Chapter 3.

Processing - Findamentals

The fabrication of composites is a complex process and it requires simultaneous

consideration of various parameters such as component geometry, production volume,
reinforcement & matrix types, tooling requirements and process and market economics.
Fabricating a composite part is generally concerned with placing and retaining fibres in the
direction and form that is required to provide specified characteristics while the part performs its
design function.

3.1 Fundamentals
The chemical reaction of a thermosetting resin forming cross linking is called curing. The
length of time required to properly cure a part is called the cure cycle. Polymer matrices go
through several phase transformations during the curing cycle. When the temperature of a
thermoset matrix is raised to begin the curing cycle, the polymer assumes a fluid state with
significantly reduced viscosity appropriate for flow necessary for complete penetration of the
fiber array. As the cross-linking reaction advances, the physical characteristics of the resin
changes from a liquid to a rubbery state and then to a glassy state. The glass transition
temperature (Tg) is a function of the extent of cure of the thermoset polymer and can be strongly
in influenced by the thermal curing history. Measurement of the glass transition temperature
yields important information regarding the extent of cure as well as the upper use temperature of
the composite system.
The two important parameters that control the manufacturing techniques are temperature
and pressure. High temperature is required to initiate and sustain the chemical reaction that
transforms the uncured or partially cured material into a fully cured solid whereas high pressure
is required to force the highly viscous resin to flow into the fibers and to bind the fibers as well
as for the consolidation of individual un-bonded plies into a bonded laminate. The magnitude of
these two important process parameters, as well as their duration, significantly affects the quality
and performance of the molded product. Since the cure cycle determines the production rate for a
part, it is desirable to achieve the proper cure in the shortest amount of time. It should be noted
that the cure cycle depends on a number of factors, including resin chemistry, catalyst reactivity,
cure temperature, and the presence of inhibitors or accelerators.

3.1.1 Degree of Cure

Gelation is a term that defines the degree of cure wherein the polymer is transformed
from the liquid state to the rubbery state by the presence of the cross-link network. The decrease
in polymer viscosity with temperature and its increase with degree of cure requires that the
necessary flow be achieved prior to gelation. The instantaneous degree of cure of a thermoset
polymer is measured by the fraction of total heat generated at a given time divided by the total
heat of reaction.
The degree of cure at any time t, is defined by,
αc = H/HR
where, H is the amount of heat released in time t and HR is the total heat of reaction

Thus, the degree of cure ranges from 0 to 1.0 and can be measured using Differential
Scanning Calorimetry (DSC), which determines the heat generation and heat of reaction as a
function of time. αc increases with both time and temperature; however, the rate of cure
decreases as the degree of cure attains a maximum value. If the cure temperature is too low, the
degree of cure may not reach a 100% level for any reasonable length of time. Higher cure
temperatures increase the rate of cure and produce the maximum degree of cure in shorter
periods of time. On the other hand, the addition of a low-profile agent, such as a thermoplastic
polymer, to a polyester or a vinyl ester resin decreases the cure rate.

3.1.2 Viscosity
The viscosity of a fluid is defined as the slope of the shear stress–shear rate curve. It is a
measure of resistance of the fluid to flow under shear stresses. Low molecular-weight fluids,
such as water and motor oil, have low viscosities and flow readily. High molecular-weight fluids,
such as polymer melts, have high viscosities and flow only under high stresses.
The two most important factors determining the viscosity of a fluid are the temperature
and shear rate. For all fluids, the viscosity decreases with increasing temperature. Shear rate does
not have any influence on the viscosity of low molecular-weight fluids, whereas it tends to either
increase (shear thickening) or decrease (shear thinning) the viscosity of a high-molecular-weight
fluids (Figure 3.1). Polymer melts, in general, are shear-thinning fluids since their viscosity
decreases with increasing intensity of shearing.

