Polymer International Polym Int 52:164–171 (2003)

DOI: 10.1002/pi.1038

Crystallization and morphology of metallocene

polyethylenes with well-controlled molecular
weight and branching content
Ya Peng,1 Qiang Fu1* and Fang-Chyou Chiu2
1
Department of Polymer Science and Materials, Sichuan University, State Key Laboratory of Polymer Materials Engineering, Chengdu,
Sichuan 610065, People’s Republic of China
2
Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan, Taiwan 333

Abstract: The crystallization and morphology of some metallocene polyethylenes with well-controlled
molecular weight and branching content were investigated by DSC, WAXD, PLM and SALS. The
banded spherulites observed in linear PE are not seen in crystallization of branched PEs. The small
spherulites with small lamellae or fringed micelle crystals are formed when branching content is
higher, as suggested by PLM and SALS. The expansion of the unit cell was observed by WAXD as the
molecular weight and branching content increased. At even higher branching content (more than
7 mol%), a shrinkage of the unit cell was seen, probably due to a change of crystal morphology from
lamellar-like crystals to fringed micelle-like crystals. Crystallization temperature, melting point and
crystallinity are greatly decreased for branched PEs compared with linear PEs. The equilibrium
melting temperature cannot be determined via the Hoffman–Weeks approach for branched PEs since
Tm is always 5–6 °C higher than Tc and there is no intercept with the Tm = Tc line. Our results show a
predominant role of branches in the crystallization of polyethylene.
# 2003 Society of Chemical Industry

Keywords: metallocene polyethylene; crystallization; morphology

INTRODUCTION uniform branching content is used. Hsieh et al 8 proved

The single-site feature of metallocene catalysis leads to
narrow molecular weight distribution (MWD) and
uniform short chain branch (SCB) distribution. Due
to its superior mechanical and thermal properties
compared to low density polyethylene (LDPE), short-
chain branched polyethylene (SCBPE) has received a
lot of attention both industrially and academically
since its first synthesis.1–5 So far, polyethylene with a
well-defined molecular architecture can be synthesized
using such single-site metallocene catalysts.
Can we consider that metallocene SCBPE truly has
a unique molecular architecture which includes uni-
form distribution of SCB and narrow molecular
weight distribution? Our previous work,6,7 showed
not only intermolecular heterogeneity but also intra-
molecular heterogeneity in metallocene polyethylene;
that is to say, the distribution of SCB differs not only
intermolecularly but intramolecularly as well. The way
to determine the intramolecular heterogeneity is the
same as for intermolecular heterogeneity. The differ-
ence is that for intermolecular heterogeneity a sample
with broad branching content distribution is used,
while for intramolecular heterogeneity a sample with
that in solvent gradient fraction (SGF) of branched
PE, the higher molecular weight molecules with higher
comonomer content will be found in the same SGF
fraction as the low molecular weight molecules with
lower comonomer content. It is well known that the
crystallization behaviour and crystal morphology of
branched PE are closely related to the molecular
weight, the molecular weight distribution, the branch
type, the branch content, the sequence length of
ethylene segments and crystallization conditions. With
increasing branching content, crystallization kinetics is
dramatically slowed down, and crystal morphology
could be changed from well-defined spherulites to
irregular spherulites, and only fringed micelle tiny
crystallites can be obtained when branching content is
higher.9,10 Our previous results showed a large
difference between SGF sample and cross-fractiona-
tion (CF) sample with respect to their crystallization
kinetics, melting temperature and crystal morphology
even if they have the same molecular weight and
branching content.7 Consequently, detailed informa-
tion about SCB distribution, and in particular the
intermolecular and intramolecular distributions of

* Correspondence to: Qiang Fu, Department of Polymer Science and Materials, Sichuan University, State Key Laboratory of Polymer
Materials Engineering, Chengdu, Sichuan 610065, People’s Republic of China
E-mail: fuqiang1963@yahoo.com
Contract/grant sponsor: China National Distinguished Young Investigator Fund
Contract/grant sponsor: National Natural Science Foundation of China
(Received 8 October 2001; revised version received 30 March 2002; accepted 9 May 2002)

