Melt rheology - Capillary rheometry

Melt rheology – Melt flow rate measurement

1. Introduction
Studying the melt state and the flow of polymers and knowing the various factors affecting
their viscosity is of high importance, especially in the processing of thermoplastic polymers.
Most plastics are processed in the melt state, usually by extrusion or injection molding. These
are technologies with high production rates that involve high shear stresses.

2. Theory
2.1. Rheology, flow
Rheology is the science that deals with the way materials deform when forces are applied
to them. The term is most commonly applied to the study of liquids and liquid-like materials
such as paint, ketchup, oil well-drilling mud, blood, polymer solutions, and melts. Rheology
also includes the study of elastic materials that do not flow, particularly cross-linked
elastomers.
The two keywords of rheology are deformation and force. To learn anything about the
rheological properties, we must either measure the deformation resulting from a given force
or measure the force required to produce a given deformation. In the following section, we
discuss the basic types of deformation and the basic concepts of rheology.
2.1.1. Elastic deformation
In the case of elastic deformation, the deformation occurs immediately when the stress is
applied and completely recovers when it ceases. The deformation () is proportional to the
stress () that creates it. The constant of proportionality (E) is called Young's modulus, and
this relationship is called Hooke's law (Eq. 2.).
𝜎 =Eε (1)
2.1.2. Flow
Under the influence of shear forces, a constant deformation rate (flow) develops in the
fluids, which, unlike elastic deformation, is not reversible. Viscosity () is the property of a
material that describes its resistance to continuous deformation. Unlike elasticity, stress is not
related to the amount of deformation but to the deformation rate. For simple shear, this
behavior is described by a linear relationship between the shear stress () and the shear rate
(𝛾̇ ):
𝜏 = 𝜂𝛾̇ (2)
A material that obeys the Newton's law (Eq. 1.) of flow, with the viscosity independent of
shear rate, is called a Newtonian fluid.

Molten plastics are rheologically complex materials that can exhibit both viscous flow
and elastic deformation. A general equation has not been developed for these materials yet.
Our present knowledge of their rheological behavior is mainly empirical. These facts
complicate the description and measurement of their rheological properties. On the other hand,
therefore polymer rheology is an interesting and challenging field of study.

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 Melt rheology - Capillary rheometry

2.1.3. The flow mechanism in polymers

The flow mechanism in polymers and low
molar mass materials show several similarities; the
size of the elemental molecular units of flow differs,
and so does the order of magnitude of viscosity and
the theoretical interpretation of specific
characteristics of the mechanism of flow. Both the
flow of low molar mass materials and polymers can
be described using the model developed by Eyring.
According to the model, places in a grid are
occupied by individual molecules or segments in
Figure 1. The grid model of the flow
the case of polymers (Fig. 1.). The basic units
change their positions by "hopping" to vacant places. These hoppings also occur among
equilibrium conditions; this is the self-diffusion of the liquid. The process requires activation
energy, i.e., the elemental unit has to cross an energy barrier to change positions (Fig. 2.). The
frequency of these crossings depends on the activation energy required. External forces,
however, decrease the height of the potential barrier in the direction of the force; thus, the
elemental units hop from one stable position to a vacancy more frequently in this particular
direction: and the material starts to flow.
In the case of low molar mass compounds, the
whole molecule changes its position, being the basic
unit of flow. Although macromolecules are too large
to jump to a vacant place in the grid, their molecular
structure and the flexibility of the polymer backbone
enable the independent movement of individual
chain sections. The basic units of flow, in this case,
are the segments. The center of mass of the
macromolecule has to shift during flow, which
requires the cooperative movement of its segments.
Accordingly, the viscosity of polymer melts is
determined by their molar mass and the interactions
between the macromolecules. Also, it exceeds the
Figure 2. Deformation of the energy barrier viscosity of low molar mass liquids by several
during the flow
orders of magnitude. The physicochemical
interaction of macromolecules, similarly to other
materials, involves the formation of secondary bonds. Physical interaction, the formation of the
fluctuation network, is even more important, resulting in significantly increased viscosity.