Fig. 3.1 Schematic shear stress vs. shear rate curves for various types of liquids

The starting material for a thermoset resin is a low-viscosity fluid. However, its viscosity
increases with curing and approaches a very large value as it transforms into a solid mass or in
other words, viscosity increases with increasing cure time and temperature. The rate of viscosity
increase is low at the early stage of curing. After a threshold degree of cure is achieved, the resin
viscosity increases at a very rapid rate. The time at which this occurs is called the gel time. The
gel time is an important molding parameter, since the flow of resin in the mold becomes
increasingly difficult at the end of this time period.
A number of important observations can be made from the viscosity data reported in the
literature:
1. A B-staged or a thickened resin has a much higher viscosity than the neat resin at all
stages of curing.
2. The addition of fillers, such as CaCO3, to the neat resin increases its viscosity as well as
the rate of viscosity increase during curing. On the other hand, the addition of
thermoplastic additives (such as those added in low-profile polyester and vinyl ester
resins) tends to reduce the rate of viscosity increase during curing.
 3. The increase in viscosity with cure time is less if the shear rate is increased. This
phenomenon, known as shear thinning, is more pronounced in B-staged or thickened
resins than in neat resins. Fillers and thermo- plastic additives also tend to increase the
shear-thinning phenomenon. 

4. The viscosity η of a thermoset resin during the curing process is a function of cure
temperature T, shear rate , and the degree of cure αc :

The viscosity function for thermosets is significantly different from that for
thermoplastics. Since no in situ chemical reaction occurs during the processing of a
thermoplastic polymer, its viscosity depends on temperature and shear rate. 

5. At a constant shear rate and for the same degree of cure, the η vs. 1/T plot is linear.

The activation energy for viscous flow increases with the degree of cure and approaches a very
high value near the gel point.

3.1.3 Resin flow

Proper flow of resin through a dry fiber network (in liquid composite molding [LCM]) or a
prepreg layup (in bag molding) is critical in producing void-free parts and good fiber wet-out. In
thermoset resins, curing may take place simultaneously with resin flow, and if the resin viscosity
rises too rapidly due to curing, its flow may be inhibited, causing voids and poor inter-laminar
adhesion.
Uneven distribution of resin may result from non-uniform flow of the polymer through
the fiber reinforcement. This is particularly pronounced for laminates with curvilinear geometry
and tapered thickness, in which local pressure gradients occur. The velocity of flow of a polymer
through a porous medium such as a fiber array has been shown to be proportional to the pressure
gradient and inversely proportional to the polymer viscosity. The proportionality constant is
known as the fiber array permeability.

3.1.4 Consolidation
Consolidation of layers in a fiber network or a prepreg layup requires good resin flow and
compaction; otherwise, the resulting composite laminate may contain a variety of defects,
including voids, interply cracks, resin-rich areas, or resin-poor areas. Good resin flow by itself is
not sufficient to produce good consolidation.
Both resin flow and compaction require the application of pressure during processing in a
direction normal to the dry fiber network or prepreg layup. The pressure is applied to squeeze out
the trapped air or volatiles, as the liquid resin flows through the fiber network or prepreg layup,
suppresses voids, and attains uniform fiber volume fraction. The average effective pressure on
the fiber network increases with increasing fiber volume fraction, that is, the fiber network
begins to take up an increasing amount of the applied pressure. On the other hand, the average
pressure on the resin decreases with increasing compaction, which can lead to void formation.

3.1.5 Gel-time test

The curing characteristics of a resin–catalyst combination are frequently determined by the gel-
time test. In this test, a measured amount (10g) of a thoroughly mixed resin–catalyst combination
is poured into a standard test tube. The procedure of the test is as below:
 1. Take resin and catalyst and mix them thoroughly.
2. Pour the mix into a standard test tube which is suspended in 82°C (or 180°F) water bath.
3. Insert a thermocouple in the test tube to monitor the temperature rise.
4. Record the time and the corresponding temperature rise.
5. Plot the graph Time vs Temperature.
6. From the graph, note down the point at which there is a sudden rise in temperature. The
time corresponding to that point gives the gel time.

