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Development in Thermoplastic

Composites: A Review of Matrix Systems


and Processing Methods
Recent

I. Y. CHANG AND J. K. LEES


E. I. du Pont de Nemours and Company, Inc.
Composites Centers
Chestnut Run Plaza 702
Wilmington, Delaware 19880-0702
ABSTRACT
Manufacturers of composite materials have been developing high strength fiber reinforced composites with thermoplastic matrix systems exhibiting enhanced performance in
fracture toughness and damage tolerance with the potential of reduced manufacturing cost
for both primary and secondary structure components. A review will be made of principal
thermoplastic matrix systems and processing methods used to fabricate the fiber reinforced composites, which have been developed during recent years. Included is a comparison of the neat matrix resins chemical structure, thermal/tensile properties, fracture
toughness, melt viscosity, solvent resistance, morphology and melt processability. The
matrix-dominated mechanical properties of thermoplastic composites are given, including
flexural, short beam shear and compression strengths, interlaminar fracture toughness
and/or compression-after-impact performance. Innovative process development in
thermoplastic composites including thermoformable sheets, filament winding, 3D braiding and impregnation will also be reviewed and discussed.

INTRODUCTION
decade

advances have been made in the developon organic polymer matrix systems reinforced with high performance fibers as metal replacements in aerospace, automotive, recreational and industrial applications. As a result of continuous improvements in fiber/matrix properties and development of innovative fabrication
technologies, advanced composite structures offer possibilities for major leaps in
design, manufacturing, energy conservation, product utility and diversity [1].
In the course of organic polymer matrix development the thermoset systems
such as 350F cured epoxies reinforced with high strength boron or graphite
fibers were initially evaluated for primary structure of subsonic military aircraft.
Although the thermoset systems showed superior tensile, shear and compressive
strengths, several deficiencies were uncovered with the epoxy-based composites,

major
URINGof advanced composites
ment
based
THE PAST

Journal

of THERMOPLASTIC COMPOSITE MATERIALS,

J1J1.

1-,Iuly 1988

0892-7057/88/03 0277-20 $4.50/0


@ 1988 Technomic Publishmg Co , Inc.

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277

278

namely, inferior performance

in damage tolerance, hot/wet stability, and high


associated with the conventional hand-layup fabrication process. Significant progress has been made for improving the fracture toughness
property of the thermoset systems, but other problems associated with hot/wet
stability and manufacture cost remain unresolved. These needs have drawn attention to the potential use of thermoplastic matrix systems.
Fiber reinforced thermoplastic composites were initially made via solvent impregnation with amorphous polymers such as polyethersulfone (PES) and
polyetherimide (PEI). Fiber reinforced composites with semi-crystalline matrix
resins including ICIs PEEK (polyether-ether-ketone) and Phillips PPS
(polyphenylene sulfide) were later developed via film/fabric stacking, melt or
powder impregnating processes. Recently, new thermoplastic matrix systems including DuPonts K-polymer (an amorphous polyimide), J-polymer (an amor-

manufacture

cost

phous polyamide) and PEKK (a semi-crystalline polyether-ketone-ketone) covering a wide range of end-use temperature applications have been demonstrated for
advanced composites with superior performance in mechanical properties, fracture toughness and damage tolerance [2-4]. Several additional thermoplastic
matrix systems with high T. have been developed by other material suppliers
[5-9]. Innovative processing methods have been developed to produce a variety
of thermoplastic prepregs and preforms. This paper will review the recent
development in thermoplastic material systems and processing/fabrication
methods including the development work performed at DuPont.
THERMOPLASTIC MATERIAL SYSTEMS DEVELOPMENT
Attributes of

Thermoplastic Matrix Systems

The most important difference between thermoplastic and thermoset matrix


systems is best described by their distinguishable chemical characteristics. While
thermosets are &dquo;crosslinkable&dquo; polymers, thermoplastics may be characterized as
&dquo;linear&dquo; polymers which normally need no &dquo;cure&dquo; during consolidation into a
composite. The consolidated thermoplastic composites are remoldable and reformable. The thermoplastic prepregs or preforms can be stored in any ambient
environment with infinite shelf life unless they contain solvent which may limit
their shelf life. In contrast, the thermoset prepregs with a crosslinkable matrix
require refrigerated storage, must be consolidated through &dquo;cure&dquo; (chemical reaction) and are not reformable after &dquo;cure.&dquo;During the past several years,
&dquo;reprocessibility&dquo; and &dquo;reformability&dquo; of fiber-reinforced thermoplastic composites were demonstrated with a variety of high performance thermoplastic
matrix systems characterized as &dquo;linear&dquo; polymers such as PEEK, PEKK, PPS,

J-polymer, K-polymer,

etc.

