SPECIALITY MATRIX RESINS
David A.Shimp
5.1 INTRODUCTION
Bismaleimide (BMI) and cyanate ester (CE)
resins were first commercialized in the 1970s as
250-300°C Tgclass laminating resins for circuit
board substrates. In the early 1980s structural
prepregs were introduced to an aircraft indus-
try searching for primary structure composites
with higher service temperatures and
improved damage tolerance relative to multi-
functional epoxy based composites. Both BMI
and CE resins have since evolved as easy-to-
process thermosetting resins qualified for
177°C (350°F) hot-wet service. Toughening
technologies provide compression-after-impact
ratings approaching or matching the damage
tolerance of thermoplastic resin composites.
Bismaleimides, with higher modulus values
and established higher thermal ratings, earned
a strong position in military aircraft primary
structures with recent selection for the F-22
fighter. Cyanate esters, with superior dielectric
loss properties and lower moisture absorption,
are strong contenders for radomes, skins cover-
ing phase-array antennae, advanced Stealth
composites and space structures.
5.2 RESIN CHEMISTRY
Cyanate ester monomers are prepared by react-
ing bisphenols or polyphenols with cyanogen
chloride in the presence of an organic base
(Rottloff, 1977).Crystalline monomers are ther-
mally advanced to amorphous prepolymer
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
5
resins by resin suppliers accomplishing from
1550% of the cyclotrimerization curing reac-
tion using closely controlled reactor processing.
Figure 5.1 illustrates formation of the s-triazine
ring (cyanurate trimer) by the cycloaddition of
three cyanate groups. Formulators catalyze
amorphous monomers or prepolymer resins
with latent catalysts which promote full con-
version to the thermoset polycyanurate with
subsequent heating to 177-250°C. Cyanates
also serve to cure epoxy resins, forming cost-
effective hybrids retaining an anomalously
high fraction of CE homopolymer properties
(Shimp, 1992).
Bismaleimide monomers are prepared by
the reaction of aromatic diamines with maleic
anhydride in the presence of dehydrating
agents (Stenzenberger, 1990). Homopolymers
of BMI monomers are excessively brittle and
in practice are co-reacted with chain-extending
diamines, diallyl bisphenols or dipropenyl
phenoxides to develop toughness via reduced
cross link density. Figure 5.2 illustrates chain
extension with aromatic diamine (Bargain,
1971) to form longer linear segments which
ultimately crosslink by homopolymerization
of maleic double bonds. Kerimid@resins and
Fiberite PI molding compounds are examples
of commercial BMIs using aromatic amine
modification.
Figure 5.3 depicts a series of reactions
whereby o-allyl-phenols add across the maleic
double bond via the 'ene' reaction and a second
maleimide enters into a Diels-Alder ring-form-
ing reaction with the now conjugated propenyl
residual double bond. The proposed reaction
100 Speciality matrix resins

0 0

I
MICHAEL ADDITION
VI

I
HOMOPOLYMERIZATION
VI
Prepolymer resin
0 0 0 0

Curing via
cyclotrimerization

Y Y

X = alkylidene Y = alkyl or H

Fig. 5.2 Sequence of chemical reactions for advanc-

ing BMI monomers with aromatic diamines to resin
adducts by chain extension and ultimately to
toughened thermoset plastics.
0
R
mechanism includes isomerization to form the
i aromatic ring. Crossllnking can occur by a con-
Thermoset plastic
(polycyanurate) tinuation of these reactions (difunctional
components) or via residual maleic double
Fig. 5.1 Dicyanates cure by forming triazine rings bond homopolymerization. The chemistry by
on heating, advancing to prepolymers (up to 50% which o,o'-diallyl bisphenol A coreacts with and
conversion) and to thermoset plastics at -O-C=N toughens 4,4'-bismaleimido-diphenylmethane
conversions >60-64%. (BMI-DAB) is described by Zahir (1978) and
 Matrixformulation 101

