Thermoplastic vs.

Thermosetting
Structural Composites
JOHN D. MUZZY
School of Chemical Engineering
Georgia Institute of Technology
Atlanta, GA 30332
and
ANCIL 0. KAYS
Lockheed-Georgia Company
Department 72-77, Zone 415
86 South Cobb Drive
Marietta, GA 30063
High performance composites are normally fabricated from
continuous fiber and fabric reinforcements embedded in a
thermosetting resin. Currently, thermoplastics are receiving
considerable attention as matrix materials in structural com-
posites. These thermoplastic composites can be fabricated by
novel techniques which are less cumbersome and potentially
faster than curing in an autoclave. In this paper, fabrication
techniques and physical properties of thermosetting composites
will be compared. Applications where thermoplastic compos-
ites are particularly well suited will be presented.

INTRODUCTION action byproducts during cure; hence, void forma-

he matrix of structural composites reinforced
T with continuous filaments or fabric is normally
a thermosetting resin. By starting with a low viscos-
ity reactive liquid, good penetration of the fiber
network can be achieved. After curing, composites
with exceptional mechanical properties and a broad
range of environmental stability are obtained.
As composites are considered for higher volume
products, the incentives for reducing fabrication
costs increase. Fabricating structural composites is
normally labor intensive and requires elaborate,
lengthy cure cycles. By using thermoplastic matri-
ces substantial reductions in forming time and labor
are anticipated.
Typical thermosetting structural composites will
be compared with thermoplastic systems under de-
velopment. Material, processing, and property
comparisons will be presented. Applications in air-
craft components will be emphasized since much of
the development work has occurred in this indus-
try. In structural aircraft components high fiber
loadings (e.g., 60 percent by volume) using contin-
uous filament or fabric are required; hence, these
high performance composites are emphasized.
This paper is an overview of established thermo-
setting composites compared to developing ther-
moplastic composites. An exhaustive review of the
literature has not been attempted.
MATRIX MATERIALS
In aircraft applications rigid epoxy matrices are
most prevalent. These epoxies do not produce re-
tion is minimized and curing shrinkage is low. The
curing cycles for these epoxies are elaborate and
relatively long. Epoxies adhere well to reinforcing
fibers and retain a high percentage of their me-
chanical properties up to 300°F. The moisture and
chemical resistance of rigid epoxies is good.
Alternative thermosetting resins generally don’t
provide the same balance of properties for aircraft
applications. Unsaturated polyesters, although eas-
ier to process, usually don’t have sufficiently high
maximum service temperatures. Vinyl ester resins,
a vinyl adduct to an epoxy base, may provide a
suitable compromise between the ease of process-
ing polyesters and the properties obtained with
epoxies. Phenolic and amino resins are not normally
used to fabricate structural composites; however,
epoxide cured phenol-aralkyl resins are being eval-
uated in carbon fiber composites (1). For higher
service temperatures than the epoxies a variety of
thermosetting polyimides are being evaluated.
One of the first considerations in looking at can-
didate thermoplastics for matrices is the need for
maximum service temperatures equal to or higher
than the epoxies currently in use. Consequently,
high performance rather than commodity thermo-
plastics must be considered. Some high tempera-
ture thermoplastics are listed in Table 1 along with
their reported transition temperatures. In each case
the highest transition temperature exceeds 150°C.
There are other high temperature thermoplastics,
such as polyamides and fluorocarbons, which have
high transition temperatures but have not been
studied extensively in structural composites.

