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Rheometry

Part 2
Introduction to the Rheology of
Complex Fluids

Dr. Aldo Acevedo - ERC SOPS

Rheometry

Making measurements of rheological material


functions

To measure a material function, an experiment must


be designed to produce the kinematics pescribed in
th edefinition of the material function, then measure
the stress components needed and calculate the
material function.

Dr. Aldo Acevedo - ERC SOPS

Viscometer vs Rheometer
Viscometer measures viscosity
Rheometer measures rheological properties
A rheometer is a viscometer, but a viscometer is not a
rheometer.

Dr. Aldo Acevedo - ERC SOPS

Experimental Methods/ Instruments

Capillary viscometers

Rotational rheometers

Cup
Glass
Extrusion rheometers
Parallel plates (disks)
Cone-and-plate
Couette
Brookfield viscometers

Falling ball viscometers


Extensional rheometers

Dr. Aldo Acevedo - ERC SOPS

Rotational Rheometry
Rotational instruments makes it possible:
1.

2.

To create within the sample the homogeneous


regime of deformation with strictly controlled
kinematic and dynamic characteristics
Maintain assigned regime of flow for unlimited
period of time

Different regimes of deformation:


1.

2.

Constant angular velocity/frequency (constant


shear rate)
Constant torque (constant stress)

Dr. Aldo Acevedo - ERC SOPS

Rotational Rheometry
Advantages:
1.
2.
3.
4.
5.

Small quantities of materials


Smaller instrument sizes
Preferred for samples which are sensitive to contractions and
expansions
Longer residence times /testing times
Multiple testing or complex testing protocols

Disadvantages:
1.
2.
3.
4.

Lower maximum shear rates/stresses


Lower shear rates (~10-3 s-1) limited by power drive and speed
control (reducing gears)
High shear rates heating of the sample (bad energy
dissipation), Weissenberg effect, flow instabilities
Wall slip and ruptures (detachment from wall)

Dr. Aldo Acevedo - ERC SOPS

Constant frequency of rotation


Typical experimental results:

1.
2.

3.

4.

Low speed monotonic dependence of T(t) until steady state flow is reached
Increasing speed, during the transient stage, the shear stress maximum
(stress overshoot) appears.
The stress overshoot becomes more pronounced, and although the steady
flwo is observed it is followed by a drop in torque (approach to unstable
regime of deformation)
High speeds, steady flow is generally impossible.

A drop in torque is an indication of rupture in the sample or its detachment from the solid
rotating or stationary surface.
Dr. Aldo Acevedo - ERC SOPS
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Constant torque
Typical experimental results:

1.
2.

3.

Low torque slow monotonic transition to the steady viscous flow


Higher stresses - speed passes through a minimum and only then is steady
flow reached.
At very high stresses a steady flow is generally impossible due to a gradual
adhesive detachment of sample from the measuring surface or a cohesive
rupture of sample.

Dr. Aldo Acevedo - ERC SOPS

Parallel Disks (Parallel Plates)


The upper plate is rotated at a
constant angular velocity , the
velocity is:

0

v v
0
rz
With this velocity field, and assuming incompressible flow, the continuity
equation gives:

1 (rvr ) 1 v vz

0
r r
r z
v
0

Dr. Aldo Acevedo - ERC SOPS

Parallel Disks (Parallel Plates)


Assuming simple shear flow in -direction with gradient in z-direction
(i.e. the velocity profile is linear in z)

v A(r ) z B (r )
The boundary conditions:

v 0 @ z 0
v r @ z H
Solving:

rz
v
H
The rate-of-deformation tensor is then:

v (v)T
Dr. Aldo Acevedo - ERC SOPS

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Parallel Disks (Parallel Plates)


The rate-of-deformation tensor is then:

v (v)T

v v

r
r

v v

r
r
0
v
z

0
v
0

0
0
rz

0
0
v
z

0
v
z
0

rz

r
H

At the outer edge, we can write

Dr. Aldo Acevedo - ERC SOPS

r
R
R
R
R
H

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Parallel Disks (Parallel Plates)


The strain also depends on radial position:

r
rt
(0, t ) (t )dt dt
H
H
0
0
t

Assuming all curvature effects are negligible and unidirectional flow,


viscosity can be calculated from:

21 z

Dr. Aldo Acevedo - ERC SOPS

r R

R
0
R
H
21 21 r R

0
R

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Parallel Disks (Parallel Plates)


The strain also depends on radial position:

rr 0

0
0
z

z
zz rz

From the equation of motion (i.e. Cauchy-Euler), and assuming pressure


does not vary with , then:

z (r , z )
0
z

z C (r )

Unknown function

To measure shear stress, we must take measurements at specific values of r and


evaluate viscosity at each position.

