Rheol Acta (2002) 41: 232–244

Springer-Verlag 2002 ORIGINAL CONTRIBUTION

Claus Gabriel Influence of long-chain branches

Helmut Münstedt
in polyethylenes on linear viscoelastic
flow properties in shear

Abstract This contribution presents ethylenes whereas the highly

Received: 12 July 2001
Accepted: 30 October 2001
C. Gabriel* Æ H. Münstedt (&)
Institute of Polymer Materials,
Department of Materials Science,
University Erlangen-Nürnberg,
Martensstr. 7, 91058 Erlangen,
Germany
e-mail: polymer@ww.uni-erlangen.de
*Present address:
C. Gabriel
Basell Polyolefine GmbH, SPR-CCC,
M510, Carl-Bosch-Str. 38,
67056 Ludwigshafen, Germany
a survey on the influence of long-
chain branching on the linear visco-
elastic properties zero shear-rate
viscosity and steady-state recover-
able compliance of polyethylene
melts. The materials chosen are
linear and slightly long-chain
branched metallocene-catalyzed
polyethylenes of narrow molecular
mass distribution as well as linear
and highly long-chain branched
polyethylenes of broad molecular
mass distribution. The linear visco-
elastic flow properties are deter-
mined in shear creep and recovery
experiments by means of a magnetic
bearing torsional creep apparatus.
The analysis of the molecular struc-
ture of the polyethylenes is per-
formed by a coupled size exclusion
chromatography and multi-angle
laser light scattering device.
Polyethylenes with a slight degree
of long-chain branching exhibit a
surprisingly high zero shear-rate vis-
cosity in comparison to linear poly-
branched polyethylenes have a much
lower viscosity compared to linear
samples. Slightly branched polyeth-
ylenes have got a higher steady-state
compliance in comparison to linear
products of similar polydispersity,
whereas the highly branched poly-
ethylenes of broad molecular mass
distribution exhibit a surprisingly
low elasticity in comparison to linear
polyethylenes of broad molecular
mass distribution. In addition sparse
levels of long-chain branching cause
a different time dependence in com-
parison to linear polyethylenes. The
experimental findings are interpreted
by comparison with rheological re-
sults from literature on model
branched polymers of different mo-
lecular topography and chemical
composition.
Key words Long-chain
branching Æ Zero shear-rate
viscosity Æ Steady-state recoverable
compliance Æ Polyethylene

Introduction processes already used for a long period of time new

The influence of long-chain branching on the flow
properties of polyethylenes has gained much interest in
the scientific community as well as in industry during the
last few years. Long-chain branches in polyethylenes
lead to a significantly improved processing behavior due
to increased shear thinning and the appearance of strain
hardening in elongational flow. Besides the high pressure
production processes using metallocene and constrained
geometry catalysts are able to polymerize polyethylenes
exhibiting these important features. Interestingly enough
sparse levels of long-chain branching are sufficient to
improve the processing behavior in the desired manner.
The level of long-chain branching in these new
polyethylenes is sometimes so low that it cannot easily
be detected by standard analytical methods. The

mechanism of long-chain branch formation is generally
viewed as the incorporation of vinyl-terminated chains
into the growing backbone (e.g., Hamielec and Soares
1996). In a series of publications Malmberg et al. (1998,
1999, 2000) and Kokko et al. (2000) have demonstrated
in which way polymerization conditions in metallocene
catalysts may change the branching structure.
Rheological measurements are sensitive enough to
detect small changes in molecular structure. Several
papers have dealt with this subject in the last few years.
Nevertheless, most of these papers suffer from the fact
that the linear viscoelastic flow regime of polyethylenes
with a slight degree of long-chain branching is not
accessible using standard rheological equipment like
dynamic-mechanical analysis. Several publications re-
port for this new type of long-chain branched polyeth-
ylene an elevated low shear-rate viscosity in comparison
to linear polyethylene of the same molecular mass (Vega
et al. 1998; Malmberg et al. 1999; Shroff and Mavridis
1999; Bin Wadud and Baird 2000; Wood-Adams et al.
2000). Due to long relaxation times the zero shear-rate
viscosity could in many cases not be determined. For the
same reason, no information is provided for the steady-
state recoverable compliance, which is a well-defined
measure of elasticity. This quantity is significantly
influenced by small amounts of long-chain branches as
Gabriel and Münstedt (1999) demonstrated for a com-
mercial polyethylene.
Several other publications dealt with the influence of
long-chain branches on the frequency dependence of
dynamic-mechanical material functions and the corre-
sponding relaxation time spectrum. Wood-Adams et al.
(2001) describe how the appearance of different peaks in
the relaxation time spectrum corresponds with the
branching structure in metallocene-catalyzed polyethy-
lenes and related molecular dynamics models. Using the
experimental data of Wood-Adams et al. (2000), Garcia-
Franco et al. (2001) give an interpretation of the similar-
ities they observed between gelation and the rheological
response of long-chain branched metallocene-catalyzed
polyethylenes. Trinkle (2001) describes how the van
Gurp-Palmen plot can be used to obtain information
about the branching structure of polymers. The method
was applied to long-chain branched model polymers as
well as to metallocene-catalyzed polyethylenes.
Another lack of some of the cited publications is the
fact that no explanations for the experimental findings
from the point of molecular structure are presented. It
does not become clear why such low amounts of long-
chain branching would lead to the reported significant
changes in flow behavior. The only recent publication
that explains the molecular mass dependence of zero
shear-rate viscosity of long-chain branched polyethy-
lenes is a paper by Janzen and Colby (1999). The authors
come to the conclusion that the molecular mass between
branch points is decisive for the viscosity behavior of
233
long-chain branched polyethylenes. An increase in zero
shear-rate viscosity is found in the case where the
molecular mass between branch points is much larger
than the entanglement molecular mass. For a high
branching density the molecular mass between branch
points becomes small and therefore leads to a reduced
zero shear-rate viscosity in comparison to linear
polyethylene. Janzen and Colby (1999) propose a
quantitative model that is able to determine the amount
of long-chain branches. Nevertheless, this approach
does not take into account the heterogeneity of branch-
ing structures that is still present in metallocene-
catalyzed polyethylenes. As for the publications cited
above, an approach to an explanation of elastic
properties of branched polyethylenes is missing.
The aim of this paper is to describe the influence of
small amounts of long-chain branches on the zero shear-
rate viscosity and the steady-state recoverable compli-
ance. These material parameters can be viewed as
weighed integrals over the relaxation time spectrum.
By comparison with model polymers a qualitative
explanation is presented that is able to interpret the
experimental findings on polyethylenes with a slight
degree of long-chain branching. In addition, the rhe-
ological behavior of classical low-density polyethylenes
(LDPE) can be explained using the same framework.
This type of polyethylene is generally viewed as a highly
branched material, i.e., with a high number of long side
branches per molecule. For a thorough description of
the molecular structure of LDPE the reader is referred to
an article by Kulin et al. (1988). For the LDPE
investigated in this IUPAC round robin test a degree
of long-chain branches of 1–7 per 1000 carbon atoms
was found experimentally.
Materials and methods
A broad variety of linear and long-chain branched polyethylenes
has been selected for this study. Two of the linear high-density
metallocene-polyethylenes investigated (Table 1) are homopoly-
mers (mHDPE 2 and 3), and a low comonomer content of 1-butene
is present in the case of mHDPE 1. These materials of similar
polydispersity differ mainly with respect to their weight average
molecular mass as will be described below. Two linear low-density
metallocene polyethylenes of similar density and melting temperat-
ure but different type of comonomer serve as additional reference
materials of narrow molecular mass distribution (mLLDPE 1 and
2). Two Ziegler-Natta LLDPE (ZN-LLDPE 1 and 2) are investi-
gated because of their slightly broader molecular mass distribution
in comparison to the two mLLDPE. The characteristics of these
polymers are given in Table 1.
The selection of long-chain branched materials consists of four
commercial LDPE (1, 2, 5, and 6) of broad molecular mass
distribution and high degree of branching. Also commercial
metallocene-catalyzed low-density polyethylenes with sparse long-
chain branching (LCB-mLLDPE 1 and 2) have been selected. These
materials are copolymers of ethylene and 1-octene. They were
chosen in order to separate the effects of long-chain branching and
molecular mass distribution by comparison with the two linear
234