King (1984). Allyl functional phenoxy com- 5.3 COMMERCIAL RESINS

pounds follow the same reaction path while
The chemical structure of seven commercial
propenyl functional phenoxides eliminate the
di(po1y)cyanate ester monomers is shown in
'ene' reaction step (Stenzenberger,1990).
Table 5.1 along with supplier information,
physical state and key homopolymer proper-
ties. The three crystalline monomers are
r! Ri usually supplied only as amorphous prepoly-
I mers in semisolid, hard resin, or ketone
+ laminating solution form. CE homopolymer

@-OH I
properties are not affected by prepolymer
advancement, which is only an interruption of

I "ENE" REACTION

Ri
the ring-forming curing reaction to alter phys-
ical state and rheological properties. Monomer
asymmetry, e.g. AroCy@L-10, can yield low RT
viscosity. CEs have a low toxicity profile and

bv2b
storage stability comparable to epoxies.
Table 5.2 describes several BMI monomers,
advanced resins, reactive tougheners with
OH allyl and propenyl functionality and RTM

1 yy Ri resins. Most BMI monomers have a crystalline

DIELS-ALDER I physical state. Eutectic blends of monomers
REACTION are available as resolidified melts of lower
melt point. Resins prepared by prereacting a
molar excess of BMI with tougheners have a

e.
9
% db
MERIZATION - HOMOPOLY-
powder or hard resin physical state. Allyl and
propenyl functional reactive tougheners are
usually viscous liquids which serve to dissolve
crystalline BMIs at temperatures below 110°C
to offer convenient melt processibility.

1I
OH
AROMATIZATION
5.4 MATRIX FORMULATION

-
HoMoPoLY-
MERIZATION
Fig. 5.3 Sequence Of reactions between Phe-
nols and BMI monomers involves grafting via the
'ene' reaction and fused ring formation via
Diels-Alder. Crosslinking with di(po1y) functional
components involves completion of these reactions
and/or maleic double bond homopolymerization.
5.4.1 MEETING RHEOLOGICAL
REQUIREMENTS
Both resin classes offer a wide selection of
monomers and prepolymers enabling the
fomulator to satisfy the rheological properties
of fluid RTM compounds, tack and cohesive
integrity of compliant prepreg and the short
flow of compression molding compounds.
Figure 5.4 illustrates the limiting direct rela-
tionship in families of thermosetting resins
between fluid monomer (150 mPa s viscosity)
temperature and Tg On curing. High
temperature polyimides locate Off-sCalein the
102 Speciality matrix resins

Polycyanate monomer structure/ Trade name/ Homopolymer property

arecursor supplier/ T.2 wt.% Dk G,
physical state O e H,O MHz J m-2
~~

AroCy B
e c - ~ c ~ ~ + c ECibaNSpecialty Chem.*
CH3 BT-2000 289 2.5 2.91 140
Mitsubishi GC

Bisphenol A Crystal

943 p 3 AroCy M
N E c - o o { *)N Ciba Specialty Chem. 252 1.4 2.75 175
$ Crystal
dH3 CH3
Tetramethylbisphenol F

AroCy F
,oOcP*ZN Ciba Specialty Chem. 270 1.8 2.66 140
CF3
Crystal
Hexafluorobisphenol A

AroCy L-10
Ciba Specialty Chem. 258 2.4 2.98 190

Liquid
Bisphenol E

XU-366
Ciba Specialty Chem. 192 0.7 2.64 210

Semisolid
Bisphenol M

Primaset PT 270
Lonza, Inc.
to 3.8 3.08 60
XU-371
Ciba Specialty Chem. >350
Novolac resin Semisolid

XU-71787
*CZN Dow Chemical 244 1.4 2.80 125

Dicyclopentadienyl bisphenol Semisolid

~

* The complete name of the Ciba company supplying AroCy cyanate resins is Ciba Specialty Chemicals Corp.,
Performance Polymers Group.
 Matrix formulation 103

