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Applied Rheology in Polymer

The development of mathematical
relationship between the input
parameters and the corresponding
response variables, which will describe
all the factors of material deformation, is
an impossible proposition.
Rheological and Constitutive equations.
Theoretical rheologists however, have
developed some generalized constitutive
equations like Criminale-Erickson-Filbey
(CEF) and Goddard-Miller (G-M)
These equations however fall seriously
short of actual practical applications.
Practical rubber and plastic scientists,
engineers and technologists therefore
rely mostly on developing the empirical
correlations based on the experimental
data, and there are a large number of
such relationships available in the
Rheological and Constitutive equations
Some important empirical correlations,
their applicability and limitations
Rheological and Constitutive equations
The flow of polymer melts and
solutions invariably show shear thinning
or pseudoplastic nature having three
distinct regions,
i) Low shear rate or the lower or intial
Newtonian region of constant
viscosity (SectionAB)
ii) Intermediate rate of shear or shear -
thinning region of falling viscosity
(Section CD)
iii) High shear rate or the upper
Newtonian region of constant
viscosity (Section EF)
The small sections in the curve, i.e., BC
and DE represents the inflection
regions where the slope of the
curve varies in the nonlinear
Variation of viscosity with rate of
Pseudoplastic fluids
Rheological and Constitutive equations
Polymer solutions and low molecular weight melts show all
the three regions but high mol. wt. polymer melts develop
melt fracture in the high shear region and may not show the
upper Newtonian region.
The development of rheological empirical correlations has
centered on the basic nature of flow with additional
parameters to describe other variations like occurrence of
yield stress or time and temperature dependency.
Both the constant viscosity regions are well described by
one parameter Newtons law of viscosity for incompressible
Pseudoplastic fluids
Rheological and Constitutive equations
To describe the behaviour of non-Newtonian fluids a number
of empirical correlations have been proposed by different
The complexity of these equations varies depending on the
rate of shear range the data covers.
These correlations can be broadly categorized as
i. Two parameter models
ii. Three parameter models
iii. Four parameter models
iv. Generalized correlations and
v. Polynomial equations.
Rheological and Constitutive equations
Two - parameter models
These models contain two adjustable material parameters, which
depend on temperature, concentration (for solutions) and the
filler loading (for filled systems)
i) Ostwald de waele or power law model
K - consistency index
n - non newtonian or flow behaviour index
- shear stress

- rate of shear
For n < 1 the fluid is pseudoplastic
n = 1 the fluid is newtonian
n > 1 the fluid is dilatant
= k (
Rheological and Constitutive equations
i) Ostwald de waele or power law model
When equation 1 is plotted on a double log scale gives a
straight line with a slope of n and an intercept of k.
The apparent viscosity
can be calculated as

= /
= k (
This equation shows the viscosity to be function of
such that
it will increase with
for n > 1 and decrease for n < 1
The equation (1) gives a good data fit for a large number polymer
and rubber melts, polymer solutions, low to moderately filled rubber
in the intermediate range of rate of shear.
Depending on the material the intermediate range i.e. between 10
to 10
. In the low and high shear region the power law model
deviates considerably from the experimental data and should not be
extended to these ranges at all.
To describe the behavior in these zones other equations have been
Rheological and Constitutive equations
Two - parameter models
ii) Eyring Prandtl model
This model has been derived from the Eying kinetic theory of
liquids and is applicable only to the pseudoplastic fluids in the
low and intermediate shear region. The equation is
= Asin h
Where Aand B are two adjustable parameters as

A/B (constant), giving the
Newtonian behavior at low shear rate. This equation is
unable to predict the high shear rate behavior
Rheological and Constitutive equations
Two - parameter models
iii) Bingham model
This model describes the fluids, which show the yield stress and
then flow as Newtonian fluids. Such liquids are known as
Bingham plastic fluids and follow the below two equations
for =

= 0 for <

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