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29
Continuous Molding of
Thermoplastic Composites
A. G. GIBSON
University of Newcastle upon Tyne, UK
2.29.1 INTRODUCTION
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14
2.29.1
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INTRODUCTION
Figure 1 Alternative fabrication routes for the processing of thermoplastic matrix composites.
2.29.2
Figure 2
The problem of impregnating a roving, containing a large number of small diameter fibers, with a
viscous thermoplastic resin.
dx K dp
dt Z dx
ZX2
2KP
The capillary pressure, discussed in greater detail elsewhere (Connor, 1995), results from the
change in surface energy when the polymer wets
the surface of the reinforcement. Unfortunately, capillary pressure values for polymer/
fiber systems are generally relatively small, in
the range 440 kPa, as observed by Ahn et al.
(1991), so the impregnation time would be very
long if one relied on capillary effects alone to
achieve impregnation (Lee and Springer, 1987).
In most impregnation processes the capillary
pressure is small enough to be neglected in
comparison to the applied pressure needed to
drive the process at an economic rate.
Permeability is a key parameter in impregnation processes. Assuming the fiber bed to consist of an array of parallel fibers, the
permeability can be estimated from the modified CarmanKozeny equation
K
r2f 1 vf 3
4c
v2f
Process Modeling
Figure 4 Model prediction for impregnation time (log scale) vs. applied pressure for various thermoplastic
composite systems of interest, using model parameters given in Table 1.
Table 1 Parameter values used in the process model.
Viscosity, Z (Pa.s)
vf
rf (mm)
10
100
100
500
0.3
0.3
0.6
0.6
9
9
3.5
3.5
Capillary pressure, Pc = 0.04 MPa; Kozeny constant, c = 9; P' = 2 bar; impregnation length,
X = 100300 mm.
2.29.3
PROCESS MODELING
Figure 5 Impregnation time (log scale) vs. pressure, as in Figure 4, with process windows for different
impregnation techniques superposed.
which extends the applicable pressure and compounding extrusion, traditionally used for
injection molding materials, which is applicable
only to short fiber products.
2.29.4
IMPREGNATION PROCESSES
In this review of materials systems and processes, the need for compatibility and a strong
interface between the matrix resin and the fibers
is, in most cases, an important requirement that
significantly influences properties and applications. The advent of fibers specifically tailored
for use with engineering thermoplastics is a
significant advance and improvements are continuing in this area.
The glass/polypropylene system is worthy of
special note, as this is one of the most commercially significant material combinations (Gibson, 1994). Although pure polypropylene is
nonpolar, and adheres poorly to glass, the addition of an internal coupling agent in the form
of a functionalized polyolefin with maleic or
acrylic acid groups grafted on to the main chain
can confer a considerable improvement in interlaminar properties (Adur et al., 1989; Constable et al., 1989; Constable and Adur, 1991;
Rijsdijk et al., 1993). Functionalized additives
of the Polybond2 type are most effective when
used in conjunction with glass fibers treated
with a suitably compatible size. Another benefit, specific to polypropylene, is the ability to
clip the high molecular weight tail from the
polymer by melt processing with an organic
Impregnation Processes
Figure 6 The extrusion compounding process for the manufacture of short fiber reinforced thermoplastic
injection molding granules.
Melt Impregnation
Extrusion compounding
Until about 1980 the main examples of thermoplastic matrix composites were short fiber
reinforced injection molding materials (see
Chapter 2.30, this volume), manufactured by
the process of extrusion compounding, shown
in Figure 6. This is still one of the most effective
methods of producing molding pellets and
accounts for more than half the current tonnage
of glass fiber reinforced thermoplastics.
Significant improvements have taken place
over the years in the design of compounding
extruders. These include the facility for downstream addition of the reinforcement, which
reduces work by allowing the polymer to be
fully melted before it is brought into contact
with the fibers. Nevertheless, significant levels
of fiber breakage are virtually unavoidable if
the fibers are to be fully wetted by the melt
compounding route.
The residual fiber length in injection molding
compounds is usually 100600 mm, with a
weight average fiber length of about 250 mm.
This compares to critical fiber length values of
about 200 mm for nylon and 400 mm for polypropylene. While the addition of short glass
fibers to polymers such as polypropylene or
nylon undoubtedly results in useful increases
of stiffness and strength the reinforcing efficiency is only of the order of 40%, as observed
d max vf
This is consistent with the results of the experimental studies of Milewski (1973, 1978) on
random fiber packing (for an experimentally
determined value of k = 5.3), and also describes
the residual fiber length after melt compounding in many cases. Equation (2), therefore,
places a fundamental restriction on the fiber
length that can be retained in processes that
randomize the orientation of the fibers.
2.29.4.1.2
Figure 7 Cross-head die, or wire coating extrusion process for the continuous manufacture of partially
impregnated injection molding materials.