Table 5.2 Commercial BMI monomers, resins (adducts), reactive tougheners and compounds

Supplier Trade name/structure Description

~

Basic BMI monomer

Ciba Crystalline powder
m.p. 150-160°C
0 0

Matrimidm5292A

o,o'-DiallylBisphenol A
Ciba Reactive toughener
12 000-20 000 mPa s at 25°C

Matrimid 5292B

Inspec CornpimidemMDAB Basic BMI monomer

Inspec Compimide 353 Resolidified BMI melt

Eutectic monomer blend 400-1400 mPa s at 110°C

Inspec Compimide 796 Resolidified BMI resin melt

Proprietary BMI adduct 10004500 mPa s at 110°C

Bisallyl polyphenoxide
Inspec Reactive toughener
Compimide TM 121 120-250 mPa s at 71°C

a r' Bispropenyl phenoxy

benzophenone
Reactive toughener
Inspec 1000-1600 mPa s at 71°C
0
Compimide TM 123

Inspec Compimide 15 MRK Powder for molding compounds

Inspec Compimide 65 FRW Resolidified melt for filament

winding and RTM
Ciba designates Ciba Specialty Chemicals Corp., Performance Polymers. Inspec designates Inspec Fine Chemicals Co.

Table 5.1 (on facing page) Commercial cyanate ester monomers, suppliers, physical states and homopoly-
mer properties. Water absorption is wt.% at saturation. D, = dielectric constant
104 Speciality matrix resins

400

300
I BM' I
0
d,
0
AROCY R T ~ T m -

-
I- L-10
366 EPOXIDE
z 200
v)
n
U
w
[r DlEPOXlDE
O
w VINYL
a
2100 -
POLYESTER

0
0 50 100 150
MONOMER TEMP. ( " C ) at 150 MPA.S

Fig. 5.4 Relationship between fluid monomer tem-

perature and cured T g in families of thermosetting - 21 0 0 20 40 60 80 1
10
resins.Higher service temperature is normally asso- AROCY L-10, WEIGHT %
ciated with increasing processing difficulties.
Fig. 5.5 The asymmetric structureof AroCy L-10 dis-
upper right quadrant. AroCy L-10, derived rupts crystallinity, permitting optional use of this
from an asymmetric bisphenol, breaks the pat- ring-forming resin as a reactive diluent.AroCy num-
tern and can be used as a 250°C T g resin or as bers are the % cyanate conversion of prepolymers.
a reactive diluent of 120mPas viscosity
(Fig. 5.5). but predissolving in 2-6 phr (parts per hun-
dred resin) alkyl phenol, e.g. nonyl or dinonyl
phenol, forms stable liquid packages which
5.4.2 CURE CATALYSTS
are readily miscible (Shimp, 1988). The alkyl
Catalysts are not required to cure BMI resins at phenol provides the active hydrogen co-cata-
temperatures above 200"C, but several types lyst and can serve as a monofunctional
provide effective cure acceleration. Tertiary reactant to increase conversion and resistance
amines, imidazoles and free radical generators to boiling water at marginal cure temperatures
are noted by Zahir (1978). Boyd (1987) (Fig. 5.6). Extension of this principle to AroCy
describes the preferred latency of tri- XU-366 enables this monomer to convert satis-
phenylphosphine and its phosphonium halide factorily at 121°C for use with high modulus
derivatives as prepreg catalysts. polyethylene fibers (Shimp, 1994a) and with
Cyanate esters require catalysis to cure at composite tools.
practical rates. Copper (most active at low
temperatures) and cobalt (latent) acetylaceto-
5.4.3 TOUGHENING TECHNIQUES
nates provide 295% conversion within 2-6 h at
post cure temperatures in the range of Concentrated effort over the last decade has
200-250°C. Metal coordination catalysts in produced composite toughening techniques
general are difficult to solubilize in neat resins, which satisfy damage tolerance requirements

