Polymer 45 (2004) 7549–7561

www.elsevier.com/locate/polymer

Blends of propylene-ethylene and propylene-1-butene random

copolymers: I. Morphology and structure
Zbigniew Bartczaka, Valeria Chionob, Mariano Pracellab,*
a
Centre of Molecular and Macromolecular Studies, Polish Academy of Science, Sienkiewicza 112, Lodz 90-363, Poland
b
Institute for Composite and Biomedical Materials, IMCB-CNR, Section of Pisa, Via Diotisalvi 2, Pisa 56126, Italy
Received 17 February 2004; received in revised form 15 June 2004; accepted 16 July 2004
Available online 15 September 2004

Abstract
Samples of propylene-ethylene (EP) and propylene-(1-butene) (BP) random copolymers with various comonomer content (2–3.1 wt%
ethylene, 9.9 wt% 1-butene), were melt-mixed in Brabender internal mixer at various compositions (25/75, 50/50, 75/25). Films of
copolymers and blends, as well as of a homopolymer sample (iPP), obtained by compression moulding and with different thermal history
were characterized by optical and scanning electron microscopy (OM, SEM), small-angle light scattering (SALS), small- and wide angle
X-ray scattering (SAXS, WAXS) and differential scanning calorimetry (DSC). It was found that all copolymers and blends studied
crystallized exclusively in monoclinic a-modification forming spherulitic structure in a very broad undercooling range. The average size of
spherulites is smaller in the copolymer containing 1-butene as compared to those containing ethylene or to iPP homopolymer, due to
enhanced heterogeneous nucleation in BP copolymer. SEM microscopic observations demonstrated that EP and BP copolymers were
miscible at all examined compositions and form homogeneous blends. Structural and morphological analysis indicated that the comonomer
units are incorporated into growing crystallites in both EP and BP copolymers, while the non-crystallizing material is rejected out of the
crystallites. For small concentrations of comonomer some of non-crystallizing species are pushed ahead of the front of growing spherulite
into interspherulitic regions. For higher comonomer concentration these species are mostly trapped in intraspherulitic regions. Melting
behavior of copolymers reflects the incorporation of comonomer into crystalline phase: melting temperature and crystallinity degree decrease
in copolymers and blends as compared to plain iPP.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Polypropylene copolymers; Blends; Morphology

1. Introduction structure–property relationships of PP have been widely

Polyolefins and their blends, especially those based on
isotactic polypropylene (PP), have been extensively inves-
tigated in the recent years due to their useful properties and
advantageous cost/performance ratio, which make them
available for large applications in various industrial sectors
[1,2].
The properties of polypropylene can be widely modified
through changes of the crystallization behaviour in the
presence of comonomer units randomly distributed along
the chain. The effect of type and concentration of a-olefin
comonomers (ethylene, 1-butene, 1-octene, etc.) on the
* Corresponding author. Tel.: C39-50-511-229; fax: C39-50-511-266
E-mail address: pracella@ing.unipi.it (M. Pracella).
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.07.055
studied. It was found that the introduction of ethylene co-
units into PP chains makes the crystallizable sequence short
enough to induce the growth of g-form PP crystals instead
of conventional a-form crystals [3–5]. Laihonen et al. [4]
and Mezghani et al. [5] demonstrated that the amount of g-
phase was proportional to the ethylene content and that
crystallization in the g-form was enhanced at low super-
coolings and low cooling rate.
The distribution of comonomer units with respect to
crystalline phase is a key factor governing mechanical
properties of a copolymer. However, for copolymers of
propylene with a-olefins the location of the comonomer
units in the solid state is still a subject of controversy. For
copolymers with ethylene Laihonen et al. [4] reported that
the average length of 3/1 helices of the copolymer was
7550 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
shorter than that of homopolypropylene, and concluded that
inclusion of ethylene unit into the crystals occurs to some
extent. On contrary, Monasse and Haudin [6], Feng and Hay
[7], and Pérez et al. [8] on the basis of the decrease of both
crystallinity and temperature of melting with increasing
ethylene content draw an opposite conclusion, i.e. that
ethylene units are excluded from the crystals. Zimmermann
[9] also postulated exclusion of ethylene units from the
crystals, which view based on the invariance of the heat of
fusion when reduced to 100% crystallinity and on the
decrease of the long period as well as lamellar thickness
with increasing ethylene content. The observed changes
were mainly ascribed to the severe disturbance of helical
regularity of PP by the ethylene units [10].
The influence of 1-butene comonomer on the overall
crystallization rate and melting behaviour of polypropylene
was examined by Crispino et al. [11]. The incorporation of
1-butene units into the polypropylene lattice was also
reported [12–14]. This results in an increase of lattice
dimensions and in a reduction of crystallization and melting
temperature as well as enthalpy of fusion. According to
Hosoda et al. [14], 1-butene is easily incorporated in the
crystalline phase, which gives rise to expansion of the unit
cell, so that the amount of comonomer in the crystalline
phase is comparable with that in the amorphous phase. The
degree of inclusion of 1-butene in the crystals was found to
be much higher than that of ethylene. This was attributed to
the similarity of the chain conformation of isotactic
polypropylene and polybutene-1 sequences, while ethylene
units simply interrupt the polypropylene 3/1 helices, which
consequences in shortening of the crystallizable sequence
and significant exclusion of ethylene units into amorphous
phase.
In recent years several new copolymers of propylene
with higher a-olefins have been synthesized and investi-
gated due to introduction of new metallocene catalysts.