High-Performance Thermoplastic Matrix Resins


Several high-performance thermoplastic resins with chemical structures (or
descriptions) are listed in Table 1. These thermoplastic polymers containing stiff
aromatic or cyclic chains in the polymer backbone have relatively high Tg as

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Table 1.

High-performance thermoplastic matrix systems.

279

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280

compared with other engineering resins such as polyethylene-terephthalate


(PET), nylon 66, etc. Due to high T, and high melt viscosity of these matrix
resins, a relatively high processing temperature (T,) is required for fabrication
and consolidation of the composites. In particular, K-polymer (DuPont), HTX
(ICI), &dquo;PAS-2&dquo; (Phillips) and &dquo;Radel&dquo;-C PES (Amoco) with T, above 200C
were recently developed as high-performance matrix candidates for carbon fiber
reinforced composites to be used on advanced military aircraft [2,5-8]. These
thermoplastic resins have high toughness with a fracture energy, G,, ~it 1.0
kJ/m2, superior to BMI (bismaleimide) or aerospace epoxies such as Narmcos
5208 or Hercules 3501. The semi-crystalline thermoplastic polymers (PEEK,
PEKK, HTX) are generally more resistant to organic solvents than the amorphous polymers such as PEI (&dquo;Ultem&dquo; 1000), PES and &dquo;PAS-2.&dquo; It has been
found that the amorphous K-polymer and N-polymer have excellent solvent resistance. Recently, a new class of PEI, &dquo;Cypac&dquo; X 7005, was reported to have
improved solvent resistance over other unmodified PEI resins [9].
A new semi-crystalline polyetherketoneketone (PEKK) polymer is being
developed at DuPont as a potential high performance thermoplastic matrix
system for advanced composites [4]. This resin with upper use temperature between those of K-polymer (polyimide) and J-polymer (polyamide) has potential
advantages such as retention of mechanical properties in hot/wet environment or
after exposure in organic solvents. PEKK also has excellent flame resistance
with flammability rating V-O (UL-94), Limiting Oxygen Index 40%, low NBS
smoke density, and heat release rate (OSU) less than 65/65, which are required
for civil aircraft by a new FAA regulation in the U.S.A.
K-polymer and N-polymer, developed by DuPont with a dry T, of 250 C and
350C, respectively, show excellent neat resin properties and are suitable for
high use-temperature applications [2,10]. These high-temperature thermoplastic
matrix systems are more difficult to process than most other thermoplastics as a
result of extremely high melt viscosity. As a &dquo;linear&dquo; organic polymer, either
N-polymer or K-polymer is classified as a thermoplastic matrix despite its high
melt viscosity.
Because of its unique chemical makeup, N-polymer comprises one of the most
thermally and oxidatively stable organic polymer systems known. Three chemical features give it this extraordinary thermal oxidative stability and toughness.
First, its polymer chain is completely aromatic with no unstable linkages.
Second, its chemistry limits branching or crosslinking which could possibly
introduce weak links in the polyimide structure. And, third, the hexafluoroisopropylidene group present in the 6FTA monomer is chemically inert and its
bulkiness introduces a kink in the polymer chain, helping to prevent crystallization.
A partially fluorinated polyimide thermoplastic with dry Tg at 430C and good
thermal stability has been recently commercialized as &dquo;EYMYD&dquo; L-30N by
Ethyl Corporation, requiring molding temperature up to 454C and pressure up
to 27.6 MPa (4000 psi) [ 11 ] . Mechanical properties of the neat polymer and its
fiber-reinforced composites have not yet been published by the manufacturer or
users.

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281
Other

high performance

matrix systems

including polyimide

LARC-TPI

(Mitsui Toatsu) and polyamideimide &dquo;Torlon&dquo;-C (Amoco) [12] with dry Tgs of
264C and 288C, respectively, also show excellent mechanical properties and
melt viscosity requiring high processing temperature. Due to presence of
amide groups in the polymer chains, &dquo;Torlon&dquo;-C is more sensitive to moisture
than the polyimide or polyetherketone systems previously discussed. Recently,
a new derivative of polyamideimide with less moisture sensitivity such as
AMCOs AI-696 was reported with a dry T, of 243 C and equilibrium water
sorption at 1.8% by weight of polymer. However, the flexural modulus (2.83
GPa) and the tensile strength (90 MPa) of this resin are lower than those of
&dquo;Torlon&dquo;-C PAI neat resin [8,12].
The neat resin properties of various thermoplastic matrix systems mostly
obtained from sources cited in the reference list are given in Tables 2 and 3. The
performance comparison of matrix systems is given in Table 4.

