Brno, 28-29th march 2012 School of Rheology

Part I: Rotational Rheometry

How to measure Shear Viscosity correctly?

Rotation

Outline

Basic terms in shear rheometry

Principle of Operation: Rotational Rheometer

Applications:
A) Steady State Flow Curves using a Rotational Rheometer:
Impact of particle size, volume fraction and polydispersity on dispersion flow
properties, Polymer Melt Rheology
B) Time-dependent Flow Behaviour
Yield Stress of Dispersions and it`s relation to Zeta Potential, Thixotropy,
Structure Recovery

- with Live Tests on Kinexus Rheometer

Basic Terms in Shear Rheometry

displacement u
Tangential-force F

area = a b
Gap = s

u
=
s
.
d
=
dt
Ftan
=
A

strain []

Shear rate [1/s]

Shear stress [Pa=N/m2]

Typical Shear Rate Ranges

Sagging,
Levelling

Extrusion, Injection Moulding

Roll Coating, Spraying

Mixing, Blade Coating, Brushing

10-3

10-1

100

101

102

103

104

106

s -1

Rotational-Rheometer
Sample: Water up to solids
Results: Shear-Viscosity, Yield Stesses, Visco-Elasticity, Relaxation...

High Pressure Capillary-Rheometer

Sample: Water up to high viscous
Results: Shear-Viscosity, Elongational-Viscosity, Wall Slip...

Shear Viscosity
Resistance of a sample against the flow

=


.

Shear Viscosity
Shear Stress
Shear Rate

Typical Shear Viscosities

Material

Shear-Viscosity (Pas)
10-6
10-4
10-3
10-1
100
103
108
1012
1040

Air
Aceton
Water
Olive Oil
Glycerol
Molten Polymers
Bitumen
Glass at 500C
Glass at ambient
Units:
Pascal second
Poise

Pas (SI)
P (CGS)

Remember
1 Pas = 10 P
1 mPas = 1 cP

Shear-Viscosity depends on

(, p, t, ) =

Physical-chemical structure of the sample

Temperature (up to 20% / K)
Pressure
Time
Shear Rate

Steady-State Flow Behaviour

Shear Thinning

Shear Rate

Shear Rate

Shear Rate

Shear Rate
Cornflower
.

Shear Rate

Viscosity

Inks, Paints
Viscosity

Viscosity

Silicon Oil, Suspension

Shear Thickening

Stress

Stress

Stress

Newtonian

Shear Rate

Principle of Operation: Rotational Rheometer

Stress- and
Strain Control
possible.
Motor

Air bearing

Position
sensor

Upper Measuring
Plate

The drive is situated above the sample,

not below.
The driven spindle is air bearing
supported so torque can be measured.
The separate torque transducer is
eliminated!
Advantages:

Sample

Temperature
Controller

Wide Torque Range 10e-9 to 10e-1 Nm

Short Response times
Small inertia design
Direct Stress and Direct Strain

Choice of Geometry: From Fluids to Solids

Apply Torque /
Measure Torque

Measure Displ.
Apply Displacement

R
the higher the viscosity,
the smaller the geometry

Rule of Thumb
for dispersions:
Gap Size > 10 * D90
Parallel Plates

the higher the shear rate,

the smaller the gap.

Cup&Bob

Solids Fixture

Cone-Plate / Plate-Plate

Cone Adv: Const Shear Rate along

the complete gap, easy cleaning,
low sample volume, wide viscosity
range

Cone DisAdv: only for

homogeneous samples, for
disperse samples D90 < 10 x gap,
solvent evaporation

Plate Adv: flexible gap, auto-tension

possible, low sample volume, often
used for temperature dependent
tests, good for disperse systems

Plate DisAdv: shear rate

dependency, solvent evaporation

0s-1

10s-1

10s-1

10s-1 10s-1

Cup & Bob / Double Gap

Cup&Bob Adv: large gap, works well

for disperse systems, also for samples
showing sedimentation, large surface
area, nearly no evaporation effects,
good for low viscous samples, less
impact of loading errors

Cup&Bob DisAdv: high moment of

inertia limits oscillation and transient
steps, high cleaning effort, large
sample volumes (ca 2ml 15ml)

Double Gap Adv: highest sensitivity for

low viscous samples, lower inertia
compared to cup&bob, nearly no
impact on loading errors

Double Gap DisAdv: large sample

volume (ca. 15ml 30ml), difficult
cleaning

Cup&Bob acc DIN53019

Double Gap

Basic Viscometry: How to run a flow curve

CS-Mode: Steady state and non-steady state measurements

Steady state:

Table of stresses

t
non-steady state:

Linear ramp

1. Steady State Flow Properties

Newton:

Flow Curve:

= ()

equivalent

CR-Mode
Shear Viscosity
Curve:

= ()

= ()
CS-Mode

equivalent

= ()

Steady State Condition

Kinexus Rheometer

J=

dLnJ/dLnt = 1 for pure viscous flow!

