Wormlike Micelles Research Articles

From nonionic to zwitterionic: Novel CO2-responsive zwitterionic wormlike micelles based on zwitterionic surfactant and bola-type asymmetric diamine

CO2 enhanced oil recovery (CO2-EOR) is one of the CO2 utilization methods which can also geo-sequestrate greenhouse gases. Due to the weak adsorption on rock surface and excellent viscoelasticity performance, CO2-responsive zwitterionic wormlike micelles (WLMs) has been recognized as a promising method to control CO2 channeling. A novel CO2 responsive zwitterionic WLMs was developed by blending N-octadecyl-N,N-dimethyl-3-ammonio-2-hydroxy-1-propane-sulfonate (OHSB), N,N,2,2-tetramethyl-1,3-propanediamine (TADPA) and sodium salicylate (NaSal). The responsive behaviors induced by varying agents (CO2 and HCl) are systematically studied by rheology tests and cryo-TEM measurements. The molecular structures of products are confirmed by 1H and 13C NMR. Moreover, the responsive mechanism is discussed in detail. The OHSB/NaSal/TADPA system shows morphological transformations between spherical micelles (a good flowing capacity) and WLMs (conducive to plugging) before and after purging CO2. The viscoelasticity and molecular structure of the system with CO2 bubbling is different from that with HCl titration, because TADPA molecules can react with CO2 to form a novel zwitterionic product: NH+(CH3)2-CH2-C(CH3)2-CH2-NHCO2− (TAH+DPACO2−, 78.95 %–83.52 %). This work provides a new strategy for the design of CO2-responsive zwitterionic WLMs and their applications in CO2 utilization schemes, including clean fracturing, mobility control, and CO2 foam flooding, etc.

Gas channeling control with an in-situ smart surfactant gel during water-alternating-CO2 enhanced oil recovery

Undesirable gas channeling always occurs along the high-permeability layers in heterogeneous oil reservoirs during water-alternating-CO2 (WAG) flooding, and conventional polymer gels used for blocking the “channeling” paths usually suffer from either low injectivity or poor gelation control. Herein, we for the first time developed an in-situ high-pressure CO2-triggered gel system based on a smart surfactant, N-erucamidopropyl-N,N-dimethylamine (UC22AMPM), which was introduced into the aqueous slugs to control gas channeling in WAG processes. The water-like, low-viscosity UC22AMPM brine solution can be thickened by high-pressure CO2 owing to the formation of wormlike micelles (WLMs), as well as their growth and shear-induced structure buildup under shear flow. The thickening power can be further potentiated by the generation of denser WLMs resulting from either surfactant concentration augmentation or a certain range of heating, and can be impaired via pressurization above the critical pressure of CO2 because of its soaring solvent power. Core flooding tests using heterogeneous cores demonstrated that gas channeling was alleviated by plugging of high-capacity channels due to the in-situ gelation of UC22AMPM slugs upon their reaction with the pre- or post-injected CO2 slugs under shear flow, thereupon driving chase fluids into unrecovered low-permeability areas and producing an 8.0% higher oil recovery factor than the conventional WAG mode. This smart surfactant enabled high injectivity and satisfactory gelation control, attributable to low initial viscosity and the combined properties of one component and CO2-triggered gelation, respectively. This work could provide a guide towards designing gels for reducing CO2 spillover and reinforcing the CO2 sequestration effect during CO2 enhanced oil recovery processes.

Saturated C22-tailed cationic surfactant in concentrated brine: Structural evolution of wormlike micelles and rheological properties

Saturated C22-tailed ultra-long-chain imparts cationic surfactant stable chemical structure and strong hydrophobic interaction that favors the generation of wormlike micelles in brine. Such viscoelastic wormlike micellar fluid is expected to exhibit excellent salt-resistance and temperature-resistance. In this work, the self-assembled microstructures and microscopic flow properties of docosyl(trimethyl)azanium chloride (DCTAC) NaCl solutions were systematically investigated by means of cryogenic transmission electron microscopy (cryo-TEM), rheo-small angle neutron scattering (rheo-SANS), steady-state and dynamic rheology. It is found that DCTAC forms long, linear or branched, flexible or stiff wormlike micelles depending on NaCl concentration. The increase in salt content simultaneously promotes the growth of worm length and the formation of branches. While the worm chain elongation plays a dominant role in mid-range of NaCl concentrations, the branching formation acts as a leading role in supper high NaCl concentrations, which results in rheological properties experiencing a significant increase followed by a certain decrease upon increasing NaCl content up to ∼ 20 wt%. Moreover, DCTAC shows much better thickening power than corresponding homologue surfactants bearing shorter hydrophobic tail in brine, and DCTAC solution also shows much better temperature-resistance than them. These findings are helpful to understand salt effect on cationic surfactant self-assemble behavior, and the relationship between microstructure and solution macroscopical properties.

