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Emulsion Rheometry and

Texture Analysis
*Food Structure and Functionality Laboratories
Department of Food Science & Biotechnology
University of Hohenheim
Garbenstrasse 21, 70599 Stuttgart, Germany
Jochen Weiss
Emulsion Workshop
November 13-14
th
, 2008, Amherst, MA
1
Background on Emulsion
Rheometry
Fundamental of Rheology
Concepts of Stress and Strain as
Related to Experimental Designs
2
Rheometry/Texture Analysis of Emulsions
Rheology is the science that describes the
response of a material (deformation) to a
superimposed stress (force per unit area)
Rheometry is the measurement of the
rheological properties of a material
Texture Analysis: Extentional/compressional
rheometry typically at large strains
Emulsion rheology influences:
Texture, Mouth Feel, Shelf Life,
Processing
3
Emulsion Rheometry:
Parameters Impacting Quality of the Product
Emulsion Property Industrial Branch Quality of Endproduct
Mean droplet size
Droplet size
distribution
Droplet shape
Droplet interactions
Mechanical strength of
droplet
Droplet porosity
Droplet density
Droplet concentration
Food Manufacturing
Shelf stability
Sensory
Consistency
Coarseness
Roughness
Filling/Dosing Behavior
Cosmetics and
Pharma
Spreading (creams, pastes)
Effectiveness (resorption,
protection)
Stability
Paints
Color intensity
Lightness
Paintability
Adhesion
Stability
4
Emulsion Rheometry:
Determination of Emulsion Material Functions
Actio
(stress)
Reactio
(deformation)
Emulsion
Stress = f(Time, Deformation) * Deformation
Emulsion material functions are deformation and time-
dependent two experiments required !!!
5
Emulsion Rheometry:
General Measurement Scheme
Induce Stress:
- shear
- compression
- large deformation
- small deformation
- static
- dynamic
Measure Response:
Rheogram
0.001
0.01
0.1
1
10
100
0.01 0.1 1 10
Shear Stress (Pa)

/

P
a

s
22%
40%
50%
6
Stress = Force per Unit Area
= F/A [N/m=Pa]
Note: a force is acting ON a body, but the body
EXPERIENCES stress.
Stress is internal, force is external.
What is a Stress?
7
Deformation (Strain) The Reaction to Stress
Motion
P
Q
x
y
z
da
P
Q
da
Strain Rate: Change of strain with time (time derivative), in
fluids equivalent to the velocity gradient
= tan

8
=
&
2. Fluids: Newtons law
1. Solids: Hookes law
= G
= F/A
= F/A
Emulsion Behavior : Between Liquids and
Solids
State depends on the nature of the emulsion (O/W) (W/O), the physical
state (crystallized, liquid), the droplet concentration and the structure
(agregated, non aggregated)
9
Different Stress Situations Require Different
Testing Methods
Shear Stress

xy

xy
Tensile and
Compressive Stresses

x
Uniaxial
Compression
p
p
p
p
p
p
p
p
Rotational Rheometer
Viscometer
Elongational Rheometer
Texture Analyzer
Pressure Cell
10
Experimental Design -
Rheometry
Rheometer Designs
Steady and Dynamic Shear
Experiments
11
Rheometer
Operating Mode
Temperature
Control
Sample
Handling
Other
Factors
Preparation
Loading
Thickness
Trimming
Conditioning
T. Expansion
T. Equilibrium
Sample bulge
Sample size
Test Selection: Time sweep, flow curve, creep/recovery, amplitude
sweep, frequency sweep, temperature sweep,
normal force, superimposed flows, squeeze flow.
Test Conditions: Number of points, time per point, integration time.
Data Analysis: Selection of regression model and interpretations of
parameters
Peltier
Convection
Electrical
Cont. strain
Cont. stress
Food Emulsion Rheometry:
Experimental Considerations
12
Basic Rheological Tests
of Food Emulsions
1. Simple Shear: Application of
constant shear measure stress
response
2. Creep Test: Application of
constant stress measure
deformation response
3. Relaxation Test: Apply constant
strain, measure decay in modulus
4. Oscillation: Apply strain rate
oscillations, measure stress
respone
5. Ramp: Increase shear rate,
measure stress increase
TEST CONDITION RESULT
13
Rheometry of Emulsions:
Rotational and Capillary Rheometers
Based on shear not on
elongation!
In capillary rheometers,
shear is generated via
pressure difference
between in and outlet of
capillary flow with
friction at the wall (v=0 at
wall, initial conditions)
In rotational rheometers,
shear is generated via
measurement tools that
have relative velocity
differences, thuis forming
a shear slit, angular
velocity as a function of
the torque.
14
Historical Rheometers
Lipowitz, first
device to measure
hardness of foods
(for fruit gels
filling of funnel with
lead beads until
sinking)
Bloom Gelometer,
(iron beeds to
increase weight of a
plunger until the
plunger penetrates
the gel)
Lers, Pectinometer
(measures force
necessary to
remove a probe that
is enclosed in a
pectin gel)
WOLDOKEWITSCH,
first force-
deformation
measurement on
solid/semisolid
foods
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Relative Rheometers Suitable For Low
Level Quality Control
Flow Methods Penetration Methods
Mixing Methods
Sedimentation Methods
Tear Methods
Relative indirect
determination via a
correlated base
parameter (e.g.
penetration depth,
time to empty a
vessel.)
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The First Viscosimeter by Wilhelm Ostwald
L V
p R
&

