Introduction Rheology

Material Science for Soft Solids & Liquids

Anamet Seminar, 2019

Dr Adrian Hill
Product Technical Specialist – Rheometry, Malvern Panalytical Limited, UK
Honorary Lecturer – Hydrocolloid Research Centre ¦ University of Chester, UK
1 © Malvern Panalytical 2019 Brno
May 2019
Agenda
Brno Seminar - Rheology

• Wednesday
• 13:30 -14:50 Kinexus
• 14:50-15:00 Break
• 15:00-15:30 Rosand
• 16:00-17:00 Complimentary techniques

• Thursday
• 10:00-12:00 Kinexus/rSpace workshop
• Hands on the machines, method development for various samples,
sample data interpretation
• 12:00-13:30 Closing remarks & Lunch
• 13:30-14:30 Remaining, 1:1 Q&A – Booked sessions

2 © Malvern Panalytical 2019 24 May 2019

Presentation Overview

• Overview and Introduction

• Basic rheology theory
• How a rheometer works

• Viscosity Measurements
• Viscosity flow curves
• Yield stress, Thixotropy

• Viscoelastic Measurements
• Amplitude sweep
• Frequency sweep

© Malvern Panalytical 2019

 OVERVIEW AND
INTRODUCTION

© Malvern Panalytical 2019

What is rheology…?

• The technical definition is:

“The science of
deformation and flow”

• But, what does this really mean?

© Malvern Panalytical 2019

Solids & Liquids

Solids DEFORM
when stressed

Liquids FLOW when

stressed
› Complex materials can show both SOLID and LIQUID like
behaviour.
› Rheology primarily describes the behaviour of these
complex materials
© Malvern Panalytical 2019
 Rheology Testing
• Typical testing in rheology splits measurements
into deformation (oscillation) and flow (viscosity)
“The science of
deformation and flow”

DEFORMATION FLOW
› Quantifies VISCOELASTICITY › Measures the VISCOSITY of a sample
› How does a sample behave before a › Mimics typical processing conditions
sample flows…?
› Predicts sample properties
› The resistance to flow

› › How thick is a paint sample

›
Sample classification
Sample stability – will it settle?
› Will the sample be pumped?

› Types of experiment:
› Types of experiment:
▪ Oscillation
▪ Viscometry
▪ Creep, Relaxation

© Malvern Panalytical 2019

Rheometer Principles –Measurement
1. Drag Cup Motor = Stress
• Directly applies a torque (which is a stress in
rheological terms)
2. Air Bearing
• Enable low torque measurements well beyond
viscometer range
3. Position Sensor = Shear Rate (Strain)
• Independently measures the resultant movement
which is determined by the viscosity of the sample. The
rheometer literally monitors the displacement in time
to convert to a shear rate
• In controlled rate, the speed (shear rate) is applied
directly and the stress required is recorded
Shear Stress Controlled Stress & Controlled
Viscosity=
Shear Rate Rate/Strain are possible

4. Geometry Recognition & Chuck

5. Measurement Geometry / Measuring System
6. Strain Gauge = Normal Force & Automatic Gap
8. Temperature Control
© Malvern Panalytical 2019
Rheometer Principles
› Rheology testing involves some standard variables:
▪ Shear stress: force (f or p) per area (a)
▪ Shear strain: displacement (u) divided by height (h)
▪ Shear (strain) rate: change in strain with time

› A sample sandwiched between two plates experiences

a strain or shear rate depending on the type of stress
applied

› The sample experiences a shear profile, and from this

typical material properties can be calculated

Top plate, surface

Viscosity ( ) =
Shear Stress  area (a) rotates u
= with force (f)
Shear Rate  h

Modulus (G * ) =
Shear Stress 
=
Shear Strain 
© Malvern Panalytical 2019
Why different measuring systems?
• A rheometer has a finite range of
torque (twisting force)
• For thick / tough samples we need to focus
this force on a small area – a small plate
(PP20)
• For weak sample we need to spread this force
on a large area – a large plate (PP50, PP60)

