Rheol Acta (2014) 53:519–535
DOI 10.1007/s00397-014-0775-1
ORIGINAL CONTRIBUTION
Quiescent and shear-induced crystallization
of polyprophylenes
Maziar Derakhshandeh · Antonios K. Doufas ·
Savvas G. Hatzikiriakos
Received: 5 December 2013 / Revised: 8 March 2014 / Accepted: 7 April 2014 / Published online: 31 May 2014
© Springer-Verlag Berlin Heidelberg 2014
Abstract In this paper, the effect of shear on the flow-
induced crystallization (FIC) of several polypropylenes of
various macrostructures was studied using rheometry com-
bined with polarized microscopy. Generally, an increase in
strain and strain rate or decrease of temperature is found
to decrease the thermodynamic barrier for crystal formation
and thus enhancing crystallization kinetics at temperatures
between the melting and crystallization points. Secondly,
popular models based on suspension theory which are used
to relate the degree of crystallinity to normalized rheological
functions (such as viscosity) are validated experimentally.
For this purpose, the space filling of crystals in the polarized
micrographs determined from image processing was plotted
as a function of normalized viscosity under various shear
rates. It is found that the constant(s) of various suspension
models should be dependent on the flow parameters in order
for the suspension models to describe the effect of shear on
FIC, particularly at higher shear rates.
Keywords Flow-induced crystallization · Polypropylene ·
Quiescent crystallization · Halftime crystallization
Introduction
Processes such as film blowing, film casting, fiber spinning,
calendaring, and injection molding are still used extensively
M. Derakhshandeh · S. G. Hatzikiriakos ()
Department of Chemical and Biological Engineering,
The University of British Columbia, Vancouver, BC, Canada
e-mail: savvas.hatzi@ubc.ca
A. K. Doufas
ExxonMobil Chemical Company, Baytown, TX, USA
to convert raw materials (mainly polyolefins) to final plastic
products. The raw materials used in these polymer pro-
cessing methods are often subjected to mixed shear and
extensional flow conditions, which cause the polymer to
experience flow-induced crystallization (FIC). The mechan-
ical and optical properties of the final products are strongly
dependent upon the processing method and the conditions
under which crystallization takes place (Eder et al. 1990;
McHugh and Edwards 1995; Kumaraswamy et al. 1999;
Kornfield et al. 2002; Janeschitz-Kriegl 2003; Scelsi and
Mackley 2008).
The kinetics of crystallization considerably improves
under flow at temperatures comparable to the melting peak
temperature and is related to both strain and strain rates
(Eder et al. 1998; Gelfer and Winter 1999; Kitoko et al.
2003; Swartjes et al. 2003; Stadlbauer et al. 2004; Tanner
and Qi 2005, 2009; Dai et al. 2006; Hadinata et al. 2006;
Chellamuthu et al. 2011; Tiang and Dealy 2012; White et al.
2012). Moreover, different types of flow deformation affect
FIC differently. For instance, in the case of fiber spinning
and film blowing, extensional flows account for the orienta-
tion and stretching of polymer molecules in the direction of
extension, thus enhancing the crystallization process signif-
icantly. Online fiber spinning data related to flow-induced
crystallization behavior of several polypropylenes (PPs)
have been reported (Paradkar et al. 2008; Patel et al. 2008).
Shearing also enhances the crystallization kinetics; how-
ever, since it is inherently a weaker flow compared to exten-
sional flow, larger strains are required to see the effect of
flow on crystallization (Hadinata et al. 2007; Derakhshan-
deh and Hatzikiriakos 2012). High shear rate data obtained
using a special sliding plate rheometer was reported for
poly-1-butene (Baert and Van Puyvelde 2006). At low shear
rates, the crystallization kinetics was enhanced mainly by
inducing a higher nucleation density. Further increasing in
520
the shear rate imposed oriented structures (Baert and Van
Puyvelde 2006).
There are relatively few available data in the literature
on the importance of different types of flows on crystalliza-
tion and even less data that address the effects of molecular
weight parameters on crystallization (Chellamuthu et al.
2011; Eder et al. 1998; Tanner and Qi 2005; Baert and Van
Puyvelde 2006; Tiang and Dealy 2012; White et al. 2012).
Therefore, it is an objective of this paper to examine
the role of temperature and shear flow on the crystalliza-
tion kinetics of several polypropylenes of various molecular
weights and polydispersities. In particular, the effects of
important parameters for crystallization such as strain rate,
strain, temperature, and molecular parameters are examined
under simple shear using rheometry coupled with polarized
microscopy.
An effective method of optimizing any industrial-scale
process and/or improving the quality of the final prod-
uct is by performing numerical simulations of the process.
To put this into perspective, in the film blowing process,
the locked-in stresses at the frost line (location of transi-
tion from liquid to solid) dictates the tensile strength of
the produced material (Han and Kwack 1983; Kwack and
Han 1983; Kuijk et al. 1999). Numerical simulation of this
process and its further optimization heavily depend on the
accuracy of the models, and for the process under discus-
sion, a reliable model for FIC is crucial (Doufas et al.
1999, 2000; Doufas and McHugh 2001; Doufas 2013). In
such models, the degree of crystallinity is often related to
normalized rheology functions (NRF) by various models
derived from the suspension theory. These models bene-
fit from being easy to implement into simulation; however,
they have their own limitations such as not being applicable
to higher deformation rates. Therefore, the second objec-
tive of this paper is to evaluate suspension models which
are typically used to relate the system zero-shear-rate vis-
cosity with the degree of crystallization. A light microscope
equipped with a polarizer and an analyzer is used with a
parallel-plate rheometer in order to determine the degree of
crystallization at various deformation rates. These data sub-
sequently are used to evaluate the applicability of various
suspension models in describing the degree of crystallinity
under flow. Previous methods related NRF with relative
crystallinity obtained from independent differential scan-
ning calorimetry (DSC) measurements (Acierno et al. 2003;
Boutahar et al. 1998; Lamberti et al. 2007; Pantani et al.
2001; Titomanlio et al. 1997). In the present paper, the rhe-
ological functions and degree of crystallization are obtained
simultaneously, thus avoiding possible errors from a differ-
ent thermal history experienced by the test specimens as
shown below.
In summary, shear effects on the FIC of a variety of
PPs is studied here using shear rheometry combined with
Rheol Acta (2014) 53:519–535
polarized microscopy with some of the effects studied here
have also been addressed previously by others (Coppola
et al. 2004; Hadinata et al. 2005; Jay et al. 1999; Baert et al.
2006; Acierno et al. 2003; Duplay et al. 2000; Bourgin and
Zinet 2010; Kim et al. 2005). However, in this paper, six
different PP resins exhibiting different behavior in terms of
nucleation (as observed by polarized optical microscopy)
and crystal growth rate are studied. The data provided
in this paper can be the basis for obtaining the model
parameters which can be further validated by comparison
with FIC behavior under extensional and/or mixed flows.
A comprehensive model should predict crystallization
behavior under quiescent, shear, extensional, and mixed
flow conditions at various temperatures. Moreover, as
mentioned by Duplay et al. (2000), extra care should be paid
when resins produced by different technologies are studied
and compared.
Material and methods
Six different PPs with different molecular weights and poly-
dispersities were used in this work, all provided by the
ExxonMobil Chemical Company. These resins are listed
in Table 1 along with their molecular weight characteris-
tics (molecular weight, Mw ; polydispersity index (PDI =
Mw /Mn ), melt flow rate, mass flow rate (MFR), and tac-
ticity). The molecular weights (weight average molecular
weight Mw and number average molecular weight Mn ) were
determined using High-Temperature Gel-Permeation Chro-
matography (Polymer Laboratories PL-GPC-220) equipped
with a differential refractive index detector (DRI) (Sun et al.
2001). Carbon NMR (13 C) spectroscopy was used to mea-
sure the tacticity of the studied polypropylenes in terms of
percent molar meso pentads (mmmm). 13 C NMR spectra
were acquired with a 10-mm broadband probe on a Varian
spectrometer having a 13 C frequency of at least 100 MHz.
The samples were prepared in 1,1,2,2-tetrachloroethane-d2
(TCE). Sample preparation (polymer dissolution) was per-
formed at 140 ◦ C where 0.25 g of polymer was dissolved
in an appropriate amount of solvent to give a final polymer
solution of 3 ml.
Differential scanning calorimetry
A Shimadzu DSC-60 calorimeter was used to study the
thermal behavior of PPs. Nitrogen purge was used in order
to avoid degradation of the test specimens. Melting and
crystallization peaks of polymers were obtained by using
multiple heating and cooling protocols applied to 1–2 mg
of sample directly harvested from pellets sealed in an alu-
minum pan. The exact experimental protocol is shown in
Fig. 1. Thermal and flow histories were eliminated by
Rheol Acta (2014) 53:519–535 521

