::: Intelligence in Rheometry

Polymer Discovery System

Today, polymers are among the most important materials in

existence as the properties of polymers can be adapted in a
very wide range to fit the field of application. Some polymers
are hard and brittle or tough and shock-resistant, while
other polymers are soft and flexible. The manufacturing and
characterization of polymers is therefore the focus of activity for
numerous industrial companies and research institutes.

Introduction
Plastics are organic or semi-organic substances with a high
molecular weight. The length of the molecular chains and the
entanglement between them are decisive parameters which
influence the properties of the material. Many of the relevant
properties can be characterized using rheological tests.

Polymers have complex chemical and morphological structures

and a wide range of variation in the composition and possibility
of modifying the material. Therefore they show complex
behaviors which need to be taken into consideration when
using or manufacturing these materials, e.g. the viscoelasticity,
non-Newtonian flow behavior, anisotropy (dependent on
orientation or modification), complex aging behavior and much
more. Describing the properties of polymers requires versatile
procedures in order to obtain the needed information.

Many methods are used for processing and manufacturing

plastics. The majority are forming and reforming procedures
(compression molding, calendering, film extrusion, blow &
injection molding, etc.). Optimizating these procedures and
their quality control is therefore extremely important in the
production of plastics.

Source: accelrys
Models of oxygen and water molecules in an amorphous polymer matrix.
Rheological Tests on Polymers

Process Simulation
Correlation to manufacturing conditions
Measurements at low shear rates are mainly used for
analyzing manufacturing problems. Whereas manufacturing
processes such as extrusion or injection molding occur
at high shear rates, differences between the materials are
usually seen at low shear rates. Manufacturing problems
often occur at low shear rates, e.g. delayed die swell with
extrusion or delay due to irregular relaxation during the
cooling phase of injection molded parts. Polymer melts
show pronounced shear thinning behavior, i.e. the viscosity
decreases with increasing shear rate. Flow curves are
important for the manufacturing of polymers to determine the
energy required for the process. Oscillatory measurements
also reveal information about the elasticity of the melt, which
can be correlated with die swell.

Material characterization
The viscosity curve becomes flatter with decreasing shear
Molar Mass Distribution rate and the polymer melt shows Newtonian behavior with
Recently, mathematical models have been developed which a constant viscosity. This region at low shear rates is called
allow the determination of the molar mass distribution via the terminal relaxation zone or the 1st newtonian plateau.
rheological measurement. The constant viscosity in this range is called the zero-shear
viscosity η0 and represents an important temperature dependent
Correlations to molar mass distribution or material branching material parameter. For most technical polymers, the zero-shear
can be seen in the viscoelastic behavior, which influence viscosity is directly proportional to the average molar mass.
both, the manufacturing process and the properties of The rheological measurement therefore clearly shows small
the end product. The molar mass is the most important differences in the molar mass.
structural parameter which affects the flow behavior of
polymers. At a constant average molar mass, the energy required for shear
thinning in the manufacturing process can be correlated with
the molar mass distribution. Polymers with a wide molar mass
distribution have more of a tendency to shear thinning, even at
low shear rates, than more narrowly distributed materials with
the same average molar mass. Broadening the molar mass
distribution aids extrusion and shaping. This means, for example,
that the surface quality of molded plastic parts can be improved
higher average > narrow <
molar mass (>M W ) MMD G' by varying the distribution width. The width of the molar mass
distribution correlates with the cross-over point between the
G''
storage modulus G’ and the loss modulus G’’ in a frequency
sweep.
longer / branched GX, ωX
molecules
lower average
molar mass (<M W )

shorter / less
branched molecules

< wide MMD >

Angular Frequency ω
Branching
The number, length and mobility of side chains influence the
rheological properties. If the side chains are not very long,
this leads to increased viscosity at low shear rates and more
pronounced shear thinning compared to the corresponding
linear polymer.
If a polymer has long-chain branching, it will display low
viscosity at low shear rates. The extent of branching can
therefore be used to control manufacturing and product
characteristics.
Fillers
Fillers also influence the manufacturing process and the
properties of the end product. Important factors are size,
form and concentration of the fillers and the interactions
between the particles. Fillers usually lead to an increase in
the melting viscosity and a reduction of die swell. From a
Conversion and analysis methods
rheological standpoint an increasing filler content results in a
smaller so-called linear visco-elastic (LVE) range, which can
be determined in an amplitude or strain sweep.
Measurements on solids
With the appropriate accessories, a rheometer can be used
to perform dynamic mechanical thermal analysis (DMTA)
on solid samples by measuring the samples in torsion.
The solid properties are usually determined as a function
of the temperature and the results give insight into the
morphological properties and behavior of the polymer when
in use. Measurement of the glass transition temperature
(Tg) and storage modulus (G’) below the glass transition
temperature gives information on the maximum service
temperature and the impact strength, embrittlement and
stiffness of the material. For crystalline or partially-crystalline
polymers the melting temperature (Tm) is another important
material parameter accessible with such a DMTA test.
Applications