Pérez et al. [8] reported that for fractions of a propylene/
1-hexene copolymer with different comonomer content the
glass transition temperature, temperature and enthalpy of
melting, and consequently the equilibrium melting tem-
perature of crystals, decrease with increasing comonomer
content. Lovisi et al. [15] studied propylene/1-hexene and
propylene/1-octene copolymers and found that thermo-
dynamic properties–such as crystallization enthalpy and
temperature, melting temperature, glass transition tempera-
ture–storage modulus and density, all decrease in a linear
pattern with increasing comonomer content. It was also
shown that the longer the alkyl branch, the less comonomer
is necessary to decrease the crystallization ability of
copolymer chains and hence to make the material behaviour
more rubbery [16].
Nitta et al. reported on the synthesis and characterization
of novel block copolymers of isotactic polypropylene and
ethylene-propylene rubber which showed single glass
transition and large orientational effects of PP phase on
drawing [17].
Polypropylene random copolymers, containing ethylene
or 1-butene as co-units, are largely used in film packaging
for their advantageous optical, mechanical and surface
properties, improved processability and weldability as
compared to PP homopolymer. Blending of these copoly-
mers offers an additional opportunity of formulation of
materials whose properties can be suitably and precisely
modulated by both blend composition and the microstruc-
tural characteristics of the components (type and amount of
comonomer), as well as the processing conditions. It is
anticipated that the type as well as concentration of
comonomer would influence the miscibility of blend
components in the melt and the crystallization process,
which in turn, should result in variation of the crystal
superstructure and bulk properties.
This paper is aimed at analysing the morphological
characteristics of blends of propylene-(1-butene) copolymer
with propylene-ethylene copolymers having different
ethylene content, crystallized from the melt at high under-
coolings, which are frequently used in production of films
for packaging. In a companion paper [18] a detailed study of
the isothermal crystallization and melting behaviour of
these blends is reported.
2. Experimental
2.1. Materials
The materials studied were commercial as well as
laboratory samples of isotactic propylene-ethylene (EP)
and propylene-(1-butene) (BP) random copolymers sup-
plied by Basell Polyolefins, Italy. One of ethylene-
propylene copolymers (coded hereafter EP2) was a
commercial product containing about 3 wt% C2H4 while
the other ethylene-propylene and propylene-(1-butene)
copolymers (coded here as EPS and BPS, respectively)
were experimental products with 2 wt% C2H4 and 9.9 wt%
C3H9, respectively. These materials were designed for
quality packaging applications, either as monolayer films or
as welding layers in coextruded multilayer structures and
were formulated with slip and antiblock agents and
antioxidants.
A sample of isotactic polypropylene homopolymer
(Moplen X305, Basell Polyolefins, Italy) of MFIZ
9 g/10 min was also studied as a reference material. The
composition and molecular characteristics of the examined
copolymers are summarized in Table 1.
2.2. Blend preparation
Binary blends of BPS and two types of ethylene
copolymers, EPS and EP2, respectively, were prepared by
simultaneous melt-mixing in a Brabender Plasticorder static
mixer at a temperature of 190 8C, using a mixing time of
5 min and a rotation speed of 40 rpm. The blends prepared
 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
Table 1
Molecular characteristic of studied polymers
Sample code Comonomer Comonomer content
(wt%) (mol%)
EPS C2H4 2.0 3.0
EP2 C2H4 3.1 4.6
BPS C4H8 9.9 7.6
iPP – 0 0 9.0
a
Measured at 230 8C and 2.16 kg.
had a BPS content of 25, 50 and 75 wt%, respectively. For
comparison the samples of plain iPP and plain copolymers
were also processed in the mixer under identical conditions.
Films of blends and plain copolymers were obtained by
compression moulding of bulk samples in a Carver press at
230 8C and subsequent quenching in liquid nitrogen to
minimize any phase separation induced by crystallization
process.
These films were used for preparation of samples
crystallized at high undercoolings in the temperature
range of 60–90 8C. For this purpose the isotropic films
obtained previously were sandwiched between two con-
stantan foils, each 40 mm thick, together with an aluminum
spacer of 150 mm thickness. The sandwiched films were
melted in a laboratory press at 190 8C and 50 atm for 2 min
and then quickly transferred to the crystallization cell
consisting of two massive cylindrical aluminum blocks
(approximately 5 kg each) equipped with electrical heaters
and temperature sensors. The temperature of each block was
controlled by an electronic controller with an accuracy
higher than 1 8C. The block surfaces contacting with the
sample were carefully polished in order to improve heat
transfer between the sample and blocks. Other details of the
cell and procedures are given in Ref. [19]. Due to small heat
capacity of thin sample, the large heat capacity of the cell
and very good thermal contact between them the sample
could be cooled down to the desired crystallization
temperature very quickly. Measurements with thin thermo-
couple embedded in the sample demonstrated that the
crystallization temperature was reached in few seconds after
transferring the molten sample into the cell. This time is
short enough to provide nearly isothermal conditions for the
crystallization process in the temperature range applied
[19]. Constantan foil was chosen as an outer layer material
in the sandwich since it does not induce any excessive
spherulite primary nucleation on the surface of polypropy-
lene sample being in contact with [20].
2.3. Optical microscopy
The morphology of the samples of the blends crystallized
at high undercoolings was examined with an optical
polarized light microscope (Leitz Ortholux II POL-BK).
