Korea-Australia Rheology Journal, Vol.14, No.4, 189-201, December, 2002
Shear-induced structure and dynamics of hydrophobically modified hydroxy ethyl cellulose (hmHEC) in the presence of SDS
E-mail:
The interaction between hydrophobically modified hydroxyethyl cellulose (hmHEC), containing approximately 1 wt% side-alkyl chains of C16, and an anionic sodium dodecyl sulphate (SDS) surfactant was investigated. For a semi-dilute solution of 0.5 wt% hmHEC, the previously observed behaviour of a maximum in solution viscosity at intermediate SDS concentrations, followed by a drop at higher SDS concentrations, until above the cmc of surfactant when the solution resembles that of the unsubstituted polymer, was confirmed. Additionally, a two-phase region containing a hydrogel phase and a water-like supernatant was found at low SDS concentrations up to 0.2 wt%, a concentration which is akin to the critical association concentration, cac, of SDS in the presence of hmHEC. Above this concentration, SDS molecules bind strongly to form mixed micellar aggregates with the polymer alkyl side-chains, thus strengthening the network junctions, resulting in the observed increase in viscosity and elastic modulus of the solution. The shear behaviour of this polymer-surfactant complex during steady and step stress experiments was examined in great detail. Between SDS concentrations of 0.2 and 0.25 wt%, the shear viscosity of the hmHEC-polymer complex network undergoes shear-induced thickening, followed by a two-stage shear-induced fracture or break-up of the network. The thickening is thought to be due to structural rearrangement, causing the network
of flexible polymers to expand, enabling some polymer hydrophobic groups to be converted from
intra- to inter-chain associations. At higher applied stress, a partial local break-up of the network occurs, while at even higher stress, above the critical or network yield stress, a complete fracture of the network into small microgel-like units, is believed to occur. This second network rupture is progressive with time of shear and no steady state in viscosity was observed even after 300 s. The structure which was reformed after the cessation of shear is found to be significantly different from the original state.
Keywords:hydrophobically modified polymer;SDS;polymer-surfactant interactions;shear-induced thickening;critical yield stress
- Annable T, Buscall R, Ettelaie R, Whittlestone D, J. Rheol., 37, 695 (1993)
- Dualeh AJ, Steiner CA, Macromolecules, 24, 112 (1991)
- Evertsson H, Nilsson S, Carbohydrat. Polym., 40, 293 (1999)
- Ferry JD, Viscoelastic Properties of Polymers, Wiley, N.Y. (1980)
- Goodwin JW, Hughes RW, Lam CK, Miles JA, Warren BCH, The Rheological Properties of a Hydrophobically Modified Cellulose, in Polymer in Aqueous Media, Am. Chem. Soc. (1989)
- Hu YT, Boltenhagen P, Pine DJ, J. Rheol., 42(5), 1185 (1998)
- Kastner U, Hoffmann H, Donges R, Ehrler R, Colloids Surf., 112, 209 (1996)
- Kjoniksen AL, Nilsson S, Thuresson K, Lindman B, Nystrom B, Macromolecules, 33(3), 877 (2000)
- Kulicke WM, Arendt O, Berger M, Colloid Polym. Sci., 276, 617 (1998)
- Kumar V, Steiner CA, Colloids Surf., 147, 27 (1999)
- Marrucci G, Bhargava S, Cooper SL, Macromolecules, 26, 6483 (1993)
- Nilsson S, Thuresson K, Hansson P, Lindman B, J. Phys. Chem. B, 102(37), 7099 (1998)
- Nishikawa K, Yekta A, Pham HH, Winnik MA, Sau AC, Langmuir, 14(25), 7119 (1998)
- Nystrom B, Thuresson K, Lindman B, Langmuir, 11(6), 1994 (1995)
- Panmai S, Prudhomme RK, Peiffer DG, Colloids Surf. A: Physicochem. Eng. Asp., 147, 3 (1999)
- Pedley AM, Higgins JS, Peiffer DG, Rennie AR, Staples E, Polym. Commun., 30, 162 (1989)
- Sadeghy K, James DF, J. Non-Newton. Fluid Mech., 90(2-3), 127 (2000)
- Sau AC, Landoll LM, Synthesis and Solution Properties of hydrophobically Modified (Hydroxyethyl) Cellulose, in Polymer in Aqueous Media, Am. Chem. Soc. (1989)
- Sivadasan K, Somasundaran P, Colloids Surf. A: Physicochem. Eng. Asp., 49, 229 (1990)
- Tam KC, Jenkins RD, Winnik MA, Bassett DR, Macromolecules, 31(13), 4149 (1998)
- Tanaka R, Meadows J, Williams PA, Phillips GO, Macromolecules, 25, 1304 (1992)
- Thuresson K, Lindman B, Nystrom B, J. Phys. Chem. B, 101(33), 6450 (1997)
- Thuresson K, Nystrom B, Wang G, Lindman B, Langmuir, 11(10), 3730 (1995)
- Tirtaatmadja V, Tam KC, Jenkins RD, AIChE J., 44(12), 2756 (1998)
- Vaccaro A, Marrucci G, J. Non-Newton. Fluid Mech., 92(2-3), 261 (2000)