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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: Oeriew 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.
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 ) Deeloping 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).
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.
Bibliography
Argeropoulos J G, Fielding C R, Oswald L J 1999 SAC 1999-01-
3244
Bourban P-E 2000 Liquid molding of thermoplastic composites.
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Bourban P-E, Bo$ gli A, Bonjour F, Ma/ nson J-A E 1998 Compos.
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Charrier J-M 1990 Polymer Materials and Processing. Hanser
Verlag, Munich, Germany
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Composites. Butterworth-Heineman, Oxford
Ma/ nson J-A E 1994 In: Chawla K K (ed.) New Demands on
Composite Materials. TMS, Warrendale, PA
Ma/ nson J-A E, Bourban P-E, Bonjour F 1995 Pat. PCT, WO
Figure 6 96\36477
Generic processing window for a thermoplastic composite Ma/ nson J-A E, Wakeman M D, Bernet N 2000 Composite
(after Ma/ nson 1994). processing and manufacturing—an overview. In: Kelly A,
Zweben C (eds.) Comprehensie Composite Materials. Perga-
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image can be a strong selling point for sports goods. Pang K P, Gillham J K 1990 J. Appl. Polym. Sci. 39, 909–33
Nowadays, it is innovation in processing that offers Schmid E, Eder R 1997 German Pat. 19 602 684 C1
the greatest scope for increasing the engineering
viability of polymer matrix composite materials, C. J. G. Plummer, P.-E. Bourban,
and for paving the way to new applications of and J.-A. E. Ma/ nson
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Polymer Matrix Composites: Matrices and Processing