=
4

Laminar flow at Re <


2300: wall friction
exclusively caused due to
viscosity
Can be modeled and
calculated
Capillaries can be circular
or rectangular (slits)
log
l
o
g

corrected
The Capillary
Viscosimeter by Wilhelm
Ostwald (1853-1932).
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Modern Capillary Rheometers
Spherical, coaxial, slit
exit geometries
High-pressure capillary
rheometer (continuous)
High pressure capillary
rheometer (batch)
Piston force can be
regulated
Piston velocity can be
regulated
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Errors in Capillary Rheometers
Error Source Reason When?
Inlet energy loss
Conversion of pressure into kinetic
energy at the inlet (Hangenback
correction)
Always
Outlet energy loss Energy loss at exit of fluid Always
Elastic pressure
loss
Elastically stored deformation energy
is partially converted into heat
Viscoelastic fluids
turbulence Heat losses due to non-laminar flows
At high Reynolds
numbers
Pressure loss
outside of capillary
Frictional losses converted into heat Piston Viscosimeter
Fluid friction
Slight time delay due to friction at the
walls of the capillary entrance
error in measuring volume flow rate
Glas capillary
viscosimeter
Surface tension
Variations in surface tension impact
capillary effects
Thin capillary
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Rotational Rheometers - Measurement
Systems
Cone/plate
Viscoelastic and viscous
Uniform shear, but small
gap at center
Plate/plate:
Viscoelastic Fluids
Variable gap, but non-
uniform shear
Concentric cylinders:
Viscous Fluids
High sensitivity
M,
F
A
M,
Motor
F
A
M,
Motor
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Rotational Type Rheometer
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Emulsion Rheometry:
Coaxial Geometries
Consist of cup and bob
assembly
Geometrical variations
available to prevent end
effects or to increase
sensivity
M
d
=F*r
i
M
d
=2r
2
L

i
=M
d
/(2R
b
2
L)

o
=M
d
/(2R
c
2
L)
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Emulsion Rheometry:
Possible Measurement Errors
Vibration and Offset error
Hysteresis - insufficient
damping
Resonance at critical RPMs,
Heating and cooling effects
Not enough time for heating
Nonlaminar flow profile
Overfilling, spinning out of
fluid, end effects
Phase separation
viscoelastic oscillations
Shear Rate
S
h
e
a
r

S
t
r
e
s
s
23
Compressive Measurements of
Concentrated Emulsions
Texture Analyzer not suitable for low
viscous emulsions, but suitable for
mayonnaise, butter, margarine etc.
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Emulsion Rheometry:
General Compressional Rheology Terms
Engineering Stress: applied force/initial cross section
True Stress: applied force / true (deformed) cross section
Engineering Strain: ratio between the deformation of specimen
and initial length, where deformation is the absolute elongation
or length decrease in the direction of applied force
Engineering Strain: True Strain if deformation is small.
Failure characteristics can be measured using compression,
tension or torsion, most commonly uniaxial compression
Assumes that shape is maintained lubrication of surfaces
In uniaxial compression, area in contact increases, Ratio in
increase in diameter but decrease in height is the Poisson Ratio
In compressive measurements: specimen stiffness, Youngs
modulus, strength at failure, stress at yield and strain at yield
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Definitions in Texture Analysis -
Compressive Tests
Engineering Strain and Engineering Stress
True Stress and Henky Strain:
Youngs Modulus and Stiffness:
Youngs Modulus for Stiff Bodies and Poisson Ration
Biaxial Stress, extensional strain rate and extensional viscosity
0
A
F
eng
=
0
L
d
eng
=
( )
eng eng h
= 1 ( )
eng h
+ = 1 ln
h
h
E

