Surfactant rheological behavior

The effects of different surfactants on the rheological behavior of cement-water dispersions were studied by a rotational-type viscometer. The type of... 

Oil-field chemistry has undergone major changes since the publication of earlier books on this subject Enhanced oil recovery research has shifted from processes in which surfactants and polymers are the primary promoters of increased oil production to processes in which surfactants are additives to improve the incremental oil recovery provided by steam and miscible gas injection fluids. Improved and more cost-effective cross-linked polymer systems have resulted from a better understanding of chemical cross-links in polysaccharides and of the rheological behavior of cross-linked fluids. The thrust of completion and hydraulic fracturing chemical research has shifted somewhat from systems designed for ever deeper, hotter formations to chemicals, particularly polymers, that exhibit improved cost effectiveness at more moderate reservoir conditions. 

Hoffmann, H., Thunig, C., Schmiedel, R and Munkert, U. (1994) The rheological behavior of different viscoelastic surfactant solutions systems with and without a yield stress value. Tenside Surf. Det., 31(6), 389MD0. 

Understanding surfactant phase behavior is important because it controls physical properties such as rheology and freeze-thaw stability of formulations. It is also closely related to the ability to form and stabilize emulsions and microemulsions. Micelles, vesicles, mi-croemulsions and liquid crystal phases have all been used as delivery vehicles for perfumes or other active ingredients. 

Let us first consider an inverted W/O emulsion made of 10% of 0.1 M NaCl large droplets dispersed in sorbitan monooleate (Span 80), a liquid surfactant which also acts as the dispersing continuous phase. At this low droplet volume fraction, the rheological properties of the premixed emulsion is essentially determined by the continuous medium. The rheological behavior of the oil phase can be described as follows it exhibits a Newtonian behavior with a viscosity of 1 Pa s up to 1000 s 1 and a pronounced shear thinning behavior above this threshold value. Between 1000 s 1 and 3000 s1, although the stress is approximately unchanged, the viscosity ratio is increased by a factor of 4. 

Emulsion Pipeline Operations. Prediction of pipeline pressure gradients is required for operation of any pipeline system. Pressure gradients for a transport emulsion flowing in commercial-size pipelines may be estimated via standard techniques because chemically stabilized emulsions exhibit rheological behavior that is nearly Newtonian. The emulsion viscosity must be known to implement these methods. The best way to determine emulsion viscosity for an application is to prepare an emulsion batch conforming to planned specifications and directly measure the pipe viscosity in a pipe loop of at least 1-in. inside diameter. Care must be taken to use the same brine composition, surfactant concentration, droplet size distribution, brine-crude-oil ratio, and temperature as are expected in the field application. In practice, a pilot-plant run may not be feasible, or there may be some disparity between pipe-loop test conditions and anticipated commercial pipeline conditions. In these cases, adjustments may be applied to the best available viscosity data using adjustment factors described later to compensate for disparities in operating parameters between the measurement conditions and the pipeline conditions. 

The viscosity of microemulsions has been studied several times in order to determine hydration and interactions between the dispersed droplets. It was found that an increase in hydration of the surfactant molecules resulted in rheological behavior more similar to that of suspensions containing solid particles in low concentrations. In any case, the microemulsions showed Newtonian flow characteristics. 

It has often been stated that DR of surfactant solutions is related to their rheological properties. A rise in shear viscosity at a critical shear rate, caused by a shear-induced structure (SIS), viscoelasticity (nonzero first normal stress difference, quick recoil, and stress overshoot), and high extensional viscosity/shear viscosity ratios ( 100) are rheological properties found in many DR surfactant solutions. After reviewing the rheological behavior of many DR surfactant solutions, Qi and Zakin concluded that SIS and viscoelasticity are not always observed in DR surfactant solutions while high extensional/shear viscosity ratios may be a requirement for surfactant solutions to be DR. ... 

Poly(methylmethacrylate), PMMA, latex particles have also served as a model colloidal system for many years (mainly as hard spheres with hydroxy stearic acid (HSA) chains being the grafting choice [91,113,114]). Tunability was achieved by varying the core size and the size of the corona chains. The comparison between chemically grafted (stable) and end-adsorbed temperature-sensitive chains (usually surfactants) has shown that the adsorbed chain particles exhibit similar rheological behavior with chemically grafted particles [115]. 

