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Abstract
During thermoset composite materials processing, the chemical reaction is highly exothermic and because of the low thermal conductivity
of the material, significant temperature and state of cure gradients can be generated in thick parts. This creates non-uniform stresses that
provoke defects. We propose to control the transformation by monitoring the temperature of the mold walls. A general inverse analysis based
on the conjugate gradient method of minimization associated to the adjoint equations is used. After having detailed the method, we propose
two examples. The first one presents an optimal cycle to obtain uniform conversion at the end of the curing of an epoxy/glass-fiber composite.
The second example is concerned with the control of the temperature variations during the curing of a polyester/glass-fiber composite. The
method is experimentally validated and proves to be very powerful and flexible.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: A. Thermosetting resin; E. Cure; E. Heat treatment
1. Introduction
Composites are more and more used in structural
applications and often reach thickness of the order of one
centimeter and this even for large series applications where
for productivity reasons the duration of the cycles becomes
relatively short. The composite materials are insulating,
and since the heat released during the chemical reaction of
curing is in the heart of the piece, the evacuation of the
heat generated is difficult. This provokes large temperature
and degree of conversion gradients. The quality of the part
is altered by the internal stresses that can provoke warpage
and in some cases cracks. The shrinkage of organic resins
reaches 7% during curing, even if thermoplastic additives
compensate partially at the end of curing [1,2]. If the
surfaces of the piece come unstuck from the mold wall
during gelation, the aspect of the surface is damaged. If
one has imperatives of surface aspect, it is therefore
necessary to control the development of shrinkage during
curing. In any case, one may try to master either the space
and time distribution of the temperature, either of the
conversion distribution, or the distribution of the shrinkage
* Corresponding author. Tel.: 33-2-4068-3137; fax: 33-2-4068-3141.
E-mail address: jean-luc.bailleul@polytech.univ-nantes.fr (J.-L.
Bailleul).
1359-835X/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S1359-835X(03)00141-6
696
Nomenclature
a
ad
b
dH
DH
f
g
l
m
r
Cp
d
F
G
J
K
L
state of cure
desired state of cure
conjugate factor
residual energy
total enthalpy of the transformation (J/g)
value of the criterion
penalization factor
thermal conductivity (W/(m2 K))
distance of descent
density (kg/m3)
specific heat (J/(g K))
descent direction
function product of KG
kinetic function of a
deviation criterion
kinetic function of T
thickness of the piece (m)
2. Cure modeling
We consider a mold filled of raw composite, after the
filling phase. The piece is of uniform thickness and its size is
such that it can be considered as a plate. The walls of the
mold are heated and cooled, but the performance of the
temperature control system is such that the heating and
cooling rates are lower than a given limit. This will be
integrated like a constraint in the optimization process. The
temperature of the mold walls will be supposed uniform on
all their surface. We will consider that the variations of
temperature along the length and the width are negligible in
comparison to the thickness. As a consequence, the problem
will be considered as unidirectional across the thickness x:
The temperature and conversion field obey the energy and
kinetic equations coupled through the heat source due to the
curing reaction, and the thermal properties that depend on
the temperature and the state of cure.
L
Q
R
t
T
U
U
x
X
Subscript
normal
0
space coordinate equal to zero
f
fiber or final state
i
lower
n
iteration index
r
resin
s
upper
t
x
x
t
>
>
>
>
>
a
>
>
FT;a
>
>
t
>
>
<
initialcondition:
>
>
>
Tx;0T0 tandax;0a0 t
>
>
>
>
>
boundaryconditions:
>
>
>
>
>
T T0;t2Ut
T TL;t2Ut
>
>
x02
xL2
l
:
Rs t
Ri t
x 0
x L
1
The signification of the parameters is given in the
nomenclature. On the boundaries x0 and xL; we
suppose the existence of thermal contact resistances Rs t
and Ri t: The boundary conditions at x0 and xL are
completed by the mold temperature Ut which is imposed
in time. The goal of our optimization method is the
determination of the mold wall temperature during the
whole process.