Table 1 The PP resins studied

along their molecular PP resin Mw (kg/mol) PDI MFR (dg/min) % molar meso pentads (mmmm) Tc (◦ C) Tm (◦ C)
characteristics and thermal
properties PP1 182 2.7 36.0 0.950 122.0 162.8
PP2 174 1.9 24.0 0.947 108.7 148.6
PP3 230 3.1 12.0 0.954 115.0 160.5
PP4 288 3.8 5.0 0.944 124.0 164.2
PP5 366 3.3 2.0 0.956 112.0 162.1
PP6 498 3.6 0.9 0.909 113.4 161.0

heating each sample at the rate of 10 ◦ C/min from 50 to
200 ◦ C and soaking it at 200 ◦ C for 15 min. Eventually,
the temperature was decreased to 50 ◦ C at 10 ◦ C/min which
was followed by reheating to 200 ◦ C using the same rate in
order to obtain the crystallization and melting temperature
peaks, respectively. History elimination was confirmed by
obtaining a third cycle, where the crystallization and melting
peaks were found almost identical to those obtained in the
second cycle. The melting and crystallization peaks Tm and
Tc , respectively, are summarized in Table 1, and the values
represent the averages of three different samples.
The halftime of isothermal crystallization was deter-
mined at different temperatures between the determined
crystallization, Tc , and melting, Tm , DSC peaks. These were
defined in DSC thermograms as the time required for a sam-
ple to reach 50 % of its final crystallinity at the designated
crystallization temperature. The percent of crystallinity as
a function of time was calculated by integrating the area
underneath the peak of the DSC thermogram.
Since the investigated PP resins exhibit different melting
and crystallization peaks, the isothermal crystallization for
the various resins was studied at fixed values  of a normal-
ized temperature defined by T = (T − TC ) (Tm − TC ).
This enables also a consistent and fair comparison of the
DSC protocol
200
Elimination
on
Cooling
halftimes of crystallization of all resins at specific values of
T = 0.25, 0.5, and 0.75 on the same graph.
Shear rheometry
An Anton Paar rotational rheometer (MCR 502) was used
to study the shear rheology of samples. Polypropylene pel-
lets were melted at the temperature of 200 ◦ C and then were
pressed in a compression molding apparatus to produce
sheets with a thickness of about 1 mm. The shear-induced
crystallization behavior of polymers was examined in sim-
ple shear flow using the parallel-plate geometry with plates
of 25 mm in diameter. These experiments are confined to
the temperature region between the crystallization and the
melting peaks found in the DSC thermograms under the
heating and cooling modes. This temperature range is of
great importance in FIC due to the tendency of molecules to
crystallize and reorient. Since higher temperatures impede
the crystallization kinetics excessively, FIC at higher tem-
peratures is extremely time-consuming. The crystallization
behavior of resins at shear rates larger than 2 s−1 could
not be investigated considering edge failure effects on the
measured torque. Thermal and flow histories of the sam-
ples were eliminated by heating up each test specimen to
200 ◦ C (around 40 ◦ C above the melting peak tempera-
ture) for 15 min prior to cooling at the rate of 10 ◦ C/min
to the desired temperature and experimental testing. Fast
History
and accurate cooling is crucial to reach the desired crystal-

lization temperature without any temperature undercooling

terminati

Validation
that would lead into premature crystallization. The Peltier
Elimination
Temperature, T (oC)

Peak De

150 system of the rheometer was used for this study since it
Peak De

can employ higher cooling rates more precisely compared

to those of the convection oven system. The influence of
terminati

several parameters such as temperature, deformation, and

Heating

100
History

deformation rates (shear) on the crystallization kinetics of

on

the PPs were studied at shear rates up to 2 s−1 .

