Surfactant systems for drag reduction: Physico-chemical properties and rheological behaviour

The first part of the work presents an overview of the physical chemistry of surfactants which in aqueous solutions reduce the frictional loss in turbulent pipe flow. It is shown that these surfactants form rodlike micelles above a characteristic concentraionc _t. The experimental evidence for rodlike micelles are reviewed and the prerequisites that the surfactant system must fulfill in order to form rodlike micelles are given. It is demonstrated by electrical conductivity measurements that the critical concentration for the formation of spherical micelles shows little temperature dependence, whereasc _t increases very rapidly with temperature. The length of the rodlike micelles, as determined by electric birefringence, decreases with rising temperature and increases with rising surfactant concentration. The dynamic processes in these micellar systems at rest and the influence of additives such as electrolytes and short chain alcohols are discussed.In the second part, the rheological behaviour of these surfactant solutions under laminar and turbulent flow conditions are investigated. Viscosity measurements in laminar pipe and Couette flow show the build-up of a shear induced viscoelastic state, SIS, from normal Newtonian fluid flow. A complete alignment of the rodlike micelles in the flow direction in the SIS was verified by flow birefringence. In turbulent pipe flow, drag reduction occurs in these surfactant systems as soon as rodlike micelles are present in the solution. The extent and type of drag reduction, i.e. the shape of the friction factor versus Reynolds number curve, depends directly on the size, number and surface charge of the rodlike micelles. The friction factor curve of each surfactant investigated changes in the same characteristic way as a function of temperature. For each surfactant, independent of concentration, an upper absolute temperature limit,T _L, for drag reduction exists which is caused by the micellar dynamics.T _L is influenced by the hydrophobic chain length and the counter-ion of the surfactant system. A first attempt is made to explain the drag reduction of surfactants by combining the results of these rheological measurements with the physico-chemical properties of the micellar systems.     

Viscoelastic properties of polymerlike reverse micelles

A dramatic increase in the viscosity of reverse micellar solutions of lecithin in a variety of organic solvents of up to a factor of 10⁶ upon the addition of a small amount of water can be observed. The formation of viscoelastic solutions can be explained by a water-induced aggregation of lecithin molecules into flexible cylindrical reverse micelles and the subsequent formation of a transient network of entangled micelles. The viscoelastic properties of these solutions are characterized as a function of water content and temperature for different organic solvents by means of dynamic shear viscosity measurements. The results are interpreted by making analogies to the behavior of semidilute polymer solutions and living polymers.Dedicated to Prof. Dr. J. Meissner on the occasion of his 60th birthday.     

Rheological characteristics of trimethylolethane hydrate slurry treated with drag-reducing surfactants

Rheological characteristics of trimethylolethane (TME) clathrate–hydrate slurry treated with drag-reducing surfactants were investigated. Friction coefficients and apparent viscosities were measured when the concentration of TME and its hydrate fraction treated with and without drag-reducing surfactants were changed in several steps. From the results, it is found that the surfactant addition causes effective drag reduction in a pipe flow when the hydrate fraction becomes high, while effective drag reduction disappears in the cases of low hydrate fraction. The results of viscosity measurements indicate that the TME molecules disturb the formation of shear-induced structures (SIS) causing drag reduction phenomena. To investigate this interaction between TME and surfactant micelles, the effect of TME concentration on viscosity and relaxation time of solutions was discussed. From this, it was found out that there exists a critical concentration of TME on the formation of SIS and that it becomes larger as shear rate increases. Thus, we conclude that this interaction between TME and micellar structures causes less drag reduction for the cases of low hydrate fraction, while the drag reduction appears in cases of high hydrate fraction because TME concentration in liquid phase becomes small.     