high

Carbon Fiber Reinforced Thermoplastic Composites


The

thermoplastic matrix systems listed in Table 1 were evaluated with high


strength continuous filament carbon fibers including AS-4 or IM-6 by DuPont or
other manufacturers. The carbon fiber composite laminates with J-polymer or
PEKK were made by compression molding from the melt impregnated AS-4
Table 2. Thermal,

morphological and rheological properties of neat

Glass transition temperature (dry)

bMelt temperature
Nominal processmg temperature

dX-ray diffraction
eAt processing temperature, 10 sec shear rate

Untoughened thermoset systems

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resins.

Table 3. Mechanical and fracture

atensile

or

toughness properties of neat

flexural modulus

bTensile strength
ctensile elongation

dGlc from compact tension test ASTM-E399.


euntoughened

thermoset

Table 4. Performance

+ +
+
-

comparison of matrix systems.

Excellent
Fair.
Poor.

282

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resins.

283
Table 5. Mechanical

properties of thermoplastic composites reinforced


with carbon fiber.ea

allnidirectional lammates mth nommal 60% fiber volume (AS-4


bwith quasi-isotropic specimen and 67 J/cm impact energy

cFlexural/compression strengths

from References

[6]

and

or

equivalent)

[7]

dUntoughened thermoset systems


tows

prepared via a proprietary melt impregnating process [3,4].

Avimidg N prepregs containing carbon fiber with K-polymer

Avimid* K

or

N-polymer
matrix were processed using vacuum bag layup and autoclave technology [2,10].
The carbon fiber reinforced composites with other matrix systems were prepared
and tested by manufacturers of these polymer resins. Several matrix-dominated
mechanical properties of the thermoplastic composite laminates at room temperature (mostly obtained from various sources cited in the reference list) are given
or

in Table 5.
The most

important feature of these high performance thermoplastic matrix


composites is their high Mode I interlaminar fracture toughness (G,,) as
measured by the double cantilever beam test and superior damage tolerance performance as measured by the compression-after-impact test. The interlaminar
fracture toughness of most thermoplastic matrix composites with carbon fiber is
equivalent to or greater than 1.0 KJ/M2 as compared with 0.2 KJ/M2 for the carbon composites of untoughened aerospace epoxies (Hercules 3501-6). Similar
results of low fracture toughness were reported for the untoughened BMI com-

*DuPont

Registered Trademark.

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284

posites. In the compression-after-impact test, the majority of thermoplastic


matrix composites retained at least 270 MPa stress and 0.6 % strain after 67 J/cm
impact as compared with 145 MPa residual stress and 0.34% strain for
AS-4/3501 epoxy after impact with the same amount of energy.
The unidirectional laminates with the new PEKK matrix and AS-4 fiber
showed excellent mechanical properties with flexural strength 1620 MPa at
23C and 1379 MPa at 93C (wet), short beam shear strength 117 MPa at 23C
and 92 MPa at 93C (wet), compressive strength 1390 MPa at 23C and 1234
MPa at 82C (wet). These properties are equivalent or superior to those of AS4/PEEK (APC-2) or AS-4/3501 epoxy [4].
The carbon composites of A vimid@ K and Avimidg N showed excellent
mechanical properties in high temperature/humid environment [2,10]. A vimid@
K/IM-6 retains more than 5 % of its mechanical strengths and other properties
at 200C with saturation of water. The carbon composite of Avimida K is being
evaluated by a major aerospace company as a leading candidate for the advanced
military fighter program due to its superior performance at high temperature.
The inherent stability of Avimidg N results in composites having exceptional
long-term durability at temperatures where many other organic-based composites exhibit rapid deterioration of mechanical properties. Our laboratory test
results show that the time it takes to lose 50 % of the original flexural strength is
approximately 50,000 hours at 260C, 5,000 hours at 316C, and 1,500 hours
at 343C. Recently, carbon-fiber/Avimid® N high-temperature tooling technology has been developed to fabricate quality parts from prepregs with thermoset or thermoplastic matrices. Because of high 7~, toughness and extraordinary
thermal-oxidative stability of Avimidg N, such tools offer potential for long,
useful life and several other advantages [10].