In parallel-plate geometry, the shear rate varies linearly
50
from the center to the edge of the plate. In this paper, the
shear rate is reported at the radial position 0.75R since the
0 20 40 60 80 100 120 140 160
difference between the true and measured viscosity assigned
Time, t (s) to the shear rate at r = 0.75R is less than 2 % as reported
Fig. 1 The DSC protocol which is used to determine the melting and by Macosko (1994). Crystallization starts at the outer edge
crystallization peaks (Tc and Tm ), respectively of the sample due to a higher shear deformation rate at this
522
location. For modeling purposes, the induction times are
usually defined at small levels of crystallinity (∼1–2 %),
and therefore the crystallization phenomenon which starts
from the outer edge has a minimal effect on the rheological
behavior captured at the induction time. When the crystal-
lization further increases, the polymer shrinks, and thus the
underlying equations used for the rheological characteriza-
tion are not applicable without modifications regardless of
the geometry used (Godara et al. 2006).
Polarized light microscopy
Polarized light microscopy (Mitutoyo microscope setup
equipped with a Lumenera LU 165 color CCD camera and
two polarizers) was used in conjunction with an Anton Paar
MCR502 in order to study the crystalline structure evolution
formed under different conditions. In a typical experiment,
the sample (disk) is placed in the space between two glass
plates of the rheometer (parallel-plate geometry of 43 mm
in diameter) and the microstructure is observed with the
microscope as a function of time. The space filling of crys-
tals in the polarized images was calculated through image
analysis as a function of time and then converted to the
degree of crystallinity by using the densities of crystal and
polymer melt (0.94 and 0.85 g/cm3 ), respectively (Natta
et al. 1955). The calculated crystallinity under quiescent
conditions at different temperatures was compared to crys-
tallinity obtained using DSC so as to validate the polarized
microscopy applicability.
As discussed above, the microscopy videos were decom-
piled to frames which were analyzed by an image process-
ing software (Matlab and ImageJ) in order to calculate the
amount of space filling. Two different image processing
methods were utilized to validate the obtained results. In the
first approach, the grayscale filter was first applied to all
extracted images to set each pixel value to a single number
that represents the brightness of the pixel. The pixel format
is typically the byte image which gives a range of possi-
ble values from 0 to 255. Frequently, zero is taken to be
black, while 255 are taken as white. Values in between 0 and
255 construct different shades of gray. Each pixel value was
normalized between 0 and 1 in Matlab in order to define
a threshold. All pixels within the microscopy images were
converted into black or white based on the specified thresh-
old, which was estimated by Matlab and further tuned by the
user. Eventually, the space filling was estimated as the ratio
of the number of white pixels to the total number of pixels
within the image. In the second approach, the area of crys-
tals was estimated by the area of circles with the same center
and radios as that of the crystals. In this method, any overlap
between the circles is considered once. Circles were drawn
manually and then processed by ImageJ software. Image
quality plays a significant role in acquiring accurate results
Rheol Acta (2014) 53:519–535
in any image processing techniques. Therefore, the errors
contributing to this technique is minimized by obtaining
clear images at a gap size of about 0.5 mm. Since the rela-
tive crystallinity and the NRF are obtained using the same
experiment, the temperature and shear deformation histories
which are imposed on the samples are identical, which is an
advantage of this experimental method.
Results and discussion
Linear viscoelasticity of the polypropylenes
The master curves of the linear viscoelastic moduli of all
PPs studied at the reference temperature of 190 ◦ C produced
by the application of the time-temperature superposition
(TTS) technique is depicted in Fig. 2a–f (Ferry 1980). For
the low molecular weight materials, the Newtonian region
(e.g., PP1, PP2) at low frequencies was reached. For the
high molecular weight materials (PP4, PP5, and PP6), stress
relaxation experiments after imposing a sudden strain were
also performed to obtain data over a wide range of frequen-
cies. This is possible by converting the relaxation modulus
to dynamic data at very low frequencies in order to deter-
mine the zero-shear viscosity (Schwarzl method) (Ferry
1980). This procedure was used just for three of the PPs
in this study, i.e., the high molecular weight resins. The
continuous lines in Fig. 2a–f represent fits of the multi-
mode Maxwell model {Gi, λi}which show that this model is
capable of representing the data very well.
Figure 3 plots the complex viscosity of all PPs as a func-
tion of frequency at the reference temperature of 190 ◦ C.
This figure is in agreement with the MFR values of the
resins listed in Table 1. The resin with the larger viscosity
has higher resistance to flow, and thus, it has a lower MFR.
Table 2 lists the activation energy for flow, Ea , using the
shift factors obtained from the construction of the master
curves depicted in Figs. 2 and 3. The Arrhenius model was
used:
  
Ea 1 1
aT = exp − − (1)
R T Tref
where Ea is the activation energy for flow, a measure of the
sensitivity of the viscoelastic properties to temperature. It
can be seen that PP5 has the highest energy of activation,
Ea .
Thermal behavior of the polymer
Figure 4a depicts a typical thermogram of one of the PPs
(PP3 in Table 1). The melting and the crystallization peak
temperatures were observed at 160.5 and 115 ◦ C, respec-
tively. As shown in Fig. 4b, the thermomechanical history
Rheol Acta (2014) 53:519–535 523

a b

d
c

e f

Fig. 2 a–f Master curves of the viscoelastic moduli of all PPs listed in Table 1 at the reference temperature of Tref = 190 ◦ C

