunable Vitrimer Matrix.

Epoxy/silica thermosets with tunable matrix (vitrimers) were prepared by thermal curing of diglycidyl ether of bisphenol A (DGEBA) in the presence of a hardener-4-methylhexahydrophthalic anhydride (MHHPA), a transesterification catalyst-zinc acetylacetonate (ZAA), and 10-15 nm spherical silica nanoparticles. The properties of the resulting material were studied by tensile testing, thermomechanical and dynamic mechanical analysis. It is shown that at room temperature the introduction of 5-10 wt% of silica nanoparticles in the vitrimer matrix strengthens the material leading to the increase of the elastic modulus by 44% and the tensile stress by 25%. Simultaneously, nanoparticles enhance the dimensional stability of the material since they reduce the coefficient of thermal expansion. At the same time, the transesterification catalyst provides the thermoset with the welding ability at heating, when the chain exchange reactions are accelerated. For the first time, it was shown that the silica nanoparticles strengthen welding joints in vitrimers, which is extremely important, since it allows to repeatedly use products made of thermosets and heal defects in them. Such materials hold great promise for use in durable protective coatings, adhesives, sealants and many other applications.

Growth of wormlike micelles of surfactant induced by embedded polymer: role of polymer chain length.

Incorporation of polymer chains into wormlike surfactant micelles, which find a large range of applications, offers the opportunity to modify their structure and properties. In this paper, using spectroscopic, scattering and rheological techniques and computer simulations, we study the incorporation of poly(4-vinylpyridine) of two different molecular weights (MWs) into entangled networks of wormlike surfactant micelles of potassium oleate. Using NMR-spectroscopy we show that, independent of its MW, the polymer incorporates into the core-corona interface of the surfactant micelles. According to SANS data, the polymer does not alter the micelle structure or the micelle radius, but diminishes the packing density of the surfactant. At the same time, rheology reveals a stark difference between the surfactant networks with embedded polymers of different MWs. Networks with the higher-MW polymer possess larger viscosity and a longer relaxation time, which we attribute to the larger length of the hybrid micelles. Moreover, we demonstrate that in an intermediate concentration range the higher-MW polymer is able to link neighbouring surfactant micelles together, which has never been previously observed. However, with a further increase in polymer content the micelles become smaller due to the high breaking susceptibility of the boundaries of polymer-containing sections, leading to the stabilization of micellar end-caps by the embedded macromolecules. This process is more prominent in the case of the shorter polymer. Our finding that an increased MW of macromolecules permits the formation of longer hybrid micelles and enhances their rheological properties is of obvious importance for the fundamental understanding of polymer-surfactant interactions and the development of new industrial formulations based on hybrid polymer-wormlike surfactant micelles.

Chitosan composites with Ag nanoparticles formed in carbonic acid solutions.

Chitosan-based hydrogels with stabilized Ag nanoparticles were synthesized in the aqueous solutions of carbonic acid, i.e. water saturated with CO2 under pressure in hundreds of bars. Such a medium is biocompatible and self-neutralizing at decompression. The influence of various parameters, such as chitosan molecular weight, molar ratio of chitosan to silver, additional stabilization of gels by genipin as a cross-linking agent, on the structure of the chitosan/Ag composites was investigated using transmission electron microscopy, scanning electron microscopy, X-ray diffraction analysis, rheology measurements. The distributions of chitosan-stabilized Ag nanoparticles in a chitosan matrix turned out to be uniform, their average size was in the range of 2-5 nm. The higher degree of Ag nanoparticles reduction could be achieved using self-eliminating gaseous hydrogen as an additional reducing agent being admixed to CO2. This was consistently confirmed by different research methods (TEM, XRDA, UV-vis spectroscopy).

Soft magnetic nanocomposites based on adaptive matrix of wormlike surfactant micelles.