Kevlar* Fiber Reinforced


Various

Thermoplastic Composites
thermoplastic resins including J-polymer, nylon 66,

PET reinforced

Table 6. Mechanical properties of composites reinforced with


KeviarO aramidor E-glass fiberb(60% fiber volume).

Finish free and

bFiber

zero

twist yarn

mth

polyurethane size for J-polymer and PEKK, fiber mth epoxy size for &dquo;Epon&dquo; 828.
%hree point bendmg mth span-depth ratio 32 for flex modulus, 16 for flex strength, 4 0 for short beam
shear strength.

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285
with Kevlarg aramid fibers were evaluated with the composites prepared from
the proprietary melt impregnated tows developed at DuPont [3,13]. The melt
impregnated tow as a precursor can be woven into a variety of fabric constructions for consolidation into porosity-free final components or for subsequent
thermoforming operation. Due to inherent fiber/matrix compatibility, attractive
mechanical properties of Kevlar®/J-polymer composites were obtained for the
unidirectional or fabric composite laminates [13]. Recently, preliminary tests
also showed good consolidation for the composite laminates prepared from the
melt impregnated tows of Kevlarg aramid with PEKK matrix. The matrixdominated mechanical properties such as flex and short beam shear strengths of
Kevlar21/J-polymer and Kevlar®/PEKK are given in Table 6. The mechanical
properties of a conventional epoxy system (&dquo;Epon&dquo; 828) reinforced with Kevlar
fiber are also given for comparison.
E-Glass Fiber Reinforced

Thermoplastic Composites

thermoplastic matrix systems such as J-polymer and PEKK have good


compatibility under &dquo;dry-as-molded&dquo; condition with continuous E-glass fiber
containing a conventional &dquo;polyurethane&dquo; size designed for thermoplastic
matrices by glass fiber manufacturers. The flex properties and short beam shear
strength of E-glass/J-polymer or E-glass/PEKK are equivalent or superior to
those of E-glass/&dquo;Epon&dquo; 828 at room temperature under &dquo;dry-as-molded&dquo; conditions (Table 6). It was found, however, that these glass reinforced thermoplastic composites have inferior hot-wet properties probably due to loss of
adhesion at fiber-matrix interface under hot humid environment. The unidirectional composite laminates showed more than 50 % loss of initial short beam
shear strength after exposure in 71 C water for 14 days and testing at 93 C . A
thermally stable size on glass fiber is required for processing at high temperature
with the advanced thermoplastic matrix systems. Recently, the high performance S-type glass fiber with such a size has been developed and should be evaluated with thermoplastic matrices under hot/wet test conditions.
The

PROCESS DEVELOPMENT IN THERMOPLASTIC COMPOSITES

Thermoplastic

Melt Flow Model

The shift from using thermosets to using thermoplastics requires a shift in our
thinking regarding the processes required to make parts. In thermoset technology the key to success is control of the crosslinking reaction which directly
affects the properties in the composites. Hence, we must deal with this issue
throughout the process stream from making prepregs to storage and shipping of
prepregs, during the layup process and finally during the autoclave process. Our
investment plan and process considerations are all affected by this chemical reac-

tion.
In thermoplastics, the

emphasis

shifts from

controlling

the

chemistry

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to con-

286
the rheology. Thermoplastics at their processing temperature have viscosities of 500-5,000 pa.s compared to thermosets which are less than 100 pa.s.
Hence the critical process elements must deal with the effects of this high viscosity. In the impregnation step viscosity affects both fiber/resin uniformity as
well as fiber wet-out which is critical for good load transfer in the final part. In
processing the final part, viscosity affects consolidation rate, fiber wash or
movement of the fibers in the part and cycle time.
The most critical phase in processing of thermoplastics is the impregnation
step. Here the fiber and resin are brought into intimate contact and the
fiber/matrix distribution is essentially set. For most thermoplastic systems this is
accomplished first before proceeding to make a part.
Several methods are used for bringing the fiber and matrix together: melt impregnation, commingling of matrix fibers and reinforcing fibers, powder impregnation and solvent impregnation. Each of these has their strengths and
weaknesses. In all cases the one-dimensional penetration of a thermoplastic melt
into a uniaxial fiber bundle may be modeled by Equation (1) derived from
Darcys law of flow through porous media [14]. By integrating the Darcy equation (over the media thickness with the time), the following relation for the onedimensional penetration is obtained:

trolling

where
x

k
P

tt

penetration depth
media permeability

coeflicient

pressure
time under pressure
media viscosity

Equation (1) shows that the penetration depth is proportional to the media
permeability, the applied pressure and inversely proportional to the viscosity.
Since the viscosity of the resin system is given and is little affected by process
conditions, then all we can hope to change is the permeability through the
porosity of the fiber bundle and the applied pressure. Hence, the most favorable
conditions for good flow required for uniformity occur at high porosity and high
applied pressure.
Thus, attempts made to simultaneously complete the impregnation process and
part forming would lead to poorer than desired fiber-resin distribution; therefore, it is important to establish the distribution early. In each of the non-solvent,
non-melt cases this is done by matching the matrix resin size to that of the reinforcing fiber to obtain a good distribution in the dry state. In the case of melt
processing this is accomplished by simultaneously controlling the resin feed
pressure and the density of the yarn bundle. When solvent is used, one can in

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287
effect reduce the viscosity to achieve the desired distribution. However, the
presence of the solvent, particularly polar solvents, can modify the fiber surface
resulting in an undesirable shift and ultimately in reduction of the fiber/matrix
shear strength.
The other variable that affects impregnation quality is the ability of the resin
to wet the fiber. This wetting is necessary for fiber-matrix adhesion needed to
achieve the desired level of stress transfer for dynamic, mechanical performance. This problem is particularly critical in the case of carbon fibers where
the carbon fiber cross section is not round but serrated. Inadequate wetting of the
fiber by the matrix resin can increase void concentration at the interface and
result in poor composite properties.
Fiber wetting is effected by the resin viscosity, surface tension and the character of the fiber surface. One can alter the resin surface tension either through
the addition of solvents or through a change in the polarity of the fiber surface
by plasma etching, chemical treatment, ozone treatment or with oxidative attack
at the fiber surface. Considerable work is being done to study the effects of these
treatments on all the major fibers using both micro techniques, such as the
Whilemy balance to study surface tension force between the resin and fiber as
well as macro studies using chemical treatment such as DuPonts high temperature polyimide sizing for carbon fiber or the amino silanes frequently used with
glass fiber. A variety of characterization methods such as surface spectroscopy,
thermal desorption, surface free energy, interfacial shear strength, photoelectric
observation, etc. to study the chemical and physical nature of the fiber-matrix interface as affected by the surface treatment were reviewed by Drzal [ 15] . This
science is still in its early stages and will continue to be a fruitful area for investigation, particularly in the area of the fiber-reinforced thermoplastic matrix

composites.
Proceeding forward in the process area we can use either a fully consolidated
prepreg (one in which all the air has been removed) or an unconsolidated form
that contains greater flexibility. Materials of both types can be made using any
of the four prepreg methods described earlier. At this stage in the process we
must focus on resin flow to provide a good interlaminate structure or to allow the
laminate to be reformed. The work of Cogswell and Leach [16] deals with the
various flow processes that occur in a direct forming process in which a flat sheet
is transformed to a complex shape. Here they define three types of shear, transverse intraply, axial intraply and interply, that take place, allowing resin flow to
occur during the shaping. This is necessary since the fibers are essentially noncompliant in this regime. This approach represents a good model for forming by
any number of processes such as match-die molding, press forming, bladder
molding or super plastic forming. The processes for thermoplastic composites
forming are described in various publications [17-23].
Thermoformable Sheets
An alternate method for handling the manufacture of formed complex shapes
is to use a thermoformable sheet with oriented discontinuous fiber structure as

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288
DuPont [24,25]. The sheet is designed such that the filament reinforcement (3-15 cm length) is aligned in each layer to such a degree that continuous fiber-like properties result. The discontinuous fiber reinforcement, however, does permit drawing required to form complex shapes. In this case the
matrix shearing differs from the earlier case because the movement of the fibers
allows axial draw to occur in the fiber structure as well as the resin. Performance
of these parts relative to parts made from continuous fibers is heavily dependent
on the quality of the fiber orientation, rather than the use of discontinuous fiber.
This is verified theoretically using shear lag theory where the length-to-diameter
ratio of the fiber (AS-4 carbon) is greater than 1000 with &dquo;critical&dquo; fiber length
L~ well below 0.1mm. In addition, experimental work in this area, although
limited, confirms this expectation as shown by comparison of mechanical properties between the composites from continuous filament and discontinuous formable sheets in Table 7.

developed at

Filament

Winding

Other methods for making parts involve processes, such as filament winding
and 3D braiding. In filament winding, as in tape lay down, we can begin with a
fully or partially impregnated prepreg. If post processing is to be used it is possible to use a partially impregnated prepreg and complete the impregnation process at the same time as one does the consolidation. In this case the rate limiting
step will be the impregnation step and will depend on the quality of fiber-resin
distribution and the wet-out required to meet the structural requirements. If the
prepreg is fully impregnated it is possible to reduce the post processing to
minutes. Here the rate limiting step is the time required to heat the part up to the
flow temperature of the resin.
For the most effective and low cost process it is desirable to directly consolidate the prepreg during the winding step such as in-situ consolidation being
Table 7.

