THERMOPLASTIC RESINS 4

Lars A.Berglund

6.1 INTRODUCTION posites offer advantages. They have very low

Thermoplastic composites form a fairly new toxicity since they do not contain reactive
group of materials. Commercial prepreg tape chemicals (therefore storage life is infinite).
such as CF/PEEK (carbon fiber/polyether Because it is possible to remelt and dissolve
etherketone) and later CF/PPS (polyphenyle- such thermoplastics, their composites are also
nesulfide) was introduced in the early 1980s. easily recycled or combined with other recy-
However, as early as 1966, Menges reported on cled materials in the market for molding
improved static strength and fatigue resistance compounds.
when epoxy was replaced by polyamide 6 as In the aerospace market, composites based
a composite matrix (Menges, 1966).In the mid on toughened epoxies dominate. The poten-
tially cheaper manufacturing of thermoplastic
1970s there was interest in CF/PSU (Po1YSu1- composites has not yet been realized to the
fone) due to expectations of better processing
methods and improved toughness characteris- extent necessary to motivate large-scale invest-
tics. However, solvent resistance was found to ment in new manufacturing equipment.
be a problem. Composites later introduced However, for the next generation of aircraft,
based on semi-crystalline thermoplastics, such interest in thermoplastic composites is high.
as PEEK and PPS, which have been introduced Higher flying speeds require higher tempera-
tures in the materials than the maximum
more recently, have excellent chemical resis-
tance and are superior to epoxy-based temperature available from epoxy-based com-
posites in use today. Since the release of gases
composites in this respect.
Enthusiasm for thermoplastic composites is during processing and inherent brittleness are
serious disadvantages of thermoset polyimides,
generated for, basically, three different rea-
sons. First, processing can be faster than for thermoplastic composites are of great interest.
In the automotive market, thermoplastic
thermoset composites since no curing reaction
composites are used extensively. Matched-die
is required. Thermoplastic composites only
compression molding of glass mat thermo-
require heating, shaping and cooling.
plastics (GMT), primarily based on glass
Secondly, the properties are attractive, in par-
ticular, high delamination resistance and fiber/polypropylene (GF/PP), is common,
because it permits fast processing cycles for
damage tolerance, low moisture absorption
fairly large components. In the established
and the excellent chemical resistance of semi-
field of injection molded components, materi-
crystalline polymers. Thirdly, in light of
als are used with long fibers (5-10mm) in
environmental concerns, thermoplastic com-
molding pellets. This leads to improved
mechanical properties compared with materi-
als based 0; shorter fibeis (Truckenmueller
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman &Hall, London. ISBN 0 412 54020 7
and 1991).
116 Thermoplastic resins

6.2 MANUFACTURING METHODS processing, for conversion into a high-viscos-

ity melt. Shaping then takes place and the
The principles for thermoplastic composites
material solidifies on cooling. In Table 6.1,
processing are very different from those for
different manufacturing methods used for
thermoset composites. During the processing
thermoplastic composites are outlined.
of thermosets, the polymer is initially a liquid
Further discussion of thermoplastic compos-
which then solidifies due to the formation of
ites processing is available in Chapter 24 of
a three-dimensional molecular network from
this book and in previous reviews (Carlsson
chemical reactions. Thermoplastics are in the
1991; Cogswell, 1992; Kausch, 1993).
solid state before processing because of their
As with thermoset composites, materials
high molecular weight. They are heated
with low fiber volume fractions show ease of
above their softening temperature during

Table 6.1 Manufacturing routes for composites based on thermoplastic resins

-

Manufact zi ring ro ii te Outline of fabrication and processing methods

Open mold processes
1. Autoclave Unidirectional or woven fibers pre-impregnated by the resin (prepreg) are
used. Other forms of prepreg have reinforcing fibers in combination with
the resin as fibers or as powder. The prepreg layers are stacked on the
mold surface and covered with a flexible bag. Consolidation is obtained by
external pressure applied in an autoclave at elevated temperature.
2. Filament winding Prepreg tape or tape with the resin as fibers or powder are wound onto a
mandrel at pre-determined angles. Heat and pressure are applied to the
tape in order to continuously weld it onto the underlying material.
3. Folding Preconsolidated sheets are heated. Simple fixtures are then used to shape
the sheets into the desired geometry.
Closed mold processes
4. Injection molding A mixture of molten thermoplastic and short fibers is injected into a colder
(short fibers, 0.1-10 mm) metal mold at very high pressure. The component is allowed to solidify
and is automatically ejected.
5. Compression molding Semi-finished sheets of glass mat thermoplastics are heated and placed in
(short fibers, 5-50 mm) the lower part of the mold in a fast press. The press is quickly closed and
pressure is applied so that the material can flow to fill the mold.
Technology is also available where the hot molding compound reaches the
mold from an extruder.
6. Compression molding The same principle as for short fiber materials.
(continuous fibers) Continuous fibers require special clamping fixtures for the sheets and can
primarily be used for simple geometries.
7. Diaphragm forming A stack of prepreg is placed inbetween two diaphragms (superplastic
aluminium or polymer film). The diaphragms are fixed whereas the
prepreg can move freely. The material is slowly deformed by external
pressure and the mold.
8. Pultrusion Prepreg tape or tape with the resin as fibers or powder is pulled through
a heated die to form beams or similar continuous structures with constant
cross-section geometry. The material is allowed to cool and solidify.
9. Resin injection Dry reinforcing fibers are placed in the mold. Monomers and/or low
molecular weight polymer with low viscosity are injected, the
reinforcement is impregnated. Polymerization to a high molecular weight
thermoplastic occurs by mixing of reactive components and/or thermal
activation.

