1

Numerical Simulation with Comsol Multiphysics of Crystallization

Kinetics of Semi-Crystalline Polymer during Cooling: Application to
Injection Moulding Process.


N. Brahmia
*, 1
, P. Bourgin
1
, M. Boutaous
*, 1
, D. Garcia
2
1
Laboratoire de Recherche Pluridisciplinaire en Plasturgie LR2P . Site de plasturgie de lINSA de Lyon
BP 807-01108 Bellignat.
2
Ple Europen de Plasturgie. 2, rue P.M. Curie -01100 Bellignat.
nadia.brahmia@insa-lyon.fr

Abstract: Thermoplastic polymers are
frequently used in several industries. They
represent the most important group of polymeric
materials. During injection moulding process,
the cooling phase including solidification is often
the most significant part of a manufacturing
cycle. For semicrystalline polymers, where
different crystal structures appear, the thermo
mechanical histories play a very important role
in the estimation of the final parts properties.
During the cooling stage, the behavior of these
polymers is very difficult to model because of
the complication of the crystallization process
which is coupled to heat transfer and material
properties change. The aim of this work is the
study of the coupling phenomena between the
crystallization and the thermal kinetics in the
polymer injection moulding process, by using
Comsol multiphysics software.

Keywords: Injection moulding, semicrystalline
polymer, crystallization kinetics, thermal
properties, heat transfer

1. Introduction

Injection moulding is one of the most widely
used processes in the polymer processing
industry. The computer simulation of the process
is an essential tool to predict the final properties
of the part. For this calculation the knowledge of
rheological and thermomechanical material
characteristics is of great importance. To
understand the crystallization process of
semicrystalline thermoplastics, during the
injection moulding process, it is necessary to
take into account the kinetics of crystallization
and to consider the temperature and
crystallization dependency of all the
thermophysical properties of the material. All
these variables parameters make the simulation
more complicated. Generally, the simulations of
injection process, consider isothermal or isobar
case. In this work we have used Comsol
multiphysics software to study the coupling
between heat transfer and crystallization kinetics
during the solidification of a semicrystalline
polymer, such as polypropylene. First, the
polymer studied was precisely characterized and
the crystallization kinetics was defined, using
isothermal and no-isothermal DSC experiments.
The results are compared to some data find in the
literature, and then the influence of several
parameters are computed and commented.


2. Experimental section

In this study, the polymer used is an injection
moulding grade of a semicrystalline polymer
which is polypropylene. Before starting
simulation, several characterizations of the
material such as, viscosity, thermal conductivity,
heat capacity and specific volume must be
determined.

2.1 Thermal properties

To study heat transfer during crystallization
of a polymer, it is necessary to take into account
these thermal properties as a function of
temperature and relative crystallinity (). This
parameter, as shown by Fulchiron [1], is defined
by:

=
X
X
c

(1)
Where X
c
is the crystallinity depending on time,
temperature and pressure and X

, the
crystallinity at the end of the solidification.
The heat capacity is described using simple
mixing rule between the solid state and the liquid
state values weighted by the relative crystallinity
:

) ( ) 1 ( ) ( ) , ( T C T C T C
a p sc p p
+ =
(2)
Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris
2
Where C
psc
and C
pa
are the heat capacity of the
solid state and the liquid state, respectively.
The specific heat C
p
in each phase of the polymer
was obtained by using calorimetric techniques
(DSC), as shown in figure (1).
For the polymer used in this work, Le Bot [2]
proposed a linear temperature dependency versus
temperature for C
psc
and C
pa:

1774.2 + T 3.4656 ) ( = T C
a p
(3)
1329.2 + T 8.3619 ) ( = T C
c ps
(4)
With T in degree C and C
p
in J.kg
-1
.K
-1
.

1000
2000
3000
4000
5000
6000
7000
8000
20 40 60 80 100 120 140 160 180 200 220 240
Temperature (C)
C
p

(
J
/
k
g
.
K
)

Figure 1: Evolution of heat capacity versus
temperature.

The thermal conductivity is also described by a
mixing rule between solid state and liquid state
as follows:
) ( ) ( ) , ( T T T
a sc
+ =
(5)

0,14
0,16
0,18
0,2
0,22
0,24
20 40 60 80 100 120 140 160 180 200 220 240 260
Temperature (C)
T
h
e
r
m
a
l

c
o
n
d
u
c
t
i
v
i
t
y

(
W
/
m

K
)

Figure 2. Thermal conductivity versus temperature.

