The resin transfer molding (RTM) process offers important advantages for cost-effective composites manufacturing, and consequently has become the subject of intense research and development efforts. Several new matrix resins have been formulated specifically for RTM applications in aircraft and aerospace vehicles. For successful use on aircraft, composite materials must withstand exposure to the fluids in common use. The present study was conducted to obtain comparative screening data on several state-ofthe-art RTM resins after environmental exposures were performed on RTM composite specimens. Four graphite/epoxy composites and one graphite/bismaleimide composite were tested; testing of two additional graphite epoxy composites is in progress. Zero-deg tension tests were conducted on specimens machined from eight-ply (+45-deg, -45-deg) laminates, and interlaminar shear tests were conducted on 32-ply 0-deg laminate specimens. In these tests, the various RTM resins demonstrated widely different strengths, with 3501-6 epoxy being the strongest. As expected, all of the matrix resins suffered severe strength degradation from exposure to methylene chloride (paint stripper). The 3501-6 epoxy composites exhibited about a 30 percent drop in tensile strength in hot, wet tests. The E905-L epoxy exhibited little loss of tensile strength (less than 8 percent) after exposure to water. The CET-2 and 862 epoxies as well as the bismaleimide exhibited reduced strengths at elevated temperature after exposure to oils and fuel. In terms of the percentage strength reductions, all of the RTM matrix resins compared favorably with 3501-6 epoxy

Dow, Marvin B.

Falcone, Anthony

English

NASA Technical Reports Server

N95-29047
THE EFFECTS OF AIRCRAFT FUEL AND FLUIDS ON THE STRENGTH PROPERTIES OF RESIN
TRANSFER MOLDED (RTM) COMPOSITES*
Anthony Falcone
Boeing Defense & Space Group
Seattle, WA
Marvin B. Dow
NASA Langley Research Center
Hampton, VA
/
SUMMARY
The resin transfer molding (RTM) process offers important advantages for cost-effective composites
manufacturing, and consequently has become the subject of intense research and development efforts.
Several new matrix resins have been formulated specifically for RTM applications in aircraft and aerospace
vehicles. For successful use on aircraft, composite materials must withstand exposure to the fluids in
common use. The present study was conducted to obtain comparative screening data on several state-of-
the-art RTM resins after environmental exposures were performed on RTM composite specimens. Four
graphite/epoxy composites and one graphite/bismaleimide composite were tested; testing of two additional
graphite epoxy composites is in progress. Zero-deg tension tests were conducted on specimens machined
from eight-ply (+45-deg, -45-deg) laminates, and interlaminar shear tests were conducted on 32-ply 0-deg
laminate specimens. In these tests, the various RTM resins demonstrated widely different strengths, with
3501-6 epoxy being the strongest. As expected, all of the matrix resins suffered severe strength
degradation from exposure to methylene chloride (paint stripper). The 3501-6 epoxy composites exhibited
about a 30% drop in tensile strength in hot, wet tests. The E905-L epoxy exhibited little loss of tensile
strength (< 8%) after exposure to water. The CET-2 and 862 epoxies as well as the bismaleimide
exhibited reduced strengths at elevated temperature after exposure to oils and fuel. In terms of the
percentage strength reductions, all of the RTM matrix resins compared favorably with 3501-6 epoxy.
INTRODUCTION
The resin transfer molding (RTM) process offers important advantages for cost-effective composites
manufacturing. Consequently, RTM is currently the subject of intense research and development efforts.
One of the main advantages of RTM composite manufacturing is that the resin and reinforcement are not
combined until a part is actually produced, eliminating the need for prior production of prepregged
materials. Other advantages of RTM include the use of a wide variety of textile reinforcments such as
woven, braided, and stitched preforms, and the ability to fabricate complex molded parts.
