Communication

Isothermal Crystallization of Isotactic

Poly(propylene) Studied by Superfast
Calorimetry

Clara Silvestre,* Sossio Cimmino, Donatella Duraccio, Christoph Schick

The isothermal crystallization behavior and the structure and morphology of isotactic
poly(propylene) (iPP) and iPP/hydrogenated hydrocarbon resin (HR) 90/10 blend were ana-
lyzed. To cover the entire temperature range, isothermal crystallizations were studied using
superfast calorimetry at a high cooling rate in the range 0 to 110 8C, and by conventional DSC
at a low cooling rate in the range 120 to 140 8C. Structural and morphological changes due to
the different thermal treatments were also analyzed. The complete crystallization curve
ranging from Tg to Tm showed bimodal crystallization behaviors for both iPP and iPP/HR
90/10 blend. This result is explained by taking into consideration the polymorph properties of
iPP. It is in fact assumed that the curve
from Tg to 60 8C referred mainly to the
crystallization kinetics of the iPP meso-
morphic form by homogeneous nuclea-
tion, whereas the curve from 60 8C to Tm
mainly represented the crystallization
kinetic curve for the monoclinic a form
by heterogeneous nucleation. This hy-
pothesis is confirmed by the analysis of
the structures obtained using wide angle
X-ray experiments. Moreover, the addi-
tion of HR to iPP causes a drastic reduc-
tion in the crystallization rate of iPP in
both regions due to the diluent effect of
the miscible resin.

C. Silvestre, S. Cimmino, D. Duraccio

Introduction
Istituto di Chimica e Tecnologia dei Polimeri, C. N. R., Via Campi
Flegrei, 34, 80074 Pozzuoli (NA), Italy
E-mail: silvestre@ictp.cnr.it The overall isothermal crystallization of several polymers
C. Schick has been deeply investigated using conventional DSC,[1]
University of Rostock, Department of Physics, 18051 Rostock, which generally provides low cooling rates (about
Germany 50 8C
min1) to cool the sample from the melting