The thermal conductivity was measured by an
apparatus based on the transient line source
method, which is ideally suited to polymers
because measurements can be made quickly,
before the onset of thermal degradation and no
sample preparation is required [3].
Figure (2) shows that the thermal conductivity of
amorphous and semicrystalline phase, are
temperature dependent and a linear fitting gives:
0.1868 + T 10 ) . / (
-4
= K m W
sc

(6)
0.1394 + T 10 ) . / (
-4
= K m W
a

(7)
Where T in C and in W.m
-1
.K
-1


The density is the inverse of specific volume
which is deduced from PVT diagrams: figure (3).
It was evaluated as a weighted mean value of the
pure amorphous and crystalline densities
according to:
) ( ) 1 ( ) ( ) , , ( T V T V P T V
a sc
+ =
(8)
Where
a
V
is the specific volume of the
amorphous sate of the material and V
sc
is the
specific volume of the solid state.
The PVT experimental results were obtained
using a piston-type dilatometer (GNOMIX

).
A linear fit for specific volume for each phase is
obtained as:
2108 . 1 10 3
3
+ =

T V
a
(9)
1.1055 + T 10 2.6
3
=
c s
V
(10)
Where T in C and V in m
3
.kg
-1

1
1,05
1,1
1,15
1,2
1,25
1,3
1,35
1,4
1,45
1,5
50 100 150 200 250
Temperature (C)
V
s
p
(
c
m

/
g
)
P = 40MP
P = 80MP
P = 120MP
P = 160MP

Figure3: PVT diagram of PP.

2.2 Crystallization Kinetic

Crystallization is the process whereby an
ordered structure is produced from a disordered
phase, usually a melt or solution. It represents a
mix between nucleation and growth. When a
semicrystalline polymer melt is cooled down into
its crystallization temperature range,
crystallization starts around discrete points called
nuclei, and the crystal grow around nuclei to
form what is referred to as spherulites. Once
Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris
3
all the spherulites meet their neighbors, the
crystallization process is complete.

The Avrami equation [4] has been widely used to
describe polymer crystallization kinetics under
isothermal conditions in the form:
) ( exp 1 ) (
n
t k t =
(11)
Where n is the Avrami index, k is the Avrami
isothermal crystallization rate constant.
For non isothermal, isokinetic conditions, and
assuming that the number of activated nuclei is
constant, Nakamura & al [5] developed the
following equation from Avrami theory [4]:
) 12 ( ) ( exp 1 ) (
0
n
t
dt T K t
(
(

|
|

\
|
=

Where K (T) is the non-isothermal crystallization

rate constant.
[ ]
|
|
|

\
|
= =
2
1
1
1
1
) 2 ( ln ) ( ) (
t
T k T K
n
n
(13)
Where
2
1
t is the crystallization half time.
|
|
|

\
|
2
1
1
t
indicates the overall rate of isothermal
crystallization. By assuming that the number of
nucleation sites is independent of temperature
and all sites are activated at the same time,
Hoffman & al [6] developed the following
expression to describe the overall rate of
crystallization as a function of temperature:
) 14 ( exp
) (
exp
1 1
*
0
2
1
2
1
|
|

\
|

|
|

\
|

|
|
|

\
|
=
|
|
|

\
|

T T
K
T T R
U
t t
g


Where T is the crystallization temperature, and
0 2
1
1
|
|
|

\
|
t
is a factor that includes all the terms which
are independent of temperature. R is the
universal gas constant, U
*
is the activation
energy of the transport of crystallizing units
across the phase boundary. T

is the temperature
under which such as transport ceases. K
g
is the
spherulite growth rate, T T T
f
= is the super
cooling. According to Hoffman & al [6] the
parameter U
*

and

T

can be assigned
universal values 6284 J/mol.K and T
g
-30K
respectively. T
g
is the glass transition
temperature of the material.
Differentiation of equation (12) leads to
differential form of Nakamura crystallization
kinetics, which is more useful in modeling:
[ ] ) 15 ( )) 1 ( ln ) 1 ( ) (
1
n
n
T K n
t

=

To determine K(T), different DSC measurements

of isothermal and no isothermal crystallization
were carried out, following a measurement
protocol used previously by Koscher [7,8] and
Juo [9] and. By fitting the experimental results
using equations (13) and (14), the parameters
which permitted to determine K (T), were
defined.

