MOLAR MASS EFFECTS ON THE SHEAR CREEP BEHAVIOUR

OF POLYPROPYLENE
MARKUS GAHLEITNER, BERNHARD KNOGLER, NORBERT HAFNER AND WILHELMINA PIRGOV
Borealis GmbH, St. Peterstr. 25, A-4021 Linz, Austria

The application of creep tests for the determination of

ABSTRACT
J(t) has shown advantages here over the more widely
The shear creep behaviour of a series of isotactic used dynamic and relaxation measurements. Starting with
polypropylenes, both commercial and experimental the pioneering work of Schwarzl [12,13], a lot of
grades, was investigated. This measurement allows the experience has been gathered in this field over the last
determination of the zero shear viscosity in a wider molar years. An evaluation of the creep curve not only allows a
mass range and with better reproducibility than the determination of the retardation spectrum, but - in a more
dynamic test. Also, with the equilibrium compliance a simple form - also gives access to h0 (connected to the
second fundamental parameter of the linear viscoelastic terminal relaxation region of the polymer [14]) and Je,0,
behaviour can be determined. The attempt to establish (the correlation of which to the polydispersity is
correlations between these parameters and the molar generally accepted), which are hard to determine
mass distribution was only partially successful. otherwise, especially for high molar mass polymers [15-
18].
KEYWORDS: POLYPROPYLENE, MOLAR MASS
DISTRIBUTION, CREEP TEST, ZERO SHEAR VISCOSITY, In the present work we therefore present an attempt
EQUILIBRIUM COMPLIANCE to correlate the creep behaviour to the MMD of a wide
range of both commercial and experimental iPP grades.
INTRODUCTION
The application of melt rheological methods to gain No. Catalyst MFR h0 h0*
information about the molecular characteristics of (g/10min) (MPa) (MPa)
polymers is widely accepted in both academic and
P01 MC 1500 6 6
industrial research today [1]. If compared to the direct
determination of molar mass distributions (MMD) as in P02 MC 800 14 13
size exclusion chromatography (SEC), rheology offers P03 MC 250 25 25
advantages especially in the high molar mass region, P04 MC 80 125 125
which is often dominating the processing behaviour of a P05 MC 10 926 1047
polymer for various reasons. P06 MC 3,2 4875 4378
In recent years, a multitude of research works has L01 ZN 177 130 127
been published dealing with the problem of L02 ZN 54 511 525
interconversion between linear viscoelastic data and the L03 ZN 29 904 916
MMD of a polymer. Roughly, these papers can be split
L04 ZN 136 172 168
into two categories:
L05 ZN 88 242 231
· Development of empirical or semi-theoretical
L06 ZN 7,0 3983 3765
correlations between singular parameters of the linear
L07 ZN 144 168 166
viscoelasticity - like zero shear viscosity h0, equilibrium
compliance Je,0, crossover frequency and modulus of L08 ZN 3,0 11340 11930
G’,G’’(w) - and parameters of the MMD like weight L09 ZN 7,0 78000 ---
average MW or polydispersity MW/MN [2-4]. In some L10 ZN 7,0 94020 84770
cases, also more general rheological data like the melt L11 ZN 7,0 99990 84190
flow rate (MFR) are included into these considerations C01 ZN (CR) 19,0 871 860
[5]. C02 ZN (CR) 8,0 2150 2080
· Full-scale interconversions between the MMD and C03 ZN (CR) 8,0 2383 2420
linear viscoelastic curves like G(t) or G’,G’’(w), which C04 ZN 8,0 3757 3790
make up the majority of work in this area [6-10]. These C05 ZN 1,9 31210 31420
correlations can also be expanded to predictions or
C06 ZN (CR) 1,1 16940 17100
interpretations of the processing behaviour [11].
C07 ZN 0,3 95150 ---
APPLICATION OF CREEP MEASUREMENTS
One of the problems involved with the calculation of Table 1. Catalyst type, production characteristics, MFR
MMD data from rheological data is the necessity to and zero shear viscosity of investigated materials
obtain these data in a wide range of frequency of time, as
this “experimental window” will determine the
predictable range of relaxation (or retardation) times of
the investigated polymer.

