Polymer Rheology and Processing

Ref: Polymer Rheology Lawrence E. Nielsen.

 Polymer Processing
In the use of polymers, it is generally the
mechanical properties which are important.
However, the mechanical behavior of an object is of
little interest if the object first can not be fabricated
quickly and cheaply.
In nearly all cases, flow is involved in the
processing and fabrication of such materials in
order to make useful objects.
 Polymer Rheology

Rheology can be defined as the science of the

flow and deformation of materials.

Formany simple fluids, the study of rheology

involves the measurement of viscosity. However, the
rheology of polymers is much more complex
because polymeric fluids show nonideal behavior.
 Polymer Rheology

Rheology can be defined as the science of the

flow and deformation of materials.
For many simple fluids, the study of rheology
involves the measurement of viscosity. However, the
rheology of polymers is much more complex
because polymeric fluids show nonideal behavior.
In addition to having complex shear viscosity
behavior, polymeric fluids show elastic properties,
normal stress phenomena, and prominent tensile
viscosity.
 Polymer Rheology

All these rheological properties depend upon

the rate of shear, the molecular weight and
structure of the polymer, the concentration of
various additives, as well as upon the
temperature.
 Polymer Rheology
Unit:The traditional unit of viscosity is the poise,
which has the dimensions of dyn-s/cm2 or g/cm/s.

The viscosity of water is about 0.01 poise.

Typical polymer melts have viscosities generally
of the order of 103 to 104 poise.

The SI units for viscosity are Pas. Pa (N/m2)

 Measurement of Viscosity
Ideal fluids are called Newtonian. Their viscosity
is independent of the rate of shear.
The shear viscosity may be defined as follows:
 Measurement of Viscosity
Another viscosity can be measured in tension
instead of by shearing tests.

ForNewtonian liquids, the tensile viscosity is

three times the shear viscosity, but for polymeric
liquids the tensile viscosity may be many times
the shear viscosity.
 Normal Stresses
Normal stresses are other rheological
phenomenon encountered with non-Newtonian
fluids.
 Instruments
Capillary rheometer:
Advantage: Easy to fill.
Disadvantage: The rate of shear is not constant
but varies across the capillary.
 Instruments
Coaxial cylinder or concentric cylinder
rheometer:
Advantage: Nearly constant shear rate.
Calibrated easily.
Disadvantage:
The difficulty in filling them.
 Instruments
Cone and plate rheometer:
Advantage: Constant shear rate. The sample size
is very small. Ease of cleaning.
Disadvantage: Lower rate of shear.

Parallel plate viscometers

 Instruments
Dynamic or oscillatory rheometers:
 Instruments
Dynamic rheometers have a great advantage
over most other types of rheometers because
instruments measure the elastic modulus of
polymer melts in addition to the viscosity.

Disadvantage: Small amplitude of deformation

(In most fabrication processes, the polymer
undergoes very large deformation).
 Effects of Temperature
The viscosity of most polymers changes greatly
with temperature.
For Newtonian liquids and for polymer fluids at
temperatures far above the glass transition
temperature or the melting point, the viscosity
follows the Andrade or Arrhenius equation to a
good approximation:
 Effects of Temperature
The energy of activation for flow increases as
the size of side groups increases and as the chain
becomes more rigid.
 Effects of Temperature
For amorphous polymers at temperatures less
than 100 C above their Tg, the Andrade equation
does not fit the data well.
A much better equation is the Williams-Landel-
Ferry or the W-L-F equation:

The viscosity at Tg is often about 1013 poise.

 Effects of Temperature
The energy of activation for the W-L-F equation
not only depends upon temperature but also upon
the glass transition temperature.

The energy of activation becomes very large as

the temperature approaches Tg, especially if Tg
is large.
 Master Curves for Temperature
Dependence
Thereis a great need to predict the viscosity from
a small amount of experimental data.