Macromol. Rapid Commun. 2007, 28, 875–881

ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200600844 875

temperature (Tm) to crystallization temperatures (Tc). For
most polymers, at these cooling rates, the temperature
range where isothermal crystallization rates are measur-
able is limited to crystallization temperatures close to
the Tm. At lower crystallization temperatures, the crystal-
lization process starts during the cooling and hence the
crystallization process is no longer isothermal. Using
traditional DSC, complete crystallization curves have been
obtained for only a few polymers, generally those with
a very low crystallization rate (for example isotactic polys-
tyrene).[2] In these cases, the curve of the crystallization
rate as a function of temperature is represented by a bell-
shaped curve with a maximum between Tg and Tm. This
has been theoretically described by Turnbull-Fisher.[1,3]
The crystallization rate is zero at Tm, then, on decreasing
the temperature, increases as the thermodynamic driving
force for nucleation rises, then reaches a maximum and
finally decreases toward zero when the glass transition
temperature is approached as the cooperative conforma-
tion motion slows.
For isotactic poly(propylene) (iPP), most of the published
data on overall isothermal crystallization from the melt
concerns the temperature region between 115 and 150 8C,
where heterogeneously nucleated spherulites are pro-
duced.[4] For iPP, it has been reported that the region
of crystallization from heterogeneous nuclei extends
towards 80 8C, whereas below these temperatures, the
crystallization is mainly associated with homogeneous
nucleation.[4–6]
With common DSC, it has been shown that higher
cooling rates can be realized,[7] but in any case, this is not
comparable with the cooling conditions in some industrial
processes.[8,9] Recently, isothermal crystallization per-
formed at high cooling rates by superfast calorimetry
has proved to be a valuable procedure for defining the
isothermal crystallization rates for some polymers in a
temperature range (low Tc) where traditional isothermal
DSC measurements are generally not possible.[10,11] The
combination of the values obtained using both procedures
can provide the entire crystallization curve between Tg
and Tm.
In this work, the isothermal crystallization behavior of
iPP and an iPP/hydrogenated hydrocarbon resin (HR) 90/
10 blend was analyzed to obtain information on the
crystallization of these systems over the entire crystal-
lization temperature range and, therefore, also under
conditions comparable to industrial processing conditions,
where high cooling rates are usually used.
In a recent paper, De Santis et al.[12] reported cooling and
heating scans for iPP at high cooling rates. They found that
when the iPP was solidified with a cooling rate greater
than 160 K
s1, an exothermic process started to appear at
temperatures below 40 8C. It was hypothesized that this
process was related to the formation of the mesomorphic
Macromol. Rapid Commun. 2007, 28, 875–881
876 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
C. Silvestre, S. Cimmino, D. Duraccio, C. Schick
form. No studies of the crystalline structure and morphol-
ogy were performed. The paper, therefore, provided some
information on the range of temperatures for meso-
morphic phase formation and dependence on the cooling
rate, but did not define the crystallization kinetics of iPP at
low crystallization temperatures, where the mesomorphic
phase forms.
The modification of isotactic poly(propylene) with low
molecular mass resins up to 20–30 wt.-%, aimed at
obtaining films for use in the packaging sector, is one of
the areas that our research group has studied for several
years.[13–16] Generally, this addition causes drastic mod-
ifications in the structure and morphology of poly(propyl-
ene), which also depend critically on the crystallization
conditions.
A synthetic hydrogenated resin (HR), produced by
Eastman (MBG273), was introduced a few years ago and
added to iPP in order to improve its properties.[17–19] HR is
an oligomer obtained in three steps: polymerization of
monomers like styrene, a-methylstyrene, vinyltoluene,
cyclopentadiene and indene to form the aromatic pre-
cursor resin; a weak hydrogenation reaction to saturate
the backbone; a strong hydrogenation reaction to destroy
the aromaticity of the ring and to create a fully alicyclic
resin. The system formed by iPP and HR (up to 30% in
weight) was extensively investigated in order to study
the influence of the composition on phase structure and
the properties of blends and derived films.[17] After mixing
at room temperature, all the blends were made up of a
crystalline phase of iPP and one homogeneous phase
consisting of HR and amorphous iPP, characterized by a
single glass transition temperature (Tg). Analysis of the
tensile properties indicated an increase in Young’s
modulus and a decrease in the elongation at break of
films as a function of the HR content in the blends.
Permeability measurements showed a reduction of the
water vapor permeability with HR content. The addition
of HR always induced, at a given Tc, a reduction in the
isothermal radial growth rate of spherulites and in
the isothermal overall crystallization rate measured in
the temperature range 120–145 8C.
The crystallization behavior is an important industrial
factor as it affects the production time and dictates sample
morphology and hence the solid state properties of
polymers. This is even more evident in the case of iPP
which is known to be a polymorphic material with several
crystal modifications (a, b and g forms and a modification
with a low crystalline order, called the mesomorphic form).
The development of these structures is critically depen-
dent upon crystallization conditions and pressure and
has a great impact on the mechanical properties as it has
been described in detail elsewhere.[4,20,21] Therefore, a
study of the structural changes due to different thermal
treatments (high and low cooling rates) of iPP and an
DOI: 10.1002/marc.200600844
Isothermal Crystallization of Isotactic Poly(propylene) Studied . . .
iPP/HR 90/10 blend was also performed using WAXS and
is reported here.
Experimental Part
The materials used were a commercial isotactic poly(propylene)
(iPP) [Moplen X30S produced by Montell, Mw ¼ 3.5  105 g
mol1,
Mn ¼ 4.69  104 g
mol1, Mz ¼ 2.06  106 g
mol1, M. F. I. (190 8C,
2.16 kg) ¼ 9 g
10 min1, density ¼ 0.9 g
cm3] and a hydro-
genated hydrocarbon resin (MBG273) [Eastman (The Netherlands),
Mw ¼ 1.47  103 g
mol1, Mn ¼ 9.0  102 g
mol1, Mz ¼ 2.4  103
g
mol1]. The glass transition (Tg) of the HR MBG273 resin was
detected at about 82 8C by DSC. Traditional isothermal crystal-
lization at a ‘‘low cooling rate’’ was performed using a classical
heat flow differential scanning calorimeter, METTLER DSC-822.
The following procedure was used. Each sample was heated from
30 to 200 8C at 30 K
min1, kept at this temperature for 10 min to
allow complete melting and then cooled to the crystallization
temperature (Tc) at 30 K
min1. It was then kept at Tc for the time
necessary for crystallization.
Isothermal crystallization at a ‘‘high cooling rate’’ (2 000 K
s1)
was performed with a thin film chip calorimeter (SFCC), developed
by Schick et al.,[10,11] based on the thermal conductivity gauge
TCG-3880 from Xensor Integration, NL.[22] The thermal conduc-
tivity gauge TCG-3880 consisted of a 0.5 mm Si3Nx membrane with
a thin film thermopile and a resistive thin film heater placed at the
center of the membrane. All electrical connections were covered
by an additional 0.7 mm SiO2 layer for electrical insulation and
protection. All the samples analyzed had a mass of ca. 250 ng.
Figure 1. Thermoanalytical curve of iPP and iPP/HR blends during isothermal crystallization at Tc ¼ 130 8C, by classical DSC.
Macromol. Rapid Commun. 2007, 28, 875–881
ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Wide angle X-ray scattering (WAXS) measurements were
carried out using a Philips (PW 1050 model) power diffractometer
(CuNi-filtered radiation) equipped with a rotative sample holder
device. WAXS measurements were performed on very thin film
samples rapidly moved from the melt into water at different
temperatures to reproduce the cooling rates of the process
occurring in the SFCC.
Small-angle light scattering (SALS) analysis was performed
using a Spectra Physics model 162A Argon ion laser (l ¼ 496.5 nm).
Scattering patterns were recorded on Polaroid film.
Results and Discussion
In order to cover the entire temperature range, isothermal
crystallizations from 0 to 110 8C were studied using
superfast calorimetry at a high cooling rate and isothermal
crystallizations from 120 to 140 8C were studied using
conventional differential scanning calorimetry.
Examples of isothermal crystallization curves obtained
by classical DSC for iPP and iPP/HR blends are reported in
Figure 1. From these curves, the crystallization time (the
time needed to reach the maximum value of heat evolved
during the crystallization process) as a function of
temperature can be derived. The dependence of this time
on temperature for the two systems under analysis is
reported in Figure 2. In the range of crystallization
temperatures analyzed, the dependence increased with
temperature and, for the same temperature, the values
www.mrc-journal.de 877