processing but low stiffness and strength. On
the other hand, materials with high fiber con-
tent have high stiffness and strength but
require slow processing and are difficult to
shape into geometrically complicated struc-
tures. For high fiber content materials, the high
viscosity of a molten thermoplastic usually
requires some kind of prepreg fabrication step
before final processing. The prepregs may need
to be combined into the consolidated, semi-fin-
ished sheets before the final processing step.
Regular autoclave processing can be used
for thermoplastic composites. For most high-
performance thermoplastics, however,
temperatures have to be higher than the typi-
cal 177°C used for epoxy-based composites.
Often, the composite manufacturer must pur-
chase a new autoclave if this is the preferred
processing route. Autoclave processing of
thermoplastics has been modeled (Lee and
Springer, 1987). Consolidation of the prepreg
layers is an important issue. At a given tem-
perature, sufficient time must be available for
the polymer molecules to diffuse from one
prepreg layer into the other and form strong
physical entanglements (Howes, Loos and
Hinkley, 1989). In addition, the air initially
present in the material must be displaced.
For thermoplastic composites, filament
winding has demonstrated good economic
potential (Egerton and Gruber, 1988). The
major problem is in the welding of filaments or
the tape onto the underlying composite layers.
Heat has been applied by means of a gas flame,
IR, laser beam or simply from a hot metal sur-
face. Pultrusion of thermoplastic composites
offers potential for faster processing than with
thermoset composites (Astrom, Larsson and
Pipes, 1991), due to the absence of exothermal
heat generation from chemical reactions.
Profiles may also be produced by roll-forming
techniques similar to those used in metal-
working. The shape of existing profiles can be
changed. The low-cost folding technique (GE
Plastics, 1990) has been used commercially by
Fokker and TenCate in Holland for quite large
components of fairly simple geometry.
Material forms 117
Compression molding of glass mat thermo-
plastics (GMT) is a wide-spread process of
great sigruficance in the automotive industry
(Berglund and Ericson, 1994).Resin injection of
polymerizing prepolymer molecules of low
viscosity is in principle the same process as for
thermosets although the chemical reactions
lead to increased molecular weight rather than
to cross-linking. Such a process does not pro-
vide the advantages of infinite storage life
materials with low toxicity. Diaphragm form-
ing is a processing route where the problem of
low extensibility of prepreg-based materials is
addressed (Mallon, O’Bradaigh and Pipes,
1989).
6.3 MATERIAL FORMS
Thermoplastic composites are usually sup-
plied as semi-finished materials, with the
exception of resin injection materials. In Table
6.2, material forms for thermoplastic compos-
ites are presented. Prepregs of high fiber
volume fractions (V, = 0.6) may be prepared
by solvent-, melt-, prepolymer- or powder-
impregnation of the reinforcing fibers.
Solvent-impregnation is limited to amorphous
resins with high solubility. Melt-impregnation
is a technique successfully developed by IC1
(Cogswell, Hezzell and Williams, 1981) pro-
ducing high-quality prepreg. The resulting
prepreg is considered too stiff, for some pro-
cessing situations with little drapability in
comparison with CF/EP (epoxy) prepreg. This
problem is addressed in prepolymer- and
powder-impregnated prepreg. One example is
the FIT-technology where small tubes contain-
ing reinforcing fibers and polymer powder are
used (Thiede-Smet, 1989). In addition, com-
mingled weaves (prepregs) are available. The
resin is present in the form of fibers which are
melted during processing to form a matrix.
Composites produced from commingled
material forms may have a fairly inhomoge-
neous distribution of fibers (Olson, 1990).
Film-stacking is a simple method often
used for preparation of laboratory samples
118 Thermoplastic resins