EXPERIMENTAL WORK
For the present study, which can be seen as the
expansion of earlier work in the field [3], a set of 24
different iPP-homopolymer grades was selected (see table
1). All materials had been polymerised in liquid
propylene with 4th generation Ziegler/Natta type or
metallocene catalysts (MC). The “C#”-materials are
commercial grades, while the “P#”-materials were
produced in a pilot plant and the “L#”-materials in a lab
reactor. For some commercial grades, the molar mass had
been reduced by controlled degradation with peroxides
(CR-grades [19]).
different series of materials in a log/log - plot. Deviations
and scatter increase with the molar mass of the materials
and are especially obvious for laboratory products with
bimodal MMD.
An even better correlation can be found between the
weight average of the MMD and h0 (see figure 2). The
good coincidence of the information content of both
parameters for homogeneous series of materials has been
shown before [3,4], but here materials based on different
catalyst types and with different MMD-shape are
compared in one log/log - plot.
1E+05

All materials were characterised as follows: MFR P#/MC

measurement at 230°C/2,16 kg acc. to ISO 1133, 1E+04 C#/ZN

h 0 (Creep, 210°C) / Pa.s

determination of the MMD in SEC (Waters 150 C, at C#/ZN(CR)

135°C in trichlorobenzene) and melt rheology in plate- 1E+03

plate geometry at 210°C (Rheometrics SR 2000 stress
controlled rheometer), starting with compressed plaques. 1E+02
Both dynamic and creep measurements were performed.
The zero shear viscosity h0 was determined from the 1E+01
slope of the stationary creep and, if possible, also from
the low frequency plateau of the complex viscosity
1E+00
assuming validity of the Cox/Merz relation (denoted h0* 1E+01 1E+02 1E+03 1E+04
in table 1). Mw (GPC) / kg/mol

1E+04
Figure 2. Correlation between weight average of the
MFR (230°C/2,16kg) / g/10min

MMD and zero shear viscosity for three series of

1E+03
investigated materials
1E+02
The equilibrium compliance is often claimed to
1E+01 P#/MC reflect the broadness of the MMD to some extent [4,5],
L#/ZN therefore we also tried to plot Je,0 over the polydispersity
C#/ZN(CR)
1E+00 (MW/MN) of the MMD. As figure 3 shows, not even
C#/ZN
within one series a satisfactory correlation can be
1E-01 obtained and the deviations are much worse than for the
1E+00 1E+01 1E+02 1E+03 1E+04 1E+05
empirically established relation between the inverse of
h0 (Creep Test, 210°C) / Pa.s the crossover modulus (1/GC) and the polydispersity
[2,3]. Quite obviously the higher statistical moments of
Figure 1. Correlation between zero shear viscosity and the MMD - especially MZ, defining the obliqueness of
MFR for the different series of investigated materials the distribution - have a significant influence on Je,0 as
well. This can also be explained from the theories of
For all materials, the equilibrium compliance Je,0 was linear viscoelasticity.
determined from the creep test by extrapolating the linear
1E+00
part of the curve to t=0. In some cases, the value was also
determined from the creep recovery test, which turned P#/MC
Je,0 (Creep, 210°C) / 1/Pa

out to give reasonable results only in case of higher molar 1E-01 C#/ZN
masses. c#/ZN(CR)

The creep measurements were continued for a

1E-02
sufficiently long time to reach the equlibrium, which was
checked by a continuous calculation of Je,0 and h0. Only
after a steady value for both parameters was reached the 1E-03
measurements were concluded. This resulted in very long
measuring times for the materials with higher molar
masses and broad MMD. 1E-04
0 2 4 6 8
RESULTS AND DISCUSSION Mw/Mn (GPC) / ---

In the following evaluation we tried to establish
correlations between the viscoelastic parameters, the
parameters of the MMD and the MFR. As figure 1
shows, a rather good linear relation between the zero
shear viscosity and the MFR can be established for the
Figure 3. Correlation between the polydispersity of the
MMD and equilibrium compliance for three series of
investigated materials

From the first investigated series, the P#-materials
based on MC-catalyst, a rather linear relation between Je,0
and h0 was assumed (see figure 4). This, however, turned
out to be not a general one after completing the pictures.
A more detailed investigation of the structural effects
would be necessary to elucidate the reasons for the
obvious deviations in this diagram.
1E+00
Je,0 (Creep, 210°C) / 1/Pa
1E-01
1E-02
1E-03
1E-04
1E+00 1E+01 1E+02
h0 (Creep, 210°C) / Pa.s
Figure 4. Correlation between zero shear viscosity and
equilibrium compliance for the different series of
investigated materials
CONCLUSIONS
The shear creep experiment is an ideal complement to
the dynamic test of polymer melts, as it gives access to
the long time (ie. low frequency) behaviour with very
good reproducibility. Especially the zero shear viscosity
and the equilibrium compliance, which both are
fundamental parameters of the linear viscoelastic
behaviour, can be easily calculated from the resulting
data.
The investigation of a series of iPP-homopolymers
with different production characteristics clearly shows
the possibilities and limits of establishing relations
between these parameters and the MMD. Further
investigations should rather be directed towards
integrating shear creep (compliance) data into modelling
the material behaviour, which is presently mostly based
on dynamic data alone.
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