Blute, I., Effect of hydrotropes on nonionic surfactant/water system. Phase and rheological behavior, manuscript in preparation. 

In the following examples some of the matrix effects observed between rheology modifiers and different surfactants are illustrated. The case of a crosslinked ASE polymer in the presence of a nonionic alkyl polyglucoside (APG) surfactant is shown in Figure 5.6. The rheological profiles of the polymer in different concentrations of APG are very similar to those of the aqueous polymer results, indicating that the surfactant has very little effect on the rheological behavior of the ASE polymer. 

In the case of liquid adsorption layers, the deformation by shear occurs at any small load (Fig. 11-29, line 2), and the shear rate, e, is proportional to the applied stress, xs (the torque angle of the thread). The latter allows one to estimate the surface viscosity of the adsorption layer, which is strongly dependent on the nature of surfactants. The adsorption layers may also reveal more complex rheological behavior, intermediate between that of liquids and solids (Fig. 11-29, curve 3). 

Polymer-surfactant interactions are the basis for the rheological behavior of MHAPs. Other surfactant-polymer systems have previously been investigated. One example is the interaction of surfactants with polymers such as poly(ethylene oxide), which results in greater solution viscosities than with the polymer alone (e.g., ref. 25 and references therein). The interaction of surfactants or latexes with hydrophobically modified water-soluble polymers has also been shown to produce unique rheology (2, 5, 26, 27). In these systems, the latex particles or the surfactant micelles serve as reversible cross-link points with a hydrophobic region of a polymer molecule in dynamic association with a latex particle or surfactant micelle (27). 

The balance of the many possible interactions in these MHAP produces unique rheological behavior (20-24, 27). Thus, the surfactant in the MHAP is an integral component of the polymer-surfactant system, serving a dual function of aiding the formation of the polymer architecture during polymerization as well as being reversible cross-link points in solution. 

Ohlendorf, D., Interthal, W., and Hoffmann, H., Surfactant systems for drag reduction physicochemical properties and rheological behavior, Rheol. Acta, 25, 468-486 (1986). 

Great emphasis has been placed on the fact that viscosity and rheological behavior are a function of the effective volume fraction. Solvation is another mechanism that alters ( ), and it occurs when a thick adsorbed layer of continuou,s phase or surfactant develops on the surface of particles. In this sense, may be estimated in two ways. In the first. 

In this chapter, a brief theoretical background on the rheological behavior of viscoelashc worm-like micelles is given. It is followed by a discussion on the temperature-induced viscosity growth in a water-surfactant binary system of a nonionic fluorinated surfactant at various concentrations. Finally, some recent results on the formation of viscoelastic worm-like micelles in mixed nonionic fluorinated surfactants in an aqueous system are presented. 

Worm-Like Micelles in Diluted Mixed Surfactant Solutions Formation and Rheological Behavior... 

Kunieda s group reported numerous viscoelastic worm-like micellar systems in the salt-free condition when a lipophilic nonionic surfactant such as short hydrophilic chain poly(oxyethylene) alkyl ether, C EOni, or N-hydroxyethyl-N-methylaUcanolamide, NMEA-n, was added to the dilute micellar solution of hydrophilic cationic (dodecyltrimethylammonium bromide, DTAB and hexade-cyltrimethylammonium bromide, CTAB) [12-14], anionic (sodium dodecyl sulfate, SDS [15, 16], sodium dodecyl trioxyethylene sulfate, SDES [17], and Gemini-type [18]) or nonionic (sucrose alkanoates, C SE [9, 19], polyoxyethylene cholesteryl ethers, ChEO [10, 20], polyoxyethylene phytosterol, PhyEO [11, 21] and polyoxyethylene sorbitan monooleate, Tween-80 [22]) surfactants. The mechanism of formation of these worm-Hke stmctures and the resulting rheological behavior of micellar solutions is discussed in this section based in some actual published and unpublished results, but conclusions can qualitatively be extended to aU the systems studied by Kunieda s group. 

In this section, some contribuhons that try to understand surfactant-cosurfactant interachons and their effect in rheological behavior of the systems will be discussed. 

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