Rheometry: Introduction To The Rheology of Complex Fluids

Rheometry
Part 2
Introduction to the Rheology of
Complex Fluids
Dr. Aldo Acevedo - ERC SOPS 1

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.

Viscometer vs Rheometer
Viscometer – measures viscosity

Rheometer – measures rheological properties
A rheometer is a viscometer, but a viscometer is not a

rheometer.

Experimental Methods/ Instruments
 Capillary viscometers
 Cup
 Glass
 Extrusion rheometers
 Rotational rheometers
 Parallel plates (disks)
 Cone-and-plate
 Couette
 Brookfield viscometers
 Falling ball viscometers
 Extensional rheometers
 …

Rotational Rheometry
Rotational instruments makes it possible:

1. To create within the sample the homogeneous
regime of deformation with strictly controlled
kinematic and dynamic characteristics
2. Maintain assigned regime of flow for unlimited
period of time
Different regimes of deformation:

1. Constant angular velocity/frequency (constant
shear rate)
2. Constant torque (constant stress)

Rotational Rheometry
Advantages:
1. Small quantities of materials
2. Smaller instrument sizes
3. Preferred for samples which are sensitive to contractions and
expansions
4. Longer residence times /testing times
5. Multiple testing or complex testing protocols
Disadvantages:
1. Lower maximum shear rates/stresses
2. Lower shear rates (~10-3 s-1) limited by power drive and speed
control (reducing gears)
3. High shear rates – heating of the sample (bad energy
dissipation), Weissenberg effect, flow instabilities
4. Wall slip and ruptures (detachment from wall)
Constant frequency of rotation
Typical experimental results:
1. Low speed – monotonic dependence of T(t) until steady state flow is reached
2. Increasing speed, during the transient stage, the shear stress maximum
(stress overshoot) appears.
3. 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)
4. 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
7
Constant torque
Typical experimental results:
1. Low torque – slow monotonic transition to the steady viscous flow

2. Higher stresses - speed passes through a minimum and only then is steady
flow reached.
3. 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.

Parallel Disks (Parallel Plates)
The upper plate is rotated at a

constant angular velocity Ω, the
velocity is:
0
 
v   v 
0
  rz
With this velocity field, and assuming incompressible flow, the continuity
equation gives:
1  (rvr ) 1 v v z
  0
r r r  z
v
0

Assuming simple shear flow in θ-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:
rz
v 
H
The rate-of-deformation tensor is then:
  v  (v)T
  v  (v)T
 v v   
 0  0   
 r r  0 0 0 
 v v v  v

  0  0 0 
 r r z   z 
 v   v 
 0 0   0 0 
 z  rz  z  rz
r
   
H
At the outer edge, we can write   R
r R
  R R 
Dr. Aldo Acevedo - ERC SOPS R H 11
The strain also depends on radial position:
r rt
t t
 (0, t )    (t )dt    dt  
0 0
H H
Assuming all curvature effects are negligible and unidirectional flow,

viscosity can be calculated from:
 21   z r R
R
0   R
H
  21   21 r  R
 
Dr. Aldo Acevedo - ERC SOPS
0 R 12
The strain also depends on radial position:
 rr 0 0 
 
   0    z 
0   
 z zz  rz
From the equation of motion (i.e. Cauchy-Euler), and assuming pressure

does not vary with θ, 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. 13
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 zH )( r )( 2rdr )
0
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 0 14
Now we need an expression of viscosity in terms of torque:
First, lets change variable from r to shear rate


2R 3 R 3
T
R 0  d
Now to eliminate the integral, we differentiate both sides by the shear

rate at the rim and using Leibnitz rule:
0
R
d  T   
 2R3 R     ( )d   (R )R
3 3
dR    0 R

Rearranging:
T

2R 3 
3 d ln( T / 2 R 3
)
 (R ) 
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.

It is also popular for SAOS where the results are:
2 HT0 sin 
 ( ) 
SAOS material functions R 4 0
2 HT0 cos 
for parallel disk apparatus
 ( ) 
R 4 0

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

Φ-direction with gradient in the (-rθ)-direction):
v
0

Thus,
Dr. Aldo Acevedo - ERC SOPS v  C1 (r )  C2 19
Cone and Plate
The boundary conditions:
v  0   /2
v  r    / 2  0 The small cone angle.
Applying BCs:
r   
v    
0  2 
The rate-of-deformation tensor:
   v  
 0 0 r   
 r  r  
 0 0 0 
sin    v    
   0 0    0 0  
 r   sin     0 
  v    0  rz
 sin    v 
 r      0 
 r  r  r   sin    r
20
Cone and Plate
Since θ is close to π/2, sin θ ~1 and:
sin    v 
   
r   sin  
1 v 
  
r  0
Thus,

    
0
The strain is then:
t  t t
 (0, t )    (t )dt    
dt 
0 0  0
0

Cone and Plate
The viscosity is thus:
1 v 
0    
r  ( )  0
 21   
  21   
 
0 
Looking for an expression for the stress using torque:
T   (stress )(lever_arm )dA

A Since shear rate is constant through
2 R the flow domain, the viscosity and
T   (  
0 0