causes a difference of 2.5 ◦ C between the first heating peak
(163.0 ◦ C) and the melting peak temperature (160.5 ◦ C).
The difference between the second and third heating peaks
is only 0.2 ◦ C, which is within experimental error. This
further indicates that the sample soaking time of 15 min
at 200 ◦ C is long enough to eliminate the thermal his-
tory (Fig. 4b). Similar comments apply to the crystalliza-
tion/cooling peaks as well as to the DSC results for all other
samples listed in Table 1.
Figure 5 plots the quiescent halftimes of crystalliza-
tion obtained from DSC thermograms as a function of the
normalized temperature, T for all PP resins. This normal-
ization of the temperature facilitates the comparison of
halftimes of crystallization for various resins as discussed
above. At very low normalized temperatures (i.e., close to
crystallization peak), the halftime of crystallization for all
polypropylenes are very small as normally expected. In this
region (T < 0.2), the halftimes of crystallization of differ-
ent resins show a small difference of 5 %, which is within
experimental error. The crystallization kinetics varies signif-
icantly between various resins as the temperature increases.
The difference is potentially attributed to differences in (i)
524
Fig. 3 The master curves of the complex viscosity of all PPs listed in
Table 1 at the reference temperature of Tref = 190 ◦ C
tacticity (see Table 1), (ii) the catalyst system, and (iii)
the nucleation density, e.g., affected by additives such as
nucleating agents.
Figure 6 depicts polarized optical microscopy (POM)
images obtained for various resins studied at the normalized
temperature of T = 0.5 under quiescent conditions. As can
be seen from Fig. 6, PP3 and PP5 exhibit similar nucleation
density (the lowest), and therefore they revealed compara-
ble kinetics under quiescent conditions (Fig. 5). PP4 has the
highest nucleation density and thus has shown the lowest
induction times in the temperature range investigated. PP1
has a higher nucleation density compared to PP2, and thus
it has shown enhanced crystallization kinetics. Since PP6
has a higher nucleation density compared to PP2, it should
possess a lower growth rate in order to reveal the same
overall crystallization kinetics as that of PP2. All resins
except PP2 were produced using a similar catalyst system,
and thus, their growth rate could be compared. It has been
reported that the Mw affects the crystal growth rate under
quiescent conditions. Specifically, the growth rate of crys-
tals decreases with increase of Mw due to less chain mobility
of the system (Wunderlich 1976). Therefore, since PP6 pos-
sesses the highest Mw among all PPs studied, it should also
possess the slowest growth rate. Since PP5 and PP3 have
similar nucleation density and since PP3 has a smaller Mw ,
Table 2 The PP resins studied along with their activation energy for
flow, Ea
PP Resin Ea (kcal/mol)
PP1 9.55
PP2 7.63
PP3 9.63
PP4 10.56
PP5 11.27
PP6 9.91
Rheol Acta (2014) 53:519–535
it exhibits slightly increased crystallization kinetics due to
its chain mobility (smaller Mw ).
Flow-induced crystallization under shear flow
Figure 7a, b demonstrates the effect of cooling rate from
T = 200 ◦ C to the test temperature of 142.4 ◦ Cor
T = 0.5 on the shear stress growth coefficient η+ = τ γ̇
as a function of time for PP1 at two different shear rates.
These tests were performed to identify the optimum cool-
ing rate that would best satisfy the conditions of isothermal
flow-induced crystallization. Cooling rates smaller than a
value of about 5 ◦ C/min allow the polymer to crystallize
non-isothermally as it takes significant time for the quench-
ing. For example, this is reflected in an earlier upturn of
the shear stress growth coefficient when the cooling rate
of 1 ◦ C/min is used at both shear rates (Fig. 7a, b). This
earlier upturns are clearly due to premature crystallization
before reaching the test temperature. Cooling rates greater
than about 10 ◦ C/min allow nearly isothermal crystalliza-
tion by minimizing premature crystallization. The results
become independent of cooling rate for values greater than
10 ◦ C/min.
To show this effect more clearly, the time required to
observe the onset of crystallization (induction time, tind ) is
defined as the time at which η+ becomes 20 % (arbitrary
value) greater than its steady-state value (Derakhshandeh
and Hatzikiriakos 2012). The induction times as functions
of cooling rates are plotted in Fig. 8 for two different shear
rates for PP1 at T = 0.5. High cooling rates (greater than
20 ◦ C/min) may also impose undercooling (undershooting
in the temperature profile due to limitations in the tem-
perature control of the rheometer in fast transient tests).
Therefore, in this study, the cooling rate used is 10 ◦ C/min
in order to minimize the effect of undercooling and, at the
same time, to eliminate the effect of premature crystalliza-
tion due to long transients, except at temperatures close to
the crystallization peak as discussed below.
The effect of temperature on flow-induced crystalliza-
tion for PP1 is demonstrated in Fig. 9. Initially, imposition
of shear flow causes the shear stress growth coefficient to
increase with time, reaching its steady-state value after a
certain time. The dashed horizontal lines in the graph show
the steady-state viscosity of crystal-free melt which can be
used as a basis to determine the induction time. The nor-
malized temperatures of 0.5 and 0.75, in combination with
the cooling rate (10 ◦ C/min), are high enough to minimize
premature crystallization during the cooling period before
shearing as well as during the initial ascending part of the
shear stress transient. However, crystallization occurs after a
certain time that causes a sudden increase of the shear stress
growth coefficient. At the lower normalized temperature
of 0.25, the shear stress growth coefficient, η+ , increases
Rheol Acta (2014) 53:519–535 525

Fig. 4 a The DSC thermogram 10

0
of resin PP3. The second PP3 TC=115oC
PP3
melting and crystallization DSC DSC
peaks were observed at 160.5
and 115 ◦ C, respectively. b The
5

Heat, Q (mW)
DSC thermogram of PP3 for

Heat, Q (mW)
three consecutive
heating/cooling cycles. Thermal 0
history elimination is
demonstrated by the small
differences obtained between First heating
-5 Tm=160.5oC Second and third peak
second and third melting peaks
heating peak
a b
-5
100 200 150 155 160 165 170 175
o o
Temperature,T ( C) Temperature,T ( C)

before reaching its steady state. The times for the onset
of crystallization and transient to reach its steady state are
comparable as shown in the graph. In addition, nucleation
that evolved during the cooling period (due to the low tem-
perature) also contributes to this deviation. As seen from
Fig. 9, the temperature has a noticeable effect on the induc-
tion time. A decrease of roughly 10 ◦ C (for example, from
T = 0.5 to 0.25) causes the onset of crystallization to
occur at times of roughly 1 order of magnitude earlier. In
general, crystallization kinetics is significantly enhanced as
temperature decreases.
The gradual increase of viscosity as the crystallization
begins can be used to determine the induction time which is
arbitrarily defined as the time at which a 20 % of increase of
the viscosity is obtained. These induction times correspond
to a small degree of crystallinity (typically 1–2 %) and if the
true viscosity is measured in parallel plate (i.e., γ̇ reported
at r = 0.75 R), the increase in torque caused by crystal-
lization does not influence the induction time measurements
10000
PP1
PP2
8000 PP3
Crystallization half time, thalf (s)
significantly. In the parallel-plate geometry, the shear defor-
mation rate varies linearly with radial position, being zero
at the center and attains its highest value at the edge. The
effect of this nonhomogeneous shearing on the nucleation
density of PP1 is shown in Fig. 10. The nucleation density
increases significantly from the center (Fig. 10a) to the edge
(Fig. 10c). Moreover, shear also induces crystal alignment
with the highest alignment and nuclei density close to the
edge of the parallel-plate geometry.
Figure 11 depicts the shear stress growth coefficient as
a function of the time for various imposed shear rates at
T = 0.5 for PP1. A larger shear rate stretches and ori-
ents molecules more effectively after a certain strain. This
activates more nuclei which is also supported by more
spherulites of smaller size in the microscopy images (Huo
et al. 2004). Therefore, a larger deformation rate decreases
the induction time for the onset of crystallization by enhanc-
ing the nucleation density (Fig. 10) and possibly crystal
growth rates as mentioned in previous studies (Duplay et al.
2000).
Figure 12 plots the shear stress growth coefficient data
of Fig. 11, this time as function of strain. Typically,
the required shear strain for the onset of crystallization
increases with increase of the applied deformation rate. In
other words, more strain is needed at higher shear rates to