=
d
F
stiffness =
0
0
L d
X X
=
( )
2
2
2
2
285 . 14
1 16
Dd
F
E

=

0 0
h A
Fh
A
F
B
= =
( ) t u h
u
z
z
B

=
0
1
&
B
B
B

&
=
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Emulsion Rheometry on Texture
Analyzer With Back Extrusion
For low viscous systems
such as emulsions with
medium droplet
concentration, back
extrusion may be used
Material is pushed
through the annular gap
between the plunger and
the sample cell
Flow situation very
complex
Exact mathematical
description difficult
27
Experimental Design -
Rheometry
Rheometer Designs
Steady and Dynamic Shear
Experiments
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Emulsion Viscosity
From Latin: mistletoe = viscum, a plant that
exudes a viscous sticky sap when harvested
Ratio of shear stress to shear rate (Pas, N/m
2
s)
shear rate is the velocity of the fluid at a given
point in the fluid divided by the distance of that
point from the stationary plane.
An internal friction coefficient! as fluid layers
of different velocities move relative to each
other, the friction generates heat and energy is
dissipated
Viscosity is an energy loss term.
29
Range of Viscosities and Shear Rates for
Food Products and Processes
Typical Material
Typical
Viscosity
Air ~10
-5
Water at 20 C 10
-3
Milk 10
-2
Salad Dressing 10
-1
Mayonnaise 1
Margarine 10-100
Butter 10
2
Typical
Process
Shear
Range
Stirring (low) 1-10
2
Pumping 1-10
2
Blending 10-10
4
Extrusion 10
2
-10
4
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Apparent viscosity:
Viscosity at a
specific shear rate!
Rheogram: Graphical representation of the flow behavior,
showing the relationship between stress and strain rate.
Steady Shear Flow Curves Rheogram
( )


&
&
= = f

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High Shear
Rate Range
V
i
s
c
o
s
i
t
y




Shear Rate
Viscosity Behavior of Multiphase Dispersed
Systems (Emulsions)

1

2

0
Disp. Phase Cont.
Structural forces
Disp. Phase Cont.
Yield Stress
0
Hydrodynamic forces
Disp. Phase Cont.
Disp. Phase Cont.
Disp. Phase
Cont. Phase
32
Emulsion Flow Curves In Absence of Time-
Dependent Behavior
Yield Stress:
Emulsions that
maintain shape
(dont deform) as
long as they are
subjected to
stresses below a
critical level.
Can be an important
quality parameter
(mayonnaise)
Can pose problems
in processing
Y
i
e
l
d

S
t
r
e
s
s
Shear Rate
S
h
e
a
r

S
t
r
e
s
s
33
Shear Rate [1/s]
0.001 0.01 0.1 1 10 100 1000
S
h
e
a
r

S
t
r
e
s
s

[
P
a
]
2
5
20
50
1
10
100
upcurve
downcurve
Time-Dependent Behavior Becomes
Apparent at High Droplet Concentrations
Rheometry can
reveal time-
dependence of
colloidal
interactions
Reformation of
flocculated
structures after
disruption
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Observations:
Materials like rubber
instantaneously deform when
loaded with strain.
When the load is removed,
elastic materials recover
immediately
Emulsions require time and
may not recover at all
plastic behavior especially at
high droplet concentrations
Emulsions are
VISCOELASTIC
Time

Time

solid
Visco-
elastic
liquid
Time Dependence of Emulsion Flow
Behavior
35
Emulsions: Lossy Materials with Spring and
Damper Similarities
Elastic materials store energy
Emulsions are viscous and
dissipate energy:
Emulsions with high droplet
concentration store and dissipate a
part of the energy
t
E
n
e
r
g
y
E
n
e
r
g
y
E
n
e
r
g
y
t
t
Time Dependence !!!
36
1. For small strains, the material function is ONLY a
function of time:
d = G
*
d
2. After a step-strain experiment, the stress of viscoelastic
materials decreases exponentially:
G(t) = G
0
* exp (- /l)
3. If we conduct the step strain experiments at different
intervals, well find that for each time well get a different
relaxation the overall relaxation is the sum!
G(t) = G
k
* exp(- /l
k
)
How to Describe Time Dependence of Emulsions?
- Maxwells Approach
37
Maxwells Approach Visualized as Springs
and Dampers
t
o
e

=
1 2 3
1 2 3
..............
n
t t
t t
n e
e e e e





= + + + +

d
n
Relaxation
time
A series of springs and dampers
each having a characteristic
response time
38
-3
-2
-1
0
1
2
3
0 13
time
s
t
r
e
s
s

o
r

s
t
r
a
i
n
-3
-2
-1
0
1
2
3
0 13
time
s
t
r
e
s
s

o
r

s
t
r
a
i
n
-3
-2
-1
0
1
2
3
0 13
time
s
t
r
e
s
s

o
r

s
t
r
a
i
n
0
o
< < 90
o
= 90
o
2/
ELASTIC
VISCOUS
VISCOELASTIC
How to Measure The Time Dependence? -
Oscillation
G
elastic

=
The stress response is the sum of
an elastic and viscous response:
Apply oscillatory deformation:
( ) t sin
0
=

&
G
viscous

=
f 2 =
( ) ( ) t G t G
sum
cos sin
0 0

+

=
G: Shear Storage Modulus
G: Shear Loss Modulus
=atan(G/G): phase angle
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Response of an Emulsion to Frequency Sweep
Storage Modulus (E' or G')
Loss Modulus (E" or G")
Terminal
Region
Rubbery
Plateau
Region
Transition
Region
Glassy
Region
1
2
l
o
g

G

a
n
d

G
"

low droplet conc.