Characterization of micellar structure dynamics for a drag-reducing surfactant solution under shear: normal stress studies and flow geometry effects

Some surfactant solutions have been observed to exhibit a strong drag reduction behavior in turbulent flow. This effect is generally believed to result from the formation of large cylindrical micelles or micellar structures. To characterize and understand better these fluids, we have studied the transient rheological properties of an efficient drag-reducing aqueous solution: tris (2-hydroxyethyl) tallowalkyl ammonium acetate (TTAA) with added sodium salicylate (NaSal) as counter ion. For a 5/5 mM equimolar TTAA/NaSal solution, there is no measurable first normal stress difference (N ₁) immediately after the inception of shear, but N ₁ begins to increase after a well-defined induction time — presumably as shear-induced structures (SIS) are formed — and it finally reaches a fluctuating plateau region where its average value is two orders of magnitude larger than that of the shear stress. The SIS buildup times obtained by first normal stress measurements were approximately inversely proportional to the shear rate, which is consistent with a kinetic process during which individual micelles are incorporated through shear into large micellar structures. The SIS buildup after a strong preshear and the relaxation processes after flow cessation were also studied and quantified with first normal stress difference measurements. The SIS buildup times and final state were also found to be highly dependent on flow geometry. With an increase in gap between parallel plates, for example, the SIS buildup times decreased, whereas the plateau viscosity increased.     

An experimental study on the flow behavior of micellar solutions

At higher concentration levels, the inner structure of micellar solutions cannot be detected directly by optical means. Nevertheless, the flow behavior of the micellar solutions reflects their micellar structures. Hence, in this study the material behavior of micellar surfactant solutions was investigated by rheometrical means in steady and oscillatory shear flows. The flow behavior of the solutions was found to be strongly dependent on the concentration of the surfactants. At very low concentrations, the surfactant solution shows Newtonian behavior. With increasing concentration, a transition to shear thinning behavior and increasing viscoelasticity was found. The complex material structure is modeled according to the flow behavior by discrete and continuous relaxation time spectra, depending on the concentration. Received: 3 May 2000/Accepted: 18 September 2000     

Effect of a hydrotrope on the viscoelastic properties of polymer-like micellar solutions

Low-viscosity micellar aqueous solutions of cetyltrimethylammonium bromide (CTAB) undergo a major change in the presence of the hydrotrope, potassium 1-phenylmethylsulfate (KPhMS), producing a highly viscoelastic entanglement network of polymer-like micelles. The system studied here shows typical shear banding flow behavior, which tends to disappear with increasing the hydrotrope-to-surfactant concentration ratio (C _H / C _S). The linear rheological response was analyzed with the model of Granek–Cates, whereas the nonlinear behavior was reproduced with the Bautista–Manero–Puig (BMP) model. Both models introduce a kinetic equation to account for the breaking and reformation of the micelles, and they predict the linear and nonlinear rheological data very well. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Thinning and thickening effects induced by shearing in lecithin solutions of polymer-like micelles

 The effects of shear flow on the lecithin organogels consisting of reverse polymer-like micelles have been investigated by dynamic rheology. It was established that the shear effects depended on the molar ratio of water to lecithin that determined the micellar type in the system. For an organogel with linear flexible polymer-like micelles, thinning was observed. The main features of the rheological behavior bore a resemblance to previously investigated aqueous systems made up of similar but direct polymer-like surfactant micelles. The thinning effects are explicable on the basis of alignment of micellar aggregates along the flow direction and their disentanglement. An organogel with branched micelles did not demonstrate any notable response to the shearing. Unusual behavior was noticed in the case of a jelly-like phase that included the highest amounts of water. The applied steady shear flow induced a thickening effect. This was followed by restructuring of the micellar system at the level of polymer-like micelles and their network. The shearing effects were characterized by slow kinetics. In addition, the system did not revert to the original state after the cessation of steady shear flow even within 8 h. Measurements performed in an oscillation regime on this system showed that shearing should promote a substantial growth of the polymer-like micelles and affect their alignment. Received: 18 May 1999 Accepted: 27 March 2000     

Solutions of xanthan gum/guar gum mixtures: shear rheology,porous media flow,and solids transport in annular flow