3. Mathematical modeling

Our aim is the analysis of a cooling of plate
of semicrystalline polymer like in the cooling
phase of injection moulding process. The system
is composed of a plate of polymer between two
blocks of metal. The thickness of each block is
of 30 mm, and of the plate is of 5mm. The width
of the system is of about 50 mm (Figure 4).


Figure 4: Model Geometry

The general energy equation has been used to
describe the heat transfer in the system:

) 16 ( ) , ( ) , ( ) , ( Q
y
T
T
y t
T
T C T
p
+
|
|

\
|

Where Q is a term source defined by:
t
H T Q

=

) , (
(17)
H is the total enthalpy released during
crystallization process.
The crystallization kinetics is given by
Nakamura equation as follows:
n
n
T K n
t
1
)) 1 ln( ( ) 1 ( ) (

=

(18)
The Nakamura constant K (T) as proposed by
Koscher [7, 8] is given by:
Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris
4
) 19 (
) (
exp .
) (
exp
) (
3
4
) (
*
0
3
1
0
|
|

\
|

|
|

\
|

\
|
=

T T T
K
T T R
U
G T N T K
f
g

The polymer tested by Koscher [7, 8] is an
injection grade of isotactic polypropylene (Eltex
HV 252). The values of different parameters in
K(T), are listed as follows:
) 1 . 15 ) ( 156 . 0 ( exp ) (
0
+ = T T T N
f
(20)
G
0
=
2
10 83 . 2 , K
g
=
5
10 5 . 5 (K
2
), U
*

= 6284
J/mol.K, T
f
=

210C, T

= -30C, H =9010
3

J/kg and n =3.
The material properties are defined by the
general equations: (2), (5) and (8). For
amorphous and semicrystalline states the
functions are listed in table 1:

C
pa
(, T) 2124 10 . 3 + T
C
p sc
(, T) 1451 68 . 10 + T

a (, T) 189 . 0 10 25 . 6
5
+

T

sc
(, T)
31 . 0 10 96 . 4
4
+

T

a
(, T)

) 10 773 . 6 138 . 1 ( 1
4
T

+


sc
(, T) ) 10 225 . 4 077 . 1 ( 1
4
T

+


Table 1: Material properties of PP Eltex HV225

4. Results and discussion

4.1 Numerical validation of the model

The objective of this section, is to ensure that
Comsol multiphysics, solves correctly the
problem, without any numerical errors. To do,
we have opted to compare the results to those
find in the literature. Due to the lake of data
obtained in similar systems, the phenomenon
was simplified. We have assumed that the
system is cooled at constant cooling rate as in
differential scanning calorimeter (DSC). The
temperature is homogenously distributed in the
polymer, and decreases linearly:
t V T T
ref
=
0
, where T
0
represent the initial
temperature of the system and V
ref
is the cooling
rate value. The Nakamura crystallization kinetics
was then solved using diffusion equation in
general module of Comsol multiphysics
software, and also by Matlab software using a
finite differences scheme to discretize the
equations.

0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
90 100 110 120 130 140 150
Temperature (C)
R
e
l
a
t
i
v
e

c
r
y
s
t
a
l
l
i
n
i
t
y
Simulation _Comsol
Simulation_Matlab

Figure 5: Evolution of relative crystallinity versus
temperature: Comparison between Comsol
multiphysics and Matlab results for constant cooling
rate (20C/min).

For the same time step, the evolution of relative
crystallinity was calculated for a cooling rate of
20C/min. The result shows no difference
between the two calculations and this had
permitted us to validate our model numerically.

4.2. Comparison with experimental results:

The second validation of the model is made
by comparison with experimental results from
literature [8]. The system which was simplified
before, as a simple case of DSC, was studied for
constant and variable temperatures. The relative
crystallinity was calculated for several constant
values of cooling rates and temperatures.
Comparison between our simulations results,
Koscher & al [8] experimental results and their
own calculations were carried out as shown in
figure (6) and (7).

For constant cooling rate, our results were more
representative of the experimental results,
compared to those calculated in the literature.
This simulation permitted to improve the
calculation of crystallization kinetics. In the
figure (6), we can see that the Comsol
simulations follow with a good agreement the
experimental results.