Several processes occur during flow under the effect of external stress, typically shear
stress. On the one hand, the center of mass of the macromolecules shifts according to the
mechanism discussed above. On the other hand, the molecules are no longer in an equilibrium
state due to external forces. Thus their conformation also changes: they orient in the direction
of these forces (Fig. 3.). The extent of orientation depends on the type (shear, tension) and
degree of external stress. Under processing conditions common in practice, most of the

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orientation gets preserved when the polymer is cooled down, which affects the material's
properties to a great extent.

Figure 3. The orientation of macromolecules during plastic flow

Besides the conformation change, another structural factor also affects viscosity and
viscous flow. The entanglement of the molecules hinders their movement; thus, their molar
mass appears to be considerably higher than that of the individual macromolecules. The
rearrangement of the physical network during processing takes time and energy. The changing
conformation and the deformation of the physical network lead to the shear dependence of
viscosity. The rate of relaxation is rather low, leading to elastic effects.

2.2. Types of fluids

The phenomena mentioned above taking place during plastic flow cause the time and
shear dependence of the viscosity of polymers.
Perhaps the most important factor during the
processing of polymers is shear stress; certain
technologies (e.g., injection molding) involve very
high shear rates. Based on the shear dependence of
their viscosities, materials can be classified as
follows:

– Newtonian fluid; no shear dependence,

– Bingham fluid; behaves like a Newtonian fluid
above critical stress,
– dilatant fluid; viscosity increases as a function
of shear rate (a typical example is the shear-
induced crystallization of specific elastomers),
– pseudoplastic materials; viscosity decreases as
a function of shear rate.
Most polymers belong to the last category.
Accordingly, both time- and shear-dependent Figure 4. Classification of fluids based on the
shear dependene of their viscosity
phenomena occur during polymer melts' flow. The
shear dependence of the viscosity of materials according to the classification discussed above
is presented in Fig. 4.

The most common structural time dependence type is shown in Fig. 5. The shear stress
decreases with time after the start of steady shear flow. This type of behavior, in which the
viscosity decreases with time, is called thixotropy. If the shearing is stopped, the viscosity will

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gradually increase as the particles respond to inter-

particle forces without shear stress. However, the
time required for the complete reformation of the
equilibrium structure can be very long. Some
materials, such as corn starch suspensions exhibit
the opposite effect. The stress increases with time
after the start-up of steady shear. This type of
behavior is called rheopexy. In the case of
thixotropy, the shear tends to break down structure
that has been established in the unsheared material,
while in the case of a rheopectic material, shearing
promotes the buildup of structure

2.3. Parameters affecting viscosity

Viscosity is the rheological property most often
used to characterize molten plastic. It is relatively
easy to measure, provides information about Figure 5. Classification of fluids based on the
time dependence of their viscosity
molecular structure, and plays an important role in
melt processing. Like all rheological properties, the viscosity of a polymer depends on the
following factors.
2.3.1. Shear
The shear dependence of a polymer melt is often divided into three regions, and several
characteristic values are determined. Fig. 6. presents a general correlation. At very low shear
rates, the effect of shear on viscosity is negligible; the melt behaves as a "Newtonian fluid".
The deformation in this region is so small that flow, i.e., the movement of the molecules, is so
limited that deformation takes place through the rearrangement of the fluctuation network.
Accordingly, the viscosity extrapolated to
zero shear is called Newtonian viscosity
(𝜂0 ). As this latter is related to the
deformation of the physical network, its
value reflects the structure of the polymer
in the melt state. It depends on the
characteristics of the polymer chain (the
type and number of branches, the
interactions between the chains, the
density of the physical network).