POLYMER COMPOSITES, JULY, 1984, Vol. 5, No. 3 169

 John D. Muzzy and A n d 0.Kays

Table 1. Selected High Temperature Thermoplastics Table 2. Subjective Assessment of Thermoset (TS) and
Thermoplastic (TP) Processing
Transition Temperatures’
Aspect Advantage Reason
Polymer Symbol
PBT
Tg, OC Tu,OC
-
Ref
Prepreg Formation
Poly (butylene terephthalate) 40 228 2,3 Viscosity TS Lower
Poly (ethylene terephthalate) PET 80 265 2 Solvents TS Greater choice
b
Polysulfone PS 190 1 Hand TS More flexible
Poly (phenylene sulfide) PPS 93 288 2,3 Tack TS Prepolymer variable
b
Poly (ether sulfone) PES 230 1 Storage TP Not reactive
Poly (ether ether ketone) PEEK 143 340 3 Quality Control TP Fewer variables
b
Polyimidies PI >280 1 Composite Fabrication
b
Poly (ether imide) PEI 21 0 4 TS Ease of handling
Layup
* 1,: glass transition; 1.: melting point. Degassing TP Fewer volatiles
amorphous polymer. Temperature Changes TP Fewer
Maximum Temperature TS Lower
Pressure Changes TP Fewer
Due to the large number of available thermoplas- Maximum Pressure TS Lower
tics, additional criteria besides maximum service Cycle Time TP Lower
temperature can be applied in selecting thermo- Post Cure Cycle TP Not required
plastics for specific structural composite applica- Repair TP Remelt
Post Forming TP Remelt
tions. Processing considerations, mechanical prop-
erties, and environmental resistances are critical
factors. These are discussed in the ensuing sections.
prepreg are stacked, formed, and cured. The curing
PROCESSING cycle for thermosetting resins can be elaborate and
To achieve weight savings in comparison to high lengthy. For example an epoxy system may require:
strength metals frequently more than 60 percent (a) degassing under vacuum, (b) preheating under
by volume of fiber reinforcement is required. The vacuum, (c) pressure forming at high temperature,
matrix resin should have a low viscosity in order to (d) curing under pressure and higher temperature
penetrate the reinforcing structure and adequately and (e) cooling under vacuum. This curing cycle
wet the fiber. By using low viscosity resins, fiber can exceed 6 hours. Other resins may require
damage and distortions can be minimized. Normally longer curing cycles as well as post curing at high
a thin prepreg is formed with the desired ratio of temperatures and ambient pressure. Kourtides (5)
fiber to matrix prior to fabricating the composite presents specific examples of curing cycles for a
product. For thermosets the resin is applied as a number of matrices.
solution or low molecular weight prepolymer to the Thermoplastic resins typically require simpler
reinforcing fabric or tow. Then the prepreg is dried and shorter composite fabrication cycles from pre-
to remove residual solvent and/or partially cure the pregs. Since the resin must melt and flow higher
resin. Since the prepreg is partially cured it is more temperatures and pressures may be necessary. Post
sensitive to environmental conditions than the fully curing (annealing) isn’t required. Cycles times less
cured composite. Consequently, the prepreg must than one hour have been reported for PES ( 5 ) ,PBT
be stored in controlled environments and will have (6) and PET (6) composites. In addition, thermo-
a finite storage life. plastic composites have been successfully fabri-
To prepare thermoplastic prepregs solution or cated without prepregs by interleaving film and
melt coating of the fiber reinforcement is used. reinforcing fabric ( 3 , 6, 7).
Compared to epoxies the viscosity of thermoplas- A subjective assessment of composite fabrication
tic solutions are higher and the choice of solvents is presented in Table 2. In addition to the fabrication
is more limited. Melt processing requires much features just discussed, it should be easier to repair
higher temperatures and pressures; but, solvent fabrication defects by remelting and reforming.
evaporation and recovery isn’t necessary. Since re- Also, thermoplastic composites can be thermo-
actions do not occur in forming thermoplastic pre- formed or hot stamped after lamination (8, 9), pro-
pregs storage and quality control requirements are viding greater diversity in forming or reshaping
less stringent compared to epoxies. Conversely, by laminates.
manipulating the degree of cure the hand and tack Summarizing Table 2, thermosetting prepregs are
of epoxy prepregs can be modified whereas this easier to produce but thermoplastic prepregs ex-
option is not available in producing thermoplastic hibit numerous advantages in composite fabrica-
prepregs. tion. At Boeing a 25 percent fabricated cost saving
Table 2 summarizes some of the differences in has been estimated for constructing the outboard
preparing thermoplastic and thermoset prepregs. elevator on the wing of the YC-14 airplane. The
Since processing is strongly dependent on the par- saving is due to replacing a graphite/epoxy com-
ticular resins being processed and there are so many posite with a graphite/PS composite (10).
resin alternatives, there are many exceptions to the
subjective evaluations offered in Table 2. Kourtides PROPERTIES
( 5 ) provides a number of specific examples of pre- At room temperature the mechanical properties
preg formation. of thermoplastic and thermosetting composites are
To fabricate composites, a number of plies of the similar. Tensile and shear properties for epoxy and