I L
' I
".
0 2 4 6
NONYLPHENOL CONC. (phr)
I I I 5.4.4 EPOXY RESIN MODIFIERS
0 10 20 30 40
Meq OHIOCN
Fig. 5.6 Increasing concentrations of alkyl phenols
in cyanate ester homopolymers increase conversion
(numbersat right) for a given cure temperature and
increase resistance of 3 mm thick castings to hydrol-
ysis in boiling water. Cure temperature: a: 250°C;
A,:210°C; 0 :177°C. (for AroCy B)
of primary aircraft structures and microcrack
resistance in earth orbit and cryogenic service.
BMI resins earlier required the development of
allyl, propenyl and amine functional reactants
to achieve >2% tensile elongation-at-break, a
minimum requirement for efficient secondary
toughening with thermoplastic polyimides.
Boyd (1990) describes the development of
improved chain extending reactants by cou-
pling 2- or 4-propenyl phenol with diepoxides.
Incorporation of thermoplastic polyimide fine
particles of 5-15 pm diameter, described by
Boyd (1991a),increased the compression-after-
impact (CAI) performance of BMI composites
to 2276 MPa (240 ksi). Further toughening to
Matrix and composite properties 105
the CAI performance level of 245 ksi was
demonstrated (Boyd, 1993a) by combining in
situ epoxy extension of o,o'-diallylbisphenol A
with thermoplastic polyimide particles.
CE monomers and prepolymers dissolve
powdered amorphous thermoplastics (Tps) of
the polysulfone, polyethersulfone, polyether-
imide, polyphenylene oxide and copolyester
families, then subsequently phase separate
these thermoplasticsduring cure. Co-continuous
morphologies are developed at Tp concentra-
tions 215% which increase GI, values in a non-
linear response to concentration (Shimp,
1994a). Lee (1991) describes the development
of a CE matrix formulation toughened with
polyoxazolidinones, polyethersulfone and co-
polyester Tp resins. Table 5.3 lists a number of
Tp resins used to toughen both CE and BMI
resins as well as reactive rubbers used to elim-
inate microcracking in orbital service.
Epoxy resins derived from epichlorohydrin
co-react with CE resins at equivalent ratios of
up to 1.2 epoxides per monomer cyanate.
Hybrids with typical epoxy weight fractions of
50-70'/0 develop Tg values in the 180-200°C
range and retain dielectric constants 13.1 with
loss tangents generally below 0.010 (Shimp,
1992). The use of diepoxides to toughen BMI
resins via chain extension of alkenyl (bis)phe-
nols was described in the previous section.
Epoxides can also react with the secondary
amine formed by the Michael addition of aro-
matic diamine to the BMI maleic double bond.
5.5 MATRIX A N D COMPOSITE PROPERTIES
The following acronyms will be used to
denote BMI resin system properties in figures
used thoughout this section:
BMI-MDA = the reaction product of 4,4'-bis-
maleimidodiphenyl methane (molar excess)
with methylene dianiline.
BMI-DAB = the equimolar reaction product of
106 Speciality matrix resins

Table 5.3 Thermoplasticand reactive rubber tougheners

Classification Product Used Supplier

with

Soluble T,"
Polyethersulfone Victrex 5003P 203 CE ICI/Mitsui
Polysulfone Udel P-1700 175 CE Amoco
Polyetherimide Ultem lOOO(P) 215 CE General Electric
Polyphenyleneoxide PPO 202 CE General Electric
Polyimide Matrimid 5218 300 CE Ciba
Elastomeric T,
Copolyester Vitel PE-307 14 CE Bostik
Reactive rubbers
Solublea(OH) ATX-013 <25 CE Echo Resius
Soluble"(Epoxy) Hycar ETBN <25 CE B.F. Goodrich
Preformed Core/Shellb CRS (exp.) <25 CE Dow Chemical
Polysiloxanes
Epoxy functional Experimental <25 CE Proprietary
Maleimide functional PAP Series <25 CE National Starch
Particulate T,"
Polyimide P-84 290 BMI Lenzing AG
Polyimide Matrimid 5218 300 BMI Ciba
Polyamide 1002 D NAT 85 CE Atochem Corp.
a Initially soluble but phase separate during cure.
Small particles swell but do not completely dissolve with cure.
Note: Most of this toughening technology is described in patents.