Cellulose nanocrystals enhanced viscoelasticity and temperature-resistance of rosin-based wormlike micelles: Inducing the formation of hydrogels

Wormlike micelles are attractive soft materials, their further combinations with nanoparticles providing a novel kind of functional materials in various applications. Using rosin as the starting materials, a biobased surfactant (CMPA2Na) was synthesized. Its structure was characterized using 1H NMR, FT-IR and MS. Viscoelastic wormlike micelles were prepared using CMPA2Na with cetyltrimethylammonium bromide (CTAB). Wormlike micellar system enchanced by cellulose nanocrystals (CNCs) was further constructed. The viscoelasticity, microstructure and interaction mechanism of the CMPA2Na/CTAB/CNCs system were comprhesively investigated using FT-IR, rheology and Cryo-TEM. The viscoelasticity monotonously increased with increasing addition amount of CNCs. And the viscoelastic solutions transformed into hydrogels as the addition amount of CNCs was larger than 0.5 %. Unexpectedly, a dramatical increase of 67 times in viscosity and 10 times in elasticity were obtained, surpassing the reported wormlike micelles combined with nanoparticles. In addition, the wormlike micelles enhanced with CNCs could maintain the excellent viscoelasticity under high temperature. The network of the wormlike micelles was prominently strengthened by the strong hydrogen bonds and electrostatic interactions between the wormlike micelles and CNCs. The study provided a biobased wormlike micelle modified by nanoparticles with high viscoelasticity and excellent temperature-resistance, facilitating the applications of biomass resources in the petroleum industry.

Dilution Driven Self-assembly and Re-entrant Phase Transition in Molecular Hydrogels

TX-100 molecular hydrogels exhibited re-entrant melt-gel-sol phase transition driven solely by dilution, which sequentially altered the self-assembly of the micellar formations and their population was investigated through the monitoring of the physical parameters namely, solution viscosity, particle size histogram, ergodicity, and gel rigidity modulus. This phenomenon was noticed at 20°C in the TX-100 concentration region of 0.2 to 1.2 M much above the critical micellar concentration of 0.22 mM. The particle size histograms revealed the presence of spherical micelles (size »3 nm) in the solution ([TX-100] < 0.5 M) which formed entangled wormlike cylindrical micelles (apparent hydrodynamic radius » 50 nm) when (0.5 M< [TX-100] < 0.9 M) giving rise to a gel-like structure. Further increase in the TX-100 concentration increased the propensity of these wormlike cylindrical micelles that got randomly distributed creating a dense melt phase. Interestingly, we observed transition solely driven by dilution which defined complete re-entrant behavior at room temperature. These molecular gels could be created by dilution of the melt or concentration of the sol unlike in the polymer gels. Remarkably, this hitherto little known unique phenomenon was exhibited by a simple system of non-ionic surfactant solution. Thus, we have a hydration reversible gel at our disposal which has a special place in soft matter arena.

Effect of self-assembly gel crosslinking property and the wetting characteristics of coal under different acid solution

In view of the serious dust pollution in coal mines, the self-assembly gels that can uniformly distribute acid are investigated. The effect of acid type and concentration of the self-assembly gel on the viscosification and wettability in coal, as well as the internal mechanism for the changes are revealed. The results show that the formed micelles of the inorganic acid self-assembly gels are compact and thick, and the high potential enhances the interaction force inside the micelles. In the organic acid environment, it is not conducive to assemble the surfactant molecules, to be specific, the wormlike micelles are sparse and short, but has a better wettability and the minimum surface tension of 12.50 mN/M. In the inorganic acid environment, the wettability is poor, however, it shows a strong adsorption on the coal, and imposes the greatest influence on -OH group in coals. • The viscosification behavior of self-assembly gel in different acid solutions were found. • The wettability of self-assembly gel in different acid solutions were found. • The internal mechanism in viscosification and wetting were obtained.