• Similarly, a rheometer has a finite

movement range
• Samples rotate more with a larger gap for stiff
materials

© Malvern Panalytical 2019

Typical measuring systems

• The most common measuring systems are:

• Parallel plate
• First choice for oscillation testing
• Benefits of flexible gap (~0.5 – 2mm)
• Cone and plate
• First choice for viscosity testing
• Absolute viscosity from uniform shear rate
• Fixed, small “truncation” gap (~0.03 – 0.15mm)
• Cup and bobs
• Legacy/specialist testing
• Low viscosity at low shear rates
• Larger dispersed particle testing
• Volatile sample testing

© Malvern Panalytical 2019

 Special Measuring Systems

• Some sample types do not lend themselves to be measured using

conventional tools and require a modified interface. Here are some
common examples:

▪ Reduce wall slip (e.g.

Vane Tools slurries)
▪ Measurement of delicate
structures (e.g. yield
stress determination for
foams and soft solids)

Serrated & ▪ Reduce slip effects (e.g.

concentrated dispersions
roughened
& semi-solids)
surfaces

© Malvern Panalytical 2019

 VISCOSITY
MEASUREMENTS

© Malvern Panalytical 2019

This Photo by Unknown Author is licensed under CC BY-SA
Viscosity

•Introduction to Viscosity
• Defining shear stress and shear rate
• Viscometers and rheometers
• Identifying the appropriate shear rate
• Shear thinning and why it occurs

•Viscosity Measurements
• Viscosity flow curves
• Yield stress
• Thixotropy

© Malvern Panalytical 2019

 Rheology Testing
• Typical testing in rheology splits measurements
into deformation (oscillation) and flow (viscosity)
“The science of
deformation and flow”

DEFORMATION FLOW
› Quantifies VISCOELASTICITY › Measures the VISCOSITY of a sample
› How does a sample behave before a › Mimics typical processing conditions
sample flows…?
› Predicts sample properties
› The resistance to flow

› › How thick is a paint sample

›
Sample classification
Sample stability – will it settle?
› Will the sample be pumped?

› Types of experiment:
› Types of experiment:
▪ Oscillation
▪ Viscometry
▪ Creep, Relaxation

© Malvern Panalytical 2019

 What is Shear Rate?

• Really just a deformation rate. How much work are we putting into
the sample?
Process Typical shear rate range (s-1)
Reverse gravure 100,000 - 1,000,000
Roller coating 10,000 - 1,000,000
Measurable
Spraying 10,000 - 100,000
on a Rosand
Blade coating 1,000 - 100,000 capillary
Mixing/stirring 10 - 1,000 rheometer
Brushing 10 - 1,000
Pumping 1 - 1,000
Measurable
Extrusion 1 - 100
on a
Faster processes, Curtain coating 1 - 100
Kinexus
squeezing Levelling 0.01 - 0.1 rotational
materials through Sagging 0.001 - 0.1 rheometer
smaller gaps Sedimentation 0.000001 - 0.0001
© Malvern Panalytical 2019
Match Shear Rate to
Processes…
• Take an everyday simple example… hand cream
Storage SAMPLE STORAGE
Very low shear rates: ~ 0.001s-1
How stable is it, sample quality…

SAMPLE DELIVERY
Medium shear rates: ~10s-1
Pumpability? Scoopability?

SAMPLE APPLICATION 1
Low shear rates: ~1s-1
Flows away? Flows off hand?

