POLYMER

TESTING

Prof. Dr.-Ing. Ahmed

Elsabbagh

SS 23
 RHEOLOGY MEASUREMENTS
LECTURE
CONTENT
 Types of viscosity

 Rheology Measurement

 Flowability Measurement

2
VISCOSITY &
RHEOLOGY
WHAT IS VISCOSITY?

Viscosity is simply the resistance to shear 

Material Property

4
TYPES OF FLUIDS

https://www.youtube.com/watch?v=5YEaXa3X3dk

5
WHAT IS RHEOLOGY?
Science studying the flow behavior of materials

6
WHY ARE THEY VERY IMPORTANT?
Thumb rule: by every 1°C increase in temp., the viscosity decreases by 3%

7
Types of solids and fluids

8
UNDERSTANDING VISCOSITY

We have two extremes

Hookean Newtonian
elastic solid Fluids
(like rubbers) (like water)

 Applying forces  Applying forces (shear)

(shear) causes causes deformation
deformation  Deformation is irreversible
 Deformation is  Shear rate doesn’t have
reversible an influence on the
resulting deformation
Our polymer lies
in between
9
MODELLING VISCOSITY

Water Rubber
All energy is lost in Deformation
deformation can be fully
“No recovery “ recovered
Pure Pure
VISCOUS ELASTIC

10
MODELLING VISCOSITY  MAXWELL MODEL
Thermoplastics
VISCOELASTIC materials
Part of the energy is dissipated in deformation.
The other part is restored through relaxation

Maxwell model, which is graphically depicted by an

instantaneous change of the spring and a time-dependent
reaction, t + Δt, of the dash-pot in series
When deforming complex materials such as polymers, there will always be
a viscous and an elastic force component. 11
VISCOSITY COMPONENTS
G’ Storage Modulus G’’ Loss Modulus G* Complex Modulus
= Elastic component = Viscous component = Viscosity (Visco-elastic
behavior)

12
 VISCOSITY TYPES
Dynamic Viscosity “Shear Viscosity” Complex Viscosity

 Resistance to shear  describes the overall resistance to deformation.

Usually plotted against angular frequency to correlate
shear viscosity & Shear rate

Kinematic Viscosity Intrinsic Viscosity

 Ratio of polymer dynamic viscosity to  It reflects the viscosity of polymer solution so as to

its density indicate the viscosity dependent only on the molecular
structure and not on the interaction between chains.

13
MEASUREMENT
OF VISCOSITY
RHEOMETRY/VISCOMETRY  CAPILLARY

Low Pressure High Pressure

15
KINEMATIC VISCOSITY MEASUREMENT - DIN 51 562

Once the viscometer has been filled, the polymer solution is sucked up to a gauge. Subsequently,
the fluid is allowed to return through the capillary and the throughput time is recorded.

16
INSTRINSIC VISCOSITY MEASUREMENT
For intrinsic viscosity [η] measurements, samples (1 wt %) are dissolved in a

mixture of phenol/tetrachloroethane (60:40 w/w) at 30◦C, and their flow time was

measured using an Ubbelohde viscometer (Schott Gerate GMBH, Hofheim,

Germany) at 25◦C. The [η] value of each sample was calculated using the following

Solomon-Ciuta equation:

[η] = [2{t/t0 − ln(t/t0) - 1}]1/2/c

c: concentration of the solution;
t0 :flow time of pure solvent;
t: flow time of solution.

Three different measurements are repeated for each sample to ensure the

accuracy of the results, and the average value is calculated

Comparing the flow time of the solution with that of the pure
solvent
17
INSTRINSIC VISCOSITY

18
INSTRINSIC VISCOSITY

ASTM D 4603 (Standard Test Method for

Determining Inherent Viscosity of Poly(Ethylene
Terephthalate)-PET)

determination of the intrinsic viscosity of a PET

sample by measuring the flow time of the solution
with a single concentration.

ASTM D 2857 (Standard Test Method for Dilute

Solution Viscosity of Polymers)

additional measurements of flow times by doing

successive dilutions of the original solution

19
HIGH PRESSURE CAPILLARY RHEOMETER - DIN 54 811
Two canals of 15 mm diameter ending with dies of length / diameter
of 0/1 and 15/1 mm. Its speed is 0.00005 - 40 mm/s which can impart
shear rate up to 1E6 1/s. Such shear rate simulates the injection
molding shear conditions and thereby covering all shear rate ranges
actually occurring in polymer processing.
(Capillary diameters range from 0.5 to 5 mm, and capillary lengths
from 5 to 60 mm)

Measured Characteristic parameters

 Pressure drop over capillary length PvT Curve

 Volume throughput per time unit Viscosity vs. Pressure

 Temperature Thermal Conductivity

20
HIGH PRESSURE CAPILLARY RHEOMETER - DIN 54 811
Capillary rheometers function according to the following measuring principle. After appropriate
temperature adjustment, the fluid to be characterized is fed from a reservoir and through a capillary
either by means of gravity or under pressure. By the time the end of the capillary has been reached, the
pressure corresponds to environmental pressure. This pressure gradient, as well as the volume passing
through the capillary per unit of time, are measured and the resulting rheological parameters calculated.
When capillary viscometers are used for measurement, pressure difference Δp can be specified and
volume flow Q can be measured

