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Polymer Matrix Composites: Matrices there is considerable overlap, the toughness of FRPs

based on both classes of resins being highly sensitive


and Processing to, for example, fiber morphology, interfacial ad-
hesion, and the presence of additives (see Composites:
Polymer matrix composites, and fiber-reinforced plas- Interfaces, Continuous Parallel Fiber Composites:
tics (FRPs) in particular, are commonplace in the Fracture). Moreover, each class of resins encompasses
industrialized world; their applications range from a wide variety of materials and materials properties,
primary structural aircraft components to tennis which will now be presented in more detail along with
racquets, and many household appliances incorporate typical applications. A more systematic discussion of
some form of fiber reinforcement. The development of the applications of polymer matrix composites is to be
engineering FRPs began once significant quantities of found in Polymer Matrix Composites: Applications.
glass fiber became available in the 1940s, and was
initially performance driven (e.g., for aerospace). Since
then, reduction of materials costs has greatly widened
their range of applications, and the impetus for 1.1 Thermoset Resins
continued development stems mainly from economic There are several main types of thermosets, distin-
factors such as efficient fabrication and transform- guished by their chemistry, curing mechanisms, and
ation, and a need for the energy savings possible with final properties (Charrier 1990). Those discussed here
low-weight, high-strength, and high-modulus ma- are the most important for FRPs, namely polyesters,
terials. However, FRPs have the major disadvantage epoxies, and high-performance thermosets, although
with respect to metal- and ceramic-based structural other thermosets, including polyurethanes (PUs), sili-
materials that their service temperatures are limited to cone rubbers, and phenol–formaldehydes (PFs), are
below 400 mC, even for the most advanced matrices. also sometimes used as FRP matrices (e.g., PF–aramid
An overview is given in this article of the most composites for aircraft interiors).
widely used FRP matrix materials and their relative
merits. The various stages of processing to form
composite parts are discussed, with reference to cost
forecasting, life cycle engineering, and developing (a) Unsaturated polyesters. Unsaturated polyesters
technologies. Finally, the important question of (UPs) are the most widely used thermosets for FRPs.
process–structure–property relationships in thermo- They consist of prepolymers cross-linkable by ad-
set- and thermoplastic-based FRPs is addressed. dition, initiated photolytically or by thermal de-
composition of peroxides. Processing involves most
of the methods described in the next section, and in-
deed UPs were originally developed for use in FRPs.
1. Matrix Materials However, to ensure adequate flow behavior, up to
50 wt.% styrene co-reagent is often added to give a
Apart from injection molding thermoplastics, which so-called UPE resin. Environmental concerns have
typically contain short ( 1 mm) fibers, most FRPs since led to the use of low styrene emission additives
are based on thermoset resins. Thermosets can be in UPEs. These segregate to, and seal, the surface dur-
cured catalytically, thermolytically, or photolytically ing the final stages of cure, compromising adhesion
over a wide range of temperatures to give highly cross- in some cases. Another potential difficulty is excess-
linked solids. One of their principal advantages for ive shrinkage, but this is largely avoided by the use
FRPs is their low initial viscosity, which facilitates of thermoplastic low profile additives. Once cured,
fiber impregnation, particularly where the base ‘‘A- unsaturated polyesters have heat deflection tempera-
stage’’ resin consists of monomeric or oligomeric tures (HDTs) ranging from 80 mC to 150 mC in certain
components. Partial cure may then be used to produce vinylester resins (the HDT is a softening temperature
solid ‘‘B-stage’’ prepregs used as precursors for a measured according to industrial norms and marks
variety of processing routes. There is nevertheless the approximate upper limit to the range of service
great interest in thermoplastic polymers; although the
high molar mass of thermoplastics implies that higher Table 1
processing temperatures or specialized techniques are Property and process characteristics of thermosets and
needed for impregnation, this may be outweighed thermoplastics.
by other factors: (i) they are generally nonreactive,
implying an indefinite shelf-life for precursors; (ii) Property Thermoset Thermoplastic
forming processes are reversible, facilitating recycling Modulus High Medium
and repair; and (iii) cycle times are not limited by Service temperature High Medium
reaction kinetics, and mixing steps, which may involve Toughness Medium High
toxic precursors and need careful control to ensure Viscosity Low High
reproducibility, are eliminated. Table 1 summarizes Processing temperature Low High
the main trends, although it should be stressed that Recyclability Limited Good