By further increasing shear,

Figure 6. The viscosity of polymers over a wide shear rate
viscosity decreases. In practice, the
range processing of polymers takes place in
this shear-dependent region. Under such
conditions, viscosity cannot be characterized by a single, constant value; thus, whenever

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viscosity is discussed, the respective shear rate (𝛾̇ ) and shear stress (𝜏) should also be given.
The apparent viscosity (𝜂𝑎 ) can be determined based on these values; however, unlike the
viscosity of Newtonian fluids, 𝜂𝑎 is not a well-defined, constant property of a given material:
𝜂𝑎 = 𝜏 (3)
𝛾̇

In the third region, as shear rates become very high, the macromolecules are assumed to
be fully straightened, and viscosity (𝜂∞ ) remains unchanged as a function of shear rate. In
practice, this region is difficult to reach; thus, the value of 𝜂∞ generally cannot be determined.
Extreme shear leads to the degradation of the polymer; thus, even if a viscosity value can be
measured, it does not reflect the characteristics of the material.

The phenomena discussed above reveal that shear conditions fundamentally determine the
plastic flow of polymers and their viscosity. Although many equations attempt to quantify this
correlation, in practice, the most commonly used is the Ostwald-de Waele relationship, also
known as the Ostwald-de Waele power law:
𝜏 = 𝑘𝛾̇ 𝑛 (4)

where 𝜏 is the shear stress, 𝛾̇ is the shear rate, and n and k are constants. The correlation
only describes a narrow range of the function presented in Fig. 6. It also has several theoretical
and practical drawbacks. Nevertheless, it is still widely used due to its simplicity.
2.3.2. Molar mass
Viscosity increases as a function of molar mass, as the flow of the material involves the
cooperative motion of more and more segments. The correlation can be quantified as follows:
𝜂0 = 𝑘′𝑀𝑛𝛼 (5)
where k' is a coefficient. The value of 𝛼 depends
on a certain critical molar mass (Mc, Fig. 7.), below
which 𝛼 = 1-1.2, while above it is 𝛼 ≅ 3.4. The critical
molar mass can be attributed to the formation of the
physical network that results in a considerable
increase in viscosity. The critical chain length exceeds
the segment size by far, and the two should never be
confused.
2.3.3. Temperature
Viscosity decreases as a function of temperature, Figure 7. The zero-shear viscosity plotted
against the molar mas of polymer
as the number of vacancies in the grid increases, while
the relative size of the energy barrier also decreases compared to thermal energy. The
temperature dependence of viscosity can be described with an Arrhenius-type equation
𝐸
𝜂 = 𝐴𝑒 𝑅𝑇 (5)
where A is the pre-exponential factor and E is the activation energy of the flow. This latter is
related to the size of the segment. The correlation is only valid across a narrow temperature
range.

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2.3.4. Pressure
Increasing pressure decreases free volume (i.e., the number of vacancies in the grid),
which leads to increased viscosity. Its value can be almost 10 % higher as a result of a 1000
bar increase in pressure. The pressure dependence of viscosity can be described using the
Doolittle correlation based on the free volume theory
𝐵𝑉
𝜂 = 𝐴𝑒 ( 𝑉 0 ) (5)
𝑓

where V 0 is the free volume at a certain reference temperature, V f is the free volume at the
actual temperature, and A is the pre-exponential constant.
2.3.5. Other factors
Other factors, e.g., shear-induced crystallization, cross-linking or degradation during
processing, and the effect of additives, can also affect the viscosity of polymers.

2.4. Flow anomalies

As mentioned above, polymer melts' viscous flow is always accompanied by rubbery
elastic deformation. This leads to a different behavior compared to low molar mass materials.
The typical phenomena related to these flow anomalies are the following.

Die swell. The diameter of the polymer exiting a capillary or die (tube, profile) exceeds
the respective size of the die (Fig. 8.). This increase is due to capillary
the relaxation of the elastic deformation developed during the 00
flow of the melt in the capillary to achieve equilibrium 0
conformation. The degree of die swell depends on external
conditions (shear, temperature, pressure) and the structure of
the polymer chain (rigidity, branching, molar mass). This
phenomenon should always be considered in the design of dies
for polymer processing. polymer
die swell
Elastic turbulence is also known as melt fracture. At
melt fracture
high shear rates, the material's surface exiting the capillary or
Figure 8. Flow anomalies
the die becomes rough. The irregularities often occur
periodically. Melt fracture can also be related to elastic effects, although its mechanism has not
been completely clarified. Melt fracture indicates the upper limit of the processing rate.

