Professional Documents
Culture Documents
STP768 Eb.1415051 1 PDF
STP768 Eb.1415051 1 PDF
STP768 Eb.1415051 1 PDF
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
COMPOSITES FOR
EXTREME ENVIRONMENTS
A symposium
sponsored by ASTM
Committee D-30 on
High Modulus Fibers and
Their Composites
Bal Harbour, Fla., 11 Nov. 1980
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Copyright ® by AMERICAN SOCIETY FOR TESTING AND MATERIALS 1982
Library of Congress Catalog Card Number: 81-69769
NOTE
The Society is not responsible, as a body,
for the statements and opinions
advanced in this publication
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Foreword
The symposium on Composites for Extreme Environments was held on 11
Nov. 1980 in Bal Harbour, Fla. ASTM Committee D-30 on High Modulus
Fibers and Their Composites sponsored this symposium. N. R. Adsit of
General Dynamics/Convair Division served as symposium chairman and
edited this publication.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Related
ASTM Publications
Joining of Composite Materials, STP 749 (1981), 04-749000-33
Methods and Models for Predicting Fatigue Crack Growth Under Random
Loading, STP 748 (1981), 04-748000-30
Test Methods and Design Allowables for Fibrous Composites, STP 734
(1981), 04-734000-33
Fractography and Materials Science, STP 733 (1981), 04-733000-30
Fatigue of Fibrous Composite Materials, STP 723 (1981),
04-723000-33
Nondestructive Evaluation and Flaw Criticality for Composite Materials,
STP 696 (1979), 04-696000-33
Composite Materials: Testing and Design (Fifth Conference), STP 674
(1979), 04-674000-33
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
A Note of Appreciation
to Reviewers
This publication is made possible by the authors and, also, the unheralded
efforts of the reviewers. This body of technical experts whose dedication,
sacrifice of time and effort, and collective wisdom in reviewing the papers
must be acknowledged. The quality level of ASTM publications is a direct
function of their respected opinions. On behalf of ASTM we acknowledge
with appreciation their contribution.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Editorial Staff
Jane B. Wheeler, Managing Editor
Helen M. Hoersch, Senior Associate Editor
Helen P. Mahy, Senior Assistant Editor
Allan S. Kleinberg, Assistant Editor
Virginia M. Barishek, Assistant Editor
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Contents
Introduction
MOISTURE ENVIRONMENTS
SUMMARY
Summary 175
Index 177
Copyright by
Downloaded/printed by
(PDVSA
STP768-EB/Apr. 1982
Introduction
N. R. Adsit
General Dynamics/Convair Division, San
Diego, Calif. 92138; symposium chairman
and editor.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
T. T. Serafini^ andM. P. Hanson^
' Head, Polymer Matrix Composites and materials engineer, respectively. National Aeronau-
tics and Space Administration, Lewis Research Center, Cleveland, Ohio 44135.
^Serafini, T. T., Delvigs, P., and Lightsey, G. R., "Thermally Stable Polyimides from Solu-
tions of Monomeric Reactants," Journal of Applied Polymer Science, Vol. 16, No. 905, 1972.
Experimental Procedure
Materials
Style 182 fabric woven from Union Carbide T300 graphite fibers and Her-
cules HTS-2 graphite fiber tows were used as reinforcing materials. The T300
fibers consisted of 3000 filaments in a one-ply construction and were sized
with an epoxy compatible sizing. The HTS-2 fibers consisted of 12 000 fila-
ments per tow.
The polyimide resin used in this investigation was the high-temperature
polyimide designated as PMR-15. The monomers used to formulate PMR-15
are shown in Fig. 1. The monomethyl ester of 5-norbornene-2,3-dicarboxylic
acid (NE) and 4,4'-methylenedianiline (MDA) were obtained from commer-
cial sources. The dimethyl ester of 3,3', 4,4'-benzophenonetetracarboxylic
acid (BTDE) was prepared as a 50 weight percent solution by refluxing a
suspension of the corresponding dianhydride in anhydrous methanol for ap-
proximately 2.75 h. The monomer stoichiometry for the PMR-15 solution
'Davis, J. G., Jr.. "High Temperature Resin Matrix Composites for Aerospace Structures."