# 2003 Society of Chemical Industry. Polym Int 0959–8103/2003/$30.00 164


SCB, is of paramount importance in determining the
thermodynamic and crystallization behaviour of
SCBPE.
In order to get a better understanding of the effect of
molecular weight and branching content on the
crystallization behaviour and crystal morphology of
metallocene polyethylene, it is necessary to use
samples with well-controlled molecular weight and
branching content. Collaborating with Philips Com-
pany, we have obtained a set of metallocene poly-
ethylenes with narrow molecular weight distribution
and uniform chain branching content (after CF
fractionation). Of course, the intramolecular hetero-
geneity still remains for these branched PEs as shown
in our previous paper. The effect of the molecular
weight and branch content on the crystallization
behaviour and morphology of polyethylenes have been
investigated by Wide angle X-ray diffraction
(WAXD), polarized light microscopy (PLM), small
angle light scattering and differential scanning cao-
lorimetry (DSC). Followings are our main results.
EXPERIMENTAL
Materials
The polymer materials examined in this study were
narrow MWD metallocene catalyzed short-chain
branched polyethylene (SCBPE) fractions obtained
by using solvent gradient fractionation (SGF) and
cross-fractionation (CF) techniques. The copolymer
sample was synthesized using a Zr-based homo-
geneous metallocene catalyst. SGF applied to the
whole polymer material produced nearly monodis-
persed molecular weight distribution fractions
(TREF). Part of SGF fractions was then further
resolved, using a temperature gradient fractionation
technique, according to their comonomer differences.
Detailed molecular characteristics of these fractions
are listed in Table 1. Samples can be divided into three
groups: (1) linear polyethylenes with different mol-
ecular weights (used just for comparison), (2) low
molecular weight PEs with different branching con-
tents (branching effect can be explored) and (3) high
molecular weight PEs with different branching con-
tents (molecular weight effect as well as branching
effect can be obtained and compared with group 2). It
should be noted that the comonomer used is 1-butene,
hence the side branches should be ethyl groups.
Sample ID Sample description a Mw b103 (k) Mn b103 (k) Mw /Mn SCB type c Mole%
1 9507-1
9507-2
2 9507-3
9507-4
3 9507-5
9507-6
a
SGF: Solvent Gradient Fraction CF: Cross Fraction.
Table 1. Molecular characteristics of
b
in g mol
1.
c
metallocene polyethylenes used SCB type: short-chain branch type.
Polym Int 52:164–171 (2003)
Crystallization and morphology of metallocene polyethylenes
Moreover, the molecular weight distribution is very
narrow for all the samples (Mw /Mn is around 1) and
the branching content is relatively high for the
branched samples (the lowest is 5.51 mole%).
Instrument and measurements
DSC measurements were conducted on a computer-
ized Perkin-Elmer differential scanning calorimeter,
Model Pyris 1. The specimens were weighted in the
range 3–5 mg. During the measurement, dried N2 gas