SAMPLE APPLICATION 2
Higher shear rates: ~100s-1
Too thick to spread? Nice feel?
End use
© Malvern Panalytical 2019
 Flow Curves
• Three general flow behaviours
• Viscosity is a function of shear rate

Newtonian Shear-Thinning Shear-Thickening

(Pseudoplastic) (Dilatent)
Viscosity

Viscosity
Viscosity

Shear Rate Shear Rate Shear Rate

e.g. silicone oil, low e.g. polymers, e.g. cornflour, high
concentration dispersions dispersions solid content TiO2

› Most, real, samples are shear thinning with Newtonian regions

› Viscosity testing is most powerful when it is used to simulate or mimic

processes
© Malvern Panalytical 2019
Simple Flow

© Malvern Panalytical 2019

Not Simple
Flow

• Need to measure to understand

behaviour

• Shear thickening

© Malvern Panalytical 2019

Flow Curve Measurements

“YIELD STRESS”
An ever increasing viscosity as the
shear rate approaches zero, i.e. a does
not flow / solid like when stationary.
Log Viscosity

ZERO SHEAR VISCOSITY

The viscosity plateau’s as the shear rate
approaches zero, i.e. flows / liquid like
when stationary.

Rheometer measurement range

Viscometer
Measurement range

10-6 Log Shear Rate 106

Studying weaker Studying stronger
interactions interactions
© Malvern Panalytical 2019
V001 – Flow Curve: Typical
Results
› This tests shows how materials behave under
different conditions, which are mimicked by
shear rates

“YIELD STRESS”
Hand Cream (Blue)

ZERO SHEAR VISCOSITY

Shower Gel (Red)

• Notice how it is only at low shear rates that shower gel and hand cream
are different; they are different when in the bottle
• At higher shear rates, i.e. being applied, they have similar viscosities, as
both are expected to behave the same under these conditions
© Malvern Panalytical 2019
Why does shear thinning occur?

© Malvern Panalytical 2019

YIELD STRESS

© Malvern Panalytical 2019

 Yield Stress
› Some samples require a certain stress
until they flow – a yield stress
› A transition to go from solid to liquid

• For example:
• Why toothpaste needs to be squeezed to
get out of the tube but 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 have a start-up time

© Malvern Panalytical 2019

 Yield Stress Measurement
› Apply an increasing rotational
Applied profile:

Stress
“squeeze”, i.e. shear stress to a
material

Time
› A material with yield stress
Viscosity

will stretch easily, until the

yield point, then flow
Yield Stress
› The stress at the peak in
viscosity is the force
required to go from solid
like to liquid like, i.e. the
Shear Stress yield stress
› No peak (dotted line), no
force needed
© Malvern Panalytical 2019
V003 – Stress Ramp: Typical Results

• Typical results from a stress ramp experiment shows clear differences between
a yield stress type material, and that of a zero shear viscosity system

No peak, no yield stress

Shower Gel (Red)

Peak = yield stress

Hand Cream (Blue)

› It is typical to only quantify the yield stress when a sample exhibits one in
the flow curve
› rSpace can measure the peak in the data directly© Malvern Panalytical 2019
THIXOTROPY

© Malvern Panalytical 2019

Thixotropy – Not Just Shear
Thinning

• 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

Store paint Stir paint Apply paint

Low shear High shear Low shear

rate rate rate

Appears Becomes Termed thixotropic: it

“thick” thinner, shear takes time to become
thinning. thick again / rebuild
© Malvern Panalytical 2019
 V002 Thixotropic Store paint Stir paint Apply paint

Measurement Low shear

rate
High shear
rate
Low shear
rate

Appears Becomes Termed

“thick” thinner, thixotropic: it takes
shear time to become
thinning. thick again / rebuild

Shear rate
• Apply a step sequence of shear rates.
Simulate a process

Time
Viscosity

Bad paint – leaves brush

Shear Thinning

marks
Rebuilds too thick too quickly

Good paint – leaves smooth

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

› A shear thinning material may be thixotropic

› However, a thixotropic material will always be shear thinning
© Malvern Panalytical 2019
 V002 – Three Step Test:
Typical Results
• This tests shows how a material rebuilds its structure after a high shear
process

The shear rate profile (Blue)

Monitor the thixotropic rebuild (Red)

Typical solid in liquid dispersion - Indigestion Relief Liquid

› The longer a material takes to rebuild, the more thixotropic the sample is
› Thixotropy also affects how long a sample takes to get to steady flow
› Thixotropy is not only an important material parameter. It is important to
understand for reproducible measurements, i.e. repeat when fully rebuilt
© Malvern Panalytical 2019
 VISCOELASTIC
MEASUREMENTS

© Malvern Panalytical 2019

Overview

• Viscoelastic Measurements

• Oscillation Amplitude Sweep

• Frequency Sweep

• What is a solid, and what is a liquid!

