•Rheology

•Constitutive Equation

See
http://www.physics.iitm.ac.in/~compflu/Lect-notes/chhabra.pdf
Chapter-8 of the “Transport Phenomena” by Bird, Stuart and Lightfoot
Bird RB, Armstrong RC, Hassager O (1987) Dynamics of polymeric liquids. Vol I, 2nd
edn. Wiley, New York

1
 Materials and Rheology

Elasticity
Solid mechanics
or strength of
materials Plasticity
Rheology
Non-
Newtonian
Fluid mechanics fluids
Newtonian fluids
Rheology is the study of the deformation of Material
2
 Viscosity, Shear Stress and Shear Rate/Strain
Rate

F Vx

A d

 yx    yx

For Liquids:
Viscosity decreases with increase in temperature
increases with increase in pressure
For Gas:
Viscosity increases with increase in temperature
and pressure 3
Stress components in three dimensional flow

Y  xx  xy  xz
 yx  yy  yz
yy
yx
yz xy
zy
xx
 zx  zy  zz
zxxz`
zz
X
Z

4
Materials and their Basic Properties
Elastic Viscoelastic Viscous
Non
Hookean Newtonian
Newtonian
  G   f (  ,  , t )        
  f   ,  , t 

Basic Prop. Static &

G=constant Dynamic
Moduli
Creep
Memory Compliance
Tan  5
 Why Rheology
Mixing, Polymer Processing involves flow of
polymer in varying conditions of pressure,
temperature, shear stress, shear rate

Understanding of the flow characteristics

Establish the flow rate- Energy consumption
relationship

6
Experiment of Newtonian and
Non Newtonian Behavior

N P P

7
Normal Stress Effects: Rod Climbing

•the streamlines are closed circles

•the extra tension along these lines "strangulates" the
fluid and forces it inwards against the centrifugal force
upwards against the gravitational force. 8
Effects due to visco-elastic effect

•Die Swelling: 13% larger or smaller than the capillary

9
diameter for N-liquid, 300% for P
Effects due to visco-elastic effect
Tubeless siphon

10
 Why polymer shows different
behavior?
• Long chain nature of polymer
– Spectrum of relaxation times
– Gives partial memory/fading memory of
duration of the longest relaxation time

• Each molecule in a polymeric sample is

different

11
 Deborah Number, De

De 
t flow

De  0: Newtonian fluid behavior

De ∞: Fluid behaves more like
Hookean elastic solid.
 : 10-3 for dilute polymer solution, 103 for
concentrated polymer
solution or melt

"The mountains flowed before the Lord" by Prof. Markus Reiner

 Stress components in
three dimensional flow

 xx  xy  xz
 yx  yy  yz
 zx  zy  zz

13
 Constitutive equation
• expression for the stress tensor in terms
of strain tensors

• In complex materials these equations

may include other variable such as time,
temp. Pressure.
• Shear Modulus=stress/strain
• Shear compliance=strain/stress

14
 Newtonian and Non Newtonian Fluids
• Newtonian Fluid: Constant viscosity, xx=yy=zz=0
• Constant viscosity Boger Fluid: xx,yy,zz exists
• Non-Newtonian Fluids: 

f  
1.Generalized Newtonian fluid :
Also known as purely viscous, inelastic, time-
independent or generalized Newtonian fluids (GNF)
(a)Shear thinning (b)Viscoplastic ©Shear
Thickening

15
 Newtonian and Non Newtonian Fluids
(a)Shear thinning
• Powerlaw or Ostwald de Waele model dvx
 yx   m n 1

dy

• Carreau viscosity equation
 
0 

 1     a

 n 1 / a

a=2 for many polymer solutions and melts, 

and n are fitted parameters
• Ellis fluid model 0
  1
  yx 
1   

Deviation from the power law model  is significant
 1/ 2  only at low
shear rates
16
 Visco plastic behavior