3. Optimization method
The inverse Lagrangian method [8] is based on the
elaboration of a criterion. We try to determine a state of cure
as uniform as possible at the end of the cycle for which the
temperature does not exceed the boundary limit beyond
which degradation starts. We use an optimization method
which is detailed in Appendixes A and B. We thus define the
following criterion to be minimized:
22
JU kaU 2 ad k21 gkU 2 Uk
with
tf L
kf k21
f 2 dxdt
kf k22
tf
f dt
dn t 27J n t bn dn21 t
697
and:
8
tf L
>
>
7J n 7J n dxdt
>
>
>
0
0
n
< b t L
f
7J n21 7J n21 dxdt
>
>
0
0
>
>
>
: 1
b 0
t
0 0
L tf
T
a
T
2 rXm DH
2
rC p
l
Q1 dtdx
x
t
t
x
0 0
5
where Q1 and Q2 are Lagrange multipliers associated to T
and a; respectively. The increment of the Lagrangian is
defined by:
dLa; T; U; Q1 ; Q2
L
L
L
dT
dU
da
a
T
U
Q 1
F
>
>
Q
r
l
W
>
>
t
x
x
T 2
>
>
>
>
>
>
>
Cp T
l T
>
>
Q1
8
r
>
<
T t
T x
>
>
Cp T
>
Q 1 Q 2
F
Q
>
>
W
Q1 rXDH 1
Q2 r
>
>
t
t
>
>
>
>
>
>
l T Q 1
>
:
2a 2 ad
a x x
with the boundaries conditions:
Q
Q 0; t
Q
Q L; t
2 l 1 xL 1
2l : 1 x0 1
Rs t
Ri t
x
x
Moreover, when T and a satisfy the direct system, i.e. the
integral terms equal to zero in the Lagrangian expression
698
(5), we have:
dLa; T; U; Q1 ; Q2
L
dU 7JUdU
U
so
L
7JU
U
The derivative of the Lagrangian versus U provides the
gradient of the criterion, which is used to calculate dn t
from Eq. (4).
We are now concerned with the determination of the
descent depth m (Appendix B). For U and d fixed, the
scalar m is determined by the solution of the optimization
problem:
minimize JU mdn fm
with m . 0
10
We have:
22
fm kax; t; U m dn 2 ad k21 gkU m dn 2 Uk
11
15
tf L
tf
dndt
2m
a 2 ad da dxdt g U 2 U
0
12
which can be written as:
fm A 2Bm Cm2
13
dT
l
l
T
l
da dT
x
x
x
a
T
x
da
rDHX
14
t
da
F
F
dT
da
t
a
T
with the boundary conditions:
8
dT 2dn
dT
l
l
T
>
>
>
< Rs l x a da T dT x ;t;x 0
> dT 2dn
dT
l
l
T
>
>
;t;x L
l
da dT
:2
Ri
x
a
T
x
4. Demonstration examples
In order to check more surely the validity of the
calculations we have used an experimental method.
4.1. Example 1. Partial uniform curing at the end
of the processing cycle
The objective is to obtain a uniform predefined
distribution of curing at the end of the process. This is
necessary to measure the thermal conductivity la; T of a
sample as a function of the state of cure a: In order to use
classical methods to measure thermal conductivity such as a
guarded heat plate or a function estimation it is easier with a
uniform cure. For the guarded heat plate method, if a is not
uniform we can not know for what value of a the results
correspond. For function estimation, it is very difficult to
identify simultaneously the temperature and state of cure
dependence of the thermal conductivity. It would be an
estimation method for two functions what is very difficult.
The progression of the reaction must reach the required
value at the end of the partial curing process with a curing
rate equal to zero to prevent the continuation of the reaction
after the end of the cycles as illustrated by Fig. 2. The
measure of the thermal conductivity will correspond to a
fixed and not time dependant state of cure. The evolution
curves 1 and 2 illustrating the state of cure evolution at are
considered correct because they provide a degree of curing
with a plateau between t1 and tf ; unlike evolution curve 3
which keeps on rising beyond tf :
To reach a curing rate equal to zero at the end of the
cycle, the ultimate progression stage must remain constant
at the ad value on the interval t1 ; tf : In this example, we use
699
Table 1
Parameters of the kinetic function K for the epoxy resin
where Cp0 is the specific heat of the raw resin and Cp1 is
the specific heat of the cured resin. By measurement, we
obtain the specific heat in J/g K, with T in Celsius:
Cp0 T 1:584 3:259 1023 T
^0:06 J=g K
17
before Tg 135 8C :
Cp1 T 1:213 4:338 1023 T
^0:1 J=g K
after Tg :
Cp1 T 1:944 1:378 1023 T
^0:05 J=g K
l lr a; T
1 vf lf T 1 2 vf lr a; T
1 2 vf lf T 1 vf lr a; T
Value
Tref (K)
kref (s-1)
A
423
6.988 1023
17.631
T
20
KT kref exp 2A ref 2 1
T
Cp a; T Cp0 Ta Cp1 T1 2 a
Parameter
18
G n a
kp
X
a k ak
21
k0
Value
a0
a1
a2
a3
a4
a5
a6
a7
0.042
5.078
28.502
2265.238
727.932
2961.274
627.499
2162.547
raw composite :
19
cured composite :
700
Fig. 5. Evolution of temperature in the heart of the sample at 50% curing for
a 10 mm part.
axi ; tf 1 2
dHi
Xi DH
22
a_ Kp 1 2 aR
dR
2fKd I
dt
dI
2Kd I
dt
where,
23
24
25
701
Table 3
Physical properties of polyester-glass fiber composite
Properties
Resin
Fiber
Composite
Density (kg/m3)
Specific heat (J/kg K)
Thermal conductivity (W/m K)
1100
1680
0.168
2560
670
1
1567
1152
0.13
Table 4
Kinetic parameters of the polyester resin
Fig. 7. Descriptive diagram of the operating mode.
E
Kd Ad exp 2 d
RT
26
Ep
a m
Kp Ap0 exp 2 0 1 2
af
RT
27
28
Parameter
Value
f
af
Ad
Ap0
Ed J=mol
Ep0 J=mol
It0
Rt0
Hr J=g
m
0.1
1.0
5.55 1016
0.38 1010
1.41 105
4.27 104
5.208 1023
0
244
4
702
Value
Tref (K)
kref (s21)
A
361.5
6.192 1023
29.887
Parameter
Value
0 # a< 0:1
a0
a1
a2
a3
a4
a5
a6
0.0546
31.627
2431.148
3015.48
211,399.6
21,690.4
216,248.8
a0
a1
a2
a3
a4
a5
0.646
6.862
243.252
96.90
2104.198
45.373
a0
a1
a2
a3
2.116
26.107
5.777
21.782
0:8 # a
a0
a1
a2
a3
4.632
214.787
15.729
25.575
703
Fig. 13. Comparison of the curing rate given by the mechanistic model
(Eqs. (23)(27)) and by the phenomenological model (Eq. (28)) for a series
of constant temperatures presented in Ref. [3].
5. Conclusion
Fig. 14. Initial and optimized representation of the mold wall temperature.
704
T
a
A1
rCp a; T
la; T
rDH r
x
t
x
t
a
WhTFa; T
t
with
hT
tind
0
T
exp 2B ref 2 1 dt 2 tref
Tt
Wx 0
if x , 0
Wx 1
if x # 0
T0; x T0 x
dUt
# Vmax
dt
A3
Tx; t # Tmax
ax; tf ad
The Lagrangian L associated to the minimization
problem is introduced by:
La;T;U;Q1 ;Q2
L tf a
2WhTFa;T Q2 dtdx
JU
0 0 t
L t f
T
T
a
2 rDH r
Q1 dtdx
rCp a;T 2
la;T
t x
x
t
0 0
A4
A5
D2
0 , t , tf
0 , t , tf
f 2 x; tdtdx
T
Q
la; T
x 1
dt
L tf
la; T
T Q 1
dtdx
x x
A6
with
tf
2
JU kaU 2 ad k2 gkU 2 Uk
Vmin #
D2
ad x; t and Ut
are given on the intervals 0; tf and
0; L; and g . 0: ad x; t is the state of cure that we want to
reach. We are searching a curing cycle Ut which
minimizes the criterion:
kf k2
Umin # Ut # Umax
0,x,L
a0; x a0 x 0 , x , L
T
Tt; 0 2 Ut
la; T
Rs
x x0
T
Tt; L 2 Ut
la; T
Ri
x xL
L tf
L tf
T Q1
dtdx
la; T
x x
tf T0; t 2 Ut
Q1 0; t
Rs
0
TL; t 2 Ut
Q1 L; t dt
Ri
0
A7
A2
Then, the Lagrangian expression in which Ut appears
explicitly becomes:
La; T; U; Q1 ; Q2
JU
L tf a
0
I1
da
a
2 WhTFa; T Q2 dtdx
L tf
0
la; T
T Q1
dtdx
x x
tf T0; t 2 Ut
Rs
Q1 0; t
TL; t 2 Ut
Q1 L; t dt
Ri
A8
1 L tf a 1 da
a
2
2 WFa 1 da; T
1!0 1 0
t
t
0
L tf da
WFa; T Q2 dtdx lim1!0
t
0
0
Fa 1 da; T 2 Fa; T
2W
Q2 dtdx
1
A15
lim
L tf
T
r a
2 rDH
rCp a; T
Q1 dtdx
t
t
0 0
A9
L
L
L
dT
dU
da
a
T
U
A10
L
da
a
J
I
I
I
I
1 2 3 4 da
a
a
a
a
a
daQ2 t0f dx 2
L t f Q
2
da dtdx
0
0 t
Q2 x; tf 0
; [ 0; L;
J
1
2
da lim ka 1da 2 ad k2 gkUa 2 Uk
1!0 1
a
L tf Q
I 1
F
da
2 2 2W
Q2 da dtdx
a
t
a
0
0
A13
2rCp
T
a
rDH r X
Q1 dtdx:
t
t
L tf C 2C T
pa
p
r da
lim
2 rDH X
r
Q1 dtdx
1!0 0 0
1
t
t
A20
A19
ka 1da 2 ad k2
ka 2 ad k2 21a 2 ad da 12 :kdak2
A18
it comes finally:
A12
A17
L t f da
Q2 dtdx:
0
0 t
2
2 ka 2 ad k2 2 gkU 2 Uk
A16
A11
F
da Qda2
a
I
dL
705
A14
By writing:
Cpa Cp 1
Cp
da Qda2
a
A21
706
We choose Q1 so that
Q1 x; tf 0
; [ 0; L
and we use a procedure similar to the one used for the case
of I1 :
L tf C T
I 2
Q
p
Q1 rDH r X 1 da dtdx
da
r
a
a t
t
0
0
A22
The fourth term of (A11) is the derivative of I3 versus a:
It is obtained by a procedure analogous to the one used for J:
We obtain:
L tf l T Q
I 3
1
da dtdx
da
A23
a
0 a x x
0
L tf
C p T
L
F
dT
Q2 r
Q
2W
T
T
T t 1
0
0
C p Q 1
l T Q 1
2r
t
T x x
Q1
l
2
dT dtdx
x
x
A28
2
;t
[
0;
t
:
f
x xL
Ri
I 4
da 0
a
L
dT 0
T
A24
Q
2 2 2W
Q r
t
a 2
a t 1
0
0
rDH r X
Q 1
l T Q 1
da dtdx
t
a x x
L
da 0
a
;da
A26
C p T
Q 2
F
Q
W
Q1 rDH r X 1
Q2 r
t
a
a t
t
l T Q 1
2a 2 ad
a x x
on td ; tf
Cp T
l T Q1
Q
T t 1 T x x
A31
with
2:l
Q1
Q1 0;t
Q1
Q1 L;t
;t[0;t
l
;t[0;tf
x0
f
xL
x
x
Rs
Ri
A27
tf
I4
dU 2
U
0
Q1 0; t
Q L; t
1
dUdt
Rs
Ri
A33
with
(
Q
W
Q2
r
l 1
x
t
T
x
A25
A30
;dT
Q1 x; tf 0
;x [ 0; L
Q2 x; tf 0
;x [ 0; L
tf
L
Q1 0; t
Q1 L; t
dU
2gU 2 U 2
dUdt
Rs
Ri
U
0
A34
We can now express dL from Eq. (A10). Due to the
choice of the adjoint variables Q1 and Q2 which verify Eq.