Figure 8 The pin impregnation process for continuous pultrusion of well-impregnated unidirectional
tows: (a) impregnation bath and (b) mechanism of
impregnation.
Bradt (1959, 1962) employed a technique similar to this, as did those of Moyer (1976) and
Hattori et al. (1977), in which a feedstock based
on a polymer melt or aqueous latex was combined with glass fibers to form fiber concentrates. Experiments on cross-head extrusion
were also reported by Bader and Bowyer
(1973).
Cross-head extrusion, followed by chopping
of the strand into pellets for molding, seemed to
offer a number of advantages over the compounding extruder, including reduced machine
wear and lower power consumption. However,
in the early continuous strand process impregnation was incomplete, with the melt rarely
penetrating beyond the outer layers of the pellet. In hindsight, it can be seen that the reason
for this is the pressure dependence of the permeability mentioned earlier: the external pres-
Impregnation Processes
Figure 9 Arrangement of impregnation cells on a production unit for long fiber injection molding
materials.
Peltonen et al. (1992), Bijsterbosch and Gaymans (1993a, 1993b), and Bates and Charrier
(1999). As might be expected, there have been
several variants of the process, some of which
have been patented. Benefits have been variously claimed, for instance, for rotating the
pins, varying the pin surface profile, injecting
the resin through slots in the pin, or through a
porous pin material. Commercial versions of
the process generally employ many impregnation cells, side by side, fed from a common
extruder, as in Figure 9. In an alternative configuration a single broad impregnation cavity
may be employed, through which many separate rovings are passed and the pins may be
replaced by curved, wavelike, or angled spreader surfaces (Hawley, 1982).
Although many thermoplastics have been
processed by melt impregnation, nylon 66 and
polypropylene have been found to work very
effectively. The molecular weight needed for
good mechanical properties in thermoplastic
matrix composites is substantially lower than
that required in conventional thermoplastic
products, permitting the use of thermoplastic
melts of much lower viscosity than would normally be encountered: 30 Pa.s and even as low
as 10 Pa.s have been advocated (Cogswell et al.
1981a, 1981b). Low viscosity grades of polypropylene, which are particularly suitable for
this process, may be prepared by compounding
the resin with an organic peroxide. It has also
been suggested that viscosity can be lowered in
the vicinity of the impregnation pins by heating
them to a higher temperature than the rest of
the bath.
In most processing operations a compromise
has to be achieved between line speed, degree of
2.29.4.1.3
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Figure 10 The melt process for the manufacture of stampable glass mat thermoplastics (GMTs).
2.29.4.2
2.29.4.2.1
Figure 11 Powder impregnation: (a) powder impregnated roving and (b) schematic of a powder
impregnation process.
Powder Processes
Aligned fiber techniques
Impregnation Processes
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Figure 12 The melt bridge model for powder impregnation (Connor et al., 1993) shows bridges between
fibers which flow axially under applied pressure, to achieve impregnation.
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Figure 13 The Radlite process for the manufacture of GMT sheet from thermoplastic powder and fibers.
2.29.4.2.2
2.29.4.3
Fiber Co-mingling
A further method of achieving initial intimacy between fires and matrix is by the random
intermingling of fiber and matrix materials in
the form of parallel fibers (Coldicott et al., 1989;
Hamada et al., 1993; Miao et al., 1994; Svensson et al., 1998). Co-mingling, Figure 14(a), can
be achieved with either continuous or discontinuous fibers. In the processes employed by
Vetrotex (St. John, 1995) and Trevira Neckelmann (1999) glass and thermoplastic fibers are
mingled continuously to form a single tow. It
should be remembered that, even when the two
different fiber types are dispersed in a completely random manner, fiber-rich and resin-rich
areas will naturally be present, so the flow
length needed to achieve complete impregnation may be several times the interfiber spacing,
as shown in Figure 14(b). The co-mingled systems used most widely are glass/polypropylene,
glass/PET (and the copolymer, PETG), and
glass polyethylene.
The largest commercial tonnage of comingled material processed is glass/polypropylene. It is recognized, however, that the interlaminar properties achievable with glass/
polypropylene may not be sufficient for some
structural applications. Although the technology exists to achieve good coupling between
polypropylene and glass (Constable et al.,
1989), the relatively low glass transition tem-
Impregnation Processes
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Figure 14 Fiber co-mingling: (a) co-mingled fibers tow and (b) resin and fiber-rich regions resulting from
random dispersal.
2.29.4.4
Solvent-based Processes
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ally applicable to amorphous, rather than crystalline polymers, as the latter are not usually
easy to dissolve under normal conditions. Polymers that can be conveniently processed by
solution techniques include thermoplastic polyetherimide (PEI), polysulfone, polyether sulfone, and polyphenyl sulfone.
Solutions of thermoplastic polymer can be
used to impregnate either unidirectional tows
or woven fabrics. The most significant technical
problem is in handling the complete removal of
the solvent after wet-out of the prepreg, since
residual solvent can be deleterious to the properties of the composite.
