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Chemical engineering aspects of tire curing simulation

Article  in  KGK rubberpoint · June 2007

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 KONSTRUKTION UND SIMULATION
CONSTRUCTION AND SIMULATION

Tire curing • Mathematical

model • Thermal diffusivity of compos-
Chemical Engineering Aspects
of Tire Curing Simulation
ites • Effective thermal diffusivity •
Specific heat
Mathematical models of tire deforma-
tion, rubber curing and plastic shaping
incorporate physical properties of used
materials. A model of heat transport in
a cured tire requires the thermal diffu-
sivity, the thermal conductivity, the
specific heat, the reaction heat and the
density of each material in the tire. Nowadays almost every research as well as model also has to take into account the fact
Physical data have to reflect the tem- development of industrial products is im- that the properties of particular regions of
perature and pressure changes during proved by physical and mathematical mod- the cured body and of the mould are differ-
the process to be representative and ac- els (PMM). Industrial production processes ent and dependent on temperature.
curate. The effect of temperature on can not be controlled by means of comput- For a certain region, denoted by the index i,
these quantities is significant. There- ers without corresponding PMM’s going on. with given values of heat transfer and ki-
fore advanced laboratory methods
The first step in modelling is the description netic properties, the model contains the lo-
have been developed by which these
physical quantities were determined at of the processes by adequate physical mod- cal enthalpy balance:
similar conditions than those in a curing els and then drawing a set of corresponding
st %Hri sCi
press. Computer simulation of curing is
simplified if a new quantity “effective
thermal diffusivity” is applied.
Physikalische Daten von Gum-
mimaterialien zur Simulation
der Vulkanisation von Reifen
Reifen • Vulkanisation • mathema-
tisches Modell • thermische Diffusivi-
tät von Kompositen • effektive ther-
mische Diffusivität • spezifische Wär-
mekapazität
Mathematische Modelle der Reifende-
formation, Reifenvulkanisierung und
Formung von Plasten enthalten physi-
kalische Eigenschaften der angewende-
ten Materialien. Um den Wärmetrans-
port in einem vulkanisierenden Reifen
zu modellieren benötigt man: die ther-
mische Diffusivität, die Wärmeleitfä-
higkeit, die spezifische Wärmekapazität,
die Reaktionswärme und die Dichte von
jedem Material im Reifen. Die physika-
lischen Daten müssen die Temperatur-
und Druckveränderung im Prozess wi-
derspiegeln um repräsentativ und ge-
nau zu sein. Die
Temperaturabhängigkeit dieser Größen
ist ausgeprägt.deutlich. Deshalb wurde
eine verbesserte Methode entwickelt,
durch die diese physikalischen Größen
denen in einer Vulkanisationspresse
entsprechen.
Die Computersimulation einer Vulkani-
sation kann durch Einführung einer
neuen Größe nämlich der „effektiven
thermischen Diffusivität“ vereinfacht
werden.
308 KGK · Juni 2007
equations. These equations contain many
parameters which describe physical proper-
ties of the processed materials under con-
sideration. However, these parameters have
to be determined experimentally.If the val-
ues of the parameters are known, the solu-
tion of the mathematical models by numer-
ical methods is usually not a difficult task.
This contribution is focused on the thermal
transport properties of rubber, plastics and
composite materials which are necessary
for mathematical modellization. At the
present time the main problem of computer
simulations of industrial processes is to
know how representative values of the
physical quantities can be obtained.
The physical data necessary for a model of
tire curing are published earlier by the au-
thor [1, 2]. It was shown that the influence
of the rubber properties and those of rub-
berised cords upon the results of the curing
simulation is rather significant.
Model of tire curing
The model for each rubber compound and
each used material consists of
– enthalpy balance
– kinetics of curing
– initial and boundary conditions
The curing process is a transient one and has
to be described by a set of partial differen-
tial equations.
Temperature distribution fields in the tire
compound and in the press mould at cho-
sen times can be calculated from this model.
These fields enable the computation of the
curing degree fields. The parts of the tire
and of the press mould having various phys-
ical properties are also called regions. The
model contains a series of sets of equations
describing the processes in the regions. The
 ai‹2t  (1)
sU Si cpi sU
and the kinetic equation related to the for-
mation of sulfidic and polysulfidic bonds in
the network during the curing process
sCi
 k(cin) (1  Ci )ni (2)
sU
where the rate constant depends on tem-
perature by the following relation
 E ¬
knci  exp žžžS1i  1i ­­­ (3)
Ÿ RT ®
For safety processing rubber compounds
have different incubation times also de-
pending on temperature. This plot is de-
fined as:
 E ¬
Ui  exp žžžS2i  2i ­­­ (4)
Ÿ RT ®
Processes taking place in the tire during the
curing are described by i sets of the above
given equations. The attained degree of
crosslinking is often expressed by the cur-
ing degree X instead of the concentration of.
crosslinks Ci.
Authors
M. Bafrnec, J. Haydary, Bratislava
(Slovakia)
Corresponding author
Milan Bafrnec
Institute of Chemical and Environ-
mental Engineering
Slovak University of Technology
Radlinského 9
812 37 Bratislava, Slovakia
E-Mail: milan.bafrnec@stuba.sk
The notation of symbols of the above given
1 1 Thermal diffusivity
quantities is as follows X=C/Cvi – curing de-
of rubber
gree at time W, C – instantaneous molar vol- compound
ume concentration of crosslinks, C vi – final
molar volume concentration of crosslinks,
ai – thermal diffusivity. 'Hri – reaction en-
thalpy of the rubber compound curing, Ui –
density, Cpi – specific heat, k(cin) – rate con-
stant of the reaction of n-th order, ni – reac-
tion order, t – temperature, T – temperature
in K, E1i and E2i -activation energies and
S1i, S2i – constants of kinetic equations.
Initial conditions in each of particular mate-
rials forming i regions are given by temper-
ature fields at the time