The paper describes a new type of soft magnetic nanocomposite (SMN) based on a transient network of wormlike surfactant micelles with embedded oppositely charged submicron particles of magnetite acting as cross-linking agents. We study the change of the rheological properties of the SMNs with different contents of particles in response to magnetic field. We show that even at low field strengths the system acquires solid-like behavior, which can be attributed to the aggregation of particles into chain-like/column structures. A solid-like behavior appears at a rather small volume fraction of particles (0.002-0.04) indicating weak restrictions imposed by the matrix to the reorganization of particles under magnetic field, which can be due to the self-assembled structure of the micellar network. In the oscillatory rheological measurements, SMNs show a linear viscoelastic response in an unusually wide region of values of strain, magnetic field strength and content of particles, which is caused by the viscoelastic contribution of the micellar network. Upon gradual increase of magnetic field strength H, the dynamic moduli G' and G'' demonstrate slow growth followed by a sharp rise with a scaling law H 3.0 and reach a plateau at 0.15 T. The highest values of the storage modulus G' in SMNs are close to those in magnetorheological fluids with liquid Newtonian carrier, where particles move freely and the G' value is defined by the interactions of magnetized particles and chain-like/columns structures. SMNs have a yield stress, which grows with the increase of magnetic field strength and finally levels off just at the same magnetic field strength at which the G' and G'' values reach a plateau indicating the saturation of the particles magnetization. The concentration dependencies of the elastic modulus and yield stress suggest the transition from chain-like to columnar structures of the particles. The new SMNs possessing the features of both magnetic fluids and magnetic gels have promising potential in a wide range of applications requiring responsiveness to magnetic field.

Impact of Salt Co- and Counterions on Rheological Properties and Structure of Wormlike Micellar Solutions.

Rheological properties of aqueous solutions of long-tailed cationic surfactant erucyl bis-(hydroxyethyl)methylammonium chloride (EHAC) were examined as a function of concentration Cs of different inorganic salts (KCl, CaCl2, and LaCl3) at a fixed surfactant concentration of 0.6 wt %. The structural evolution of micelles was followed by small-angle neutron scattering and cryogenic transmission electron microscopy. It was observed that, upon addition of salt, the zero-shear viscosity η0 of semidilute surfactant solutions goes through a maximum by passing the following three regimes: η0 ∼ Cs10 (regime I), η0 ∼ Cs3.5 (regime II), and η0 ∼ Cs-2 (regime III). In regime I, the micelles grow in length; in regime II, the linear growth of micelles proceeds simultaneously with their branching; and in regime III, the branching becomes dominating. With increase in the salt valence, the viscosity curves shift to a lower salt content, indicating that these salts are more effective in inducing micellar elongation and branching, as they contain a larger amount of anionic species Cl- screening the repulsion between cationic surfactant heads. Diverse roles of salt co- and counterions (i.e., salt ions that are similar and oppositely charged with respect to surfactant head groups) at different salt concentrations were demonstrated. It was shown that at low salt concentrations corresponding to the rising branch of the viscosity curve (regimes I and II), salt counterions (Cl-) fully determine the rheological behavior of the system. At high salt concentrations, when the electrostatic repulsions between micelles and salt co-ions are essentially screened, the co-ions start affecting the rheological properties. Under these conditions, monovalent co-ions (K+) provide much lower viscosity of surfactant solutions than the multivalent ones (Ca2+, La3+), which is consistent with theoretical predictions that suggest the penetration of K+ inside the micellar corona increasing the charge of the micelles and therefore hindering their growth.

Rheological Behavior of Oil-Swollen Wormlike Surfactant Micelles.

We study the rheological properties of wormlike micellar aqueous solutions of an anionic surfactant potassium oleate containing solubilized 1-phenyldodecane. We show that upon increasing the amount of absorbed hydrocarbon the rheological behavior of semidilute micellar solutions changes drastically, showing a sequence of different regimes: (i) a "fast-breaking" entangled regime, when very long micellar chains form a network; (ii) an "unbreakable" entangled regime, when the shortening of the micelles leads to the decrease of their reptation time up to the values close to the breaking time; (iii) an unentangled regime (for the first time evidenced for wormlike micelles), where the micelles are so short that they cannot interlace. Within the entangled regime, an unusual rheological behavior has been discovered, probably characterized by the dominant role of end or bond interchange reactions or "breathing" modes, which leads to a novel hypothesis that hydrocarbon is distributed nonuniformly along the micellar length, thus increasing the probability of micellar breakage at certain points.

Viscoelasticity of smart fluids based on wormlike surfactant micelles and oppositely charged magnetic particles.