Comparison

of mechanical properties-continuous filament


discontinuous formable sheet.

Quasi-isotropic layup

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vs.

289
In this particular case the time for heat up and consolidation is in the order of seconds. This can only be accomplished with fully
impregnated feed material. However, full consolidation of the feed is not required but may eventually limit the winding speed. To date little has been published on the subject but it appears the fiber winding at economically attractive
rates is possible. Tubes with both thin (less than 0.25 mm) and thick (approx. 5
cm) sections have been made with acceptable translation of properties.

developed at DuPont [26].

3D

Braiding
Finally in 3D structures the primary focus has been on the formation of the
structure with high fracture toughness. While this focus is possible for use in
thermosets which have low viscosity and can penetrate the 3D network when it
is opened up, it requires additional technology for use with thermoplastics.
Work has been done at DuPont and by a number of speciality companies to both
braid and weave pre-impregnated yarns in order to make thermoplastic 3D structures. Again the degree of impregnation plays an important role in deciding on
the process techniques required to fully consolidate the structure. For in-line
consolidation a fully impregnated yarn is required. For off-line post consolidation, the cycle times will again be controlled by the impregnation flow equation.
A new process with &dquo;in-line&dquo; consolidation was developed at DuPont for forming 3D braids with thermoplastic melt impregnated tows that can form a wide
range of structure shapes [27]. A rectangular slab with 50 % fiber volume was
demonstrated, using axial AS-4 carbon tows which was melt impregnated with
a thermoplastic matrix (J-polymer) and braiding Kevlarg aramid tows melt impregnated with the same matrix. The ratio of AS-4 to Kevlarg aramid was 6 to
1. The consolidated structure showed good flex/shear properties with high interlaminar fracture toughness.
Impregnation
Because of the importance of the impregnation step to both the economics and
part quality, it is worth looking into this process step in more detail. As noted
earlier there

are four primary processes: (a) solvent impregnation; (b)


pregnation ; (c) commingling; and (d) powder impregnation.

melt im-

SOLVENT IMPREGNATION
This process is employed by several firms such as American Cyanamid and
Ten Cate in Europe. In both of these cases the matrix resin is a polyetherimide
(PEI). The benefit of this process is derived from the low viscosity of the resulting resin solution which allows both unidirectional tapes and woven fabrics to be
used as feed material. However, there are two big drawbacks: the potential for
residual solvent in the prepreg, and inability to use higher performance resins
that have excellent solvent resistance. In the case of PEI the solvent used is NMP
(N-methyl pyrrolidone). For other resins like polyamides solvents as aggressive
as formic acid would have to be used and for polyetherketone like ICIs PEEK
or DuPonts PEKK, there are no good solvent systems. In addition to en-

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290
vironmental restrictions, investment would be required to
As a result this approach is in limited use today.

recover

the solvent.

MELT IMPREGNATION
The second approach &dquo;melt

impregnation&dquo; is defined as a process in which the


final prepreg form has each of the fibers coated by resin (i.e., impregnated). The
material may be either fully consolidated or partially consolidated.
Three basic approaches are used to achieve this type of preform: (1) film
stacking with either a roll or belt type continuous process to melt the resin and
work it into the yarn bundle; (2) adding the matrix as a powder then melt it and
work it into the yarn bundle in the same way as described for the film feed
system; (3) direct melt injection into the yarn bundle. In the first two cases it is
necessary to prepare the matrix resin for use in these processes. Again both tapes
and tows that are fully consolidated can be made this way. The third approach
uses the matrix resin in granule form and melts it to make a partially consolidated tow that is flexible enough to be woven into a fabric. This flexibility differs
from that for the fully consolidated tows. A majority of manufacturers including
DuPont, ICI and Phillips use the melt impregnation process with either of these

approaches.
COMMINGLING PROCESS
This is a relatively easy process to use. Any thermoplastic resin can be made
to work if it can be made into a fiber. Here the trick is to insure that the fiber diameter of the matrix fiber is matched to that of the reinforcing fiber in order to
assure good distribution of the two fibers. It also requires a texturing process to
open the yam bundle without damaging the brittle fiber. This is particularly
difficult to accomplish for a high filament count carbon tow such as 6K or 12K
AS-4 or IM-6. In addition, there is an added cost to make the fiber form of the
matrix. Resins like polyester that are inexpensive in fiber form dont suffer this
added cost, but conversion of resins like PEEK into fiber in small lots will increase the resin cost by 2X. This concept has been practiced by BASF in its joint
development with Concordia. Recently, the advances in commingled yarn technology with a wide range of polymer matrices and reinforcement fiber types

(AS-4, S2-glass, etc.)

were

reported [28].