170 POLYMER COMPOSITES, JULY, 1984, Yo/. 5, No. 3

 Thermoplastic vs. Thermosetting Structural Composites
polysulfone unidirectional composites are pre-
sented in Table 3. Due to the high strength and
modulus of the graphite fiber, the tensile strength
and modulus in the fiber direction, O", are domi-
nated b y the volume fraction of fiber present. The
traverse, 90°, properties and short beam shear
strength are dominated by the matrix resin. Both
systems have similar properties at room tempera-
ture because at room temperature both resins are
below their glass transition temperatures. Glassy
polymers below Tg have comparable tensile prop-
erties and reinforcing glassy polymers leads to com-
parable increases in these tensile properties pro-
vided adequate adhesion between the fiber and
matrix is achieved.
At higher temperatures mechanical properties
are retained until Tg is approached for the thermo-
setting matrices and amorphous thermoplastics. In
crystalline polymers a moderate drop in modulus
occurs in the glass transition region. Normally a
major drop in mechanical properties does not occur
until the melting temperature of the crystalline
polymer is approached. A number of investigators
have reported on the high temperature properties
of thermoplastic composites (3, 6, 7, 9, 10). The
trends obtained with increasing temperature are
similar to the trends observed in short fiber com-
posites.
The fracture and fatigue properties of thermo-
plastic structural composites have not been studied
extensively. Since many thermoplastics can tolerate
higher strains prior to failure compared to ther-
mosets, thermoplastics usually exhibit better frac-
ture toughness and fatigue endurance. These gen-
eral trends have been observed in both neat and
short fiber reinforced resins (13). In addition, crys-
talline polymers normally have better fracture and
fatigue resistances than amorphous polymers (1 3).
Similar trends are expected in continuous filament
and fabric reinforced polymers. For example, sub-
stantially higher fracture energies have been ob-
served in polysulfone systems compared to epoxy
systems with and without graphite fabric reinforce-
ment (14).
Humid aging can reduce the maximum service
temperature of composites. In graphite composites
the matrix is the limiting component in wet envi-
ronments. The physical impact of water is to plas-
ticize the matrix, lowering the glass transition of
the system. The plasticized composite will have
lower mechanical properties. The room tempera-
Table 3. Mechanical Properties of UnidirectionalGraphite
Composites at Room Temperature
EPOXY Polysulfone
Resin Content (Vol. O/O) 40 43
Oo Tensile Strength (lo3psi) 220 182
0" Tensile Modulus (1' 0 psi) 16 15
90° Tensile Strength (lo3psi) 8 6
90' Tensile Modulus (1O6 psi) 2.2 1.2
Short Beam Shear Strength (lo3psi) 10 11
Reference 12 13
POLYMER COMPOSITES, JULY, 1984, Vol. 5, No. 3
Table 4. Water Absorption of Selected Polymers ASTM D 570,
24 hours, Roam Temperature'
Polymer" % Absorbed
Epoxy 0.05-0.2
PBT 0.08-0.09
PET 0.1-0.2
PS 0.3
PPS <0.02
PES 0.43
PEEK' 0.14
PI 0.24
PEI not reported
' 1981-1982 Modern PIasUcs Ency&pedia, except lor PEEK.
Refer to Table f for symbds.
ICI, Lld. data sheet, 40 perrent mlalive humidity.
ture water absorption of some polymers of interest
is presented in Table 4 . All of these polymers exhibit
low water absorption at room temperature; but, the
extent of water absorption increases at higher tem-
perature. At high temperatures hydrolytic degra-
dation reactions can occur, further deteriorating
the matrix.
Humid aging tests are time consuming; hence,
comparative data for evaluating the performance of
alternative matrices is limited. Comparable tests on
graphite composites with epoxy and polysulfone
matrices indicate both systems retain a substantial
portion of their mechanical properties up to 250°F
following humid aging (12). Humid aging of poly
(phenylene sulfide) (PPS)/graphite composites in-
dicate a 54 percent loss in flexural strength and 24
percent loss in flexural modulus in comparing wet,
250°Fproperties with dry, room temperature prop-
erties (7).The substantial drop in flexural strength
can be attributed to exceeding the glass transition
of PPS, which is 20O0F, rather than water absorp-
tion. Humid aging tests of PPS, PBT, and PET glass
fabric composites indicate 75 percent or higher
tensile property retention at 180°F compared to
dry, room temperature properties (15). These lim-
ited results indicate that selected thermoplastic ma-
trices can perform as well as epoxy matrices. Mois-
ture resistance data from material suppliers indicate
that some thermoplastics may perform better than
epoxies in humid, high temperature environments.
In aircraft applications resistance to specific fuels,
hydraulic fluids, and solvents is essential. Epoxies
and some of the amorphous polymers listed in Table
I, PS and PES, deteriorate in methylene chloride
(9, 16), an aircraft paint stripping solvent. Norbor-
nene end capped polysulfones have been synthe-
sized which alleviate this sensitivity to methylene
chloride (1 6). A number of crystalline polymers,
PBT, PET, and PPS, are resistant to these specific
chemicals (6, 7 , 15). Environmental stress cracking
tests of PEEK indicate it is generally resistant to
these chemicals (1 7).
In summary, composites with virtually equivalent
strength and modulus properties at room tempera-
ture can be obtained using thermoplastic or ther-
mosetting matrices. The environmental resistances
of these composites to temperature, humidity, and
aircraft chemicals are dependent on the transition
171
 John D.Muzzy and A n d 0.Kays
temperatures and specific chemical interactions of
the matrix polymer. Similarly, the fracture tough-
ness and fatigue resistance of the composites de-
pends strongly on the properties of the matrix.
Crystalline polymers appear to offer greater oppor-
tunities for overall property enhancement com-
pared to amorphous thermoplastics since crystalline
polymers tend to have better environmental and
fatigue resistances. Since there is considerable re-
search effort on developing modified thermosetting
matrices it is not possible to claim that thermoplas-
tics will perform better than modified thermosets.
CONCLUSIONS
Thermoplastic matrices offer the potential for
reducing the cycle time for fabricating structural
composites and expanding the options for rapidly
forming parts after lamination. Thermoplastics are
available which can provide equivalent or improved
performance compared to epoxies. However, insuf-
ficient processing and performance data is available
to specify thermoplastic composites in critical, high
performance applications. Currently thermoplastic
structural composites are limited to specialty appli-
cations (18). Due to the existing data base using
thermosetting matrices and the continuing devel-
opment of thermosets, a gradual penetration of
thermoplastic matrices into structural composite
applications is anticipated.
172
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POLYMERCOMPOSITES, JULY, 1984, Vol. 5, No. 3