Bingham plastic model

B B
 yx   0   B  yx for yx   0

 yx   0H  m yx
n
for yx   0H

Herschel-Bulkley fluid model

1/ 2 1/ 2 1/ 2
 yx   0c   c  yx for yx   0c

17
 Newtonian and Non Newtonian Fluids
2. Time dependent Fluids

Systems for which the relation between  and  shows further

dependence on
the duration of shearing and kinematic history; these are called
time-dependent
Fluids

(a) Thixotropy
(b)Rheopexy

18
 Time dependent Fluids

(a) Thixotropy

19
 Time dependent Fluids
(b)Rheopexy

20
 Newtonian and Non Newtonian Fluids
3. Viscoelastic Fluid
Systems which exhibit a blend of viscous fluid
behavior and of elastic solid-like behaviour. For
instance, this class of materials shows partial
elastic recovery, recoil, creep, etc.
Accordingly, these are called visco-elastic fluids.
Maxwell, Voigt model

21
LIMITATIONS OF GENERALIZED NEWTONIAN FLUID

MODELS AND RECOMMENDATIONS FOR THEIR USE

• Can be used for calculating Q vs. P for

steady flow in rectilinear conduits of constant
cross section, provided that the viscosity
function describes the viscosity data well.
• Should not be used in following cases
– elongational flows, flows rapidly changing in time,
flows with several nonzero velocity components,
etc.—the generalized Newtonian fluid should not
be used, except as a last resort
 Normal Stress Difference
 11   22  xx   yy
• 1st Normal stress differences in shear flows X- directional flow
• Large negative value

Y  yy   zz
 22   33 x
• 2nd Normal stress differences in shear flows
• Usually zero, some cases positive values
• In a shear Flow fluids exhibit a small extra
tension along Z direction
23
 Material Function
• Incompressible Steady Simple Shear
flow: v x   y; v z  0; v y  0
dv x
 yx   
dy
2
 dv x 
 xx   yy   1 
 dy 
2
 dv x 
 yy   zz   2  
 dy 
24
Interpretation of free surface Shapes
in the Rod Climbing Experiments
  1, r  2, z  3


v2

1d
 r rr      dp
r rdr r dr
0   2  r  r 
1d 2
r dr
d d
 zz  p    zz   rr        rr 

v2
dr dr r r
d d
 zz  p    zz   rr       rr   v2
d ln r d ln r

d r 2 r

dr r
d
  zz  p   d   rr   zz        rr   v 2
d ln r 2d ln  r
25
d r 2  r

dr r
d d
  zz  p     rr   zz        rr   v 2
d ln r 2d ln  r

Newtonian fluid : the normal pressure exerted

on the lubricated lid increases with the radius
Polymeric fluid : the normal stresses may
cause the total normal pressure to decrease
in the radial direction
26
 Viscometry and Rheometry
• Viscosity • Viscosity as
a function of
shear rate,
shear stress
• Normal
stresses
• Viscoelastic
response
27
 Simple Shear Flow of Newtonian
liquid
Find out the velocity distribution for steady
laminar flow of incompressible Newtonian fluid
kept in between two parallel plates, one of which
is stationary and another one is moving at a
velocity V. Separation between two plates is H.

 y
vx  V  
H 
28
Cone & Plate Rheometer
  / 2  
v  v x  r  
  / 2  1 
Constant
Sin 
   v / Sin 
 r 
 1   v   1 
    
r    / 2  1 

29
 Cone & Plate Rheometer
Torque required to maintain the motion

As   Const   Constant
R
T     r 2rdr
0

3T  1 
        
2R   / 2  1 
3

 3T   / 2   
 
2R 3

30
Cone & Plate Rheometer
(1)Torque on the cone surface, T
(2)Total Normal Thrust, F
(3)Pressure distribution  P    
  / 2

Reported Parameters:
  ( ), 1 , 2
3T   / 2   

2R 3

31
 Normal Stress Function
p 1   r 2 rr      
0  2 
r r r r
p (r )  p ( R )   2 rr        ln  r / R 
@ r  R, rr   pa
  p ( R )   rr   pa
R
F  R 2 pa     p  r      2rdr  0
0