Synergistic interaction of α-olefin sodium sulfonate/cocamidopropyl betaine surfactant mixtures and preparation of wormlike micelles

The unique structure and macro-rheological properties make worm-like micelles an important basic system for surfactant applications, which are widely used in many fields and have received extensive attention from researchers. In this paper, α-olefin sodium sulfonate (AOS) and cocamidopropyl betaine (CAPB) were mixed in aqueous solution to prepare viscoelastic worm-like micelles, which can be observed by cryogenic-transmission electron microscopy (cryo-TEM). It was found that the concentration of AOS and temperature have a greater impact on the formation and rheological behavior of worm-like micelles. The typical characteristics of wormlike micelles were shown in the range of AOS concentration from 0.7 wt% to 1.7 wt%; when the temperature was too high, the worm-like micelles were destroyed. In addition, the surface tension, foaming property and wettability of AOS/CAPB mixed solutions with different ratios were studied. The two show excellent synergistic effect, in which electrostatic interaction is the decisive factor, which can provide basic data for practical applications. This work further enriches the basic theoretical research on the preparation of worm-like micelles from anionic-zwitterionic surfactant systems.

Micelle-Derived Palladium Nanoparticles for Suzuki–Miyaura Coupling Reactions in Water at Room Temperature

Despite the wide utility of colloidal palladium (Pd) nanoparticle (NP)-catalyzed Suzuki–Miyaura cross-coupling reactions in laboratory and industrial synthesis, the easy construction of colloidal Pd NPs and the detailed role of surfactants remain the focus of attention. Here, we present a simple and sustainable strategy to construct a nanoreactor by connecting micelles with Pd NPs. The strategy enables us to employ a pH-induced morphological transition of sugar-based surfactant aggregates, such as worm-like, spherical, and tubular micelles, to investigate the solubilization of organic substrates. Pd NPs are mainly synthesized by the reduction of phenylboronic acid, further stabilized by the sugar-based surfactant micelles. A kinetic model is established, and the apparent activation energy of this reaction in aqueous micellar solutions is determined to be 46.7 kJ/mol. Notably, the recycled aqueous reaction mixture containing the micelles and Pd NPs can be reused.

On the startup behavior of wormlike micellar networks: The effect of different salts bound to the same surfactant molecule

We report on shear startup data for two wormlike micellar solutions, differing only in concentration and type of two binding aromatic sodium salts. The surfactant molecule is cetylpiridinium chloride at a fixed concentration (100 mM). Sodium salicylate (NaSal) and diclofenac sodium (Diclo) are used as binding salts at concentrations 68 mM NaSal and 52 mM Diclo such that both systems are fully entangled and their linear viscoelastic response is essentially identical. Both systems show the linear response typical of a wormlike micellar solution, with terminal behavior at low frequencies, a well-defined moduli crossover, and a plateau modulus. In the nonlinear regime, however, the behavior of the two systems is totally different, suggesting that the molecular structure difference of the salts and their binding activity to the surfactant molecule are both crucial to determine the fast flow behavior. The NaSal solution shows a very complex rheological response, with strain hardening and very sharp stress peaks, whereas the solution containing Diclo behaves much like ordinary linear polymers, exhibiting pronounced overshoots as well as moderate undershoots in the transient shear viscosity, before approaching the steady state. This polymerlike behavior has also been proved by successfully comparing data with predictions of a constitutive equation recently adopted for both entangled polymers and linear wormlike micelles. As far as NaSal is concerned, a phenomenological model based on rubber network theory is developed, which describes the flow singularities. A physical interpretation of the different behavior in the nonlinear regime is also suggested.

Physicochemical characterization of green sodium oleate-based formulations. Part 3. Molecular and collective dynamics in rodlike and wormlike micelles by proton nuclear magnetic resonance relaxation

HypothesisSodium oleate (NaOL) self-aggregates in water forming rodlike micelles with different length depending on NaOL concentration; when KCl is added wormlike micelles form, which entangle giving rise to a viscoelastic dispersion. It is expected that aggregates with different size and shape exhibit different internal and overall molecular motions and collective dynamics. ExperimentsTwo low viscosity NaOL/water and two viscoelastic NaOL/KCl/water formulations with different NaOL concentration (0.23 and 0.43 M) were investigated by 1H fast field cycling NMR relaxometry over broad temperature and Larmor frequency ranges, after a first screening by 1H and 13C NMR spectroscopy at high frequency. FindingsThe analysis of the collected data indicated that fast conformational isomerization and rotation of NaOL about its long molecular axis and lateral diffusion of NaOL around the axis of the cylindrical aggregates are slightly affected by the aggregate shape and length. On the other hand, fluctuations of the local order director are quite different in the fluid and viscoelastic systems, reflecting the shape and size of the aggregates. Quantitative information was obtained on activation energy for fast internal and overall motions, correlation times and activation energy for lateral diffusion, and coherence length for collective order fluctuations.