2
)( r )( rdd r ) shear stress are constant, too.
22
Cone and Plate
2 3
T  R     
3 2
Thus viscosity is:
  21   3T0
  
0  2R 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.
23
Cone and Plate
The total thrust on the upper plate:
 2 
F  2   
 rdr   R Patm
2
 0 2 
2 F 0
First Normal-stress 2
coefficient in cone-and-plate 1  2 2
R 
  0Reit 
SAOS for cone-and-plate 3 0T0 sin 
 
2R 30
3 0T0 cos 
  
Dr. Aldo Acevedo - ERC SOPS 2R 30 24
Couette (Cup-and-Bob)
The velocity field is:
0
 
v   v 
0
  rz
The velocity:
k(r  R )
v 
k 1
Shear rate:
k  21   r
 
k 1  v
0  
k
 
r k 1
 
  21   r
0  25
Couette (Cup-and-Bob)
Torque:
T  (stress )(lever_arm )(area )

T  ( r r  kR
)( kR)(2kRL)
Viscosity in Couette flow

(bob turning):
T (k  1)

2R 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.
Commercial Rotational Rheometers
The biggest players:
 TA Instruments (originally Rheometrics
Scientific)
 Bohlin
 Paar Physica
 Haake (now part of Thermo Fisher)
 Reologica

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

Capillary Flow
The flow is unidirectional in which cylindrical surfaces slide past each other.
Near the walls, except in the θ-direction, this flow is simple shear flow.
The velocity is:
 0 x2 
 
v 0 
 0 
 123
Assuming cylindrical coordinates:
 21    rz r  R
vz vz
0  
 r  r
Capillary Flow
  v  (v)T
 v z 
 0 0 
 r 
   0 0 0 
 v z 0 0 
 r
  rz
vz
    
r
Thus,  vz r r  R is the shear at the wall
vz
( R)    R
r r R
30
Capillary Flow
The viscosity for capillary flow is then:
  21  rz r  R  rz r  R
  
0 v 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

Capillary Flow
The equations of motion:
0  P - 
P  P  gz
Assumption:
• stresses and pressure are independent of θ-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 θ-component of the equation of motion gives:
1  2
r r
2

r  r  0 
Capillary Flow - Stress
Solving: C1
 r  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

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 tθθ. Thus, it seems reasonable to assume that this
stress will be small or zero in a flow with assumed θ-symmetry.
Thus, the condition that both must be zero should be met easily by most
materials.
P
0
Dr. Aldo Acevedo - ERC SOPS r 34
Capillary Flow- Stress
P ( z ) 1 
Rearranging the z-component   r rz (r )
z r r
 P0  PL  r C1
Solving:  rz    
 L 2 r
Again, taking the stress as finite in the

center, the integration constant must be
zero.
Shear stress in
capillary flow
 P0  PL  r
 rz   r   R
 2L  R
Capillary Flow – Shear Rate
For Newtonian fluid, calculate the expression for the velocity directly:
2Q  r 
2
v z (r )  2 1    
R   R  
dvz 4Q r
 
  3
dr R R
4Q
R  3

R
The viscosity is then:
  21  R
  4Q 1 ( P0  PL ) R
0
 R  a 

R 3
 2L
( P0  PL ) R  R 3 
     1
2L  4Q  a   R

Not so easily done for unknown material. 36

Dr. Aldo Acevedo - ERC SOPS However, it was observed that Q can be related to pressure drop.
Weissenberg-Rabinowitsch expression:
R
Q  2  vz (r )rdr
0
Integrating by parts:
R
Q    r 2 dr
0
Applying a change in variables:

3 R
r R
 rz   R Q  3   rz d rz
2

R R 0 37

4Q 4 R
3 
    ( ) rz d rz
2
R R 0
3 a rz
Differentiate with respect to tR and apply Leibnitz rule

R
a R 3  4   ( rz ) rz 2 d rz
0
 

d R

( a R )  4   ( rz ) rz 2 d rz  4 ( R ) R 2
3

d R 0
 R
0
Rearranging:
1  d ln a 
 ( R )  R  a   3  
4  d ln  R 
Weissenberg-Rabinowitsch correction
Capillary Flow – Viscosity
1
4 R  d ln a 
 (R )   3  
a  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.