Table 6.2 Material forms for composites based on thermoplastic resins

Material forms Outline of preparation procedure

Prepregs
1. Solvent impregnated Reinforcing fibers are impregnated by a mixture of solvent and
thermoplastic. The solvent is removed by evaporation.
2. Melt impregnated Reinforcing fibers are impregnated by thin molten films to which pressure
is applied.
3. Prepolymer impregnated Low viscosity prepolymers are used to impregnate the fibers.
Polymerization to high molecular weight thermoplastic takes place during
processing.
4. Powder impregnated Fibers are enclosed by thermoplastic powder, either in small tubes
containing reinforcing fibers and powder or by powder particles adhering
to the fibers from partial melting in a fluidized bed.
Other material forms
5. Film stacked composites Stacks with alternating layers of dry fibers and polymer film are heated
and compressed.
6. Fiber hybridized weaves Roving of commingled reinforcing fibers and the matrix in fiber
and roving form. Weaves are produced from the roving.
7. Prepolymer liquid and Reinforcing weaves are impregnated by prepolymer liquid and
dry reinforcement polymerized to a thermoplastic composite.
8. Semi-finished glass mats Supplied as sheets prepared in belt press by extrusion and melting of
(low fiber content) films which impregnate fiber mats. Porous sheets are produced from slurry
of fibers and thermoplastic powder in water, by technology similar to
manufacturing of paper. Recycled material can be used.
9. Pellets Often prepared by pultrusion of unidirectional fibers and matrix
(low fiber content) followed by chopping into pellets. Used in injection molding or in
plasticizing and/or compounding unit combined with compression
moulding. Recycled material is easily incorporated.

(Hartness, 1982) although the technique has
also been used commercially. In the category
of materials with low fiber volume fraction
(V,=: 0.2), semi-finished sheets of GMT-materi-
als are available. They usually have random,
chopped or continuous fiber mat reinforce-
ments. Unidirectional prepreg may be used in
order to selectively provide additional stiff-
ness, strength a n d creep resistance. A n
interesting step forward is provided by extru-
sion compounded GMT (Composite Products
Inc, 1994; Hoechst AG, 1994). No semi-finished
sheets are used, instead a special extruder is
used to produce a hot, soft 'cake' constituted
of chopped fibers and the polymer matrix,
often PP. The cake is placed in a press and
molded. The investment in technology is
higher than for conventional GMT molding.
On the other hand, the material cost and
energy consumption is reduced, greater free-
dom in materials selection is obtained and
recycling is facilitated. Suppliers of thermo-
plastic composites are listed in Table 6.3.
6.4 THERMOPLASTIC RESINS
Thermoplastics have either amorphous or
semi-crystalline structure (Sperling, 1992). The
large, chain-like polymer molecules do not
show long-range order in amorphous thermo-
plastics, which may be viewed as polymer
glasses and, in the absence of color pigments,
are usually transparent. Thermosets are also
amorphous. In contrast, crystalline polymers
have regions of molecular order. In melt-
processed crystalline polymers, a spherical
 Thermoplastic resins 119

