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V94-91E Rheometer

Characterization of a Polyethylene Melt

H. Braun, W. Marquardt

1. Test material made down to 0.01 Hz. Lower frequency

Two different samples of polyethylene which
behave differently in their application were
measured. The differences were surprising
because they were produced in a similar
polymerization process. The samples are
labeled A and B for identification in this
report. The test material was dried for 4 hours
prior to the measurements at 80C to remove
all moisture which can influence the results.
The following results show the possibilities for
a rheological characterization using HAAKE
Rheometers and Software.
2. Instrumentation
The rheometer used for these tests was the
RheoStress RS with the high temperature
measuring system TC500, ceramic rotors and
the electric cone heating system. Sample
preparation and loading was simple, because
the samples were available already as a sheet. If
the test material consists of pellets or powder,
air bubble free sample preparation is crucial.
All measurements have been done under
nitrogen gas to minimize possible reactions
with oxygen.
values have not been used to shorten the
testing time but this limited the available
information as can be seen in the data. The
rheometer allows one to preset values as low as
-4
2*10 Hz which is several decades lower than
the lowest frequency used here in this report.
The data in figures 1 and 2 show that the
settings used were not the best choice because
the frequency data are not low and not high
enough to give clear trends for the polymer
behavior. The measuring window was 3
decades which could be extended using the
Time-Temperature-Superposition Principle.
The first information is, that one can either
measure at low frequencies which takes long
time or measurements are to be performed
over a wide temperature range. Both methods
normally give the same information and it is
up to the operator and the stability of the
sample (time or temperature) to prefer one
over the other method.

3. Measurements

The samples have been tested in dynamic

(oscillation) mode at different temperatures
from 200C down to 140C with parallel plate
sensor PP20 (ceramic shaft) and an initial gap
of 1 mm. The temperature settings were
chosen in steps of 20C to obtain overlapping Fig.1: Frequency sweeps of sample A
data in a master curve. Thanks to Thermo-
Gap the temperature dependent gap setting
was accomplished by the software with a rate
of 1.15 micrometer per1K.

All tests have been run in the frequency range

from 30 down to 0.1 Hz collecting 6 data
points per decade. Some measurements were

