ABSTRACT
A pH-responsive threadlike micellar system was developed by mixing alkyl bis(2-hydroxyethyl)methylammonium chloride (EO12) and trans-o-coumaric acid (tOCA). The rheological response of this system to pH is unusual in that it has viscoelasticity at both high and low pH levels, while it shows water-like behaviors at medium pH. Cryogenic transmission electron microscopy (Cryo-TEM) images confirmed the presence of TLMs at pH 3.5 and pH 9.8. This system also had DR (drag reduction) capability at low and high pH. The unusual rheological and micellar responses of this system to pH are caused by the dual pK(a)'s of tOCA. (1)H NMR and zeta potential results support this hypothesis.
ABSTRACT
A photoresponsive micellar solution is developed as a promising working fluid for district heating/cooling systems (DHCs). It can be reversibly switched between a drag reduction (DR) mode and an efficient heat transfer (EHT) mode by light irradiation. The DR mode is advantageous during fluid transport, and the EHT mode is favored when the fluid passes through heat exchangers. This smart fluid is an aqueous solution of cationic surfactant oleyl bis(2-hydroxyethyl)methyl ammonium chloride (OHAC, 3.4 mM) and the sodium salt of 4-phenylazo benzoic acid (ACA, 2 mM). Initially, ACA is in a trans configuration and the OHAC/ACA solution is viscoelastic and exhibits DR (of up to 80% relative to pure water). At the same time, this solution is not effective for heat transfer. Upon UV irradiation, trans-ACA is converted to cis-ACA, and in turn, the solution is converted to its EHT mode (i.e., it loses its viscoelasticity and DR) but it now has a heat-transfer capability comparable to that of water. Subsequent irradiation with visible light reverts the fluid to its viscoelastic DR mode. The above property changes are connected to photoinduced changes in the nanostructure of the fluid. In the DR mode, the OHAC/trans-ACA molecules assemble into long threadlike micelles that impart viscoelasticity and DR capability to the fluid. Conversely, in the EHT mode the mixture of OHAC and cis-ACA forms much shorter cylindrical micelles that contribute to negligible viscoelasticity and effective heat transfer. These nanostructural changes are confirmed by cryo-transmission electron microscopy (cryo-TEM), and the photoisomerization of trans-ACA and cis-ACA is verified by (1)H NMR.
ABSTRACT
Drag-reducing (DR) surfactant fluids based on threadlike micelles are known to suffer from poor heat-transfer capabilities. Accordingly, the use of these fluids is limited to recirculating systems in which heat exchange is not important. Here, we show for the first time that light-responsive threadlike micelles can offer a potential solution to the above problem. The fluids studied here are composed of the cationic surfactant Ethoquad O/12 PG (EO12) and the sodium salt of trans-ortho-methoxycinnamic acid (OMCA). Initially, these fluids contain numerous threadlike micelles and, in turn, are strongly viscoelastic and effective at reducing drag (up to 75% DR). Upon exposure to UV light, OMCA is photoisomerized from trans to cis. This causes the micelles to shorten considerably, as confirmed by cryo-transmission electron microscopy (cryo-TEM). Because of the absence of long micelles, the UV-irradiated fluid shows lower viscoelasticity and much lower DR properties; however, its heat-transfer properties are considerably superior to the initial fluid. Thus, our study highlights the potential of switching off the DR (and in turn enhancing heat-transfer) at the inlet of a heat exchanger in a recirculating system. While the fluids studied here are not photoreversible, an extension of the above concept would be to subsequently switch on the DR again at the exit of the heat exchanger, thus ensuring an ideal combination of DR and heat-transfer properties.
ABSTRACT
Drag reduction effectiveness of two dilute quaternary ammonium surfactant aqueous solutions with different pairs of mixed aromatic counterions was investigated along with their micellar nanostructures revealed by cryo-TEM imaging, zeta potential, particle size, and (1)H NMR measurements. Certain combinations of aromatic counterion mixtures showed significant synergistic effects. They dramatically improved drag reduction effectiveness relative to either single aromatic counterion. Using mixed aromatic counterions with different sizes and binding abilities, the effective drag reducing temperature range can be significantly expanded and higher shear stress stability can be achieved. The synergistic effects are believed to be induced by increased degree of branching in the surfactant micellar networks as shown by cryo-TEM images.