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Parallel Disks (Parallel Plates)


Although it is possible to measure stress, it is easier to measure the total
torque required to turn the upper disk

T (stress)(lever_arm)dA
A
R

T ( z
0

zH

)(r )(2rdr )

The viscosity at any value of r can be written as:

21 z (r )

(r )
0
(r )
Rewritting in terms of viscosity, then:
R

T 2 r 2 dr
Dr. Aldo Acevedo - ERC SOPS

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Parallel Disks (Parallel Plates)


Now we need an expression of viscosity in terms of torque:
First, lets change variable from r to shear rate

2R 3 R 3
T
d

R 0
Now to eliminate the integral, we differentiate both sides by the shear
rate at the rim and using Leibnitz rule:

d
dR

3
3
2R 3 R ( )d (R )R
0 R

Dr. Aldo Acevedo - ERC SOPS

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Parallel Disks (Parallel Plates)


Rearranging:

(R )

2R 3 d ln(T / 2R )

R
d ln R

To measure viscosity at the rim shear rate:


data at a variety of rim shear rates (rotational speeds) must be taken
torque must be differentiated
A correction must be applied to each data pair

Warning Since the strain varies with radius, not all material elements
experience the same strain. The torque however, is a quantity measured from
contributions at all r. For materials that are strain sensitive this gives results
that represent a blurring of the material properties exhibited at each radius.

Dr. Aldo Acevedo - ERC SOPS

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Dr. Aldo Acevedo - ERC SOPS

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Parallel Disks (Parallel Plates)


It is also popular for SAOS where the results are:

SAOS material functions


for parallel disk apparatus

Dr. Aldo Acevedo - ERC SOPS

2 HT0 sin
( )
R 4 0
2 HT0 cos
( )
R 4 0

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Cone and Plate


Eliminates the radial dependence of shear rate (and strain).
Homogeneous flows produced only in the limit of small angles.
The velocity is:

0

v 0
v
r
Assuming that single shearflow takes place in the
-direction with gradient in the (-r)-direction):

Thus,
Dr. Aldo Acevedo - ERC SOPS

v C1 (r ) C2

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Cone and Plate


The boundary conditions:

/2
v r / 2 0
v 0

Applying BCs:

The small cone angle.

v

0 2

The rate-of-deformation tensor:

v
r
r r

0
0
sin v

sin

v

r r
0 0

sin v

0 0
r sin
0

0
r
r


0 rz
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Cone and Plate


Since is close to /2, sin ~1 and:

Thus,

sin v


r sin
1 v

r
0


0
The strain is then:
t

dt
0
0
0

(0, t ) (t )dt
0

Dr. Aldo Acevedo - ERC SOPS

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Cone and Plate


The viscosity is thus:

1 v


r ( ) 0

21
21

Looking for an expression for the stress using torque:

T (stress)(lever_arm)dA
A
2 R

(
0 0

Dr. Aldo Acevedo - ERC SOPS

)(r )(rdd r )

Since shear rate is constant through


the flow domain, the viscosity and
shear stress are constant, too.
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Cone and Plate

2 3
T R
3

Thus viscosity is:

3T0
21

0
2R 3
In the limit of small angle, the cone-and-plate geometry produces
constant shear rate, constant shear stress and homogeneous strain
throughout the sample.
The uniformity of the flow is also an advantage with structure forming
materials, such as liquid crystals, incompatible blends, and suspensions
that are strain or rate sensitive.
Also, the first normal stress difference can be calculated from
measurement of the axial thrust on the cone.
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Dr. Aldo Acevedo - ERC SOPS

Cone and Plate


The total thrust on the upper plate:

2
F 2
0
First Normal-stress
coefficient in cone-and-plate

2
rdr R Patm

2 F 0
1 2 2
R
2

0Re it
SAOS for cone-and-plate

Dr. Aldo Acevedo - ERC SOPS

3 0T0 sin

2R 3 0
3 0T0 cos

2R 3 0

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Couette (Cup-and-Bob)
The velocity field is:
0

v v
0
rz

The velocity:

k(r R)
v
k 1
Shear rate:

k

k 1

Dr. Aldo Acevedo - ERC SOPS

21 r
v
k


r
k 1

21 r
0

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Couette (Cup-and-Bob)
Torque:

T (stress)(lever_arm)(area)
T ( r

r kR

)(kR)(2kRL)

Viscosity in Couette flow


(bob turning):

T (k 1)

2R 2 Lk 3
Advantages:
Large contact area boosts the torque signal.
Disadvantages:
Limited to modest rotational speeds due to instabilities due to inertia or
elasticity.
Dr. Aldo Acevedo - ERC SOPS

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Commercial Rotational Rheometers

The biggest players:

TA Instruments (originally Rheometrics


Scientific)
Bohlin
Paar Physica
Haake (now part of Thermo Fisher)
Reologica

Dr. Aldo Acevedo - ERC SOPS

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The toppings

Many other attachments or options may be used in


rotational rheometers. These provide additional
tests or independent measurements of data on the
structure of fluids.

Magnetorheological cells
Electrorheological cells
Optical Attachments
UV- and Photo- Curing accessories
Dielectric Analysis

Dr. Aldo Acevedo - ERC SOPS

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Capillary Flow
The flow is unidirectional in which cylindrical surfaces slide past each other.
Near the walls, except in the -direction, this flow is simple shear flow.
The velocity is:

0 x2

v 0
0

123
Assuming cylindrical coordinates:

21 rz

r R

v z
v z
0

r
r
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Capillary Flow
The rate-of-deformation tensor is then:

v (v)T

0
v z
r

0
0
0

v z
r
0

0
rz

vz

r
Thus,

vz r r R

is the shear at the wall

( R )
Dr. Aldo Acevedo - ERC SOPS

v z
r

R
rR

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Capillary Flow
The viscosity for capillary flow is then:

rz r R
rz r R
21

v
0
R
z
r r R
Now expressions for both the shear rate and stress in terms of
experimental variables must be obtained.

The flow is assumed to be unidirectional and the fluid incompressible,


thus, the continuity equation gives:

vz
v
0
z

Dr. Aldo Acevedo - ERC SOPS

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Capillary Flow
The equations of motion:

0 P -
P P gz
Assumption:
stresses and pressure are independent of -direction
the flow field does not vary with z (fully developed flow)
capillary is long, such that end effects are diminished
stress tensor is symmetric
Thus, the -component of the equation of motion gives:

1 2
r r 0
2
r r

Dr. Aldo Acevedo - ERC SOPS

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Capillary Flow - Stress


Solving:

C1
2
r

Using the mathematical boundary condition that the stress is finite at the
center (r=0). Thus, it equals zero.

The z-component:

P (r , z ) 1
r rz (r )

z
r r
The r-component:


P 1

(r rr )
r r r
r
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Capillary Flow - Stress


Using the r-component and expressing it in terms of the normal stress
coefficients:

P rr rr

r
r
r
r
P N 2 N 2

r
r
r
r

N2 is very small (negative) for polymers.


Less is known about t. Thus, it seems reasonable to assume that this
stress will be small or zero in a flow with assumed -symmetry.

Thus, the condition that both must be zero should be met easily by most
materials.

Dr. Aldo Acevedo - ERC SOPS

P
0
r

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Capillary Flow- Stress


Rearranging the z-component

P ( z ) 1
r rz (r )

z
r r
P0 PL r C1
rz

L 2 r

Solving:

Again, taking the stress as finite in the


center, the integration constant must be
zero.
Shear stress in
capillary flow

r
P0 PL
rz
r R
R
2L
Dr. Aldo Acevedo - ERC SOPS

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Capillary Flow Shear Rate


For Newtonian fluid, calculate the expression for the velocity directly:
2

2Q
r
vz (r ) 2 1
R R
dvz 4Q r


3
dr R R
4Q

R 3
R

The viscosity is then:

21 R

0
R
( P0 PL ) R R 3

2L
4Q

Dr. Aldo Acevedo - ERC SOPS

4Q
1 ( P0 PL ) R

a
3
R

2L
1
a R

Not so easily done for unknown material.


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However, it was observed that Q can be related to pressure drop.

