23522 – Rheology of Food and Biological Materials

Ioannis S. Chronakis
Outline:

• Introduction to Rheology

• Viscoelasticity

• Rheology of Fluids

• Texture & Texture Analyzer

• Mechanical rheological models

Introduction to Rheology
Rheology - Introduction

• Rheology pertains to the study of deformation and flow of materials

Rheology - Introduction

• It applies to substances which have a complex structure:

suspensions, polymers, many foods, bodily fluids, and other biological materials
Types of products
Product examples
Characteristics

• Relation to consumer preferences?

 What is deformation

• Two types of deformation are used

in reological characterisation
(a) Longitudinal deformation
(b) Lateral deformation

• The extent of deformation is characterised by

- strain : the distance travelled by the moving
surface divided by the initial height of the sample

- stress: the resistance to deformation is

defined as force per unit area

Strain = L / L
Stress = F / A
Viscosity and flow

• Viscosity can be thought of as a liquid’s internal resistance to flow

• The force that moves the liquid is known as shearing force or

shear stress

• The velocity gradient is known as shear rate

Classification of rheological behavior
Hookean solid

• Hookean solid: the resistance (rigidity, Pa) is independent of the rate of

deformation, but increases linearIy with the extent of deformation

Young's modulus (longitudinal) :

E= 

Shear modulus (lateral):

G=
 Newtonian liquid

• Newtonian liquids: viscosity (the ratio of stress/rate)

the increases linearIy with shear rate

Steady shear viscosity (Pas):

 =

• Viscosity: the resistance to flow

Rheology introduction

• Partitioning materials into fluids and solids is an idealized view.

• Depending on the typical timescale, a material can be considered as a solid (e.g.,

exhibiting an elastic behavior) or a fluid.

• For instance, over ‘short’ timescales, a glacier is a solid, whereas at long

timescales (e.g., several years), it behaves like a liquid.

• Relaxation time: the relaxation time is the characteristic time needed for a
material to flow.
Rheology introduction

• Deborah number : is the ratio between the characteristic time/duration of an

observation/experiment tobs and the relaxation time tr

• When De << 1, the observer has not the time to register any fluid/creep motion
and the material behavior can be considered as solid.

• When De >> 1, the material has time to relax and modify its structure as a
response to the applied forces; the material behaves like a fluid.
Rheology introduction

• For some materials, the Deborah number De = 1, , which means that the material
can exhibit both solid and fluid properties.

• Real food products have intermediate behaviour, with elements of both solid-like
(elastic) & liquid-like (viscous) response to deformation: viscoelastic

• Whether these behave as solids or liquids depends on how long the stress is
applied.
Rheology introduction – viscoelastic materials

• A good example is the material known as "silly" putty. If this is stressed in

short times, it behaves elastically - thus it will bounce. If, however, a
stress is applied over a long time, it will flow - it behaves as a
viscous liquid.

• The visco-elastic materials behave as solids when they are stressed in

short times but as liquids when the stress is applied over long periods.

• Examples
Rheology introduction – viscoelastic materials

• In viscous fluids, the rotating shaft causes centrifugal forces, throwing the liquid away
from the center.

• for viscoelastic materials, the rotating shaft induces normal stresses which exceed the
centrifugal forces resulting in forces that pull the material up the
shaft.

•This rod climbing is known as the Weissenberg effect

Deviations from Newtonian behavior, due to high normal stress
differences, can lead to processing problems

Weissenberg effect. Photo from Gareth McKinley’s

group at MIT.
 Viscoelasticity

Food Production Engineering

BioCentrum-DTU
Danmarks Tekniske Universitet
Rheology – (viscoelasticity)

Time-Dependent Viscoelastic behaviour:

solid and liquid properties of ’Silly Putty’
Rheology – (viscoelasticity)

• In some cases we would like to know more about the internal structure of
products

• Thus we need:

– To measure without destroying the structure

– Maintain equilibrium in the material

• In practise measurements are taken in the linear visco-elastic area

– Equilibrium between formation and breakdown of internal bonds

– The measurement is an oscillating small deformation

• We obtain two signals one which is in phase with the deformation and one 90
degrees out of phase
Oscillatory rheology - viscoelastic systems

• The degree of solid-like and liquid-Iike character can be quantificd by the

resistance of the sample to a small amplitude oscillatory rheology (SAOR)

• Why we use small amplitude oscillatory rheology ?