For supplementary observations of the crystallization
behaviour the microscope was equipped with a hot stage
7551
M.F.Ia (g/ Mw Mw/Mn mmmm (mol%)
10 min)
9.5 216,000 3.5 89.3
6.0 230,000 4.5 86.1
7.0 262,000 6.3 96.6
350,000 7.5 (O95)
(Linkam, model THMSE 600). In this experiment films
obtained from pellets were sandwiched between a micro-
scope slide and a cover glass, heated up to 230 8C at a rate of
30 8C/min and kept at this temperature for 10 min to destroy
any trace of crystallinity; then the films were rapidly cooled
down at a rate of 100 8C/min to the desired crystallization
temperature and allowed to crystallize under isothermal
conditions.
2.4. Scanning electron microscopy
Additional morphological study was performed with a
scanning electron microscope (SEM). The morphology of
the surface of thin samples crystallized at high under-
coolings, as well as the internal bulk morphology of thicker
specimens crystallized by slow cooling from the melt were
examined.
In order to reveal the morphological details the speci-
mens were etched with a permanganic etchant [21,22] prior
to microscopic examination, according to the improved
procedure described in Ref. [23]. The reagent consisted of
10 vol. parts of concentrated sulphuric acid, 4 vol. part of
orthophosphoric acid (85%), 1 vol. part of water and 1 wt%/
vol. of potassium permanganate. Etching was performed at
room temperature for 2 h. Samples crystallized at high
undercooling were etched without any prior preparation,
while in slowly crystallized samples the internal surface to
be etched was exposed using an ultramicrotome equipped
with a freshly prepared glass knife. Etched specimens after
appropriate washing [24] and drying were mounted on the
microscopic stages, coated with a fine layer of gold (ca.
20 nm thick) by ion sputtering device (Jeol JFC-1200) and
then examined with a scanning electron microscope (Jeol
JSM 5500LV).
2.5. Light scattering
Samples crystallized at high undercoolings were inves-
tigated by the small-angle light scattering technique (SALS)
in order to determine the average spherulite radius from the
Hv scattering pattern. A He–Ne laser (lZ632.8 nm) was
used to generate the scattering pattern. The 2-D Hv patterns
(obtained with crossed polars) were recorded using a high
sensitivity video camera coupled to a computer equipped
with miro-VIDEO capture card. From Hv patterns the
7552 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
scattering light intensity along the scattering angle q was
measured at fixed polar angle mZ458 using the ImageQuant
software (Molecular Dynamics). From the angular position
of the maximum of scattering intensity, qmax, the fifth-order
average spherulite radius hR5i was calculated using the
following formula [19,24]:
4:09l
hR5 i Z (1)
4p sinðqmax =2Þ
The number average spherulite radius hRi can be estimated
from the fifth-order average hR5i using the approximate
relation [19,25]:
hRi zhR5 i=k (2)
The value of coefficient k depends on the type of primary
nucleation and changes within the range from 1.25 (pure
instantaneous nucleation) to 1.33 (pure sporadic one) [19].
For most of practical cases however, where the fractions of
instantaneous and sporadic nuclei are not known exactly, an
intermediate value of kZ1.3 can be a satisfactory
approximation for estimation of hRi [25].
2.6. DSC analysis
The melting behaviour of the isothermally crystallized
samples was analyzed with a Perkin–Elmer PYRIS
Diamond-DSC differential scanning calorimeter, calibrated
with indium standard. The samples (5–10 mg) were heated
up to 230 8C at the rate of 10 8C/min, under nitrogen
atmosphere (1 bar). The melting temperature and enthalpy
were calculated from the position of maximum and from the
area of endothermic peaks, respectively. For the evaluation
of crystallinity the heat of fusion of 100% crystalline
polypropylene was taken as DHmZ209 J/g [26].
2.7. Small- and wide angle x-ray scattering
The lamellar structure of copolymers and blends samples
was probed by 2-D small angle X-ray scattering (2-D
SAXS) at room temperature. A Kiessig-type camera (1.1 m
long) was equipped with a tapered capillary collimator
(XOS) combined with additional pinholes forming the
beam, and an imaging plate as a detector and recording
medium (Fuji). To reduce parasitic scattering the entire
beam-path was evacuated. The camera was coupled to a
Philips PW1830 X-ray generator (sealed-tube, fine point
Cu Ka filtered source) operating at 50 kV and 40 mA. The
time of collection of the pattern was usually around 4 h.
Exposed imaging plates were read with PhosphorImager SI
system (Molecular Dynamics).
Long period (LP) was determined from the 1-D sections
of 2-D pattern (sectioning made with the ImageQuant
software). Background and Lorentz corrections were
applied to the curves. Long period was calculated then
from the position of maximum of corrected curve using the
Bragg law.
Wide-angle X-ray scattering (WAXS) analysis of the
examined materials was performed at room temperature
with DRON-2A diffractometer coupled to a source of
filtered Cu Ka radiation (ceramic sealed-tube with line focus
powered by Philips PW3830 generator operating at 50 kV
and 30 mA). The scans were performed within the range of
2qZ10–308 with scanning step of 0.01/0.028, in the
reflection geometry.
3. Results and discussion
3.1. Morphology
3.1.1. Optical microscopy
The morphology of the copolymers and their blends was
examined for samples crystallized in the temperature range
from 60 to 132 8C by using microscopy and SALS
techniques. At higher crystallization temperatures (above
110 8C) the growth of spherulites in samples of plain
copolymers and blends was observed in real time by optical
microscopy. Few exemplary optical micrographs of copo-
lymers and blends, non-isothermally crystallized from the
melt, are shown in Fig. 1. These observations showed that
for all examined samples spherulites were formed on
cooling of the melt to temperatures in the range 100–
130 8C. In all cases the characteristic spherulitic mor-
phology of isotactic polypropylene with a monoclinic
crystal structure (negative birefringence) was observed.