PP4
PP5 initiate crystallization. In particular, at the shear rates of
6000
PP6 0.01 s−1 , a strain of 70 is required to initiate crystallization,
while at the shear rate of 0.1 s−1 , crystallization occurs after
600 strain units. This is in agreement with experimental
4000
results reported by other authors (Eder et al. 1998; D’Haese
et al. 2010). The increase of the amount of strain with the
2000 increase of shear rate for the onset of crystallization (see
Fig. 12) is a counterintuitive observation.
Figure 13 shows the effect of shear rate on the induc-
0
tion time for all PPs studied. Open symbols in Fig. 13 are
0.0 0.1 0.2 0.3 0.4 0.5 0.6
obtained from rheometry as described above, while closed
Normalized temperature, T symbols are obtained by DSC. As seen, flow enhances and
Fig. 5 The quiescent (DSC) halftimes of crystallization of all PPs as speeds up the onset of crystallization mainly at rates greater
a function of the normalized temperature, T than a certain critical value. At deformation rates smaller
526 Rheol Acta (2014) 53:519–535

Fig. 6 POM images of

investigated resins at T = 0.5.
As shown, PP4 has the highest
nucleation density among all.
PP3 and PP5 exhibit comparable
nuclei density at the studied
temperature region

than this value, the flow does not disturb the molecules region (γ̇ < γ̇critical ), the crystallization behavior is essen-
from their equilibrium configurations, and thus no effect tially similar to that of quiescent condition. Larger shear
on their crystallization behavior occurs. Therefore, over this rates (γ̇ > γ̇critical ) activate more nuclei causing a dramatic

Fig. 7 The effect of cooling

Shear stress growth coefficient, + (kPa.s)
Shear stress growth coefficient, + (kPa.s)