was purged at a constant flow rate. In the case of
isothermal crystallization, the sample was kept at
160 °C for 5 min to remove residual crystals, which
might provide seeds for crystallization. Then, they
were cooled rapidly to the predetermined crystal-
lization temperature Tc at a rate of 100 K min
1 and
the temperature held constant until the crystallization
was completed. Thereafter the specimens were heated
again without prior cooling to obtain the DSC endo-
therms at a rate of 10 K min
1. The temperature
reading and calorific measurement were calibrated
using standard indium.
Connected to PLM a camera was used to observe
the macroscopic morphology. Thin films were pre-
pared by melt-pressing a small amount of the sample
between the cover glass and glass slide at a tempera-
ture of 160 °C, then slowly cooled down to room
temperature. WAXD was conducted using a Siemens
D500 diffractometer. The wavelength of the mono-
chromated X-ray from CuKa radiation was 0.154 nm
and the reflection mode was used. Melt-pressed
samples were prepared on aluminium substrates to
form films of thickness around 0.5 mm. The scanning
2y range was from 15 to 30° with a scanning rate of
5 °min
1. Laser light scattering measurements were
conducted by using a polarized HE–Ne gas laser with a
wavelength of 632.8 nm and a CCD detector. Only the
Hv geometry was used for the measurement; ie the
optical axis of the analyzer was set perpendicular to
that of the polarizer. Thin films with the same thermal
history as in PLM experiments were used.
RESULTS AND DISCUSSION
Crystal morphology
To investigate the morphology change in relation to
the molecular weight and branching content, PLM
experiments were carried out for all the samples. PLM
Low Mw homo SGF 24.9 23.0 1.08 — —
High Mw homo SGF 201 170 1.18 — —
Low Mw /high B CF 29.9 27.2 1.10 1-Butene 7.34
Low Mw /low B CF 28.5 25.9 1.10 1-Butene 5.95
High Mw /high B CF 136 119 1.14 1-Butene 8.58
High Mw /low B CF 103 92 1.12 1-Butene 5.51
165
Y Peng, Q Fu, F-C Chiu
photographs are shown in Fig 1. The samples were
prepared by slow cooling from the isotropic melt to
room temperature, in air. One observes well-defined
spherulites with banded structure for linear PEs with
both low and high molecular weights. It is believed
that there exist exact long-range orientational correla-
tions both in radial and azimuthal directions within the
banded spherulites. However, for branched PEs, the
superstructure (granular structure) size is much
Figure 1. PLM micrographs of some selected metallocene PE samples, (a) 9507-1, (b) 9507-2, (c) 9507-3, (d) 9507-4, (e) 9507-5, and (f) 9507-6.
166
smaller, and the crystal birefringence of these
samples is weaker than that of linear PEs, which can
be attributed to their lower crystallinity. Moreover, no
special superstructure is developed, and only very
weak tiny bright spots are observed for 9507-5 which
has the highest branching content. These morpholo-
gical observations indicate that the branches affect PE
morphology greatly, in agreement with other previous
findings.6–10 The higher the branch content in PEs,
Polym Int 52:164–171 (2003)