Table 1 Characteristic data of the polyethylenes

Comonomer q (25 C) g/cm3 Tm,C Mn, kg/mol Mw, kg/mol Mz, kg/mol Mw/Mn Mz/Mw
mHDPE 1 1-Butene 0.935 128 46.3 97.7 170 2.1 1.7
mHDPE 2 – 0.945 137 73.0 216 608 3.0 2.8
mHDPE 3 – 0.945 137 19.4 55.3 113 2.9 2.0
mLLDPE 1 1-Butene 0.900 99 55.0 114 188 2.1 1.7
mLLDPE 2 1-Hexene 0.900 99 52.7 115 188 2.2 1.6
ZN-LLDPE 1 1-Octene 0.919 116/127 37.6 116 278 3.1 2.4
ZN-LLDPE 2 1-Butene 0.918 116/128 40.3 127 301 3.2 2.4
LDPE 1 – 0.918 110 15.5 258 2740 16.6 10.6
LDPE 2 – 0.918 110 16.7 261 1765 15.6 6.8
LDPE 5 – 0.918 110 11.5 158 1999 13.7 12.7
LDPE 6 – 0.918 110 16.9 409 5272 24.3 12.9
LCB-mLLDPE 1 1-Octene 0.902 108 47.8 98.6 170 2.1 1.7
LCB-mLLDPE 2 1-Octene 0.902 98 38.8 92.0 167 2.4 1.8
LCB-mHDPE – 0.949 137 48.1 109 201 2.3 1.8

Table 2 Mark-Houwink constants of polystyrene and poly-
ethylene for 1,2,4-TCB at 135 C
2
Polymer K · 105 a s
PS 12.1 0.707
PE 40.6 0.725
These Mark-Houwink constants of polystyrene and polyethylene
for 1,2,4-TCB at 135 C are recommended by the IUPAC Working
Party IV,2.2: Project subgroup 5, Characterization of Polyolefins.
low-density polyethylenes mLLDPE 1 and 2. In order to separate
the effects of short- and long-chain branching an ethylene-homo-
polymer with sparse long-chain branching was polymerized (LCB-
mHDPE) at the Technical University of Helsinki.
Molecular characterization
Molecular mass distribution. For the characterization of the
molecular mass distribution a high-temperature-GPC Waters 150-
C with four Shodex columns is used at the Institute of Polymer
Materials (LSP)1. The temperature of the measurements is chosen
as 135 C, the solvent is 1,2,4-TCB stabilized with a sterically
hindered phenol (Irganox 1035 of Ciba Specialty Chemicals). The
columns are calibrated with 13 narrowly distributed polystyrene
standards from Polymer Laboratories with molecular masses
ranging from 580 g/mol to 11.6 · 106 g/mol. According to the
principle of universal calibration the calibration curve for polysty-
rene is converted to linear polyethylene using the Mark-Houwink
constants of Table 2.
Long-chain branching structure. Information about the long-chain
branching structure is obtained by a coupled SEC-light scattering
technique. This method allows for the absolute determination of
weight average molecular mass and radius of gyration of each SEC-
fraction. The experimental setup of the coupled SEC-light scatter-
ing technique used in this work consists of the high-temperature
GPC from Waters (150-C) and an 18-angle laser light scattering
apparatus Dawn EOS from Wyatt Technology which is operated
at a temperature of 135 C.
The ratio of the mean square radius of gyration of branched
hs2 ibr and linear molecules hs2 ilin of the same molecular mass as
1
In the following the abbreviation SEC (size exclusion chroma-
tography) is used instead of GPC (gel permeation chromatogra-
phy).
determined from light scattering gives a qualitative insight into the
degree of long-chain branching as a function of molecular mass:
g ¼ 2 br ð1Þ
hs ilin
The contraction factor g is equal to one for linear molecules and
decreases to values close to zero for highly branched structures.
Zimm and Stockmayer (1949) derived equations which are used to
obtain more quantitative information about the degree of
branching. Assuming unperturbed chain statistics for star poly-
mers of functionality f of the branching center the following
relation holds:
3f  2
gf ¼ ð2Þ
f2
For statistically branched polymers with a branch point
functionality of 3 the following equation relates the contraction
factor g3 of each monodisperse SEC-fraction to the number of
long-chain branches per molecule m:
 