Several new matrix resins have been formulated specifically for RTM applications in aircraft and
aerospace vehicles. For successful application in aircraft structures, composite materials must withstand
exposure to fluids in use during operation and maintenance. Extensive studies have been conducted in the
past with actual in-service exposure of graphite and boron/epoxy test coupons on operating aircraft (refs.
1, 2, and 3). The present study was conducted to obtain comparative screening data on several state-of-
the-art RTM composites after environmental exposure.
*Work performed on Contract NAS 1-18954 by Boeing Defense & Space Group.
PRECEDING PPI_E ,k!-L_;,!i'_._,:C,';_ ?ILi_,_ED
399
https://ntrs.nasa.gov/search.jsp?R=19950022626 2020-06-16T07:46:19+00:00Z
Fluidsin theoperatingenvironmentcanaffectboththematrixresinandthefiber-matrixinterface,
therebyreducingcompositeproperties.Thefiber-matrixinterfacein RTM compositesis formedduring
infiltrationof resininto thepreformandsubsequentresincure,andrequiresthoroughwettingof thefibers
bytheresin. Of interestwasthedeterminationof whateffectfluidswouldhavenotonly on theresin
matrix,butalsoon theresin-fiberinterfacein RTM composites,whichcouldbedifferentfromthe
interfacein compositestructuresproducedfrom prepreg.
Compositeteststhatwouldgivematrix-dominatedfailureswereselected.Zero-degtensiontestswere
conductedonspecimensmachinedfrom eight-ply(+45-deg,-45-deg)laminates,andinterlaminarshear
testswereconductedon32-ply0-deglaminatespecimens.Tensilestrengthandmodulusweremeasured;
however,otherpropertiescouldhavebeenselected,suchastensileyieldstrength.Thereis nogeneral
agreementonwhichpoint shouldbeselectedon thestress-straincurvefor propertycomparisonandfor
relationto compositeperformancein service.
Thepanelpreformswereproducedfrom AS4uniweavecarbonfiber fabric. Fourepoxy,composites
andonebismaleimidecompositeweretested;two additionalgraphiteepoxycompositesarem test.
EXPERIMENTAL
Zero-degtensiontestswereconductedon (+45-deg,-45-deg)laminatesperASTMD3518andD3039.
Inteflaminarshortbeamsheartestsof 0-deglaminateswereconductedperASTM D2344.Thetensiletest
specimens(Figure1)weremachinedfrom 8-ply laminateswith anominalthicknessof 1.14mm(0.045
in); theinterlaminarsheartestspecimens(Figure2) weremachinedfrom 32-ply0-deglaminateswith a
nominalthicknessof 4.57mm (0.180in). Tensiletestcouponswerefabricatedby bondingtaperedE-
glass/epoxytabs(1.52mm (0.060in) thick) to rectangularblankswithepoxyadhesive,andthencutting
specimensfrom thesebondedblanks.
ThelaminateswerelayedupandresintransfermoldedbytheDouglasAircraftCompanyfrom
uniweaveHerculesAS4carbonfiber fabric. Fiveresinswereevaluated(TableI), andpanelsfrom two
additionalresinsarebeingresintransfermoldedat Boeingfor testing(TableI). Laminateswere
ultrasonicallyscannedto locateporosityor otherdefects.Some(+45-deg,-45-deg)laminatesproduced
with E905-Lepoxyhadporosityin limited areas,possiblydueto thelocationof injectionandventing
ports,and,wherepossible,specimenswerecutoutsideof theseporousareas.Fiberandvoidvolume
fractionsweredeterminedfor selectedpanels(TableII).
Thetensileandintedaminarsheartestspecimenswereexposedto sevenfluids (TableliT). Somefluid
exposures were conducted at an elevated temperature of 71°C (160°F), and tests were run at both ambient
temperature and 82°C (180°F). The specimens exposed to JP-4 jet fuel were exposed at ambient
temperature only, since special equipment and additional safety procedures would not be required. The
specimens were exposed for 14 days (336 hours) to the fluids. The fluid exposures were accomplished by
putting the specimens in cans filled with the fluid so that the specimens were fully immersed and, for
elevated temperature exposures, the loosely capped cans were placed in an air-circulating oven at 71°C
(160°F). Control specimens (unexposed) were placed in the same oven for 14 days.