4,4'-bismaleimido diphenylmethane with Although CE resins demonstrate higher tem-

o,o'-diallylbisphenol A (Matrimid 5292).
5.5.1 MECHANICAL PROPERTIES
Table 5.4 compares properties of representa-
tive CE and BMI castings. Significant
differences are the higher room temperature
modulus values of BMI matrices (superior
stress transfer to fiber) and higher CE elonga-
tion-at-break values.
perature onsets of rapid thermal degradation
in TGA tests, available long term isothermal
aging tests in air indicate superior BMI perfor-
mance. Boyd (1993b) classifies 1-year CAI
retention life of BMI composites as >177 but
<205"C. Stenzenberger (1991) rates 2000 h life
of BMI castings as >2OO0Cbut <250"C based
on retention of shear and flexure strengths.
CE/E-glass laminates are rated at 162-180°C
for 25 000 h retention of flexure strength at
50% of the unaged values (Shimp, 1989).

5.5.2 THERMAL PROPERTIES 5.5.3 DIELECTRIC PROPERTIES

T , values average about 20°C higher for BMI Figure 5.7 ranks the dielectric constant (D,)
matrices (Table 5.5). CTE values below T,are and dissipation factor (D,) or loss tangent of
comparable while CE resins retain higher char thermoset matrix resin castings compared
yields as a result of increased aromaticity. with reference thermoplastics. Effects of
 Matrix and composite properties 107

RESIN DIELECTRIC PROPERTIES

25 O C DK 'I,
DK Df

HOMOPOLYMER

BMI-DAB
AroCy 6 , L
AroCy B AroCy M ,F

F
AroCy M
AroCy F
XU - 366

2 1
POLYETHYLENE
PTFE
0 20 40 60 80 11 0
RESIN CONTENT, Volume %
Fig. 5.8 Effect of reinforcement and concentration

1 1
AIR
I
I oe5
on dielectric constant of AroCy M composites. Test
data at 25°C and 1 MHz.

tems. Moisture locates primarily in the CE free

Fig. 5.7 Thermosetting and thermoplastic resins are
volume fraction, resulting in less swelling
ranked for dielectric constant (D,) and dissipation
factor (D,) at 1 MHz frequency. (Fig. 5. 10) than is caused by association with
strong dipoles. Plasticization of moisture-con-
moisture absorption, test temperature and fre- ditioned matrix castings, compared as a
quency are summarized by Shimp (1994b). function of flexural modulus retention at ele-
Low D , values of CE homopolymers and vated test temperatures, is minimized by the
CE/epoxy hybrids are attributed to the sym- low absorption of AroCy M o-methylated CE
metrical arrangement of electronegative resin (Fig. 5.11). Hydrolysis of AroCy M cya-
oxygen and nitrogen atoms around a central nurate linkages in 121°C steam requires >600 h
electropositive carbon atom in these struc- exposure (Fig. 5.12).
tures, resulting in weak dipoles. Dielectric
constants of CE composites compared with
5.5.5 PROPERTIES OF UNIDIRECTIONAL
fiber type and loading are plotted in Fig. 5.8.
COMPOSITES
D, and loss tangent values of quartz reinforced
BMI, CE and epoxy composites are compared Properties of intermediate modulus carbon
at four radar bandwidths in Fig. 5.9 (Speak, fiber reinforced BMI composites (Table 5.6)
1991). and CE composites (Table 5.7) indicate good
translation of fiber strength for both classes.
Damage tolerance ratings based on CAI
5.5.4 MOISTURE ABSORPTION AND EFFECTS
results at 6.7 KJ m-l impact energy fall in the
CE homopolymers absorb less moisture than 200-345 MPa (30-50 ksi) class, approaching or
BMI and TGMDA/DDS epoxy matrix sys- equaling the damage resistance of thermoplastic
108 Speciality matrix resins