m0:5 4m 0:5
g3  1 þ þ ð3Þ
7 9p
Magnetic bearing torsional creep apparatus
The shear creep and creep recovery measurements were conducted
by a magnetic bearing torsional creep apparatus that was built at
the Institute of Polymer Materials at Erlangen (Link and Schwarzl
1985). This apparatus the design of which goes back to Plazek
(1968) measures creep and recoverable compliances of polymer
melts with high accuracy due to the low frictional torque of the
magnetic bearing (Gabriel et al. 1998; Gabriel and Kaschta 1998;
Gabriel and Münstedt 1999). The oven of the rheometer is purged
with nitrogen to ensure the thermal stability of the polyethylenes.
The samples are measured at a temperature of 150 C in a plate-
plate geometry with a diameter of 30 mm and a height of 2 mm.
For the reliability of the creep recovery experiments some
preconditions have to be fulfilled. Because in many cases these
experiments take a long time the thermal stability of the polymers
has to be granted. In addition, the shear stresses and deformations
have to lie within the range of linear viscoelasticity and the
achievement of steady-state conditions in the creep as well as in the
creep recovery mode has to be ensured. These preconditions are
fulfilled for the materials investigated. An example of such tests is
published by Gabriel and Münstedt (1999) for a long-chain
branched metallocene-catalyzed LLDPE.

Fig. 1 Molecular mass distributions of selected polyethylenes
Results and interpretation
Molecular characterization
Molecular mass distribution
The molecular mass distributions of selected polyethy-
lenes that are typical of the different classes are displayed
in Fig. 1. The linear metallocene-catalyzed polyethylenes
mLLDPE 1 and mHDPE 1 have comparable narrow
distribution curves, the polydispersity index Mw/Mn is
equal to 2. The linear materials mHDPE 2 and 3 have
got broader distributions as can be seen from Fig. 1 and
Table 1. The distribution curves of ZN-LLDPE 1 and 2
(not shown in Fig. 1) are similar to those of mHDPE 2
and 3, and their weight average molecular masses fall in
between these two metallocene-homopolymers.
The polydispersities of the metallocene-catalyzed
linear and long-chain branched samples are similar as
is obvious from the comparison of LCB-mLLDPE 1,
LCB-mHDPE, and the linear mHDPE 1. Therefore,
these polyethylenes allow one to draw conclusions with
respect to the influence of low levels of long-chain
branching on the elasticity of polyethylene melts. The
molecular mass distributions of the different LDPE are
determined by calibration with well characterized
LDPE-fractions2. The resulting molecular mass distri-
bution of LDPE 2 exhibits a very high polydispersity
and also a significant amount of high molecular weight
tailing. Mean molecular masses and polydispersities of
the molecular mass distributions of the polyethylenes are
given in Table 1. For a more thorough analysis of the
presence of high molecular mass components in linear
and long-chain branched samples the data from the
2
These data were kindly supplied by Dr. Dieter Lilge, Basell
Polyolefine GmbH, Ludwigshafen, Germany.
235
Fig. 2 Comparison of light-scattering signals (LS) at different angles
with the refractive index detector signal (RI) for mHDPE 2
light-scattering detector at small scattering angles are
investigated in the following.
In Fig. 2 signals from the refractive index detector
(RI) and two light-scattering detectors (LS) at different
scattering angles are compared for the linear mHDPE 2.
It is obvious that the light-scattering sensors clearly
detect a distinct amount of high molecular mass
components (at small elution times) that cannot be
resolved by the refractive index detector. It is also
evident that there is a strong dependence of the LS-
signal upon the detector angle. This is a result of the
anisotropy of the scattering pattern of high molecular
mass components. The directly measured root mean
square radius of the high molecular mass species lies
between 100 and 300 nm. These molecular dimensions
are three to ten times larger than the critical value for
isotropic scattering of around k/20 with k being the
wavelength of the laser light (k ¼ 690 nm in the case of
Wyatt DAWN EOS used in our laboratory). The
sensitivity of the light scattering signal to small amounts
of high molecular mass components results from its
proportionality to the product of the molecular mass M
and the concentration c. In contrast, the signal from the
refractive index detector is proportional to the concen-
tration c only. Because of the fact that information from
the RI-detector is missing at small elution times it is
difficult to evaluate the amount of high molecular mass
components quantitatively. Nevertheless, from the mea-
sured radius of gyration and its molecular mass
dependence (compare the solid line for linear polyethy-
lene in Fig. 4) it can be estimated that the high
molecular mass components of mHDPE 2 are of the
order of 107 g/mol.
Figure 3 presents a comparison of light-scattering
results for different linear and long-chain branched
polyethylenes. The scattering angle shown in Fig. 3 is
236