the more difficult it is for them to form a recognizable
superstructure.
The Hv scattering patterns of the samples are shown
in Fig 2. The scattering patterns are almost qualita-
tively similar and only subtle differences exist between
the samples. The lobes for linear PEs are sharp and the
lobes for branched PEs are well defined (except 9507-
3). The intensities of the two samples with highest
branching content (9507-3 and 9507-5) are quite
weak. Based on the comonomer content, the mor-
phology of branched PE can be classified according to
four types, according to Hiltner and coworkers.9,10
Type IV exhibits a lamellar morphology with well-
developed spherulitic superstructure. Type III has
thinner lamellae and smaller spherulites. Type II has a
Figure 2. Hv small-angle light-scattering patterns from slowly crystallized samples, (a) 9507-1, (b) 9707-2, (c) 9507-3, (d) 9507-4, (e) 9507-5, and (f) 9507-6.
Polym Int 52:164–171 (2003)
Crystallization and morphology of metallocene polyethylenes
mixed morphology of small lamellae and bundled
crystals, and very small spherulites can be formed in
this case. Type I has no lamellae or spherulites.
Fringed micellar or bundled crystals are inferred from
the low degree of crystallinity, the low melting
temperature and the granular, non-lamellar morphol-
ogy. Most probably, 9507-4 and 95070-6 form type II
morphology, and 9507-3 and 9507-5 have type I
morphology.
Crystal structure
Polyethylene exhibits polymorphism and orthorhom-
bic is the most stable crystal structure. It can be
formed under normal crystallization conditions either
from the melt or from solution. It has been demon-
167
Y Peng, Q Fu, F-C Chiu
strated that methyl side-groups and a certain amount
of ethyl side-groups can be incorporated into crystal
lattices. Evidence has been provided for the incorpora-
tion of ethyl branches due to a slight expansion of the
axis of the unit cell because of the 2 gl kinks.11
However, the majority of the included ethyl side-
groups are restricted to the crystal surface rather than
being uniformly distributed in the crystallites, accord-
ing to 13C NMR measurements.12 With increasing
molecular weight and branching content, the unit cell
of PE is expanded, due to the expansion of the chain
folds caused either by the SCB-induced strain on the
fold surfaces of crystal, or high molecular weight-
induced defects in the crystal. The WAXD patterns for
samples 9507-1, 9507-2, 9507-4 and 9705-6 are
shown in Fig 3. The positions of {110} and {200}
diffraction peaks are found to shift to smaller angles
(larger dimension), as molecular weight changes from
Mw = 24.9 k to 201 kg mol
1 for linear PE (compare
9507-1 and 9507-2). Similar expansion is observed for
PE with low branching content (see samples 9507-4
and 9507-6). It should be noted that increasing the
molecular weight does not promote further expansion
of the unit cell in this case. Very interestingly, one
observes some shrinking of the unit cell when the
branching content becomes higher, for samples, 9507-
Figure 3. WAXD patterns of metallocene PEs showing expansion of unit
cell; (a): 9507-1, (b): 9507-2, (c): 9507-4, and (d): 9507-6.
168
3 and 9507-5, which have a quite high branching
content (more than 7.4 mole%). The WAXD patterns
of these two samples are shown in Fig 4. It has been
suggested that a change of lamellar to fringed micelle
morphology takes place for metallocene PE with an
octane comonomer content greater than 7 mol%.12,13
The fringed micelle crystal is assumed to be the
predominant feature for these two samples, which may
result in the reduction of unit cell and crystallinity as
well. The SCB-induced strain on the fold surfaces of
crystal, which causes expansion of unit cell, will not
exist any more in the fringed micelle crystals. Of
course, the observed change of unit cell should be
further verified by careful analysis of the data or by
other methods, since experimental artifacts may also
cause peak widening due to the high branching
content and very low crystallinity.
Non-isothermal crystallization
No molecular segmental segregation is evident by
DSC non-isothermal crystallization experiment for all
the samples due to their narrow molecular weight and
intermolecularly uniform branching distribution. One
of the examples is shown in Fig 5, which depicts the
DSC crystallization traces of PEs recorded during
cooling from the isotropic melt with a cooling rate of
10 °C min
1. One observes a dominant exothermic
peak (Tc) for all the samples, which shifts to low
temperatures for branched samples. Only a few
degrees difference in Tc is observed between the two
linear PEs even though their molecular weight differs
by almost a factor 9. However the Tc difference
between linear PE and branched PE is about
40–50 °C. It is obvious that the branching content
plays a key role to determine the crystallization
behavior of branched PE. Comparing 9507-4 and
9507-6 which have almost the same branching content
Figure 4. WAXD patterns of metallocene PEs showing shrinking of unit cell
(a) 7507-3 and (b) 9507-5.
Polym Int 52:164–171 (2003)
 Crystallization and morphology of metallocene polyethylenes