1
Polymer Matrix Composites: Matrices and Processing

temperatures). Their main composite applications in- temperatures well above the glass transition tem-
clude the construction industry, the transport indus- perature, Tg. However, since semicrystalline polymers
try (boats, car body panels), furniture, and chemical melt well above Tg, it is the melting point, Tm, that
storage tanks. defines the processing window. Whereas thermoset
designations tend to be generic, most thermoplastics
have well-defined linear architectures that undergo
little change during processing. Their property profiles
(b) Epoxy resins. Epoxy resins may also be used in are generally adjusted for different processing routes
conjunction with most composite processing tech- by varying the molar mass or additive package
niques, and are particularly suited to B-stage process- (Charrier 1990); however, it should be borne in mind
ing. Cure generally involves polyaddition with a multi- that other important properties such as toughness and
functional co-reagent, referred to as the ‘‘hardener,’’ ultimate tensile strength are also highly sensitive to
to produce a three-dimensional network with low changes in molar mass.
shrinkage, and excellent adhesion and environmental
resistance. Drawbacks of conventional resins include
somewhat higher viscosities than in UPEs, long cure
times, and moisture uptake. A wide range of resins (a) Semicrystalline thermoplastics. Semicrystalline
and co-reagents is nevertheless available, products thermoplastics are tough and resistant to organic
ranging from tough low-temperature epoxies to more solvents, but many inexpensive and easy-to-process
brittle, high-temperature epoxies for advanced FRPs low Tg polymers, such as polyethylene, also show
(prepregs for aircraft components account for poor adhesion owing to their lack of functionality,
around 30% of total production). Commonly used and low softening temperatures, often associated
aliphatic amine hardeners permit room temperature with excessive creep. A good compromise between
cure, but the reaction is strongly exothermic, causing cost and performance is provided by polypropylene
problems in thick moldings. Aromatic amine harden- (PP, Tm $ 170 mC), for which functionalized additives
ers require higher curing temperatures but are better are available to improve adhesion. PP is widely used
suited to large parts and give relatively high HDTs in FRP applications in the automotive industry, for
(up to 230 mC). Anhydride hardeners are less toxic example, owing notably to glass mat thermoplastic
and less polar than amines, but need an accelerator. technology. Polyamides (PAs or nylons), such as
With suitable catalysis, epoxies may also be cured PA6 and PA6,6, are also popular, having higher
thermally or photolytically without a co-reagent. HDTs than most thermosets, although they are
moisture sensitive and more than twice as expensive
as PP. Another polyamide of interest for FRPs is
PA12, the versatile synthesis and functionality of
(c) High-performance thermosets. High-performance which make it especially attractive for reactive FRP
thermosets include allyls, cyanate esters, and liquid processing.
crystalline thermosets. Among the most successful High Tg semicrystalline polymers such as
are addition polyimides, developed mainly for the poly(phenylene sulfide) (PPS) and poly(ether ether
aerospace and electronics industries. Their HDT may ketone) (PEEK) require correspondingly high process-
reach 400 mC after cure, and they have excellent ing temperatures, PEEK melting at about 345 mC, for
stiffness and environmental resistance. The cure mech- example. However, these polymers have outstand-
anism is thermally induced free radical addition of a ing properties, including exceptional toughness and
polyimide precursor via reactive end groups in the fatigue resistance. Particular effort has gone into
presence of peroxide, avoiding problems with the PEEK–carbon fiber composite technology, leading to
volatile by-products of conventional condensation the so-called aromatic polymer composite (APC)
reactions. Applications include jet and automobile prepregs, considered to be a major step in the
engine components, heat-resistant panels, etc. How- development of advanced thermoplastic matrix FRPs
ever, some potential future applications of high- (Cogswell 1992). However, PEEK is nearly two orders
performance FRPs, such as reusable launch vehicles, of magnitude more expensive than PP (Charrier 1990).
will require HDTs in excess of 500 mC, setting the
standard for the next generation of thermoset matrix
materials.
(b) Amorphous glassy thermoplastics. Aromatic high-
performance amorphous thermoplastics such as
poly(ether sulfone) (PES, Tg $ 230 mC) or poly(ether
1.2 Thermoplastic Resins
imide) (PEI, Tg $ 215 mC) have also attracted interest
Both semicrystalline and amorphous glassy polymers as advanced FRP matrix materials. They are less ex-
form viscous melts that need to be processed at pensive than PEEK and tougher than thermosets,