Fig. 3 Comparison of the light-scattering signals of linear and long-

chain branched polyethylene samples at a detector angle of 18 Fig. 4 Root mean square radius as a function of molecular mass for
long-chain branched polyethylenes
equal to 18, which is the smallest angle available in case
of the Wyatt Dawn. Besides mHDPE 2, ZN-LLDPE 1
and ZN-LLDPE 2 (not shown in Fig. 3 as the LS-signal
is similar to that of ZN-LLDPE 1) also exhibit a distinct
high molecular mass component. The narrowly distribu-
ted mLLDPE 1 does not show a high molecular mass
component in the light-scattering signal.
Interestingly enough, the LS-signal of the slightly
branched LCB-mHDPE is very similar to that of
mLLDPE 1 at small elution times. The slight increase
of high molecular mass tailing has already been observed
in the SEC-experiments as described above (Fig. 1). For
LDPE 2 a huge amount of high molecular mass
components is observed in the light-scattering signal at
small detector angles. This pronounced bimodality in
the LS-signal of LDPE 2 translates into an extremely
broad molecular mass distribution as is plotted in Fig. 1.

Long-chain branching structure

The long-chain branching structure of the different
polyethylenes is described for selected samples of small
and high degree of branching (LCB-mLLDPE 1, LCB-
mHDPE, and LDPE 2). In Fig. 4 the measured root
mean square radius is plotted as a function of molecular
mass for three different long-chain branched polyethy-
lenes. In comparison to the dependence of linear
samples, which is shown by the solid line having a slope
of 0.51 and a constant of proportionality of 0.0585,
long-chain branches lead to a decrease in the root mean
square radius at a fixed molecular mass. The high degree
of long-chain branching in the case of LDPE 2 is
responsible for the strong decrease compared with the
two slightly branched metallocene catalyzed polyethy-
lenes which cannot be distinguished in the plot of Fig. 4.
Fig. 5 Molecular mass dependence of the contraction factor g(M)
for long-chain branched polyethylenes
From Eq. (1) the molecular mass dependence of the
contraction factors g(M) is calculated (Fig. 5). The long-
chain branched samples LCB-mLLDPE 1 and LCB-
mHDPE are quite similar with respect to g(M) especially
in the high molecular mass regime. For these long-chain
branched materials the degree of branching increases
with molecular mass, which is reflected in a correspond-
ing decrease of g(M). In contrast, the classical LDPE 2 is
highly branched as the low values of g(M) demonstrate.
The contraction factors g(M) of LDPE 1, 5, and 6 were
found to be similar to that of LDPE 2. As the various
LDPE were polymerized by the same process it can