Novel viscoelastic smart suspensions based on cationic wormlike micelles (WLMs) of erucylbis(hydroxyethyl)methylammonium chloride and oppositely charged submicron magnetite particles in the presence of added low molecular weight salt were prepared and investigated. The suspensions demonstrate remarkable stability against sedimentation, which can be due to the incorporation of particles into the network of entangled WLMs by linking to energetically unfavorable micellar end-caps. Added particles enhance significantly the viscosity, the plateau modulus, and the relaxation time of the system, acting as additional multifunctional physical cross-links in the micellar network. The increase of plateau modulus stops when the concentration of particles reaches ca. 1.5 wt %, indicating that all micellar end-caps available in the system are linked to the particles. Further addition of particles may lead just to the redistribution of micellar ends between the particles without creation of new elastically active chains. The increase of rheological characteristics by added particles is more pronounced in suspensions with a smaller content of low molecular weight salt KCl when the WLMs are shorter in length and therefore contain a larger amount of end-caps responsible for the interaction with the particles. Magnetite particles not only enhance the rheological characteristics but also impart magnetoresponsive properties to the suspension. Upon application of magnetic field, the liquidlike system transforms into a solidlike one, demonstrating a constant value of storage modulus in all frequency range and the appearance of yield stress, which is due to the formation of field-aligned chainlike aggregates of particles opposing the flow. A combination of responsive properties inherent to both the matrix and the particles makes these smart fluids very competitive with other magnetic soft matter materials for various applications.

How a viscoelastic solution of wormlike micelles transforms into a microemulsion upon absorption of hydrocarbon: new insight.

In this article, we investigate the effect of hydrocarbon addition on the rheological properties and structure of wormlike micellar solutions of potassium oleate. We show that a viscoelastic solution of entangled micellar chains is extremely responsive to hydrocarbons-the addition of only 0.5 wt % n-dodecane results in a drastic drop in viscosity by up to 5 orders of magnitude, which is due to the complete disruption of micelles and the formation of microemulsion droplets. We study the whole range of the transition of wormlike micelles into microemulsion droplets and discover that it can be divided into three regions: (i) in the first region, the solutions retain a high viscosity (∼10-350 Pa·s), the micelles are entangled but their length is reduced by the solubilization of hydrocarbons; (ii) in the second region, the system transitions to the unentangled regime and the viscosity sharply decreases as a result of further micelle shortening and the appearance of microemulsion droplets; (iii) in the third region, the viscosity is low (∼0.001 Pa·s) and only microemulsion droplets remain in the solution. The experimental studies were accompanied by theoretical considerations, which allowed us to reveal for the first time that (i) one of the leading mechanisms of micelle shortening is the preferential accumulation of the solubilized hydrocarbon in the spherical end caps of wormlike micelles, which makes the end caps thermodynamically more favorable; (ii) the onset of the sharp drop in viscosity is correlated with the crossover from the entangled to unentangled regime of the wormlike micellar solution taking place upon the shortening of micellar chains; and (iii) in the unentangled regime short cylindrical micelles coexist with microemulsion droplets.

Dominant role of wormlike micelles in temperature-responsive viscoelastic properties of their mixtures with polymeric chains.

Temperature effects on the rheological properties of viscoelastic solutions containing entangled wormlike micelles of potassium oleate and hydrophobically modified polyacrylamide were studied in a wide range of polymer concentrations. A very pronounced drop of viscosity by four orders of magnitude was observed at heating from 20 to 78 °C both in the presence and in the absence of polymer indicating that the wormlike micelles are mainly responsible for this effect. The highly thermosensitive behavior was attributed to the shortening of micellar chains induced by heating. Although the decrease in viscosity is almost the same for both surfactant and surfactant/polymer systems, the absolute values of the viscosity in the presence of polymer are by few orders of magnitude higher, which is due to the formation of a common network of entangled polymer and micellar chains. As a result, the added polymer allows one to get highly temperature responsive system that keeps viscoelastic properties in a much wider range of temperatures, which makes it very promising for various practical applications.

Self-assembled networks highly responsive to hydrocarbons.

Rheological studies were performed with aqueous salt solutions of anionic surfactant potassium oleate and its mixtures with hydrophobically modified polyacrylamide. Semidilute solutions of the surfactant in the presence of salt (KCl) demonstrate viscoelastic properties due to the formation of a transient network of entangled wormlike micelles. These systems are highly responsive to hydrocarbons: the addition of n-heptane or n-dodecane reduces the viscosity of solutions by up to 4 to 5 orders of magnitude, thus inducing the transition of a gellike system to a fluid one. It is the transformation of cylindrical surfactant micelles into spherical ones upon absorption of hydrocarbon that disrupts the network. The addition of a small amount (0.5 wt %) of associating polymer leads to up to a 5000-fold increase in the zero-shear viscosity and enhances the susceptibility to hydrocarbons. SANS data show that independently of the presence of polymer the radius of wormlike micelles is roughly equal to the length of a surfactant molecule, whereas the radius of spheres formed upon the absorption of hydrocarbon is 2-2.5-fold higher. A possible structure of the spherical micelles is discussed.