The 14-day exposure period is somewhat arbitrary and was selected based on the time required for thin
graphite/epoxy laminates to reach moisture saturation at 71°C (160°17). In the Boeing specification for
secondary graphite epoxy structure, BMS 8-212 (ref. 4), a 14-day exposure period to moisture is used,
while in the Boeing specification for toughened graphite/epoxy (ref. 5), a 6-day fluid exposure period is
used. The exposure period is selected to produce a desired amount of fluid absorption in the composite
test specimens. These time periods are not related to the lifetime exposures to which composite airplane
400
structures are subjected. The testing performed in this effort was intended to provide a relative indication
of composite performance.
The ends of some of the specimens were wrapped with aluminum foil and aluminum foil tape to reduce
solvent absorption by the tabs and tab adhesive; only the specimen gauge area was exposed to the solvent.
The short-beam shear specimens were held within small folded wire screen sections to keep specimens
from the same material grouped together.
Weight gain was measured to determine the percent of fluid absorbed by some of the short beam shear
specimens (Table IV). The percent of weight gain was usually small, except for water at 71 °C (160°F) and
methylene chloride. Additional weight gain measurements will be obtained to confh-rn this data.
Five specimens were mechanically tested for each material, fluid, and condition. Both shear strength
and shear modulus were measured for the tensile specimens. The modulus was measured for only two of
the five specimens in each group. A biaxial extensometer (Figure 3) was used to measure displacement in
both the axial and transverse directions to determine the shear modulus. All tensile specimens were tested
to failure, which usually took 30 to 40 minutes per specimen due to the high elongation of the specimens.
A crosshead speed of 1.27 mm (0.05 in.) per minute was used. One of the test machines is shown in
Figure 4, and the environmental chamber used to heat the specimens is shown in Figure 5.
RESULTS AND DISCUSSION
The mechanical test results for all groups of specimens are summarized in bar charts for the tensile test
specimens (Figures 6 through 10) and for the interlaminar shear specimens (Figures 11 through 15). In
general, test results indicated that all of the composites retained adequate strength after exposure to JP-4 jet
fuel, commercial hydraulic fluid, turbine oil, methyl ethyl ketone, deicing fluid, and water. Methylene
chloride exposure usually caused significant deterioration of mechanical properties.
Tensile coupons immersed in methylene chloride usually retained only 50% to 60% of the room-
temperature control specimens' shear strength with the exception of AS4/3501-6 epoxy, which retained
80% of its strength. Decreases in interlaminar shear strength similar to tensile strength degradation did not
occur for all composites tested, however. Since methylene chloride is readily absorbed by polymeric
materials, it should not be used around composite aircraft structures.
Other than methylene chloride, water at 82°C (180°F) caused the next largest drop in properties,
usually a 10% to 25% decrease in shear strength. The AS4/CET-2 epoxy, however, showed no drop in
shear strength under this hot/wet exposure, and the AS4/3501-6 showed its greatest drop (24%) in shear
strength. Interlaminar shear strength typically showed a 10% reduction at 82°C (180°F) after 14 days
exposure in 71°C (160°F) water.
The AS4/CET-2 material exhibited a 16% drop in shear strength after exposure to hydraulic fluid and
testing at 82°C (180°F). A similar decline was not observed in the interlaminar shear strength, however.
It could not be determined why the AS4/5292 bismaleimide control specimens had a low room
temperature shear strength. The ambient interlaminar shear strength did not show a similar trend.
Exposure to JP4 jet fuel also caused an appreciable (19%) decrease in shear strength of AS4/5292.
JP4 jet fuel did not cause significant property deterioration in the RTM composites under these
exposure conditions, however, more significant deterioration can occur with longer exposures (ref. 6).
