A R H E O L O G I C A L V I E W P O I N T O F

T H E R M O P L AS T I C M E L T S
By Dr. Robert Marsh, Bohlin Instruments, 2003

Introduction
Rheology is the science of studying the flow and deformation of materials rooted in the laws of
th
elasticity and viscosity proposed by Hooke and Newton in the late 17 Century. Thermoplastic
polymer melts are widely used in many modern industrial processes to manufacture a multitude of
objects. Polymers are used because they are relatively cheap to form into complex shapes in the
molten state and therefore, we need to understand how they flow when being processed.

Polymers are complicated materials to characterise rheologically because there are many factors that
influence their flow properties. Examples of factors that influence the flow behaviour may include:
Processing temperature; Rate of flow; Residence time etc.

Furthermore the rheological properties of polymers are in between those of a liquid and a solid. This
leads to time dependence of the flow properties and other important characteristics, some of which are
discussed below.

Melt viscosity is well known to be critically dependent on temperature. By lowering the temperature of
a mould until the part being produced has a matt finish, the processor can learn the minimum
temperature (hence maximum resin viscosity) at which the process can be run without surface defects
becoming apparent. Reducing the mould temperature saves energy and can reduce cycle times and
so an understanding of the temperature dependence of melt viscosity is very useful.

Polymer melts are known to exhibit die swell when extruded. This phenomenum reveals itself as an
increase of diameter of an extrudate after exiting a die. The amount of die swell is related to the
amount of elastic deformation of the material at the inlet of the die. A further fact to be considered is
that the degree of die swell (more correctly extrudate swell) is dependent on the length of the die when
material is extruded at constant throughput. In other words polymer melts exhibit time dependency as
the material forgets the elastic deformation applied at the entrance of the die, the more time the
material spends within the die the less die swell.

Melt elasticity can also have profound implications for many other polymer processes such as:

Blow Moulding where the wall thickness of the blown component depends on the degree of swell that
has taken place during the extrusion process prior to the mould being closed.

Vacuum Forming or Thermoforming where the polymer must maintain a degree of elasticity to prevent
the material sagging before it is pulled by vacuum over the cold forming die. If the material does not
have sufficient elasticity it is likely to come into contact with the chilled die before the vacuum or
pressure is applied.

Polymer processing properties also depend on the concentration of lubricants, plasticisers, fillers and
other componenents in the compound being processed.

From this brief introduction one can appreciate that proper characterisation of polymer melt flow
behaviour is likely to require sophisticated and versatile instrumentation.

From the point of view of the rheologist polymer flow behaviour can be conveniently separated into
three components: Shear and extensional flows which are characterised by the corresponding
viscosities and Elastic behaviour which is characterised by measurement of modulus or swell ratios.

To fully characterise a material, instrumentation is required which has the capability of extracting these
parameters over a range of temperatures and shear/extension rates.
Modern laboratory rheological test apparatus can be divided into two broad categories:

• Rotational Rheometers
• Capillary Extrusion Rheometers

Rotational Rheometers
These instruments normally require a small specimen of the material to be tested in the form of disk –
typical dimensions being 25mm diameter and 1mm thick. The sample is placed between a pair of
parallel plates or upper cone and lower plate whose temperature can be maintained by an external
heating device such as a blown gas oven or electrical heating of the plates.

Modern rotational rheometers are capable of a number of test types to allow full characterisation of a
material over a range of temperarures and flow rates.

Examples of the types of the types of tests available are:

• Flow curves to measure the shear viscosity versus shear rate or shear stress. At sufficiently low
shear rates a constant value for the viscosity will be attained. This so called zero shear viscosity
has been shown to depend on the average molecular weight of the polymer and the length of the
plateau (how high a rate before the viscosity decreases) is known to reflect the width of the
molecular weight distibution. Software packages are available to determine the average molecular
weight and molecular weight distribution from such data.

• Creep tests (application of constant stress for a defined period of time) allow an alternative means
of determining the zero shear viscosity. When combined with recovery testing (removal of the
stress) these tests enable the amount of elasticity in the sample to be measured because a
material will with elasticity will recoil and attempt to recover its original shape.

• Stress Relaxation tests apply an instantaneous deformation (strain) to the sample and record the
time dependent decay of stress with time. The rate of decay of the stress depends on the
viscoelasticity of the polymer at the test temperature. The data is often displayed as relaxation
modulus versus time. Integration of the modulus versus time function is an often forgotten but rapid
means of determining the zero shear viscosity and hence average molecular weight. Differentiation
of the modulus/time function produces the continuous relaxation time distrubution curve. This
rather complex function in principle contains information relating to the molecular weight distribution
of the polymer.