Selected NASA Research in Composite Materials and Structures. NASA CP 2142. National
Aeronautics and Space Administration. 1980. pp. 143-182.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS
(• -OH
0 <) O
" o "
DIMETHYL ESTER OF 3,3'.4.4'- BTDE
MiO-C Y C-OMc BENZOPHENONETETRACARBOXYLIC ACID
0 O
HO-C C-OII
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
8 COMPOSITES FOR EXTREME ENVIRONMENTS
nates. All plies for the fabric laminates were stacked with their warp yarns in
the 0-deg direction.
Composite Testing
Flexural tests conformed essentially to the ASTM Tests for Flexural Prop-
erties of Plastics and Electrical Insulating Materials [D 790-71 (1978)]. Tests
were made on a 3-point loading fixture with a variable span. Tests were per-
formed using a span-to-thickness ratio of approximately 32. The rate of cen-
ter loading for flexural testing was 0.127 cm/min. Interlaminar shear
strength tests were conducted in accordance with the ASTM Test for Appar-
ent Interlaminar Shear Strength of Parallel Fiber Composites by Short Beam
Method (D 2344-76) using a constant span-to-thickness ratio of 4. For the
elevated temperature tests, the load was applied to the specimens after the
chamber had equilibrated at the test temperature for 10 min. A limited
number of temperature spike tests were performed on moisture-saturated
specimens. For these tests, the load was applied to the specimen immediately
after the specimen was installed in the preheated test fixture.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS 9
O T300 FABRIC
O HTS-2 FIBER
bers were taken from Delvigs, Alston, and Vannucci/ The superior thermo-
oxidative stability of the HTS-2 fibers is clearly evident. After 800 h of expo-
sure in air at 316°C, the weight loss of the HTS-2 fibers was only 4.2 percent,
compared to the 50 percent weight loss exhibited by the T300 fibers after
500 h in air at 316°C. The comparatively poor elevated temperature thermo-
oxidative stability of T300 fibers very likely would be manifested in inferior
composite performance at temperatures approaching 316°C.
The weight loss behavior of T300 graphite fabric/PMR-15 composites as a
function of exposure time is shown in Fig. 3 for composites exposed in air at
260, 288, and 316°C. In contrast to the behavior of the bare unprotected
T300 fibers, which exhibited a weight loss of 50 percent after 500 h of expo-
sure at 316°C, the weight loss of theT300/PMR-15 composites was only 4.8
percent after 500 h at 316°C. The significant increase in the rate of composite
weight loss after about 400 h at 316°C is clearly evident. Similar weight loss
behavior has not been reported previously for graphite fiber reinforced
PMR-15 composites exposed at 316°C. The significantly increased weight
loss rate found in this study for the T300/PMR-15 composites is undoubt-
edly due to the limited thermo-oxidative stability of the T300 fibers at 316°C.
As expected, the T300/PMR-15 composites exhibited improved oxidative
stability at 260 and 288°C. After 1000 h at 288°C and 500 h at 260°C, the com-
posite weight losses were only 4.2 and 0.8 percent, respectively. The results of
these composite weight loss studies indicate that the useful life of
T300/PMR-15 composites at 316°C is likely less than 400 h and is at least
1000 h at 260 and 288°C.
Figure 4 shows the flexural and interlaminar shear properties retention
characteristics of O.I4-cm-thick laminates and the flexural properties reten-
tion characteristics of 0.28-cm-thick laminates. Specimens of both thick-
nesses were exposed at 316°C for various time intervals, and then tested at
"Delvigs. P., Alston, W. B., and Vannucci. R. D., "Effects of Graphite Fiber Stability on the
Properties of PMR Polyimide Composites." NASA TM 79062 and AVRADCOM TR 78-62,
National Aeronautics and Space Administration, May 1979.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
10 C O M P O S I T E S FOR EXTREME E N V I R O N M E N T S
EXPOSURE
TEMPERATURES,
°C
316
260
1000
288°C. It can be seen that during exposure at 316°C, the 288°C flexural
strengths and moduli of both laminate thicknesses decreased rapidly, whereas
the interlaminar shear strength of the 0.14-cm-thick laminate decreased
more gradually. After 620 h of exposure at 316°C, the flexural strength and
modulus retention values for the 0.14-cm-thick laminates were 33 and 40
percent, respectively, compared to a retention value of 78 percent for inter-
laminar shear strength. In view of the limited oxidative stability of the T300
fibers and T300/PMR-15 composites at 316°C, the rapid degradation of
flexural properties was expected. However, it was difficult to account for the
large difference between the retention values for the flexural and interlam-
inar shear properties only on the basis of surface degradation. To ascertain if
the difference might have resulted from structural features that were present
in the as-fabricated composites or were introduced during elevated tempera-
ture exposure, cross-sections of as-fabricated and exposed specimens were
examined metallographically.