The commingled product cannot be used effectively in high speed process like
filament winding because of the lack of bundle integrity. It was observed during
filament winding of a 3K AS-4/PEEK commingled tow in our laboratory that the
PEEK filaments in the tow were separating from the carbon filaments as tension
was applied for &dquo;in-situ&dquo; consolidation. The resulting tube showed a low torque
strength of 390 Nm with a high level of voids after post consolidation via
autoclave. In contrast, a melt impregnated AS-4/PEEK tow with good bundle
integrity was successfully processed with &dquo;in-situ&dquo; consolidation. The resulting
tube showed a high torque strength of 650 Nm.
On the positive side the commingled yarn flexibility which is derived from the
lack of connectivity since no fusion of the matrix has occurred makes this form
much easier to braid and weave, hence reducing costs in this step. Some of this
I

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291
is then lost due to the longer cycle times required to consolidate the part.
laboratory tests showed that it took twice as long to consolidate the commingled tows into a plaque as it did for the melt impregnated tows under similar
molding conditions.

gain
Our

POWDER IMPREGNATION
This process generally produces a flexible tape or tow in which the matrix
resin is held in place but stays in a powder form in the same way as the resin
stays as a separate entity in the commingling process. There are two published
methods for powder prepregs. The Atochem process encapsulates the thermoplastic resin powder in the yarn with a sheath of either the same resin or a lower
melting point resin [29]. This product can be readily woven and used in fabric
form. The disadvantage of this method is that the composite laminate produced
from the encapsulated tows may contain excessive resin-rich areas due to
presence of the sheath layer around the tows. It would be difficult to achieve a
good fiber-matrix distribution, particularly when a high fiber volume is required. The resin-rich areas are increased when a high melting-point resin
sheath is used for encapsulation.
A second approach is that employed by BASF wherein the powder is put in an
aqueous suspension that is then used to impregnate the fibers. This yields a tacky
product similar to a thermoset prepreg. When a woven fabric is to be used it is
possible to make the fabric then impregnate it because of the low shear viscosity
of the slurry. The water is then driven off during the forming process. Again the
process requires a step to obtain the particle size necessary to match the fiber
dimensions. This can result in a 50% increase in the cost of the matrix resin
except in cases such as nylon 11or PEEK where the matrix is produced as a

powder.
The

ity

most important advantage of powder impregnation technology is its abilto process matrix systems with very high melt viscosity and high melt tem-

perature. BASF claims that they made consolidated laminates via powder im-

pregnation with PMR-15 and PEEK of high viscosity grades [30]. This
technology has attracted a lot of attention because most high performance ther-

moplastic matrix systems have high melt temperature with high melt viscosity.
It is difficult to process these matrix systems through the melt impregnation.
Table 8. Relative cost of prepregging for thermoset
thermoplastic tows.

versus

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292

However, there are two major concerns for the powder impregnated prepregs
currently being evaluated in the trade. First, the unidirectional carbon prepreg
lacks sufficient transverse strength. Thus, it requires extraordinary care and effort to handle the prepreg during layup to form a complex-shaped part. The
other is the use of a relatively large amount of polymeric binding agent as high
as 6 % of a polyacrylic acid by weight of matrix resin as described in a patent reference [31]. This crosslinkable binding agent may remain in the prepreg during
high temperature processing and cause undesirable effect on the matrix resin and
its composite properties. Further effort would be expected from the manufacturer to resolve these concerns.
RELATIVE COST OF PROCESSES