The velocity gradient dependent on capillary radius can be

determined from volume throughput:

21
HIGH PRESSURE CAPILLARY RHEOMETER - DIN 54 811

Compared to Newtonian media, structure-viscous

polymer melts exhibit decidedly higher velocity
gradients near the nozzle wall

Particularly at high throughput rates. The calculated

apparent shear rate is thus lower than the actual rate, thus
overestimating viscosity. The shear rate can be corrected
according to Weissenberg-Rabinovich

The pressure losses occurring in viscoelastic media while

flowing through nozzles caused by friction loss and elastic
deformation also require correction.

22
HIGH PRESSURE CAPILLARY RHEOMETER - DIN 54 811

At very high shear stresses, throughput,

i.e., shear rate, can increase suddenly

and substantially. This effect comes with

a scaly tearing on the surface of the

strand exiting from the capillary, which is

termed melt fracture. Melt fracture is due

to elastic properties of the melt.

The elastic properties of polymer melts can be calculated

from the flow profiles.

23
 High Pressure Capillary Rheometer – Results

PP1 EHS neu_PVT_T220tol1_.xls

1.35E+03 P [bar] 56.703

113.122 226.376

452.707 679.078
1.30E+03
905.432 1131.786

1.25E+03
Vol.sp [mm³/g]

1.20E+03

1.15E+03

1.10E+03
3.60E+01 5.60E+01 7.60E+01 9.60E+01 1.16E+02 1.36E+02 1.56E+02 1.76E+02 1.96E+02 2.16E+02

T [°C]

24
 High Pressure Capillary Rheometer – Results

Thermal conductivity
PP1 high
0.35 flow[905 bar]

0.33
Compound 1
[905 bar]
0.31

0.29 Compound 2
Wärmeleitfähigkeit [W/mK]

[905 bar]

0.27

PP1 [57 bar]

0.25

0.23
Compound 1
[57 bar]
0.21

0.19 Compound 2
[57 bar]

0.17

0.15
130 140 150 160 170 180 190
Temperatur [°C]

25
 High Pressure Capillary Rheometer – Results

Flow diagram at 200°C PP1 (high flow)

Compound 2
Compound 1
1000

100
Viskosität [Pa.s]

10

1
100 1000 10000 100000
Scherrate [1/s]

26
RHEOMETRY/VISCOMETRY  ROTATIONAL
(a) two parallel
plane plates (simple shear)

(b) flow in an annular gap

(coaxial shear/Couette flow)

(c) Flow between tubes and

capillaries (telescope shear)

(d) flow in a gap between two

parallel plane
round plates or a cone and a
flat plate (torsion shear)

(e) elongational flow

 Rotational rheometers /Oscillatory

 Capillary rheometers
 Falling-sphere viscometers and
27
 Extensional rheometers.
RHEOMETRY/VISCOMETRY  OSCILLATORY

Hookean solid Newtonian Liquid

Polymer

28
RHEOMETRY/VISCOMETRY  OSCILLATORY

29
RHEOMETRY/VISCOMETRY  OSCILLATORY
The viscosity measured in an oscillatory experiment is a Complex
Viscosity much the way the modulus can be expressed as the complex
modulus. The complex viscosity contains an elastic component and a
term similar to the steady state viscosity

Amorphous
polymer

30
RHEOMETER

31
RHEOMETER ASTM D4440-15 / ISO 3219

Plate-Plate Rheometer Cone-Plate Rheometer

A large gap can be set to On rotation a uniform

reduce the shear applied to shear rate is generated
a sample during loading across the entire sample.

ResearchGate

READING: https://www.tainstruments.com/wp-content/uploads/Boston-Rheology-Training-2019.pdf
32
RHEOMETER ASTM D4440-15 / ISO 3219

Samples Preparation
Samples are typically about 3–5 g, hence, the samples must be
homogeneous and representative of the material. For hygroscopic
samples or those containing volatile components, samples must be
stored to minimize any changes in viscosity and mass of samples.
The samples may be required for drying before the measurement.
The samples produced by injection or compression moulding shall be
in the form of a disc. Alternatively, samples in the form of pellets or
liquid or molten polymer can be placed between the plates, provided
the sample is homogeneous and free from bubbles during the
measurement. The molten samples must not sensitive to oxidation or
loss of volatile matter. Samples must not show any obvious
discolouration before and after the measurement and contain any
visible impurities, inhomogeneities or air bubbles. If these components
are present during the experiment, then the measured data does not
represent the true data of the samples. The error in the obtained data
depends on these unwanted components’ size, amount and Disk diameter = 25 mm
distribution.
The samples must completely fill the gap between the two plates of
t= 1-3 mm
the rheometer. Any excess sample material around the edges of the
plates has to be removed before the measurement. Next, the sample
and plates shall be allowed to reach the thermal equilibrium at the test
temperature. This period of time is called preheat time. Finally, the
sample’s thickness, d, is measured and shall be used in all
calculations. 33
RHEOMETER
Plate-Plate Rheometer Cone-Plate Rheometer

x x
h h3 h1

In the two-plate model, both plates are equipped with sensors. The first sensor detects the
strain or deformation, γ of the upper plate, called the angle of torque. The signal is
Represented by the strain versus time plot in a sinae curve with the strain amplitude γ A.
The second sensor detects the torque that acts upon the lower plate. This force is the
counter force to keep the lower plate in position and recorded as shear stress, σ.

