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Micro- and macro-shear viscosity in dispersed lamellar phases. (English) Zbl 1391.76032

Summary: Surfactant phases, such as dispersed lamellar gels, are extremely useful in commercial products because they are very weight-effective at building viscosity. An enduring challenge is to determine the microstructural features responsible for the bulk rheology so that we can design products with improved performance. The samples described here have very different rheological profiles as exemplified by an order-of-magnitude difference in their zero-shear-rate viscosity, and infinite-shear-rate viscosities which differ by half an order of magnitude. As a first approximation we consider the dispersed lamellar system to be analogous to a high-internal-phase-volume emulsion which is described by the well-known Kreiger-Dougherty equation. This requires us to establish the value of a number of parameters of which the continuous phase viscosity is the one that defines the baseline viscosity. We measured this in situ by a micro-viscosity technique involving Fluorescence Correlation Spectroscopy using microscopic probes: viz. a fluorescent dye molecule (rhodamine) of size 0.85 nm; a lyzozyme protein of 2 nm size and a quantum dot of 12.5 nm size. We show that the continuous phase has a viscosity about twice that of water. Moreover, this viscosity is the same for the all three probes indicating that the system is quite uniform at the microscopic level investigated. Interestingly, this micro-viscosity was practically the same for all the samples and thus could not be correlated with zero-shear-rate viscosity or other rheological characteristics. We conclude that the macro-viscosity arises from structures much larger than 25 nm (twice the hydrodynamic diameter of the quantum dot). Our future intention is to use larger probes to establish the length-scale at which the microstructure begins to be apparent in the bulk rheology characteristics.

MSC:

76A05 Non-Newtonian fluids
Full Text: DOI

References:

[1] Stokes, J. R.; Telford, J. H.: Measuring the yield behaviour of structured fluids, J. non-Newtonian fluid mech. 124, 137 (2004) · Zbl 1142.76323 · doi:10.1016/j.jnnfm.2004.09.001
[2] Berni, M. G.; Lawrence, C. J.; Machin, D.: A review of the rheology of the lamellar phase in surfactant systems, Adv. colloid interface sci. 98, 217 (2002)
[3] Eccleston, G.: Structure and rheology of pharmaceutical and cosmetic creams – cetrimide creams – influence of alcohol chain-length and homolog composition, J. colloid interface sci. 57, 66 (1976)
[4] Goldszal, A.; Jamieson, A.; Mann, J. A.; Polak, J.; Rosenblatt, C.: Rheology, optical microscopy, and electron microscopy of cationic surfactant gels, J. colloid interface sci. 180, 261 (1996)
[5] Nakarapanich, J.; Barameesangpet, T.; Suksamranchit, S.; Sirivat, A.; Jamieson, A.: Rheological properties and structures of cationic surfactants and fatty alcohol emulsions: effect of surfactant chain length and concentration, Colloid polym. Sci. 279, 671 (2001)
[6] Yoon, M.; Chung, Y.; Han, K.: A study of gel structure in the nonionic surfactant/cetostearyl alcohol/water ternary systems by differential scanning calorimeter, J. dispersion sci. Technol. 20, 1695 (1999)
[7] Diat, O.; Roux, D.; Nallet, F.: Effect of shear on a lyotropic lamellar phase, J. phys. II fr. 3, 1427-1452 (1993)
[8] Partal, P.; Kowalski, A.; Machin, D.; Kiratziz, N.; Berni, M.; Lawrence, C.: Rheology and microstructural transitions in the lamellar phase of a cationic surfactant, Langmuir 17, 1331 (2001)
[9] G. Akay, G.N. Irving, A.J. Kowalski, D. Machin, Patent WO9620270 A1.
[10] Yamagata, Y.; Senna, M.: Effects of temperature on the development of the internal structure of the cetyltrimethylammonium chloride/cetyl alcohol/water system, Langmuir 15, 7461 (1999)
[11] Van Der Linden, E.; Hogervorst, W. T.; Lekkerkerker, H. N. W.: Relation between the size of lamellar droplets in onion phases and their effective surface tension, Langmuir 12, 3127 (1996)
[12] Gisler, T.; Weitz, D. A.: Tracer microrheology in complex fluids, Curr. opin. Colloid int. Sci. 3, 586 (1998)
[13] Mukhopadhyay, A.; Zhao, J.; Bae, S. C.; Granick, S.: An integrated platform for surface forces measurements and fluorescence correlation spectroscopy, Rev. sci. Instrum. 74, 3067 (2003)
[14] Hassan, P. A.; Bhattacharya, K.; Kulshreshtha, S. K.; Raghavan, S. R.: Microrheology of wormlike micellar fluids from the diffusion of colloidal probes, J. phys. Chem., B 109, 8744 (2005)
[15] Magde, D.; Elson, E. L.; Webb, W. W.: Thermodynamic fluctuations in a reacting system — measurement by fluorescence correlation spectroscopy, Phys. rev. Lett. 29, 705 (1972)
[16] Eigen, M.; Rigler, R.: Sorting single molecules: application to diagnostics and evolutionary biotechnology, Proc. natl. Acad. sci. U. S. A. 91, 5740 (1994)
[17] Schwille, P.; Korlach, J.; Webb, W. W.: Fluorescence correlation spectroscopy with single-molecule sensitivity on cell and model membranes, Cytometry 36, 176 (1999)
[18] Banks, D. S.; Fradin, C.: Anomalous diffusion of proteins due to molecular crowding, Biophys. J. 89, 2960 (2005)
[19] Elson, E. L.; Magde, D.: Fluorescence correlation spectroscopy. I. conceptual basis and theory, Biopolymers 13, 1 (1974)
[20] Hess, S.; Webb, W. W.: Focal volume optics and experimental artifacts in confocal fluorescence correlation spectroscopy, Biophys. J. 83, 2300 (2002)
[21] Krichevsky, O.; Bonnet, G.: Fluorescence correlation spectroscopy: the technique and its applications, Rep. prog. Phys. 65, 251 (2002)
[22] Jankowski, T.; Janka, R.: Fluorescence correlation spectroscopy, theory and applications, Springer series in chemical physics, no. 65, 331 (2001)
[23] Magde, D.; Elson, E. L.; Webb, W. W.: Fluorescence correlation spectroscopy. II. an experimental realization, Biopolymers 13, 29 (1974)
[24] Sengaputa, P.; Garai, K.; Balaji, J.; Periasamy, N.; Maiti, S.: Measuring size distribution in highly heterogeneous systems with fluorescence correlation spectroscopy, Biophys. J. 84, 1977 (2003)
[25] Barnes, H. A.: Thixotropy — a review, J. non-Newtonian fluid mech. 70, 1 (1997)
[26] K. Sinclair, J. Hazekamp, J. Microsc., in preparation.
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