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Fig.2: Frequency sweeps of sample B
The recommendation for better and more
detailed data is as follows:
Run a dynamic test in two segments using
AUTO-STRAIN of 0.1 to 1% depending on
the test samples linear viscoelastic range and
viscosity. Start with the high frequency data to
see if the settings (sensor, strain, temperature)
are reasonable or need to be corrected. High
frequency tests take little time and it is a good
advice to wait 3 periods before taking a
measurement for equilibrium with viscoelastic
fluids. The test can be easily repeated 10 times
without loosing too much time (Fig. 3).
Fig.3: Settings for seg.1 in the software
The lower frequency data, below 0.1 Hz, take
more time and require practically no
equilibrium time. It is sufficient to wait for one
period before a measurement, which can be
measured 3 times to check the quality of each
data point. The HAAKE software calculates
the mean value and the standard deviation for
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Rheometer
every single data point, if repetitive tests are
done. (Fig. 4)
A complete test takes rather long and it is best
to run such experiments overnight. When the
procedure is started in the evening the data are
ready the next morning.
Fig.4:Settings for seg.2 in software
4. Master curve
The measured master curve contains the
rheological information of the test sample for
the linear viscoelastic range. This is the base
information for all further data processing. To
get the master curve, the following procedure
should be applied.
The raw data from the measurement are
loaded into the HAAKE WLF Time-
Temperature-Superposition Software and
shifted to a reference temperature of 180C.
The reference temperature depends on the
application. If data for low shear rates are
required the reference temperature should be
selected at the lower end of the measured
temperature data, high shear data are more
pronounced using higher reference
temperature values.
Remember that temperature and time have the
same effect according to the principles of
Time-Temperature-Superposition. This
means that frequency or shear rate which are
an "inverse time are reciprocal to
temperature.
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Fig.5: Selection of the reference temperature
in the HAAKE WLF softwareAs an example
the data of a sample A have been shifted for
two different reference temperatures 140 and
200 C (Fig. 6) to show the effect in the master
curve of sample A.
Fig.6: Selection of horizontal, vertical shifting.
Low reference temperature (e.g. 140C) gives
low angular velocity (frequency) data and a
high reference temperature (e.g. 200C) yields
higher angular velocity values (Fig.7).
In the HAAKE software it is recommended to
shift the data simultaneously in horizontal and
vertical direction. If this only "chains" data
together and does not shift the curves correct
or as expected, select the option "horizontal
shifting to ignore the compensation for
changes in density.
Fig. 7: Effect of the reference temperature on
sample A
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Rheometer
If the data have been shifted successfully, the
result is some new data files:
The WLF software by default saves the shift
factors aT and bT under the name of the file
chosen as the reference temperature in the
directory where the raw data have been loaded.
To differentiate it from the test results it has
the extension *.SH.
Fig.8: Shift factors calculated by the HAAKE
Software
Example: If the file name of the test data with
the reference temperature is called
POLYM200.OSD the shift factors will be
stored in POLYM200.SH. The data can be
loaded with Lotus, Excel .... by importing data
in ASCII DOS format. With any editor (DOS
EDIT/WIN Notebook) they can be loaded
and output to screen or printer.
The data of the master curve are saved in the
data directory using the HAAKE data format
with the name of the reference temperature
file plus the extension *.LSD. Additionally a
file named LSSHIFT.MC is created in the
temporary directory of the WLF software
(WLTEMP) containing the master curve data
in ASCII format. The *.LSD file can be
evaluated using the standard HAAKE software
while the ASCII data requires other software
programs like Quattro, Lotus 1-2-3, Excel,
Easy Plot, Math CAD ..
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V94-91E
Fig. 9: Master curve of sample A
Fig. 10: Master curve of sample B
The shift factors aT from the master curve
contain more information than thus far used.
As it will be shown later, the shift factors can
be used to calculate the Arrhenius activation
energy and to model the temperature
dependence of the material. The result of this
analysis can be used for QC and material
identification as well as to predict a master
curve at any other temperature.
5. Mathematical Description of the
Temperature Dependence
Until now we obtained the shift factors aT(T)
by the master curve software package. These
shift factors contain all the information
concerning the temperature dependence of the
material. In order to quantify this information
and to get a tool for further application, the
shift factors aT(T) have to be described by a
mathematical equation.
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Rheometer
There are two well-known relationships for
the description of the temperature dependence
of polymers:
The so-called Arrhenius and the WLF
equations. The preferable model depends on
the material, the temperature range of interest
as well as the glass transition temperature. Just
above the glass transition temperature TG, for
example, the thermally stimulated flexibility of
one polymer chain depends on its neighbors (a
so-called cooperative process). Well above TG
the thermal flexibility of chains is less
cooperative. This difference in the physical
behavior requires a different mathematical
description.
The software package tests both mathematical
models and indicates the best fit.
Arrhenius Equation
At temperatures well above the glass transition
(at least for T > TG + 100 K) the shift factors of
most polymers obey the following equation:
E 1 1
(1) ln a T (T ) =
R T To
E - activation energy (Nm/mol)
R - gas constant (8.314 Nm/mol*K)
To- reference temperature (K)
( T [C]=T [K] - 273.15)
T - temperature (K)
The activation energy divided by the gas
constant corresponds to the slope in a graph of
(ln aT) vs. (1/T-1/To). To calculate the
activation energy, simply perform a linear
regression analysis, take the slope and multiply
it times the gas constant R. In our example the
following values for the activation energy are
calculated
(defining To = 180C = 453.15K):
Sample A: Sample B:
slope=395 1/K slope=549 1/K
E=3283 Nm/mol E=4565 Nm/mol
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V94-91E Rheometer

Fig. 11: Calculation of the activation energy Fig. 12: WLF constants determination c1, c2