Figure 2. Crystallization time of iPP and iPP/HR 90/10 after quick
cooling from the melt inside the classical DSC.
of the crystallization times of the blend were always
higher than those of pure iPP. The presence of the
hydrocarbon resin lowered the iPP global crystallization
process, in agreement with previous results obtained on
this and similar systems.[23] The decrease of the crystal-
lization rate in the case of the blend can be attributed to
the diluent effect of the resin, which forms a miscible
system with iPP in the melt and after cooling in the
amorphous state, as confirmed by the detection of a single
Tg reported in previous papers.[14,18] The presence of resin
decreases the number of nuclei per volume unit, as shown
in the optical micrographs in ref.[17], and causes an
increase in the energy required to form a nucleus of
critical size and in the transport energy. All these effects
contribute negatively to the crystallization rate.
In Figure 3, an example of a thermoanalytical curve
obtained during isothermal crystallization using superfast
calorimetry is shown. The crystallization time was
Figure 3. Thermoanalytical curve for iPP during isothermal crystal-
lization at 110 8C by superfast calorimetry.
Macromol. Rapid Commun. 2007, 28, 875–881
878 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
C. Silvestre, S. Cimmino, D. Duraccio, C. Schick
Figure 4. Crystallization time of iPP and iPP/HR 90/10 film after
fast cooling from the melt inside the SFCC.
obtained as indicated in the figure (note, this time
represents the time needed to reach the maximum of
the temperature change during the crystallization pro-
cess). In Figure 4, the crystallization times as a function
of temperature for iPP and iPP/HR 90/10 obtained by
superfast calorimetry are reported. The crystallization time
should show a typical U-shaped temperature dependence
with a minimum between the melting and glass transition
temperatures where the crystallization time diverges. In
Figure 4, however, the crystallization time presents a peak
with a maximum at about 60 8C. The same behavior of iPP
is shown by the 90/10 blend, but the times are higher
because the kinetics of crystallization are always lower
than those of iPP. This result is in agreement with that
obtained by classical DSC.
The crystallization times obtained with classical DSC
and with SFCC are reported together in Figure 5. The results
show that the data obtained using the two different
procedures are well connected to each other.
Our hypothesis around the bimodal appearance of the
rate of isothermal crystallization is linked to a change in
crystal structure. The region between the melt and ca. 60 8C
represents the region where the monoclinic a form of iPP
can be formed, whereas the region between the glass
transition and 60 8C represents the region where meso-
morphic iPP can be obtained. Both kinetics show a typical
U-shaped dependence on temperature. To verify this
hypothesis, WAXS analyses were performed on iPP and
iPP/HR 90/10 cooled fast and crystallized isothermally at
10 8C and 80 8C, which should be the temperatures at
which the mesomorphic form and monoclinic a form
appear, respectively. Cooling was realized by rapidly
moving very thin samples from the melt into water at
the two different temperatures to reproduce the cooling
rates of the SFCC process. WAXS profiles of the iPP/HR
90/10 film are shown in Figure 6(a) and 6(b) respectively. It
DOI: 10.1002/marc.200600844
Isothermal Crystallization of Isotactic Poly(propylene) Studied . . .
Figure 5. Isothermal crystallization time for iPP and iPP/HR 90/10 film by SFCC and classical DSC.
is clearly evident that only iPP in the mesomorphic form is
present when the iPP/HR 90/10 film is crystallized iso-
thermally at 10 8C [Figure 6(a)]. In fact, the WAXS pattern
presents two diffuse diffraction peaks characteristic of the
mesomorphic structure. The monoclinic a form appears
when iPP/HR 90/10 film is crystallized isothermally at
80 8C [Figure 6(b)]. In fact, the characteristic peaks of the a
form are present (see in particular the peak between
18–19 8, corresponding to the (130) plane of the a form).
A crystallization curve with bimodal behavior was
found recently by Wunderlich et al.[24] for poly(butylene
terephthalate) and by Schick et al.[25] for iPP grafted with
maleic anhydride. One of the hypotheses made was a
change in the crystal structure or morphology of the
polymer, but whether the crystalline form assumed by the
polymer crystallized at different crystallization tempera-
tures was not checked.
It is also interesting to note that the crystallization for
the blend extends into the range of the blend glass
transition (about 10 8C), where most polymers do not
crystallize at all, probably indicating that the cooperative
conformational motions present are sufficient to produce
the mesomorphic form of iPP.
The results obtained by WAXS strongly support our
hypothesis: that the iPP in the iPP and iPP/HR 90/10 films
crystallized in the temperature range 0–60 8C is mainly in
the mesomorphic form, whereas in the range from 60 to
140 8C it assumes the monoclinic a form.
Taking into account that the crystalline structure of the
homogeneous nucleated particles was found to be
mesomorphic[26] and that crystallization temperatures
below about 60 8C are generally considered crystallization
Macromol. Rapid Commun. 2007, 28, 875–881
ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
temperatures for homogeneous nucleation for iPP,[27–30] it
can be hypothesized that, under the experimental condi-
tions used, from 0 to about 60 8C, iPP crystallizes by
superfast quenching from the melt, most probably in the
mesomorphic modification, by homogeneous nucleation.
Crystallization in the range 60–140 8C generates mainly
heterogeneously nucleated monoclinic crystals. However,
there are indications in the literature that the monoclinic
form can be also homogeneously nucleated.[5] It was
demonstrated, in a droplet experiment, that homogeneous
nucleation in iPP occurred below 85 8C. Galeski[6] reported
an abrupt increase in primary nucleation density in iPP at
about 80–85 8C and the interpretation was related to
homogeneous nucleation.
This result seems to be in some agreement with the
recent simulation of Muthukumar,[31] which suggests the
formation of mesomorphic pearls along the polymer chain
at intermediate stages in the nucleation process, evolving
from the baby nuclei which come from the growth of
density fluctuation. He concluded that the mechanism of
polymer crystallization, even in the first stage, was
nucleation and growth and that the crystallization of
the mesomorphic phase follows the polymer crystal-
lization theory with nucleation and growth phenomena
depending on crystallization temperature.
In order to investigate the morphology of the samples,
SALS experiments were performed. Hv SALS pattern for the
films crystallized at 80 8C with a monoclinic structure
indicated that a spherulitic-like texture was present, as a
sharp ‘‘four leaf clover’’ pattern was obtained. For the
samples crystallized at 10 8C, no discrete SALS patterns
were observed, indicating that no detectable spherulite
www.mrc-journal.de 879