© Malvern Panalytical 2019

 Rheology Testing
› We have looked at the first part of rheology… flow… now:
“The science of
deformation and flow”

DEFORMATION FLOW
› Quantifies VISCOELASTICITY › Measures the VISCOSITY of a sample
› How does a sample behave before a › Mimics typical processing conditions
sample flows…? › The resistance to flow
› Predicts sample properties
› How thick is a paint sample
› Sample classification › Will the sample be pumped?
› Sample stability – will it settle?

› Types of experiment: › Types of experiment:

▪ Oscillation ▪ Viscometry
▪ Creep, Relaxation
© Malvern Panalytical 2019
 Viscoelasticity
• All this means that most materials
are not completely solid nor
completely liquid like…

• They are viscoelastic

An example would be a paint:

› During storage it needs to behave like a solid to prevent
sedimentation

› When painting it needs to behave like a fluid so that it flows

in the bristles of the brush and can be evenly painted
© Malvern Panalytical 2019
 Pitch Drop Experiment
• Timescale is also important in Rheology!

› Pitch behaves as a SOLID on

short timescales (high
frequency) – shatters when hit
with a hammer

› ….but behaves like a LIQUID on

long timescales (low frequency)
– drips at rate of 1 drop every 10
years

http://www.science.uq.edu.au/uq-science-webcams
© Malvern Panalytical 2019
 Oscillation Testing
TOP PLATE ROTATES AT A CONSTANT
ROTATIONAL VELOCITY

› To determine the Viscosity we apply a

constant Shear Stress and measure the
resultant Shear Rate (or vice versa)
› To determine the
Modulus we apply an
TOP PLATE OSCILLATES AT
oscillatory Shear
A GIVEN STRESS OR STRAIN
AMPLITIDE
Stress and measure
the resultant Shear
Strain (or vice versa)

› Modulus is given by the max stress

(amplitude) divided by the max strain
© Malvern Panalytical 2019
Complex Modulus - G*

› G* is measure of overall material stiffness with contributions from viscous

and elastic elements
▪ Some stress required to stretch the elastic components
▪ Some stress required to translate viscous components
Input Stress
Calculated from how much a
sample moves for a given Measured Strain

force.


Max Stress
G =
*

Units of Pascal's (Pa) Max Strain

© Malvern Panalytical 2019
 Phase Angle
› We can also calculate the phase angle
› Different types of materials have a different lag / phase
angle between the applied and measured sinusoidal
signal

Input Stress
Measured Strain

Time


Phase angle
© Malvern Panalytical 2019
Phase Angle - δ

› For a Purely Elastic Material – Solid-like behaviour

• the stress is in phase with the strain (δ = 0)
› For Purely Viscous Material – Liquid-like behaviour
• the stress is in phase with the shear rate (δ = 90°)
› For Viscoelastic Material – Mixed behaviour
• The phase angle is somewhere in between (0 < δ < 90°)

Max stress Max stress Max stress

δ

Max strain Max strain δ Max strain

Elastic (δ = 0) Viscoelastic (0 < δ < 90°) Viscous (δ = 90°)

© Malvern Panalytical 2019
Solid or liquid like…?
› Yogurt and honey can have the
same complex modulus or same
stiffness, however...