Q2

Figure 6. DSC heating traces of 9507-2 crystallized at selected

Figure 5. DSC cooling traces for sample at a cooling rate of 10 °C min
1 (a)
temperatures, (a) Tc = 120°C, (b) Tc = 121 °C, (c) Tc = 123°C and (d)
9507-1, (b) 9707-2, (c) 9507-3, (d) 9507-4, (e) 9507-5, and (f) 9507-6.
Tc = 124°C.

but a molecular weight four times higher for the latter

one observes only 3 °C difference in Tc. The peak
temperature (Tp) at which crystallization occurs the
fastest, melting temperature (Tm), heat of fusion
(DHm), exotherm (DHc) as well as crystallinity
calculated from the exotherms for all the samples are
listed in Table 2. The corresponding melting result
indicates that the low molecular weight linear PE has
the highest melting temperature and heat of fusion.
Increasing the molecular weight decreases slightly the
melting temperature and heat of fusion. However the
melting temperature and heat of fusion are greatly
lowered for branched PEs. 9507-5, which posseses the
highest molecular weight and branching content, has
the lowest melting temperature and heat of fusion.

Isothermal crystallization
DSC also was used to study the isothermal crystal-
lization and subsequent melting behaviour of the
samples. Figures 6 and 7 show the heating traces of
9507-2 and 950704 isothermally crystallized at various
temperatures without prior cooling to room tempera-
ture. Only one melting peak (Tm) is found for linear
PE, independently of the crystallization temperature
(Tc). Tm is much higher than Tc (more than 14–16 °C)
due to the thickening effect during crystallization.
However, two melting peaks are found for branched
PE 9507-4. The higher temperature peak (Tm2)
remains practically constant and does not change with
Tc. Most probably, the high Tm2 is due to the melting
Figure 7. DSC heating traces of 9507-4 crystallized at selected
temperatures, (a) Tc = 85 °C, (b) Tc = 90 °C, (c) Tc = 91°C, and (d) Tc = 93°C.
of crystals formed by longer ethylene sequences during
quenching from isotropic melt to crystallization
temperature. The low temperature peak (Tm1) changes
as Tc increases and should be due to the melting of
crystals formed during isothermal crystallization. The
difference between Tc and Tm1 is quite small and
always around 5.5 °C at all the crystallization tem-
peratures explored, ie Tm1 ( °C) = Tc þ 5.5. A similar
phenomenon is observed for other branched PEs, and
Fig 8 depicts the DSC heating traces of 9507-5

Sample ID Sample description Tp ( °C) Tm ( °C) Xc DHm (J g
1) DHc (J g
1)

9507-1 Low Mw homo SGF 117.5 134.2 72.7% 213
213
9507-2 High Mw homo SGF 114.1 136.5 52.6% 158
154
9507-3 Low Mw /high B CF 70.5 90.3 21.5% 52.2
63.0
9507-4 Low Mw /low B CF 78.8 97.8 26.7% 64.3
78.3
9507-5 High Mw /high B CF 59.6 78.4 15.2% 44.4
44.5
Table 2. Various crystallization parameters of 83.1
the samples at 10°C min
1 cooling and heating
9507-6 High Mw /low B CF 75.8 98.3 22.8% 56.0
66.8
rate