Figure 5 shows representative photomicrographs of specimens from 0.14-
cm-thick T300 graphite fabric/PMR-15 as-fabricated laminates and from
laminates that had been exposed at 316°C. Figure 5a shows that the as-fabri-
cated laminates were defect free. In Fig. 5/», it can be seen that a few through-
the-surface-ply cracks had developed after 120 h of exposure. Figure 5c
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS 11
O FLEXURAL STRENGTH
• FLEXURAL MODULUS
A INTERLAMINATE SHEAR
SOLID LINE - 0.14 cm THICK
DASHED LINE-0.28 cm THICK
120^
S 6 0 -
FIG. 4—Property retention ofTSOO graphite fabric/ PMR-15 composites exposed at 316''C and
tested at 288°C.
shows that after 624 h of exposure, the cracks were more numerous. As is
known, specimens subjected to flexural testing fail at one of the surfaces by
either a tensile or compressive failure mode, whereas shear specimens fail at
the neutral plane of the specimen. Hence, it appears that surface cracking as
well as surface degradation (weight loss) are responsible for the large differ-
ence between flexural and shear properties. More importantly, it appears
that the overall degradation which occurs at 316°C limits the useful lifetime
of T300/PMR-15 composites at 316°C to about 100 h.
Figure 6 shows the flexural and shear properties retention characteristics
for 0.14-cm-thick laminates that were exposed and tested at 288°C. As ex-
pected, the composites exhibited improved properties retention characteris-
tics after exposure at 288°C than after exposure at 316°C. For example, the
flexural and interlaminar shear strength retention values were 75 and 96 per-
cent, respectively, after 500 h at 288°C, compared to retention values of 46
and 88 percent for the same properties after 500 h at 316°C. Figure 7 shows
photomicrographs of laminate cross-sections after exposure at 288°C for 500
and 1000 h. It can be seen in Fig. 7a that only a limited number of through-
the-surface cracks had developed after 500 h of exposure at 288°C. Figure 7b
shows that the surface cracking had become extensive after 1000 h exposure.
Based on the results of the 288°C exposure studies, it may be concluded that
the useful lifetime of T300/PMR-15 composites at 288°C is limited to about
500 h.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
12 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS 13
O FLEXURAL STRENGTH
• FLEXURAL MODULUS
A INTERWMINAR SHEAR
0.14 cm THICK
1000
FIG. 6—Property reterttion ofT300 graphite fabric/PMR-15 composites exposed at 288°C and
tested at 288°C.
Hydrothermal Characteristics
As is known, the absorption of moisture by polymer matrix composites
adversely affects the strength and elastic properties of the composites at ele-
vated temperatures. It has been shown that the reduction in elevated temper-
ature properties is caused by the plasticizing effect of moisture on the matrix
reducing its glass transition temperature, or Tg.' In this study, unidirectional
graphite fiber (HTS-2) and graphite fabric (T300) reinforced PMR-15 com-
posites were exposed to moisture until saturation had been achieved. To as-
sess the effect of moisture on laminate properties, the flexural strengths, mod-
uli, and interlaminar shear strengths of the saturated materials were
determined at various.temperatures.
'Browning, C. E,, "The Mechanics of Elevated Temperature Property Losses in High Per-
formance Structural Epoxy Resin Matrix Materials After Exposure to High Humidity Envi-
ronments," AFML TR-76-153, Air Force Materials Laboratory, March 1977.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
14 COMPOSITES FOR EXTREME ENVIRONMENTS
•<«^- -i-«-'r
^^^^mS'XM^
(a) 500 hr AT 2 K ° C.