The positive-birefringent spherulites of b-modification were
sporadically observed only in samples of plain iPP. No
change of spherulite appearance was detected with varying
the copolymer structure or blend composition. The copoly-
mer components did not show any phase separation
phenomena during relative slow crystallization at moderate
undercoolings.
In all observed samples most of the boundaries between
impinged spherulites was shaped as straight lines, which is
typical for instantaneous heterogeneous nucleation [27]. In
fact, morphological observations with scanning electron
microscope, reported later in Section 3.1.3, revealed foreign
inclusions frequently located in the spherulite centres (cf.
Fig. 6b), that evidences the heterogeneous nature of
numerous primary nuclei. The number of spherulites per
unit area varied with the type of copolymer and blend
composition. Among pure copolymers, EP2 exhibited
spherulites of the largest size at a given crystallization
temperature, indicating a reduced nucleation density with
respect to other copolymers.
The spherulitic structure of samples crystallized at high
undercoolings (TcZ60–90 8C) could be observed only in
completely solidified specimens, due to very high crystal-
lization rate at such extreme conditions. Fig. 2 shows the
optical micrographs of copolymer samples crystallized at
 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
Fig. 1. Polarized light micrographs of thin film samples of (a) EP2,
(b) BPS/EP2 75:25 and (c) BPS/EP2 25:75 blends, taken during non-
isothermal crystallization (cooling rate 2 8C/min) in the range 100–115 8C.
the temperatures indicated. These micrographs are sup-
plemented with 2-D Hv SALS patterns (crossed polars). The
micrographs show the spherulitic structure present in all
copolymers, regardless the crystallization temperature. The
micrographs are somewhat diffuse since the spherulites
grown at the reported range of temperature are substantially
smaller than the specimen thickness (150 mm). However,
7553
the characteristic 4-lobe shape observed in the Hv SALS
patterns of specimen clearly evidences the presence of
spherulites in all copolymer samples. Similar micrographs
and SALS patterns (not presented here) were obtained for
samples of blends crystallized at the same conditions.
Similarly to samples crystallized at TcR110 8C the
spherulitic structure formed at TcZ60–90 8C consisted of
spherulites of the a-form. Few b-form spherulites was
observed only in specimens of iPP crystallized at 80 and
90 8C (cf. Fig. 2a), while for iPP crystallized at lower
temperatures, as well as for copolymers and their blends no
b-form spherulites were observed.
3.1.2. SALS analysis
In order to determine the average radius of spherulites in
the studied samples the Hv SALS patterns of samples
crystallized at TcZ60-90 8C were recorded (Fig. 2); similar
patterns were obtained for the blends samples (not presented
here). Samples crystallized at temperatures above 90 8C did
not produce clear scattering pattern due to large size of
spherulites.
The polar angle respective to the scattering intensity
maxima was determined for every pattern and then the fifth-
order average spherulite radius hR5i was calculated using Eq.
(1) [19,24]. Note, that this high-order average favours large
spherulites, so that the SALS-determined average spherulite
radius is substantially higher (by 1.3 approximately [19,25])
than the number average spherulite radius, which can be
determined by other methods, e.g. microscopy. Fig. 3a
presents the fifth-order average spherulite radius hR5i as a
function of crystallization temperature, as determined for
samples of plain iPP and copolymers. Fig. 3b and c show the
dependencies determined for BPS/EPS and BPS/EP2
blends, respectively.
It can be seen that for all samples the average spherulite
size increases as Tc increases. The largest variation can be
observed between 60 and 80 8C. In this temperature range
the average spherulite radius increases more than twice,
from about 2–5 mm to approximately 5–12 mm, depending
on the copolymer type (cf. Fig. 3a). For a given Tc the
average radius hR5i measured for plain polymers changes in
the following order: RBPS!REP2!REPS!RiPP; i.e. the
average spherulite size decreases with increasing amount
as well as length of side branches in the copolymer chains.
In the case of blends, the variation of spherulite radius is
controlled by the blend composition. For both BPS/EPS and
BPS/EP2 blends, at any Tc, the spherulite size decreases
with increasing fraction of BPS copolymer in the blend (Fig.
3b and c).
Since the average spherulite size is determined by the
number density of primary nuclei, the decrease of size with
decreasing temperature of crystallization, observed in all
samples studied, can be associated with a substantial
increase of primary nucleation at temperatures below
80 8C. This is likely due to activation of the homogeneous
nucleation mode in addition to already active heterogeneous
7554 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
Fig. 3. The dependence of fifth-order average spherulite radius hR5i on
crystallization temperature for (a) plain copolymers, (b) BPS/EPS blends,
and (c) BPS/EP2 blends.
nucleation at temperatures between 70 and 80 8C. For
isotactic polypropylene, as well as for its homogeneous
blends with atactic polypropylene, a jump of primary
nucleation has been reported to occur at crystallization
temperatures above 70 8C, and was ascribed to activation of
the homogeneous nucleation mode [19]. The experimental
data presented here suggest the activation of homogeneous
primary nucleation occurring in both iPP and copolymers at
Fig. 2. Polarized light micrographs of samples of (a) iPP, (b) EPS, (c) EP2, and (d) BPS, crystallized at temperatures indicated. Every micrograph is
supplemented with the Hv SALS scattering pattern obtained for the respective sample.