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris
5

Figure 6: Comparison at constant cooling rate of
relative crystallinity, between Comsol multiphysics
results, Koscher measurements and Koscher
calculations [8]


Figure 7: Comparison of relative crystallinity for
isothermal crystallization, between Comsol
multiphysics results, experimental measurements, and
Koscher calculations [8]

4.3 Simulation of effective cooling of the
polymer plate: coupling of the heat and
the crystallization equations

In this section, we consider the system
presented in figure (4). Some simplifications are
assumed compared to the reel conditions in
injection moulding process.
- At initial time, the temperature of all the system
(mould and polymer) is homogeneous T (t =0) =
T
0
.
- The cooling boundary conditions are imposed
at the interface metal/polymer. Due to the plate
dimensions, the heat transfer occurs only by
conduction in one dimensional direction. The
contact between the polymer and the mould is
assumed to be perfect, without any thermal
contact resistance.
- In order to control the thermal kinetics in the
polymer, we have assumed a linear decrease of
the temperature at the interface metal/polymer as
follows:
t V T T
Cooling
=
0

Where, V
cooling
represents the cooling rate.

Figure (8) shows the temperature evolution in
the plate during the cooling process, at several
locations. At the middle of the plate (at x= 0),
due to the polymer thermal inertia, the
temperature diminution begins after 60 sec. The
variation which occurs between (725 and 895)
sec corresponds to the crystallization of polymer.
It is characterized by a plateau that appear at
147C, and which corresponds to the release of
latent heat of crystallization. After 920 sec the
polymer is entirely solidified. The temperature
evolution in the solid phase tends to an
asymptotic form (the system tends to be
thermally homogeneous).


Figure 8: Temperature evolution at different positions
in the polymer plate, (V
cooling
= 6C/min)

Figure (9) presents the evolution of relative
crystallinity as function of time at different
locations in the plate. We notice that the polymer
in the skin layer crystallizes more quickly then in
the core layer. The total crystallization time is
about 180 sec.

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris
6
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
300 400 500 600 700 800 900 1000
Time (s)
R
e
l
a
t
i
v
e

C
r
y
s
t
l
l
i
n
i
t
y
x = 0
x = 2 mm
x = 3.5 mm
x = 4.8 mm

Figure 9: Evolution of relative crystallinity at
different position of the plate, for V
cooling
= 6C/min.

4.3.1 Effect of the cooling rate

In order to study the effect of the cooling rate
on the material properties, several simulations
with different boundary conditions are made.
The effect of the thermal kinetics on the
crystallization rate can be observed on the figure
(10). As expected, we observe that the decrease
in initial temperature leads to the acceleration of
the crystallization and conversely.

10
30
50
70
90
110
130
150
170
190
210
0 100 200 300 400 500 600 700 800 900
Time (s)
T
e
m
p
e
r
a
t
u
r
e

(

C
)
Vcooling = 12C/min
V cooling= 30C/min

Figure 10: Evolution of temperature at core polymer
for two different cooling rates

The cooling time is reduced of about (242 sec)
when we increase the V
Cooling
of about 18C/min.

Figure (11) shows the evolution of relative
crystallinity at the polymer core for different
cooling rates. It shows that the crystallization is
shifted to the lower temperatures when the
cooling rate is more important. A difference of
10 C between the corresponding temperatures
of the half-time transformation is observed, for
two different thermal kinetics: V
Cooling
= 12
C/min and V
Cooling
= 30C/min.

-0,1
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
70 80 90 100 110 120 130 140
Temperature (C)
R
e
l
a
t
i
v
e

C
r
y
s
t
a
l
l
i
n
i
t
y
Vcooling = 12C/min
Vcooling = 30C/min

Figure 11: Effect of cooling rate on crystallization at
polymer core layer.

4.3.2 Effect of initial temperature

To explore the polymer thermal history, we have
studied the effect of the initial temperature in the
material behavior, figure (12).

0
20
40
60
80
100
120
140
160
180
200
220
0 100 200 300 400 500
Time (s)
T
e
m
p
e
r
a
t
u
r
e

(

C
)
T0 = 180C
T0 = 190C
T0 = 200C
T0 = 208 C

Figure 12: Effect of initial temperature on
temperature profile at polymer core.