Polym Int 52:164–171 (2003) 169

Y Peng, Q Fu, F-C Chiu
Figure 8. DSC heating traces of 9507-5 crystallized at selected
temperatures (a) Tc = 67 °C, (b) Tc = 69 °C, (c) Tc = 71 °C, (d) Tc = 72 °C, and
(e) Tc = 73°C.
crystallized at indicated temperatures. Three peaks
instead of two are seen at lower crystallization
temperature. In general, the lower the crystallization
temperature, the higher the melting peaks. Here again,
the highest peak stays relatively constant and the
lowest peak increases as the crystallization tempera-
ture increases. Again, Tm is somehow always 6.0
degree higher than Tc, ie Tm ( °C) = Tc þ 6.0. Similar
results have been observed by Mandelken and cow-
orkers,13 Kim et al 14 and Wang et al 15 in the studies of
the branch effect on the crystallization of branched PE.
Figure 9 shows the plots of apparent melting peak
temperature (Tm1) as a function of crystallization
temperature (Tc). The results for two linear PE
samples are also included in Fig 9 for comparison.
Clearly, the application of the Hoffman–Weeks
approach to determine the equilibrium melting tem-
perature for branched PEs is not possible because of
the absence of intercept with the Tm = Tc line. The test
of the Flory and Sanche–Eby theories to determine the
equilibrium melting point of branched PE can be
found in Kim’s work.14 The level of melting tempera-
Figure 9. Plots of apparent melting peak temperature as a function of
crystallization temperature.
170
ture is associated with the crystal thickness (or
perfection), ie thicker and more perfect crystals melt
at higher temperatures, and vice versa. Thus, a broad
melting thermogram of branched PE is an indication
of a broad distribution of crystal thickness. Since the
samples could be assumed intermolecularly homo-
geneous after CF fractionation, the broad distribution
of crystal thickness most likely is due to the broad
distribution of ethylene sequences (ie intramolecular
heterogeneity).
CONCLUSION
The crystallization and crystal morphology of metal-
locene polyethylene are dependent on molecular
weight and branching content. The branching content
plays a dominant role and the molecular weight effect
can be neglected when the molecular weight is high
enough and the molecular weight distribution is
narrow enough. Branching content has no effect on
crystal structure and the orthorhombic form is always
obtained when crystallization starts from the melt. The
expanse of unit cell is seen for high molecular weight
sample and branched samples. However, there is a
shrinking of the unit cell, when the branching content
is higher than 7.0 mol%, due to a change of lamellar
crystals to fringed micelle crystals. Crystal morphology
changes, from well-defined spherulites of linear PE to
fringed-micelle crystal, may occur when branching
content is higher. Also, crystallization temperature,
melting temperature and crystallinity are substantially
decreased. The equilibrium melting temperature can
not be determined via the Hoffman–Weeks approach
since Tm is always 5–6 °C higher than Tc, and that
there is no intercept with the Tm = Tc line.
ACKNOWLEDGEMENTS
We would like to express our great thanks to the China
National Distinguished Young Investigator Fund and
National Natural Science Foundation of China for
financial support. The authors wish to thank Dr Eric
T. Hsieh (Phillips Petroleum Company, Bartlesville,
Oklahoma, 74004, USA), for kindly supplying
samples and helpful discussions. We also would like
to express our most sincere thanks to Professor
Stephen ZD Cheng at The University of Akron for
his suggestion and comments on this work.
REFERENCES
1 Hosoda S, Polym J 20:383 (1988).
2 Adission E, Ribeiro M, Deffieux A and Fontanille M, Polymer
33:4337 (1992).
3 Italia H, Angew Makromol Chem 219:139 (1994).
4 Cerrada ML, Benavente R, Pena B and Perez E, Polymer 41:5957
(2000).
5 Jordens K, Wilkes GL, Janzen J, Rohlfing DC and Welch MB,
Polymer 41:7175 (2000).
6 Fu Q, Chiu FC and Cheng SZD, J Macromol Sci, Physics B36:41
(1997).
Polym Int 52:164–171 (2003)

7 Fu Q, Chiu FC, He T, Liu J and Hsieh ET, Macromol Chem Phys
202:927 (2001).
8 Hsieh E, Fu Q and Cheng SZD, Jmacromol Sci, Physics B36:568
(1997).
9 Bensason S, Minick J, Moet A, Chum S, Hiltner A and Baer E, J
Polym Sci, Polym Phys 34:1301 (1996).
10 Bensason S, Tepanov EV, Chum S, Hiltner A and Baer E,
Macromolecules 30:2436 (1997).
11 Martinez-Salazar FJ and Balta-Calleja FJ, J Cryst Growth 48:282
(1979).
Polym Int 52:164–171 (2003)
Crystallization and morphology of metallocene polyethylenes
12 Russell KE, Mcfaddin DC, Hunter BK and Heyding RD, J
Polym Sci, Polym Phys 34:2447 (1996).
13 Alamo RG, Chan EKM, Mandelken L and Voigt-Martin IG,
Macromolecules 25:6381 (1992).
14 Kim M-H, Phillips PJ and Lin JS, J Polym Sci, Polym Phys 38:154
(2000).
15 Wang C, Chu M-C, Lin T-L, Lai S-M, Shih H-H and Yang J-C,
Polymer 42:1733 (2001).
171