A typical temperature–time curve (also known as exotherm curve) obtained in a gel-time test is
illustrated in Figure 3.2

Fig. 3.2 Typical temperature–time curve obtained in a gel-time test.

On this curve, point A indicates the time required for the resin–catalyst mixture to attain
the bath temperature. The beginning of temperature rise indicates the initiation of the curing
reaction. As the curing reaction begins, the liquid mix begins to transform into a gel-like mass.
Heat generated by the exothermic curing reaction increases the resin–catalyst mixture
temperature, which in turn causes the catalyst to decompose at a faster rate and the reaction to
proceed at a progressively increasing speed. Since the rate of heat generation is higher than the
rate of heat loss to the surrounding medium, the temperature rises rapidly to high values. As the
curing reaction nears completion, the rate of heat generation is reduced and a decrease in
temperature follows. The exothermic peak temperature observed in a gel-time test is a function
of the resin chemistry (level of unsaturation) and the resin–catalyst ratio. The slope of the
exotherm curve is a measure of cure rate, which depends primarily on the catalyst reactivity.
Shortly after the curing reaction begins at point A, the resin viscosity increases very rapidly,
owing to the increasing number of cross-links formed by the curing reaction. The time at which a
rapid increase in viscosity ensues is the gel time and is indicated by point B in Fig.3.2
3.1.6 Shrinkage
Shrinkage is the reduction in volume or linear dimensions caused by curing as well as
thermal contraction. Curing shrinkage occurs because of the rearrangement of polymer
molecules into a more compact mass as the curing reaction proceeds. The thermal shrinkage
occurs during the cooling period that follows the curing reaction and may take place both inside
and outside the mold.
The volumetric shrinkage for cast-epoxy resins is of the order of 1%–5% and that for polyester
and vinyl ester resins may range from 5% to 12%. The addition of fibers or fillers reduces the
volumetric shrinkage of a resin. However, in the case of unidirectional fibers, the reduction in
shrinkage in the longitudinal direction is higher than in the transverse direction.
High shrinkage in polyester or vinyl ester resins can be reduced significantly by the addition of
low shrink additives (also called low-profile agents), which are thermoplastic polymers, such as
polyethylene, polymethyl acrylate, polyvinyl acetate, and polycaprolactone. These thermoplastic
additives are usually mixed in styrene monomer during blending with the liquid resin. On curing,
the thermoplastic polymer becomes incompatible with the cross-linked resin and forms a
dispersed second phase in the cured resin. High resin shrinkage is desirable for easy release of
the part from the mold surface; however, at the same time, high resin shrinkage can contribute to
many molding defects, such as warpage and sink marks.

3.1.7 Voids
Among the various defects produced during the molding of a composite laminate, the
presence of voids is considered the most critical defect in influencing its mechanical properties.
The most common cause for void formation is the inability of the resin to displace air from the
fiber surface during the time fibers are coated with the liquid resin. The rate at which the fibers
are pulled through the liquid resin, the resin viscosity, the relative values of fiber and resin
surface energies, and the mechanical manipulation of fibers in the liquid resin affect air
entrapment at the fiber–resin interface. Voids may also be caused by air bubbles and volatiles
entrapped in the liquid resin. Solvents used for resin viscosity control, moisture, and chemical
contaminants in the resin, as well as styrene monomer, may remain dissolved in the resin mix
and volatilize during elevated temperature curing. In addition, air is also entrapped between
various layers during the lamination process.
Most of the air or volatiles entrapped at the pre-molding stages can be removed by (1)
degassing the liquid resin, (2) applying vacuum during the molding process, and (3) allowing the
resin mix to flow freely in the mold, which helps in carrying the air and volatiles out through the
vents in the mold.
The presence of large volume fractions of voids in a composite laminate can significantly
reduce its tensile, compressive, and flexural strengths. Large reductions in inter-laminar shear
strength are observed even if the void content is only 2%–3% by volume. The presence of voids
generally increases the rate and amount of moisture absorption in a humid environment, which in
turn increases the physical dimensions of the part and reduces its matrix-dominated properties.