Table 5.4 Mechanical properties of CE and BMI resins

AroCy AvoCy AroCy Matrimid

B M L 5292

Composition (PBW)
- -
AroCy B-30 100 -

AroCy M-20 - 100 - -

AroCy L-10 - - 100 -

Matrimid 5292A - - - 100

Matrimid 5292B - - - 85
Nonylphenol 2 2 2 -

Cobalt acetylacetonate 0.13 0.13 0.13 -

Property of casting"
Tensile strength, MPa 88 76 87 82
ksi 12.7 11.0 12.6 11.9
Tensile elongation, YO 3.2 2.7 3.8 2.3
Flexure strength, MPa 174 159 187 167
ksi 25.2 23.0 27.1 24.2
Young's modulus Flexure Flexure Flexure Tensile
25"C, GPa 3.17 2.97 3.24 4.28
msi 0.46 0.43 0.47 0.62
149"C, GPa - - - 2.42
msi - - - 0.35
163"C, GPa 2.55 2.35 2.28 -

msi 0.37 0.34 0.33 -

204"C, GPa - - - 2.00

msi - - - 0.29
G,,, J m-2 140 175 190 170
in lb in-2 0.80 1.00 1.08 0.97
aStep-cure with post cure of 2 h at 250°C for CE; 6 h at 250°C for BMI. Data courtesy of Ciba Specialty Chemicals Corp.,
Performance Poiymers Group.

composites. BMI composites have demon- KorexTMaramid/phenolic honeycomb core

strated hot-wet performance in 177°C rated
aircraft. CE composites may attain that goal
with AroCy M resin, but insufficient 177°C
hot-wet compression data has been published
for commercial materials of this class.
5.6 DESIGN CONSIDERATIONS
5.6.1 SELECTION OF ARAMID FIBER AND
CORE
Aramid fiber and core reinforcements for CE
composites should be selected from second
generation materials wluch absorb <2% mois-
ture in the workplace. Kevlar@aramid fiber and
(DuPont) are recommended for use with CE
resins catalyzed with copper or cobalt acety-
lacetonates to eliminate blistering associated
with post cures >190°C. (Shimp, 1993; 1994a).
5.6.2 GALVANIC CORROSION
Both BMI and CE carbon fiber composites
have been reported to undergo resin degrada-
tion in accelerated galvanic cell tests
producing strongly alkaline conditions at
cathodic sites (Boyd, 1991b; Olesen, 1991).
Figure 5.13 compares the onsets and rates of
alkaline hydrolysis (etching) for CE and BMI
matrix castings. (See also Boyd, 1991b).
 Suppliers of prepreg and other formulated products 109

Table 5.5 Thermal properties of CE and BMI resins

AroCy AroCy AroCy Matrimid

B M L 5292

Composition (PBW)
AroCy B-30 100 - - -
AroCy M-20 - 100 - -
AroCy L-10 - - 100 -
Matrimid 5292A - - - 100
Matrimid 5292B - - - 85
Nonylphenol 2 2 2 -

Cobalt acetylacetonate 0.13 0.13 0.13 -

Property of casting"
HDT, "C
Dry 254 252 249 273
Wet 197 226 183 217
T,' "C
by DMA 289 267 270 295
by TMA 257 255 259 273
CTE by TMA, ppm/"C
40 to 200°C 64 66 64 63
TGA at 10"C/min
Onset in air, "C 411 406 408 371
Char in N,, Yo 41 46 43 29
Specific gravity at 25°C 1.201 1.151 1.228 1.232
aStep-cure with post cure of 2 h at 250°C for CE: 6 h at 250°C for BMI. Data courtesy of Ciba Specialty Chemicals Corp.,
Performance Polymers Group.