Mixtures of xanthan and guar gum in aqueous solution were studied in two flow situations: simple shear and porous media. In addition, solids transport in vertical annular flow of sand suspensions was explored. The zero shear rate viscosity of the solutions displayed a pronounced synergy: the viscosity of the mixture is higher than that of the polymer solutions in a wide range of relative concentrations of the two polymers, in agreement with previous literature. However, at relatively high shear rates, the viscosity approaches the value of the more viscous xanthan gum solutions at mass fractions of xanthan gum between 0.1 and 0.15, and the degree of synergy substantially decreases. Stress relaxation experiments in simple shear indicate that the polymer mixtures exhibit a well-defined yield stress after relaxation that is absent in solutions of pure polymers. In porous media flow experiments, a synergistic behavior mimicking the shear flow results was obtained for the polymer mixtures at low shear rates. However, at a critical shear rate, the apparent viscosity in porous media flows exceeds the shear viscosity due to the elongational nature of flow in the pores. The solids transport capacity in annular flows is well-represented by trends in shear viscosity and stress relaxation behavior. However, the lack of viscosity synergy at high shear rates limits the applicability of the mixtures as a way to improve solids suspension capacity in annular flows.     

The effect of NaCl addition on the rheological behavior of cetyltrimethylammonium <Emphasis Type="Italic">p</Emphasis>-toluenesulfonate (CTAT) aqueous solutions and their mixtures with hydrophobically modified polyacrylamide aqueous solutions

In this paper, the influence of NaCl addition, up to very large concentrations, on the rheological properties of cetyltrimethylammonium p-toluenesulfonate (CTAT) solutions and their mixtures with two hydrophobically modified polyacrylamides (HMPAM) has been studied under simple shear. The CTAT concentrations employed were above the critical rod concentration. As salt is added to CTAT aqueous solutions, the zero-shear viscosity first increases, goes through a maximum, and at very high ionic strengths increases once more. The overlap concentration of worm-like micelles decreases as the concentration of NaCl increases. The results are explained by the salt addition-induced growth of worm-like micelles and salting out effects at the highest contents of NaCl. The influence of ionic environment on the rheological properties of CTAT with two HMPAM solutions with different contents of hydrophobic moieties was also studied under simple shear. When NaCl is added to HMPAM/CTAT solutions, the same trends observed in CTAT/NaCl solutions were repeated but the viscosity increases were largely magnified. The large viscosity enhancements with salt increments in HMPAM/CTAT solutions were explained by the formation of an interpenetrated network of hydrophobically modified polymer chains and worm-like micelles with hydrophobic sequences embedded within its structure.     

Shear-thickening flow of suspensions of carbon nanofibers in aqueous PVA solutions

The suspensions of carbon nanofibers in aqueous poly(vinyl alcohol) solutions were prepared in the presence of spherical carbon black particles, and the steady-shear viscosity and dynamic viscoelasticity were measured for complex suspensions. Although the single suspensions of carbon black are highly stable, the flocculation of carbon nanofibers is promoted by the addition of carbon black particles. The complex suspensions show remarkable shear thickening in the steady-flow and strain hardening in oscillatory shear with large amplitude. The nonlinear responses strongly depend on the carbon black concentration, whereas the dynamic viscoelasticity at low strains in the linear ranges is not significantly influenced. As the highly elastic effects arise from the long-range motion of particles, the possible mechanism may be the orientation of nanofibers in strong shear fields. The suspensions show the time-dependent behavior of viscosity when the time-scale of measurements is shorter than that of structural recovery to the isotropic states.     

Pressure-driven flow of wormlike micellar solutions in rectilinear microchannels

In this paper the inhomogeneous response of the (two species) VCM model (Vasquez et al., A network scission model for wormlike micellar solutions. I. Model formulation and homogeneous flow predictions, J. Non-Newtonian Fluid Mech. 144 (2007) 122–139) is examined in steady rectilinear pressure-driven flow through a planar channel. This microstructural network model incorporates elastically active network connections that break and reform mimicking the behavior of concentrated wormlike micellar solutions. The constitutive model, which includes non-local effects arising from Brownian motion and from the coupling between the stress and the microstructure (finite length worms), consists of a set of coupled nonlinear partial differential equations describing the two micellar species (a long species ‘A’ and a shorter species ‘B’) which relax due to reptative and Rouse-like mechanisms as well as rupture of the long micellar chains. In pressure-driven flow, the velocity profile predicted by the VCM model deviates from the regular parabolic profile expected for a Newtonian fluid and exhibits a complex spatial structure. An apparent slip layer develops near the wall as a consequence of the microstructural boundary conditions and the shear-induced diffusion and rupture of the micellar species. Above a critical pressure drop, the flow exhibits shear banding with a high shear rate band located near the channel walls. This pressure-driven shear banding transition or ‘spurt’ has been observed experimentally in macroscopic and microscopic channel flow experiments. The detailed structure of the shear banding profiles and the resulting flow curves predicted by the model depend on the magnitude of the dimensionless diffusion parameter. For small channel dimensions, the solutions exhibit ‘non-local’ effects that are consistent with very recent experiments in microfluidic geometries (Masselon et al., Influence of boundary conditions and confinement on non local effects in flows of wormlike micellar systems, Phys. Rev. E 81 (2010) 021502).     