7555
the same temperature range. Comparing the experimental
curves with those calculated for several model cases of
primary nucleation, presented in Ref. [19], it appears that
the difference of spherulite radii between samples of iPP and
copolymers originated mainly from different density of
heterogeneous nucleation (being the lowest in iPP and
increasing with increasing comonomer fraction), while
homogeneous nucleation has been less affected. The
homogeneous nucleation rate likely decreased with increas-
ing comonomer content due to shortening of crystallizable
sequences within copolymer chain, which decreased the
probability of formation of stable nuclei and hence the
nucleation rate. Thus, the observed increase of hetero-
geneous nucleation density must be mainly related to higher
number of solid heterogeneities present in copolymer
samples as compared to PP homopolymer.
The plots of average spherulite radius hR5i of EPS/BPS
and EP2/BPS blends, presented in Fig. 3b and c show a
monotonic decrease of the radius with both crystallization
temperature and increasing content of BPS in the blends
within an envelope given by the curves of plain components.
These curves indicate that the changes of primary nuclea-
tion in blends simply follow the variation of their
composition.
3.1.3. SEM analysis
The morphology of spherulites was additionally exam-
ined by scanning electron microscopy (SEM). Observations
of the spherulitic structure on the surface of films crystal-
lized at high undercoolings were in agreement with
the SALS estimations of average spherulite sizes in the
samples. Unfortunately, it was difficult to examine the
structure in more details since the final morphology of that
surface was formed in contact with the metal foil in a
sandwich sample. The presence of the foil induces
modification of the sample morphology at the surface. As
a consequence, the SEM micrographs of that surface were
rather poor in details even after appropriate and careful
etching.
Finer details of the spherulitic structure were revealed by
observations of the bulk morphology of samples crystallized
non-isothermally by slow cooling. The morphology was
analysed by cutting the material out with an ultramicrotome
followed by an appropriate etching, as described in Section
2. Figs. 4–6 present the representative SEM micrographs
of plain copolymers, BPS/EPS and BPS/EP2 blends,
respectively.
The micrograph of plain iPP (Fig. 4a) shows typical a-
type spherulites bordering the b-spherulite (on the right-
hand side of the micrograph), which is occasionally found in
iPP. Due to cross-hatched arrangement of lamellae in a-type
spherulites [28] the appearance of this crystal modification
7556 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
Fig. 4. SEM micrographs of the etched internal planes of bulk specimens crystallized non-isothermally from the melt: (a) iPP, (b) BPS. (c) EPS, (d) EP2.
is much more compact than that of b-type spherulites, in
which lamellae orientation and shape can be easily
recognized. In a-spherulites, however, the lamellar mor-
phology is rather indistinct and only outlines of some
lamellae can be seen at higher magnification. In the interior
of any spherulite several small circular pits are observed,
which presumably are artifacts resulting from over-etching
(too long and/or too severe etching conditions can lead to an
excessive local etching in occasional places, e.g. around
existing surface defects or inclusions of material of lower
etching resistance; this would produce some artificial
features which were not necessarily related to the original
structure of the sample [22]). The boundaries between
a-type spherulites in iPP are compact and filled with
interpenetrating lamellae of adjacent spherulites.
The morphology of a-type spherulites in EPS copolymer
(Fig. 4c) is a little more open and loose than that of
spherulites of iPP. The main difference is in the appearance
of the interspherulitic boundaries; the pits presumably
produced by over-etching are concentrated along these
boundaries (where the concentration of non-crystalline
material is higher). This suggests some segregation of
non-crystallizable molecules that are pushed by the front of
growing spherulite into interspherulitic regions. Similarly,
yet even stronger, features can be observed for the EP2
copolymer, with a higher concentration of ethylene co-units
(Fig. 4d). Both spherulite interior and interspherulitic
boundary display a less compact structure than that of PP
homopolymer.
Micrographs of propylene-(1-butene) copolymer (BPS)
show relatively open and loose structure of spherulites with
many visible pits and holes, distributed evenly in the
observed cross-section of spherulite (Fig. 4b). On the other
hand, the interspherulitic boundaries are more irregular and
much more diffuse as compared to PP and propylene-
ethylene copolymers, but there is no evidence of any over-
etching. These features probably result from relative large
amount of non-crystallizable species in this copolymer
(9.9 wt% 1-butene), which are most probably rejected
preferably into interlamellar layers and trapped here rather
than pushed ahead by the growing front of the spherulite.
Due to the large amount of non-crystallizing material the
front of growing spherulite becomes quite rough and
irregular and the boundaries between adjacent spherulites
appear diffused and vague [29].
Micrographs of the blends BPS/EPS and BPS/EP2 are
 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
Fig. 5. SEM micrographs of the etched internal planes of bulk specimens of
(a) 25:75, (b) 50:50, (c) 75:25 BPS/EPS blends crystallized non-
isothermally from the melt.
shown in Figs. 5 and 6, respectively. These micrographs
reveal quite open internal structure of spherulites in
blends, resembling that found in plain copolymers. In
both sets of blends the morphology of spherulites
changes with the blend composition. The observed
changes correlate well with the concentration of BPS
7557
Fig. 6. SEM micrographs of the etched internal planes of bulk specimens of
(a) 25:75, (b) 50:50, (c) 75:25 BPS/EP2 blends crystallized non-
isothermally from the melt.
in the blend: the morphology of 25:75 BPS/EPS and
BPS/EP2 blends is close to that of plain EPS or EP2,
respectively, while that of the 75:25 blends show the
features similar to these of plain BPS copolymer. In any
of the blend no phase separation of components was
detected suggesting that BPS is miscible with both EPS
and EP2 propylene-ethylene copolymers in the entire
range of composition studied.