-^•-v»?""7T«l
^tlt- f"??
'••*i^>5»^AiSi^
(b) 1000 hr AT 2 8 ^ C.
FIG. 1—Typical photomicrographs ofTiOO graphite fabric/PMR-15 composites after various
thermal-oxidative exposures {X50).
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS 15
O FLEXURAL STRENGTH
• FLEXURAL MODULUS
A INTERLAMINAR SHEAR
0.14 cm THICK
1201—
1000
FIG. 8—Properly retention ofTSOO graphite fabric/PMR-15 composites exposed at 260° C and
tested at 288°C.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
16 COMPOSITES FOR EXTREME ENVIRONMENTS
(a)5(»hrAT26rf'C.
'MSmt^i
,^«^^^^^#f^
(btlOOOhr AT26CPC.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS 17
WET
BASELINE
TAIlfD SYMBOLS
TEMP SPIKE
180)(lfl.-
160
120
o.
22x10^
<l
- 0- TT-^
a
3Q:-
50 150 250
TEMPERATURE. "C
PMR-15 composites from 336°C in the dry state to perhaps 236°C.' Thus,
the much greater reduction in flexural properties of temperature-spiked spec-
imens, especially at the higher test temperatures (for example, reductions of
49 and 25 percent, respectively, for flexural strength and modulus at 316°C,
compared to reductions of 12 and 6 percent for the same properties at 204°C)
indicate that in the temperature-spike tests, the specimens were tested above
or near the Tg of wet HTS-2/PMR-15 composites. In contrast to the behav-
ior found for flexural properties, no discernible differences were observed
between the interlaminar shear strengths of temperature spiked specimens
and temperature equilibrated specimens. A possible explanation for the con-
trasting behavior is as follows.
It is well known that the exposure of a laminate plate to moisture estab-
lishes a moisture gradient through the laminate thickness. Also, as was dis-
cussed in the Fiber and Composite Thermo-Oxidative Stability section of
this paper, shear failure of an interlaminar shear specimen occurs at the neu-
tral, or midplane of the specimen. It is possible that the moisture concentra-
' Serafini, T. T. and Delvigs, P. in Proceedings of the 1978 International Conference on Compos-
ite Materials, B. Noton, Ed., American Institute of Mining, Metallurgical, and Petroleum Engi-
neers, New York, 1978, pp. 1320-1329.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
18 COMPOSITES FOR EXTREME ENVIRONMENTS
O WET
BASELINE
a TAItfO SYMBOLS
TEMP SPIKE
120x10-
80
ccz 40
J \ \ I
12xlC^
— O-
^11 1 ^_
50 150 250
TEMPERATURE, °C
tion at the neutral plane was not altered by subjecting the specimen to either
the 10 min equilibration period or to the temperature spike; hence, wet spec-
imens tested in either manner failed at the same load. It also should be re-
called that failure of a flexural specimen occurs at one of its surfaces. Appar-
ently, during temperature-spike testing of flexural specimens, the moisture
concentration of the surface plies remained at a higher level than the mois-
ture concentrations of the surface plies of specimens which had been equili-
brated for 10 min at elevated temperature. The higher moisture concentra-
tion in the surface plies of temperature-spiked specimens would have caused
them to undergo compressive failures at lower loads than was observed for
specimens which had been equilibrated at the elevated temperatures prior to
loading.
Figure 11 compares the properties of wet 0.14-cm-thick T300 fabric rein-
forced PMR-15 laminates with baseline properties as a function of test
temperature. Because the trends observed for this composite system are sim-
ilar to those observed for wet HTS-2/PMR-I5 laminates tested at elevated
temperatures, the points discussed for wet HTS-2/PMR-15 are also perti-
nent to T300/PMR-15; accordingly, they will not be repeated.
In summary, the results of this study on the effects of hydrothermal expo-
sure on the properties of graphite fiber reinforced PMR-15 composites indi-
cate that absorbed moisture causes a reduction of Tg, which is reflected in
lower properties at elevated temperatures. It must be noted, however, that
the absorption of moisture is reversible.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SERAFINI AND HANSON ON ENVIRONMENTAL EFFECTS 19
Conclusions
Based on the results obtained in this investigation, the following conclu-
sions can be drawn.