• Small amplitude sinusoidal Oscillatory Testing as function of test frequency is a rapid and often
used method to measure the viscous and elastic properties of a polymer simultaneously. Two
parameters are most often reported – Storage (Elastic) modulus and Viscous (Loss) modulus (G’’)
which represent the relative degrees of the material to recover (elastic response) or flow (viscous
response) respectively as the rate of deformation (test frequency) changes. A typical response for
a polymer melt is to exhibit elastic dominated behaviour at high frequencies and viscous dominated
behaviour at low frequencies. This means that there is a critical frequency at which the two
responses are equal. This is obviously a well-defined point and conveniently this “cross-over”
frequency and modulus has been shown to depend on the molecular weight and molecular weight
distribution of some linear polymers. A potential advantage of utilising this point as a quality control
tool is that the cross-over of elastic and viscous moduli occurs at significantly higher frequencies
than the point at which a constant value of shear viscosity occurs.Testing times may therefore be
considerably reduced when compared to making flow curve measurements or performing creep
tests.
Examples of typical responses for these test modes are shown in the following figures.

Figure 1 Flow curve for LDPE at 190ºC showing low shear rate plateau for viscosity.
The magnitude of the zero shear viscosity is determined by the average molecular weight of the polymer.

Figure 2 Creep (Blue) & Recovery (Red) Curve Polypropylene at 190ºC allow zero shaer viscosity to be
determined and equilibrium recoverable compliance.

Figure 3 Stress Relaxation data LDPE at190ºC The relaxation time distribution curve includes information
about the molecular weight distribution of the polymer.
 Figure 4 Frequency Sweep for Polypropylene at 190ºC.
The Cross-Over Point is determined by the average molecular weight and molecular weight distribution.

A full discussion of the relationship between molecular parameters and processing performance is
beyond the scope of this short article, but the following examples are included to illustrate how visco
elastic characterisation of polymers has solved real processing problems:

A) Variability of tube and pipe gauges in extrusion processes

Oscillatory testing at low frequencies (below 0.1 Hz) revealed differences in the elastic modulus
between different batches of material. Clearly pipe gauge will depend on the degree of recovery of
the polymer after being extruded and so not surprisingly, the pipes and tubes with the higher
gauge have greater elastic modulus.

120000
Storage Modulus / Pa

100000

80000

60000

40000 Thick
Thin
20000

0
0.0 20.0 40.0 60.0 80.0 100.0
Freq / rad s-1

Figure 5 Frequency Sweep data for two HDPE pipes.

The sample with higher elastic modulus produced the larger gauge pipe.

B) Reducing Inconsistent Fibre Spinning Properties

Low frequency oscillatory testing was able to show differences in the elastic properties of different
batches of material. No differences were observed in the viscosity, indicating the material was of
consistent molecular weight. The differences in elasticity at low frequency are related to
differences in the molecular weight distribution (MWD) with the result that the broader MWD
results in increased molecular chain entanglement which hinders the draw down process of the
fibre spinning process. This in turn causes inconsistency in the final product.

Complex Viscosity / Pa.s

100000

10000

1000
Bad
100 Good

10

1
0.0 0.5 1.0 1.5 2.0 2.5
log Freq / rad s-1

Figure 6 Complex Viscosity as a function of frequency for good and bad PP Fibre samples.
Note that no discernable difference is evident.

140

120

100
G' / Pa

80

60
Bad Sample
40
Good Sample
20

0
0.1 0.3 0.5 0.7 0.9
Freq / rad s-1

Figure 7 Storage Modulus as a function of frequency for good and bad PP Fibre samples.
The bad sample had more elasticity causing inconsistent fibre diameter.
Capillary Extrusion Rheometers
Advanced capillary extrusion rheometers comprise a temperature-controlled barrel incorporating one
or more precision bores fitted with capillary dies at the exit. Melt pressure transducers are mounted
immediately above the dies to record the pressure drop as polymer melt is extruded through the dies
at programmed flow rates. By the use of a capillary die and an “orifice”or “zero length” die the shear
and extensional visscosities of a polymer melt may be determined simultaneously against shear and
extension rates.

Additional accessories are available to record die swell by means if a laser scanning gauge and or
extrudate melt strength by passing the strand of polymer through a series of speed controlled nip
rollers and recording the force (melt tension) as a function of haul off speed.

As a general rule, capillary rheometers are used to measure melt properties at higher shear rates than
rotational rheometers and allow determination of flow behaviour under typical processing conditions. A
particularly important consideration is the ability to measure extensional (elongational) properties at
higher extension rates than by other techniques (such as counter rotating pulley devices) and more
importantly at extension rates encountered on a processing line.