High droplet con./
W/O emulsions
Not observable with standard
rheometry
40
1 0 0
1 , 0 0 0
1 0 , 0 0 0
P a s
| * |
1 0
0
1 0
1
1 0
2
1 0
3
1 0
4
1 0
5
1 0
6
P a
G '
G ' '
0 . 0 0 1 0 . 0 1 0 . 1 1 1 0 1 0 0 1 , 0 0 0 1 / s
A n g u l a r F r e q u e n c y
F r e q u e n c y S w e e p P
P C f s
|* | C o m
G ' S t o
G ' ' L o s
P C f s
|* | C o m
G ' S t o
G ' ' L o s
P C 2 4
|* | C o m
G ' S t o
G ' ' L o s
P C 2 5
|* | C o m
G ' S t o
G ' ' L o s
Low Strain Frequency Sweep of O/W Emulsion at
Increasing Temperatures
20 C
30 C
40 C
50 C
Temperature
Angular Frequency [Hz]
41
Can yield
information about
structural changes
upon heating
Fast relaxation at
higher
temperatures
increasingly
viscous behavior
C
o
m
p
l
e
x

V
i
s
c
o
s
i
t
y

(
m
P
a
s
]
E
l
a
s
t
i
c

M
o
d
u
l
u
s
Time-Temperature Superposition
42
10
5
10
6
10
7
10
8
10
9
10
10
Pa
G'
G''
-200 -150 -10
2
-50 0 50 10
2
150 200 C
TemperatureT
Temperature Sweep, Torsion Bar PB-PS Copolymer
Storage Modulus
Loss Modulus
10
2
10
3
10
4
10
4
10
1
10
5
G

,
G

[
m
P
a
]
Temperature [C]
20 30 40 50 60 70 80 90 100
Crystallized
Outer Phase
Melting and
Breakdown
43
Rheological Investigation of Margarine Breakdown
Texture Analysis of Emulsions
Large strain deformation
Simple compression
between two plates
More complex tests
possible with additional
probes
No rheological
information is using
complex probes
x
F
Sample
Displacement x
F
o
r
c
e

F
E
F*
Critical
Force
44
The Instruments: Texture Analyzer
Control
Panel
Servo-
motor
Loading
Cell
Platform
45
Metal versus Teflon Sensors

46
Standard Tests:
I. Compression and Decompression
Elastic Material (ideal)
Nonideal Elastic
Material
Emulsion
Deformation
F
o
r
c
e
47
Recoverable Work
Total Work
Deformation
F
o
r
c
e

(
N
)
Compressio
n
Decompression Recoverable Work
Relationship between recovered work and total
deformation yields information about material elasticity
Important in highly concentrated emulsions
48
Standard Tests:
II. Multiple Compression Cycles
During multiple
compressions, material
may irreversible deform
The amount of
recoverable work
typically decreases
Can give insights about
structural changes
sustained during the
compression
Important for Emulsion-
Gels
F
o
r
c
e
Deformation
Multiple Cycles
1
st
2
nd
3
rd
49
Standard Tests:
III. Relaxation Tests
Viscoelastic Materials
(Emulsions):
Intermediate behavior
Structural and
molecular reorientation
Progressive
breakdown
Stress relaxation
elastic
viscoelastic
viscous
Time
F
o
r
c
e
Holding
Compression
50
Example of Relaxation Tests
0
50
100
150
200
250
300
0 50 100 150 200
0
50
100
150
200
250
300
0 2 4 6 8 10
F
o
r
c
e

(
N
)
Time (s)
Height (mm)
Tomato paste
Mayonnaise
Mustard
Courtesy of Dr. Corredino, UMASS
Tomato paste
Mayonnaise
Mustard
51
Standard Tests:
IV. Creep
1
2
3

4
>
0
D
e
f
o
r
m
a
t
i
o
n
Creep
Recovery
Permanent
Deformation

0
Time
1
100 g
100 g
100 g
2
3
4
4
52
Creep in Emulsions
Time Time
IDEAL SOLID IDEAL LIQUID
Equilibrium
Continuous Flow
D
E
F
O
R
M
A
T
I
O
N
Emulsion behavior can vary between these two extremes
53
Standard Tests:
V. Texture Profile Analysis
Originally developed
by General Foods
Good correlation
with sensory
parameters
Very important:
consistent sample
preparation
Same size, avoid
edges, degree of
compression,
plunger size and
crosshead speed
should stay the
same
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