2.5. Viscosity measurement

In the plastics industry, data from rheological measurements are used for the following
purposes:
- Polymer characterization: Data provide information about the melt structure, including
average molecular weight, molecular weight distribution, branching, and structure.
- Quality control, statistical process control: This is a specialized type of characterization
in which a particular rheological characteristic is used to indicate the degree to which a
batch of resin adheres to product specifications.

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 Melt rheology - Capillary rheometry

- The measure of processability: In developing new polymers or new grades of existing

polymers, it is highly desirable to evaluate the potential of a candidate resin for use in a
melt-forming process using a small sample.
- Data for process simulation: The simulation of melt-forming operations requires a model
describing rheological behavior, and data are required to develop such models. However,
advances in process simulation are currently limited by the availability of reliable
constitutive models for nonlinear viscoelastic flow behavior. It is important to distinguish
between two types of rheological characterization.
2.5.1. Types of equipment
The most-used tools used to make rheological measurements on melts are capillary
rheometers, rotational rheometers, and extensional rheometers (Fig. 9.). Rotational rheometers
are used to obtain linear behavior but are of limited utility in exploring nonlinear behavior.
Capillary rheometers are used to determine viscosity at moderate to high shear rates and to
study the occurrence of flow instabilities and melt fracture. There are a variety of both on/in
and offline rheometers on the market today that provide rheological information ranging from
simple, single-point comparative data to complete, comprehensive material' fingerprints'.

In order to use these instruments effectively, the user must understand how the raw data
are related to the property to be measured and must have the skill required to obtain reliable
data. Rheological measurements on melts are challenging in several ways. Issues of concern
include residual stresses, flow instabilities, thermo-oxidative degradation, and wall slip.
Additional issues in the case of rotational rheometers are fixture alignment and sample rim
trimming.

Figure 9. Measurement methods and their typical measurement range

2.6. Capillary rheometers

The essence of the method consists of measuring the resistance to liquid flow through a
calibrated channel. The term "capillary" usually means any tube (channel) with arbitrary length
and cross-section, though, as a general rule, cylindrical tubes (capillaries) with a large length
to radius L/R (or diameter, D) ratio are used. The measurement principle is simple. A pump
(extruder, gear pump, ram) pushes test fluid through a capillary of a constant cross-section. The

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volume flow rate (Q) and the pressure gradient (ΔP) in the fully developed flow region are
measured to determine the shear viscosity (Fig. 10.).

The basic theory of capillary viscometry uses the following assumptions:

- no velocity in the radial and angular directions of the capillary
- the polymer is incompressible
- the flow is fully developed, steady, isothermal, and laminar.

In reality, the viscosity measurements require several

corrections intended to account for deviations of specific
experiment conditions from idealized requirements. Even in
measurements of the viscosity of a Newtonian liquid,
deviations from the linearity of dependence of volumetric
flow rate on imposed pressure can be observed. These
deviations are caused by factors that lead to the introduction
of corrections. (kinetic, temperature, entrance and pressure
corrections, corrections for slip at wall).