Deviations show measurement errors!

Steady State Calculation

(t )
d ln

d ln J
d (ln (t ) ln ) d ln (t ) d ln

=
=

=
d ln t
d ln t
d ln t
d ln t
d ln t

0
t

Newtons Law : = dt =

(t ) = const , (t ) = const


d ln t
d ln
d ln (t ) d ln
+ d ln t d ln =
d ln =
=

=
d ln t
d ln t
d ln t
d ln t
d ln t
d ln t d ln t
=

d (ln ln ) d ln t d ln
+

d ln t
d ln t d ln t

d ln d ln d ln t d ln

d ln t d ln t d ln t d ln t

d ln J
=1
d ln t

for steady state.

Comparison Stress- and Rate Controlled Test

Shower Gel:
Comparison CS und CR Shear Viscosity Curve

Live Measurement on Kinexus:

Shower Gel Flow Curve

Normal Stress Difference N1

Shower Gel
Ft
Fn

Edge failure

Always watch the Normal Stress during a Shear Viscosity Measurement!

Steady State Flow Curves: Impact of Particle Size

(Pa.s)

102
101

175 m

100

Increase the size of latex

particles in a pressure sensitive
adhesive from D50=175m to
D50=750mm
Polydispersity and Volume
Fraction similar

10-1

750 m

10-2
10-1

100

101

102 103
.
(s-1)

104

105

106

Smaller size means an increase in number of particles which causes an

increase in particle-particle interactions. Hence an increase in low shear
viscosity.

Reason for Shear Rate Dependency

Log

Entanglement Network / Particle-Particle-Interaction

Log

Equilibrium

Destruction >
Recovery

No Entanglements

Molecules / Particles
Entanglements / Particle Interaction

Steady State Flow Curves: Impact of Particle Loading

Changing the Volume Fraction of Particles
Newtonian

< 0.1

0.1 <

< 0.5

Log Zero Shear Viscosity

Shear Thinning

Shear Thickening

> 0.5

Krieger-Dougherty:

medium
Volume Fraction

= 1
m

[ ] m

Shear Thickening of concentrated dispersions

Kinexus Rheometer

those shear thickening effects can have negative impact on processability

see section capillary rheometry

Steady State Flow Curves: Impact of Polydispersity

We keep the volume fraction () constant
But changing polydispersity
Particle Size Distribution

Volume (%)

20
15
10
5
0
0.1

10
Particle Size (m)

What happens to the viscosity?

100

1000

3000

Impact of Polydispersity on Flow Behaviour

Zero Shear Viscosity

Fine talc of different D50, mixed into an epoxy resin

100%
175 m

100%
750 m
Krieger-Dougherty
0%

Increasing amount of 175 m particles 100%

100%

Increasing amount of 750m particles

0%

medium

= 1
m

If you want to increase the solid content of the sample but keep the viscosity the same,
increase the particle size distribution (polydispersity) as well.
Conversely, narrow the particle size distribution to increase the viscosity.

[ ] m

Steady State Flow Curves: Impact of Matrix Additives

Xanthan Solution - measured with Cone Plate and Double Gap
1000

sp

Mw= 2.400.000 g/mol

1%

100

M =

Shear viscosity[Pas].

0.5%

= [ ] + k h [ ] c
2

10
N
3

R h3

[ ]

10

1%
0.3%

0.5%

0.3%
0.1% CP

0.1%
0,1

0.1% DG

0,01

0,001
1,0E-04

1,0E-03

1,0E-02

1,0E-01

1,0E+00

1,0E+01

1,0E+02

1,0E+03

Shear Rate [1/s]

==> the higher the concentration of Xanthan, the higher the zero shear viscosity.