1. The useful lifetimes of T300 graphite fabric reinforced PMR-15 compos-
ites exposed in air at 316 and 288°C are approximately 100 and 500 h, respec-
tively. The useful lifetime in air at 260°C is at least 1000 h.
2. Absorbed moisture reduces the elevated temperature properties of
graphite fiber reinforced PMR-15 composites.
3. Temperature-spike testing of moisture saturated composites provides a
more realistic assessment of the effect of absorbed moisture on the elevated
temperature properties of composites.
4. The absorption of moisture by graphite fiber reinforced PMR-15 com-
posites is reversible.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
L. McKague^
REFERENCE: McKague, L., "V378A Polyimide Resin—A New Composite Matrix for
the 1980's," Composites for Extreme Environments, ASTM STP 768, N. R. Adsit, Ed.,
American Society for Testing and Materials, 1982, pp. 20-32.
20
Screening Program
For screening evaluations, eight graphite composite prepreg materials
were obtained from four companies. The following materials were obtained:
F-178, a bis-maleimide; CPI-2272, a bis-maleimide; X5231, a modified bis-
^Hinrichs, R. and Thuen, J., Society of Aerospace Material and Process Engineers Journal.
Vol. 15, No. 6, Nov./Dec. 1979, pp. 12-21.
'Browning, C. E., Husman, G. E., and Whitney, J. M. in Composite Materials: Testing and
Design (Fourth Conference), ASTMSTP 617, American Society for Testing and Materials, 1977,
pp. 2-20.
^McKague, E. L., Reynolds, J. D., and Halkias, J. E., Journal of Applied Polymer Science,
Vol. 22, 1978, pp. 1643-1654.
'Street, S. W., The 1980's—Payoff Decade for Advanced Materials, Vol. 25, Society for the
Advancement of Material and Processes Engineering, 1980, pp. 366-375.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
22 COMPOSITES FOR EXTREME ENVIRONMENTS
ENVIRONMENTAL EFFECTS
• Thtrmal Aginfl
• ThtrmalSptkas
• Glut Trantttion
FLEX a SMEAR
POSTCURE CYCLE
145 TENSION
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
McKAGUE ON NEW COMPOSITE MATRIX 23
OAPPLV VACUUM
OAPPLY.6MPaAN0
VENT VACUUM
HEATfNG RATE • 3>C/MII)
HOURS HOURS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
24 COMPOSITES FOR EXTREME ENVIRONMENTS
Processibility
Self-adhesion tack
Cure with present equipment (maximum 190°C, 0.7 MPa)
Seven days out-life at 27''C
Unrestrained postcure (maximum 343°C, 6 h) resulting in crack-free (0/±45/0), laminates
General Properties
Room-temperature mechanical propertiesrties like epoxy
lative humidity (RH
177°C service capability after 75% relative (RH)
Specific Target Criteria
Environmental
Thermal aging; no cracks formed in (0/±45/0), laminates after 25 h at 171°C plus 264 h at
135°C
Thermal spikes: maximum weight gain of 0.15% when exposed intermittently to 75% RH and
177°C spikes
Glass transition temperature (Tg):
minimum dry = 288''C
minimum wet (75% RH) = 177°C
Flexure and shear
Dry 0° flexure
minimum RT flex strength = 1724 MPa
minimum strength retention at 177°C = 80% of 24°C value
minimum RT modulus = 127 GPa
Short beam shear
minimum dry at 24°C = 90 MPa
minimum dry at 177''C = 69 MPa
±45 tension
Minimum initial wet (75% RH) modulus at 177°C = 10.3 GPa
Minimum wet (75% RH) ultimate stress at 177''C = 73 MPa
Minimum wet (75% RH) ultimate strain at 177°C = 2.3%
Critical strain energy release rate (G,c): minimum value of 87 5 J / m ' at 24°C
over 0.15 percent more weight than unspiked controls in the same 75 percent
relative humidity chamber. Meeting this crite:rion would demonstrate a
material's resistance to matrix cracking caused by moisture and thermal
transients.