ABSTRACT
Compared with quaternary ammonium cationic surfactants with saturated alkyl chains, quaternary ammonium cationic surfactants with one double-bond in their alkyl chains, when mixed with appropriate counterions (in certain molar concentration ratios, ξ), can reach much lower effective drag-reduction temperatures, while maintaining the upper drag-reduction temperature limit of the corresponding saturated drag reducing surfactant solutions. No previous study has compared the effects of cis- vs. trans-unsaturated alkyl hydrocarbon tail configurations (oleyl vs. elaidyl) trimethyl ammonium chloride cationic surfactants at different counterion/surfactant concentration ratios on micellar nanostructures, (1)H NMR spectra and on rheological and drag-reduction behavior of their solutions. Since neither pure oleyl (cis-) nor elaidyl (trans-) trimethyl ammonium chloride surfactants are commercially available, they were synthesized and their 5mM solutions with NaSal counterion at concentrations of 5mM, 7.5mM and 12.5mM were studied.
ABSTRACT
Drag-reducing surfactant solutions are very sensitive to shear. Shear can induce nanostructural transitions which affect drag reduction effectiveness and rheological properties. Literature reports on the effects of shear on different micellar solutions are inconsistent. In this paper, the effects of shear on three cationic drag-reducing surfactant solutions each with very different nanostructures and rheological behaviors, Arquad 16-50/sodium salicylate (NaSal) (5 mM/5 mM) (has thread-like micelles, shear-induced structure and large first normal stress (N(1))), Arquad S-50/NaSal (5 mM/12.5 mM) (has branched micelles, no shear-induced structure and first normal stress is about zero) and Arquad 16-50/sodium 3,4-dimethyl-benzoate (5 mM/5 mM) (has vesicles and thread-like micelles, shear-induced structure and high first normal stress (N(1))) are studied by small-angle neutron scattering (SANS), together with their rheological properties, drag reduction behavior and nanostructures by cryogenic-temperature transmission electron microscopy(cryo-TEM). The differences in the rheological behavior and the SANS data of the solutions are explained by the different responses of the nanostructures to shear based on a two-step response to shear.
ABSTRACT
Some quaternary cationic surfactants, when mixed with a counterion, are known to self-assemble into threadlike micelles in water. Such behavior causes drastic changes in rheological properties of even very dilute solutions, allowing them to be used as drag reducing agents (DRA) in turbulent pipe flow circulating systems, such as district cooling/heating systems. Surfactant self-assembly is a physicochemical phenomenon whose character depends on surfactant nature and concentration, nature of the solvent, temperature and type and concentration of counterions. This study investigates drag reduction (DR) and rheological properties of two cationic surfactants, Ethoquad O/12 (oleyl bis(hydroxyethyl)methylammonium chloride) and Ethoquad O/13 (oleyl tris(hydroxyethyl) ammonium acetate), with excess salicylate counterion (NaSal), in mixed solvents containing 0 to 28 wt% ethylene glycol (EG) and water. The addition of EG to the solvent had greater effects on solutions' DR ability, shear viscosity, apparent extensional viscosity and viscoelasticity at 25 degrees C than at approximately 0 degrees C. Cryo-TEM images show threadlike micelle in these systems. DR at low temperatures in solutions containing moderate amount of EG can be utilized in a new approach to energy saving in district cooling systems using EG-water based mixtures as the cooling fluids.
ABSTRACT
The influence of concentration on rheological properties, including shear viscosity, shear instability, transient stress start-up and relaxation, apparent extensional viscosity, viscoelastic behavior, and microstructure by cryo-TEM, were studied with surfactant Ethoquad O/12, commercialized oleyl methyl bishydroxyethyl chloride, with counterion sodium salicylate. Counterion to surfactant molar ratios, xi, were 1.0 and 2.5. Concentrations for the xi=1 series are 5 mM/5 mM, 10 mM/10 mM, 50 mM/50 mM, 100 mM/100 mM, and 200 mM/200 mM (surfactant/counterion); those for the xi=2.5 series are 5 mM/12.5 mM, 10 mM/25 mM, 50 mM/125 mM, 100 mM/250 mM, and 200 mM/500 mM. The experimental results showed complicated rheological behavior with concentration changes. Shear viscosity decreases with increases in concentration for the xi=1 series. At xi=2.5 apparent viscosity increases with concentration above 10 mM. Viscoelasticity of the solutions also decreases with increases in surfactant concentration. At high concentration, a high shear rate is needed to induce viscoelasticity. A high extensional rate induces supermicellar structures. Gelation was observed during shear for the 100 mM/250 mM and 200 mM/500 mM solution in the cone-and-plate geometry. Cryo-TEM results revealed that all of the solutions examined had wormlike network micelle microstructures. Copyright 2001 Academic Press.