Further Factors Influencing Dispersion Rheology

Spray Particle
Analyzer

Laser Diffraction

volume fraction,

Particle size

Particle size distribution

Digital Microscopy

Vs

Light Scattering
Size and Zeta
Electrostatic interactions

Steric Hindrance

Particle shape

Dry
+

------

Wet

Polymer Melt Rheology: Determination of Mw from Flow Curves

Polymer Melt Rheology: Effect of Molecular Weight Distribution

Log Viscosity (Pa.s)

A Polymer with a broad MWD exhibits nonNewtonian flow at a lower rate of shear than a
polymer with the same 0 but has a narrow MWD

Narrow MWD

Broad MWD

Log Shear Rate (1/s)

2. Time Dependent Flow Properties

Viscosity is not only dependent on shear rate it is
also time dependent.
Think of paint. Thick in the can when left in the
shed for months, but thins when stirred.
However, it is thixotropic as it does not rebuild
straight away on stopping the stirring.

Shear rate

Thixotropic Example
Two samples one very thixotropic, one not so
thixotropic.

Viscosity

Time

Bad paint leaves brush

marks.
Rebuilds too thick too quickly.

Good paint leaves smooth

finish.
Rebuilds quite slowly. Enough
time to allow ridges to smooth
out.

Time

Thixotropy 3- Step-Shear profile

Thixotropy: Decrease of viscosity vs. time at
constant shear + complete recovery under rest
1 2

1 = Initial Viscosity at low shear

2 = high shear phase (time-and rate dependent)
3 = Recovery

Another Time Dependent Property: Yield Stress

Some samples require a certain stress until they
flow a yield stress.
A transition to go from solid to liquid. Or
Why toothpaste needs to be squeezed to get
out of the tube.
However, does not flow into bristles on tooth
brush.
Why Heinz tomato sauce needs a whack.
But still looks thick on the plate.

Or why pumps take time to get going.

Relation to Flow Curves

YIELD STRESS
An ever increasing viscosity as the
shear rate approaches zero, i.e. a does
not flow / solid like when stationary.
ZERO SHEAR VISCOSITY

Log Viscosity

The viscosity plateaus as the shear rate

approaches zero, i.e. flows / liquid like
when stationary.
THIXOTROPIC
Both materials can be, and tend to be
thixotropic viscosity depends on time.

Rheometer measurement range

Viscometer
Measurement range
10-6
Studying weaker
interactions

Log Shear Rate

106

Studying stronger
interactions

Yield Stress Determination by Stress Ramp and

Creep Tests
Viskoses Fleen
Schubspannung
3Pa

Schubspannungen
1Pa, 1.5Pa, 2Pa, 2.5Pa
Fliegrenze = 3Pa

Linear or logarithmic Stress Ramp

Energy absorbed - strong association - no flow

Mutliple Creep Tests at different

Stresses

Usually Stress Ramp is used as a pre-test, whereas Multiple Creep

gives precise Yield Stress

Example: Stable Metal Oxide Dispersions

In this case study we have a sample of silica
(silicon oxide) which has an average particle size
greater than 1 micrometer.
Conventional colloidal theory of
increasing the zeta potential
to 30mV is insufficient to
counter the effect of gravity
on these large particles

Particle Size
Sample characterised on a Mastersizer 2000,
showing a particle size greater the 1 micrometer.

Laser Diffraction

Zeta Potential
Titrating a silica sample with HCl on a
Zetasizer Nano with MPT-2 autotitrator.

The isoelectric point (where the zeta potential is

zero) is in the very acidic (pH 1) region.

Steady-Shear Viscosity vs Zeta-Potential

Log Viscosity

Suspension with micron particles

and zeta potential -> 0mV

Associated structure
strong enough to induce
a yield stress.
Suspension with
sub-micron particles
and high zeta potential

Log Shear Stress

At isoelectric point the zero shear viscosity gets infinite

Stronger associated structures which resist even

high shear stresses.

Resultant Rheology for the Silica Supsension

As the particles associate more, with pHs closer
to the iso-electric point, the viscosity increases.

pH2.42
pH3.97

pH3.52

Materials with higher low shear viscosities are

regards as more resistance to separation.

Resulting Yield Stress for the Silica Suspension

Yields stress measurements (the stress at the peak of
instantaneous viscosity) is a measurement of the internal
strength of material.

pH2.42 yield stress = 15.8 Pa

pH3.52 yield stress = 2.5 Pa

pH3.97 no yield stress

Thank you for your attention!

Please join our sessions on:

Capillary Rheometry and Oscillatory Rheometry.

Any Questions? torsten.remmler@malvern.de