2F
     
R 2
 1 
    
  / 2  1 
32
Elongational Flow

33
 Material Function

• Steady state Elongational Flow/Shear

free flow
 x  y
v z   z; v x   ; v y  
2 2
 dv z 
 zz   xx    
 dz 

34
 Strain
Tensile Force
• Cauchy Strain dL L  L L
c   0
 1
(Engineering Strain) L0 L0 L0

L
dL  L
h    ln 
• Henky Strain L0
L  L0 
 ln1   c 
35
 Mechanical Properties
• Static: Tensile, Shear
• Dynamic: Creep test (constant load); Stress
relaxation test (constant strain)
 Strain
Simple Shear Force
F

A0
X
tan    
C

Hooke’s Law
J=1/G
  G

37
 Tensile Force
Strain
dL L  L0 L
• Cauchy Strain c    1
L0 L0 L0
(Engineering Strain)
Young's modulus/Tensile modulus

  E


 38
Tensile Force
Strain

• Henky Strain
L
dL  L 
h    ln 
L0
L  L0 
 ln 1   c 

39
 Creep
Cause Effect
Elastic

Strain
Stress

0 t0
0 t0 t
t

Strain
Strain

0 t0
t
0 t0 Viscoelastic
t Viscous
Regions of Creep behavior
Tertiary creep:
manifestation of nonlinear
Increasing Load
viscoelasticity
Secondary creep
Strain

primary creep

0
t t0

Viscoelastic
 Cause Stress relaxation
0
Strain

0 t0
Effect
Stress

Elastic

t0
 Cause Stress relaxation
0
Strain

0 t0
Effect t Elastic Relaxation modulus
E(t)=(t)/0
Stress

Viscoelastic Elastic

Viscous Viscoelastic
Relaxation Recovery
t0
 Deformation Forces
• Tensile
• Torsion
• Compression
• Flexural
• Shear
 
E D
0 0
Modulus
Compliance
Characterization of Viscoelasticity

• Dynamical Mechanical analysis

– Measures stress response to an
application of sinusoidal strain
– The properties are at low strain
Applied Strain and Resulting Stress

   0 sin t 

   0 sin t   

The stress of an ideal viscous fluid is

always /2 out of phase
 Dynamic response using complex
number notation
 *   0 exp it 

 *   0 exp i t    
 *
0 0
E  *  E   iE  
*
cos   i Sin
 0 0

Storage Modulus
E  Loss modulus
tan  
E
 Dynamic response using complex
number notation
 *   0 exp it 

 *   0 exp i t    
* 0 0
D*  1 / E  *  D'iD" 
*
cos   i Sin
 0 0

Storage Compliance
D" Loss Compliance
tan  
D'
 Mechanical Models of
Viscoelastic Behavior

49
 Maxwell Element
d s 1 d s

dt E dt 

d d  d
 ; d s E
dt 
d d s d d 1 d 
   
dt dt dt E dt 

50
 Creep Experiment
d d  s d  d 1 d   0
    
dt dt dt E dt  
0
   0  t ;  0 is the instantaneous strain
 response of the spring
Compliance
 0 t t
D(t )     D
0 0  
51
 Stress Relaxation Experiment
d d s d d 1 d 
    0 d E dt
dt dt dt E dt    dt  
  
 t
 ln 
Relaxation time    D 0 
E

   0 exp(t /  )
Relaxation Modulus
 0
 exp(t /  )  E exp(t /  )
0 0
52
 Dynamical Mechanical Response
 *   0 exp i  t  
d 1 d 
 
dt E dt 
0 0
 i exp i  t    exp i  t  
E 
0
 (t 2 )   (t1 )   exp i  t 2    exp i  t1  
E
0
  exp i t2    exp i t1  
 i
53
 Dynamical Mechanical Response
 (t 2 )   (t1 )   0  exp i t 2    exp i t1  
Compliance
1 1 iD
D  i
*
 D
E  