2
Polymer Matrix Composites: Matrices and Processing

but there remain (arguably unjustified) concerns over preconsolidated sheets or prepregs also facilitates
their solvent resistance. certain processes (see Fig. 1). These are available
as impregnated fabrics or continuous warp sheet
typically containing 60–65 vol.% uniaxially oriented
2. Processing fibers. Impregnation with thermosets may be achieved
by dipping or hot melt processing (rolling of the fibers
Figure 1 summarizes the various routes by which raw
together with a resin film). When the viscosity is high,
materials (resin plus fiber) are transformed into the
flow distances must be kept to a minimum, and
final part (Ma/ nson 1994). A description of the most
intimate mixing of fine polymer powders or fibers with
important of these now follows. Further details
the fiber reinforcement often precedes melt processing
concerning specific types of reinforcement, and glass
of thermoplastic composites. Solvent processing is one
fibers in particular, are to be found in Fibrous
alternative; it may lead to problems with residual
Reinforcements for Composites: OŠerŠiew and Glass
solvent in the later stages of fabrication but has been
Fibers.
used with success for PEI prepregs, for example.
Another possibility is to chain extend relatively low
molar mass precursors in situ by reaction of suitable
2.1 Fibers, Prepregs, Feedstocks
end groups, an approach frequently used for high-
Fibers are usually supplied in the form of rovings performance thermoplastic FRPs.
(glass fibers) or tows (carbon fibers). Rovings consist Sheet and dough molding compounds are mostly
of straight continuous glass-fiber strands or bundles of based on unsaturated polyester resins containing filler
about 200 filaments; the number of strands depends on and chopped fibers. Sheet molding compounds
the end use, and these may be several kilometers long. (SMCs) are produced from chopped strand mat placed
Tows are likewise available in various configurations. between layers of filled resin containing thickening
The fibers are typically sized (coated) during pro- agents to promote moldability. Impregnation involves
duction to promote wetting and adhesion, silane rolling of the resulting sandwich structure. SMCs
coupling agents being widely used for glass fibers. usually contain 25–35 wt.% fibers but the fiber content
They may be woven into fabrics if required, including can be up to 65 wt.%, in which case they are called
ad hoc fiber preforms for specific applications. Chop- HMCs. XMCs are similar to SMCs, but incorporate
ped fiber lengths range from less than 1 mm for surface layers containing continuous fiber rovings.
injection, to around 50 mm in randomly oriented mats Dough molding compounds (DMCs), or bulk molding
for laminates. compounds (BMCs), contain shorter fibers than
Of major concern in FRP processing are trapped air SMCs and are produced by mechanical mixing, which
and volatiles, since voids substantially reduce the final results in a more markedly three-dimensional fiber
strength. Low-viscosity resins, vacuum outgassing, orientation distribution. Glass mat thermoplastics
and consolidation all help reduce porosity. Use of (GMTs) can be produced in a similar manner to

Figure 1
Alternative manufacturing routes: from resin and fiber to finished part (after Ma/ nson 1994).