30 30
rate on the shear stress growth a b
coefficient η+ of PP1 at the
shear rates of a 0.005 s−1 and b
0.1 s−1 at T = 142.4 ◦ C or 10 10
T = 0.5
PP1
.
PP1 = 0.1000 s-1
. T=0.5
= 0.005 s-1
T=0.5 1oC/min
o
1oC/min 5 C/min
5oC/min 10oC/min
10oC/min 20oC/min
20oC/min 30oC/min
1 1
102 103 104 102 103 104
Time, t (s) Time, t (s)
Rheol Acta (2014) 53:519–535
Fig. 8 The effect of cooling rate on the induction time, tind , for the
onset of crystallization in startup of steady shear experiments for the
resin PP1 at T = 142.4 ◦ C or T = 0.5 for two different shear rates
reduction of the induction time. Similar observations were
reported for other polymers (Coppola et al. 2004; Paradkar
et al. 2008). Differences in the molecular parameters of the
investigated resins such as molecular weight, molecular
weight distribution, and tacticity likely contribute to differ-
ences in the induction times observed in Fig. 13. Among the
resins, PP5 and PP3 have the slowest crystallization kinetics
at small shear rates. However, flow enhances crystalliza-
tion kinetics of PP5 and causes dramatic reductions of its
induction time so that flow-induced crystallization is faster
compared to other resins. A similar induction time under a
very low deformation rate was observed between PP6 and
Fig. 9 The shear stress growth coefficient η+ of PP1 at the normalized
temperatures, at T of 0.25, 0.5, and 0.75 at the shear rate of 0.005 s−1
527
PP2; however, increasing shear rate enhances the crystal-
lization kinetics of PP6 more than that of PP2. PP2 does not
have as long-chain tail as PP6 due to its narrower molecu-
lar weight distribution (MWD) (Table 1) and thus requires
higher shear rate before significant reduction of the induc-
tion time occurs. PP6 has higher Mw and broader MWD
than that of PP2 which likely cause the induction time to
drop at a lower shear rate.
It is noted from Fig. 13 that the halftimes of crystalliza-
tion do not agree quantitatively with the induction times
from simple shear experiments at very small shear rates. The
former are greater than the latter for all resins. The half-
times of crystallization correspond to the times where 50 %
of relative crystallinity is formed. Polypropylenes studied
here have crystallinity of ∼46 %, and therefore 50 % of rel-
ative crystallinity corresponds to roughly 23 %. On the other
hand, the induction time determined from the flow experi-
ments is defined as the time at which the viscosity increases
by 20 % above its steady-state value for samples free
of crystallinity. Therefore, these two times are different,
and therefore, the halftimes of crystallization are expected
to be somehow higher than those obtained from shear
testing at very small shear rates where the effect of flow
is minimal. To see this more clearly, we consider the sus-
pension model η/ηa = (1 − a/A)−2 , where A is a shape
constant, ηa is amorphous viscosity, and α is relative crys-
tallinity. Setting the ratio η/ηa = 1.2 (induction time)
with A = 0.6 (frequently assumed), the crystallinity X is
calculated to be about 0.024 (2.4 %), which is the time
determined from shear experiments. This time is expected
to be lower than the halftime of crystallization (α =
0.50) which corresponds to roughly 23 % of crystallinity.
For the two times to be comparable, the induction time
for crystallization in shear should have been defined as the
time at which the ratio, η/ηa , becomes equal to η/ηa =
(1 − 0.5/0.6)−2 = 36, that is when the viscosity increases
to 36 times its steady-state value, instead of 1.2 times. In
spite of these qualitative differences, these two times agree
qualitatively.
In Fig. 13, two different regimes of crystallization can be
defined. At very low deformation rates, the crystallization
kinetics essentially resembles that of quiescent condition
where the shear rate does not change the induction time
(Coppola et al. 2004). The increase of deformation rate
causes chain orientation, lowers the thermodynamic barrier
for crystallization, and thus enhances the kinetics of crys-
tallization. In this region, shear rate significantly decreases
the induction time as mentioned by other authors (Coppola
et al. 2004). These two regions are more clearly defined for
PP2 and PP6 in Fig. 14 by means of two lines, namely a
horizontal where the induction time in independent of the
rate of shear and a line having a negative slope showing
the decrease of induction time with increase of shear rate.
528
Fig. 10 Crystal density observed at various radial positions in the parallel-plate geometry for PP1 at T = 0.5 and shear rate of 2 s−1 a at center
of the geometry, b at r = 0.75R, and c r = R, with crystal alignment to increase with the radial position
The intersection of these two lines defines the critical shear
rate required to start observing the effect of flow. These
critical shear rates for all resins studied are summarized in
Table 3. As mentioned by Acierno and Grizzuti (2003), the
orientation of chains under shearing (low Weissenberg num-
ber) is sufficient to enhance the crystallization phenomenon
by inducing a higher nucleation rate compared to quies-
cent conditions (Godara et al. 2006; Devaux et al. 2004;
Koscher and Fulchiron 2002). Large deformation rates (i.e.,
large Weissenberg numbers) stretch chains in the direction
of flow, changing the mechanism of crystallization from
spherulitic to rodlike nucleation which further facilitates the
kinetics of crystallization. POM images in our case sug-
gest spherulitic crystallization at low Weissenberg numbers
(typically of the order of 1).
It was hypothesized earlier that dormant nuclei exist
within polymer matrix. These precursors are activated by
imposing undercooling and/or applying deformation rates
(Janeschitz-Kriegl and Ratajski 2005; Janeschitz-Kriegl
et al. 2003). Higher deformation rates and higher degree of
undercooling activate more dormant nuclei. It was assumed
and supported by experimental data that at very high defor-
mation, the nucleus density saturates, and no more nuclei
Fig. 11 The shear stress growth coefficient η+ of PP1 at shear rates
ranging from 0.005 to 0.1 s−1 at 152.6 ◦ C or T = 0.75
Rheol Acta (2014) 53:519–535
are formed (Janeschitz-Kriegl et al. 2003). These behav-
iors were also supported by various works done previously
(D’Haese et al. 2010, 2011). PP4 has the highest nucleation
density among all of the investigated resins (i.e., closer to
the saturated state), and thus a higher critical shear rate is
needed to enhance the quiescent crystallization kinetics as
seen in Table 3. As previously mentioned, applying flow
usually causes the polymer to induce a higher nuclei density.
PP2 uses a different catalyst for its production and thus can-
not be compared with the other resins. The different catalyst
system for production can introduce a different growth rate
and kinetics since it imposes different molecular structures
(Wunderlich 1976). PP5 and PP3 have very similar tacticity
and PDI. PP5 has a higher molecular weight in compari-
son with PP3 and thus shows lower critical shear rate for
flow-enhanced crystallization. Although PP6 has the high-
est molecular weight and PDI, it exhibits a higher critical
shear rate than PP5, PP3, and PP1 due to its lower tacticity.
Tacticity seems to play a major role in FIC.
Figure 15 depicts the effect of shear rate on the
induction time at various normalized temperatures for PP1.
DSC results for T = 0.75 could not be obtained since
the heat of crystallization which is released at this high
temperature is not detectable by the DSC apparatus used.
The induction time increases by 1 order of magnitude for a
change of roughly of 10 ◦ C. On the same time, an increase
of shear rate from 0 to 0.5 decreases the induction time by a
factor of 2.
Crystallization kinetics using optical microscopy
In addition to rheometry, polarized light microscopy was
used in conjunction with the Anton Paar MCR-502 parallel-
plate rheometer in order to study crystallization kinetics
of PPs under shear. The microscope is equipped with a
polarizer and an analyzer which are always crossed dur-
ing experimental testing. Therefore, only crystals which are
present within the polymer matrix can be observed due to
their birefringence (Wang and Dou 2008). Similar heat-
ing and cooling protocols as described in the experimental
section were used so as to eliminate flow and thermal
history.
Rheol Acta (2014) 53:519–535
Fig. 12 The shear stress growth
coefficient η+ of PP1 at shear
rates from 0.005 to 0.1 s−1 at
152.6 ◦ C or T = 0.75
Quiescent crystallization of resins at desired tempera-
tures was investigated by both optical microscopy and DSC
in order to experimentally validate the accuracy of this
setup. As a first step, the relative crystallinity of PP as
a function of time was calculated by integrating the area
underneath the peak of the DSC thermogram and then nor-
malizing it by the total area. In a second step, the degree
of space filling of crystals in the polarized images was
calculated from optical microscopy by using the image pro-
cessing techniques described above. The degree of space
filling was converted to degree of crystallization using
Fig. 13 The effect of shear rate on the induction time for the onset of
crystallinity for all PPs at T = 0.5. The closed symbols correspond to
the halftime quiescent crystallization obtained from DSC
529
the density of crystals (0.94 g/cm3 ) and that of the melt
(0.85 g/cm3 ) (Natta et al. 1955). The relative crystallinity
obtained from the optical microscopy was compared to that
obtained from DSC to check for accuracy of the optical
microscopic technique.
Table 4 shows typical microscopy images before and
after image processing with methods 1 and 2 described in
the experimental section. A satisfactory agreement between
the DSC and image processing results was found, as can
Fig. 14 The effect of shear rate on the induction time for the onset
of crystallinity for PP6 and PP2 at T = 0.5. A critical shear
rate is observed at which transition from quiescent to flow-induced
crystallization occurs
530
Table 3 The critical shear rate above which the effect of flow on
crystallization becomes evident at T = 0.5
Resin Critical shear rate (s−1 )
PP1 0.02
PP2 0.31
PP3 0.03
PP4 0.10
PP5 0.02
PP6 0.06
be seen from the comparisons in Fig. 16a. The differences
are small and can be attributed to experimental errors origi-
nating from a slightly different thermal history in DSC and
rheometer as well from errors in the resolution of the image
processing technique. Samples used in DSC are relatively
small (1–2 mg) sealed in an aluminum pan, and thus, the
crystallization heat released can be carried out of the sys-
tem by convection effectively. However, in the rheometer,
the polymer is sandwiched in between two quartz plates of
43 mm in diameter with the upper plate having a thickness
of 6.4 mm. In the microscopy setup, the heat of crystal-
lization cannot be convected out rapidly. This can impede
crystal growth rate in the POM measurements and con-
tributes to the lower degree of crystallinity as also shown
Rheol Acta (2014) 53:519–535
is essential in order to capture the true crystallization behav-
ior of resins. Previous works typically measured the relative
crystallinity from DSC and then relate it with rheological
measurements (Acierno et al. 2003; Boutahar et al. 1998;
Lamberti et al. 2007; Pantani et al. 2001; Titomanlio et al.
1997). As depicted in Fig. 17, the data at very low shear rate
(γ̇ < 0.5 s −1 ) shows comparable crystallization behavior.
Increasing the shear rates alters the crystal-melt interaction
and thus causes the normalized viscosity to show upturns at
lower degrees of space fillings (crystallizations).
Viscosity-crystallinity suspension modeling
Different models based on the suspension theory were used
to model the crystallization behavior of the PPs. These mod-
els were studied before using the data generated from the
coupling of the degree of crystallinity obtained by DSC and
normalized rheological function obtained by the rotational
rheometer (Lamberti et al. 2007). The first model examined
was the one proposed by Graham (1981) for concentrated
suspension of rigid interacting spheres. Graham proposed
an additional term into Eq. 2 which modifies the behav-
ior for concentrated suspension of rigid interacting spheres
(Graham 1981).
η
= 1 + 52 ∅ + 
ηa
9 
4 1
 