The apparent viscosity can

be calculated from such
curves at a given shear
rate by:
 Master Curves for Temperature
Dependence

This
is a very powerful technique since for many
polymers the shift factors are independent of
molecular weight.
 Master Curves for Temperature
Dependence

Mostpolymer melts become Newtonian at very

low rates of shear and have a zero shear viscosity,
0, which is a function of temperature.
 Effects of Pressure
The Andrade equation for the temperature
dependence of viscosity can be modified to:

The most direct influence on free volume should

be the pressure.
The viscosity of polystyrene increased by a factor
of 135 times when the pressure was increased
from zero to 18,000 psi at 385 F.
 Effects of Rate of Shear
An outstanding characteristic of polymer melts is
their non-Newtonian behavior whereby the
apparent viscosity decreases as the rate of shear
increases.

ForNewtonian liquids, n = 1 and K = ; the

value of n is less than one for non-Newtonian
polymer melts.
 Effects of Rate of Shear on Polymer
Rheology
At
very low rates of shear, the entanglements
have time to slip and become disengaged before
enough stress can develop in them to orient the
molecules.
 Effects of Rate of Shear on Polymer
Rheology
Athigher rates of shear the segments between
entanglements become oriented before the
entanglements can disappear.
 Effects of Rate of Shear on Polymer
Rheology
As a load-bearing entanglement disappears, there
develops in the melt a steady state condition in
which the rates of formation and destruction of
entanglements become equal.
At very high rates of shear practically no
entanglements can exist. The viscosity should
reach a relatively small value which becomes
independent of the shear rate. In other words,
polymer melts may be expected to become
Newtonian in behavior at very high rates of
shear.
 Theories Describing The Shear Rate
Dependence of Viscosity
TheCross equation (empirical) for the effect of
shear rate on the apparent viscosity is:
 Dynamic Properties

At low frequencies where the dynamic viscosity is

independent of , the elasticity as measured by G is very
small.
The dynamic viscosity and the steady-flow viscosity
are nearly identical at low frequencies or rates of shear.
 Effects of Molecular Weight and
Structures
Among the structural factors determining the
rheology of a polymer, the molecular weight is the
most important.

Meis the molecular weight at which chain

entanglements become important.
Effects of Molecular Weight and
Structures

Shear stress or rate increased!!

 Effects of Molecular Weight and
Structures

Molecular weight increases

Molecular weight increases

 Effects of Structure on Polymer
Rheology
Branching:
Short branches generally do not affect the viscosity
of a molten polymer very much.
Branches which are long but which are still shorter
than those required for entanglements decrease the
viscosity when compared to a linear polymer of the
same molecular weight.
 Effects of Structure on Polymer
Rheology
If the branches are so long that they can participate
in entanglements, the branched polymer may have a
viscosity at low rates of shear greater than that of a
linear polymer of the same molecular weight. (But)

Athigh rates of shear, branched polymers in

nearly all cases have lower viscosity than linear
ones of the same molecular weight.
 Effects of Structure on Polymer
Rheology

Other structural factors:

Flexibility, specific interactions, and polarity which

affect the glass transition temperature tend to affect
viscosity.
 Effects of Solvents, Plasticizers, and
Lubricants
Insome cases the liquids are added for a purpose
such as to plasticize the polymer, to improve its
processibility or to stabilize the polymer to
processing conditions.

Tg, Me, dilution.

 Effects of Solvents, Plasticizers, and
Lubricants
The Kelley-Bueche theory appears to be the best for
predicting the viscosity of concentrated polymer
solutions using the viscosity of the pure polymer as
the reference.

FP = 0.025 + 4.5 x 10-4 (T-Tgp)

FL = 0.025 + L (T-TgL)
Effects of Solvents, Plasticizers, and
Lubricants
 Effects of Solvents, Plasticizers, and
Lubricants
Lubricants may be defined as materials which are
added to polymers in small amounts to improve
their processibility. (soluble and insoluble)
Insoluble: waxes, mineral oil, metal stearates, and
silicon oils.
 Normal Stresses and Die Swell
Normal stresses are primarily manifestations of the
elasticity of polymeric materials.
The normal stresses differences increase with the
square of the rate of shear:
 Normal Stresses and Die Swell

Normal stresses produce a number of phenomena

not found with Newtonian liquids.