3
Polymer Matrix Composites: Matrices and Processing

SMCs, but the high matrix viscosity means that success advantage over press molding of cheap tooling for
is very dependent on the choice of fiber mat. Powder large parts and being ideal for complex structures
processing routes are an interesting alternative in this such as honeycomb core sandwich composites. In-
case. deed almost all prepreg material used in the aero-
It is sometimes advantageous to preassemble rein- space industry is autoclaved. It is less suited to
forcing fibers to fit a given shape, rather than rely on high-volume manufacture, although progress in
flow to distribute them throughout a mold. If dis- automatic cutting and lay-up operations has led
placement of the fibers during subsequent introduc- to considerable cost reductions and new market
tion of the resin is a problem, they can be anchored in opportunities.
place by spraying with a binder, or substituted by a
preimpregnated fabric shaped into a suitable perform.

(c) Resin transfer molding, reaction injection molding.


In resin transfer molding (RTM), the fiber reinforce-
2.2 Shaping and Forming Techniques ment (either dry fibers or a preform) is placed in the
mold cavity, and the resin then introduced by injec-
The simplest forming technique is hand placement, tion. RTM generally requires low-viscosity resins,
where woven fabric or chopped strand mat is placed but impregnation can also be improved by vacuum-
on a nonstick former and premixed liquid thermoset assisted injection. It is used to produce large mold-
resin added with a brush, say, or by spraying. It is ings such as car body shells, and the low injection
versatile and requires low investment, but the resulting pressures mean the molds themselves can be made
mechanical properties are limited and the manufac- from FRP, with considerable cost savings. However,
turer may fall foul of legislation against volatiles. It is although RTM is cheaper than prepreg processing,
used for one-off or short production runs, including it is more limited in its range of application. Reaction
large objects, such as boat hulls. However, for repro- injection molding (RIM) makes use of rapidly react-
ducible, high-quality, cost-effective production other ing components mixed just prior to injection, permitt-
techniques must be considered. ing very short cycle times, and short fiber reinforce-
ment can also be introduced in one or both reagents
(this is called reinforced reaction injection molding
(RRIM)). It is competitive with press molding for the
(a) Press molding. Press molding using matched male manufacture of a variety of automotive and domestic
and female tools is the most widely used technique components.
for volume production of FRPs, being suitable for
most types of precursor. With SMCs or DMCs, com-
plex shapes can readily be formed at pressures of
3–15 MPa with cycle times of the order of minutes (d ) Pultrusion. Pultrusion is the continuous fiber
depending on the cure rate and the part size. It is also FRP equivalent of extrusion, permitting continuous
used for continuous fiber FRPs, but the limited flow production of constant profile parts such as fishing
restricts the practically attainable range of wall thick- rods, antennas, and channel profiles (or constant
ness and curvature. For mass production, steel tools section parts, if the profile is modified in situ). Unlike
and hence additional capital investment may be neces- in extrusion, however, the reinforcing fibers them-
sary, but for short runs, epoxy composite tools are selves are used to pull the material through a heated
often adequate. Variations include rubber-pad press forming die, as shown schematically in Fig. 2.
molding, hydroforming, diaphragm forming, and Rovings or tows are passed through a resin bath fol-
cold stamping. lowed by a series of carding plates or ‘‘preformers,’’
which force the resin into the fibers. The impregnated
fibers are then pulled through the die, where the resin
gels and cures. Preheating by radio-frequency meth-
(b) Vacuum and autoclaŠe molding. In vacuum mold- ods may be used to increase throughput, resulting in
ing, atmospheric pressure consolidates the material production rates of up to several meters a minute. In
during cure, avoiding the need for a press. A prepreg some cases the resin is also injected directly into the
or fabric laminate is placed on a mold, covered with die, eliminating the need for a preimpregnation step.
a flexible membrane and the assembly sealed and evac-
uated. It provides a low-cost alternative to press mold-
ing for large, thin shells. If further consolidation is
needed, cure may be done in an autoclave. Auto- (e) Filament winding. Strong, stiff shell structures can
claves usually operate at up to 1.5 MPa pressure and be made by winding bands of continuous fibers
are widely used in the aerospace industry, having the impregnated with resin onto mandrels, which are re-

4
Polymer Matrix Composites: Matrices and Processing

Figure 2
Schematic of the pultrusion process.