WLF Equation 6. Prediction of the Material Behavior at

other Temperatures
This relationship was derived by Williams,
Landel and Ferry. The equation describes Having a suitable equation for the temperature
aT(T) above the glass transition temperatureof dependence of the shift factors, one can predict
(linear) polymers and is approximately valid in the rheological behavior at other temperatures
the temperature range: where the material has not been tested before.
TG < T < TG+100 K. From a physical point of view, however, a
prediction is only recommended within the
c1 ( T To ) temperature limits used for the original
(2) lg a T ( T) = measurements (interpolation) instead of an
c 2 + ( T To )
extrapolation.
While both the parameters c1 and c2 depend on
In principle, curves of all measured quantities
the reference temperature and the material,
can be transformed to another chosen
their product c1*c2 is a characteristic value
temperature:
independent of To.
dynamic data: G, G, tan , J*, .=f()
The values c1 and c2 can be determined with
transient data: G, J, +, ...=f(t)
the help of a linear regression analysis in the
steady data: , , N1,. ..= f( & )
plot ((T-To)/lg aT) vs. (T-To). The slope of the
curve is the value (-1/c1) and the intercept
It can be done in the following way:
with the ordinate corresponds to (-c2/c1).
Therefore,
(i) Calculate the shift factor aT at the desired
temperature Tx;
c1 = -1 / slope (from regression)
use Eqs. (1) or (2) with T = Tx.
c2 = - intercept (from regression) * c1
(ii) transform:
In our example (To=180C) the regression
- time axis to t * aT
values are:
- frequency axis to / aT
Sample A: Sample B:
- shear rate axis to & / aT
slope = -1.6584 slope = 0.10886
intercept = -208 K intercept = -115 K
c1 = 0.603 c1 = 9.186 (iii) transform all rheological quantities which
c2 = 126 c2 = 1056 are of interest as follows:
c1*c2 =76 c1*c2 = 9704