7558 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
3.2. X-ray analysis
Fig. 7a presents diffractograms of the plain copolymers,
while Fig. 7b and c show those obtained for BPS/EPS and
BPS/EP2 blends, respectively, all crystallized at TcZ90 8C.
The diffractograms obtained for copolymers and blends
crystallized at other temperatures do not differ from those
shown in Fig. 7, and therefore are not presented. The
Fig. 7. WAXS diffraction curves of (a) plain iPP and copolymers,
crystallized at TcZ90 8C; (b) BPS/EPS and (c) BPS/EP2 blends at various
composition, crystallized at TcZ90 8C.
diffraction curves were all characteristic of the a-mono-
clinic modification of polypropylene, in accordance with the
microscopic observations which evidenced mainly the
occurrence of a-spherulites. The only exception was a
sample of iPP crystallized at TcZ90 8C in which a very
small fraction of the hexagonal b-modification could be
detected (small peak centered around 2qZ16.18, which can
be attributed to the (300) reflection of the b phase).
Moreover, no trace of the g-modification was found in
any of copolymer or blend samples. The g-modification was
reported to appear in propylene-ethylene copolymers with
relatively high concentration of ethylene units, crystallized
at low undercoolings [3–5]. The samples studied here have a
relatively low concentration of ethylene (2–3 wt%), and
were crystallized at high undercoolings. However, samples
crystallized at moderate and low undercoolings (above
110 8C) also did not reveal any trace of g-modification.
An examination of position of the diffraction maxima
demonstrates that the diffraction peaks of copolymers are
slightly shifted towards lower diffraction angles as com-
pared to the reference iPP homopolymer. This can be easily
seen, especially for (110), (040) and (130) peaks, in the
diffraction curves of copolymers presented in Fig. 7a. The
shift of the diffraction peaks is small for EPS and EP2
copolymers (yet increasing with increasing concentration of
ethylene comonomer) while it is rather pronounced in the
case of BPS copolymer. Such shift can be accounted for by
the expansion of the crystal lattice in copolymers as
compared to plain iPP. In particular, the relatively largest
shift of the peak of (040) plane indicates that the expansion
of the lattice in [010] direction is stronger than in any other
[hk0] direction. An increase of the average size of the unit
cell indicates that the comonomer units had to be
incorporated in crystals at least to some extent. Similar
conclusions were already reported in Refs. [12–14] for
copolymers containing 1-butene. The X-ray data here
reported for propylene-ethylene copolymers show that the
unit cell increases its average size with increasing the
content of comonomer, which suggests that ethylene co-
units were also incorporated within crystals as they grew
[4]. However, the lower expansion of crystal lattice for EP
copolymers, as compared to BP copolymers, is to be
ascribed to the fact that methyl side groups disturb the size
of PP helix much less than the bulky ethyl branches.
The diffraction curves obtained for the blends of BPS
with EPS and EP2 (Fig. 7b and c) show the gradual
expansion of the lattice as the composition of the blends
change from EP-rich to BP-rich. This behaviour can support
the previous conclusion on miscibility of these copolymers.
The lamellar structure of the copolymers and blends was
probed with SAXS. Exemplary one-dimensional scattering
curves extracted from 2-D SAXS patterns are shown in Fig.
8. The long period values (LP), determined from the
background and Lorentz-corrected curves, are given in
Table 2. These data demonstrate that the presence of
ethylene units in copolymer chains results in slight
 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561 7559

reduction of the long period as compared to the homo- Table 2

polymer. Such a reduction was observed in the entire range Long period determined from SAXS data
of the crystallization temperature and probably reflects the Sample code Composition Tc (8C) LP (nm)
shortening of the crystallizable sequence due to the presence (wt/wt)
of ethylene co-units in the chain. Similar observations were IPP – 90 13.1
already reported for propylene-ethylene random copoly- EPS – 90 12.5
mers in Refs. [9,10]. On the other hand, the long period EP2 – 90 12.4
BPS – 90 12.8
determined for BPS copolymer practically does not differ
IPP – 60 10.9
from that of iPP (within the limits of experimental error). EPS – 60 10.2
This is in spite of a noticeable reduction of crystallinity EP2 – 60 10.5
degree of the propylene-(1-butene) copolymer with respect BPS – 60 11.5
to the homopolymer, as evaluated from DSC measurements BPS/EPS 50:50 90 12.3
BPS/EP2 50:50 90 12.2
(discussed in the next section).
For BPS/EPS and BPS/EP2 blends, the values of LP of
crystals are also reduced as compared to iPP and close to temperature. Experiments with different heating rates
those observed for EP copolymers, crystallized at the same demonstrated that the lower melting peak increases its
temperature. This reflects the fact that the crystallinity size with respect to the upper melting peak when the heating
degree of EPS and EP2 copolymers is higher than that of rate increases. This indicates that the latter peak arises from
BPS at the same crystallization conditions. Thus, in the recrystallization phenomena of less perfect and/or smaller
50/50 blend the relative amount of crystalline component crystals, since the samples were unable to form more perfect
formed from EPS (or EP2) is larger than that from BPS, and crystals when crystallized at high undercooling. Moreover,
consequently the long period of the blend is similar to that of for all copolymers and their blends the temperature of
plain EP copolymers. melting peaks decreases in linear fashion with decreasing
the overall content of PP units in the system (calculated on
3.3. Melting behaviour the basis of blend composition and the content of PP units in
its copolymeric components), as shown in Fig. 10. This
The melting behaviour of isothermally crystallized relationship does not include plain iPP for which melting
samples of plain copolymers and their blends is illustrated temperature is noticeably higher than for any copolymer.