When a polymer is extruded from an orifice, a

capillary, or a slit, the diameter or thickness of the
resulting strand is considerably greater than the
diameter of the hole from which is came. (die swell)
 Normal Stresses and Die Swell

In contrast, rotating shafts in

Newtonian liquids cause a
depressing of the liquid
surface due to centrifugal
forces.
 Normal Stresses and Die Swell
Ifholes are drilled in the plates parallel to the
rotating axis, liquid will be forced up through the
holes. (Normal stresses can be calculated by
measuring the height to which a liquid will ascend
up a tube for a given speed of rotation. The first
normal stress difference is proportional to the
height of the liquid in the tube.)
Cone and plate, two rotating plates.
Difficulty and low accuracy.
 Normal Stresses and Die Swell
The first normal stress difference is generally positive
which means that the tension resulting from the molecular
orientation is parallel to the flow streamlines.
The second normal stress difference is generally negative
and its value is very small.
 Normal Stresses and Die Swell

For a given rate of shear, the die swell decreases as the

length to diameter ratio of the capillary increases.
Factors which increase the shear modulus of a polymer
melt tend to increase the die well. (Molecular weight, PDI,
long-chain branching)
 Extensional Flow and Fracture
Phenomena
The type of viscosity calculated when tensile forces
are used is the tensile, elongation, or extensional
viscosity.

For polymers, the tensile viscosity may be hundreds

of times greater than the shear viscosity. (Newtonian
liquids: 3~6 times)
 Extensional Flow and Fracture
Phenomena

The tensile viscosity decreases with temperature,

but the role of such factors as molecular weight,
entanglements, and polymer structure is not clear.
 Extensional Flow and Fracture
Phenomena
Atlow rates of shear, polymer melts flow through
capillaries, channels, and ducts to produce smooth
strands.

Athigher rates of shear, several kinds of flow

instabilities can develop in which the surface of the
extruded strand becomes rough or nonuniform in
cross section, and the rate of flow no longer is
steady but pulsates.
 Extensional Flow and Fracture
Phenomena
The surface roughness types of defects (orange peel
and sharkskin) and some of the defects resulting in
variations in cross section seem to be due to a slip-
stick phenomenon at the polymer-capillary wall.

The defects which result in variations in cross

sectional area are due to fracturing of the polymer
melt.
 Extensional Flow and Fracture
Phenomena
Melt fracture generally is the result of tensile
stresses rather than shear stresses. (Size of the flow
channel goes from a larger to a smaller cross
section.)

Experimentally, it has been observed that die swell

goes through a maximum and then decreases at rates
of shear near values of where melt fracture starts.
 Suspensions, Latices, and Plastisols
Latices may be suspensions of rigid polymer
particles in water.
Plastisols are suspensions of polymer particles in a
liquid plasticizer.
The presence of a filler in Newtonian liquids
produces profound effects on the rheological
behavior of the suspension.
The rheology becomes even more complex if the
liquid phase is non-Newtonian.
 Suspensions, Latices, and Plastisols
Einsteins simple equation predicting the effect of a
filler on the viscosity of a Newtonian fluid. (only for
very low concentration of particles)
 Suspensions, Latices, and Plastisols

The equation implies that the relative viscosity is

independent of the size and nature of the particles.
The magnitude of the Einstein coefficient is
determined by the degree to which the particles
disturb the streamlines in a flowing system.
 Suspensions, Latices, and Plastisols
Mooney equation
(predicting moderate concentration):

The viscosity of a suspension

approaches infinity as the concentration
approaches maximum packing fraction.
(large number of particle-particle
contacts restricted)
 Suspensions, Latices, and Plastisols

Allthree equations indicate

that particle size has no
effect on the viscosity.
However, the distribution of
the size of spheres can affect
the viscosity. (large and
small particles, packing
densely)
Suspensions, Latices, and Plastisols
Suspensions, Latices, and Plastisols
Suspensions, Latices, and Plastisols