The figure below shows both shear and extensional data, which illustrates an important and often
neglected point: Two polymers may have almost identical shear flow behaviour, but may exhibit
considerbly different extensional properties. As noted previously, many polymer procesess (fibre
spinning, blow mouilding) are essentially extensional processes and so determination of extensional
viscosity is more important than measuring shear viscosity.

10000
Shear viscosity (Pa.s)

rubber B 110°C
1000
rubber A 110°C

100
10 100 1000
Shear rate (/s)

Figure 8 Shear viscosity versus shear rate. The data for the two rubbers is indistinguishable.
 Extensional viscosity vs. Extension rate

10000
Extensional viscosity (kPa.s)

rubber B 110°C
1000
rubber A 110°C

100
0.1 1 10 100
Extension rate (/s)

Figure 9 Extensional viscosity versus extension rate for the same materials shown in figure 8.
There are clear differences in the extensional properties of the two materials.

Capillary rheometers are often used to examine processing behaviour, rather than determine
rheological parameters: Two examples could be determination of regions of flow instability and
measurement of wall slip or critical stress.

Flow instabilitiy or melt fracture is generally the result of tensile stress when the melt flows from a large
cross-section to a smaller one. If the tensile stress becomes large enough, the melt fractures. The
effect of melt fracture becomes less noticeable as the length of die is increased and as the die
temperature is increased. Increasing die length damps out the effect of the cross-section change at
the entrance of the die and increasing temperarure reduces the viscosity and also the stress at the
same shear rate. In a capillary rheometer a region of melt fracture is revealed as a regular oscillation
of the melt pressure signal as shown below. The melt effectively fractures and then reforms with the
effect that adjacent elements have experienced different extensional histories and so will swell
differently upon exiting the die.

35
3000 /s
30

25
Pressure (MPa)

20

15

10

0
0 50 100 150 200 250
Time (s)

Figure 10 Evidence of Melt Fracture is shown by the oscillating pressure signal.

The material is Polypropylene measured at 190ºC.
A fundamental assumption when calculating rheological properties with a capillary rheometer is that
the material at the wall of the capillary die is stationary – this is the so-called stick condition. In practice
polymer melts deviate from this situation at a critical stress and the material flows as combination of
shear flow superimposed onto a plug flow. Wall slip and determination of the critical stress can be
analysed in a capillary rheometer by measurement of flow curves at the same temperature for at least
three sets of capillary dies with the same length to diameter ratio. For a material not experiencing wall
slip identical shear stress verus shear rate profiles will be generated. In the case of wall slip ocurring,
shear stress will decrease as the die diameter increases at constant shear rate. Analysis of the flow
data allows the “slip velocity” and critical stress to be determined. These parameters are often required
by computational fluid dynamics software packages along with shear and extensional viscosity data to
predict the flow of melts in moulds and extrusion profiles.
Unfilled HDPE at 200°C

220

200
Line of constant
16 x 1 m m
Shear Stress

180

8 x 0.5
Shear Stress (kPa

mm
160 12 x 0.75
12 x 0.75 m m mm
16 x 1 m m

140 8 x 0.5 m m

120

100

80
50 100 150 200 250
Shear Strain Rate (/s)

Figure 11 Rheograms for HDPE at 200ºC. The line of constant stress reveals evidence of Wall Slip.

W all Slip Velocity of Unfilled HDPE at 200°C

7

5
Wall Slip Velocity (mm/s

0
100 110 120 130 140 150 160 170 180 190
W all Shear Stress (kPa)

Figure 12 Slip velocity versus shear rate for HDPE at 200ºC. Slip velocity is calculated by Mooney’s method.
The two examples above show how a capillary extrusion rheometer may be used to help predict the
processing performance of a polymer melt. Other test regimes are also possible: Determination of
polymer degradation by multiple flow curve measurments or viscosity versus time; Measurement of
critical temperature for flow to commence at constant extrusion pressure; Stress relaxation after flow
cessation; Melt compressibility at constant temperature etc.

Conclusion
Polymer melt rheology is a complex subject that requires careful experiment design in order to obtain
the information needed to meet an investigator’s requirements. Rotational rheometers are the
preferred choice when the requirement is to obtain information concerning the molecular structure and
how this affects processing characteristics. In particular, the ability to easily extract information about
the average molecular weight and molecular weight distribution via measurment of the viscoelastic
properties makes the rotational rheometer a powerful tool. The capillary rheometer extends the shear
rate range attainable in the laboratory beyond that available in a rotational instrument and allows the
flow properties to be measured under typical processing conditions. In addition, the ability to readily
determine both the shear and extensional properties under real life conditions provide the polymer
producer and processor with information that is vital to the successful use of a polymer melt. Finally,
the capillary rheometer enables processing problems to be investiagated in a controlled environment
without the need to stop production on the factory floor.