Effective design practices for susceptible com-
posites are use of titanium rather than
aluminum rivets, placement of a fiberglass
reinforced insulating ply and/or modification
of CE resin with 55-70% epoxy resin.
5.6.3 MICROWAVE TRANSPARENT
COMPOSITES
Composite design for radomes, antennas and
advanced stealth structures should utilize low
dielectric loss materials (Speak, 1991; Shimp,
1994b; Stonier, 1991a,b). Figure 5.14 summa-
rizes microwave interactions with a radome
wall. Reflection weakens returning signals and
overheats emitter sources; refraction distorts
signal quality; absorption decreases signal
strength and generates destructive heat, limit-
ing power and range. CE composites curing at
121°C (250°F), e.g. Bryte Technologies'
EX-1515, are thermally compatible with high
modulus polyethylene reinforcement. Such
composites are characterized by D, values as
low as 2.6 and D, values as low as 0.004 when
measured at 10 GHz.
5.7 SUPPLIERS OF PREPREG AND OTHER
FORMULATED PRODUCTS
Table 5.8 lists suppliers of BMI and/or CE
prepreg, adhesive, syntactic foam, RTM/fila-
ment winding systems and chopped fiber
reinforced molding compounds formable by
compression, injection or transfer processes.
110 Speciality matrix resins

4.0 I 1
IIELECTRIC I I
CONSTANT

3.5

3.0 J
XBAND KaBAND UBAND WBANC
8-12 26-40 40-60 75-100
GHz GHz GHz GHz
0.030

TANGENT
0.020

0.0 10

CE tI
0.000 '
XBAND KaBAND UBAND W BAND

Fig. 5.9 Comparison of typical quartz reinforced radome composites for dielectric loss properties measured
at four radar bandwidths. Redrawn from Speak, S.C., Sitt, H and Fuse, R.H.. 1991. Novel cyanate ester
based products for high performance radome applications. Int. S A M P E Symp., 36 pp. 336-347.

i
I +
P

10' 1o2 1o3 1o4

Hours at 25°C & >95% RH
Fig. 5.10 Changes in 3 mm thick bar volumes during water immersion for a period of one year indicate
swelling rates and limits of thermoset resins. The ratio of volume increase to total volume of water
absorbed (numbers on right) indicates the fraction of water associated with dipoles.
A: BMI-MDA; X: BMI-DAB; 0: TGMDA-DDS; 0:AroCy B; 0 :XU-366
 Suppliers of prepreg and other formulated products 111

Table 5.6 Properties of BMI/IM-7 unidirectional composites

Mechanical st rengtk Rigidite Rigidite

5250-4" 5260b

0" Tensile, MPa (ksi)

25°C 2618 (380) 2691 (390)
0" Compression, MPa (ksi)
25°C Dry 1820 (235) 1746 (253)
105°C Wet - - 1346 (195)
149°C Wet - - 1276 (185)
177°C Dry 1310 (190)
177°C Wet 966 (140)
0" Compressive modulus
25"C, GPa (msi) 158 (23) 152 (22)
Open hole compression, MPa (ksi)
25°C Dry 420 (61) 352 (51)
177°C Dry 351 (51) 269 (39)
191°C Wet 303 (44) 221 (32)
Compression after impact
At 4.5 kJ m-l, MPa (ksi) 248 (36) 380 (55)
At 6.7 kJ m-l, MPa (ksi) 214 (31) 345 (50)
Edge delamination, MPa (ksi)
25°C 241 (35) 358 (52)
~~

a Data courtesy of Cytec. Post cure 6 h at 227°C; 60% fiber vol.

Data courtesy of Cytec. Post cure 6 h at 215°C; 60% fiber vol.