Table 6.3 Suppliers of thermoplastic composites

Supplier Materials
Ba ycomp Unidirectional tapes. Matrices PP, HDPE, PA12
Burlington, Ontario, Canada PC, PEI, PBT, PES, PPS, PEEK, ABS, PPO. Fibers: glass, carbon,
aramid and stainless steel.
CYTEC, Anaheim Commingled yams. Carbon fiber with PEEK, PEKEKK, PA6,6, TPI
CA, USA (Aurum@).GF/PA6,6.
DuPont de Nemours Prepreg based on Avimid@K,thermoplastic polyimide, and
Bad Homburg, Germany and carbon fiber. Sheets laminated of continuous fiber thermoplastic
Newark, DE, USA composites or unidirectional discontinuous fibers. Molding
compounds of lower fiber content. Matrices: PA6,6, PEKK, PET and
others. Fibers: carbon, glass and aramid.
Electrostatic Technology Prepreg fabrication by deposition of polymers in powder form
Branford, C, USA on tow and fabrics. Wide variety of resins and fibers.
GE Plastics GMT-materials based on glass fiber mats and PP, PBT, PC and
Amsterdam, Netherlands and blends PC/PBT. Unidirectional GF/PP.
Pittsfield, MA, USA
Hoechst Unidirectional prepreg of GF/PP, GF/PA6, GF/PE, CF/PPS,
Frankfurt, Germany CF/PA6. Pellets > 12 mm for use in plasticating extruder combined
with compression moulding.
Huls GF/PA12 fabric prepreg.
Marl, Germany
ICI/Fiberite APC-2 (CF/PEEK) prepreg tape and tow and developmental
Monchengladbach, Germany materials, primarily for high-temperature applications.
and Laguna Hills, CA, USA
Porcher Textile FIT-weaves (Thiede-Smet, 1989).Matrices PA12, PEI, PEEK. Glass
Lyon, France and carbon fibers. Enichem, Milano, Italy reportedly produces
GF/PP, PET, PBT with FIT-technology.
Quadrax Corp Prepreg fabrics and unidirectional tape, consolidated sheets.
Portsmouth, RI,USA Matrices PA6,6, PMMA, PEI, PPS and PEEK. Carbon, glass and
aramid fibers.
Schappe Techniques Spun yarns combining reinforcing and matrix fibers for subsequent
Charnoz, France weaving. Matrices PP, PA6, PA6,6, PPS, PC, PEI, PEEK. Carbon, glass
and aramid fibers.
Symalit AG Glass mat thermoplastic sheets based on GF/PP.
Lenzburg, Schweiz
TenCate Advanced Composites Prepreg fabrics and unidirectional tape, consolidated sheets.
Nijverdal, Netherlands and Matrices PES, PEI and PA12. Carbon, glass and aramid fibers.
Fountain Valley, CA, USA
120 Thermoplastic resins
morphology, termed spherulitic, is often
observed (Bassett, 1981). Crystalline lamellae
are present within the spherulites although
disordered regions exist between and within
the lamellae. This is because the large size of
polymer molecules inhibits perfect crystalliza-
tion. The crystalline thermoplastics are
therefore more correctly described as semi-
crystalline, since the degree of crystallinity
never reaches 100%. Semi-crystalline thermo-
plastics can be viewed as two-phase materials
with a crystalline and an amorphous phase.
To illustrate the difference in behavior of
semi-crystalline and amorphous thermoplas-
tics, polyethylene terephthalate (PET),may be
used as an example. PET is a thermoplastic
polyester which crystallizes fairly slowly.
Therefore, upon rapid cooling from the
molten state, crystallization can be sup-
pressed and an amorphous polymer is
obtained (similar behaviour is shown by
PEEK). Samples of PET with different degrees
of crystallinity can be produced by changing
the conditions of cooling. The shear modu-
lus G' (obtained from dynamic mechanical
thermal analysis, DMTA) is plotted against
temperature for such samples in Fig. 6.1. The
I I I
I
50 100
Temperature ("C)
Fig. 6.1 Shear modulus (G') compared with temperature for PET of different degrees of crystallinity.
amorphous sample shows a dramatic drop in
modulus at the Tg (glass transition tempera-
ture). The drop in modulus for semi-crystalline
samples is less dramatic: the higher the crys-
tallinity, the slower the drop. Above T,,
material modulus is maintained by the crys-
talline phase (although strength usually
decreases dramatically). Another effect of
reduced degree of crystallinity is reduced
chemical resistance.
A disadvantage with semi-crystalline poly-
mers is the high processing temperature, see
Tables 6.4 and 6.5, compared with the heat
deflection temperature (see next section, Table
6.11). The melting temperature, Tm,of the crys-
talline phase must be exceeded during
processing, although the maximum use tem-
perature, as for amorphous polymers, is still
below T,.
Characteristic temperatures of thermoplas-
tics used in applications where only moderate
temperatures are experienced are presented in
Table 6.4. These materials are available from
many different chemical companies, therefore
trade names and suppliers are not listed. In
Table 6.5, thermoplastics for applications at
higher temperatures are listed. These polymers
I
I
I I
150 200 250
 Thermoplastic resins 121

Table 6.4 Characteristic temperatures for thermoplastic resins with T,< 90°C

Polymer Chemical Structure T T,,, Processing

type name ("C) ( "C) temp. ("C)
___ ~ - ___
Polyolefin Polypropylene Crystalline -10 165 200-240
(PP)
Polyamides Polyamide 6,6 Crystalline 55 265 270-320
(pA6,6)
Polyamide 12 Crystalline 35 180 220-260
(PA12)

Polyesters Polyethylene Crystalline 70 265 280-310

terephthalate
(PET)
Polybutylene Crystalline 20 240 260-290
terephthalate
(PBT)

Table 6.5 Characteristic temperatures for thermoplastic resins with T, 290°C

Polymer Chemical Trade name Structure T, Processing

fYPe name and supplier ("Ci temp. ("C)
~~ ~~ ~~

Polyester Polycarbonate Lexan, GE Amorphous 150 none 280-330

(PC) Makrolon, Bayer
Polyarylene Polyphenylene Ryton, Phillips crystalline 90 280 300-340
ether or sulfide
sulfide (PPS)
Polyarylene PAS-2, Phillips Amorphous 215 none 330
sulfide
PEEK Victrex PEEK, IC1 Crystalline 143 343 380400
PEEKK Hostatec, Hoechst Crystalline 165 365 390-415
PEKK Declar, DuPont Crystalline 155 340 380400
PEKEKK Ultrapek, BASF Crystalline 175 375 400420
Polyketone Victrex HTX, IC1 Crystalline 205 385 420430

Poly- Polysulphone Udel P1700, Amoco Amorphous 190 none 300-350

sulfones (PSU)
Polyether- Victrex 4100G, IC1 Amorphous 220 none 300-320
sulfone (PES) Ultrason E, BASF