54
 Voigt Element
d s 1 d

dt E dt
d d 

dt 
s  d  
d
 s   d    E  
dt
55
 Creep Experiment
d s 1 d

dt E dt
d d 

dt 
 0  d
 
  dt
  t 
D(t )  D 1  exp  
    56
 Comparison of Simple Models
Expt Maxwell Voigt Model
Model
Creep D(t ) t   t 
 1  1  exp  
D     

Stress E (t )
 exp(t /  )
Relaxation E

Dynamic
Mechanical
57
Idealized temperature scan of a
polymer

58
 Maxwell-Boltzmann
Superposition Principle
“The state of the solid depends not only on the forces actually
impressed on it, but on all the strains to which it has been subjected
during its previous existences.”
James C. Maxwell (1866)

The stress in the material=SUM of all the

stress contributions from all strains applied
in past times.  
t 
E ( t  t ' ) ( t ' )dt '


59
Comparison of experimental relaxation modulus data on a
polydimethylsiloxane sample to (a) the single exponential
model, with  = 0.1 s and E = l05 Pa and
(b) a five-constant model, with the constants
 A crosslinked polymer can be represented by two
Maxwell elements in parallel with constants:
E1=E2=105 Pa and relaxation times 1=10s and
2=infinity
(a)What stress is required for a sudden (t=0)
elongation to twice the original length? (b)What will
be stress after 10 s at twice the original length?

e=(2l0-l0)/l0=1
 Time-Temperature Superposition

   C (T  T )
1 ref
log(a T )  log

 
 C  (T  T )
 ref  2 ref

62


 Mechanical Models of
viscoelastic behavior
• Maxwell Element

• Voigt element
 Stress relaxation

Relaxation modulus
E(t)=(t)/0
 Mechanical Models of
viscoelastic behavior
• Maxwell Element
 Experimental Techniques
• Semi log Plot of G’ and G” (or tan ) as
a function of temperature at one or
more frequencies
• Free Vibration
• Forced Oscillation
Rheometry
Oscillatory Tests: Basics (1)

Two-Plates Model

Ideally elastic behavior

of a totally stiff sample
(e.g. a stone, or steel):

There is no shift between

the sine curves of
shear strain (deformation)
and shear stress :
the curves of  and 
are “in phase“ 68
Rheometry (Oscillation)
Amplitude Sweeps, preset

Preset:
constant frequency

(e.g. the angular frequency

 = 10rad/s or 10s-1)

and

variable strain
(deformation)
Frequency Conversion:  = 2  f
with angular frequency  s-1 and frequency f Hz
(since Hz is not an SI unit !)
69
Viscoelastic Behavior
Amplitude Sweeps
Limiting value
of the LVE - range

Result:
storage modulus G' (elastic behavior),
loss modulus G'' (viscous behavior),
limiting value of the linear viscoelastic (LVE- ) range when reaching L
- at the given test conditions, i.e., at the preset (angular) frequency -

left side: G‘ > G‘‘ (“gel-like structure“) in the LVE - range

right side: G‘‘ > G‘ (“liquid structure“) in the LVE - range 70
Viscoelastic Behavior
Amplitude Sweeps
coatings
comparison of two coatings
100
Pa top coat: G' > G''
primer

10

lg G'
top coating
primer: G'' > G'
lg G''
1 in the LVE range

ω = 10 rad/s
T = +23°C
0.1
0.01 0.1 1 10 100 % 1000
strain lg 
71
 Viscoelastic Behavior
Amplitude Sweeps, Flow Point cosmetics
comparison of two tooth pastes, flow points
10,000

Pa

1000
lg G'
paste 1
flow point: f = 125 Pa

lg G'' 100
paste 2
flow point: f = 24.9 Pa

10  
0.01
0.01 0.1 1 10 100 Pa 1.000

shear stress lg 
72