› Yogurt is elastically dominated, it

behaves as a solid
▪ Pour it and it drops
▪ Leaves ridges, doesn’t flow well

› Honey is viscously dominated, it

behaves as a liquid
▪ It pours and strings
▪ Settles with a smooth finish

© Malvern Panalytical 2019

Elastic and Loss Modulus
› G* can be broken down into its component parts using simple
trigonometry
› These components are termed:
• Storage (elastic) modulus, given by G’ = G*cosδ
• Loss (viscous) modulus, given by G’’ = G*sinδ

› G’ is a measure of the energy

stored and is related to the stress G”
contribution (or stiffness) from the
materials elastic structure G*
› G” is a measure of the energy
dissipated (or lost) and is related
to the stress contribution from the
viscous elements δ G’
© Malvern Panalytical 2019
 Storage and Loss Modulus

• Rheology language tends to use a combined form of

complex modulus and phase angle

• Storage (elastic) modulus G’

• Loss (viscous) modulus G’’

• If G’ > G’’, phase angle less than 45° - SOLID LIKE

• If G’’ > G’, phase angle greater than 45° - LIQUID LIKE

• G* - modulus, is still a measure of toughness

© Malvern Panalytical 2019

AMPLITUDE SWEEP

© Malvern Panalytical 2019

Amplitude Sweep

› Determines the Linear Viscoelastic region (LVR) where stress/strain ratio

and hence G*, G’ and G” are constant
› Hookes law is only applicable within the LVR so stress or strain value kept
within LVR for further linear testing

› Structural breakdown (yielding) is

observed at stresses/strains outside
the LVR which is why G’ drops
› A large LVR means a ‘more ductile’
material and a small LVR “ a more
brittle” material

© Malvern Panalytical 2019

 O001 Amplitude Sweep:
Typical Results
• This tests records the linear viscoelastic region (LVER) of a material

LINEAR VISCOELASTIC REGION - LVR

0.08 % for a body lotion

› Typically G’ is the most sensitive to the LVER

› The limit of the LVER is where the structure of the material starts to break
down
› G’ is a direct measurement of the structure in the sample
› G’’ is the viscous or flow property, as such this tends to flow instead of
breaking down
© Malvern Panalytical 2019
FREQUECY SWEEP

© Malvern Panalytical 2019

Solid AND Liquid “like”
› Your inks want to behave like…

© Malvern Panalytical 2019

O002 Frequency Sweep: Results
• The test records the viscoelastic spectrum
of the material
G’’ – Loss (Liquid like) modulus

 – Phase angle
G’ – Storage (Solid like) modulus

Malvern Play Putty

A solid in liquid dispersion

Low frequencies High frequencies

Long timescales Fast timescales
G’’ > G’ G’©>Malvern
G’’Panalytical 2019
LIQUID LIKE SOLID LIKE
Material Behaviour
• Three general material behaviours
• Material property at rest (0Hz) classifies behaviour

› VISCOELASTIC SOLID: phase angle  0° at 0Hz.

› VISCOELASTIC LIQUID: phase angle  90° at 0Hz.
› GEL: phase angle independent of frequency.
© Malvern Panalytical 2019
VISCOSITY VS. OSCILLATION

© Malvern Panalytical 2019

 Solid or Liquid? Play Putty

• Play Putty is actually a

VISCOELASTIC LIQUID!
Phase angle  90° at 0Hz
Liquid like at rest

Zero shear viscosity

Flows at rest

© Malvern Panalytical 2019

 Solid or Liquid? Hand Cream

• Hand cream is actually

VISCOELASTIC SOLID!
Phase angle  0° at 0Hz
Solid like at rest

Yield stress
Does not flow at rest

© Malvern Panalytical 2019

 SUMMARY
&
OVERVIEW

© Malvern Panalytical 2019

THIXOTROPY- VISCOMETRY FLOW CURVES - VISCOMETRY

YIELD STRESS - VISCOMETRY

RHEOLOGY MEASUREMENTS © Malvern Panalytical 2019

 Structure
break down
Linear region

SINGLE FREQUENCY - OSCILLATION AMPLITUDE SWEEP - OSCILLATION

FREQUENCY SWEEP - OSCILLATION

RHEOLOGY MEASUREMENTS
© Malvern Panalytical 2019
Thank you for your attention

Any questions?

adrian.hill@malvern.com

www.malvernpanalytical.com

© Malvern Panalytical 2019