by representative DSC curves in Fig. 9. The detailed The overall melting enthalpy of samples crystallized at
analysis of crystallization and melting behaviour of these TcZ60–90 8C is strictly influenced by the comonomer
polymers is reported in a companion paper [18]. Here we content and blend composition. This behaviour is shown for
note only that all plain homo- and copolymers as well as BPS/EPS blends in Fig. 11, as a function of EPS content. On
blends crystallized at Tc!90 8C show a double melting the other hand, if the same enthalpy data, supplemented with
peak, which is rather usual behaviour of iPP and its data for plain polymers, are plotted against the overall
copolymers crystallized below 100 8C [1,30,31]. The
temperature of both lower and upper melting peak
components changes linearly with the crystallization

Fig. 8. 1-D raw scattering profiles extracted from 2-D SAXS patterns of
plain iPP and copolymers samples, crystallized at Tc Z90 8C Fig. 9. DSC melting curves of BPS and EPS copolymers and 50:50
ðsZ 2 sinðQÞ=lÞ BPS/EPS blend, crystallized at various temperatures.
7560 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
Fig. 10. Temperature dependence of the of the lower (TM1) and upper (TM2)
melting peaks on the overall content of PP units in plain copolymers and
blends crystallized at TcZ90 8C. Open symbols indicate upper melting
peak, while filled ones the lower peak: (>, %) plain iPP, (B, C) BPS/EPS
blends and (,, -) BPS/EP2 blends. The shaded area marks samples of the
blends, the points outside of this refer to plain components.
content of PP units in the system, then a monotonic decrease
with decreasing content of PP units can be observed. This
behaviour is illustrated in Fig. 12 where the melting
enthalpy was recalculated to overall crystallinity, assuming
a single value (209 J/g) of the heat of fusion of 100%
crystalline PP [26] for all samples of copolymers and blends
(solid lines). The crystallinity of the copolymers and blends,
evaluated in such a way, is noticeably lower than that of PP
homopolymer and even lower than it could be anticipated in
these systems on the basis of reduction of the amount of PP
in the system, alone. Such a discrepancy can be accounted
for by assuming either exclusion of an extra part of PP units
from the crystallization process (due to shortening of PP
sequences in the copolymer chains), or alternatively,
inclusion of some comonomer units in the crystals, resulting
in the formation of very imperfect crystals and in
consequent reduction of the temperature and enthalpy of
Fig. 11. The dependence of melting enthalpy on composition of the blend
for BPS/EPS blends crystallized at TcZ60 and 90 8C.
Fig. 12. Degree of crystallinity calculated from the enthalpy of melting for
copolymers and blends crystallized at TcZ60 and 90 8C. Symbols and solid
lines indicate values calculated using DH8m of homopolymer (209 J/g);
broken lines were calculated on the basis of DH8m for plain copolymers
[18]. Open symbols refer to TcZ90 8C, while filled ones to TcZ60 8C: (>,
%) plain iPP, (B, C) BPS/EPS blends and (,, -) BPS/EP2 blends. The
shaded area marks the samples of the blends, the points outside of this refer
to plain components.
fusion. In the former hypothesis the temperature of melting
of crystals should not differ too much from that of iPP,
which apparently is not the case here (cf. Fig. 10); on the
other hand, the latter hypothesis predicts a suppression of
the melting temperature, which is consistent with our
experimental results. This hypothesis is additionally sup-
ported by the diffraction data which suggest a reduction of
crystalline thickness and an expansion of crystalline lattice.
Moreover, the results of DSC analysis of samples
isothermally crystallized at Tc’s above 110 8C indicated
that the melting behaviour of copolymers is consistent with
the incorporation model. On the basis of melting data, the
equilibrium melting enthalpy, DH8m, of copolymers was
estimated (200.7 J/g for EPS and 197.1 J/g for EP2 and
BPS) [18]. These enthalpies were lower than that of plain
PP. Using these values of DH8m the variation of overall
crystallinity of copolymers and blends is represented by
broken lines in Fig. 12. It can be seen that even after such a
correction is applied, the crystallinity of copolymers and
their blends results to be depressed more than one could
expect on the basis of reduced amount of PP units in the
copolymer (such reduction should not exceed 4% for the
highest content of comonomer in the BPS sample).
4. Conclusions
The polypropylene-based copolymers with ethylene and
1-butene co-units, as well as the blends of these copolymers,
were found to crystallize in spherulitic fashion in a broad
temperature range, down to 60 8C. The primary nucleation
of spherulites was mostly the heterogeneous nucleation
 Z. Bartczak et al. / Polymer 45 (2004) 7549–7561
above TcZ80 8C. When crystallization was carried out
below this temperature also homogeneous, sporadic nuclea-
tion became effective. The heterogeneous nucleation was
stronger in the copolymer with 1-butene than in copolymers
with ethylene and even stronger than in the reference iPP
homopolymer. This was probably due to larger number of
heterogeneities dispersed in copolymers as compared to
plain iPP.