Capillary Flow Shear Rate


Weissenberg-Rabinowitsch expression:
R

Q 2 v z (r )rdr
0

Integrating by parts:
R

Q r 2 dr
0

Applying a change in variables:

r
rz R
R
Dr. Aldo Acevedo - ERC SOPS

3 R

R
2

Q 3 rz d rz
R 0

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Capillary Flow Shear Rate

4Q
4 R
2

a
rz
rz d rz
3
3
R
R 0
Differentiate with respect to tR and apply Leibnitz rule
R

a R 3 4 ( rz ) rz 2 d rz
0

R
d

3
(a R ) 4
( rz ) rz 2 d rz 4 ( R ) R 2
d R
R
0

Rearranging:

1
d ln a

( R ) R a 3
d ln R
4
Dr. Aldo Acevedo - ERC SOPS

Weissenberg-Rabinowitsch correction

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Capillary Flow Viscosity

4 R
(R )
a

d ln a
3

d ln R

Thus viscosity may be calculated by measurements of Q to obtain the


shear rate and measurements of pressure drop to obtain stress, and
the geometric constants R and L.

Dr. Aldo Acevedo - ERC SOPS

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Capillary Flow
Advantages:
1.
Simple experimentally and equipment set-up
2.
Inexpensive
3.
Higher shear rates
Disadvantages:
1.
May need multiple corrections:

End effects

Wall slip

Temperature
2.
No good temperature control

Dr. Aldo Acevedo - ERC SOPS

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Capillary Flow Glass Viscometers

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Dr. Aldo Acevedo - ERC SOPS

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Extensional Rheometers

Difficult to measure, difficult to construct.


Usually home-made rheometers
Common for solids, not for fluids

Dr. Aldo Acevedo - ERC SOPS

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Filament Stretching Extensional Rheometers

Devices for measuring the extensional viscosity of moderately


viscous non-Newtonian fluids

A cylindrical liquid bridge is initially formed between two circular


end-plates. The plates are then moved apart in a prescribed manner
such that the fluid sample is subjected to a strong extensional
deformation.

Dr. Aldo Acevedo - ERC SOPS

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Filament Stretching Extensional Rheometers

The kinematics closely approximate those of an ideal


homogeneous uniaxial elongation.

The evolution in the tensile stress (measured mechanically) and


the molecular conformation (measured optically) can be followed
as functions of the rate of stretching and the total strain imposed.

Extensional flows are irrotational and extremely efficient at


unraveling flexible macromolecules or orienting rigid molecules.

If it was possible to maintain the flow field, all molecules would


eventually be fully extended and aligned.

McKinley and Sridhar, Filament-Stretching Rheometry of Complex Fluids, Annual Reviews of


Fluid Mechanics, 34 375-415 (2002)
Dr. Aldo Acevedo - ERC SOPS

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Instrument Design

The drive train accommodates the end


plates, and the electronic control system
imposes a predetermined velocity profile
on one or both of the end plates.
The principal time-resolved
measurements required are the force F(t)
on one of the end plates and the filament
diameter at the mid-plane.
The geometric dimensions and motor
capacity of the motion-control system
determine the range of experimental
parameters accessible in a given device.

Dr. Aldo Acevedo - ERC SOPS

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Operating Space

The maximum length, Lmax, and


the maximum velocity, Vmax,
bound the operating space.
An ideal uniaxial extensional flow
is represented as a straight line on
this diagram, with the slope equal
to the imposed strain rate.

A given experiment will be limited


by either the total travel available
to the motor plates or by the
maximum velocity the motors can
sustain.
A characteristic value is the critical
strain rate E* = Vmax/Lmax, where
both limits are simultaneously
achieved.

Operating Space
The operation space accessible for a given fluid may be constrained by
instabilities associated with gravitational sagging, capillarity or elasticity.
The instabilities can arise from either the interfacial tension of the fluid or
the intrinsic elasticity of the fluid column.

Dr. Aldo Acevedo - ERC SOPS

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Flow

Initial aspect ratio Lo/Ro.


The diameter of the filament is axially uniform as desired for homogeneous
elongation.
However, the no-slip condition at the endplates does cause a deviation from
uniformity.
Dr. Aldo Acevedo - ERC SOPS
Thus,
the diameter is usually measured at the middle of the filament.

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Flow

Initial aspect ratio Lo/Ro.

The diameter of the filament is axially


uniform as desired for homogeneous
elongation.

However, the no-slip condition at the


endplates does cause a deviation
from uniformity.
Thus, the diameter is usually
measured at the middle of the
filament.