Effect of scission on alignment of nonionic surfactant micelles under shear flow.

We investigate the alignment of wormlike micelles under shear flow with dissipative particle dynamics simulations of nonionic surfactant solutions. To reveal the effect of micellar scission on alignment, we evaluate the shear-rate dependence of the mean orientation angle and the average lifetime of micelles for fixed aggregation numbers. Our numerical results demonstrate the presence of two distinct shear-rate regimes of micellar alignment. In the low shear-rate regime, where flow-induced scission does not occur, wormlike micelles align more in the flow direction with the shear rate. In contrast, flow-induced scission suppresses micellar alignment in the high shear-rate regime. In addition, comparing the alignment of wormlike micelles with that of polymers without scission, we find that the mean orientation angle of wormlike micelles is larger than that of polymers when flow-induced scission occurs. This comparison confirms that flow-induced scission yields the unique behavior of micellar alignment. Furthermore, we demonstrate that flow-induced scission suppresses micellar alignment for fixed aggregation numbers by reducing the effective longest relaxation time of micelles.

Extracting microscopic insight from transient dielectric measurements during large amplitude oscillatory shear.

Probing the transient microstructure of soft matter far from equilibrium is an ongoing challenge to understanding material processing. In this work, we investigate inverse worm-like micelles undergoing large amplitude oscillatory shear using time-resolved dielectric spectroscopy. By controlling the Weissenburg number, we compare the non-linear microstructure response of branched and unbranched worm-like micelles and isolate distinct elastic effects that manifest near flow reversal. We validate our dielectric measurements with small angle neutron scattering and employ sequence of physical processes to disentangle the elastic and viscous contributions of the stress.

3D printable, thermo-responsive, self-healing, graphene oxide containing self-assembled hydrogels formed from block copolymer wormlike micelles.

Graphene oxide (GO) containing block copolymer nanocomposite hydrogels formed from poly(glycerol monomethacrylate-block-hydroxypropyl methacrylate) (PGMA-PHPMA) wormlike micelles were prepared by either mixing GO and copolymer at low temperature or via in situ reversible addition-fragmentation chain-transfer (RAFT) polymerisation-induced self-assembly (PISA) of HPMA in the presence of a PGMA macromolecular chain-transfer agent and GO flakes. Hydrogels containing 15-25% w/w copolymer and 0 and 8% w/w GO, based on copolymer, were investigated and the maximum gel strength measured was ∼33 kPa for a 25% w/w copolymer gel prepared by in situ polymerisation and containing 2% w/w GO based on copolymer. This gel strength represents a fifteen-fold increase over the same copolymer gel without the addition of GO. The nanocomposite gels were found to recover efficiently after the application of high shear, with up to 98% healing efficiency within seconds. These gels are also 3D printable, self-healing, adhesive and temperature responsive on cooling and re-heating. The observed properties were both GO and copolymer concentration dependent, and tensile testing demonstrated that the nanocomposite gels had higher moduli, elongation at break and toughness than gels prepared without GO.

Toughening of epoxy thermosets by self-assembled nanostructures of amphiphilic comb-like random copolymers.

Amphiphilic comb-like random copolymers synthesized from poly(ethylene glycol) methyl ether methacrylate (PEGMMA) and stearyl methacrylate (SMA) with PEGMMA contents ranging between 30 wt% and 25 wt% were demonstrated to self-assemble into various well-defined nanostructures, including spherical micelles, wormlike micelles, and vesicle-like nanodomains, in anhydride-cured epoxy thermosets. In addition, the polymer blends of the comb-like random copolymer and poly(stearyl methacrylate) were prepared and incorporated into epoxy thermosets to form irregularly shaped nanodomains. Our research findings indicate that both the comb-like random copolymers and polymer blends are suitable as toughening modifiers for epoxy. When added at a concentration of 5 wt%, both types of modifiers lead to substantial improvements in the tensile toughness (>289%) and fracture toughness of epoxy thermosets, with minor reductions in their elastic modulus (<16%) and glass transition temperature (<6.1 °C). The fracture toughness evaluated in terms of the critical stress intensity factor (KIC) and the strain energy release rate (GIC) increased by more than 67% and 131% for the modified epoxy thermosets containing comb-like random copolymers.