Fig. 6 Calculated number of long-chain branches per molecule for
various polyethylenes
therefore be assumed that their branching structures are
similar as well.
The number of long-chain branches per molecule
calculated according to Eq. (3) is similar for the two
metallocene-catalyzed LCB-mLLDPE 1 and LCB-
mHDPE (Fig. 6). In the measurable range of molecular
masses between 60 and 500 kg/mol the number of long-
chain branches per molecule of the metallocene-cata-
lyzed polyethylenes increases from values of around 0.5
to 5. In the low molecular mass regime the two
polyethylenes can be regarded as T-shaped or star-like
molecules of low branch point functionality, whereas in
the high molecular mass regime H-shaped or statisti-
cally branched molecules have to be taken into account.
From comparison with long-chain branched polymers
of similar polymerization conditions that were analyzed
by 13C NMR (Malmberg et al. 1998) the long-chain
branching degree of LCB-mHDPE is estimated to be
between 1 and 2 branches per 10,000 carbon atoms. For
LDPE 2, expected to be the most highly branched
polyethylene investigated in this study, the number of
long-chain branches per molecule increases nearly
exponentially from values close to one up to 100, as
Fig. 6 indicates.
Assuming a star-like structure the molecular mass Ma
of the long-chain branches is estimated by dividing the
overall molecular mass M by the number of long-chain
branches per molecule3 (Fig. 7). The outcome of this
estimation is that Ma for the slightly branched long-
chain metallocene-catalyzed polyethylenes increases
3
To obtain correct values for Ma a value of two has to be added to
the number of long-chain branches per molecule (e.g., a three-arm
star has got one long-chain branch per molecule).
237
Fig. 7 Estimated molecular mass Ma of the long-chain branches of
three polyethylenes. The simplifying assumption underlying this
estimation is a star-like branching structure of the polyethylenes
with increasing molecular mass from values of 20 kg/
mol up to 70 kg/mol in the high molecular mass regime.
The highly branched LDPE 2 exhibits much lower arm
molecular masses Ma. A plateau value of 20 kg/mol is
observed in the high molecular mass regime. This arm
molecular mass is smaller by a factor of three in
comparison to the two slightly branched mPE.
The conclusion from the molecular characterization
is that the slightly branched metallocene-polyethylenes
can on average be regarded as molecules with a very
small number of long-chain branches in an intermediate
molecular mass regime; in the high molecular mass
region higher branching degrees are present. In order to
be able to explain qualitatively the rheological results,
the slightly branched polyethylenes are viewed – in a
simplistic way – as star-like molecules with a low
functionality of the branch points. A consequence of
the small branching functionality of these polyethylenes
is that their branches are quite long achieving molecular
masses that are 50 times larger than the entanglement
molecular mass of polyethylene. Classical LDPE exhibit
a very high branching functionality and quite short
branches of a molecular mass which is only 20 times
larger than the entanglement molecular mass Me of
polyethylene (1300 g/mol).
Creep recovery experiments
The experimental results of the influence of molecular
mass and long-chain branching on rheological proper-
ties as well as their interpretation will be discussed
separately for viscous and elastic properties.
238
Fig. 8 Comparison of the creep compliances of linear and long–chain
branched polyethylenes. The applied shear stresses are of the order of
10 Pa, i.e., in the linear regime
Creep experiments and zero shear-rate viscosity
The time-dependent creep compliances of linear and
long-chain branched samples are displayed in Fig. 8.
The indicated slope of 1 in Fig. 8 demonstrates that for
the polyethylenes investigated a steady state of creep
could be obtained at long times which is the precondi-
tion for a precise determination of the zero shear
viscosity.
For the linear samples of different weight average
molecular mass (mHDPE 1, mLLDPE 1, and mHDPE
2) the creep compliances are shifted to lower values as
the molecular mass increases. As a consequence the zero
shear-rate viscosity, which determines the long-time
regime of the creep compliance, increases in the order
mHDPE 1, mLLDPE 1, and mHDPE 2. As is obvious
from Fig. 9 these polyethylenes fulfill the well-estab-
lished power law dependence of the zero shear-rate
viscosity on the weight average molecular mass Mw with
an exponent of 3.4 and a coefficient of 7.6 · 10)14, which
is taken from literature (Münstedt 1986). Other linear
polyethylenes like ZN-LLDPE 2 also fit in with this
dependence for linear polyethylenes within the accuracy
of rheological and chromatographic measurements.
The creep compliances of the slightly branched
polyethylenes LCB-mLLDPE 1 and LCB-mHDPE are
shifted to much lower values in comparison to linear
polyethylenes of comparable molecular mass (e.g.,
mHDPE 1). This type of long-chain branched polyeth-
ylene therefore exhibits a significantly elevated zero
shear-rate viscosity, as is demonstrated in Fig. 9.
The creep compliances of LCB-mLLDPE 1 and
LDPE 2 possess comparable values in the long-time
regime. A high degree of long-chain branching in LDPE
2 is responsible for the comparatively low zero shear-
rate viscosity being reduced in comparison to linear
Fig. 9 Dependence of zero shear-rate viscosity on molecular mass
and branching structure (T ¼ 150 C). The arrows indicate that the
actual zero shear-rate viscosity is higher than the plotted value,
because a steady-state could not be obtained in the measurements.
The viscosity data of LPDE 6 were supplied by Schwetz et al. (2001)
polyethylene of the same average molecular mass
(Fig. 9). In Fig. 9 other LDPE-melts of comparable
molecular structure are included which show a similar
behavior as LDPE 2. Such a behavior is expected from
the literature (e.g., Laun and Münstedt 1983; Laun
1987). The reduction of zero shear-rate viscosity due to
long-chain branching is attributed to the reduced radius
of gyration. Interestingly enough, LDPE-melts exist that
exhibit a viscosity which is close to the value of linear
polyethylene at high values of Mw (Fig. 9).
Comment on the influence of polydispersity
on the zero shear-rate viscosity
From literature data on polyethylenes and polystyrenes
of different polydispersities (Münstedt 1986) and from
polyisobutylene blends presented by Pechhold et al.
(1981) the conclusion can be drawn that the polydisper-
sity of the molecular mass distribution does not have a
major influence on the zero shear-rate viscosity. The
same results have been obtained in an early work of
Masuda et al. (1970) on bi- and trimodal blends of
polystyrene. The mean molecular masses of the blend
components differed significantly (up to a factor of ten),
but the zero shear-rate viscosity of the blends followed
the same dependence upon the weight average molecular
mass as the blend components of narrow molecular mass
distribution. Nevertheless, contradictory references can
be found in literature that report a dependence of the
zero shear-rate viscosity on the polydispersity of the
molecular mass distribution. Experimental data on
polydisperse polyethylenes are given by Wasserman
and Graessley (1996) and by Kazatchkov et al. (1999).

