Nicolas

BOYARD

Laboratoire de Thermociné:que de Nantes

nicolas.boyard@univ-nantes.fr / 02 40 68 31 15

« BMC » composite material

(Bulk Moulding Compound)
BMC molding by injec1on process

1. BMC in injec:on unit

2. Mould filling

BMC : complex composi:on (organic and inorganic elements)

à Some:mes compression molding
3. Packing phase and crosslinking

Understand composite molding

requires a mul3disciplinary study 4. Mould opening and ejec:on

•  Materials
•  Heat transfers Video :
•  Physical-chemistry of polymers hNp://www.compositec.com/
•  Kine:cs of crosslinking compositec-promo:on/injec:on-
•  Mechanics bmc
Reminders about composite materials
ï General defini:on : Arrangements of reinforcements surrounded by a matrix which
has lower mechanical resistance.
ï Matrix à ensure cohesion and maintain fibre orienta:on,
àtransmit sollicita:ons to which parts are subjected,
àsome:mes ensure a chemical protec:on.

ï Reinforcement à improve mechanical resistance and and s:ffness of the part.

Avoid confusion between reinforcement and filler !
ï Filler à modify a property of the material to which it is added
Ex: viscosity, impact resistance, UV and fire resistance…

ï Dis:nc:on between composites for large diffusion (GD)
high performances (HP)
 ï Raw material :
- glass fibres (type E, D, R)

Reinforcement
- carbon, aramide, natural fibres
ï Architecture : random mul4direc4onal
à short or grinded fibres (BMC)
The reinforcement has a sizing on its surface.

ï Thermose@ng resin (unsaturated polyester)

à mainly used for composites LD (Large Diffusion)
à contain an unsaturated monomer (styrene)
à crosslinking : with ini:ator (peroxyde)
Advantages
Drawbacks and/or catalyst
Good adhesion on glass fibre inflammability
Translucide
Low resistance in vapor and boiling water à exothermal reac:on and irreversible
Good chemical resistance Hifgh shrinkage (up to 10 vol%)
Easy processing
Low pot life:me (up to an infusible solid).
Temperature resistance (>150°C) Styrene emission
Low price
ï BMC is a semi-product obtained by wet method
Fibres are impregnated with TD resin during the blending. Resin and fibres are thus ini:ally
separated.
Ex : RTM, contact moulding, projec:on moulding, assisted-vacuum moulding.

≠ dry method which consists in processing pre-impregnated reinforcements (with TD or TP matrix) :

semi-product is thus already ready for use.

TD composites
prepregs / preimpregnates

ï Prepregs do not have any fillers, thickeners, ï P reimpregnates are more dedicated to
dyes or addi:ves. manufacturing of LD composites and reinforcement
is mainly short fibres.
They are characterized by low thickness and the
composite is made from the molding of several
layers with specific orienta:ons. SMC and BMC
SMC (Sheet Molding Compound) (1)
500 mm

50 c
m

Fibre bundle SMC semi-product

Paste condi:onning in roll
ï Matrix :
Polyester resin with ini:ator and inhibitor, filled with calcium carbonate + other addi:ves
(release agent, pigments, flame-retardant fillers …).
ï Reinforcement :
Glass mat from cuNed glass fibres (25 to 50 mm long) obtained from « roving ».
It represents 15 to 40 wt%. Glass fiber

ï Storage in a « matura4on room »: Cuqng system Protec:ve film

Paste
à Aper several days, blend viscosity increases
thanks to thickening agent (MgO). Paste

Product is between plas:c films to avoid s:cking Calendering

during handling
Protec:ve
ïLimited storage 4me. film
hNps://vimeo.com/154151312
SMC (Sheet Molding Compound) (2)

Stacking of pieces of
SMC sheets Heated mould at ~ 150°C


50 c The preform
m
Posi:onning of Mould closure
the preform ~ 4 - 10 s
~ 10 s
Ejec:on Mould filling
3 – 5 s

Curing
120 – 180 s
Cooling of the moulded part in ambient air

Keeping mould closed under high pressure (50

– 100 bars) during the solidifica:on stage
ï Building

Rear spoiler BMW X5 Tractor fender

ï Transport
Manufacturing of BMC

Step 1 Step 2

The paste (low viscosity), is then pumped to go to the s:rrer

Step 1 : Prepara:on of premix in a blender

Step 2 : Manufacturing of semi-product in double-arm s:rrer
Step 3 : Condi:oning (and storage) before processing à Time of storage is limited.
Step 4 : Processing by injec:on (mainly) or compression à The gain of mass compared to a steel
piece is varying between 20 and 30%.
Examples of applica1on
Video injec:on BMC :
hNps://www.youtube.com/watch?v=VG5kHYysuaE
ï Electric material : ï Automo4ve :

Headlamp

ï Household Equipment :

BMC has 2 main characteris4cs:

1- Excellent surface aspect (« A class »)
2- Non negligible dimensional shrinkage induced by crosslinking
Descrip1on of inorganic components

Reinforcement: Mineral fillers: 50 to 60 vol% of semi-product.

à Mechanical proper4es à Parameters influenced by fillers:

à Requirements: - viscosity,

- lightness, - Flame-retardant proper:es,

- shrinkage (dimensional stability),
- heat resistance,
- resin compa:bility, - density, elas:city modulus, hardness, tensile and flexural
strength.
- adapted to the selected process,
à Reinforcing (hollow glass beads , mica) / non-reinforcing
- low cost fillers (CaCO3, kaolin, talc)
à  Others:
pigments (insolubles) and colorings (solubles)
Release agent:
ï  facilitate the demoulding of the piece.
ï  2 types of release agents:
à  external : The product is directly applied on the mold surface.
à  internal : addi:ve is incorporated in the blend (case of BMC). We use faNy acids named
« stearates » (calcium, zinc, magnésium).
Descrip1on of organic components
Unsaturated polyester resin:
ï  Role : To form the solid matrix of the composite by polymeriza:on during the
molding of the piece.
ï  The resin is a prepolymer. Its polymeriza:on leads to an unfusible and insoluble
material.

ï  Unsaturated polyesters are macromolecules with double bonds C=C. These double
bonds are involved in the polymeriza:on reac:on (also named « crosslinking »).

Example of synthesis
60 - 130°C
HC CH
C C
+ HO H2C CH2 OH HO C HC CH C O CH2 CH2 OH
O O O O O
Maleic anhydrid Ethylene glycol « mono-ester »

Polycondensa:on reac:on :
n HO C HC CH C O CH2 CH2 OH
(1)
Unsaturated polyester
(2)
O O
160 - 200°C

HO C HC CH C O CH2 CH2 O H + (n-1) H2O

n
O O
ï  Dilu4on of resin in a reac4ve solvent :
At the end of synthesis, the resin is cooled and has a solid or pasty state. It is then very difficult to
handle.
à The resin is thus diluted in an ethylenic monomer. This diluted state is named unsatured polyester
resin. The monomer used for dilu:on purpose has two func:ons:
1- to adjust the viscosity
2- to copolymerize with polyester molecules during the cure cycle, following a free-radical
polymeriza:on.
CH2
HC
The styrene is a usual reac:ve diluent: good compa:bility and reac:vity with
prepolymers, boiling temperature rela:vely high, aNrac:ve cost. HC CH
Op:mal propor:on: 30 to 45 wt%. HC CH
C
H

ï  This polyester resin is finally inhibited to ensure its life :me during the storage and to ajust its reac:vity.

ï  The monomer content influences the type of bond and the final morphology of the material.
It is characterized by an unsatura4on molar ra4o defined as the number of C=C monomer over the number
of C=C prepolymer.
A high molar ra:o will favour the homopolymeriza:on of the monomer.
 Ini4ator Inhibitor
à Copolymeriza:on reac:on is ini:ated by a system à Stabilize the resin by avoiding the ini:a:on of
reac:on,
ini:ator and/or catalyst. Its choice is crucial and is
à Ensure the BMC life:me during its storage.
notably func:on of the working temperature.
Then it enables to regulate, by its delaying
à Generally, the ini:ator is a peroxyde, which effect, the beginning of the crosslinking.
decomposes thermally by producing free radicals by
the break of O-O bond. CH3 OH CH3

H3C CH3
HO OH CH3 CH3
Température
R-O-O-R’ R-O• + R’-O• Hydroquinone CH3
2,6 di ter butyl para crésol

à R-O• are going to stabilized energe:cally by

reac:on with styrene C=C and prepolymer. They are
thus bonded on a molecule and form new radicals.
This is an auto-cataly4c chainwise polymeriza4on.
 Thermoplas4c addi4ve:

ï Crosslinking of UP resinà volume shrinkage ranging between 5 and 10% (conforma:onal

reorganisa:on of macromolecular chains).

à  Drawback for the process of composites: the shrinkage leads to piece deforma4on,
cracks and aspect defaults.

à  Addi:on of thermoplas:c addi:ve (between 7 and 20 wt%) to UP/St blend to
compensate the shrinkage, but is not a reactant.

The efficiency of the addi:ve is used to classify the BMC according to the final linear
shrinkage level of a piece:
P Quality « low-shrink » : shrinkage is between 0,05 and 0,3%,
P Quality « low-profile » : shrinkage is lower than 0,05%. We obtain high quality of
surface aspect (« A class »).

ï Well-known thermoplas:c addi:ves: PVAc, PU and saturated polyesters are « low-profile »
addi:ves (LPA – Low Profile Addi:ve). They are miscible with the resin.
* CH2 CH n * CH3
* CH2 CH *
O * CH2 C *
n
n
O C C O CH3

CH3 O

Poly(acétate de vinyl) Poly(méthacrylate de méthyl) Poly(styrène)

* C N R N C O R' O n *
H H
O O

Poly(uréthane)

ï PMMA and PS are not ini:ally miscible in UP and belong to the category « low-shrink »
addi:ves .
ï Mechanism of shrinkage compensa4on :
à Thermal expansion AND micro-porosity forma:on
 Crosslinking kine1cs of BMC

The crosslinking is an important feature of thermoseqng polymers

à Different mechanisms (depending on the chemical nature of the resin)
à Exothermal reac1on (analyzed by DSC)
à Reac1on rate (kine:cs), depending on resin formula:on, T°C

Modeling the kine:cs ? à to predict the degree of cure and temperature field during the
part processing (is it cured aper the imposed curing cycle?)

DSC curve 1.00

Φ (mW)
ΔH 0.80

dh(t) dh(t )

Avancement
X (t ) =
0.60

h(t)
ΔH
0.40

m1 0.20

s) m2 t (s) 0.00
0 400 800 1200 1600 2000

Cp change is taken m m2 Temps (s)

into account dh(t ) = ∫ Φdt ΔH (t ) = ∫ Φdt

m1 m1
Kine1cs : mecanis1c vs macroscopic approach

Polyester Empirical descrip4on of the conversion degree

(free-radical polymeriza4on)

1 : Decomposi:on of peroxydes : R 2 → 2 R •

2 : Inhibitor comsump:on : R • + Z → Z •
For given T and α , reac:on rate is
3 : ini:a:on step: R• + M → M • assumed to be unique.

4 : Propaga:on step : M i• + M j → M i•+ j

n-th order model
5 : Terminaison step: M n• + M •p → M n + p

dα ⎛ E ⎞ n
Kine:cs is a func:on of :
= K 0 .Exp⎜ − ⎟.(1 − α )
dt ⎝ RT ⎠
Concentra:on of the remaining chemical func:ons…
…and other species with their own reac:on rates. Autocataly:c model

dα ⎛ E ⎞ m n
à Complex mechanis:c models because of the = K 0 .Exp⎜ − ⎟.α .(1 − α )
requirement to take all reac:ons into account
dt ⎝ RT ⎠
Kine1cs : empirical models
n-th order model Autocataly:c model
Maximum of reac:on rate at t=0
dα ⎛ E ⎞ m n
= K 0 .Exp⎜ − ⎟.α .(1 − α )
dα ⎛ E ⎞ dt ⎝ RT ⎠
n
= K 0 .Exp⎜ − ⎟.(1 − α )
dt ⎝ RT ⎠
- Maximum of reac:on rate RTM6
for α ≈ 30 to 40%.
Iden:fica:on of parameters from - At least one product of reac:on is
DSC measurements (isotherms or involved in the crosslinking
at constant hea:ng rate).

Model of Kamal & Sourour

dα ⎛ ⎛−E ⎞ ⎛ − E2 ⎞ m ⎞ n
= ⎜⎜ K1 exp⎜ 1 ⎟ + K 2 exp⎜ ⎟.α ⎟⎟.(1 − α )
dt ⎝ ⎝ RT ⎠ ⎝ RT ⎠ ⎠ Epoxy

Enable to take into account that reac:on rate (during

isotherm) can be ≠ 0 when it starts.
Kine1cs : empirical models (2)

Models assume that α=1 at the end of reac:on… it is true if T > Tg∞, otherwise :

It is also possible to introduce a func:on describing the diffusion phenomenon…

Bailleul’s model

dα ⎧> 0 for 0 ≤ α < 1 ⎡ ⎛ Tréf ⎞⎤

= K (T ).G (α ) with G (α ) ⎨ K (T ) = (kréf )exp⎢− A⎜⎜ − 1⎟⎟⎥
dt ⎩ = 0 for α = 1 ⎣ ⎝ T (t ) ⎠⎦

Ruiz’s model

dα ⎡ ⎛ Tref ⎞⎤
= K1 exp⎢− E1 ⎜ − 1⎟⎥G (α )(1 − α ) n
dt ⎜ T ⎟
⎢⎣ ⎝ ⎠⎥⎦
 Kine1cs : details of the Bailleul’s model

Func:on K BMC Temperature function K

0.04
⎡ ⎛ Tréf ⎞⎤
α=α* 120 °C
K (T ) = (kréf )exp⎢− A⎜⎜ − 1⎟⎟⎥
⎣ ⎝ T (t ) ⎠⎦
115 °C
Vitesse de réaction (1/s)

110°C
105 °C
0.02
100 °C

∂α i
= K (T ) ⋅ G (α i ) -3.00
0.00 ∂t Y = -24.0458 * X + -3.95069
0 10 20 30 40 50 60 70 80 90 100 Hypothesis : R-squared = 0.997273
Degré d'avancement

Ln((K(T))
( )
Gi α * = 1 -4.00

Formula4on “G” :
kréf = 0.0192527186 s-1
A=24.046 ∂α
-5.00
-0.02 0.00 0.02 0.04 0.06
= K (T ) Tréf./T-1
∂t α =α *
Formula4on “H” : Determina:on of A and (kréf)
kréf = 0.0134981 s-1
A=21.933
 Func:on G Conversion degree function G

K func:on being determined, G func:on is G(α ) = ∑ (an )α n

simply obtained : n

1.1
∂α
∂t α 1.0
G (α ) = 0.9
K (T ) 0.8
0.7
0.6
G(X)
0.5
0.4
0.3
0.2
0.1
0.0
0 10 20 30 40 50 60 70 80 90 100
Degré d'avancement

Interpola:on of experimental data points ⇒ polynome coefficients

Kine1cs : details of inhibi1on func1on

Inhibi:on func:on K2 Inhibition function K2

Reac:on starts for ν(T)=0 ⎧0 si I d (T ) > 0

K 2 (I d (T ) ) = ⎨
And if T(t) is constant ⎩ 1 si I d (T ) ≤ 0
tind
⎛ ⎛ Tréf ⎞⎞
I d (T ) = ∫ exp⎜ − B⎜
⎜ ⎜ − 1⎟⎟ ⎟⎟dt − (t réf )
⎡ ⎛ Tréf ⎞⎤ 0 ⎝ ⎝ T (t ) ⎠ ⎠
(tréf ) = (tind ). exp⎢− B⎜⎜ −1⎟⎟⎥
⎣ ⎝ T ⎠⎦ Determination of B and (tréf)

Formula:on “H” : Formula:on “G ”:

Tréf = 385.65 K = 112.5 °C Tréf = 353.15 K = 80 °C
B = 33.8841 B = 68.47
tréf = 7.36668 s tréf = 44.29 s
 Kine1cs : examples

BMC RTM6
0.04
Expérimental
Vitesse de réaction-1(1/s)
)

0.03 J.L. Bailleul

Reac:on rate (s

Kamal et Sourour
0.02
35, 25 et 17°C/minute
0.01

0.00
150 200 250 300 350 400 450 500 550
Temps (s)
Time (s)

Tréf = 385.65 K = 112.5 °C

B = 33.8841
tréf = 7.36668 s
kréf = 0.0134981 s
A=21.933
EXERCISES
Exercise 1:

1)  An induc:on :me is required when modelling the crosslinking kine:cs
of a BMC material. Why?

2)  This induc:on :me is introduced in the kine:c model

⎧0 si I d (T ) > 0
K 2 (I d (T ) ) = ⎨
⎩ 1 si I d (T ) ≤ 0
tind
⎛ ⎛ Tréf ⎞⎞
I d (T ) = ∫ exp⎜⎜ − B⎜⎜ − 1⎟⎟ ⎟⎟dt − (t réf )
0 ⎝ ⎝ T (t ) ⎠ ⎠

The induc:on :me tind was experimentally determined for several temperatures. Ploqng
ln(:nd) versus to (Tref/T)-1, we obtain a straight line with a slope equal to 40.6 and the Y-
intercept equal to 2.727.

Determine the values of B and tref.

What would happen if one forgets to add inhibitor in the chemical formual:on of the
BMC?
Exercise 2:

1) The kine:cs describing the crosslinking of the studied unsaturated polyester resin
follows an autocataly:c model in which diffusion effects (due to glass transi:on) are
taken into account :
dα/dt=kαm(αmax-α)n
with k(T)=A exp(-E/RT) , R=8.314 J.K-1.mol-1 and αmax represents the maximal
conversion degree for a given curing temperature. The func:on k(T) has been
experimentally obtained for several isothermal crosslinking (see the Table).

Determine the values of A and E. Do not forget the units.

2) The figure represents the evolu:on of the conversion degree of the BMC
crosslinking for 4 temperatures.

Explain why these curves are shiped in :me and why the maximum of conversion degree
increase with temperature.
Physico-chemical aspects of crosslinking
Global mechanism of radical copolymerisa:on :
1 : Peroxide decomposi:on
2 : Inhibitor consump:on
3 : Reac:on ini:a:on
4 Reac:on propaga:on
5 : Reac:on stop (terminaison step)

UP/St copolymerisa:on leads to the forma4on of infinite tridimensional network by crea:ng

irreversible covalent bonds. The resin passes from a liquid state to a solid state (visco-elas:c).

(a)  et (b) Intermolecular bond without or with monomers .

(c) et (d) Intramolecular bond without or with monomers .
(e) Reac4on between monomer and unsatura4on.
(f) Homopolymeriza4on of monomer
1 2 34

Evolu4on of viscosity and network forma4on
2 important transi1ons during the crosslinking

1) Gela4on:
This transi:on is defined by the conversion degree Xgel for which the molar mass Mw (and the viscosity)
becomes infinite. An unsoluble frac:on of polymer exists.
Another defini:on is the percola:on of giant macromolecule in the whole system.

Liquid Crosslinked gel

Detec:on / quan:fica:on : Measurements of viscosity, mechanical proper:es (complex modulus,

loss factor - tan d).

Effect of Tcrosslinking : Xgel = constant of the material… but tgel changes !

Example of gel point determina1on:
G' RTM6 (epoxy)
Mul1-frequency analysis
5
1.0x10 G'' 26
24

4
22
8.0x10
20 40 f = 5 Hz
8

18 f = 10 Hz Xgel = 0.77
G' et G'' (Pa)

4
6.0x10 16 f = 15 Hz 6
14

tan δ
12 30
4
4.0x10 10 4 intersection des courbes : tgel
8
vitrification
6

tan δ
4
2.0x10 2
4 20
2
0 0
6000 6500 7000 7500 8000 8500 9000 7400 7600 7800 8000 8200 8400 8600 8800 9000

Temps (s) 10

0
6500 7000 7500 8000 8500 9000
Temps (s)

Xgel = 0.05-0.1 for UP resin

For UP resin, the criterion open used to determine tgel is when G’=G’’ (tan δ=1). The
reac:on is very rapid and the gel point is low. It is thus difficult to carry out a mul:-
frequency analysis.

Another criterion is to measure the :me, from which the viscosity reach about 103 – 104 Pa.s.
2) Glass transi4on:
The glass transi:on is an important characteris:c of the polymer behaviour. It is defined as the
evolu:on from a glassy state to rubbery state (and vice versa).

vitrifica:on
Liquid or gel Liquid or glassy gel

In the rubbery state, macromolecular chains have a rather high mobility (coopera:ve movements, i.e.
chain movements in rela:on to each other).

When the temperature decreases, chain movements slow gradually and become difficult up to a low
possibility to move. At Tg, the macromolecules conforma:on is frozen; they are in the glassy state
(movements s:ll exist but are very low and local).

Determina:on : Glass transi:on includes strong changes of several physical proper:es such as : viscosity,
thermal ones (Cp, expansion coefficient, conduc:vity), specific volume and mechanical proper:es.

During the crosslinking: Tg depends on Tcrosslinking and increases with X

Determina1on of Tg – Importance of curing cycle:

4.85E-4 3,5
3/kg)
Volume spécifique (m3/kg)

3
4.84E-4

Tg
Specific volume (m

2,5

Tg
4.83E-4

Flux (mW)
2

4.82E-4 1,5

4.81E-4
0,5
ligne de base d'intégration

4.80E-4 0

35 55 75 95 115 135 155 175 -0,5

Température (°C) 80 85 90 95 100 105 110
Température (°C)

Tg is a 2nd order transi:on (discon:nuity of dH/dT or of dvspe/dT)

ï Evolu:on of Tg versus X is important :

In the rubbery state, mobility is high enough and the reac:on evolves normally.

In the glassy state (relaxa:on :me of the chains becomes large), the reac:on is strongly slown down and the
crosslinking contributes to increase these relaxa:on :mes. The reac:on finally stops. Only a temperature
increase will allow a restart of the reac:on.

à  From a process point of view, Tg is a minimum temperature from which the crosslinking stops
rapidly.
 The rela4on between Tg and the conversion degree is unique à One can es:mate X whenTg is
experimentally known and vice versa. This rela:onship can be modeled according to the Pascault-
Williams equa:on.
(T
g − Tg0 )
=
k ⋅α

240
Epoxy Resin RTM6 (Tg∞ − Tg0 ) $%1− (1− k ) ⋅ α &'
220
200 Tg0 = -15°C k is a parameter to adjust
180
160 Tg∞ = 220.6°C
140
Tg (°C)

120 l = 0.2784
100
80
60
40
20 Vinylester resin
0
-20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Conversion degree α

For UP resin : Tg0 ≈ -20°C, Tg∞ ≈ 150°C

Defini:on of CTT diagram (Conversion – Time – T°C)

Predic:on of the reac:on evolu:on :

Isothermal crosslinking Hea:ng

Cure cycle along the vitrifica:on curve

à The composite has to be always in the rubbery state during the reac:on (i.e. Tg < Texp)
to avoid a strong decrease of the rate.
EXERCISE:
DSC experiments were carried out to get the evolu:on of the glass transi:on
temperature on an unsaturated polyester resin versus the degree of cure. Results are
given in the figure below.
150

Température de transition vitreuse (°C)

Glass transi:on temperature (°C)
140
130
120
110
100
90
80
70
60
50
0 10 20 30 40 50 60 70 80 90 100
Degree of cure (%)
Degré d'avancement de la réaction (%)
Figure 3
a)  Give the main elements which are the most characteris:c of the crosslinking of this
a) De manière générale, décrivez de manière concise la réticulation de la résine polyester insaturé (donner
thermoset resin.
les points qui vous semblent essentiels).
b) In which physical state is the resin if we are below the curve? Above the curve?
b) Dans quel état se trouve la résine lorsqu’on se place en dessous de la courbe ? Au-dessus de la courbe ?
c) En vous aidant de la courbe de la figure 3, indiquer ce qui va se passer si la résine réticule à une
c) From the figure, explain what will happen if the resin crosslinks in isothermal condi:on
température constante de 90°C ?
at T=90°C ?
d) Comment pouvez-vous obtenir une réticulation complète de la résine ? Justifiez votre réponse.
d) How can we obtain a full crosslinking (i.e. 100% reac:on) ?
Kine1cs : effects of vitrifica1on and diffusion
(Thermoseqng Polymers, Pascault et al)

Chemical control vs diffusion control

Key step is the forma:on of Key step is the consump:on of

products (decomposi:on of reactants (forma:on of ac:vated
ac:vated complex) complex)

-  slowdown of the reac:on is due to the decrease of the diffusion of the reac:ve species
(induced by the crosslinking, i.e. densifica:on of the network),
-  Strong decrease of kine:cs induced by vitrifica3on (overall control of the reac:on rate
by diffusion; it is difficult to describe by a straigh„orward model).
These phenomena are more or less important according to the kind of reac:on, chemical
nature of molecules (which have different reac:vi:es).

dα dα
= K global (T , α )G (α ) = K chimique (T )G(α ) f (T , α )
dt dt

- Rabinovitch approach:
1 1 1
= +
K global kc kd

kc is the temperature func:on of classical kine:c model
kd is the Arrhenius func:on, which describes the evolu:on kine:cs due to diffusion.

⎛ Ed ⎞ ⎛ b ⎞
f g (α ) = 0.00048(T − Tg (α )) + 0.025
( )
kd T = Ad exp⎜ − ⎟ exp− ⎜⎜ ⎟⎟
⎝ RT ⎠ ⎝ fg ⎠

And Tg is given by the rela:on of Pascault-Williams :
(Tg − Tg0 ) = l ⋅ α
240
( Tg∞ − Tg0 ) $%1− (1− l ) ⋅ α &'
220
200
180
160
140
Tg (°C)

120
100
80
60
Modified K&S model
40
20 ∂α ⎛ k1.k d k .k ⎞ n
0 = ⎜⎜ + 2 d α m ⎟⎟(1 − α )
-20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
∂t ⎝ k1 + k d k 2 + k d ⎠
Conversion degree α
 1
-Chern and Poehlein model: f (α ) =
1 + exp C F (α − α C (T ))



where αc(Tg) is given by the rela:on of Pascault-Williams and CF is an ajustable parameter
(dependent of T…?)

Modified K&S model Modified Bailleul model
∂α ∂α
∂t
( ) n
= k1 + k 2α m (1 − α ) f (α )
∂t
= K (T )G (α ) f (α )

vinylester

RTM6
Descrip1on of heat transfers
General energy equa:on (conduc:on – convec:on):
DT DP 2
! ! ∂α
ρ ( P, α , T )C p (α , T ) = βT "
+ ηγ + ∇.(λ (α , T )∇T ) + ρ ( P, α , T )ΔH
Dt Dt ∂t
! !
D /Dt is the operator ∂ ∂t + v .∇

Conduc:on heat transfer equa:on:

∂T
ρ (α , T )C p (α , T )
∂t
( )
= div λ (α , T )gradT + ρ (α , T )ΔH
∂α
∂t

Heat transfers along the thickness: 1D Equa:on

∂T ∂ ⎛ ∂T ⎞ ∂α
ρ (α , T ).C p (α , T ). = ⎜ λ (α , T ) ⎟ + ρ (α , T ).ΔH
∂t ∂x ⎝ ∂x ⎠ ∂t

Solving the equa:on à Determina4on of Cp, λ, ΔH, kine4cs

BMC crosslinking and thermophysical proper4es

1) Specific heat:

DSC
reference measure

heaters
thermistances
electric
Nitrogen power
circuit
Cooling circuit

Power compensa:on DSC DSC « Tzero » (1 furnace)

dTe T (°C)
φ = mC pe
dt
t (s)
 with I = 1 + tanh  
2  δ 
BMC crosslinking and thermophysical proper4es
where d is the half temperature range of glass transition (17.5°C in our case), and δ ( equal to
17°C in our case) is a temperature factor to be determine by adjusting the model curve on the
experimental data. Cp measurement for RTM polyester resin

Cured rubbery
state
liquid resin

Cured glassy state

Glass transition

Models :

For resin :
Figure 2.4. Specific heats in different states of vinylester resin
Cprésine (α , T ) = αCprésine Caoutchoutique (1, T ) + (1 − α )Cprésine (0, T ) Mixing law
2.6 Determination and modelling of Tg evolution with degree of cure
For composite :
Glass transition temperature ‘Tg’ is the temperature at which thermoset polymer changes
Cpfrom glassy state to rubbery state or vice versa. It has a strong effect on thermophysical
( ) ( ) (
composite α , T = XCp résine α , T + 1 − X Cp fibre T) ( )
properties and kinetics of reaction of resin during curing or when the sample temperature
 BMC crosslinking and thermophysical proper4es

Cp measurement for BMC

ï Difficulty : low mass sampleà random Vfibre à scaNering of results.

1800
Approximation linéaire des résultats
expérimentaux

1600
BMC is studied considering the
paste (no fibre)
Specific heat (J/g.K)
Chaleur spécifique (J/kg.K)

1400

1200
Model :
Etat cuit
1000
Etat cru
Cp (α , T ) = Y .Cp pâte (α , T ) + (1 − Y ).Cp fibre (T )
800
Représentation de la chaleur spécifique du BMC (composite)
calculée suivant le modèle and
600 Cp pâte (α , T ) = α .Cp (1, T ) + (1 − α ).Cp (0, T )
20 40 60 80 100 120 140 160 180 200
Température (°C)

Uncured paste:
Cp(T) = 3.10*T + 996 (J/Kg.K) T en °C E-glass fibre :
Cured paste: Cp(T) = 3.11*T + 714 (J/Kg.K) T en °C
Cp(T) = 2.51*T + 891 (J/Kg.K) T en °C
Main devices to measure thermal conduc4vity / diffusivity

Hot guarded plate

Laser Flash
y

Planar heat
source
(Gustaffson) x

Hot wire

Planar heat source

(C-Therm)
BMC crosslinking and thermophysical proper4es

2) Thermal conduc4vity:
ï Injec:on of BMC induces fibre orienta:on à λ anisotropy in the plane.

Hypothesis: 1D heat transfer through the thickness of the plate à λtransversal.

ï  Experimental determina:on: Garde en BMC réticulé

Garde en mousse

Verin Echantillon
Echantillon
Thermocouple supérieur
Circuit Thermocouple à coeur
fluide
Thermocouple inférieur
Thermocouples

Echangeur
hélicoïdale
Résistance
chauffante

For raw TD resin

Es:ma:on of conduc:vity using an inverse method

BMC crosslinking and thermophysical proper4es

Example of measurement of a polyester resin

200

160
Température (°C)

120
Surface temperature : lower side
Température surface : côté bas

Core temperature
Température à coeur
80
Température surface : côté haut
Surface temperature : upper side

40

0
0 400 800 1200 1600 2000 2400
Temps (s)

⎧∂ ⎡ ∂T ⎤ ∂T
⎪ ∂x ⎢ λ (T ) ⎥ = ρ .C p (T ). 0< x< L
⎪⎪ ⎣ ∂ x ⎦ ∂t Inverse method
⎨T (0, t ) = T1 (t ) t >0 (conjugated gradient)
⎪T (L, t ) = T (t ) t >0
2
⎪
⎪⎩T (x,0) = T0 (x ) 0< x<L
BMC crosslinking and thermophysical proper4es

Results for RTM polyester resin

0.22

glassy state

thermique (W/m.K)
0.20
Etat vitreux

Thermal conduc:vity (W/m.K)

0.18
Cured resin
0.16

0.14
rubbery state
Etat caoutchoutique

0.12
Liquid state
Etat caoutchoutique
Conductivité

0.10

0.08
Extrapolation état caout. polymérisé
0.06

0.04
20 30 40 50 60 70 80 90 100 110
Models : Température (°C)

For resin:
λresin (α , T ) = αλ resin rubbery (1, T ) + (1 − α )λliquid resin (0, T ) Mixing law

For composite :

λ⊥composite (α , T ) = λre sin (α , T )

(1 + τ )λ (T ) + (1 − τ )λ (α , T )
f fibre f re sin

(1 − τ )λ (T ) + (1 + τ )λ (α , T )
f fibre f re sin
 BMC crosslinking and thermophysical proper4es

Results and modeling for a BMC

0.7
Thermal conduc:vity (W/m.K)
Conductivité (W/K/m)

0.6

Etat cru Experimental determina:on of λ⊥(T) for

0.5 Approximation linéaire (état cru)
BMC in raw and cured states
Etat cuit

+
Approximation linéaire (état cuit)

0.4
20 40 60 80 100 120 140 160 180 200
Température (°C)

(1 + υ f ).λ f + (1 − υ f ).λ p λ⊥raw paste (T)

λ⊥exp, BMC = λ p . λ⊥cured paste (T)
(1 − υ f ).λ f + (1 + υ f ).λ p

λp(α,T)= (1 - α).λp_raw(T) + α.λp_cured(T)

(1 + υ f ).λ f + (1 − υ f ).λ p (α , T )
λ⊥ mod el , BMC (α , T ) = λ p (α , T ).
(1 − υ f ).λ f + (1 + υ f ).λ p (α , T )
BMC crosslinking and thermophysical proper4es

3) Density:

ï  Possible modeling : ρBMC ≈ 1800 - 2000 kg.m-3.

ρ(α)= (1 - α).ρ_cru + α.ρ_cuit

ρuncured is calculated from mass frac:ons of cons:tuent densi:es,

Knowing ρ of the cured resin, ρcuit can be thus determined as ρuncured.

ï Determina:on of ρBMC is not an easy task :

- Porosity in the cured state,
- Fillers absorbs quickly the liquid used during an « immersion » experiment (e.g. using
a gradient column).
à Uncertain:es on the results. However, the evolu:on of ρ remains rather small
(UPcru : d ≈ 1,1 et UPcuit : d ≈ 1,3), the consequences on the calcula:ons are thus
limited.
Other possibili:es : determina:on of the specific volume (see PVTX mould) and find a
law between this parameter and the conversion degree.
BMC crosslinking and thermophysical proper4es

4) Reac4on enthalpy:

ï Measurement on the paste using DSC.

∂T ∂α
φ( t ) = m.C p . − m.ΔH r .
ï Exothermal reac:on, ∂t ∂t

ï High reac:vity of the material à impossible to do an isothermal reac:on à

influence of Cp which has a non-negligible varia:on with T.

Integra:on of exothermal peak using a sigmoïd as baseline.

Pâte : ΔH ≈ 100 J/g

à For calcula:ons, this result is weighted by the wt% of fibres.

Remark : The total enthalpy of reac:on for a binary blend UP/St is about 420-430 J.g-1.
Coupling between heat transfers and kine1cs
⎧ ∂T ∂ ⎛ ∂T ⎞ ∂α
⎪⎪ ρ .Cp (α , T ). = ⎜ λ (α , T ) ⎟ + ρ (α , T ).Y .ΔH
∂t ∂z ⎝ ∂z ⎠ ∂t
1D case ⎨
⎪ ∂α = W (ν (t ) ).K (T ).G (α ) wt% paste
⎪⎩ ∂t

Ini:al condi:ons for temperature and conversion degree :

X(z,0) = X0(z) and T(z,0) = T0(z),
Initialisation
des données
Boundary condi:ons :
T(0,t) = T0(t) and T(etot,t) = Te(t), Calcul du champ d’avancement:
Construction d’un critère d’écart
entre deux itérations. (1)

Calcul du champ de température:

Construction d’un critère d’écart
entre deux itérations (2)
non
Vérification des
deux critères
oui
Passage au pas
de temps suivant
 Epaisseur BMC G : 5mm
pas d'espace : dx = 0.25mm
vitesse de montée en température = 10°C/min

ï 5mm thick BMC part heated from 40°C to 180°C at 10°C/min :

180 140

Epaisseur BMC G : 5mm

160 pas d'espace : dx = 0.25mm
130
vitesse de montée en température = 10°C/min

140
120

Température (°C)
Température (°C)

120
110

100

100

80

90
60

80
40 350 400 450 500 550 600 650
0 100 200 300 400 500 600 700 800 900 Temps (s)
Temps (s)

1 courbe toutes les 30s

180
10
Ecart de température entre la surface
et le coeur de l'échantillon 170

8
160
Ecart de Température (°C)

6 150

140
4 Température (°C)

130

2
120

0 110

100
-2
0 100 200 300 400 500 600 700 800 900
Temps (s) 90

80
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Epaisseur (m) -3
x 10
ï 10mm thick BMC part heated from 40°C to 180°C at 10°C/min :

150
30

140 25

20
130

Ecart de température (°C)

15
Température (°C)

120
10

110
5

100 0

-5
90

-10
0 100 200 300 400 500 600 700 800 900
80 Temps (s)
400 450 500 550 600 650
Temps (s)

180
Comparison with experiment:
210 25
170

160 180 20

Différence de température (°C)

150

150 15
140 Température (°C)
Température (°C)

130 120 Expérimental 10

Simulation
120

90 Différence de température 5
110

100 60 0

90

30 -5
80
0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.01
Epaisseur (m) 0 300 600 900 1200 1500
Temps (s)
ï 5mm thick BMC part in more real process condi:ons :

Temperature step: 40°C à 140°C

180
40

Temperature difference (°C)

160
20
140
0

Ecart de T°C (°C)

Température (°C)

120
-20
100
-40

80 -60

60 -80

40
0 10 20 30 40 50 60
-100
Temps (s) 0 20 40 60

Remark : rather representa:ve of compression molding but not totally for injec:on
(filling and packing phases have to be considered).

Induced problems : crosslinking heterogenei:es à problems of Tg

à development of high stress level