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Rheology and Processing of Rubbers

(RT60015)

by

Narayan Ch Das
Rubber Technology Centre
I.I.T Kharagpur 721302

Reference Books

Polymer Processing Technology- B.R. Gupta


Polymer Science and Technology, P. Ghosh
Handbook of rubber technology Steven Blow
Textbook of polymer science F.W. Billmeyer
Rubber technology and manufacture C.M. Blow and C.
Hepburn
Rubber engineering Indian Rubber Institute
Science and Practice of Rubber Mixing-Nobuyuki Nakajim
Rubber Processing Peter S. Johnson
Rubber Technology Maurice Morton

What is the Rheology?


To the layperson, rheology is
Mayonnaise does not flow even under stress
for a long time; honey always flows
Silly Putty bounces (is elastic) but also flows (is
viscous)
Dilute flour-water solutions are easy to work with
but dough's can be quite temperamental
Corn starch and water can display strange
behavior poke it slowly and it deforms easily
around your finger; punch it rapidly and your
fist bounces off of the surface

To the scientist, engineer, or


technician, rheology is
Yield stresses

Viscoelastic effects

Memory effects
Shear thickening and shear
thinning

For both the layperson and the technical person, rheology is a set of
problems or observations related to how the stress in a material or force
applied to a material is related to deformation (change of shape) of the
material.

What is the Rheology Anyway?


Greek > rhe meaning to flow. It is applicable to all materials, from gases to solids.
Rheology is the science of flow and deformation of matter and describes the
interrelation between force, deformation and time.
The science of rheology is only about 70 years of age. It was founded by two
scientists (Prof. Marcus Reiner and Prof. Eugene Bingham) meeting in the late '20s
and finding out having the same need for describing fluid flow properties. Greek
philosopher Heraclitus described rheology as panta rei - everything flows.
Translated into rheological terms by Marcus Reiner this means everything will flow
if you just wait long enough.
Fluid rheology is used to describe the consistency of different products, normally by
the two components viscosity and elasticity. By viscosity is usually meant resistance
to flow or thickness and by elasticity usually stickiness or structure.

Goal of the scientist,


engineer, or technician:
Understand the kinds of flow and deformation effects exhibited by
complex systems
Apply qualitative rheological knowledge to diagnostic, design, or
optimization problems
In diagnostic, design, or optimization problems, use or devise
quantitative analytical tools that correctly capture rheological effects

How do we reach these goals?

Rheology and Processing


RHEOLOGY:
The science relating to the study of the inter-relationships
between the flow and other deformations of matter and the
factors causing and controlling the flow and deformation.

PROCESSING:
Technique steps to get the final product from raw or gum
materials and also to get the shape or practical shape and
to set/retain the shape of the finish products.

Why is Rheology Important?

Rheology is the study of flow and deformation of materials and how


that flow affected by stresses, strains and time

Definition of Rheology

Rheology is the science of flow


and deformation of matter.
Flow is a special

case of deformation

Deformation is a
special case of flow

Deformation is followed by flow!!

Deformation
Flow
Elastic deformation
(takes place irreversible
(takes place instantaneously on application
and permanent deformation)
of force or stress and disappears instantaneously
upon release (reversible deformation)
Non-Newtonian
Bingham
plastics

Newtonian

Non-Bingham
plastics
Elastic viscous

Non-elastics viscous

Fundamentals of Rheology
The fundamental definition of rheology indicates that for a material to flow its
original structural composition must first exceed a critical limited deformation.
Rheology, the science of deformation and flow of materials characterizes
materials through parameters such as;

storage modulus (G)


loss factor (Tan )
viscosity ()
characteristic times (, )
...

loss modulus (G)


critical deformation c
yield point (y)
flow index (n)

With exquisite presicion, rheology describes the behavior of materials as


viscoelastic fluids (G>G and -> 90)
to
viscoelastic solids (G>G and -> 0)
Information commonly used to improve formulations optimize processes, select
aplication conditiosn, evaluate product performance, determine shelf life,
evaluate product economy, and more.