Its clear from the evolution of temperature
profile in the polymer core, that initial
temperature affects drastically the cooling
kinetics. When T
0
increases, the crystallization
begin with a delay, but the rate of cooling and
the temperature of crystallization doesnt
changes.

Figure (13) shows, the evolution of relative
crystallinity at the interface (mould/polymer) and
at polymer core.
Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris
7
-0,1
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
60 70 80 90 100 110 120 130
Temperature (C)
R
e
l
a
t
i
v
e

C
r
y
s
t
a
l
l
i
n
i
t
y
T0 = 180C, x = 0
T0 = 208C, x = 0
T0 = 180C, x = 4.5mm
T0 = 208C, x = 4.5mm

Figure 13: Effect of initial temperature on relative
crystallinity at polymer core layer for V
cooling
=
30C/min.

We note that crystallization begins
approximately at the same temperature at the
interface mould/polymer and also at the polymer
core, but it continues on more important ranges
of temperatures at the interfaces. Indeed, at the
polymer core, crystallization plateau slow down
considerably the cooling, so, the temperature
changes less quickly, whereas crystallization
continues. At the interface, temperatures
decrease quickly, and the crystallization takes a
large range of temperatures.

5. Conclusion

Comsol multiphysics software was used to
simulate the cooling of a polymer as in the
injection moulding process of a semicrystalline
polymer. To simplify the injection mould
configuration, we have considered a one-
dimensional heat transfer in a system of
polypropylene plate, initially at melt
temperature, cooled between two metallic
blocks. To take into account crystallization
process of the material, Nakamura differential
equation was coupled to the equations system.
Simulations permitted us to determine profile
temperature and relative crystallinity evolution at
different positions of the system. The good
agreement between Matlab calculations and
Comsol multiphysics simulations, in a simplified
case, permitted us to validate our model. The
study of the effect of different parameters such
as the initial temperature of the system and the
cooling rate, on the crystallization was also
carried out. In spite of simplifyied Nakamura
crystallization model, relative crystallinity had
been well represented. The difficulties of
numerical simulations, with the coupling
between the heat transfer equation and
crystallization equation, are easily solved and
interesting results and comparisons are obtained.
The next objective will be to use a more
developed crystallization kinetics model in a 3D
simulation of the heat transfer in the injection
moulding process.
.
6. References

1. R. Fulchiron, E. Koscher, G. Poutot, D.
Delaunay, G. Rgnier, Analysis of Pressure
Effect on the Crystallization Kinetics of
Polypropylene: Dilatometric Measurements and
Thermal Gradient Modelling, J. Macromol. Sci,
Phys., Vol. (3-4), pp 297-314 (2001).
2. P. Le Bot, Comportement Thermique des
Semi-Cristallins Injects: Application la
Prdiction des Retraits, thse de doctorat, Epun
de Nantes, 1998.
3. H. LOBO, C. Cohen, Measurement of
Thermal Conductivity of Polymer, Polymer
Engineering and Science, Vol.30, pp 65-70, N2
(1990).
4. M. Avrami, Granulation, Phase Change and
Microstructure: Kinetics of Phase Change,
Journal of Chemistry and Physics, Vol. 9, pp177-
184 (1941).
5. K. Nakamura, T. Watanabe, Some Aspects of
Non-Isothermal Crystallization of Polymers: I.
Relationship between Crystallization
Temperature, Crystallinity, and Cooling
Conditions, Journal of applied Polymer, Vol. 26,
pp 1077-1091 (1972).
6. J.D. Hoffman, G. T. Davis and J.I Lauritzen,
Crystalline and Non-Crystalline Solids, Treatise
on Solids, J. B. Hannay, Plenum., New York
(1976).
7. E. Koscher, R. Fulchiron, Influence of Shear
on Polypropylene Crystallization: Morphology:
Development and Kinetics, Polymer, Vol.43, pp
6931-6942 (2002).
8. E. Koscher, Effets du Cisaillements sur la
Cristallisation du Polypropylne : Aspects
Cintiques et Morphologiques, thse de doctorat,
universit Claude Bernard Lyon 1, 2002.
9. J. Juo, Numerical Simulation of Stress-
Induced Crystallization of Injection Molded
Semicrystalline Thermoplastics, PHD Degree,
Faculty of New Jersey Institute of Technology,
(2001).

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris