Composites Science and Technology 64 (2004) 629–644

www.elsevier.com/locate/compscitech

Resin transfer molding of natural fiber reinforced composites:

cure simulation
David Rouisona, M. Sainb,*, M. Couturiera
a
Department of Chemical Engineering, University of New Brunswick, NB, Canada
b
Earth Science Centre/Forestry/Chemical Engineering, 33 Willcocks Street, University of Toronto, ON, Canada M55 363

Received 7 January 2003; received in revised form 30 May 2003; accepted 29 June 2003

Abstract
In this work hemp/kenaf fiber-unsaturated polyester composites were manufactured using a resin transfer molding (RTM) pro-
cess. The fiber mats, with a moisture content of 4.3% at 50% relative humidity, were dried in the mold under vacuum to reach a
moisture content around 1–2%. RTM composites with various fiber contents, up to 20.6% by volume, were manufactured. The
wetting of the fibers was very good. The resin injection time was observed to increase dramatically at high fiber contents due to the
low permeability of the mat. Keeping a constant mold temperature is the key to obtain fast and homogeneous curing of the part.
The cure of the resin in the mold was simulated. It was shown to be in good agreement with experimental results obtained by
thermal measurements at different positions in the cavity. The performance of these samples was evaluated by measuring tensile
strength and flexural strength.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: B. Curing; B. Mechanical properties; C. Finite element analysis (FEA); Natural composite

1. Introduction pectin) and hemicellulose. The strength and stiffness of

In recent years there has been a growing interest for
the use of natural fibers in composite applications,
especially in the automotive industry. These types of
composites present many advantages compared to syn-
thetic fiber reinforced plastics such as low tool wear,
low density, cheap cost, availability and biodegrad-
ability. The most common natural fibers used in com-
posite applications are the bast and leaf qualities (hard
fibers) with fibers such as hemp, jute, flax, kenaf or
sisal. These materials have already been embraced by
European carmakers. This trend has reached North
America and the Natural Fiber Composite Industry
has registered a 40–50% growth in 2000. An annual
growth rate of 54% is projected in the comprehensive
report on the Opportunities for Natural Fibers in
plastic composites 2000–2005 by Kline & Company
Inc. (http://www.klineonline.com/Studies).
Natural fibers consist mainly of cellulose fibers. These
fibers are made of microfibrils in a matrix of lignin (or
* Corresponding author. Fax: +1-416-978-3834.
E-mail address: m.sain@utoronto.ca (M. Sain).
0266-3538/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2003.06.001
the fibers are provided by hydrogen bonds and other
linkages. The overall properties of the fibers depend on
the individual properties of each of its components.
Hemicellulose is responsible for the biodegradation,
moisture absorption and thermal degradation of the
fiber. On the other hand lignin (or pectin) is thermally
stable but is responsible for the UV degradation of the
fiber. On average natural fibers contain 60–80% cellulose,
5–20% lignin (or pectin) and up to 20% moisture [1].
The thermal stability of the reinforcing fibers is a key
parameter in composite processing, especially in the
case of thermosetting resins and their exothermic curing
behavior. Wielage et al. [2] studied the thermal stability
of flax and hemp fibers using differential scanning
calorimetric (DSC) and thermo-gravimetric (TGA)
methods. They noticed a slight decrease of the mass of
natural fibers between 200 and 220
C. Above this last
temperature irreversible degradation was observed.
Below 160
C no degradation is taking place. These
results suggest that hemp and flax fibers have the ther-
mal stability to endure thermoset cure reactions
encountered during composite manufacturing. Saheb
and Jog [1] reported similar results for jute fibers. They
630 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644

In their extensive report on ‘‘Composites Reinforced

Nomenclature with cellulose based fibres’’ Bledzki and Gassan [3] gave
some data for various natural fibers as well. As
r, f and c subscripts are used for resin, fiber and observed previously the characteristic values of natural
composite respectively fibers are comparable to those of glass fibers. The
a,b adjustable parameters in the wall’s strength of natural fibers greatly depends on the process
temperature expression used to produce them. In theory the elastic moduli of
Cp heat capacity cellulose chains can reach values of 250 GPa. However
Hu ultimate heat of cure there is no existing procedure to separate these chains
k, kx thermal conductivity from the microfibrils and therefore obtain such values.
k2 cure rate constant Right now the pulp and paper industry is able to pro-
kinhib inhibitor rate constant duce cellulose fibers with moduli around 70 GPa.
mr, mf resin and fiber mass fraction respectively Moreover some experimental data obtained from flax
m, n kinetic parameters in the rate of cure and pineapple fibers show that the tensile strength of
expression these fibers is significantly more dependent on the length
dQ/dt heat generation of the fiber than for the case of glass fibers. Natural
t time fibers seem to be less homogeneous than synthetic
T temperature in Kelvin fibers. From these papers it can be concluded that even
T0 initial temperature of the mold if natural fibers are well suited to replace glass fibers in
Vr resin volume fraction composite materials many improvements can still be
Z inhibitor concentration done concerning their mechanical properties. Experi-
Z0 original inhibitor concentration mental data giving the tensile strength, flexural strength,

degree of cure modulus, impact force and compressive force are avail-

max maximum degree of cure able in the literature for different types of natural-fiber
 correcting factor composites.
 density New systems using biodegradable resins were also
investigated. Williams and Wool [6] prepared all-natural
composites using hemp and flax fibers with recently
explained that the degradation of hemicellulose was developed soy oil resins. The tensile and flexural prop-
responsible for the low temperature degradation of the erties of the resins were shown to be improved by the
fiber. In the higher temperature range the degradation addition of the fibers as observed for regular thermoset
was due to lignin (or pectin). resins. However this type of composite gave lower
Another important aspect is the moisture content of values than traditional composites. Wollerdorfer and
natural fibers. These fibers are hydrophilic and absorb Bader [7] made similar observations for different all-
water. As stated before the moisture content can go as natural composites.
high as 20%, but in most cases it will be in the range In the literature most of the natural fiber composites
5–10%. This can affect the final properties of the com- studied are produced by hand lay-up or press molding
posites. During processing the presence of water can techniques. Very little research is available for industrial
create voids in the matrix and also lead to a poor adhe- processes such as resin transfer molding (RTM). The
sion of the fibers with the hydrophobic resin.1,3 The RTM process is commonly used in the aerospace and
hydrophilic nature of natural fibers can be a problem in automotive industry. The process consists of mixing
the finished composites as well. resin with a hardener and injecting at low pressure the
Li et al. [4] reviewed many papers concerning the combination into a mold, which contains fibers. The
mechanical properties of natural fibers. It was shown resulting part is cured at room temperature or above till
that the tensile properties of these fibers are not uniform the end of the curing reaction. Several types of resins
along their length. Much research has also been done (epoxy, polyester, phenolic and acrylic) can be used for
varying the experimental conditions. Parameters such as this process as long as their viscosity is low enough to
fiber length, test speed, gauge length, fiber age or tem- ensure a proper wetting of the fibers.
perature were all found to have effects on the mechan- Richardson and Zhang [8] presented an experimental
ical properties of sisal and sun-hemp fibers. Most of study of the mold filling process for a non woven hemp-
these effects are explained by the internal structure of phenolic resin system. Fiber washing (unexpected dis-
the fibers (cell structure, microfibrillar angle, imperfec- placement of the reinforcement in the mold during the
tions, water content. . .). However Van Voor et al. [5] RTM process) was shown to be a problem at low fiber
found that the temperature and the moisture content concentration due to poor clamping. This could lead to
have a limited influence on the tensile strength of sisal the failure of the process. This effect was reduced by
and flax fibers. increasing the fiber concentration and improving the
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
Fig. 1. Diagram of resin transfer molding equipment.
clamping system. Edge flow was observed during the
mold filling as well. It was found to be very sensitive to
fiber concentration. Using preforms larger than the
mold solved this problem. Finally, in the rectangular
mold used for this study, the ‘‘quasi-one dimensional
steady state’’ flow (equal resin advancement distance or
velocity at any moment during the injection in the resin
advancement direction) was required to obtain a com-
plete preform impregnation. All these parameters were
found to depend greatly on the injection pressure and
on the fiber concentration.
A few other studies investigated the possibility of
using the RTM process to prepare natural fibers com-
posites. O’Dell [9] made similar observations for jute
and glass composites prepared in a RTM mold. The
flow and the fiber wet-out were found to be the same in
both cases. Some increase in backpressure occurred
when the resin was injected through five plies of jute.
Sèbes et al. [10] obtained very good results for hemp
fiber-reinforced polyester composites. No major prob-
lem was noticed during the RTM process. Williams and
Wool [6] did not report any problems as well with nat-
ural fibers–soy oil resins systems. More recently Oks-
man [11] manufactured high quality flax fiber
composites using a RTM process. Good flow properties
were observed in the mold and high fiber content was
attained. The composites were found to have very pro-
mising mechanical properties.
A great number of studies can be found in the litera-
ture concerning the RTM process for synthetic fiber
composites. Number of simulations of the mold filling
process and cure processes are proposed, many experi-
mental data sets have been presented. The knowledge of
all the operating steps is very important to obtain high
quality parts. Lebrun and Gauvin [12] investigated the
temperature and pressure evolution in a heated mold
using thermocouples and pressure transducers. The filling
and curing stage of the process were studied. Parameters
631
such as injection pressure, fiber content or mold tem-
perature were shown to have a great influence on the
development of the temperature profiles and the thermal
boundary layers, especially for thin cavities. An impor-
tant temperature gradient was measured through the
thickness of the resin during filling, which could result
in important defects in the part. They also observed that
the resin cure started at mid-thickness (the peak tem-
perature was observed first at mid-thickness) and pro-
gressed towards the mold surface.
The mold filling is a critical stage of the RTM process
as discussed previously. Models predicting the flow of
the resin in the mold can avoid defects such as voids and
poor wetting of the fibers. Lim and Lee [13] presented a
three-dimensional mold filling process simulation using
the control volume finite element method. They con-
sidered a moving boundary problem and discretized the
governing differential equations. The degree of cure and
the temperature were computed as well. The results
were compared to exact solutions for simple geometries
and to experimental data. They were found to be in
good agreement. With this model any three dimensional
geometry can be simulated. Simacek and Advani [14]
used a finite element/control volume approach to model
the mold filling in three dimensions for a RTM system.
They found that the accuracy of the predictions depen-
ded mainly on the accuracy of the permeability of the
preform. Various aspects of the mold filling such as
draping, compacting and corner deformation were
addressed as well.
Another approach was presented by Chiu et al. [15]
who compared an experimental analysis of the heat
transfer and resin reaction in flow with a numerical
simulation based on a mixed Eulerian–Lagrangian
model. The cure reaction kinetics was based on
mechanistic considerations. Once again good agreement
was found between the simulations and the experiments.
A more specific work on the curing simulation of
632 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
thermoset composites was done by Blest et al. [16]. They
solved resin flow, heat transfer and the curing of multi-
layer composites in an autoclave. Using a finite difference
scheme on a moving grid they discretized the governing
differential equations. More precisely the energy equa-
tion with an internal heat generation term was solved by
an alternating-direction implicit method. Some of the
results were compared with experiments and showed
good agreement. One important comment from this
work is that most of the assumptions made in this kind
of simulation—such as constant thermal conductivity,
specific heat and density or the use of the rule of mixture
to calculate the composite thermal conductivity—are
not fully valid. If greater precision in the results is nee-
ded these parameters’ variations should be taken into
consideration. At this point it is worth mentioning the
reference study of Bogetti and Gillepsie [17] on the cure
simulation of thick composites. This extensive work
gave in details the procedure to solve the energy equa-
tion with an internal heat generation in two dimensions.
As discussed before important temperature and degree
of cure gradients were predicted. Michaud et al. [18]
presented a similar study and predicted the thermal
gradients during cure of thick-sectioned composites.
Semling et al. [19] proposed an algorithm to calculate
the optimal process temperature for a RTM system.
This method permitted to minimize the processing time,
which is a very important parameter in the industry.
Most of these numerical studies are usually associated
with experimental works to validate the numerical
models proposed. In a closed mold process such as
RTM the online monitoring of temperature, pressure or
degree of cure for instance is not an easy task. A few
techniques are now well accepted and well documented.
For the online monitoring of temperature the use of
thermocouples seems the easiest solution [12].
From this review it can be noticed that all the curing
experiments and simulations deal with composites rein-
forced with synthetic fibers. There are no such studies
involving natural fibers. Most of the papers focus on the
mechanical properties obtained using a specific process
and only a few give some information about the flow
and wetting part of the process. The purpose of this
work is to provide a model predicting the cure behavior
of a natural fiber composites and to optimize the RTM
process to obtain a high degree of cure in a minimum
time.
2. Experiments
2.1. Resin transfer molding
A number of polyester/natural fiber composites were
manufactured in the lab. The final dimensions of the
parts were 380 by 380 by 6.7 mm thick. The mold, made
entirely of aluminum, was opened and closed manually
with 16 screws distributed around the cavity. The two
inlet ports were situated under the mold and a vent port
was located on the top (Fig. 1). It was kept at constant
temperature during the curing reaction by water flowing
inside its upper and lower sections. The water, circulated
in a closed loop through a tank, was kept at constant
temperature with a temperature controller connected to
a thermocouple and an immersion heater of 2000 watts.
To compensate for the heat produced during the
exothermic crosslinking reaction cold water was kept
running permanently in a copper coil placed in the tank.
This system balanced itself around the preset temperature
during the experiment. It should be noted that the
thickness of the composite was defined by a frame
placed between the upper and lower sections of the
mold; it could therefore be modified in further
experiments.
Prior to a typical experiment the surfaces of the mold
were cleaned with the Frekote1 PM mold cleaner and
then coated with the Frekote1 B-15 Sealer and the
Frekote1 700-NC mold release agent. Once these coat-
ings were cured layers of natural fibers’ mats having the
mold’s size were placed in the cavity. The mold was
tightly closed and a vacuum of 725 mm of mercury was
created in the cavity through the vent port connected to
a venturi aspirator placed on a tap. At this point the
fibers were dried for 2 h by circulating water at 55
C.
The mold was then cooled down with cold water. In the
meantime the resin was mixed with the initiator and
placed in the injection pot. From there the resin was
injected in the mold with compressed air at a constant
gauge pressure of 1.72105 Pa. This pressure was kept
constant in the pressure pot by continuously adjusting
manually the compressed air valve. The injection time
of course varied with the amount of fibers present in the
mold. This will be commented in the discussion part of
this paper. Once the resin was observed at the outlet, the
vent port was closed. A small flask was placed between
the vent port and the tap for safety, to prevent any resin
from flowing to the tap water. The resin was left flowing
at the inlet for 5 min more to make sure that the mold
was filled completely. Then the inlet ports were closed as
well and hot water at constant temperature was circu-
lated in the mold. The composite was cured under these
conditions for 1 h. Meanwhile the injection pot and all
the tubes were cleaned with acetone to avoid any clog-
ging due to cured resin.
The evolution of temperatures in the part was monitored
at four different locations with bare type T thermocouples.
One wire was situated at the wall of the mold’s cavity
and the three others at evenly spaced positions between
the surface and the center of the part. After each
experiment a new set of thermocouple wires had to be
used. The signals from the wires were recorded on a
computer through a data acquisition system.
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
2.2. Thermophysical properties
A good knowledge of the composites’ thermophysical
properties is essential to predict accurately the curing
behavior of the resin in the mold. The densities of the
liquid resin and composite parts with different fiber
contents were measured by weighing samples of well
known volumes. The thermal properties at different
fiber contents were measured for the solid composite
using the k-a apparatus described by Couturier et
al.[20]. The steady state portion of one experiment was
used to obtain the thermal conductivity (k) of the part
whereas the transient portion allowed to calculate
(kCp)1/2 and hence get the heat capacity (Cp). However
it is well known that thermal properties of plastics vary
with temperature as well as the degree of cure. A brief
study of these variations seemed therefore necessary to
evaluate their magnitude. First the thermal conductivity
of the liquid resin was measured using the hot wire
method [21].
The evolution of Cp with temperature for the solid
and liquid resin was measured using a differential scan-
ning calorimeter (DSC) TA Instruments DSC 2010 fol-
lowing the Standard ASTM Method E1269-99. A
similar experiment was performed for the fibers as well.
The measurements were taken between 25 and 200
C at
a heating rate of 10
C. The variations of the resin’s Cp
with the degree of cure were recorded at 35
C using a
modulated temperature differential scanning calorimeter
(MTDSC) TA Instruments DSC 2920 with a tempera-
ture modulation of 0.5
C every 80 s. Van Assche et
al.[22] gave a detailed description of this method applied
to thermosetting systems.
Finally the moisture content of the fibers, which is
another essential parameter, was determined as a func-
tion of the relative humidity. Various saturated salt
solutions were prepared in sealed buckets to have con-
stant relative humidity environments. Three fiber mat
samples, previously dried at 105
C for 2 h and weighed,
were kept in these buckets for 48 h. They were then
weighed again and their moisture content was calcu-
lated. Table 1 summarizes the different salt solution
used and the relative humidity achieved. The rate of
moisture absorption by the fibers was also determined.
Various fiber mat samples were dried at 105
C for 2 h
and then swiftly placed on a scale where the weight’s
Table 1
Equilibrium relative humidity values for selected saturated aqueous
salt solutions
Temperature Magnesium nitrate Sodium chloride Potassium nitrate
(
C) Mg(NO3)2 (%) NaCl (%) KNO3 (%)
20 54.40.2 75.50.1 94.6 0.7
25 52.90.2 75.30.1 93.6 0.5
30 51.40.2 75.10.1 92.3 0.6
633
evolution with time was recorded. These experiments
were performed in a standard room at 23
C, 50%RH.
2.3. Mechanical properties
The tensile and flexural strength of the composites
were determined using a SATEC T10000 Materials
Testing System. The tensile properties of the materials
were measured following the ASTM standard method
D638-99. The flexural properties were obtained accord-
ing to the ASTM standard method D790-99. The size
and shape of the different samples were chosen depend-
ing of their thickness as mentioned in these methods.
2.4. Materials
In this study the commercial unsaturated polyester
resin Stypol 040-8086 from Cook Composites and
Polymers was chosen. This resin is manufactured for use
in closed mold processes such as RTM. It is a low vis-
cosity resin, which starts reacting by addition of an
initiator. In this case the chosen initiator was MEKP
DDM-9 from Ato-FINA. The resin manufacturer
recommends to use an initiator concentration between
0.9 and 2.3% by weight. Therefore three different con-
centrations were investigated during the kinetic study: 1,
1.5 and 2%. Following this kinetic study it was decided
that a MEKP concentration of 1.5% should give the
best results. As most commercial products this resin
contains small amounts of inhibitor and promoters.
The fibers used in this study were manufactured by
Flaxcraft, Inc. The Bastmat 100 was a 4 mm mat made
of 67% hemp fibers and 33% kenaf fibers.
3. Model
In this study a one-dimensional curing model was
used. The dimensions of the mold allowed the one-
dimensional model to predict accurately the tempera-
ture variations in the part at a reasonable distance from
its sides. If one wanted to predict the temperatures close
to the mold’s sides a two or three-dimensional model
would have to be implemented. The process as well as
the nature of the resin permitted a few more assump-
tions that simplified the problem greatly:
 the resin was assumed to start curing after the
filling process, once the mold was heated up. This
is a valid assumption, even though the filling time
increased with increasing fiber content, since the
mold was filled at a temperature between 15 and
20
C at which the resin did not cure right away
[23].
 it was assumed that there was no significant
deformation during curing. The resin was
634 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644

expected to shrink during curing, however the
max ¼0:3339þ0:6661=ð1 þ expð ðT 284:725Þ=18:798ÞÞ
presence of fibers limited this effect. ð7Þ
 the radiative and convective heat transfer were
neglected. For unsaturated polyester resin the
chemical gelation (when a macroscopic network The Crank–Nicholson finite difference method was
is formed for the first time in the curing material) used to integrate the governing equations [25]. For a
is known to occur at a conversion lower than 5% one-dimensional problem this method was shown to be
[24]. This effect added to the presence of fibers in very stable with time step size. First the domain was
the composite limited greatly the effect of con- divided in N 1 equal intervals with the grid size being
vection. The fact that the reaction took place in a x=e/(N 1), where e is the thickness of the mold. The
closed mold heated with water allowed to neglect nodes i=1 and i=N corresponded to the boundaries of
radiative heat transfer. the domain (the upper and lower wall of the mold’s
cavity). In the time domain the grid size was t and the
With the assumptions made above the temperature index j was used to count the time, such as tj=j(t).
solutions are based on Fourier’s heat conduction equa- The partial differential equations in Eq. (1) were eval-
tion for one-dimensional, transient heat transfer and an uated at time tj+t/2:
internal heat generation term [16–18]:  
@T Ti;jþ1 Ti;j
 ð8Þ
@T @2 T @Q @t i;jþ1=2 Dt
c Cpc ¼ kx 2 þ ð1Þ
@t @x @t  
where c, Cpc and kx are density, heat capacity and @2 T 1

thermal conductivity of the composite material @x2 i;jþ1=2 2
 
respectively. These parameters depend on the fiber Tiþ1;j 2
Ti;j þ Ti 1;j Tiþ1;jþ1 2
Ti;jþ1 þ Ti 1;jþ1
content, the degree of cure of the resin and tempera- þ
ðDxÞ2 ðDxÞ2
ture. The study of these thermophysical properties
ð9Þ
allowed to decide whether they should be kept con-
stant or not. The results are presented and commented The source term in Eq. (1) could not be evaluated at
later. tj+t/2, therefore, as an approximation, it was eval-
The heat generation source in Eq. (1) represents the uated at t using Eq. (2), giving:
exothermic effect of the curing reaction. This term is    2   
@T @ T @Q
directly related to the rate of cure by the following c Cpc ¼ kx 2
þ ð10Þ
equation: @t i;jþ1=2 @x i;jþ1=2 @t i;j

dQ d

¼ r Vr Hu ð2Þ For each j this system had to be solved on all the
dt dt
spatial domain, for i=2..N 1. The temperatures at
where
is the degree of cure, Hu the ultimate enthalpy the wall (i=1 and i=N) were known as functions of
of cure per unit mass of resin, Vr the volume fraction of time and used as boundary conditions. This led to a
resin in the composite, r the density of the resin and (N 2,N 2) tridiagonal matrix that was solved using
d
/dt the rate of cure reaction. the Thomas algorithm [25]. Once the temperature in
The curing rate of the resin was studied by DSC in a the domain at tj+t were found the cure rate
previous publication [23] using the following empirical expression had to be integrated as well, to track the
autocatalytic model: degree of cure at each node. The degree of cure at
d
tj+t was:
¼ k2
m ð
max
Þn ð3Þ  
dt d


i;jþ1 ¼
i;j þ
Dt ð11Þ
dt i;jþ1
The different parameters were found to be tempera-
ture dependent and were defined as follow for a 1.5%
initiator concentration: The cure rate was computed from Eq. (3), which
m ¼ 0:5 ð4Þ made Eq. (11) nonlinear. A dichotomy method was used
to solve this system at each node.
  A Visual Basic code was written to solve all these
43755:2
k2 ¼ 50147:8
exp ð5Þ equations and compute the evolution of temperature,
RT
degree of cure and cure rate in the mold during a typical
n ¼ 0:00022
T 2 0:1155
T þ 15:6181 ð6Þ experiment. The wall temperature were measured
experimentally and used as boundary conditions to
increase the accuracy of the modeling work.
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
4. Results and discussion
4.1. Thermophysical properties
Prior to any experimental work with the mold the
moisture content of the fiber mat was measured at dif-
ferent relative humidity levels. This is a critical variable
T 2 0:0172
T þ 2:548 ð12Þ
in composite processing since the presence of too much
water in the fibers could create gas bubbles in the
material leading to voids and poor mechanical proper-
ties. Fig. 2 shows the results of these experiments. It can
be observed that the moisture content at 50%RH was
only of 4.1%. The amount of water present in the fibers
started increasing dramatically above this point to reach
over 12% at 94%RH. The fibers were therefore kept in
a standard room at 23
C, 50%RH permanently to
avoid any moisture build up due to variations in atmo-
spheric conditions. The rate of moisture absorption of
the fibers after drying for 2 h at 105
C was also mea-
sured. Fig. 3 shows that the fibers absorbed moisture
quite fast in the first 15 min, to reach a level of 1.5%
moisture content. Then the rate of absorption slowed
down and it took many hours for the fibers to reach their
equilibrium moisture content. Hence, to avoid any
problem with moisture during processing, the fibers were
dried in the mold under vacuum. This way the fibers
could not absorb any water after the drying process.
The heat capacity of the fibers was measured as well
using DSC. Fig. 4 shows that the fiber’s Cp increased
from 1.2 to almost 2.3 J/g K with increasing tempera-
ture up to 130
C. After this point the signal started to
level off and then decreased above 160
C. This final
drop could be explained by the decomposition of the
fibers [1]. The signal’s discrepancies, around 70 and
Fig. 2. Moisture content of the fiber mat at different relative humidity levels.
635
150
C, can be explained by some measurements
errors from the DSC equipment due to the very small
amount of fibers analyzed (less than 3 mg). The var-
iation of the fiber’s heat capacity could be fitted quite
well by a polynomial of the second order in the range
35–130
C:
Cpf ¼ 41:30e 6
Other fibers properties, such as density or thermal
conductivity, could not be measured easily. The density
of flax and hemp fibers was assumed to be 1.45 g/cm3 in
the rest of this study to evaluate the volume fractions of
fibers in the composites [6].
The different properties of the resin were measured
for the liquid and solid material. They are summarized
in Table 2. It can be seen that the difference in thermal
conductivity and density between the liquid and the
fully cured resin was not dramatic (10–15%). For this
reason these two parameters were kept constant for the
modeling part of this work and equal to the values for
the solid polyester. The heat capacity however showed a
much more important drop in value between the liquid
and solid resin. A more detailed study of this property
was therefore needed prior to any modeling.
The evolution of the heat capacity with the degree of
cure was first measured using a MTDSC apparatus. An
isothermal experiment, at 35
C, was performed. This
low temperature was chosen because the slower reaction
is easier to follow. The software calculated the varia-
tions of Cp along the experiment. The results were plot-
ted versus the degree of cure, Fig. 5. The heat capacity
started by decreasing slowly with increasing degree of
cure. As the degree of cure approached the point of
vitrification, which corresponds to the maximum degree
636 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644

Fig. 3. Water absorption rate of the fibers under standard conditions after drying for 2 h at 105
C.

Fig. 4. Heat capacity of the fiber mat measured by DSC in the range 35–200
C.

Table 2 for the liquid resin (within 5%). The heat capacity
Thermophysical properties of the liquid resin and the fully cured resin values shown here were calculated directly by the soft-
Property Liquid resin Fully cured resin ware, without any corrections and calibrations. Little
trust could be put in these values, however in this case
Thermal conductivity (W/m K) 0.14 0.16 the evolution with the degree of cure was the important
Density (kg/m3) 1094.9 1184.9
Cp (J/kg K) (at 35
C) 1630 1120
trend to measure. Limited access to the MTDSC appa-
ratus did not allow any other measurements. From
these data it can be concluded that using the heat capa-
of cure in an isothermal experiment [22] (around 86% at city of the liquid resin in the model would be a good
35
C), the drop in heat capacity accelerated dramati- approximation. In the next step the heat capacity of the
cally. The experiment was stopped slightly too early, resin was hence measured as a function of temperature.
before the heat capacity had reached a stable value for Fig. 6 presents the results obtained by DSC measure-
the solid resin at 35
C. However this graph shows that ments. It can be seen that the non-cured resin’s heat
for most of the curing experiment (below a degree of capacity increased linearly with temperature in the
cure of 75%) the Cp values were close to the initial value range 35–160
C. The values varies from 1.65 to 2.05 J/g
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644 637

Fig. 5. Heat capacity as a function of the degree of cure measured with a MTDSC apparatus at 35
C.

Fig. 6. Variations of the liquid resin’s heat capacity with temperature.

K approximatively. These variations could not be Cpc ðTÞ ¼ Cpr ðTÞ

mr þ Cpf ðTÞ
mf ð14Þ
neglected in the model and the following linear rela-
tionship was used as the resin’s heat capacity in J/g K:
Cpr ¼ 0:00346
T þ 0:551 ð13Þ
To predict accurately the temperature variations in
the mold the heat capacities of the composite materials
were needed as well. However a study of the variations
of Cp with the fiber content and temperature was not
feasible in this study. It was therefore decided to evalu-
ate the heat capacity of the composite using the rule of
mixture with Eqs. (12) and (13):
where mf and mr are the mass fraction of fibers and
resin, respectively.
The thermal conductivity of some solid composite
samples was measured as well using the k-a apparatus.
The results are presented in Table 3. It can be observed
that the thermal conductivity of solid composites did
not vary much with fiber content. This could be
explained by the low volume fractions of fibers in the
composites and the low thermal conductivity of the
fibers themselves. Cellulose has a conductivity of 0.44
638 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
Table 3
Thermal conductivity of natural fiber composites with various fiber
contents
Fiber volume content (%) Thermal conductivity (W/m K)
0 0.16
10.7% 0.16
16.2% 0.17
20.6% 0.17
W/m K and the fibers are hence expected to be below
this value. This is one of the main differences with syn-
thetic fibers. Fibers such as fiberglass or carbon fiber
have a high thermal conductivity compared to the
matrix. It is therefore expected that the natural fiber
composites will have more thermal build up during
processing. This is a major issue for the manufacture of
such materials since the fibers are very sensitive to high
temperatures. This will be developed in the next section
of this work.
4.2. Resin transfer molding of natural fiber composites
As explained earlier composites with various fiber
contents were prepared using the RTM process. The
fiber mats were first placed in the mold and dried under
vacuum. The water evaporating from the fibers could be
observed in the liquid trap connected to the vent port.
Since some of the moisture was expected to flow
through the flask to the tap, these results were not very
consistent and are not presented here. However the
mass of water trapped was measured each time and,
knowing that the initial moisture content of the fibers
was approximately 4.5%, an approximate moisture
content after drying could be calculated. It was found
that the moisture content of the fibers for every experi-
ment was below 1.5%. Once the fibers were dried for 2
h, resin was injected at a constant gauge pressure of
1.72105 Pa. This pressure was chosen by trial and
error to provide the shortest injection time possible
coupled with a proper wetting of the fibers (knowing
that the maximum gauge pressure in the system should
not exceed 2.07105 Pa for safety).
The mold being entirely made of aluminum the flow
front could not be observed during the resin’s injection.
The injection time increased dramatically with increas-
ing fiber content. Table 4 summarizes the injection time
for various fiber contents. Time collection was started
with the injection of the resin and the values in Table 4
correspond to the time when the resin was first observed
exiting the mold through the vent port. These results
were expected since an increase in fiber’s content
decreased the permeability of the fabric in the mold,
hence increasing its resistance to resin’s flow. More
work is needed to quantify these permeability and com-
pare them to the ones obtained with synthetic fibers.
Table 4
Injection time for a 1.72105 Pa gauge pressure at various fiber con-
tent
Fiber volume content (%) Injection time (min)
0 1.5
10.7% 6
16.2% 11
20.6% 19
Composites with fiber content higher than 22% by
volume could not be manufactured without risking cur-
ing the resin before the end of the injection process. In
that case all the piping system as well as the pressure pot
and the ports could be clogged. The injection time could
be decreased easily by drilling two more inlet ports.
However the main limitation for not reaching fiber
contents above 22% was the fact that the mold had to
be closed manually. The natural fiber mats have a ten-
dency to spring back when they are compressed, and
placing more than 12–13 layers of fibers in the mold
(around 22% fiber content by volume) made it almost
impossible to close it because of the manual mode of
operation in the lab set-up. Hence the initial design was
kept unmodified. One possible solution would be to pre-
press the mats at a high temperature (above 80
C) and
at a defined thickness to reduce their spring back beha-
vior and allow more fibers to be placed in the mold.
This is currently under investigation.
Once the mold’s filling was completed the data acqui-
sition system was started to record the temperatures at
different locations in the mold. The temperature at the
wall of the cavity was essential for the modelization of
the curing reaction, since it was used as boundary con-
dition in the model. A typical temperature profile at this
location is presented in Fig. 7. It can be seen that the
temperature increased quite fast till the point where it
reached the set point. The water temperature being
controlled by a heater and a cooling coil, small fluctua-
tions could be observed. To be implemented easily in
the model the temperature at the wall was fitted by the
following function for each experiment:


TðtÞ ¼ T0 þ a 1 bt ð15Þ
where T0 is the initial temperature in the mold, a+T0
the final temperature and b an adjustable parameter. It
can be seen in Fig. 7 that this type of function fitted
perfectly the experimental data. The same agreement
was observed for all the other experiments. In the rest of
this work all the curves corresponding to wall’s tem-
peratures will be fitted curves, for clarity.
First a plastic part with no fibers was manufactured to
test the model. One important comment at this stage is
that the kinetic model presented earlier [Eqs. (3)–(6)] did
not take into account the presence of inhibitor in the
resin. This means that if the model was implemented as
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644 639

Fig. 7. Temperature at the wall: experimental and fitted curves.

such the curing would start right away. However in the
reaction the inhibitor decomposes first and then the
exothermic curing reaction starts. In the early stage of
the RTM process, once the mold starts heating up, the
variations of temperature observed in the resin would
therefore only be created by conduction. In the litera-
ture it was found that most inhibitors exhibited zeroth
order disappearance [18]. The change in relative inhi-
bitor concentration is therefore given by:
Z d

d ¼ k2
m ð
max
Þn
Z0
¼ kinhib ð16Þ
dt
where Z is the inhibitor concentration, Z0 its original
concentration and kinhib the rate constant which is
assumed to follow an Arrhenius relationship.
The different parameters for this equation could not
be determined experimentally. The isothermal DSC
experiments performed to study the kinetics of the resin
[23] did not permit to measure the induction times
accurately. It was therefore decided that the influence of
the inhibitor would be evaluated by trials and errors in
the model. This way, and with enough experimental
data, the parameters of Eq. (16) could therefore be cal-
culated afterwards.
A comparison between the experimental data col-
lected for the pure resin system in the centre of the mold
and the model is presented in Fig. 8. This experiment
was performed with a constant wall temperature of
approximately 53
C. It could be immediately noted
that the model over predicted by 20
C the temperatures
measured at the centre of the part. The position of the
peak predicted by the model was shifted to the left
compared to the experiment as well. However the first
part of the curve, when the centre of the part slowly
heated up by conduction, was very well predicted. In
this portion there was no heat created by the curing
reaction. It was found by the trials and errors method
that the cure reaction started around 51.5
C. Obviously
the model predicted too much heat generated by the
resin, and therefore too high curing rates. A correcting
factor b was introduced in the model to reduce the cur-
ing rates, and Eq. (3) was rewritten as follow:
ð17Þ
dt
The results given by the modified model for =0.6,
are presented in Fig. 9. The predicted temperatures were
in very good agreement with the experimental data. The
model predicted the degree of cure and the rate of cure
of the resin with time as well, as shown in Fig. 10. After
an induction time of approximately 3.5 min the curing
rate of the resin increased sharply with time to reach a
maximum after 9 min or at a degree of cure of 26%.
After this point the rate of cure decreased first rapidly
and then slower and slower with time. The model pre-
dicted a degree of cure of 86.3% after an hour of curing
under these conditions. To validate these predictions the
experiment with the pure resin system was stopped after
1 h and the mold was cooled down as fast as possible
with cooling water to stop the reaction. The residual
enthalpy of reaction was then measured for two sam-
ples as close as possible to the centre of the part. These
two specimens had degree of cure of 85.9 and 86.6%
and were therefore in complete agreement with the
model. This experiment with no fibers permitted to
modify the model to fit fairly well the experimental
data. The value assigned to  for this experiment with
640 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644

Fig. 8. Comparison of RTM experiment and simulation for pure resin system.

Fig. 9. Comparison of RTM experiment and corrected model for a pure resin system.

a pure resin system was then used for all the other
systems with fibers.
This correcting factor was chosen after verification of
all the parameters used in the model. Even though some
approximations were made for the thermophysical
properties of the system none can explain the tempera-
ture overshoot observed in Fig. 8. This difference could
be due to the fact that a different batch of resin was used
for the kinetics study and the experiments with the
mold. Moreover the initiator was close to reach its shelf
life when the experiments were performed. These two
reasons could explain the necessity for a correcting fac-
tor in the model. Experiments are currently performed
with a new batch of initiator. The results will be repor-
ted in a future publication.
The results obtained for composites with fiber con-
tents of 9.5 and 16.7% (by volume) are reported in
Figs. 11 and 12 respectively. It can be seen that the
model fitted fairly well the experimental data. Some
discrepancies could be explained by the approximations
made to describe the thermophysical parameters of the
system. Some variations such as the evolution of the
density or the heat capacity of the system with the
degree of cure were neglected for instance. Fig. 12 shows
the temperatures at two different positions in the mold
for a system with 16.7% fiber content. The temperature
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644 641

Fig. 10. Evolution of the degree of cure and the rate of cure with time at the centre of the mold for a pure resin system.

Fig. 11. Comparison of RTM experiment and model for a system with 9.5% fibre content.

in the centre of the part was substantially higher than at
2.6 mm from the wall. The different experiments pre-
sented in Figs. 10–12 could not be compared with each
other because the wall temperatures were not identical
for each system. Moreover the presence of fibers in the
mold created some pressure on the cavity’s walls and
made them bulged. This effect increased with increasing
fiber content due to the sprint back behavior of the
mats. Therefore the thickness of the parts was not con-
stantly equal but varied from 6.7 mm on the edges to a
maximum in the centre slightly above 8 mm for the
highest fiber content studied (around 21%). Hence,
after each experiment the location of each thermocouple
had to be determined very precisely along with the
thickness and the density at this particular point. These
parameters were the ones used in the model to predict
the temperatures. However it is possible to notice that
even in the presence of fibers the crosslinking reaction
produced an important exotherm at the centre of the
part. Similar trend would be observed at higher fiber
contents since the thermal conductivity is only slightly
modified by the presence of natural fibers. This behavior
is different than that observed for synthetic fiber com-
posites. The addition of glass fibers or carbon fibers, for
instance, to a thermoset matrix changes its properties
and reduces significantly the exotherm in the centre of
642 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
Fig. 12. Comparison of RTM experiment with model for a system with 16.7% fiber content.
the part. One major change in this case is a substantial
increase in thermal conductivity, as mentioned before,
which allows a better conduction of heat towards the
walls of the mold. Since the thermal conductivity of the
natural fiber composites were very close to the thermal
conductivity of the matrix the exotherm were still
important. Only a slight reduction could be noticed and
was easily explained by the decrease in resin’s volume
fraction in the part.
These last comments are very important when it
comes to optimize the process. The final degree of cure
predicted by the model for the experiment presented in
Figs. 11 and 12 are shown in Table 5. The values
obtained are all in the same range, around 86–87%. It
can be seen from the experiment with 16.7% fiber con-
tent that the final degree of cure is slightly higher in the
centre of the part, as expected. As observed in other
publications the curing reaction starts at the wall and
progresses towards the centre, then, due to the higher
temperature in the centre of the part, the crosslinking
occurs at a faster rate in the middle leading to a higher
degree of cure. The extents of cure obtained in these
experiments were quite low. To obtain optimum
mechanical properties this value should be closer to
Table 5
Final degree of cure predicted by the model for the experiments
presented in Figs. 11 and 12
Experiment Degree of cure (%)
Fig. 11—centre 85.9
Fig. 12—wall 86.7
Fig. 12—2.6 mm 87.2
Fig. 12—centre 87.3
100%. One objective is to obtain the best parts possible
in a minimum time. There are two ways of reaching this
goal. First the model could be used to optimize the wall
temperature, for a specified fiber content, to reach a
high degree of cure in a shorter time. In the meantime
the temperature at the centre of the mold should not
exceed 140
C to avoid any decomposition of the fibers.
It is expected that the model would be less accurate at
high temperature since the curing kinetics was studied in
the range 25–65
C [23]. The second way would be once
again to use the model but this time to reach as fast as
possible a degree of cure of 85% for instance, respecting
the same upper temperature limit as just mentioned.
Then the part could be post cured at a temperature of
120
C to make sure that the degree of cure would be
100%. This operation could be performed inside the
mold by ramping the temperature of the heating med-
ium to the post cure level. However any of these pre-
dictions would have to be supported with some
experimental measurements. In its current design the
mold used in this work could not perform any of these
tasks since the heating medium was hot water. The
highest temperature that the system could reach and
kept balanced was around 75
C, far from the require-
ments to reach 100% degree of cure. Further work will
have to be performed to optimize the process and vali-
date the new procedure.
The natural fiber composites manufactured by the
RTM process in this work were found to be of good
quality. An excellent wetting of the fibers was obtained
and the drying of the fibers prior to resin’s injection
permitted to avoid the formation of small gas bubbles in
the part due to water evaporation. The experiments
coupled with the model showed that the final degree of
 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644 643

Fig. 13. Tensile strength of natural fiber composites.

Fig. 14. Flexural strength of natural fiber composites.

cure was quite low for every part produced and could
therefore be improved. The tensile and flexural strength
tests were performed using samples made from parts
that reached final degree of cure around 86–87% as
shown in the previous section.
The tensile strength results are shown in Fig. 13. As
expected the tensile strength of the samples increased
with increasing fiber content. A substantial increase was
observed between the pure resin and the sample with
20.6% fibers, from 13.1 to 44.3 MPa. After break, fiber
pull out could be observed on the specimens, proving
that the fiber-matrix adhesion could be substantially
improved. For comparison the tensile strength for a
typical fiberglass composite with 20% fibers is around
100 MPa. Similar results were found for the flexural
tests (Fig. 14), with a highest value of 71.4 MPa for the
sample with 20.6% fibers. In this case fiberglass parts
reach a flexural strength of about 180 MPa. In both
cases the mechanical properties measured were well
below the ones obtained with fiberglass. However, the
results should be improved if the degree of cure was
closer to 100%.
5. Conclusions
In this work the manufacture of natural fiber compo-
sites using a resin transfer molding was investigated.
The thermophysical properties of these composites were
studied in details and showed some major differences
when compared to synthetic fiber composites, especially
for the thermal conductivity and density. For the first
time the curing behavior of such materials was pre-
dicted using a curing model based on the resolution of
the one-dimensional Fourier’s heat conduction equa-
tion. Once the model was corrected it predicted very
644 D. Rouison et al. / Composites Science and Technology 64 (2004) 629–644
well the temperatures in the mold. It was observed that
the temperature in the centre of the mold increased
substantially compared to other kinds of composites
due to their lower thermal conductivity. The degree of
cure in the parts was predicted as well. The values were
found to be below 90% for all cases, which is quite low
for such materials. The model could be used to optimize
this process and find the proper procedure to produce
highly cured parts in a minimum time.
The parts obtained in this work were of good quality.
The drying process before the resin’s injection permitted
to obtain a good wetting of the fibers as well as to avoid
any formation of gas bubbles during curing. The
mechanical properties of the specimens were acceptable
and increased with the fiber content. However there is a
lot of room to improve these properties, first by making
sure that the matrix is fully cured and, more impor-
tantly, by improving the fiber-matrix adhesion. But this
will be the topic of another study.
Acknowledgements
The author sincerely acknowledges the financial sup-
port from Network of Centre of Excellence-Auto 21-
Canada, NSERC and Industry partners. Author would
like to take this opportunity to thank the technicians
Keith Rollins and Jody Chessie, for all their help to
make this work possible.
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