Polyamide- Polyamide- Torlon C, Amoco Amorphous 275 none 350400

imides imide (PAI) Torlon AIX-159 Amorphous 290 none 350400
Amoco

Polyimides Polyetherimide Ultem, GE Amorphous 217 none 335420

(PW
Polyimide (TPI) Avimid KIII, Du Pont Amorphous 250 none 340-360
Polyimide (TPI) Aurum, Mitsui Crystalline 260 390 400420
Toatsu
122 Thermoplastic resins

are more expensive and are often termed ’high- of static mechanical properties of the resins is
performance’ resins. The higher cost of these given in Table 6.6. Resins with low Tg,such as
materials is due to small material volumes, PP and PA12, have lower modulus and
more expensive monomers and more difficult strength. Their fracture toughness is high and
polymerization procedures. valid data according to linear elastic fracture
Many resins used in injection molding are mechanics are difficult to obtain. Among poly-
so called blends, physical mixtures between mers with T, well above room temperature, the
two thermoplastics. In the field of commercial modulus is fairly similar. It is controlled by
composite materials, this technology is pri- weak physical forces between the molecules.
marily used for GMT-materials, where Viscoelastic effects such as creep and stress
composites based on PC/PBT blends are relaxation during loading will affect the data.
available (Table 6.3). However, for high-per- Tensile strength varies more widely than mod-
formance resins, blending amorphous with ulus between different resins. As a material
semi-crystalline thermoplastics is an interest- property it is unfortunately not very reliable. It
ing route to improved chemical resistance. is sensitive to loading rate, specimen geometry,
Most polymer mixtures form immiscible two- specimen preparation and the presence of
phase structures although PEEK and PEI may microscopic flaws on the specimen surface. In
be mixed to form a miscible blend (Crevecoeur addition, uniaxial resin tensile strength is dif-
and Groeninckx, 1992). ferent from resin strength in the composite
where the stress state is different.
Thermoplastics have higher fracture toughness
6.5 PROPERTIES AND DESIGN
than epoxy and other thermosets, although
CONSIDERATIONS
epoxy fracture toughness can be improved by
In contrast to thermoset resins, thermoplastics addition of a thermoplastic (Bucknall and
can be dissolved and melted. In general, vis- Gilbert, 1989) or other means. Although not
coelastic and plastic effects are more apparent from the table, epoxy modulus is usu-
pronounced in thermoplastics. A presentation ally slightly higher than for thermoplastics.

Table 6.6 Mechanical properties of thermoplastic resins

Material Tensile Tensile Fract lire

modulus strength toughness
E (GPu) 0,( M W G,? (kJ m-2)
-__
PP 1.l-1.6 3040 -

PA6,6 2.5-3.8 50-80 -

PET 2.74.0 50-70 -
PC 2.3-3.0 60-70 -

Amorph. PA a-2) 3.2 100 1.6

PPS (Ryton) 3.5 80 0.5-0.9
PAS (PAS-2) 3.2 100 -
PEEK 3.1-3.8 90-100 4.0
PSU (Udel P1700) 2.5 70 2.5
PES (Victrex) 2.6 80 1.9
PA1 (Torlon) 2.84.4 90-190 3.4
PEI (Ultem) 3.0 105 3.3
TPI (Avimid K-111) 3.5 100 1.5
TPI (LaRC-TPI) 3.7 120 1.8
EP(thermoset) 2.8-3.5 40-120 0.1-0.5
 Properties and design considerations 123

Many mechanical properties of composites
are dominated by the influence of fiber mod-
ulus, fiber strength and fiber volume fraction.
This is usually true for longitudinal tensile
modulus and strength as well as flexural
modulus and strength. For thermoplastic
composites based on AS-4 carbon fiber, typi-
cal tensile data are: longitudinal tensile
modulus E,= 130 GPa, longitudinal tensile
strength (5, = 1950 MPa. In the present con-
text, we are more interested in properties
dominated by the matrix and the fiber/matrix
interface. One such property is the transverse
tensile strength of unidirectional laminates.
When a multidirectional laminate is loaded in
in-plane tension, the first major damage
mechanism is likely to be matrix cracking in
the plies with transverse orientation to the
maximum load direction. This reduces lami-
nate stiffness and initiates other damage
mechanisms such as delamination. In Table
6.7, transverse strength and modulus are pre-
sented for different thermoplastic composites.
Fiber volume fractions are high, V ,= 0.5-0.6,
For composites based on brittle epoxies, typi-
cal transverse strength is 40 MPa. Composites
based on LaRC-TPI, J-2, PAS-2 and K-111 show
transverse strengths in the range 3 2 4 1 MPa.
Otherwise, typical transverse strengths for
thermoplastic composites are in the range
60-90 MPa. Toughened epoxy composites also
show fairly high transverse tensile strengths,
typically around 75 MPa.
The use of transverse tension data in failure
criteria will lead to conservative estimates.
Data are higher for transverse plies in multidi-
rectional laminates (Berglund, Varna and
Yuan, 1991). The modulus data for carbon
fiber composites in Table 6.7 appear insensi-
tive to small differences in matrix modulus.
Variations in fiber volume fraction and trans-
verse fiber modulus between the materials
mask any such effect. The detrimental effect of
glass fiber as opposed to carbon fiber is appar-
ent from the GF/PA6,6 and CF/PA6,6 data.
GF/PP shows very poor performance, proba-
bly due to poor fiber/matrix interfacial
adhesion (note the low V, ). Interfacial weak-
ness is also likely to explain the low strength
for Kevlar / PEKK. For thermoplastic compos-
ites based on AS-4 carbon fiber, Table 6.7 can
be used to estimate typical data: transverse

