Group: K (07402011, 07402012, 07402013); Report No.5 Experiment performed on: 26th Feb.

2008 RHEOLOGY OF A VISCOELASTIC FLUID Aim: To study the viscoelastic properties of given liquid sample with the following objectives: a) To measure the viscosity of the given viscoelastic fluid as a function of shear rate and use Ellis model to fit the data. b) To measure the storage and loss modulus as a function of frequency and determine the relaxation time (), and the plateau modulus (G ) using Maxwell model. Apparatus: Chemicals required: a) b) Instrument: Software: Theory: Viscoelastic fluids and their rheology: Based on rheological properties, fluids can be classified as Newtonian and nonNewtonian. Newtonian fluids are those which can be characterized by a linear relationship between shear stress and shear strain; the constant of proportionality is called viscosity. Fluids on which shear stresses do not result into linear shear strain are called non-Newtonian (e.g. polymeric fluids and colloidal suspensions). On deformation, non-Newtonian fluids show viscoelastic properties (both viscous and elastic characteristics). These properties can be studied either by specifying deformation and measuring stresses, or imposing a stress and measuring the velocity Cetyltrimethyl ammonium bromide (CTAB) solution in water. Sodium salicylate solution in water. HAAKE RT 20, Rotoviscometer. Rheowin Job manager and Rheowin data manager.

or deformation field. Based on these studies two standard flows are classified: simple shear flow and simple shear-free flow. Simple shear flow can be produced by placing the given viscoelastic liquid between the walls of two concentric cylinders where one is stationary while other is rotating at a steady rate. For such flow, the total stress is the summation of the pressure and shear stress components experienced by the system. Another method utilized to produce shear flow involves oscillatory shear where the shear rate varies sinusoidally. For this kind of flow the ratio of shear stress and shear strain is equal to the summation of (a) the component of shear stress in phase with the strain, G (), (Storage modulus, a measure of elasticity), (b) the component of shear stress out of phase with the strain, G() (Loss modulus, a measure of viscosity). Worm-like micelles: Conventional micelles are fluid aggregates of surfactants with shape and size decided by packing of individual surfactants. In the charged micelles, micellar growth occurs as a consequence of the reduction of the repulsion between the surfactant headgroups, which can be induced by adding salts, strongly binding counterions or cosurfactants. Reported systems mainly include cationic surfactants with aromatic counterions or halide anions. Among the few reports on anionic surfactant, majorities have focused on sodium dodecyl sulfate. Some nonionic surfactants can also form worm-like micelles under certain conditions. Through these studies it became clear that by mixing surfactants (hydrotropes) of opposite charges, cationic and anionic, but with varying chain lengths one can control the degree of precipitation of the surfactants to produce different supramolecular structures like vesicles and polymeric micelles. One can also produce tubules, ribbons, etc. by controlling the solubility of surfactants. This facilitates an easy control over the aggregate structure and hence it is possible to induce transformations from vesicles to micelles by a proper choice of additives which are cationic, anionic or neutral.

Rheological studies on worm-like micellar solutions provide useful information concerning phenomena such as micellar growth, entanglement, branching and shear induced transitions. Various flow models used to fit the data of rheological studies: Flow models are mathematical equations that can describe rheological data, such as shear rate-shear stress data in a basic shear diagram, and provides a convenient and concise manner of describing the data. Some models that are used to fit rheological data are: a) Newtonian Model b) Ellis Model for low shear rate data containing o c) Sisko model for high shear rate data containing d) Cross model for data over a wide range of shear rates e) Carreau model for data over a wide range of shear rates f) Power law model used extensively in handling applications g) Bingham model h) Herschel-Buckley model i) Casson model used specially in treating data on chocolates j) Mizrahi and Berk model, a modification of the Casson model k) Generalized model of Ofoli et.al (1987) l) Vocadlo model m) Maxwell model We have used Ellis model and Maxwell model to fit the data from this experiment. The Ellis model equation is o/ = 1 + ( /1/2)-1 where and 1/2 are parameters. The Maxwell model equations are: G = G 22/( 1+ 22) G = G /( 1+ 22) where G is the plateau modulus and is the relaxation time.

Procedure: 1. Solution preparation: 0.1 M, 100 ml solution of NaSal (Mol. Wt: 160.10) was prepared by dissolving 1.6 gms of NaSal in water. To this solution, 1.82 gms of C-TAB (Mol. Wt: 364.46) was added to get the ratio of molarities as 2. Carrying out the experiment: a) 60 ml of this solution was poured into the outer cylinder of the Rheometer. b) After pouring, the inner cylinder was installed and further controls were performed by computer interface Rheowin Job manager. c) In the Rheowin Job manager, Z40 Din Tin 8mm Senser was affixed, d) For Rotation (ROT)set up: Step rotation was selected and the parameters were adjusted (CR, Shear rate: 5-15 sec., Steps: 10) e) For Oscillation (OSC)set up: The parameters were adjusted (CD, Frequency: 0.11 radians/sec., Acquisition waiting time: 1 period) f) GAP was affixed and the instrument was started by clicking START g) After processing the data was acquired from the interface. Calculations: 1. Viscosity vs. Shear rate

[C TAB ]

[ NaSal ]

=2

Viscocity Vs Shear rate

2. Storage modulus (G) vs. frequency ()

Shear stress Vs Frequency

3. Loss modulus vs. frequency ()

Loss Modulus Vs Frequency

4.

G, G vs. frequency on a single plot showing the crossover frequency

G', G" in Pa

G" in Pa

10 G' Vs Frequency G" Vs Frequency 1 0.1 0.1 in rad/sec 1 10

At G = G, c = 1.35 rad/sec = 2 f Therefore the relaxation time is given by, = 1/f = 4.655 s

5. Ellis model fit: Ellis model describes the rheological data and it is a flow model. It has and 1/2 parameters.
Ellis Model Fit
0.5 0 2.25 -0.5 -1 -1.5 -2 ln() y = 4.9021x - 12.203

Ellis model is represented as: o/ = 1 + ( /1/2)-1 Equation of straight line: y = 4.9021x 12.203 Comparing with ln (o/ 1) = (-1) ln - (-1) ln (1/2) we have, (-1) = 4.9021 ; ie. = 5.9021 Now (-1) ln (1/2) = 12.203 1/2 = 12.053 Pa. 6. Maxwell model fit:

ln(o/ -1)

2.3

2.35

2.4

2.45

2.5

2.55

2.6

16 14 12 10 8 6 4 2 0

10

Maxwell model equation for G is: G = G 22/( 1+ 22) The best fit for experimental data is seen at G = 13.0Pa. Therefore, G = 14.0 Pa.

8 7 6 5 4 3 2 1 0

10

Maxwell model equation for G is: G = G /( 1+ 22) The best fit for experimental data is observed at G = 40 Pa. Therefore, G = 16.0 Pa. Results: Ellis model parameters were found to be: = 5.9021 and = 4.655 s Plateau modulus was obtained from Maxwell model fit using G: G = 14.0 Pa. and using G: G = 16.0 Pa. Average G = 15.0 Pa. In Maxwell model fit, the curve through experimental data points matches that from the model, especially in the graph of G versus , which means that it represents the data 1/2 = 12.053Pa Relaxation time was found to be:

well. The data does not fit Ellis model well because the points show a varied distribution on either side of the straight line. Possible sources of error: a) Air bubbles and impurities in the sample solution, b) Unclean cylinders of the apparatus, c) Loose screwing of the inner cylinder, d) Inadequate filling of the sample solution in the instrument, e) Wrong inputs for the parameters and the GAP in the computer interface of the Rheometer.