ϕ(1+0.5ϕ)(1+ϕ) 2

in Fig. 16a. Therefore, the differences observed in Fig. 16a 3 ∅  (2)
are clearly caused by the different thermal histories in each ϕ=2 1 − ∅max 3 ∅
∅max
case. Heat transfer calculations explained in Appendix A
demonstrate that the temperature rises in the POM samples ∅max is the maximum volume fraction occupied by the
in the range from 0.2 to 1.9 ◦ C at the crystallization tem- spheres. For the same system, Mooney (1951) proposed
peratures of 131.4 to 121.7 to 131.4 ◦ C. Using the Avrami
equation (see details in Appendix B) and the temperature
rise calculated from the heat transfer equations, the relative
crystallinity as a function of time was calculated for the case
of POM results, indicating excellent agreement in Fig. 16b.
This clearly explains the origin of the differences observed
in Fig. 16a.
The effect of shear on flow-induced crystallization was
also examined by the optical microscopy technique. Differ-
ent shear rates in the range of 0.0 to 2 s−1 were chosen to
investigate the effect of shear. The captured images were
undergone with image processing to obtain the degree of
space filling and relate this to degree of crystallization as
discussed above. The obtained shear stress growth coeffi-
cient (η+ ) from the rheometry was normalized by using
the value of steady-state viscosity that corresponds to a
crystal-free melt at the corresponding rate and tempera-
ture, indicated as ηa . The normalized viscosity as a function
of space filling is plotted in Fig. 17. Both space filling Fig. 15 The induction time for the onset of crystallinity as a function
of shear rate for PP1 at different normalized temperatures. The closed
images and normalized viscosity were obtained from the symbols correspond to halftime quiescent crystallization obtained from
same experimental test (identical temperature history). This DSC
Rheol Acta (2014) 53:519–535 531

Table 4 Optical microscopy images before and after image processing

Material Before image processing After image processing - method 1 After image processing - method 2

PP5
Morphology structure of PP5 Morphology structure of PP5 Morphology structure of PP5
after 685s at 138.8 ◦ C after 685s at 138.8 ◦ C after 685s at 138.8 ◦ C

Morphology structure of PP5 Morphology structure of PP5 Morphology structure of PP5

after 985s at 138.8 ◦ C after 985s at 138.8 ◦ C after 985s at 138.8 ◦ C

the following equation, while Frankel and Acrivos (1967) Richmond 1980; Kitano et al. 1981; Kataoka et al. 1978).
suggested Eq. 4: The latter is useful for the concentrated suspension of par-
  ticles of any shape with A being a shape coefficient (for
η 5 ∅
= exp ×  (3) instance, A = 0.68 for smooth spheres):
ηa 2 1−∅  − 5 ×∅max
∅max η 
= 1 − ∅ ∅max
2
(5)
 1/ ηa
∅ 3
η 9 ∅max η   −2
= × (4) = 1−∅A (6)
ηa 8  1/ ηa
1 − ∅ ∅max
3
To compare the capabilities of these equations, we have
The last two formulae which were studied in this work have set the adjustable parameters in such a way that all models
a similar form and were proposed by Ball and Richmond result in the same induction time at low shear rates. This
in 1980 (Eq. 5) and Kitano et al. in 1981 (Eq. 6) (Ball and induction time corresponds to the space filling required to