Table 5.7 Properties of CE unidirectional composites

Cytec Fiberite Hexcel

5245C 954-2 HX-1562

Reinforcementhre
Carbon fiber IM-6 IM-7 IM-7
Max. cure temp., "C 210 232 177
Mechanical strength
0" Tensile, MPa (ksi) 2439 (356) 2814 (408) 2610 (378)
0" Compression, MPa (ksi)
25"C, Dry 1690 (245) 1573 (228) 1700 (246)
121"C, Wet 1350 (196) 1331 (193) - -
132"C, Wet 1310 (190) - - 1140 (165)
149"C, Wet 987 (143) 1290 (187) - -

CAI, MPa (ksi)

At 6.7 kJ m-I 214 (31) 262 (38) 317 (46)
Edge delamination, MPa (ksi) 262 (38) 269 (39)
112 Speciality matrix resins

Fig. 5.11 (left) Moisture plasticization of cast

matrix systems is inversely related to the percent-
age of dry room temperature flexural modulus
0 ° 1 1 O0
retained at elevated test temperatures.
79
74 : at 149°C wet;
: at 177°C wet.
61

Fig. 5.12 (below) Hydrolysis of unsubstituted CE

(bisphenol A dicyanate) homopolymer begins to
reduce mechanical properties after 200 h exposure
~
to 121°C steam autoclave at 15 psig. Ortho-methy-
AroCy AroCy BMI/ lation is an effective technique for increasing
hydrolytic stability of cured CE resins in aggressive
environments. 0: AroCy B; 0:AroCy M.

% WEIGHT GAIN
121

91 AROCY B

0 200 400 600

TIME, HOURS

Table 5.8 Sources of formulated/compounded CE and BMI products

Supplier Prepreg Adhesive Syntactic RTM Compression molding

foam compound compound

Bryte Technologies CE CE CE CE -
Cytec BMI, CE BMI, CE BMI, CE BMI -
Hexcel BMI, CE BMI - - -

Fiberite, Inc. CE - - - BM1,CE

YLA CE CE CE CE -
 AppIications 113

+1.0
AROCYBIEKXY

w H.5
P3 -I
AROCYM
I

0 10 20 30 40 50 60
DAYS IMMERSION IN 20% NaOH AT 50°C
Fig. 5.13 Cured CE and BMI resins hydrolyze (etch)
in strongly alkaline solutions, as indicated by the
onset of weight loss. Ortho-methylated CE resin
and blends with epoxy resin (50/50 blend shown)
increase resistance to alkaline environments gener-
ated in galvanic cells.
5.8 APPLICATIONS
Toughened BMI/carbon fiber composites have
been specified as the principal composite mate-
rial for F-22 fighter primary and secondary
structures (Fig. 5.15).BMI service temperatures
are sufficiently high for cowlings, nacelles and
thrust reversers of jet engines. CE composites
t
Y
TRANSMISSION
Fig. 5.14 Interactions of microwaves with a radome
wall.
were used to construct EFA (Eurofighter) pro-
totypes and are used in construction of the
Dassault Rafale. Both materials are candidates
for HSCT (High speed civil transport) use.
Principal applications for CE composites
(McConnell, 1992) include radomes for mili-
tary aircraft, fighter aircraft retrofitted with
improved tracking systems, skins over phase
array radar, weather tracking aircraft radar
and missile nose cones. CE prepreg reinforced
with high modulus pitch-based carbon fibers
are preferred materials for earth orbit service,

Fig. 5.15 F-22fighter constructed with BMI composites. Photograph courtesy of Lockheed.
114 Speciality matrix resins
demonstrating low outgassing, microcrack
resistance and resistance to lo9rads of ionizing
radiation (Willis, 1991). Applications in space
include communication satellites, solar arrays,
parabolic antennas, optical benches and preci-
sion segmented reflectors.
BMI film adhesives are employed in jet
engine or high speed aircraft sandwich panels
where hot-wet service up to 190°C is required.
CE film and paste adhesives are used together
with syntactic foams in the construction of
radomes. BMI molding compounds reinforced
with up to 65 wt.% of chopped reinforcements
are used to mold ducts, drive sprockets for
heated rolls in copy machines, helicopter gear
boxes and missile strongback mounting sup-
ports.
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