Computational and experimental studies on the micellar morphology and emission mechanisms of AIE and H-bonding fluorescent composites.

In this work, we use density functional theory (DFT) calculated competitive hydrogen bonds and dissipative particle dynamics (DPD) simulated micellar structural information to uncover the CO2-expanded liquid (CXL)-aided self-assembled structure and emission mechanisms of the self-assembled fluorescent composites (SAFCs). Herein, the SAFCs are formed through the self assembly between diblock copolymer polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) blend and the dye molecule 4-(9-(2-(4-hydroxyphenyl)ethynyl)-7,10-diphenylfluoranthen-8-yl)phenol (4) in CO2-expanded toluene at 313.2 K and varied pressures. Firstly, from DPD simulation, we have demonstrated that the addition of CO2 to toluene favors both the expansion of the solvophobic P4VP phase and contraction of solvophilic PS chains, which facilitates the continuous morphological transitions of SAFCs from spherical micelles (3.0 MPa) through wormlike plus spherical micelles (4.0-4.8 MPa) to large vesicles (6.0-6.5 MPa) with pressure rise. Secondly, the DFT calculated bonding energies and IR spectra of the competitive hydrogen bonds help us to clarify the major type of hydrogen bonds determining the fluorescence (FL) performance of the SAFCs. Furthermore, we have revealed the SAFC emission mechanism via the pressure-tunable changes in the aggregation degrees and amount of hydrogen bonds involving 4 and P4VP chains. This work provides a good understanding for the morphology-property control of the self-assembled polymer composites in both microscopic and mesoscopic scales.

Abrupt changes in sedimentation velocity of a sphere falling through a wormlike micelle solution

Abrupt changes in sedimentation velocity of a sphere falling through a wormlike micelle solution

SANS contrast matching for the unambiguous localization of anionic dye in cationic surfactant micelles.

Contrast variation in small-angle neutron scattering (SANS) was successfully applied to localize the anionic azo dye Blue in co-assemblies with the cationic surfactant dodecyltrimethylammoniumbromide (DTAB). For this purpose, the scattering contrast between DTAB and the aqueous solvent was eliminated by SANS contrast matching, leaving only the scattering signal from Blue to be detected. Results obtained by contrast matching were confirmed by NOESY NMR-spectroscopy, showing that Blue interacts with the positively charged DTAB head groups and with up to the 4th neighbouring methylene group of the DTAB C12-alkyl chain. Its localization in the outer layer of the Blue-DTAB co-assembly explains the uniaxial growth of spheroidal DTAB micelles to wormlike micelles with increasing [Blue] : [DTAB] ratio from 0 : 1 to 1 : 3. This is in line with the concept of the packing parameter for amphiphilic substances.

Probing water mobility in confining channels of reverse wormlike micelles.

Reverse wormlike micelles are a potential template for chemical reactions in confined environments. Here, we use time-domain NMR to demonstrate the solvent effect on the mobility of water molecules. The higher the cohesive energy of alkanes, the lower the water mobility, and the less viscous the solution.

Universal Character of Breaking of Wormlike Surfactant Micelles by Additives of Different Hydrophobicity.

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.

A pH-triggered reinforcement of transient network of wormlike micelles by halloysite nanotubes of different charge

Soft viscoelastic nanocomposites based on entangled linear wormlike micelles of cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride and aluminosilicate clay halloysite nanotubes with a surface charge triggered by pH were prepared and studied by rheometry, ξ-potential measurements, thermogravimetric analysis, and cryo-TEM. It was shown that the nanotubes induce an increase of viscosity, which can be attributed to their incorporation into the network of entangled wormlike surfactant micelles via the attachment of micellar endcaps to the surfactant double layer on the surface of the nanotubes. The junctions between the micelles and the nanotubes were visualized by cryo-TEM. The soft nanocomposites demonstrate peculiar flow curves with two shear thinning regions and a plateau between them. The two slopes were attributed to the orientation of the nanotubes (at lower shear rates) and then of the micellar worms (at higher shear rates) along the direction of flow. The intermediate viscosity plateau may represent a stable flow when all nanotubes are oriented, while the micellar worms are not. The nanocomposite system was shown to be pH responsive. Its viscosity increases by 30 times with increasing pH from 4 to 9, which was explained by increasing surface charge of the nanotubes favoring the interaction with oppositely charged WLMs. Such soft materials with easily triggered rheological properties are very promising for various applications.