Course Content
Rheological or Constitutive Equations
(Different parameters models)
Viscoelastic Behaviour
(Static Stress Relaxations and Creep Test
(Dynamic Stress Relaxations and Creep Test)
Mechanical Model: Maxwell & Voigt Kelvin
Model
Parameters Influencing the Polymer Rheology
Effect of Temperature
Effect of Pressure
Effect of Mol. Wt and Polydispersity
Effect of Filler

Rheological Parameters
Force: Tensile, compressive, shear > Stress
Strain
Rate of strain
A mathematical function of the form

f ( , , ) 0
represents a general function between different rheological parameters

Materials
Viscous

Elastic

Hookean
Solids

Non-Hookean
Solids

Newtonian
Fluids



Basic properties
Modulus, G

Visco-elastic

Non-Newtonian
Fluids

f ( )

Basic properties
viscosity,

f ( )

Newtonian,
Pseudoplastics,
Dilatant,
Bingham Plastics,
Yield Stress,

n=1
n<1
n>1
n=1

Time ind.
Vis. fluid

f ( )

Time dep.
Vis. fluid

f ( , , t )

Thixotropic, increases with t


Rheopectic, decreases with t

Linear
Visco-elastics

Non-Linear
Visco-elastics

f ( , , t )
Basic properties
Static & Dynamic
Moduli, creep
Compliances, tan

Basic
properties
independent of
input function

Basic
properties
change with
input function

Constitutive Equation

f ( , , ) 0
6
4

Viscosity, Pas

A: Low shear rate or Newtonian region


B: Shear thinning at intermediate shear rate
E: Newtonian region at high shear rate

100

8
6
4
2

10

8
6
4

1
-2
10

E
-1

10

10

10

10

Shear rate, s

10

10

B & C represent the inflection regions-slope


varies in the nonlinear fashion

10

-1

Polymer solution and low Mol. Wt. melts shows all three region, but high Mol. Wt.
show melt fracture at high shear rate;

Constitutive Equation
Equation/model for non-Newtonian fluid can be categorized as:
1.
2.
3.
4.
5.

Two parameters model


Three parameters model
Four parameter model
General correlations equation
Polynomial equations

Two parameter models


Two adjustable material parameters: depends on Temperature,
concentration (for solution) and the filler loading (for filled
systems)
1. Ostwald de Waele or power law model:

k ( ) n

Where k is consistency index and n is the non-Newtonian or the flow behavior index.
For n=1, the fluid is Newtonian, n<1, the fluid is Pseudoplastics, n>1, the fluid is Dilatant,

The apparent viscosity, a:

a / k ( ) n1

2. Eyring Prandlt model: only applicable to pseudoplastics fluids in the


low and intermediate shear region:
A sinh 1 (

1
)
B

Where A and B are two adjustable


parameters.

0, a A / B(constant)
This represents the Newtonian
behaviour at low shear rate.

Two parameter models


3. Bingham model.
Describes fluids which show the yield stress and then flow as
Newtonian.

y
0

for y

Where y is the yield stress and is consistency index or the coefficient of rigidity or
the coefficient of plastic viscosity.

Three parameter models


1. Viscoplastics fluid model:
Fluids have both yield stress as well pseudoplasticity.

y ( ) n
0

for y

Where is consistency index and


n is the non-Newtonian or the flow
behavior index.

2. Ellis model: only applicable to polymer or rubber melts in the low an


intermediate shear region
0 Lim a , Zero shear visosity
0

1 / 2 at / 2

1
1

1 / 1 / 2

0 1
1/ n
0=1/0 is the fluidity of the system at very low shear rate
(0+)/2
o

1
and 1

0 1 / 2

If >1, the fluid is Pseudoplastics For =1, the fluid is Newtonian,


<1,, the fluid is Dilatant,

As

0, the model reduces to a Newtonian model.

0/2

1/2

Three parameter models


1. Eyring-Powell model:
Modified model of Eyring-Prandtl model and applicable to high shear region.
Both upper and lower shear region,
this reduces to Newtonians law of
viscosity.
.
.
.
.
As 0 , [A+1/BC] and a 0=[A=1/BC] and as , A
and a =A
1
A (1 / B) sinh 1 ( )
C

2. Carreau model: only applicable to low and intermediate region


[ A /(1 B C )]

A, B, C are three materials parameters. This model give a better representation for
the polymer as compared to the Ellis model. This is also applicable to different
temperatures
.
.
.
.
.
As 0 , A and as , A /(B )c

Four parameter models


1. Meter model:
Can be applied to the entire range range of shear rate.

1 / m

0 Lim a ,
0

1/ 2

Zero shear visosity

at o / 2

1/ n

(0+)/2

The constants, 0, and have similar


significance as in the case of Ellis model.

0/2

m (shear stress )= (0+ )/2

1/2

2. Modified power law model: Can be applied to the entire range range
of shear rate.

( b c d )