Work at Boeing on military airplane programs has indicated that the water that collects in fuel systems is
more detrimental to composite properties than the fuel itself.
401
CONCLUSIONS
In these tests, the various RTM resins demonstrated widely different strengths, with 3501-6 epoxy
being the strongest. As expected, all of the matrix resins suffered severe strength degradation from
exposure to methylene chloride (paint stripper). The 3501-6 epoxy composites exhibited about a 30%
drop in tensile strength in hot, wet tests. The E905-L epoxy exhibited little loss of tensile strength (< 8%)
after exposure to water. The CET-2 and 862 epoxies as well as the bismaleimide exhibited reduced
strengths at elevated temperature after exposure to oils and fuel.
In terms of the percentage of strength reductions, all of the RTM matrix resins compared favorably
with 3501-6 epoxy. By inference, an adequate fiber-matrix interface is apparently forming in these RTM
composites, indicating that the fibers are sufficiently wet-out with resin in the RTM process.
ACKNOWLEDGEMENTS
This work was performed under contract from the NASA Langley Research Center (Contract NAS 1-
18954) and their support is gratefully acknowledged. Resin transfer molded laminates were supplied by
the Douglas Aircraft Company; Mr. Raymond Palmer of Douglas Aircraft and Mr. William Avery of the
Boeing Defense & Space Group provided recommendations on fluid exposure testing. Boeing
technicians, Mr. Oscar Davis and Mr. Allen Kelly, conducted the mechanical tests. Ms. Erica Smith, a
summer intern at Boeing, measured most of the specimens and performed the initial mechanical property
calculations.
REFERENCES
.
2,
*
.
.
.
Dexter, H. B.: Long-Term Environmental Effects and Flight Service Evaluation, Engineered
Materials Handbook, vol. 1, Composites. ASM International, 1987.
Dexter, H. B. : Long-Term Environmental Effects and Flight Service Evaluation of Composite
Materials, NASA TM-89067, National Aeronautics and Space Administration, Jan. 1987.
Tanimoto, E. Y.: Effects of Long-Term Exposure to Fuels and Fluids on Behavior of Advanced
Composite Materials, NASA CR-165763, National Aeronautics and Space Administration, Aug.
1981.
Boeing Material Specification 8-212: Epoxy Preimpregnated Graphite Tapes and Woven Fabrics -
350°F (177°C) Cure, The Boeing Company, Revised Nov. 1987.
Boeing Material Specification 8-276: Advanced Composites - 350°F (177°C) Cure Toughened-Epoxy
Preimpregnated Carbon Fiber Tapes and Fabrics, The Boeing Company, Revised Nov. 1991.
Curliss, D. B., Carlin, D. M., and Arnett, M. S.: The Effect of Jet Fuel Absorption on Advanced
Aerospace Thermoset and Thermoplastic Composites. SAMPE, v. 35, 1990.
402
Table I. RTM Matrix Resins Under Investigation
Carbon fiber fabric used with all resins: 3K AS4 uniweave fabric at 145 g/m 2.
Testing has been completed on:
Manufacturer
Dow Chemical Company
Shell Chemical Company
Hercules
BP Chemicals
Ciba Geigy Corp.
Testing is in progress on:
Matrix resin
Tactix* CET-2 Epoxy
Epon** DPL 862 Epoxy/Curing Agent W
3501-6 Epoxy
E905-L Epoxy
Matrimid*** 5292 Bismaleimide
Identification
code
D
S
H
B
C
Manufacturer Matrix resin Identification
code
Dow Chemical Company
Shell Chemical Company
Tactix* CET-3 Epoxy
RSL 1895 Epoxy/Curing Agent W
T
R
*Trademark of the Dow Chemical Company
**Trademark of the Shell Chemical Company
***Trademark of Ciba Geigy Corp.
Table II. Selected RTM Laminate Physical Properties*
Laminate
0-deg, 32 plies, AS4/E905-L epoxy
0-deg, 32 plies, AS4/5292 bismaleirnide
0-deg, 32 plies, AS4/CET-2 epoxy
+45-deg, 8 plies, AS4/E905-L epoxy
+45-deg, 8 plies, AS4/CET-2 epoxy
Density
(_/cm3)
1.59
1.58
1.77
1.49
1.75
Fiber vol.
