Short introduction into rheology

Basics, testing in rotation, creep and oscillation, extensional rheology

Contents
Viscosity Controlled shear rate (CR), shear stress (CS), deformation (CD) Rotational testing - Newtonian and Non-Newtonian flow behavior - Yield stress - Thixotropy Viscoelasticity Structural reasons, modeling Creep & recovery testing - Description with Burgers model - Elastic and viscous share Oscillatory testing - Time sweep e.g. relaxation, gelation, sedimentation - Amplitude sweep Linear viscoelastic range (LVR), stability - Frequency sweep liquid, paste-like or elastic? - Temperature sweep e.g. cross-linking - Cyclic testing stability Extensional Rheology
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. Shear stress t, deformation g and shear rate g

Sample height: h Deflection: x Deformation: g Shear stress t : force F applied to area A

x g = h
Shear rate = change of deformation per time unit

F t = A
x h
Direction of force

. dg g =
dt

Typical shear rates

Application Sedimentation Phase separation Leveling, running Extrusion Dip Coatings Chewing Pumping, stirring Brushing Spraying Shear rate (s-1) 10-6 - 10-4 10-6 - 10-4 10-1 - 101 100 - 102 101 - 102 101 - 102 101 - 103 101 - 104 103 - 104

Absolute and relative viscosity

"Resistance to flow" Viscosity can be determined indirectly: torque M * A factor shear stress t Viscosity = = . = shear rate g

rotational speed * M factor

Absolute viscosity readings with known measuring geometry only!
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Relative viscosity
Any scale reading S (time, distance, angular deflection) is set into ratio with a known viscosity standard Viscosity of unknown material calculates as follows:

unknown

= Standard

sStandard

Sunknown

Parameters of testing (rotor, speed, filling ) strictly need to be kept constant.

Calibration possible for Newtonian Liquids only!
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Dynamic and kinematic viscosity

(Dynamic) viscosity [Pas]

t = shear stress [Pa] . g = shear rate [1/s]

1 Pas = 1000 mPas 1 mPas = 1 cP (centi Poise) Kinematic viscosity n [mm/s2]

t = g
n=

= density [kg/m]

1 mm/s = 1 cSt (centi Stokes)

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Viscosity of fluids: Measured at 20C

Substance Water Milk Olive oil Engine oil Honey Bitumen

Viscosity 1 mPas 5 - 10 mPas

100 mPas
1000 mPas 10 000 mPas 100 000 000 mPas

Measuring flow behaviour

Determination of flow behavior as a function of varying shear stress or shear rate
Shear Stress t [Pa] . Shear Rate g [1/s]
Ramp (Thixotropy) Steps (Steady state)

Time t [s]
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Newtonian flow behavior

Example: Oil
t - Shear Stress . - Viscosity g - Shear Rate
500 450 400 100

Flow curve
[Pa s]
.

350

[Pa]

300 250 200 150 10

Viscosity curve

100
50 0 0 5 10 15 20 25 30 35 40 45 50 1

[1/s]
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Shear thinning flow behavior: Structural reasons

Orientation

Extension

Deformation Dis-aggregation

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Flow behavior: Flow curve

Linear plot Newtonian Pseudoplastic (shear thinning) Dilatant (shear thickening)

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Flow behavior: Viscosity curve

Double-logarithmic plot Newtonian Pseudoplastic (shear thinning) Dilatant (shear thickening)

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Yield stress t0 / yield point a model

The yield stress t0 is the shear stress t required - to overcome elastic behavior and - obtain viscoelastic flow behavior

Shear stress t

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Yield stress t0: Determination

Controlled deformation (CD) mode:

t0: Maximum of the curve shear stress t vs. time t

(linear scaling)
Controlled rate (CR) ramp:

t0: Extrapolation of flow curve to shear rate g = 0

(linear scaling) Controlled stress (CS) ramp:

t0: Intersection of tangents in the change in slope of the curve

log deformation g vs. log shear stress t

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Yield stress t0: Determination in CD-mode

Input: deformation g (constant) Measurement: shear stress t Result: shear stress t = f(time t) Evaluation: Determination of the curve maximum (= yield stress t0)
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250

200

Shear Stress [Pa]

150

100

Curve discussion : Method

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--------------------------Maximum 0.3161
0 0.5 1.0 1.5 Time t [min] 2.0

t [min] t0 [Pa]

224.9
2.5

Yield stress t0: Determination in CR-mode

Input: . shear rate g (varying)
120

Measurement: shear stress t

100

80

Result: . shear stress t = f(shear rate g)

Evaluation: yield stress t0 by Extrapolation of flow curve . to shear rate g = 0 using a rheological model
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[Pa]

60

40

Extrapolation Casson: t0 = 8.808 [Pa]

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0 0 10 20 30 40 50 60

[1/s]

Yield stress t0: Determination in CS-mode

Input: shear stress t (increase logarithmic) Measurement: deformation g Result: log deformation g = f(log shear stress t) Evaluation : Transition between the linear regimes (= yield stress t0)
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100.000

Deformation [-]

10.000

1.000

0.100

0.010

t0 = 16 Pa
0.001 0.1 1.0 10.0 100.0

Shear Stress [Pa]

Bingham flow behavior

Example: Tooth paste
t - Shear Stress 550 - Viscosity 500 . g - Shear Rate
450 400 350 [Pa] 300 250 200 [Pa s] 100

Decrease in due to yield stress

Flow curve

Bingham 100 yield stress: 50 = 29 Pa 0

0 5 10 15 20 25 [1/s]

150

Viscosity curve
10 30 35 40 45 50

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Thixotropy: Structural behavior

Time-dependent behavior: Primary particles Agglomerates

Network

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Thixotropy: Definition and determination

Definition of thixotropic flow behaviour:
- Decrease of viscosity as a function of time upon shearing, - 100% recovery (= regaining the original structures) as a function of time without shearing.