By examining each of the impregnation processes in terms of the resin form


required and the potential throughput rate we can estimate the relative cost of
these processes. As can be seen in Table 8, the added costs range from 1.8X-3X
of those for a thermoset prepreg with the melt and solvent processes having the
lowest potential cost. In Table 9 we have also examined the cost of part fabrication from each of these using filament winding. Thus, despite the higher costs
for the thermoplastic prepreg the part costs are 40 % below the thermoset part
cost for the melt and solvent processes, 20% below or equal to the thermoset
part cost, respectively, for the powder or commingling process.
As can be seen there are available several cost effective methods for prepregging with thermoplastics that lead to economic part manufacturing. The choice
of the specific prepreg form will be determined by the matrix resin used and the
type of part fabrication technology needed.
The relative forming cost of continuous filament tape/tow versus thermoformable drawable sheet for various types of part are given in Table 10. It shows that
while the drawable sheet technology (with discontinuous filaments) is interesting
as previously discussed, it is not to be used indiscriminately. For simple shapes,
like a single curvature skin, the 30 % reduction in forming cost shown in Table
10 will not offset the added cost of making the formable sheet. However, sections like a hat section or multiple indentation shape, and a rib where the exterior
geometry must be maintained, will justify the use of this product form because
of the 30-50% reduction in cost plus the reduction in scrap material.

FUTURE DEVELOPMENT OF THERMOPLASTIC COMPOSITES


To demonstrate manufacture of thermoplastic composite parts with the projected cost reduction will be a major challenge for the aerospace industry and the
material suppliers. Effort will focus on design, manufacture and testing of large
complex-shape thermoplastic composite parts to be used for new advanced
weapon systems including the advanced military fighter plane and V-22 Osprey
tilt-rotor aircraft. The advanced thermoplastic composites are under evaluation
for both primary and secondary structure components on next generations of
subsonic and high-speed civil transport. Westland Helicopters in Great Britain
has taken a lead to produce a complete &dquo;tailplane&dquo; assembly comprising hori-

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293
Table 9. Effect

on

downstream cost for filament

winding.

zontal and vertical stabilizers with the carbon fiber thermoplastic composites
[32]. After successful testing and demonstration, it is expected that engineers
and designers at Westland and other aerospace companies will move toward
using the thermoplastic composites in helicopter fuselage, wing structures, tail
cones and even dynamic components [33].
The Air Force Materials Laboratory has taken a lead position and initiated
several major thermoplastic composites programs to exploit unique materials
and processing characteristic of thermoplastic matrices. Major universities and
aerospace manufacturers have been jointly and actively involved with these programs including &dquo;Manufacturing Science of Complex Shape Thermoplastics&dquo;
with the objective to develop, demonstrate and validate a science base for processing thermoplastic composites. A major aerospace company will continue
under an Air Force contract to work on &dquo;Design and Development of Databases
for Thermoplastic Composites&dquo; with the projection of producing the first prototype of the computerized thermoplastic composites data base in 1991. It is
believed that completion of these programs will be most beneficial for us in
future development of advanced thermoplastic composites.
We continue to believe along with several other major users of composites and

Table 10. Relative forming cost of parts via continuous filament


tape/tow and discontinuous drawable sheet-thermoset

(TS)

versus

thermoplastic (TP).

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294
the Air Force Materials Laboratory that thermoplastic composites represent a
future direction. To fulfill the promise of these systems, we need to demonstrate
the viability of the technology reviewed in this paper in real applications, not
only to meet aerospace needs, but also to serve a wide range of industrial as well
as automotive markets.

ACKNOWLEDGEMENTS
The authors wish to thank their colleagues, Drs. R. K. Okine, J. F. Pratte, M.
W. Egerton and P. Popper, for valuable discussions and/or providing test results
of thermoplastic composites process development at DuPont. The authors would
like to thank Dr. R. A. Baker for his assistance in developing the relative cost
estimates of processing with thermoset versus thermoplastic matrix systems.
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BIOGRAPHIES
I. Y.

Chang

Dr. Chang is a Research Associate with the Composites Division (R&D)


of
E. I. du Pont de Nemours & Company, Inc. He received his Ph.D. in Physical
Chemistry from the University of Texas. After graduation, he worked for one
year as a Senior Research Chemist at Tracor, Inc., Austin, Texas. He joined
DuPont as a Research Scientist and has been working on numerous research
projects in polymer and fiber. During the past several years he has been responsible for the development of new thermoplastic matrix systems such as
J-Polymer and PEKK for advanced composites reinforced with carbon or

Kevlarg fiber.

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296

J. K. Lees
Dr. Lees received his Ph.D. in Physics from Carnegie-Mellon University. He
has worked in the field of Composites, Polymer Alloys and Blend Technology
with several departments at DuPont. Currently he is the Manager of the Composites Research and Development Group at DuPont.

Downloaded from jtc.sagepub.com at FLORIDA STATE UNIV LIBRARY on December 20, 2014