Fig. 1: FLOW AND VISCOSITY CURVE … or

how to get information about the flowability of a
thermoplastic:
Flow and viscosity curves give information about the flowability of
thermoplastics under different shear and process conditions. The zero-
shear viscosity η0 at low shear rates is an important material property
and is directly proportional to the average molar mass Mw. In order to
determine a viscosity curve over a broad range of shear rates a master
curve can be constructed using time temperature superposition in
combination with the conversion method according to Cox Merz. In
addition, conversions from transient tests and a direct measurement
with controlled shear rate provides the whole spectrum of shear rates.
Powerful regression methods may help to calculate the zero-shear
viscosity η0 and the infinite-shear viscosity ηinf in a shear range where
all the molecules are totally disentangled and oriented.

Fig. 2: TIME TEMPERATURE SUPERPOSITION

TTS… or looking deep into the macromolecular
structure of a polymer melt:
The Dynamic mechanical analysis (DMA) in torsion, determined
via time temperature superposition TTS, provides shear and
time dependent information about the viscoelastic properties of
a material. Predictions regarding "Die Swell” are possible. All the
information about the polymeric macro-structure and its short
and long term behavior is already included in the "Master Curve”.
Comparative average molar mass and molar mass distribution,
as well as the calculation of their absolute values, are supported.
Conversions into transient and oscillatory material functions are
applicable.

Fig. 3: CROSS OVER POINT Gx… or how to

compare the molar mass of thermoplastics within
10 minutes:
Within 10 minutes, the molecular structure can be analyzed with
respect to the average molar mass Mw and the molar mass distribution
MMD. A powerful and model free method is given for a relative
comparison of thermoplastics. A qualitative measure for the average
molar mass is expressed by the horizontal position of the cross-over
point Gx while the vertical position of Gx indicates the MMD. In addition
the degree of branching can lead to a horizontal shift of Gx while
comparing polymers of the same type.
Fig. 4: MOLAR MASS CALCULATION … a method
used not only for short or narrow distributed
polymer melts:
Processability and product performance depend very much on the
molecular structure of the polymer melt, so it is important to analyze
thermoplastics with respect to their molecular structure. A rheological
dynamic mechanical measurement (DMA) in combination with the
latest sophisticated MMD analysis methods has major advantages
and is still easy to use. The thermoplastic material can be measured
as molten material and does not need to be diluted in an aggressive
solvent. The method has no upper limits regarding length and
distribution of the molecules; rather there are advantages due to
the higher sensitivity with increasing average molar mass Mw. Input
data for the method include a frequency sweep showing zero-shear
viscosity and cross-over point Gx.

Fig. 5: DYNAMIC MECHANICAL THERMAL

ANALYSIS (DMTA) in TORSION … or how to
determine phase transitions of thermoplastics,
thermosets and elastomers:
This test provides the essential information about the material’s
phase transitions. Glass transition (Tg), melting (Tm) and
crystallization temperature (Tc) can be determined with high
precision using the environmental chamber CTD 600. Information
about the degree of crystallinity or cross-linking is expressed in the
slope of the material functions G’ and G’’. With the film and fibre
fixture, DMA and DMTA tests in tension can be performed even on
soft polymeric films and fibres. In figure 5, a multiwave experiment
is presented with the determination of the glass transition
temperature, expressed as the maximum in tan(δ). As can be seen,
Tg is a function of the applied frequency.