When choosing composites based on amorphous resins, their potential susceptibility to
specific solvents needs to be borne in mind.
Nevertheless, such materials have been used in
a range of engineering applications (Ten Cate,
1998). The most successful are those based on
PEI, which has excellent fire smoke and toxicity
characteristics. Applications of the Ten Cate
Cetex range of PEI-based composites include
aircraft interiors and external fuselage ice impact protection.
An alternative to the solvent technique is the
use of a plasticizer, which may either be allowed
to remain in the structure after processing, with
some detriment to properties, or be removed.
One such technique, appropriate to PEEK or
PPS composites has been described (Cogswell,
1992; Cogswell and Staniland, 1985; Cogswell
and Measuria, 1988) where it was claimed to be
beneficial for the impregnation of carbon fiber
fibers with minimum damage to the fibers.
2.29.4.5
Reactive Techniques
An alternative method of avoiding the difficulties associated with high viscosity is to process the matrix resin in a condition where the
molecular weight is low, and to follow the
impregnation step with a polymerization or
chain extension reaction. In situ polymerization
has been considered in the case of monomers
such as methyl methacrylate, lactams, and systems leading to polyketones (Cogswell, 1992).
Recently, an improved system has been developed for the anionic ring-opening polymerization of caprolactam and laurolactam, the
precursors for nylons 6 and 12 respectively
(EMS-Chemie, 1999). This has led to interest
in in situ polymerized polyamide 12 composites
(O'Mairtin et al., 1999; Luisier et al., 2000). In
addition to the use of chemical initiators and/or
heat to promote polymerization, light and
UV-initiated polymerization have also been
considered.
2.29.5
The processing routes available for thermoplastic matrix composites have been summarized in Figure 1. This section will deal
specifically with those techniques that involve
continuous or near continuous movement of
the reinforcement through the process, namely:
(i) thermoplastic pultrusion,
(ii) thermoplastic filament winding (including tape laying), and
(iii) helical tape winding.
The other cyclic processes are dealt with in
Chapter 2.28, this volume.
2.29.5.1
Thermoplastic Pultrusion
15
place recently with the aim of making thermoplastic pultrusion a viable commercial technique (Hawley, 1982; Larock et al., 1989;
Astrom and Pipes, 1991; Devlin et al., 1992;
Michaeli and Jurss, 1996; Miller et al., 1998).
One option is to conduct he process in-line with
one of the impregnation processes described
previously (melt impregnation, powder impregnation or fiber co-mingling). Alternatively, it
may be operated with a pre-impregnated precursor material.
The pultrusion process, shown in Figure 15,
has the following stages:
(i) in-feed,
(ii) melting of the resin in the precursor
material,
(iii) consolidation,
(iv) forming, and
(v) cooling.
Careful control of the spatial arrangement
and tension of the in-feed is essential for a
good quality product with regular spatial distribution of the reinforcement. The melting
stage should make allowance for the low thermal diffusivity of the in-feed materials. To
achieve melting throughout the section of the
in-coming product it is necessary to separate all
the tows or tapes of material prior to heating, to
maximize the area available for heat transfer.
For line speeds above about 1 m min71, infrared (IR) heating, or a mixture of this and hot air
is desirable. IR allows a high rate of energy
transfer to be achieved, and the heating effect
penetrates some distance into the material. A
frequently used design of IR oven for pultrusion preheating consists of upper and lower
shells which can be opened up in the case of a
line stoppage, to allow the energy input to the
product to be halted. This avoids the risk of
igniting the polymer.
In the case of powder impregnated or comingled precursors it is necessary to carry out
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Figure 16 Alternative die configuration for thermoplastic pultrusion (a) two die process and (b) tooling
configuration for rapid pultrusion (Miller et al., 1998).
Figure 17 Schematic of the tape-laying and consolidation process for thermoplastic matrix composites.
section permits it, rollers. With dies, it is desirable that they are split and spring-loaded, so
only moderate pressure is applied to the moving
product. The best surface finish is achieved with
low-die temperatures.
2.29.5.1.1
2.29.5.2
Roll forming
(7)
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Figure 18 Schematic of the tape-winding process used for RTP manufacture, showing thermoplastic liner,
layers of tape reinforcement, and extruded outer cover.
On the basis of strength per unit cost, nonimpregnated aramid/PE tape is less expensive
than impregnated glass/PE. Glass fiber reinforcement would be competitive in this application, however, if impregnation could be carried
out at the same time as the winding operation,
and a process has been developed to do this
(Fisher and Gibson, 1998).
At present the main applications of RTP are
in high pressure transport of natural gas and
oilfield fluids (Frost, 1999). In the medium
term, however, RTPs have a wide range of
other potential applications and the future appears excellent for processes to manufacture
this type of product.
2.29.6
REFERENCES
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