Modern concepts regarding wormlike micelles of surfactants as polymer-like objects that undergo reversible scission and recombination in solution are presented in the current review. The...

We report a new facile method for the synthesis of prolate cobalt ferrite nanoparticles without additional stabilizers, which involves a co-precipitation reaction of Fe³⁺ and Co²⁺ ions in a static magnetic field. The magnetic field is demonstrated to be a key factor for the 1D growth of cobalt ferrite nanocrystals in the synthesis. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy are applied to characterize the morphology and structure of the obtained nanoparticles. According to TEM, they represent nanorods with a mean length of 25 nm and a diameter of 3.4 nm that have a monocrystalline structure with characteristic plane spacing of 2.9 Å. XRD and Raman spectroscopy confirm the spinel CoFe₂O₄ structure of the nanorods. After aging, the synthesized nanorods exhibit maximum saturation magnetization and coercivity equal to 30 emu/g and 0.3 kOe, respectively. Thus, the suggested method is a simple and “green” way to prepare CoFe₂O₄ nanorods with high aspect ratios and pronounced magnetic properties, which are important for various practical applications, including biomedicine, energy storage, and the preparation of anisotropic magnetic nanocomposites.

Plant-derived nanocellulose particles, such as cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs), are becoming increasingly popular for a wide range of applications. In particular, when they are employed as rheology modifiers and/or fillers, a choice between CNFs and CNCs is often not obvious. Here, we present the results of a comparative study on the rheological properties of suspensions and gels of carboxymethylated CNFs and CNCs with the same surface chemistry, surface density of charged groups, and thickness. We demonstrate that, at the same weight concentration, CNF suspensions have much higher viscosity and storage modulus, which is due to their longer length providing many entanglements. However, when comparing at the same nanoparticle concentration relative to C*, the situation is reversed: viscosity and storage modulus of CNCs appear to be much higher. This may be due in particular to the higher rigidity and intrinsic strength of highly crystalline CNCs. The gel points for CNF and CNC suspensions (without crosslinker) were compared for the first time. It was found that in the case of CNFs, the gel point occurs at a 3.5-fold lower concentration compared to that of CNCs. Hydrogels were also obtained by crosslinking negatively charged nanocellulose particles of both types by divalent calcium cations. For the first time, the thermodynamic parameters of the crosslinking of carboxymethylated CNFs by calcium ions were determined. Isothermal titration calorimetry data revealed that, for both CNFs and CNCs, crosslinking is endothermic and driven by increasing entropy, which is most likely due to the release of water molecules surrounding the interacting nanoparticles and Ca²⁺ ions. The addition of CaCl₂ to suspensions of nanocellulose particles leads to an increase in the storage modulus; the increase being much more significant for CNCs. Physically crosslinked hydrogels of both CNFs and CNCs can be reversibly destroyed by increasing the shear rate and then quickly recover up to 85% of their original viscosity when the shear rate decreases. The recovery time for CFC networks is only 6 s, which is much shorter than that of CNC networks. This property is promising for various applications, where nanocellulose suspensions are subjected to high shear forces (e.g., mixing, stirring, extrusion, injection, coating) and then need to regain their original properties when at rest.

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 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.

Rheological experiments and measurements of particle settling velocity under static conditions were conducted for two types of polyacrylamide (PAA-based) fluids. The flow behavior of the viscoelastic fluids is described by a simplified, three-parameter model that integrates a constant viscosity at low shear rates with a power-law viscosity dependency at higher shear rates. The estimated dependencies of the rheological parameters and particle settling velocity on PAA concentration align with the classical power-law scaling for semi-dilute polymer solutions. The identified scaling offers valuable insight for optimizing the chemical composition of fracturing fluids, thereby improving the efficiency of hydraulic fracturing technology. By applying the lubrication approximation to the Navier–Stokes equations, a set of equations for the suspension flow in a vertical plane channel, characterized by the three-parameter rheology model, was derived. In typical fracturing conditions, the conventional power-law viscosity model used in current fracturing simulators significantly overestimates the gap-averaged apparent fluid viscosity compared to the proposed model. The novel model of the suspension flow aims to enhance the accuracy of proppant transport models applied in hydraulic fracturing simulators. Based on the three-parameter rheology model, a new model of particle settling in the studied PAA-based fluids is developed. It is based on smart Stokes' law, where viscosity is calculated according to either the plateau or power-law region, depending on the self-induced shear rate. The new model more accurately approximates experimentally determined settling velocity of proppant under static conditions across a broad range of PAA concentrations than existing models.