Determination
(1) Time Curves - Base-line of intact structure at low shear rate (e.g. CR mode: 1 1/s) or in oscillation (e.g. CD mode: 1% deformation) - Dis-aggregation at constant shear rate (e.g. CR mode: 100 1/s) - Re-aggregating time at low shear rate (e.g. CR mode: 1 1/s) or in oscillation (e.g. CD mode: 1% deformation) (2) Flow Curves - Ramp up, (peak hold,) ramp down at constant temperature. - The hysteresis area in this loop is a measure for the thixotropy.

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Thixotropy: Time curve

Base-line, dis-aggregation, re-aggregating time

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Thixotropy: Flow curve (thixotropy loop)

Input: shear rate .g - ramp up - (peak hold) - ramp down
Shear Stress [Pa] 500

450

400

350

Measurement: shear stress t

300

250

Thixotropic loop area

200

Result: viscosity = f(shear rate.g, time t) Evaluation: Determination of thixotropic loop area
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150

100

50

0 0 50 100 150 200 250 300 350 400 450 500

Shear Rate [1/s]

Viscoelasticity: Structural reasons

Entanglement in macromolecules

Structure/network of an emulsion

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How to model viscoelasticity?

Viscous flow Viscoelasticity Elastic deformation

Spring Dash pot

. t = g
MaxwellModel

Voigt/KelvinModel

t = G*g

Burgers-Model

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Testing methods for viscoelasticity

Method Shear stress ramp Creep test Time curve Input Increasing shear stress Const. shear stress Const. frequency and const. amplitude Information Yieldpoint Deformation Monitoring of chemical reaction

Amplitude sweep
Frequency sweep

Stepwise increasing amplitude

Stepwise increasing dependence

Network stability
Time frequency Temperature const. amplitude

Temperature curve
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const. frequency and dependence

Signals applied by a rheometer

. (Stepped) Ramp (g, t)

Rotational Testing
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. Jump (g, t)
Creep & Recovery

. (Co-)Sinus (g, t)
Oscillatory testing

Creep & recovery testing

Shear rate g at low stress

Zero shear viscosity 0

Equilibrium compliance Je0 Ratio of viscous and elastic properties Relaxation time l0 Elastic Modulus G0
Mostly elastic sample

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Oscillatory testing: Principle

t=0
(change of direction)

t=0
(change of direction)

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Oscillatory testing: Complex Quantities

Complex modulus Storage modulus Loss modulus Loss angle Loss factor

G* = G + i G (i2 = -1) G (elastic properties) G (viscous/damping properties ) d G* tand = G/G *= G* / i w w = 2p f

Complex Viscosity Angular frequency

d
G

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Amplitude Sweep
Example: Delicate gel

Material Stability
Gel strength correlates with the gel's yield point

The critical stress from the stress sweep is used as characteristic value. Remember the test is frequency dependent, therefore it is a relative result!

LVR

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Amplitude Sweep
Example: Gels with different carbopol (hydro colloid) content

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Frequency Sweep: Frequency and temperature dependence

122C 180C

250C
paste

elastic

flowing

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Frequency Sweep
Material Characterization Paste - Entangled solution (circles) Gel - 3D network (triangles) Cross-over

Note: A Gel is not necessarily stronger than a Paste

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Time Sweep: Gelation

Verlustanteile G"

CrossOver

Parameters:
f = 0.5 Hz g=1% T = 35C
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Curing
Pwd-cure G' = f (T) G" = f (T) 10000000

Curing of powder coating

1000000

100000

G' [Pa],G" [Pa]

10000

Storage modulus G Loss modulus G

1000

100

10

1 80

100

120

140 T [C]

160

180

200

HAAKE RheoWin Pro 2.6

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Test for prediction of temperature stability Brummer et al

Oscillation (g , w = const.) Cyclic temperature ramps (-10 ... 50C, 20 min each) Indicators: G' und G":
- G' and G" not affected - Changes in G' and G" sample is stable sample not stable

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Test for prediction of temperature stability Brummer et al

Example: Cosmetics

G [Pa]

Temp. T [C]

G [Pa]

w = konstant Time t [min]

Cyclic testing stable sample

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Test for prediction of temperature stability Brummer et al

Example: Cosmetics

G [Pa]

Temp. T [C]

G [Pa]
w = konstant
Time t [min]

Cyclic testing sample not stable

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Extensional Rheology
HAAKE CaBER 1 - Capillary Breakup Extensional Rheometer - Designed for fluids Extensional behaviour ist relevant for - Processability - Strand formation / stringiness - Time to breakup - Relaxation time - Filling of bottels etc.

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Extensional Rheology: HAAKE CaBER 1 - how it works

Sample

Laser micrometer

Calculations

Apparent viscosity

Result:
Measurement D=f(t)
Apparent extensional viscosity vs. Hencky strain

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Extensional Rheology: Bottle Filling

Subtle changes in shampoo formulation caused difference in strand detachment during bottle filling Up-line characterization would prevent costly external washing of poorly-filled bottles

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Further Reading
A handbook of elementary rheology. H.A. Barnes, University of Wales, Aberystwyth, Dyfed, U.K., 2000 Non-Newtonian flow in the process industries - fundamentals and engineering applications. Chhabra RP, Richardson JF, Butterworth Heinemann, Oxford, 1999

A practical approach to rheology und rheometry G. Schramm, Thermo Haake GmbH, Karlsruhe, 1995
Engineering rheology - Oxford engineering science series vol 52. R.I. Tanner, Oxford University Press, Oxford, 2000

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Questions ?

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