Table 6.7 Transverse tensile properties of thermoplastic composites

Material Transverse modulus Transverse strengfh

ET (GPa) (MPa)
~~~ -
GF/PP Plytron (V, = 0.35) 4 11
GF/PA6,6 E-glass/Ultramid 8.6 48
CF/PA6,6 G30-500/Ultramid 7.2 72
CF/Am. PA AS-4/J-2 9 35
CF/PPS AS-4/Ryton 7.6 72
CF/PAS T 650-42/Rade18320 8.4 61
CF/PAS AS-4/PAS-2 8.3 32
CF/PSU AS-4/Udel P1700 7 59
K49/PEKK Kevlar/PEKK LDFTM 6.2 21
CF/PEKEKK G30-500/Ultrapek 10.3 90
CF/PEEK AS-4/PEEK (ICI) 8.9 80
CF/PAI T650-42/PAI-696 7.6 67
CF/TPI AS-4/K-III 9 41
CF/TPI G30-500/’NewTPI’ 8.3 59
CF/TPI AS-4/LaRC-TPI 33
CF/EP AS-4/3501 (thermoset) 9 52
CF/EP HTA/6376C (thermoset) 9.9 75
124 Thermoplastic resins

tensile modulus E, = 8.6 GPa, transverse ten-
sile strength (T, = 75 MPa.
High interlaminar toughness is desirable
since this suppresses the tendency for delam-
ination crack formation during loading.
Interlaminar fracture toughness is determined
on double cantilever beam specimens (DCB),
usually unidirectional materials are used
(Whitney, Browning and Hoogsteden, 1982).
In Table 6.8 such data are presented.
CF/PEEK shows the highest fracture tough-
ness. All thermoplastic composites show
higher toughness than the thermoset compos-
ites. There is a difference between crack
initiation and crack propagation data (Davies,
Benzeggagh and de Charentenay, 1987). The
data presented here are crack propagation
data; crack initiation data are in general much
lower. For tough matrices one may question
the applicability of the data to design prob-
lems. In DCB experiments, the crack opening
displacement (COD) is very high, whereas the
COD at small central cracks in stiff laminates
is much smaller. Local stress fields and dam-
age mechanisms may therefore be different
and affect the measured fracture toughness.
At present, delamination fracture toughness
from DCB tests are therefore preferentially
used to compare material. It has been pointed
out that composite data are significantly
lower than resin data (Hunston, 1984).In tests
on neat resins, energy is absorbed by yielding
and other types of damage when the volume
of material is relatively large. In a composite,
the presence of fibers tends to limit this mate-
rial volume. For shear strength, no
comparable data for different thermoplastic
composites appear to be available in the liter-
ature. The interlaminar fracture toughness in
mode I1 shear loading, Glrc,is higher for ther-
moplastic than for comparable thermoset
composites (Cantwell and Davies, 1993). This
also indicates a higher shear strength for the
thermoplastic composites. A typical value for
the in-plane shear modulus of thermoplastic
composites based on AS-4 carbon fiber is
4.8 GPa which is similar to toughened CF/EP
systems but slightly lower than for brittle
matrix CF/EP composites.
Compressive strength is lower for thermo-
plastic than for thermoset composites
(Table 6.9). Most of the thermoplastic compos-
ites are in the range 900-1100MPa whereas
typical thermoset composite data are
1700 MPa. Fiber misalignment, shear stiffness
and strength have been shown to affect com-
pression strength based on plastic kink band
formation (Budiansky, 1983). Compression
modulus data in Table 6.9 are similar, in sup-
port of similar fiber volume fractions for the
materials compared. The composite based on
PA6,6 has the lowest strength; PA6,6 also has

Table 6.8 Interlaminar fracture toughness of thermoplastic composites

Material Trade name Fracture toughness

_ _ ~
-~ ~ ~
qc(kJ~m-2)
CF/Amorph. PA AS-4/ J-2 1.3
CF/PPS AS-4/Ryton 0.9
CF/PEEK AS-4/Victrex PEEK 2.1
CF/PEEK IM7/Victrex PEEK 2.5
CF/PSU AS-4/Udel P1700 1.2
CF/PAI T650/Torlon AIX-159 1.3
CF/PEI T300/Ultem 1000 0.9
CF/TPI AS-4/Avimid K-I11 1.8
CF/TPI AS-4/ LaRC-TPI 0.8
CF/EP AS-4/3501-6 (thermoset) 0.2
CF/EP IM7/8551-7 (thermoset) 0.5
 Properties and design considerations 125

Table 6.9 Compressive properties of unidirectional thermoplastic composites

Material Trade name Compression Modulus

strength (MPa) (MPa)
__ -~
CFDA6.6 G30-500 /Ultramid 700 110
CF/Amorph. PA AS-4/ J-2 1100 -

CF/PPS AS-4 / Ryton 940 130

CF/PAS AS-4/ PAS-2 900 120
CF/PEEK AS4/Victrex PEEK 1100 120
CF/PEEK IM7/Victrex PEEK 1140 -

CF /PEKEKK AS-4/Ultrapek 1310 127

CF/PSU AS-4/Udel P1700 1040 -
CF/PAI C-3000/Torlon C 1380 -

CF/TPI AS-4/Avimid K-111 1000 110

CF/EP AS-4/ 3501-6 (thermoset) 1720 140
CF/EP HTA/6376C (thermoset) 1720 130

the lowest creep modulus and yield stress of superior performance to first generation ther-
the investigated matrices. It is interesting to moset composites (AS-4/3501-6). This is