Data are sometimes reported in a flow curve of

apparent wall shear stress (𝜏𝑎 , Eq. 6.), which ignores the
entrance correction, versus apparent wall shear rate (𝛾̇𝑎 , Eq.
7.), which would be the shear rate for a Newtonian fluid.
Figure 10. The flow situation inside a The true shear rate at the wall can be determined by using
capillary rheometer
the Rabinowich correction, which requires the
differentiation of data obtained using capillaries having several radii.
𝑅∆𝑃
𝜏𝑎 = (5)
2𝐿
4𝑄
𝛾̇𝑎 = 𝑅3𝜋 (5)
From the general theory of capillary viscometry, two parameters, pressure and volumetric
flow rate, have to be measured. Typically, one of these parameters is assigned, and another is
measured. Pressure in the capillary tube viscometers is imposed by one of the following
methods: by a load of specific weight (MFR measurement), by a pressure of compressed gas,
by a pre-compressed spring, or by a power drive, in which force with the aid of the feedback
control is maintained or is regulated according to a required program. Imposition and regulation
of velocity of piston stroke (or volumetric flow rate) are achieved with the aid of a mechanical
or hydraulic drive by a method of varying velocity. The viscometers of the first group are
usually simpler by construction and more frequently used for standardized measurements. The
viscometers of the second group are equipped with a high-precision drive with an adjustable
speed of motion over a wide range. Modern instruments usually contain measuring devices
(sensors) with an output of the measured parameters acquired by a data acquisition system
connected to a computer for automatically processing measurement results using computer
programs supplied by the instrument manufacturer.

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2.6.1. MFR measurement

Widely referred to as a melt indexer, this is a primitive capillary instrument in which the
driving force is applied to the piston by placing a weight on a platform attached to its upper
end. A specific protocol for using this device was subsequently adopted by the American
society for testing and materials (ASTM) as Standard Test
Method D1238. Fig. 11. shows the essential elements of the
equipment. Polymer pellets are loaded into the barrel (6)
equipped with a thermometer (3) and surrounded by an
electrical heater (4) and an insulating jacket (5). The weight
(1) drives the piston (2), which forces the polymer through
the die (7). The standard specifies a preheat time of 4 min.
Procedure "A" involves cutting and weighing the length of
extrudate produced during a time interval indicated by a
stopwatch. Alternatives to manual operation, procedures "B"
and C" involve automatic measurement of the distance the
piston travels during a specified time interval. To calculate
the melt mass, it is necessary to know the melt density.

The recorded data is the melt flow rate (MFR), the mass
Figure 11. The cross section of a
of polymer extruded during a particular time interval, in units melt indexer
of grams per ten minutes (g/10 min). Other names commonly
used for this quantity are melt flow index (MFI), melt index (MI). A table in the standard test
method lists several standard combinations of temperatures and loads. For example, the
conditions usually used for polyethylenes are indicated as 190/2.16, which implies a
measurement at 190 C with a total load 2.16 kg. The mass of the weight is 2 kg, and that of the
piston is 0.16 kg. The mass of the sample and the time interval for collecting extrudate are
selected based on the expected value of the MFR. Obviously, MFR increases as viscosity
decreases, i.e., a high MFR resin has a low viscosity.

The MFR is now used globally. As a result, MFR is nearly always the only melt flow
property listed among the specifications of commercial thermoplastic resins. Typical values for
polyethylenes under condition 190/2.16 are: blow molding 0.2–0.8; extrusion and film blowing
1.0; rotational molding 2–10, and injection molding 1–30 g/10 min. High-flow resins for
injection molding of thin parts have values ranging up to 80 g/10 min or higher.

Even if the MFR test could be relied upon to yield a good approximation of the viscosity
at one shear stress, it still would have the limitation of being a single point characterization that
tells us nothing about the shape of the viscosity curve. As a result, two resins can have similar

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values of MI but quite different behaviors at

shear rates relevant to extrusion. Fig. 12. shows
viscosity curves of three polymers that have
very similar melt index values

Because the rheological properties of

polymers are sensitive to even small molecular
weight deviations, melt flow indexers are often
used in industry as a simple and quick quality
control method. Furthermore, melt flow
indexers are typically used to detect degradation
during processing or verify consistent material
properties between different batches or in virgin
and regrind material mixtures. Figure 12. Viscosity versus shear rate for three PE
samples

3. Report
Please use the template for the lab reports.
1. Aim of the practice
2. Description of the measurement
- Equipment used, measurement parameters, measurement process etc. Do not forget to
indicate the "Sample number"!
3. Evaluation
- Table of the raw data, MFR value and error
- Example calculation
4. Conclusion
- Explain the selected measurement parameters
- Describe the possible use of the polymer

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