Rheology and flow studies of drag-reducing gravel packing fluids

Viscoelastic additives are widely used as drag reducers in the oil and gas industry, and both polymeric additives and micellar surfactants are commonly used in well gravel packing applications. While the behaviour of polymeric additives such as the polysaccharide xanthan gum is well characterized in the literature, much less is known about how the rheology of the viscoelastic surfactants affects drag reduction, despite widespread use. In this study, we performed a number of rheological tests as well as flow loop experiments on solutions of a zwitterionic surfactant to understand the structural characteristics of the fluids in order to make better process predictions. Unlike xanthan, which displays typical viscoelastic liquid characteristics, zwitterionic surfactant-based fluids display elastic gel-like behaviour. The gel-like behaviour suggests long and relatively unbreakable chain lengths of the wormlike micelles in the viscoelastic surfactant solution at room temperature leading to gelation by entanglement. Also, a shear-thickening behaviour of viscoelastic surfactant samples at higher shear rates is observed, possibly as a result of shear-induced structures. Finally, we present a novel representation scheme to depict the flow loop results for drag in the laminar and turbulent regime, and relate this data to the rheological characterization.     

Comparison of drag reduction, rheology, microstructure and stress-induced precipitation of dilute cationic surfactant solutions with odd and even alkyl chains

Cationic surfactant systems of different alkyl chain lengths with counterion, C_nTAC(5 mmol/l)/3-Cl-Benzoate(12.5 mmol/l) (n=15, 16, 17, 18), were investigated for drag reduction, rheological behaviors, microstructure, and stress-induced precipitation. These are the first measurements of these characteristics for odd chain length (C₁₅ and C₁₇) quaternary ammonium surfactants. The lower and upper effective drag reduction temperature limits, viscoelasticity, and stress-induced precipitation temperature increased with alkyl chain length. Krafft temperature, critical turbidity temperature, and lower drag reduction effectiveness temperature limit showed a zigzag odd-even effect, while the stress-induced precipitation temperature did not. Light microscopy and cryo-TEM showed that cooling the C₁₅ solution below 20 °C produced crystals, while above that temperature threadlike micelles were present. The same was true for the solutions of C₁₈ that had threadlike micellar network microstructures when clear and crystals formed upon cooling. Micellar solutions can remain in a homogenous metastable state at a temperature below the Krafft temperature and above the critical turbidity temperature for days without external disturbance. Imposition of flow stress causes the systems to overcome the energy barrier and precipitate.     

A generalization of Reiner's mathematical model for wet sand

In this paper we modify the constitutive relation derived by Reiner (1945), to describe dilatancy in wet sand, by suggesting that the shear viscosity would depend on the shear rate and the volume fraction. We then look at the flow of a saturated densely packed bed of particles (with liquid in the pores) between two horizontal flat plates. We obtain exact solutions for a very special case.     

Linear and nonlinear rheology of micellar solutions in the isotropic,cubic and hexagonal phase probed by rheo-small-angle light scattering

Aqueous solutions of a branched nonionic surfactant were studied in the isotropic, cubic and hexagonal phase by means of rheological and small-angle light scattering (SALS) experiments. The isotropic phase behaved like a Newtonian liquid. An increase of activation energy of viscous flow was found near the overlap concentration of spherical micelles, but no shear thinning was observed. The viscosity of low concentrated samples increased slightly when the lower critical solution temperature was approached. This increase of viscosity was much smaller compared to common nonionic surfactants. The cubic phases behaved as elastic solids with a high plateau modulus, and shear melting occurred at high shear stresses. The hexagonal phase showed complex behavior. Shear orientation could be achieved by large amplitude oscillatory shear and was proved by rheo-small-angle light scattering. Two orientations were observed, at first perpendicular to the flow direction, i.e., log-rolling state and, secondly, an in-shear-plane orientation parallel to the flow direction. The linear viscoelastic region of the hexagonal phase was extremely small and was detected by simultaneous rheo-small angle light scattering. Shear alignment lead to a decrease of the moduli.     