note that AS-4/PEEK and IM-7/PEEK have because the delaminated area due to the
roughly the same strength although the IM-7 impact event is more limited for the thermo-
fiber has higher modulus. The smaller diame- plastic composites. However, toughened
ter of the IM-7 fiber appears to have a negative epoxy resin composites combined with tough-
effect as expected from Euler-buckling consid- ened interlayers between the plies do in
erations. general show as good compression strength
Compression strength after impact, a mea- after impact as thermoplastic composites. In
sure of laminate and material damage fatigue, delamination resistance is higher for
tolerance (Dorey, 1989), is presented in AS-4/PEEK compared with epoxy composites
Table 6.10. A quasi-isotropic laminate of given (Gustafsson, 1988). However, in uniaxial ten-
lay-up and geometry is subjected to impact of sion, brittle CF/EP was found to be superior to
a certain energy. Internal damage mechanisms both toughened CF/EP and the thermoplastic
such as matrix cracking and delamination composite (Curtis, 1987). Claims have been
occur in the laminate. The plate is then sub- made that this observation is due to heating
jected to compressive load and the stress and effects in the thermoplastic composite speci-
strain at failure can be determined. The data mens from testing at high frequency (Moore,
show that thermoplastic composites have 1991).

Table 6.10 Compression strength after impact of thermoplastic composites

Material Trade name Compression strength after impact

(impact energy)
(28 J) (42 1) (571)
o (MPa) o (MPa) o (MPa)
CF / PPS AS-4 /Ryton 221 179 -
CF/PEEK AS-4/Victrex PEEK 331 310 290
CF / PA1 C-3000/Torlon C 365 345 317
CF/EP AS-4/3501-6 (thermoset) 179 145 131
CF/EP AS-4/8551-7 (thermoset) - 303 -
126 Thermoplastic resins

Table 6.11 Glass and heat deflection temperatures Table 6.12 Glass melting and heat deflection tem-
for amorphous thermoplastics peratures for semi-crystalline thermoplastics

Material T, ("C) HDT ("C) Material T, ("C) T,,,

("C) HDT ("C)
PC 150 132 PP -10 165 60
Amorph. PA 160 154 PA6.6 55 265 75
PSU 190 175 PET 70 265 41
PES 220 203 PPS 90 280 135
PA1 290 278 PEEK 143 343 160
PEI 217 200 TPI (Aurum) 250 388 238
EP (thermoset) 200 180

Increased market need for polymer compos-
ites with good performance at elevated
temperature has generated interest in thermo-
plastic composites. Materials with continuous
use temperatures above 150°C are of particular
interest since they perform better than epoxies.
One question is how maximum use tempera-
ture relates to Tg. In Table 6.11, Tg and the heat
deflection temperature (HDT) for amorphous
thermoplastics are presented. HDT is deter-
mined by subjecting the material to static load
(typically 1.8 MPa) and slowly increasing the
temperature. HDT is determined as the tem-
perature at which a critical deflection of the
sample is obtained. Table 6.11 shows HDT to
be 620°C below the T of amorphous poly-
6
mers. In comparison with room temperature
strength, the strength of the composite is sig-
nificantly reduced above the HDT. The reason
is that molecular mobility in the polymer is
increased dramatically as the temperature
approaches T .
In Table 8.12, similar data to those in
Table 6.11 are presented for semi-crystalline
thermoplastics. HDT is usually somewhat
higher than Tg. However, for some semi-
crystalline polymers, HDT is below T (as for
amorphous polymers). Creep effects 'will be
very strong close to and above Tg.For this rea-
son the maximum temperature for continuous
service under significant load is unlikely to
exceed a temperature of 20°C below T' for
semi-crystalline thermoplastics. The primary
advantage of crystallinity is therefore chemical
resistance. This is apparent from Table 6.13,
where chemical resistance for different ther-
moplastics is indicated in a qualitative way.
Semi-crystalline thermoplastics have much

Table 6.13 Chemical resistance of thermoplastics

Material Structure Hydraulic Chlorinated Ketones Esters H,O abs.

fluid kydro- (Yo)
carbons
PA6,6 Crystalline - 0 0 0 8
PEEK Crystalline 0 0 0 0 0.5
PPS Crystalline 0 0 0 0 0.5
PEI Amorphous 0 D A A 1.2
PSU Amorphous A D A A 0.9
PA1 Amorphous 0 0 0 0 2 4
PES Amorphous A D A A 0.3
Am.PA Amorphous A A A 5
PC Amorphous - D A A -

0 = no effect, A = is absorbed, D = is dissolved


better chemical resistance than the amorphous
polymers. A notable exception is the high
water absorption in PA6,6 caused by
hydrophilic groups in its chemical structure.
The solvent resistance of a large selection of