Fig. 16 The relative

crystallinity of PP5 as a function
of time obtained from DSC and
optical microscopy. a Raw data
without temperature correction
showing the effect of different
thermal histories in each test. b
The Avrami prediction of PP5
under microscopy setup
532
Fig. 17 Normalized viscosity as a function of space filling (crys-
tallinity) for PP5
obtain normalized viscosity ratio, η/ηa of 1.2. The param-
eters which were used in the models are listed in Table 5.
The formulation of Frankel and Acrivos (Eq. 4) predicts an
NRF of zero instead of one at zero degree of space filling
as shown in Fig. 17. Equations 3 and 5 exhibit the strongest
NRF dependence on the degree of space filling. Equations 2
and 6 show a similar trend and seem to predict the relation
between space filling and NRF better. Experimental data
under a higher shear rate of 0.5 and 2 s−1 could not be
predicted by using the same model constants; therefore, A
constant in Eq. 6 was reduced by a factor of 50 to mimic
the behavior properly (see dash line curve in Fig. 17). The
suspension models are applicable at low deformation rates,
since there is only a dependence of the viscosity on the
degree of filling, but there is no explicit dependence on the
deformation rate (Newtonian-like models). A proper con-
stitutive equation for suspensions, however, should include
both the degree of filling (crystallinity) and the deforma-
tion rate dependencies. For relatively small shear rates (e.g.,
≤0.1 s−1 in our case), the regime of viscosity of the New-
tonian plateau at the testing temperature is reached, and the
NRF vs. degree of space filling experimental curves more
Table 5 Models’ parameter used to predict the results in Fig. 17
Equation Parameter
Eq. 6,a A 0.2
Eq. 6,b A 0.004
Eq. 5 ∅max
Eq. 4 ∅max
Eq. 3 ∅max
Eq. 2 ∅max
Rheol Acta (2014) 53:519–535
or less collapses as shown in Fig. 17. However, above a crit-
ical shear rate (e.g., 0.5 s−1 ), we likely deviate from the
Newtonian plateau, and the experimental NRF vs. degree of
filling curves deviate from the ones corresponding to the low
deformation conditions (≤0.1 s−1 ). Therefore, at the high
shear rate conditions (i.e., ≥0.5 s−1 ), the true NRF which is
affected by the shear rate and deviates from the low shear
rate curve, irrespective of the suspension model used.
The dependency of suspension model parameter on the
shear rate indicates that the viscosity of the semicrys-
talline system is a function of both crystallinity and
shear rate. Therefore, we suggest that a proper suspen-
sion/rheology model for semicrystalline systems should be a
frame-invariant constitutive equation with viscoelastic basis
and both crystallinity and deformation rate dependences
(Doufas et al. 2000; Doufas 2013; Tanner and Qi 2005,
2009).
Conclusions
Flow-induced crystallization of several PP samples under a
simple shear was studied in this work in order to elucidate
the effects of flow deformation relative to quiescent con-
ditions. In simple shear, there is a critical strain required
for the onset of crystallization at given shear rates and tem-
peratures. In shear experiments, the critical strain needed
for a polymer to crystallize decreases with decreasing rate.
Temperature was found to be an important variable in crys-
tallization as expected, and a change of temperature by a few
degrees changes the induction times for crystallization by 1
order of magnitude. The suspension models are applicable
only to low deformation rates, since there is only a depen-
dence of the viscosity on the degree of filling. A proper
model should have a viscoelastic constitutive equation basis
in order to be able to capture the crystallization behavior
well (e.g., the two-phase constitutive/microstructural model
for FIC of Doufas et al. (2000) and Doufas (2013)).
Acknowledgments Financial assistance from the Natural Sciences
and Engineering Research Council (NSERC) of Canada, the scholar-
ship program of the University of British Columbia (4YF), and the
ExxonMobil Chemical are gratefully acknowledged.
Value Appendix A
The coupled energy equations for the system shown in
Fig. 18 where the polymer in the space between two quartz
0.2313
plates is crystallized are developed. This is necessary to cal-
0.4233
culate the increase of temperature in the optical microscopy
0.2882
results due to the heat of crystallization which is accumu-
0.5
lated in the sample. This has an effect on the degree of
Rheol Acta (2014) 53:519–535 533

Fig. 18 The schematic of system used in this study

crystallinity which needs to be quantified in order to explain The heat transfer equations for the polymer and the quartz
the differences between the POM and DSC results with plate located on top of the polymer (Fig. 18) are as follows:
reference to Fig. 16a.     
ρpolymer Cp,polymer ∂T 1 ∂
∂t = r ∂r kpolymer r ∂T ∂
∂r + ∂z kpolymer
∂T
∂z + q̇
Crystal formation releases heat within the polymer at a  
ρquartz Cp,quartz ∂T 1 ∂ ∂T ∂ ∂T
∂t = r ∂r kquartz r ∂r + ∂z kquartz ∂z
rate of
(8)

q̇ = Hf (100% crystalline polymer) × ρ × ∅˙ (7)

where Hf (100% crystalline polymer) is the heat of melting if
the polymer was 100 % crystalline, ρ is the density of crys-
tals, and ∅˙ is the rate of volume fraction increase of crystals.
The equations are solved using POLYFLOW with the
following boundary conditions. A convection boundary con-
dition is imposed on the plate in contact with nitrogen gas
which is purged into the oven chamber of the rheometer as
the heating/cooling gas. The heat transfer coefficient used
in these calculations was h = 100 W/(m2 •K). The quartz
plate underneath the polymer imposes an adiabatic bound-
ary condition at the lower side of the polymer. Continuity

Fig. 19 The temperature rise at r/R = 0.75 and z/h = 0.25 in

a polymer sample that crystallizes at different temperatures. The tem-
perature increases of 0.2 to 1.9 ◦ C at the crystallization temperatures
of 131.4 to 121.7 ◦ C, respectively, explain adequately the differences Fig. 20 Fit of the Arrhenius equation to the Avrami rate parameter k
in Fig. 16a using n = 2
534
of T and heat rate at the polymer/quartz interface completes
the required BC.s.
After solving the system of Eq. 8, the temperature ele-
vation within the polymer sample can be obtained as a
function of T . The temperature rise as a function of time at
r = 0.75R and z = 0.25 mm is shown in Fig. 19. The
temperature rise in the polymer matrix decreased as the tem-
perature is increased. At higher temperatures, the kinetics
of crystallization slows down, and thus less heat is released
per unit of time. This essentially explains the larger differ-
ences between OM and DSC results depicted in Fig. 16a at
the lower temperatures.
Appendix B
The Avrami equation is often used to predict the isother-
mal crystallization behavior under quiescent condition. This
equation can be written as follows:
 n
X Xf = 1 − e−kt
(9)
where X is the degree of crystallinity, Xf is the total crys-
tallinity at the end of primary crystallization process, n is
the Avrami index with a value of 2 for the resin studied,
and k is the Avrami rate parameter. The Avrami parameter k
contains the temperature dependence of the nucleation and
crystal growth processes, while the exponent n depends on
the geometry and dimensionality of the growth as well as on
the nature of the nucleation process. The Avrami equation
best predicts the behavior in primary growth region of crys-
tals which corresponds to a relative crystallinity in between
30 and 70 %. The Avrami index determined experimentally
varied in the range of 1.9–2.5, and therefore, the theoretical
value of 2 (1.9–2.7) was chosen for the investigated tem-
peratures (120–135 ◦ C). The Arrhenius Eq. 10 is used in
this study to represent the dependency of the Avrami rate
parameter on temperature. The Arrhenius equation is then
used in combination with the Avrami equation to predict the
behavior of the sample in the microscopy setup.
     
k (T ) k (To ) = exp Ea R 1 T − 1 To (10)
The value of the Avrami rate parameter obtained using
the temperature history in Fig. 19 along with the Arrhe-
nius equation is used in the Avrami equation (Fig. 20). The
prediction of the Avrami model is shown in Fig. 16b and
compared with the experimental data from the microscopy
setup. The agreement was found to be excellent which
shows that the difference in Fig. 16a is related to different
thermal histories during crystallization.
Rheol Acta (2014) 53:519–535
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