Determination of flow activation energy at viscosity maximum for spherical and wormlike micelles of different lengths and flexibility

Steady shear rheological measurements were carried out on aqueous solutions containing 15 mM cetyltrimethylammonium bromide (CTABr) and a constant value of [MX] and temperature for MX = 2,3-; 2,4-; 2,5-; 2,6-; 3,4-; and 3,5-Cl₂BzNa with Bz^?representing C₆H₃CO_2?. Plots of zero shear viscosity (η ₀) vs. [MX] at 35 °C and 15 mM CTABr show the presence of single maximum and double maxima for MX = 2,3- and 3,5-Cl₂BzNa, respectively. Turbidity data (absorbance at 600 nm vs. [MX]) coupled with η ₀vs. [MX] data at 35 °C reveal indirectly the presence of vesicles along with wormlike micelles (WM) at MX / CTABr > 0. 7 for MX = 3,5-Cl₂BzNa. Temperature dependence of η ₀in the vicinity of the viscosity maximum shows nonlinear and linear Arrhenius behavior, within the temperature range of 20–55 °C, for MX = 2,3-; 2,4-; 2,5-; 3,4-; and 3,5-Cl₂BzNa, respectively. The values of η ₀, $\dot {\gamma }_{\text {cr}} $ (critical shear rate), and flow activation energy correlate with CTABr micellar binding constants of counterions.     

Hexagonal Defect Array Formed under Steady Shear Flow in Water-in-Cholesteric Liquid Crystal Emulsions

The relation between the liquid crystalline textures and the steady shear viscosity has been investigated in cholesteric emulsions, composed of water, surfactants, and cholesteric liquid crystals. Both at the substrate surface and at the surfactant-coated droplet surface, a homeotropic anchoring is enforced to the adjacent liquid crystal. Under a steady shear flow with the shear rate below 100 s^–1, we observed that point defects spontaneously appear, and tend to adopt a regular hexagonal arrangement in the low shear-rate range of 1–20 s^–1. In viscosity measurements, the shear-thinning behavior was found, showing a clear correspondence to the texture change. We estimated the height of point defects in the hexagonal array from the viscosity increase in the shear-thinning, assuming that the shear-thinning behavior is caused by the reduction of the effective gap between cone and plate, owing to the presence of the hexagonal array anchored on the plate. The relation between the estimated height and the measured lateral size of point defects agreed with that of the quadrilateral array, which is formed after termination of the shear. This agreement informs that the shape of a point defect is preserved in both defect arrays, independently of shearing conditions.     

An experimental investigation into the dimension-sensitive viscosity of polymer containing lubricant oils in microchannels

In many lubrication processes, lubricating oils containing polymer additives are subject to high shear rate through very small clearance channels. While the influence of shear rate on the performance of these lubricants has been well examined, very little is known about the effects of channel size. In this study a specially designed microchannel viscometer has been used to experimentally characterize the influence of channel height on the effective viscosity of oil lubricants with two different polymer additives (a radial hydrogenated styrene–isoprene copolymer and an A–B–A block ethylene–propylene copolymer) commenly used as viscosity index (VI) modifiers. The mass concentration of the polymer solutions ranged from 0.5% to 1.5% in this study. The viscosity was measured over a range of shear rates in steel slit microchannels with heights of 4.5, 7 and 11.5 μm, respectively. For all solutions a significant viscosity dependence on channel size was observed. In the higher shear rate range the smaller channels exhibited a lower viscosity while in the lower shear rate range all solutions exhibited a significant increase in viscosity. Generally, this observed increase in viscosity is more dramatic in the smaller channels. Possible causes of these behaviors were discussed in this paper.