different thermoplastic composites has been
reported (Johnston, Towel1 and Hergenrother,
1991). For most thermoplastics, e.g. PEEK,
moisture expansion coefficients of the carbon
fiber composite may be taken as 0. Thermal
expansion coefficientshave been characterized
(Barnes et al., 1990) and are similar to epoxy
composites. For AS-4/PEEK, the composite
density is 1600 kg m-3.
For polymers with high Tg, exposure to ele-
vated temperature may lead to increased
density not connected with crystallinity but
with the amorphous state. The phenomenon is
termed physical aging and leads to a more
brittle behavior of the polymer (Kemmish and
Hay, 1985). Further work is needed to eluci-
date the importance of physical aging to
composite fracture behavior under practical
service conditions. For composites processed
at high temperatures, residual stresses will
also affect fracture behavior. The magnitude of
the residual stresses and, consequently, detri-
mental effects will increase with increasing
cooling rate (Manson and Seferis, 1992).
Thermoplastic composites can be joined by
the same methods as thermoset composites.
Bolted joint performance has been compared
for thermoset and thermoplastic composites
(Walsh, Vedula and Koczak, 1989) with results
in favor of thermoplastic composites. With the
semi-crystalline thermoplastics, adhesive
bonding requires careful surface preparation
(Kinloch and Taig, 1987).This is because of the
good chemical resistance and limited solubil-
ity of these polymers. However, with careful
surface preparation, as good adhesive bonds
are obtained as with thermoset composites.
The thermoplastic nature of the matrix offers
another possibility: fusion bonding. Different
methods have been compared (Davies and
Cantwell, 1993), including hot gas, IR, laser,
ultrasonic, vibration, electrical resistance and
Applications 127
induction welding. There are difficulties in con-
trolling the processes and very few methods
offer the promise of portable equipment.
Various bonding technologies for PEEK com-
posites have been compared (Silverman and
Criese, 1989).The study favored a technique for
fusion bonding with a polyetherimide film.
This approach can also be used in repair of
damaged structures, since the temperature
needed is below the T, of PEEK.
6.6 APPLICATIONS
Thermoplastic composites can be used in sim-
ilar applications to thermoset composites. The
following examples will demonstrate some of
the reasons for choosing a thermoplastic com-
posite material. In Europe, the automotive
market for GMT composites is significant.
Rapid processing by compression molding,
cycle times of typically 30s even for large
structures, results in cheaper components. In
addition, more functions can be integrated
into each component compared with sheet
metal structures. Bumper beams dominate the
automotive market in the US whereas, in
Europe, a wider variety of applications are in
commercial production. Typical components
are subjected to minor loads or impact and
surface appearance is not important. Battery
trays, beams supporting the hood, seat sup-
ports, oil trays, engine shields and even the
complete front end have been produced for
Volvo, Volkswagen and others.
In the aerospace market, DuPont has sup-
plied thermoplastic polyimide composites to
the prototype programs for the F-22 fighter
aircraft. In the supersonic civil aircraft pro-
gram, the same thermoplastic polyimide is
considered for wing skins. The main reason
for this particular thermoplastic composite is a
continuous high maximum temperature.
AS-4/PEKK (unidirectional discontinuous
fibers) was used by Bell Helicopter Textron in
a V-22 tiltrotor thermoplastic wing rib for bet-
ter open hole compression behavior than
thermoset composites for high proportions of
128 Thermoplastic resins

Bike helmets are also produced (Fig. 6.2). A

semi-finished sheet is heated by IR, transfered
to heated dies where a selective clamping sys-
tem is used to hold the sheet. Forming and
consolidation pressure is applied and the
mold is cooled before demolding. Hoechst in
Germany present applications made by wind-
ing, a pressure vessel, tubes, sealings and
support rings (Fig. 6.3). Matrices include PA6
and PPS with carbon and glass fibers.
In the field of biomedical applications, such
as hip prostheses, semi-crystalline thermo-
plastic matrices offer good potential due to
their chemical stability (Williams and
Fig. 6.2 Bike helmet, an example of a commercial McNamara, 1987).
application of thermoplastic composites (Courtesy:
DuPont Europe).
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