In the latter paper the authors demonstrate that the zero
shear-rate viscosity changes by roughly a factor of three
for polydispersity indices ranging from 3.3 up to 12.7.
Moreover, for this series of polyethylenes the weight
average molecular mass changes from 111 kg/mol to
90 kg/mol. For polyethylenes of constant weight average
molecular mass the influence of polydispersity should be
even more pronounced. Nevertheless, the reported zero
shear-rate viscosities were not determined experimental-
ly. Instead they were obtained from Carreau-Yasuda fits
and (truncated) relaxation spectra. Graessley (1980),
using the equations of the Doi-Edwards theory, predicts
a strong dependence of the zero shear-rate viscosity on
high-molecular mass components. He finds that the zero
shear-rate viscosity is a function of the product
Mw Mz Mz + 1 .
For the linear polyethylenes of high molecular mass it
is found that the molecular mass dependence of the zero
shear-rate viscosity is in a good approximation inde-
pendent of the polydispersity of the molecular mass
distribution. This conjecture is demonstrated by the
experimental data on mLLDPE 1 and mHDPE 2 with
different polydispersities. In addition, a high molecular
mass component that is present in mHDPE 2 (Fig. 3)
does not influence the molecular mass dependence of the
zero shear-rate viscosity. The independency of the zero
shear-rate viscosity of the polydispersity of the molec-
ular mass distribution is valid as long as no significant
amounts of low molecular mass components below the
entanglement threshold are present. For example, the
zero shear-rate viscosity of mHDPE 3 is reduced due to
a significant amount of molecular masses around and
below the critical molecular mass for entanglements
(compare Fig. 1).
It can therefore be concluded that the enormous
differences in the dependence of the zero shear-rate
viscosity on the weight average molecular mass found
for linear and slightly branched polyethylenes can
certainly not be attributed to the minor differences in
the molecular mass distributions as observed in Fig. 1.
The polydispersity indices of mLLDPE 1 and LCB-
mLLDPE 1, for example, are the same within the
accuracy of SEC measurements. The observed differ-
ences therefore have to be related with the differences in
molecular topography, i.e. the existence of long-chain
branching.
Interpretation of the zero shear-rate viscosity
From the experimental results it can be concluded that
low levels of long-chain branching in metallocene-
catalyzed polyethylenes lead to an increase in zero
shear-rate viscosity in comparison to linear polyethylene
of comparable molecular mass, whereas long-chain
branching in classical LDPE effects a reduction in zero
239
shear-rate viscosity (Gabriel 2001). The amount of such
a reduction is dependent on molecular mass in the sense
that the zero shear-rate viscosity approaches the curve of
the linear polyethylenes with increasing weight average
molecular mass. The independence of the zero shear-rate
viscosity of polydispersity is an important precondition
for the interpretation of the influence of long-chain
branching on the viscosity in the linear regime.
Some light can be thrown on the g0(Mw)-relationship
of the polyethylenes investigated by taking into account
results on model branched polymers. For star-shaped
polymers an exponential dependence of the zero shear-
rate viscosity on the number of entanglements per side
branch is well established in literature both from theory
and experiment (Pearson and Helfand 1984; Ball and
McLeish 1989; Fetters et al. 1993):
 a  
Ma Ma
g0 / exp t0 ð4Þ
Me Me
In Eq. (4) Ma denotes the molecular mass of a branch
and Me the entanglement molecular mass. The constants
a and t¢ have got values of around 1 and 0.5,
respectively. The exponential dependence of the zero
shear-rate viscosity on molecular mass is much stronger
than the power law dependence for linear polymers.
Although the viscosity of star shaped polymers is
reduced at low molecular masses in comparison to
linear polymers due to the reduction in hydrodynamic
volume, the viscosity becomes much larger at higher
molecular masses. This is experimentally confirmed for
linear and star branched polystyrenes (Graessley and
Roovers 1979), polyisoprenes (Fetters et al. 1993),
polybutadienes with 1 and 2 long-chain branches per
molecule (Kraus and Gruver 1965), as well as for 3- and
4-arm stars of hydrogenated polybutadiene that can be
regarded as a model polymer for long-chain branched
polyethylene (Raju et al. 1979a, 1979b). For these star-
branched hydrogenated polybutadienes with an entan-
glement molecular mass similar to that of polyethylene
an increased zero shear-rate viscosity is observed for
star-branched molecules of weight average molecular
masses higher than 30 kg/mol.
As the molecular characterization of the metallocene-
catalyzed polyethylenes proves them to be slightly
branched (Fig. 6) the increased zero shear-rate viscosity
of these materials has to be attributed to an exponential
dependence upon the molecular mass as it is found for
star-branched model polymers. An additional precondi-
tion for this conjecture is that the molecular masses of
the metallocene-polyethylenes lie within a range for
which a strongly increased zero shear-rate viscosity is
found for star-branched hydrogenated polybutadienes.
The dashed line in Fig. 9 indicates the exponential
dependence according to Eq. (4) for a hypothetically
star-branched polyethylene with a branching function-
240
ality of 4. The factor of proportionality is chosen in the
way that the zero shear-rate viscosity of LCB-mLLDPE
1 falls onto this curve. It is obvious that LCB-mHDPE
which exhibits a similar molecular structure in reason-
able agreement with the estimated dependence.
It could be argued that the slightly branched
polyethylenes are not ideal model polymers with a
distinct functionality of the branch points. From Fig. 6
it becomes obvious that the number of long-chain
branches increases with molecular mass. Nevertheless,
it is interesting to note that also for more highly
branched model polymers an elevated zero shear-rate
viscosity compared to linear materials is observed at
high molecular masses. Roovers (1984) and Archer and
Varshney (1998) found such a behavior for H-shaped
polystyrenes and branched polybutadiene having a
POM-POM like structure, respectively. McLeish and
Milner (1999) and McLeish et al. (1999) even report an
exponential dependence of the zero shear-rate viscosity
on weight average molecular mass for H-shaped poly-
isoprenes. An exponential dependence of zero shear-rate
viscosity on molecular mass is therefore observed for
branched polymers having a more complex molecular
structure than simple stars. This observation can be
transferred to the polyethylenes of a more heterogeneous
molecular structure, thus supporting the qualitative
explanation for the increased zero shear-rate viscosity
of metallocene-catalyzed long-chain branched poly-
ethylenes which was given above.
For classical LDPE having a high branching degree
the qualitative explanation for the reduced viscosity in
comparison to linear polyethylene can also be deduced
from Eq. (4). The high degree of long-chain branching
(i.e., high functionality of the branch points) of this type
of polyethylene leads to a low value of Ma/Me, i.e., the
number of entanglements per arm, and according to
Eq. (4) to a reduced zero shear-rate viscosity. For the
LDPE investigated the exponential dependence of zero
shear-rate viscosity on molecular mass is estimated for
an average functionality of 20 (Fig. 9). As with the
slightly branched polyethylenes the factor of propor-
tionality is chosen in the way that the zero shear-rate
viscosity of LDPE 5 with the lowest Mw falls onto this
curve. A qualitatively good agreement of this prediction
is found in comparison to the experimental data for the
four LDPE having a similar branching structure.
Creep recovery experiments and steady-state
recoverable compliance
Besides creep experiments in the flow regime that give
information about viscous properties of polymer melts,
creep recovery experiments are also performed. This
experimental mode is a direct measure of the elastic
properties of an entanglement network of a macromo-
Fig. 10 Time-dependent recoverable compliances of linear polyeth-
ylenes (T ¼ 150 C). The applied shear stresses are of the order of
10 Pa
lecular system. The limiting value in the infinite time
regime, the so-called steady-state recoverable compli-
ance, can be correlated with the molecular structure.
The time-dependent recoverable compliances mea-
sured under stationary and linear conditions are
displayed in Fig. 10 for a variety of linear polyethyl-
enes4. The short-chain branched mLLDPE 1, which has
got the narrowest molecular mass distribution of the
linear polyethylenes, exhibits a steady-state recoverable
compliance of 7 · 10)5 Pa)1, which is small in compar-
ison to the other samples. The times to achieve the
steady state of recovery are short in comparison to the
other linear polyethylenes in Fig. 10. The Ziegler-Natta
samples ZN-LLDPE 1 and 2 have got a recoverable
compliance which is higher than 10)3 Pa)1. Whereas for
ZN-LLDPE 1 a steady state of recovery could be
obtained the recoverable compliance of ZN-LLDPE 2
does not reach its limiting value within the experimental
time window. Similar to these two ZN-LLDPE the
recoverable compliance of the linear mHDPE 2 of
narrow molecular mass distribution reaches very high
values without any indication of a steady state.
In contrast to some of the linear polyethylenes the
recoverable compliances of the slightly branched poly-
ethylenes LCB-mLLDPE 1 and LCB-mHDPE approach
a steady state and reach values of the steady-state
recoverable compliance around 10)3 Pa)1 (Fig. 11).
Although the polydispersities of LCB-mLLDPE 1 and
the linear mLLDPE 1 are comparable, the elasticity of
the slightly branched polyethylene is higher by nearly an
order of magnitude. Due to the high polydispersity and
the pronounced high molecular weight tailing of the
4
Tests for the linearity and the achievement of steady-state
conditions have been performed according to the examples
described by Gabriel and Münstedt (1999).