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V94-91E
- quantities which have the time in the
numerator of their unit
calculate (quantity * aT):
e.g. viscosity
[] = Pa*s (Tx) = (T) * aT
- quantities which do not have time in their
units
stay unchanged
e.g. storage shear modulus G
- quantities which have time in the
denominator of their unit
calculate (quantity / aT )
e.g. fluidity
[] = (Pa*s)-1 (Tx) = (T) / aT
(iv) plot the transformed data in a new graph -
that's all.
For our example lets assume the dynamic data
are requested for T = 150C, but values are
available only for 140, 160, 180 and 200 C.
Using Eq.(2) with the values for c1 and c2 and a
reference temperature
To = 180C, we get : aT(150)=
10^(-0.603*(150-180)/(125.6+150-180))
= 1.546.
This shift value can now be used to shift the
angular velocity horizontally by calculating
new=/aT(150C). The dynamic viscosity
has to be recalculated also with (150C) =
(180C) * aT(150C).
With this method the dynamic data (sample B
master curves for G, G and ) have been
calculated at the chosen temperatures (150 and
170C) within the limits of
TG < T < TG+100 K.
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Rheometer
7. Relaxation Time Spectrum - What is it?
The relaxation time spectrum is
a function characterizing the material most
generally (i.e. more basically than the
rheological measuring quantities, since the
mechanical material properties in this form
are free of the special experimental setup
and parameters (flow geometry, type of
flow, deformation rate, etc.)).
a function which sometimes is more
informative than the measured material
functions, although it represents the same
information, not more.
a special theoretical description of the
material, which can not be measured
directly.
In "simple" words, the relaxation time
spectrum can be understood in a polymer
picture in the following manner:
A description of the material by a spectrum is
based on the idea that the material response is
caused by different, relaxing structural units
including also possible interactions. The final
material behavior is then given by the sum
over all effects.
In the case of polymers, the main chains, side
chains, branches, chain segments or any other
structural part can be regarded as such excited
and relaxing units. Each of these units can be
excited (something like resonance) only at one
eigen-frequency and after excitation, it relaxes
within a characteristic time. Consequently, all
of these units have characteristic properties.
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What one should keep in mind for further
understanding is that
there is a certain (relative) number of units
of a special type,
each type of units has a characteristic time
(or frequency) behavior,
each type of units has a characteristic
(relaxation) strength .
For further analysis, a mathematical model has
to be developed. For material deformations
within the linear range (i.e. the response is
linear with respect to the excitation)
- the time response function of each special
type of such structural units can be modeled by
a single exponential: f(t) = exp(-t/) with the
characteristic relaxation time .
(the dynamic response function can be obtained
by a Fourier transformation: the structural
units obey a frequency behavior of the form
f() = i/(1+ i) )
- the strength of each special type of such
structural units can be modeled by a
characteristic weight of the response function,
the so-called modulus G.
- the number density n(k) (i.e. the number N(k)
of all special types of units per relaxation time
interval) multiplied by their strength Gk yield the
relaxation time spectrum h().
For better understanding, we will relate the
material functions to the described structural
units. With respect to our example we will
concentrate on G():
G() = N (k) * Gk * fk () (3)
freq.depend total number their frequency
storage sum over of weighted effects modulus
all k units k
relaxation = number * strength of
time spectrum density a k unit
h (k) = n (k) * Gk (4)
For a continuos number of units we can
transform Eq. (3) into an integral equation
often found in textbooks. Dependent on the
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Rheometer
scale of integration one can distinguish
between a linear (5) and a logarithmic (6) form:
( ) 2
G'() = h ( ) d (5)
0 1 + ( )2
( )2
G'() = H ( ) d ln (6)
1 + ( ) 2
with H () = h () (7)
H() is another form of the relaxation time
spectrum, which is sometimes called
logarithmic density function.
For the PE melt samples we calculated the
relaxation time spectrum H() [1] given in
Fig.14 in a weighted form *H(). We used a
special software based on a non-linear
regularization method.
Finally, it should be mentioned that a time
spectrum can also be derived in a similar way
from creep experiments. It is called the
retardation time spectrum.
8. Application of Relaxation Time Spectra
in Rheology
Various applications of relaxation time spectra
are thinkable. In the following, only three
examples are briefly explained, which have
been well established in rheology:
1. With the material's relaxation time
spectrum in a special range, one has all the
information necessary to predict the linear
viscoelastic behavior of this sample at any
deformation. This means that all material
functions in the time or frequency domain (e.g.
G*, J*, tan , G(t), J(t), +(t) ) as well as
material parameters (e.g. Jeo, o, 10) can be
calculated using the equations available in
many textbooks. A special software performs
all these transformations. In this way, one can
either reduce the number of measurements or
one can obtain the material behavior in a range
which is not available with a given instrument
(e.g. controlled stress data from a controlled
rate rheometer).
2. Consisting of the same information as the
experimental data, the relaxation time
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V94-91E
spectrum (or a special weighted plot of it) is
sometimes a more sensitive representation
than the original data.
This special evaluation method has been very
successfully applied to detect small amounts of
the components of a polymer blend, or of
mixtures of homopolymers with different
molecular weights. In Fig.14 the weighted
spectrum of sample A and B is plotted. In
addition to a dominating maximum, the
spectrum of sample A reveals a"shoulder" at
shorter relaxation times caused by an almost
hidden peak. This indicates that sample A has
another polymer component (in our case also
PE) in addition to the major PE component,
which is the same as in sample B. In principle
we cannot say how much and which other
polymer it is, but we can predict the following:
- The behavior of both materials is dominated
by the same major component.
- When the shoulder in the spectrum of
sample A is caused by the same type of
polymer like the major component (our case),
then we can conclude that it has a lower
molecular weight.
- Both samples A and B have a broad molcular
weight distribution.
3. If you remember the simplified description
of the structural units (cf. section 8), it is
obvious that the analysis of the relaxation time
spectrum should yield information of the
molecular weight distribution (MWD) or
related quantities. And indeed, some recent
theories for the determination of the MWD
from rheological experiments are based on the
relaxation time spectrum.
Using the unique relationship between the
terminal relaxation time and the molecular
weight M of the sample, one can transform the
spectrum into a function dependent on M. In a
very simple approximation of the theory, the
spectrum itself is almost the MWD. For more
realistic predictions, one has to take into
account more complicated relationships.
The determination of the MWD from
rheology via a relaxation time spectrum is infor
the usual results without any additional
measuring effort. This method has the
advantages of avoiding solvent problems
associated with gel permeation
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Rheometer
chromatography (GPC) analysis, and to be
more sensitive in some ranges of molecular
weight.
9. Summary
In this paper we outlined the path from the
dynamic rheological measurements of a
polyethylene melt to an advanced evaluation of
the experimental results. This analysis for
polymer rheology became possible using two
sophisticated, scientifically accepted software
packages; one for the time-temperature-
superposition principle [2] and another for the
relaxation spectrum calculation.
It should be mentioned, however, that the
procedure described here is only one
possibility. Interpretations, predictions or
applications depend on your material and the
purpose of your work. So, for example, linear
polymers are quite different from polymer
blends or material testing for optimization of
the syntheses is totally different from
predictions concerning processability.
References
[1] Honerkamp J, Weese J, Rheol.Acta,
32 (1993) 65
[2] Honerkamp J, Weese J, Rheol.Acta,
32 (1993) 57
Fig. 14 Time-weighted relaxation spectrum
The new windows software PolySoft
eliminates most of the manual work by
shifting the curves and is a significant
improvement over the previous software
used in this paper.
Gebr. HAAKE GmbH, Tel. +49 721 4094-444
Dieselstr. 4, D-76227 Karlsruhe, Germany
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