fraction (%)
61
57
55
52
46
Void
content (%)
<1
<1
<1
3
1
*Calculations based on an AS4 carbon fiber density of 1.80 g/cm 3 and resin densities of 1.24 g/cm3 for
E905-L epoxy, 1.23 g/cm 3 for 5292 bismaleimide, and 1.75 g/cm3 for CET-2 epoxy.
403
Table III. RTM Laminate Exposure Fluids and Temperatures
Code Number
1
2
3
4
5
6
7
8
9
10
11
12
13
Fluid
JP-4 jet fuel
Chevron HyJet IVA Hydraulic Fluid
MIL-L-7808 Turbine Oil
Methyl ethyl ketone
Methylene chloride
Deicing fluid
Water
Control (no fluid exposure)
JP-4 jet fuel
Chevron HyJet IVA Hydraulic Fluid
MIL-L-7808 Turbine Oil
Water
Control (no fluid exposure)
Exposure temp.
Ambient
71°C (160°F)
7 I°C (160°F)
Ambient
Ambient
Ambient
71°C (160°F)
71°C (160°F)
Ambient
71°C (160°F)
71oc (160°F)
71°C (160°F)
71°C (160°F)
Test temp.
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
Ambient
82°C (180°F)
82°C (180°F)
82°C (180°F)
82°C (180°F)
82°C (180°1:9
Table IV. Percent Weight Gain of 32-Ply Unidirectional Laminate Coupons
Exposure fluid and temperature (table III)
Laminate 1 2 3 4 5 6 7 8 9 10 11 12 13
AS4/5292 0.06 0 0 0 0.08 0.08 1.15 N/A 0.05 0 0 1.11 N/A
AS4/CET-2 0 1.76 0.02 1.42 ** 0.06 0.16 N/A 0.03 1.67 0.05 0.12 N/A
AS4/3501-6 0.07 ** ** 0 ** 0.07 ** N/A 0.06 0 0.05 ** N/A
AS4/862/W 0.04 0.06 0 ** 4.42 0.18 ** N/A 0.12 0.07 0.01 ** N/A
*Values for the AS4/E905-L epoxy laminates were high (6% to 8%) and were probably in error.
**Not measured.
404
Figure 1.
O_deg_ 45.deg
2.54 cm(1.0 in)
E_
_o
t
6-deg
1.14mm I/
(0.045 in)
A _+45-deg tensile test specimen with bonded tabs, after ASTM D3518 and D3039.
Ir
l O-deg _ o.
6.4mm ---_ _I--I -"_(0.25 in)
32 plies
4.6 mm
nominal
(0.18 in)
Figure 2. A 0-deg interlaminar shear test specimen, after ASTM D2344.
405
BLACK P_-IOTOGRAPF',
Figure 3. Biaxial extensometer on a tensile test specimen.
Figure 4. Mechanical test machine.
406
f,_l. _ ,, _ r :/_ • s -+ -_BLA.,r, ":d,_:.: ,...I , _.:,,. _,_:',:.i;APH
i
Figure 5. Mechanical test machine with environmental chamber.
Figure 6.
r1.8o18.oo _ _ ,-.Q _ ,.o _ _ 1.6o
16.oo _ _ _ _ T
i _ Z t.O r-- _ --.4-1.4014.00
"_ _ _ 4-1.20
- 10.00 1.00 co-
. _ _, |_TO°O.
t ! '=,_ o o ; |° | 0.404.00 d2.00 I_'T °20
I i 1 ', Im_'_t o oo
,_ ,-, ,-, a o o o o o S S E_ A
_. ._ ,,._
Average shear strength and shear modulus from _+45-deg tensile coupons of AS4/Dow Tactix
CET-2 epoxy after fluid exposures.