Fig. 11 Time-dependent recoverable compliances of long-chain
branched polyethylenes (T ¼ 150 C). The applied shear stresses are
of the order of 10 Pa
Fig. 12 Dependence of steady-state recoverable compliance on
molecular mass and branching structure (T ¼ 150 C). The arrows
indicate that the actual steady-state recoverable compliance is higher
than the plotted value, because a steady-state could not be reached in
the measurements
long-chain branched LDPE these polyethylenes are
expected to show high values of the steady-state compli-
ance. Nevertheless, the steady-state recoverable compli-
ance of LDPE 2 lies within the range of LCB-mLLDPE 1
and LCB-mHDPE (Fig. 12). The elastic compliance of
LDPE 2 is also much less than those of the different
linear polyethylenes of narrow molecular mass distribu-
tions (e.g., ZN-LLDPE 2 and mHDPE 2) as is obvious
from the comparison of Figs. 10 and 11.
The elastic compliances of all the polyethylenes
investigated are summarized in Fig. 12, in which they
are plotted as a function of weight average molecular
mass. Although this representation is strongly influenced
by the polydispersity of the molecular mass distribution
241
some general conclusions with respect to the influence of
long-chain branching on elasticity can be drawn. The
steady-state compliances of the three linear samples
mHDPE 1, mLLDPE 1, and mLLDPE 2 with a
polydispersity of two fall into the same region around
7 · 10)5 Pa)1.
The elastic compliances of the slightly branched
LCB-mLLDPE and LCB-mHDPE of similar polydis-
persity are higher by more than an order of magnitude.
The highly branched LDPE 2 and 5 possess steady-state
compliances that fall into the same region as for the
long-chain branched metallocene-catalyzed polyethyl-
enes, although the polydispersity index of the LDPE is
higher by a factor of eight. For most of the linear
samples (mHDPE 2 and 3 and ZN-LLDPE 2) having
polydispersity indices of about three, a steady-state of
recovery could not be obtained. The recoverable com-
pliances of mHDPE 2 and ZN-LLDPE 2 at long times
reach values higher than 10)2 Pa)1.
Interpretation of the steady-state compliance
The experimental results on the influence of different
levels of long-chain branching on the elasticity presented
in Fig. 12 are summarized in the following. They
indicate that low levels of long-chain branching in
metallocene catalyzed polyethylenes lead to an increase
in steady-state recoverable compliance in comparison to
linear polyethylenes of similar polydispersity. High
levels of long-chain branching in classical LDPE seem
to effect a relatively low elasticity compared to linear
polyethylenes of even narrower molecular mass distri-
butions. A qualitative interpretation can be obtained by
the following considerations.
The steady-state recoverable compliance of star
polymers depends linearly on the number of entangle-
ments per arm (Pearson and Helfand 1984):
Ma 1
Je0 ¼ t0 ð5Þ
Me G0N
The factor t¢ is the same as in Eq. (4), and G0N denotes
the plateau modulus which is in a good approximation
independent of branching structure (Graessley and
Roovers 1979). Equation (5) has been experimentally
confirmed, e.g., for star branched polystyrenes (Graess-
ley and Roovers 1979).
As the arm molecular mass Ma can be assumed as the
total molecular mass Mw divided by the functionality f
of the branch points, it becomes obvious that an increase
in functionality f causes a decrease in steady-state
compliance at constant molecular mass. This effect is
not only observed in the literature for star-branched
polystyrenes but also for polybutadiene combs that have
been combined to form star-branched structures of
different functionality (Roovers and Toporowski 1987).
242
The experimental findings for model polymers concern-
ing the effect of functionality upon the level of the
steady-state compliance will qualitatively be transferred
to the polyethylenes investigated in this study.
For monodisperse star branched polyethylenes of
functionalities of 4 and 20 the steady-state compliances
are plotted in Fig. 12 (thin lines) as a function of
molecular mass according to Eq. (5)5. The calculated
compliances of the two monodisperse star-branched
polyethylenes intersect the compliance level of linear
hydrogenated polybutadiene (Carella et al. 1984) at
different molecular masses as can be seen from Fig. 12.
The weight average molecular mass Mw at the intersec-
tion point is the higher the larger the functionality is
assumed. Thus, an increase in functionality of the
branch point leads to a decrease in elasticity at constant
molecular mass.
In order to give a qualitative interpretation for the
polyethylenes investigated, the influence of polydispersity
on elasticity has to be taken into account. As is well known
for linear polymers an increase in polydispersity is
responsible for an increase in elasticity. This effect can
be seen from the comparison of the steady-state compli-
ances of the linear polyethylenes of polydispersities
around 2 (mHDPE 1, mLLDPE 1 and 2) with the
compliance level of the monodisperse linear hydrogenated
polybutadiene given in the literature. Taking this influ-
ence of polydispersity into account the calculated molec-
ular mass dependence of the steady-state compliance of
star-branched monodisperse polyethylene (f ¼ 4) has been
shifted to superimpose with the recoverable compliance of
LCB-mLLDPE 1 (thick lines). It is obvious from Fig. 12
that this estimation is able to predict the elasticity of the
slightly branched polyethylenes in a qualitative way. This
result explains the increase in steady-state recoverable
compliance of the metallocene-catalyzed polyethylenes in
comparison to linear samples due to slight amounts of
long-chain branching.
In order to give a qualitative explanation for the
compliance values of the LDPE investigated a similar
procedure has been applied to the calculated molecular
mass dependence of the steady-state compliance for the
high branch point functionality of f ¼ 20. Again, the
calculated molecular mass dependence of the steady-
state compliance is able to predict the experimental data
of the LDPE in a qualitative way. The estimated
dependence for LDPE also reflects the reduction of
elasticity due to a high degree of long-chain branching if
compared to the samples of lower functionality. It can
also be concluded that the high degree of long-chain
5
The two different values of the branch point functionality have
been chosen in order to represent the different degrees of long-chain
branching of the metallocene-catalyzed LCB-mPE and the classical
LDPE. For the plateau modulus G0N a value of 2.3 · 106 Pa has
been assumed, which is typical of hydrogenated polybutadiene.
branching in the LDPE investigated compensates the
influence of the high polydispersity of these materials on
their steady-state recoverable compliances. This conjec-
ture is also able to explain the pronounced difference in
elasticity of HDPE- and LDPE-melts that were inves-
tigated by Plazek et al. (1979) and Agarwal and Plazek
(1977). The LDPE of broad molecular mass distribution
exhibited recoverable compliances that were smaller by
roughly one order of magnitude in comparison to linear
HPDE-samples at long recovery times. These results are
in accordance with the differences in elasticity of LDPE-
and HDPE-melts as observed in our study.
Interpretation of the high elasticity of some linear
polyethylenes
A striking feature of the linear samples ZN-LLDPE 1 and
2 as well as mHDPE 2 with quite narrow molecular mass
distributions is their pronounced elasticity which is
reflected by very high levels of the recoverable compliance
at long recovery times. Such a high elasticity gives rise to
the assumption that high molecular mass components are
present within the samples. Masuda et al. (1970) demon-
strated for bimodal blends of polystyrenes that the
steady-state compliance passes through a maximum at
low concentrations of a high molecular mass compo-
nent. Similar results were obtained by Pechhold et al.
(1981) and Berger and Meissner (1992) on bimodal
blends of narrow distribution polyisobutylenes. Kraft
et al. (1999) postulated a high molecular mass compo-
nent from their results on a broadly distributed HDPE
that also exhibited a high recoverable compliance in the
long-time regime. Nevertheless, a distinct high molecular
mass component could not be observed analytically.
Taking these results from the literature on bimodal
blends into account, the high elasticity of mHDPE 2 can
be explained by the high molecular mass component that
is detected by the coupled SEC-light scattering equip-
ment (Fig. 2). The pronounced elasticity of the linear
polyethylenes ZN-LLDPE 1 and 2 can be attributed to a
high molecular mass component as well. In contrast,
mLLDPE 1, for which no indication of the presence of
distinct high molecular weight tailing can be found by
analytical means, has got the smallest steady-state
recoverable compliance of the polyethylenes investigated
in this study. For LDPE 2 a distinct amount of high
molecular mass components was observed analytically.
This observation again supports the conclusion that a
high degree of long-chain branching is responsible for
the relatively low elasticity of this type of polyethylene.
Discussion
The qualitative interpretation presented in this paper is
able to give a good explanation of the rheological