W=0 t=f i(x,y,z) (5)

2 2 Thermal diffusivity
Since the only solid surfaces are in contact of the rubberised
in the tire and in the mould, boundary con- polyamide cord in
different spatial
ditions are expressed on the surfaces of
directions, 70 %
contacting regions by the relations rubber and 30 %
ki(’t)i=ki+1(’t)i+1 (6) mass polyamide
cord
where ki is the heat conductivity of the i-th
region.
Besides the parameters of the kinetic equa-
tions (2, 3 and 4), the model contains the
thermal transport properties of each used
materials – the thermal diffusivity, the ther-
mal conductivity and specific heat, as well
as the density and the reaction heat. All
these properties are temperature depend-
3 3 Specific heat of
ent. rubber compound
An example of the model solution is in the
pictures for a tire cured by steam and hot
water in the bladder, and steam in the form.
They can be seen at the end of this contribu-
tion. The tire consists of 15 different rubber
compounds and rubberised cords, e.g. re-
gions. All heat transport and kinetic proper-
ties were determined as the functions of
temperature by laboratory measurement of
material samples.

Thermal transport properties

In the following figures there is shown how
much the thermal properties of materials
depend on temperature. The thermal diffu- 4 4 Density of rubber
sivity of rubber compounds and composites compound
was measured by the method of the linear
increase of surface temperature (LIST) [1].
The error of this method is less than 7 %. The
values of the thermal diffusivity of rubber
and plastic materials can be measured by
this method in the temperature interval -30
to 300 °C (Fig. 1).
Textile and steel cords coated by rubber are
orthotropic composite materials and their
thermal conductivity is a tensor quantity.
Therefore their values of thermal diffusivity
are dependent on direction as well. There is