Fig. 6: TRANSIENT TEST TYPES (Creep, Stress

Relaxation and Stress Growth Tests) … find out
more about the time response of your material:
Step stress (creep & recovery), step strain (stress relaxation) and
step rate (stress growth / start up flow) experiments are typically
performed to measure the time (transient) response of a material to
a given constant shear stress, shear strain or shear rate. Analysis
methods enable the calculation of important material constants such
as zero-shear viscosity, plateau modulus, creep compliance and the
conversion from the transient material functions to oscillatory material
functions - G’(ω), G’’(ω). In Figure 6, a stress growth experiment is
presented.
Physica rheometers for polymer testing

Environmental Systems
Since temperature has a great influence on the rheological
behavior of all polymeric samples, precise temperature
control is crucial to obtaining reliable rheological data.
However, in practical tests, inaccurate temperature control
is still responsible for a large number of measurement
uncertainties and errors. To address these issues, our
engineers have taken great care to develop various
temperature control systems based on different principles.
These systems fulfill the requirement of accurate temperature
control in all respects and are still commercially affordable,
putting Anton Paar in the lead position with respect to
temperature control in rheology. Numerous patents and
scientific reports about the performance of the various
environmental system have been published. Some key
features include the broadest temperature range available
(-150 °C to 1000 °C) for a standard rheometer, proof of
performance, i.e. as results of temperature gradient testing,
and the availability of certified temperature sensors which
allow software controlled automatic temperature calibration in
a broad temperature range.

Electrical Temperature Device P-ETD 400

4 Electrical resistance heating
4 Specially suited for samples which are measured at high temperatures
4 Very rapid heating rates
4 The special design enables water cooling (liquid circulator) as well as
electrical heating
4 Use of liquid nitrogen for temperatures as low as -130 °C

Electrical Temperature Device H-ETD 400

4 Electrically heated hood
4 Active heating of the sample area and measuring system
4 An essential accessory for preventing temperature gradients in the
sample
4 The hood can be purged with inert gas to prevent oxidation or other
chemical reactions

Convection Temperature Device CTD 600

4 Extremely small temperature gradients
4 No temperature overshoots
4 Measured temperature always represents the sample temperature
4 No ice formation at low temperatures
4 Compact, robust design
4 Automatic adjustment of liquid nitrogen consumption
4 Easy to open, good sample access
4 Sample observation during the measurement is possible
4 Chamber can be touched at all test temperatures
4 Wide range of accessories: torsion and film/fibre tool, UV-option,
disposable plates, etc.
 Systems Polymer Discovery System Polymer Melt Rheometer

Rheometer Physica MCR Series incl. Toolmaster™ Physica MCR Series incl. Toolmaster™

Convection Temperature Control Device CTD 600

incl. accessories for polymer handling
Temp.-Control System: Electrically Heated Temperature Device ETD 400
Temperature Calibration Sensor CS/CTD

Measuring Plate PP25

Measuring System: Lower Measuring Plate PP25 with built-in Measuring Plate PP25
temperature probe

RheoPlus Software
Rotation and Oscillation

DSO Direct Strain Oscillation RheoPlus Software

Software:
Polymer Analysis Package consisting of: Rotation and Oscillation
Master curves, Relaxation Time Spectra,
Retardation Time Spectra,
Molar Mass Distribution
Solid Torsion Bar Fixture STBF
Film and Fibre Fixture
Tool for Extensional Rheology
Low Temperature Option (LN2 Evaporation Unit EVU), TruGap™

DSO Direct Strain Oscillation

Options: Polymer Analysis Package consisting of:
Master curves, Relaxation Time Spectra,
Retardation Time Spectra, Molar Mass
Distribution

Temperature Calibration Sensor CS/CTD

Helpfull accessories for the CTD 600

Included: Included:
Filling ring for melting Scraper for fast and
and molding polymer effective cleaning
granuls

Simple to remove
before measurement

Included: Option:
Trimming tool for easy Stamping press
sample trimming on This press enables the
all sides production of sample
discs in a thickness
up to 2 mm and in
diameters of 25, 12
and 8 mm.
 Fotos: Croce & Wir

Anton Paar GmbH

Anton-Paar-Str. 20
A-8054 Graz
Austria - Europe
Tel.: +43 (0)316 257-0
Fax: +43 (0)316 257 257
E-mail: info.@anton-paar.com
Web: www.anton-paar.com

International Product
Management:
Anton Paar Germany GmbH
Helmuth-Hirth-Str. 6
D-73760 Ostfildern
Germany - Europe
Tel.: +49 (0)711 72091-0
Fax: +49 (0)711 72091-630
E-mail: info.de@anton-paar.com
Web: www.anton-paar.com

Instruments for:
Density and concentration
measurement
Rheometry and viscometry
Sample preparation
Colloid science
Microhardness testing
X-ray structure analysis
CO2 measurement
Specifications
High-precision temperature subject to change
measurement without notice

02/04 B61IP08-B