moved after cure. Filament winding is widely used (Argeropoulos et al. 1999). Integrated processing (IP)
for the manufacture of reinforced plastic pipe and is aimed at improving manufacturing flexibility and
other cylindrical objects. However, modern filament adding value to composite products by combining dif-
winding techniques can also be used to produce ferent processes and materials; selective placement of
complex structures such as aircraft fuselages. In such reinforcement and integration of functions are thus
cases, the fibers must be wound along constantly achieved in short cycle times (Ma/ nson et al. 1995,
changing nonrepetitive geodesic paths to prevent Bourban et al. 1998). Reactive thermoplastics process-
slippage. Automation of this technique has led to the ing, developed for PA12-based composites, uses
development of advanced computer-based integrated monomeric precursors for impregnation followed by
design and manufacturing methods. polymerization in situ, avoiding the problems asso-
ciated with the use of melt or solution impregnation
techniques for thermoplastics (Schmid and Eder
1997, Bourban 2000).
( f ) DeŠeloping technologies. Some representative ex-
amples are now be given of developing technologies
aimed at improving, or providing alternatives to es-
2.3 Choice of Materials and Processing Routes:
tablished processing routes. The resin infusion pro-
Composite Processing Maps
cess (RIFT) and its variants, in which a vacuum is
used to draw resin into a preform or fiber bed (cf. Figure 3 shows a map of various composite processing
RTM), has been successfully applied to large objects methods arranged according to the combination of
such as boat hulls. Large injection molding body tech- resin viscosity and reinforcement aspect ratio to which
nology (LIMBT), offers a viable alternative to press they are most suited. If viscosity is an overriding
molding of SMCs and GMTs, contrary to the widely consideration it will generally dictate the choice
held notion that injection molding facilities become between thermoplastics and thermosets, but it is
prohibitively expensive as part sizes increase; for ex- immediately clear from Fig. 3 that the range of
ample, it has been used to make large automotive processes is broad enough for solutions to be available
body components from various thermoplastic FRPs for thermoplastics or thermosets for any required

5
Polymer Matrix Composites: Matrices and Processing

Figure 3
Composite processing map: viscosity and reinforcement aspect ratio (after Ma/ nson 1994).

reinforcement aspect ratio. Such ‘‘composite process- ing the use of a standard technique for a component
ing maps’’ may be based on other parameters, such as similar to those already in production. Process-
the potential for control of reinforcement orientation oriented cost models are better adapted to new
and aspect ratio; injection molding, for example, gives processes, and incorporate identification and quantifi-
little orientation control and is limited to low aspect cation of cost drivers, but require detailed process
ratios, whereas three-dimensional control and long information and a precise definition of the com-
fiber orientation require techniques such as filament ponents. Parametric models are more versatile and
winding, hand lay-up and RTM\preform technolo- allow easy manipulation of process and economic
gies. Figure 4 gives a further example that is par- factors; however, they are based on the assumption of
ticularly important for costing (see below), namely the independent manufacturing steps, and may conse-
relationship between the suitability of a given process quently underestimate costs. Such difficulties may be
route for complex shapes and its suitability for high- avoided by using process flow simulations, which take
volume production, as defined by the cycle time. into account interactions between the different manu-
facturing steps, and provide forecasting tools that are
also suitable for improvement studies, identifying
bottlenecks and estimating repair costs. Given the
2.4 Cost Modeling, Life Cycle Engineering
growing concern for environmental issues, the suc-
Since material costs are now substantially irreducible, cessful introduction of a new product or process may
and given that manufacturing often represents close to also require establishment of a life cycle plan, par-
60% of expenditure on FRP composite parts, the ticularly for the large-volume applications. As well as
processing route is generally the most critical factor in the impact of material on the environment during
cost-effective production. Assessing the economic manufacture, service, and disposal, it is important to
viability of a processing route requires comparative consider conservation of raw material value. This is a
cost analysis and hence reliable data and cost es- potentially important issue when choosing between
timation methods. A variety of approaches for eval- thermosets and thermoplastics, since recycling of the
uating manufacturing costs have been proposed former is severely limited. Furthermore, recovery from
(Ma/ nson et al. 2000): comparative studies, process- continuous fiber FRPs is difficult even for thermo-
oriented cost models, parametric cost models, and plastic matrices. One alternative under consideration
process flow simulation. Comparative studies are is recovery of the monomer via tertiary recycling (see
based on historical data and may suffice when envisag- Polymer Matrix Composites, Recycling of ).