Figure 6. WAXS profiles of film of iPP/HR 90/10 blend isother-
mally crystallized at Tc ¼ 10 8C (a) and Tc ¼ 80 8C (b) after fast
cooling from the melt.
superstructure developed in these films with a meso-
morphic structure.
Conclusion
The structure and the overall isothermal crystallization
kinetics of iPP and an iPP/HR 90/10 films as a function of
crystallization temperature were studied. The complete
crystallization curve ranging from Tg to Tm showed
bimodal crystallization behavior for both iPP and the
iPP/HR 90/10 film. This result was explained by consider-
ing the polymorph properties of iPP. It was in fact assumed
that the curve from Tg to about 60 8C referred mainly to the
crystallization kinetics through homogeneous nucleation
of the iPP mesomorphic phase with no spherulitic
Macromol. Rapid Commun. 2007, 28, 875–881
880 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
C. Silvestre, S. Cimmino, D. Duraccio, C. Schick
morphology, whereas the curve from about 60 8C to Tm
represented mainly the crystallization kinetic curve for the
monoclinic a form with heterogeneous nucleation and
spherulitic morphology. This hypothesis was confirmed by
the analysis of the structures obtained using wide angle
X-ray experiments and SALS patterns. The mesomorphic
phase followed the polymer crystallization theory with
nucleation and growth phenomena depending on crystal-
lization temperature.
It should also be noted that the addition of HR to iPP
caused a significant reduction in the crystallization rate of
iPP in both regions and hence the diluent effect of the
miscible resin was effective in both crystallization regions.
Acknowledgements: Financial support from Cost P12 ‘‘Structur-
ing of polymers’’ is acknowledged (Short Term Scientific Mission
for D. D.).
Received: November 30, 2006; Revised: January 20, 2007;
Accepted: January 31, 2007; DOI: 10.1002/marc.200600844
Keywords: crystallization; differential scanning calorimetry
(DSC); poly(propylene); superfast calorimeter; WAXS
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