Dr. Aldo Acevedo - ERC SOPS

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Equations to Analyze Flow


The time-dependent total force needed to deform the sample can be
measured by a load cell and related to the total stress as:

f (t )
zz Patm
A(t )
where, f(t) is the magnitude of the tensile force
A(t) is the changing cross-sectional area

The normal stress difference is thus:

f (t )
zz rr zz rr
A(t )
Dr. Aldo Acevedo - ERC SOPS

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Equations to Analyze Flow


If the flow is homogeneous from start-up of steady elongation:

A(t ) A0 e

0t

from the Hencky strain EQ 5.174

The elongational viscosity growth function can be calculated


from a measurement of f(t) alone.
0t
f
(
t
)
e

A0 0

The steady elongational viscosity:

f e 0t

A00

Usually not reached.


Dr. Aldo Acevedo - ERC SOPS

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Equations to Analyze Flow


It is usually difficult to measure the length, thus the diameter at mid
section is measure. However, these are not directly
proportionally.

l (t ) D0


l0
D(t )

p (t )

Ideal elongation of a cylinder -> p(t) = 2


Lubrication theory (at short times) -> p(t) = 4/3
Experimentally a two-step procedure:

Constant elongational rate based on the filament length is first imposed


and the mid filament diameter is measured.
A calibration curve of Hencky strain based on length vs Hencky strain
based on mid-filament diameter is produced.
The curve is then used in a second experiment to program the plate
separation that will result in exponentially decreasing diameter.

Dr. Aldo Acevedo - ERC SOPS

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L-D Calibration Plot

L ln(l / l0 )
D 2 ln( Dmid / D0 )

Dr. Aldo
Acevedo
ERC SOPS
Anna,
etal
An- interlaboratory
comparison of measurements from filament-stretching
rheometers using common test fluids, Journal of Rheology 45(1) 83-114 (2001)

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Controlled Filament Diameter Profiles

Dr. Aldo Acevedo - ERC SOPS

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Elongational Viscosity
The unsteady extensional viscosity is obtained from:

(0 )

( 33 11 ) ( zz rr )

0
0

Where the strain rate is obtained by fitting to the raw diameter data.
The Trouton ratio (or dimensionless extensional viscosity) is:

(0 )
Tr
0

Zero-shear steady shear viscosity

For Newtonian fluids Tr = 3.


The Trouton viscosity is defined
as 3 times the z-s ss viscosity
Dr. Aldo Acevedo - ERC SOPS

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Elongational Viscosity
Representative result

Dr. Aldo Acevedo - ERC SOPS

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Pros and Cons


Advantages:
The sample starts from a well defined initial rest state.
Except near the ends, the strain of each material element
is the same.
Disadvantages
The deformation near the ends is not homogeneous
uniaxial extension.
At short times there is an induction period during which
a secondary flow occurs near the plates due to
gravitational and surface tension forces.
Elongational rates calculated based on length differ from
those calculated on radius.

Dr. Aldo Acevedo - ERC SOPS

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Filament Evolution
The general evolution in the experiment typically exhibit three characteristic
regimes:

A. Filament elongation
the radius decreases exponentially
At short times (early strains) there is a solvent-dominated peak
in the force followed by a steady decline due to the exponential
decrease in the cross-sectional area.
Intermediate times (or strains) the force begins to increase
again owing to the strain hardening in the tensile stress. Since
the area decreases, an increase in the force indicates that the
stress is increasing faster that the exponential of the strain.
At very large strains, a second maximm in the force may be
observved after th eextensional stresses saturate and the
extensional viscosity of the fluid recahes steady-state.

Dr. Aldo Acevedo - ERC SOPS

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Filament Evolution
The general evolution in the experiment typically exhibit three characteristic
regimes:
B. Stress relaxation
The radius remains almost constant.
This region is typically short, lasting only one or two fluid
relaxation times.
As elastic stresses decay, pressure and gravity stresses
dominate and filament breakup ensues
C. Filament break-up
The force decays and the radius decreases in similar manner

Dr. Aldo Acevedo - ERC SOPS

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Haake CaBER I
Uses a high precision laser micrometer to accurately track the filament
diameter as it thins. Aside from its resolution (around 10m) the
micrometer is also immune to large ambient light fluctuations and can
resolve small filaments easily (a different issue from the resolution).
The plate motion is controlled by a linear drive motor. The fastest stretch
time is of the order of 20 ms (depending on stretch distance) and the
motor has a positional resolution of 20 m.

Dr. Aldo Acevedo - ERC SOPS

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Reference: Instruction Manual Haake CaBER I

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References

Faith Morrison, Understanding Rheology, Oxford


University Press (2001)
Malkin, A.Y. & A.I. Isayev, Rheology: Concepts,
Methods & Applications, ChemTec Publishing, Toronto
(2006)

Dr. Aldo Acevedo - ERC SOPS

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