6
Polymer Matrix Composites: Matrices and Processing

Figure 4
Composite processing map: complex shaping and volume production (after Ma/ nson 1994).

3. Process–Structure–Property Relationships the pressure maintained. Optimum processing con-


ditions may be defined with the aid of processing
The thermal cure history shown in Fig. 5(a) is typical
windows, such as that shown schematically in Fig. 6.
of prepreg and autoclave processing sequences for a
The lower bound for the cooling (and heating) rate is
thermoset FRP. During impregnation, the resin vis-
fixed by economic constraints on the cycle time. Slow
cosity first decreases owing to the rise in temperature,
cooling and heating may also result in prolonged
then increases as cross-linking proceeds. The reaction
exposure of the resin to high temperatures, leading to
is interrupted by cooling, and the resulting B-stage
thermal degradation. At very high cooling rates,
material is stored at low temperature to inhibit further
however, considerable thermal gradients may develop
reaction. During final processing, the viscosity again
through the thickness of the component, leading to
passes through a minimum, tending to infinity as the
pronounced skin–core morphologies in semicrystal-
gel point is approached. A two-step final cure is often
line resins, and excessive thermal stresses, as well as
used to improve consolidation and dimensional stab-
changes in primary morphological parameters such as
ility, after which the part is cooled and removed from
spherulite size, lamellar thickness, and the degree of
the mold or former. The final properties of thermoset
crystallinity. Increasing the hold pressure may help
FRPs are strongly dependent on the details of such
suppress defects resulting from internal stresses, but a
time–temperature trajectories. Figure 5(b) shows a
maximum pressure will be imposed either by the
schematic time–temperature–transformation (TTT)
performance of the press, or by the cost of high-
diagram illustrating the main trends (Pang and
pressure molds. High pressure may also damage the
Gillham 1990). During isothermal cure at tempera-
fiber bed and\or cause resin starvation.
tures between T gel
g
and T _
g
, the polymer gels and then
vitrifies, defining optimum conditions for final pro-
cessing. Isothermal cure between T gel g
and T g!, the
initial glass transition temperature (or melting point),
4. Conclusion
would cause the polymer to vitrify prior to gelation,
hindering further reaction. Although the initial driving force for the development
In a typical processing cycle for a thermoplastic of FRP composites was performance, economics is
FRP, the components are first heated to above Tm of now the overriding consideration. Raw material costs
the resin (or Tg for a fully amorphous resin). Pressure are generally higher than for metals, but this is offset
is applied for long enough to give adequate con- by weight reduction, increased design freedom, and
solidation, and the resulting composite is cooled with reduced ‘‘part count’’ in a given application; even

7
Polymer Matrix Composites: Matrices and Processing

log (time)

Figure 5
(a) Typical thermal cure history for a thermoset composite. (b) Isothermal TTT diagram associated with the cure of a
thermoset polymer.

these materials. Doubtless some of the techniques


under development will shortly join or supplant the
‘‘standard methods’’ referred to here.

Bibliography
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3244
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Sci. Technol. 85(5), 633–7
Charrier J-M 1990 Polymer Materials and Processing. Hanser
Verlag, Munich, Germany
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Composites. Butterworth-Heineman, Oxford
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Ma/ nson J-A E, Bourban P-E, Bonjour F 1995 Pat. PCT, WO
Figure 6 96\36477
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Polymer Matrix Composites: Matrices and Processing

Copyright ' 2001 Elsevier Science Ltd.


All rights reserved. No part of this publication may be reproduced, stored in any retrieval system or transmitted
in any form or by any means : electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or
otherwise, without permission in writing from the publishers.
Encyclopedia of Materials : Science and Technology
ISBN: 0-08-0431526
pp. 7388–7396

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