- Determination of viscoelastic properties;
- Minimal structure damage from analyses; and
- Subject same sample to a variety of test conditions

Oscillation device
Rheometer – StressTech, Reologica
Oscillatory measurments
Viscoelastic properties
are ’time dependent’

• Perfectly elastic solid:

the stress generated is
exactly in-phase with
the imposed strain

• Newtonian liquids: the

resistance to flow
(stress) is exactly out of
phase with the applied
strain

Elastic modulus, G’= in-phase stress / strain = o / o cos 

Viscous modulus, G’’= out-phase stress / strain = o / o sin 
tan  the phase lag between applied strain & stress: tan  = G’’/ G’
Oscillatory measurments
Rheology – (viscoelasticity)
Oscillatory measurements
Oscillatory measurements

• The overall resistance of the sample to the applied deformation

characterised by the complex modulus, G* :
G* = (G’2+G’’2)1/2

Complex viscosity:
* = G*/= (G2+G2)1/2

Dynamic viscosity:
 ’ = G’’ /
Oscillatory measurements

• Measurement with oscillation, can quantify :

– In phase: Storage or elastic modulus G’
– Out of phase: Loss or viscous modulus G’’

– Phase angle : tan 

• The following relations are governing:

G* = G '2 + G ''2
Oscillatory rheology - viscoelastic systems
Viscoelastic properties
are ’frequency dependent’
 Viscoelastic material: frequency dependence

SAOR features:

• Temperature effects
• Compositional effects
• Time effects
Viscoelastic material: frequency dependence

*
G’

G’’

Frequency () dependence of

G’’ * G' (---- ), G" (―• ―) and *(―) for
(a) a strong gel, (b) a concentrated
G’
solution, & (c) a dilute solution

*
G’’ G’
Viscoelastic material: frequency dependence

concentration
increase

concentrated solutions

• The analysis gives an indication of the relative viscous and elastic behaviour
of the biopolymer over different time scales
(i.e. inverse of the frequency - low frequency equates to long timescale
behaviour and vice versa)
Viscoelastic material: frequency dependence

Oscillatory behaviour of aqueous xanthan

gum solutions, at various weight percentages
Viscoelastic material: frequency dependence

Peanut butter frequency sweep for low and high fat content.
Viscoelastic material: frequency dependence

Oscillatory behaviour of a 5% crosslinked starch gel

Viscoelastic material: frequency dependence

Oscillatory behaviour of a typical oil-in-water

emulsion and a gloss paint
Viscoelastic material: frequency dependence

A HANDBOOK OF ELEMENTARY RHEOLOGY H. A. Barnes

Viscoelastic material: frequency dependence

Oscillatory behaviour of narrow molecular weight polystyrene,

Mw 0.39 M, at 160oC.

A HANDBOOK OF ELEMENTARY RHEOLOGY H. A. Barnes

Frequency & time - temperature superposition

Shift using T

12 decades
50oC 40oC

30oC 25oC

Frequency temperature superposition of the

20oC 15oC dynamic moduli G’ (—) & G’’(- - - -) for various
-carragenan conc. in 0.2 M NaI. Temperatures
range, 15–50°C, ref. temp. of 40°C
Frequency & time - temperature superposition
• By application of the time–temperature superposition principle it is possible to
extend the frequency range of the mechanical spectrum of a viscoelastic
solution or gel

• Assumes that the T only shifts the time scale of the relaxation process without
changing its nature, or the structure of the viscoelastic systems

G* ( ) = G* ( )  b

• G* is the complex modulus,  the angular frequency, and To the (arbitrarily

chosen) reference temperature, T and bT are the frequency (horizontal) &
modulus (vertical) shift factors,

• These factors are determined graphically by simply shifting the set of data
Linear viscoelastic region (LVR)
intact network micro-cracks

fracture

• A material is considered Linearly Viscoelastic if, when deformed under

small strains, the ratio of stress to strain is constant
• Hooke’s Law applies!
Linear visco-elasticity (stress sweep)

1,00E+02
G' (series 1)
G' (series 2)
G'' (series 1)
Linear viscoelastic region G'' (series 2)
Moduli (G', G') [Pa]

1,00E+01

Linear viscoelastic region

1,00E+00
1,00E-01 1,00E+00 1,00E+01
Shear stress [Pa]
Linear visco-elasticity (stress sweep)
 Linear viscoelastic region & microstructure
Stress/Strain sweep (mayonnaise)
• Coagulated and strongly flocculated
dispersions have relatively short linear
Stable regions; weakly flocculated and stable
dispersions have longer linear regions

• The onset of non-linearity result from

coalescence of the emulsion droplets, or
emulsion destabilization (phase separation
during storage)

Stable Coagulated
• The extent of linear region gives
an indication of the type of
microstructure in the food system
Oscillation – example 1
Oscillation – example 2
Rheology – phase angle δ

• The phase angle δ describes the relation between elastic and viscous behaviour

– δ < 45° Elastic properties dominates

– δ > 45° Viscous properties dominates

– For 45° G’ and G’’ are equal

– When G’ is largest we have dominantly gel properties which are becoming

more pronounced when the phase angle goes towards 0

• The gel strength depends on the magnitude of G’