findings on the different types of polyethylenes. More-
over, our interpretation is in accordance with well
established experimental data and theoretical interpre-
tations of model long-chain branched polymers. This
agreement strongly supports our approach for a qual-
itative explanation of the linear viscoelastic shear flow
properties of commercial and semi-commercial linear
and long-chain branched polyethylenes. Nevertheless, it
should be stressed again that the interpretations given
above for the dependence of zero shear-rate viscosity
and steady-state recoverable compliance on molecular
mass and degree of branching are intended to be
qualitative only. They do not take into account a
pronounced heterogeneity of the degree and the topog-
raphy of long-chain branching.
From the small degree of long-chain branching
present in the metallocene-catalyzed samples it can be
estimated that only every fifth molecule is branched.
These samples should therefore be regarded as blends of
linear molecules and long-chain branched ones of
different (and unknown) branching structure. The
pronounced heterogeneity of long-chain branches in
LDPE is obvious from the analytical data presented
above (e.g., Fig. 6). These samples certainly have to be
regarded as statistically branched or tree-like molecules.
In particular, the degree of long-chain branching of
these polyethylenes increases significantly with molecu-
lar mass. For an accurate description of the rheological
properties these samples would have to be modeled as
very complicated multicomponent blends of species of
different (and again unknown) molecular topography.
Conclusion
From the experimental results the following conclusions
can be drawn with respect to the influence of varying
levels of long-chain branching on linear viscoelastic
properties of polyethylene melts:
– Long-chain branched metallocene-catalyzed polyethy-
lenes have got a very small degree of branching. In a
simplistic way these materials can be regarded as star-
like molecules of a small functionality of the branch
point. The small functionality can lead to high
molecular masses of the side branches ranging up to
70 kg/mol in our case.
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