34
RHEOMETER

35
RHEOMETER

36
RHEOMETER
100000

Measured Parameters
PP

Force or Torque 10000

Viscosity [Pa.s]
Displacement or Angular
Displacement 1000

Linear or Angular Velocity

Normal Force
100
Temperature 0.1 1
Shear rate [1/s]
10 100

Battery Power Online

37
RHEOMETER SETTINGS

http://pages.mtu.edu/~fmorriso/cm4655/TAInstruments/2013TA_10stepstogoodrheolmeasureme
nts.pdf

38
PLATE-PLATE RHEOMETER – RESULTS (TEMPERATURE)

39
PLATE-PLATE RHEOMETER – RESULTS (TIME SWEEP)
Determines if properties are changing over the time of testing
Degradation / thermal stability
Molecular weight building
Cross-linking

40
PLATE-PLATE RHEOMETER – RESULTS (FREQUENCY SWEEP 
MATERIAL RESPONSE TO DEFORMATION)
Dynamic (oscillatory) testing can measure time-dependent viscoelastic properties more efficiently by
varying frequency (deformation time)

it is only
possible to
observe a
fragment of this
spectrum using
a standard
rheometer
which depends
on the
sensitivity of the
rheometer as
well as the
relaxation
behaviour of the
material.
https://www.degruyter.com/document/doi/10.1515/cti-2022-0010/html
41
PLATE-PLATE RHEOMETER – RESULTS (FREQUENCY SWEEP  MATERIAL RESPONSE TO
DEFORMATION)
For viscoelastic
liquid
materials, G″ > G′ is
observed at low
frequencies (liquid-
like behaviour
predominates),
while G′ < G″ (solid-
like behaviour
predominates) is
displayed at high
frequencies.

For a viscoelastic solid, G′ is

constant and dominates at low
frequencies, whereas G″
increases with increasing
frequency and dominates at high For a gel-like material, G′ and G″
frequencies. This type of material
displays a rigid consistency at
are parallel throughout the entire
rest, however, it is easily frequency range.
deformed when a sufficiently
large force is applied. Examples
of such materials are toothpaste
and lotions.

42
PLATE-PLATE RHEOMETER – RESULTS (FREQUENCY SWEEP  RELAXATION TIME

43
PLATE-PLATE RHEOMETER – RESULTS (FREQUENCY SWEEP 
MATERIAL RESPONSE TO DEFORMATION)

44
MEASUREMENT
OF FLOWABILITY
MELT FLOW INDEXER - ISO 1133.
ASTM D1238 test

The weight of the polymer in grams extruded during the

10-minute test is
the melt flow index (MFI) of the polymer.

Often used in industry to characterize a polymer melt

and as a simple and quick means of quality control.

https://www.youtube.com/watch?v=DqaPk
HXgy_M

46
 MELT FLOW INDEXER - ISO 1133.

Test conditions for

measuring melt-flow index

47
DETERMINATION OF INSTRINSIC VISCOSITY FROM MFI

https://reader.elsevier.com/reader/sd/pii/S0142941805000863?token=EE7903F5EC612DECBDF4A5E8508E7C7890481BB1873
70E269AE788DF53AA2CEE2F5C9A00B7DA7CB361B030514D11B99C&originRegion=eu-west-
1&originCreation=20211214120335

48
DETERMINATION OF INSTRINSIC VISCOSITY FROM MFI

http://www.asi-team.com/asi%20team/gottfert/Gottfert%20data/Determination%20of%20the%20Intrinsic%20viscosity_e.pdf

49
DETERMINATION OF INSTRINSIC VISCOSITY FROM MFI

http://www.asi-team.com/asi%20team/gottfert/Gottfert%20data/Determination%20of%20the%20Intrinsic%20viscosity_e.pdf

50
SPIRAL FLOW TEST
ASTM D3123-09

Spiral flow length test is one of the most important methods to

assess the flowability of a certain compound to predict its mold
filling behavior in injection molding process. The spiral has a
half circular cross section with 6 mm diameter and 9.5 mm
pitch.

51
SPIRAL FLOW TEST – RESULTS

https://www.mitsuichem.com/sites/default/files/media/document/2018/g-02_spiral_flow.pdf

52
SAMPLES AND STANDARDS
SS 2023
53