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

Capillary Flow – Glass Viscometers

Extensional Rheometers
 Difficult to measure, difficult to construct.
 Usually “home-made” rheometers
 Common for solids, not for fluids

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.

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)
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.

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.

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.
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.

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 )

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

 0t
A(t )  A0 e from the Hencky strain EQ 5.174
The elongational viscosity growth function can be calculated

from a measurement of f(t) alone.
0 t
f ( t ) e
 
A0 0
The steady elongational viscosity:
f  e0t
 
A00
Usually not reached.

It is usually difficult to measure the length, thus the diameter at mid

section is measure. However, these are not directly
proportionally.
p (t )
l (t )  D0 
  
l0  D(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.

L-D Calibration Plot
 L  ln( l / l0 )
 D  2 ln( Dmid / D0 )
Anna, etal
Dr. Aldo “An- interlaboratory
Acevedo ERC SOPS comparison of measurements from filament-stretching 54
rheometers using common test fluids”, Journal of Rheology 45(1) 83-114 (2001)
Controlled Filament Diameter Profiles

Elongational Viscosity
The unsteady extensional viscosity is obtained from:
 ( 33   11 )  ( zz   rr )
  (0 )  
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
Elongational Viscosity
Representative result

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.

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.

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

Haake CaBER I
Uses a high precision laser micrometer to accurately track the filament
diameter as it thins. Aside from its resolution (around 10μm) 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 μm.

Reference: Instruction Manual Haake CaBER I
62
References
 Faith Morrison, “Understanding Rheology,” Oxford
University Press (2001)
 Malkin, A.Y. & A.I. Isayev, “Rheology: Concepts,
Methods & Applications,” ChemTec Publishing, Toronto
(2006)

Rheometry: Introduction To The Rheology of Complex Fluids

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Rheometry

Dr. Aldo Acevedo - ERC SOPS 1

 Making measurements of rheological material

 To measure a material function, an experiment must

Dr. Aldo Acevedo - ERC SOPS 2

Viscometer – measures viscosity

A rheometer is a viscometer, but a viscometer is not a

Dr. Aldo Acevedo - ERC SOPS 3

Dr. Aldo Acevedo - ERC SOPS 4

Rotational instruments makes it possible:

Different regimes of deformation:

Dr. Aldo Acevedo - ERC SOPS 5

1. Low torque – slow monotonic transition to the steady viscous flow

Dr. Aldo Acevedo - ERC SOPS 8

The upper plate is rotated at a

Assuming all curvature effects are negligible and unidirectional flow,

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

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

T   (stress )(lever_arm )dA

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

First, lets change variable from r to shear rate

Now to eliminate the integral, we differentiate both sides by the shear

Dr. Aldo Acevedo - ERC SOPS 15

Dr. Aldo Acevedo - ERC SOPS 16

It is also popular for SAOS where the results are:

Dr. Aldo Acevedo - ERC SOPS 18

Homogeneous flows produced only in the limit of small angles.

The velocity is:

Assuming that single shearflow takes place in the

Dr. Aldo Acevedo - ERC SOPS 21

T   (stress )(lever_arm )dA

The uniformity of the flow is also an advantage with structure forming

Also, the first normal stress difference can be calculated from

The total thrust on the upper plate:

The velocity field is:

T  (stress )(lever_arm )(area )

Viscosity in Couette flow

Dr. Aldo Acevedo - ERC SOPS 27

 Many other attachments or options may be used in

Dr. Aldo Acevedo - ERC SOPS 28

The velocity is:

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

Dr. Aldo Acevedo - ERC SOPS 31

•Thus, the θ-component of the equation of motion gives:

Dr. Aldo Acevedo - ERC SOPS 33

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

Again, taking the stress as finite in the

Not so easily done for unknown material. 36

Applying a change in variables:

Differentiate with respect to tR and apply Leibnitz rule

Dr. Aldo Acevedo - ERC SOPS 39

Dr. Aldo Acevedo - ERC SOPS 40

Dr. Aldo Acevedo - ERC SOPS 41

Dr. Aldo Acevedo - ERC SOPS 43

 Devices for measuring the extensional viscosity of moderately

 A cylindrical liquid bridge is initially formed between two circular

Dr. Aldo Acevedo - ERC SOPS 44

 The kinematics closely approximate those of an ideal

 The evolution in the tensile stress (measured mechanically) and

 Extensional flows are irrotational and extremely efficient at

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

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

The drive train accommodates the end