(7), we have:
L
da 0
a
;da and
L
dT 0
T
;dT;
so:
dL
L
2 Q1 0; t Q1 L; t
dU 2gU 2 U
Rs
Ri
U
A35
707
a
WFa; T
t
By substituting Eq. (A41) into (A40), we obtain:
Tm
T
2 Cp
r Cpm
t
t
Tm
T
lm
l
2
x
x
x
x
a m
a
2
rDH r
A42
t
t
a m
a
2
Wm Fm 2 WF
t
t
dn t 27J n t bn d n21 t
da lim
A37
and
8 1
>
b 0
>
>
>
>
L tf
<
7J n 7J n dtdx
0
0
n
>
>
b L tf
>
>
>
:
7J n21 7J n21 dtdx
0
a 2 am
lim dam
m!0
m
A43
dT lim
m!0
T 2 Tm
lim dTm
m!0
m
;n . 1
Cpm Cp
lm l
Cp
Cp
dTm Q2 da2m ; dTm2
dam
a
T
A44
l
l
dT Q2 da2m ; dTm2
da
a m T m
Let us write:
Appendix B. Determination of the descent depth m
A40
a m
a
2
t
t
am
a
2
t
t
E Wm Fm 2 WF
T
a
l
rDH r
x
t
x
t
C rDH r
am
Wm Fm
t
rCp
Tm
T
lm
l
B
2
x
x
x
x
A39
rCpm
lm
rDH r
x
t
x
t
A45
A38
Tm
T
2 Cp
A r Cpm
t
t
A41
We have:
Cp
Cp
A
dT
T
r
dT
lim
rCp
da
m!0 m
t
a
T
t
A46
dT
l
l
T
:
l
da dT
m!0 m
x
x a
x
T
x
A47
lim
708
lim
m!0 m
rDH r
da
t
A48
D da
m!0 m
t
A49
lim
E WF
WF
lim
dT
da
A50
m!0 m
T
a
To completely determine the sensitivity of the system,
we consider the initial and boundaries conditions.
for t 0 we have:
dax; 0 dTx; 0 0
;x [ 0; L
at x 0 we have:
dT
l
l
T
dT 2 dU
dT
l
da
Rs
x
a
T
x
at x L we have:
dT
l
l
T
dT 2 dU
dT
2
l
da
Ri
x
a
T
x
da
t
tf
U 2 Uddt
tf
0
dddt
tf L
td
tf
0
L
td
a 2 ad dam dxdt
A61
da da dxdt
References
A53
A54
A55
A56
A60
m2
and:
b
c
A52
am ax; t; U md ax; t; U m da
m2
da
WF
WF
dT
da
t
a
T
2
JU md kam 2 am k2 gkU md 2 Uk
A59
Then we have:
A51
dT
l
l
T
dT
l
da
x
x a
x
T
x
rDH r X
df m
2b 2cm 0
dm
A58