KGK · Juni 2007 309

 KONSTRUKTION UND SIMULATION
CONSTRUCTION AND SIMULATION
5 5 Thermal conductiv-
6 6 Effect of thermal
surprisingly a great difference between the
values of thermal diffusivity parallel to the
cord threads and perpendicular to the
threads or to the cord layers (Fig. 2). The
data in the picture above were once again
measured by the method of LIST [2].
The specific heat was measured by differen-
tial scanning calorimetry (Fig. 3). The error is
less than 3 %. Liquid buoyancy method was
used to measure the density of rubber com-
pounds and composites (Fig. 4). This error is
less than 1 %.
In order to increase the accuracy of these
methods, it was decided to use samples of big
volume. The volume as much as 500 cm3 al-
lows to determine representative values of
properties of coarse composite materials as
well. The values of thermal conductivity (Fig.5)
were computed, from measured values of the
thermal diffusivity, the specific heat and the
density according to the formula
k = a U cp
The effect of different values of thermal dif-
fusivity on the temperature computed from
the model of transient heat transfer is
shown in Fig. 6. Great errors of computed
temperature in the core of a 20 mm thick
310 KGK · Juni 2007
ity of rubber com-
pound
diffusivity on com-
puted temperature
in core of 20 mm
thick plate of cured
rubber, values of
thermal diffusivity
at temperatures
1. – a20 °C = 1.44.10-7
m2/s;
2. – a100 °C= 1.22.10-7
m2/s;
3. – a180 °C= 1.09.10-7
m2/s;
4. – a = f(t)
slab occur if the constant values of thermal
diffusivity are used instead of temperature
dependent values.
The values of temperature in the prior graph
were used in next picture to show the influ-
ence of incorrect values of thermal diffusiv-
ity on curing degree of a rubber compound
(Fig. 7).
The effect of the thermal diffusivity on the
computed values of the curing degree is
quite large. The solution of the mathemati-
cal model of curing only gives reliable data
if the thermal diffusivity is considered as
the function of temperature.
Curing heat and effective thermal
diffusivity
The mathematical model of curing of rubber
and rubber composites contains the reac-
tion enthalpy. This quantity consists of the
heat released by chemical reactions in rub-
ber, latent heats of phase and structure
transitions (evaporation, melting) and the
bonding heat of rubber to the cord surface.
The sum of these heats is curing heat. The
typical values of curing heat are about
–25 J/ g for rubber compound and –60 J/g for
rubberised textile cord. It is another quan-
tity whose value has to be determined ex-
perimentally by using calorimetry.
The number of experimentally determined
quantities in equation (1) can be decreased
substantially by a different definition of
specific heat. The curing heat in the en-
thalpy balance can be included into specific
heat. This way a new quantity Cpeff, called
the effective specific heat, can be meas-
ured by differential scanning calorimetry in
the same way as the specific heat. Natural-
ly the sample is non cured rubber, and it is
heated and cured in a calorimeter. In the
Fig. 8 the specific heat of cured rubber is
compared with the effective specific heat
of the non cured rubber. The difference in
the shape of curves is mostly caused by the
influence of the curing heat.
Modification of the mathematical
model
The enthalpy balance of the mathematical
model equation (1) can be transformed
into [3]
st
 aieff ‹2t (7)
sU
if effective thermal diffusivity is defined by
the formula
k
aieff  (8)
S Cpeff
It is possible to measure this quantity in the
same way as the thermal diffusivity, by
method of LIST.
Advantages of the model
modification
The form of equation (7) allows separate so-
lution of the temperature and curing de-
gree models. The mathematical solution of
the enthalpy balance is simplified and com-
mercial FEM software can be used. The error
of the computed temperature fields is de-
creased. Instead of the experimental errors
of four quantities there is the only the error
of the effective thermal diffusivity.
The costs of the necessary experimental
data are reduced also.
Conclusion
Mathematical models of processes contain
parameters, which define particular cases.
These parameters are physical properties of
materials and have to be determined exper-
imentally. The appropriate experimental
methods were developed in our laboratory
for the determination of the properties of
rubber, plastics and composite materials.
The thermal diffusivity and the specific heat
depend strongly on temperature. Thus the
use of constant values can cause serious er-
7 7 Effect of thermal
rors. The thermal diffusivity of orthotropic
diffusivity on com-
composites depends on the direction of the puted curing de-
heat transfer and this ought to be consid- gree in core of
ered in models. 20 mm thick plate
It is useful to simplify the model of rubber of cured rubber,
curing by definition of the effective ther- values of thermal
mal diffusivity. The consequence is that diffusivity at tem-
peratures
the source term of the enthalpy balance is
1. – a20 °C = 1.44.10-7
eliminated and the heat transfer and cur- m2/s;
ing models can be solved successively. This 2. – a100 °C= 1.22.10-7
makes the solution of both models quick m2/s;
and easy. An additional essential advan- 3. – a180 °C= 1.09.10-7
tage of the use of the effective thermal m2/s;
diffusivity is the costs reduction of experi- 4. – a = f(t)
mental data since less experimental data
is needed.
8 8 Comparison of the
Literature specific heat of
[1] M. Bafrnec, M. Juma, J. Toman, J. Jurþiová, cured rubber com-
A. Kuþma, Journal of Plastics, Rubber and Com- posite and the
posites 28 (1999) 482. “effective “ specific
[2] M. Juma, M. Bafrnec, Journal of Reinforced Plas- heat of non cured
tics and Composites 19 (2000) 1024. rubber composite
[3] M. Bafrnec, M. Juma, J. Toman, R. Fujerík, Chem.
Pap. 99 (2005) 20.

The authors
Milan Bafrnec and Juma Haydary are mem-
bers of the Institute of Chemical and Envi-
ronmental Engineering, Slovak University
of Technology, Bratislava, Slovakia

KGK · Juni 2007 311

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