All copolymers and their blends, crystallized in the
temperature range 60–90 8C, formed exclusively crystallites
of the a-modification. No trace of either b or g forms were
detected. As demonstrated by X-ray diffraction the dimen-
sions of the unit cell of monoclinic a-crystals increased with
an increase of the amount and the size of copolymer units in
the chain. This was accompanied by a decrease of the long
period and by a pronounced reduction of the enthalpy of
melting of the crystallites. All these effects indicated the
incorporation of ethylene or 1-butene co-units within
growing crystallites.
SEM observations showed that the appearance of
spherulites changed from quite compact structure of iPP
towards a more open and loose structure observed in
copolymers and their blends. In propylene-ethylene copo-
lymer with low ethylene content some fraction of non-
crystallizing species was rejected and pushed ahead by the
front of growing spherulite into interspherulitic regions,
while in copolymers with higher ethylene or 1-butene
content that material remained in the intraspherulitic
regions. Although the observation of the lamellar structure
with SEM did not provide enough details, the micrographs
of copolymers and their blends suggested the occurrence of
cross-hatching morphology, similar to that characteristic for
plain iPP.
Since no phase separation was observed in any blend
sample it may be concluded that the copolymers studied are
miscible in any proportion. Copolymers and blends crystal-
lized at high supercoolings exhibited double melting peak,
where the upper peak originated from prior recrystallization
of smaller/less perfect crystals on heating. Temperature of
melting as well as crystallinity of copolymer and blends
showed a marked decrease with the total amount of
comonomer in the system. The crystallinity values resulted
to be depressed more than that expected on the basis of the
equilibrium melting enthalpy of copolymers. That behavior
was interpreted again as a result of incorporation of
comonomer units within crystallites growing in copolymers
and their blends.
Acknowledgements
This work has been carried out with partial financial
support of the Italian Ministry of University and Research,
7561
MIUR-CNR Agreement, PF.29, Project Chemistry (95/95),
Research line ‘Synthesis and Characterization of New
Polyolefin Materials for Food Packaging’, and Polish
Academy of Sciences. The authors are grateful to Basell
Polyolefins Italy for providing the polymer samples used in
this work and to Dr. Antonio Addeo for his helpful
contribution. Thanks are also due to Dr. C. Sacchi from
ISM-CNR, Milano, Italy, for the NMR characterization
data.
References
[1] Karger-Kocsis J, editor. Polypropylene: structure, blends and
composites. London: Chapman and Hall; 1995.
[2] Utracki LA. Polymer alloys and blends. Munich: Hanser; 1989.
[3] Feng Y, Jin X, Hay JN. J Appl Polym Sci 1998;68:381–6.
[4] Laihonen S, Gedde UW, Werner PE, Martinez-Salazar J. Polymer
1997;38:361–9.
[5] Mezghani K, Phillips PJ. Polymer 1998;39:3735–44.
[6] Monasse B, Haudin JM. Colloid Polym Sci 1988;266:679–87.
[7] Feng Y, Hay JN. Polymer 1998;39:6589–96.
[8] Pérez E, Benavente R, Bello A, Perena JM, Zucchi D, Sacchi MC.
Polymer 1997;38:5411–8.
[9] Zimmermann H. J Macromol Sci, Phys 1993;B32(2):141–61.
[10] Starkweather Jr HW, Van-Catledge FA, Mac Donald RN. Macro-
molecules 1982;15:1600–4.
[11] Crispino L, Martuscelli E, Pracella M. Makromol Chem 1980;181:
1747–55.
[12] Cavallo P, Martuscelli E, Pracella M. Polymer 1976;18:42–8.
[13] Abiru T, Mizuno A, Weigand F. J Appl Polym Sci 1998;68:1493–501.
[14] Hosoda S, Hori H, Yada K, Nakahara S, Tsuji M. Polymer 2002;43:
7451–60.
[15] Lovisi H, Tavares MIB, Da Silva NM, De Menezes SMC, De Santa
Maria LC, Coutinho FMB. Polymer 2001;42:9791–9.
[16] Arnold M, Bornemann S, Koller F, Menke TJ, Kressler J. Macromol
Chem Phys 1998;(12):2647–53.
[17] Nitta KH, Kawada T, Prokhorov VV, Yamahiro M, Mori H,
Terano M. J. Appl Polym Sci 1999;74:958–64.
[18] Chiono V, Pracella M, (to be published).
[19] Bartczak Z, Galeski A. Polymer 1990;31:2027–38.
[20] Gadzinowska K, Piorkowska E. Polimery 2003;48:790–9.
[21] Olley RH, Hodge AM, Basset DC. J Polym Sci, Part B: Polym Phys
1979;17:627–43.
[22] Bassett DC. In: Bassett DC, editor. Developements in crystalline
polymers-2. London: Elsevier; 1998. p. 67–114. Chapter 2.
[23] Shahin MM, Olley RH, Blisset MJ. J Polym Sci, Part B: Polym Phys
1999;37:2279–86.
[24] Stein RS, Rhodes MB. J Appl Phys 1960;31:1873–84.
[25] Prud’homme RE, Stein RS. J Polym Sci, Part B: Polym Phys 1973;11:
1683–701.
[26] Bu HS, Cheng SZD, Wunderlich B. Makromol Chem, Rapid Commun
1988;9:75–7.
[27] Galeski A. J Polym Sci, Part B: Polym Phys 1981;19:721–30.
[28] Norton DR, Keller A. Polymer 1985;26:704–16.
[29] Padden FJ, Keith HD. J Appl Phys 1959;30:1479–84.
[30] Wunderlich B. Macromolecular Physics, vol. 3. New York: Academic
Press; 1980.
[31] Monasse B, Haudin JM. Colloid Polym Sci 1985;263:822–31.