Ice cream characteristics & microstructure

heating at 1°C/min

tan 

• The G* shows how hard the sample is and the tan  when different
components in the ice cream melt
• Quantify the ease of handling of cold ice cream & the mouth feel melting
 ``Spreadability`` & components
Spreadability: inversely
• Spread softened with increasing proportional to it’s viscosity at 5°C
temperature: the two fat components
are melting at different temperatures

• The peaks in the tan δ curve indicate
that components are melting at
17°C & 23°C
tan 
• Addition of a component with a lower
melting point, or with a less
temperature dependent viscosity

will become more spreadable Rheology show the effect of different fats
and emulsifiers in a mixture, as well as the
effect of changing the processing
conditions
Tan  & network characteristics
tan  at the same frequency

• tan  provide a convenient way

of monitoring network elastic & viscous
characteristics

• The lower the phase angle, more gel-like

the more elastic a material is &
the higher, the more viscous

• Gel: soft solid

tan  of kappa-carrageenan gels
from different ion contents
Curing Test – Jam development
Curing Test – Jam development
 Gelation of viscoelastic systems

• Physical cross-linking, to develop a 3-D

network (through conformationally-
ordercd 'junction zones’ which involve
long stretches of the participating chains)

Gelation
Temp.
80oC 20oC 20oC

Gelation during cooling of kappa-

carrageenan polysaccharide in the
presence of ions
200nm (2wt% 1°C:min, 1.6 Hz, 0.5% strain)
Why do a temperature sweep test?

⚫ Commonly used to find Tgel of a material

– Point at which the structure changes due to temperature

⚫ Used to find melting temperatures of samples.

– Materials like gelatin can change from a liquid to a solid

⚫Find the amount of thinning that occurs with heating to

predict performance and design process equipment
Gelation time, gel strength & gel set / melt

• G’ and G’’ provide a convenient way

of monitoring gelation (and melting
processes) non-destructively

• Carrageenan’s gelation is temperature

induced, (sets-up when the
temperature is reduced)
Gel point
• The temperature at which the gelation
occurs will depend on the ionic and
gelant concentrations as well as the pH
The crossover point of the elastic and
Gelation Time at crossover of G´ & G´´ viscous moduli indicates when the sample
has reached a ‘gel point’
 Gelation time, gel strength & gel set / melt

• Methyl cellulose shows temperature

induced sol-gel transition with Plateau
increasing temperature

• Gelation process can be characterized via Gelation

(SAOS) by monitoring G‘ & G‘‘ in 3 areas:
Pre-gelation
- Pre-gelation
- Gelation
- Plateau
Rheometers
Standard geometries
Standard geometries

3 M
(  ) =
2 R
3
0

0
 =

Standard geometries

Schematic of a typical four-bladed vane (left)

and how it is used during measurement (right).
Standard geometries
Rheology – Overvierw
Classification of rheological behavior
Rheology - What is it about?
• To quantify information on structure and viscous properties of foods
• How is such properties perceived by the costumer
• Describe the difference between
– A brie and a semi solid cheese
– whole milk and yoghurt
• To provide ways of measuring relevant characteristics
– Texture: structure, shape, chewiness, spreadability
– Rheology: viscosity, elasticity
• How to structure sampling?
– Plan the measurements when the experiments are planned
– May constitute the difference between useful data and rubbish
Rheology – what is possible?

• What can be measured using a rheometer?

– Rotating measurements for determination of viscosity, viscous properties
and flow curves
– Oscillatory measurements for determination of elastic behaviour and also
viscous properties
• What product types can be measured?
– Liquid products, primarily in a cup
– Solids or semi-solids between plates or cone / plate
• What can be controlled?
– The forces (shear stress), temperature, time (under oscillation)
• What rheometers can not do?
– compress, break, stretch or imitate chewing
Rheology measurements

• Specific requirements for sample preparation

– Suitability for pouring in to a cup, does the product flow easily or must
force be applied?
– Transferring the product to the rheometer may affect the structure in an
undesired manner – is this intended or not?
– Must pre-shearing be applied – or are initial structure of interest?
• What to be aware of?
– Temperature deviations (in the room)
– To save results and parameter files
– To notice motion of the measuring geometry
– high geometry speed or large deformations may be undesired
– low geometry speed may not produce the desired results
General concerning measurements
• Time versus reaction in the material tested

– Short time yields information on elastic behaviour

– Long time yields information on flow properties

– The ration between the characteristic time of the deformation process and

the material is important (Deborahs number)

• Small versus large deformations (what is achieved?)

– Small deformations relevance: e.g., internal structure and elasticity

– Large deformations relevance: e.g. pumping in process plants, chewing,

swallowing and break down of structures

Rheology - Tests destructive / non-destructive

• Destructive
– ”large” movements

– rotation or flow

– large plastic deformation

– macro-structure, viscosity or viscous properties

• Non-destructive

– ”small” movements

– oscillation or small compression

– Ideally no plastic deformation

– micro-structure, internal structure, elasticity

Rheological tests used in food characterization

Journal of Food Engineering 67 (2005) 147