407
|
.=-
e-
¢..
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
14.00
12.00
10.00
8.00
6,00
4.00
2.00
0.00
--I
-I
_D
3
0
¢-.
c"
3
r.n.
Figure 7. Average shear strength and shear modulus from +45-deg tensile coupons of AS4/SheU Epon
DPL 862/W epoxy after fluid exposures.
Note: Tensile modulus, not shear modulus (G12), was measured.
408
2O.OO 20.00
-i '11-
r- _ __ r- "_ _ I
I °. _. _ i_ _ _o _ _o o i
18.00 -l-r" ,Jr" r,,: lm o r,,: r_ _ _ _ "-1- 18.00
16.00 o '_ 16.00
.- 12.00 12.00
10.00 10.00
8.00 8.00 i6.00 o _ _ _ _ _o _ _ 6.00
4.00 4.00
2.00 2.00
0.00 0.00
-7 = -,- -,- -,- --,- -,- -,- = -7 -7 -7 -7
- • " ,._ #-* cj ..o oO oO oO oO
"'_, b' '_ _ ","
Figure 8. Average shear strength and shear modulus from +45-deg tensile coupons of AS4/Hercules
3501-6 epoxy after fluid exposures.
Note: Tensile modulus, not shear modulus (G12), was measured.
409
Figure 9. Average shear strength and shear modulus from +_45-deg tensile coupons of AS4/BP
Chemicals E905-L epoxy after fluid exposures.
Figure 10. Average shear strength and shear modulus from +45-deg tensile coupons of AS4/Ciba Geigy
Matrimid 5292 bismaleimide after fluid exposures.
410
Figure 11
dO O_
9.00
8oo _ _. _
i
6.00 '_"
s00 1
4,oo
_o 3.00
g 2.00
1.oo
0.0o ', ', ', ' ' ' f ', ' ' '
• _ _ _ ,_
.--oo
Average interlaminar shear strength of AS4/Dow Tactix CET-2 epoxy after fluid exposures.
12.00
Figure 12.
10.00
2_
_, 8.00
c
(1)
6.00
#
to
E
4.00
.El
O
f-
2.00
0.00
cJ'l
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I
I
0
u3
l 1
I I
co if)
0
(%1
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u5
I I I I I I i _ I
I I I I I I I I
Average interlaminar shear strength of AS4/Shell Epon DPL 862/W epoxy after fluid
exposures.
411
16.00
14.0O
.E 12.00
lo.00
&00
E
6.00
O
'-" 4.00
Go
2.00
09 tO
-g tO _ _ ,_ "¢• _ cq _,
cO
tO
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o =
_D
,5
I I I I I I
l i
tO
c5
co
m
c_
I I I i
0,00 i i I i oO O_ i C i _ J c'J J 09
._- . '< ,< .< ,<
".
Figure 13. Average interlaminar shear strength of AS4/Hercules 3501-6 epoxy after fluid exposures.
14.00
12.00
10.00
.="
8.00
-g &oo
4.oo
g,,
2.00
0,00
_i _ _ e4 eJ e.i
o _
_6 _6
I I I I I I I I I I
rn rn n_ rn rn rn mn tn _n tn
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I
I
I
o_ co
,.'_ .b_ -# _ .o ,_ ,-,£, ,,.q, _
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Figure 14. Average interlaminar shear strength of AS4/BP Chemicals E905-L epoxy after fluid
exposures.
412
.B
o')
,,e"
a=-
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c
r-
E
t_
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O9
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Figure 15. Average interlaminar shear strength of AS4/Ciba Geigy Matrimid 5292 bismaleimide after
fluid exposures.
413



The effects of aircraft fuel and fluids on the strength properties of Resin Transfer Molded (RTM) composites

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