To help verify that the dry mechanical properties of each candidate were
like those of graphite/epoxy, tests of 0-deg flexure and short beam shear
were conducted. The minimum requirement for room temperature (RT) 0-
deg flexure strength was set at 1724 MPa (250 ksi), with 80 percent of the RT
value maintained at 177°C (350°F). The minimum flexural modulus was set
at 127 GPa (18.5 Msi). Minimum requirements for short beam shear strength
were 90 MPa (13 ksi) at RT and 69 MPa (10 ksi) at 177°C (350°F).
To evaluate the combined effects of moisture and temperature on resin-
dominated mechanical behavior, tensile stress-strain behavior of ±45 cou-
pons was determined at 177°C (350°F) following saturation in 75 percent
relative humidity. Minimum requirements were an initial modulus of 10.3
GPa (1.5 Msi), an ultimate strength of 73 MPa (10.6 ksi), and an ultimate
strain of 2.3 percent.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
McKAGUE ON NEW COMPOSITE MATRIX 25
Critical strain energy release rate (G/c) also was determined to assess each
material's resistance to delamination and flaw growth. The minimum re-
quirement was set at 87.5 J/m^ (0.5 in -Ib/in^), which represents approxi-
mately 90 percent of the value typical of T300/5208 graphite/epoxy.
Screening Results
All screening tests were conducted in the General Dynamics-Fort Worth
Division's engineering chemistry laboratory. These tests showed that proces-
sibility of all screening materials was adequate to make thin laminates (8 to
16 plies) of acceptable quality for evaluation. The laminates were all free of
porosity and cracks, and cured resin contents were all in the 27 to 30 percent
range.
All materials but two were successfully postcured and thermally aged
without forming matrix cracks. However, during postcure, X108-43A and
CPI-2272 formed matrix cracks easily visible at X60. The CPI-2272 material
was particularly unstable, forming many matrix cracks during the thermal
aging tests. In fact, this tendency to crack was a major factor in the estab-
lishment of the material's postcure cycle. The cracks in X108-43 A caused by
postcuring did not appear to worsen during thermal aging.
Three materials, XE-716-3, XE-716-5, and X5231, failed to meet the ther-
mal spike requirement. Specimens of these three materials gained over 0.15
percent more weight due to ten thermal spikes in 177°C (350°F) oil than un-
spiked specimens in the same 75 percent relative humidity chamber. All
other materials gained only 0.08 to 0.12 percent more weight in 75 percent rel-
ative humidity after ten thermal spikes.
Dry Tg for all materials but two ranged from 260 to 270°C (500 to 520°F).
V378A and the XI08-43A materials each exceeded the 288°C (550°F) target
by 5 to 10°C (9 to 18°F). Testing for wet Tg (saturated in 75 percent relative
humidity prior to test) was suspended because the moisture diffusion rate of
the polyimides was much more rapid than that of epoxies, due to higher
permeability. This higher diffusion rate caused too much specimen drying
during the thermomechanical analysis (TMA) testing.
Mechanical evaluations began with tests of 0-deg flexure and short beam
shear properties. Each material met or exceeded the RT 0-deg-flex-strength
target of 1724 MPa (250 ksi). All but XE-716-5 met or exceeded the min-
imum modulus requirement. In general, the polyimides showed good reten-
tion of strength at 177°C (350°F). All but the X108-55B polyimide met or ex-
ceeded the 80 percent retention requirement. The epoxies did not meet the
retention requirement. Short beam shear strength requirements were met by
all materials except X108-43A and X108-55B with C6000 fibers.
Only one material, V378A, met every requirement for ±45 tension behav-
ior. Figure 3 shows bar graphs of the I77°C (350°F) results for each material
in terms of initial modulus, ultimate strength, and ultimate strain. For com-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
26 COMPOSITES FOR EXTREME ENVIRONMENTS
—'
[^TARGET
1
-
i'
< ,
i
_
s
t
_
1i 5
E
i
1 -
I ULTIMATE STRENGTH I
H ULTIMATE STRAIN V
FIG. 3—±45 initial tension property comparisons at liyc {350°F) after saturating in 75 per-
cent relative humidity.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
McKAGUE ON NEW COMPOSITE MATRIX 27
ISO
12S
IM
J . _1
! «- -
t5"
SO - -
T
2t| 'B"
<
1
s
a 1 a 1I a a
E Sl l l
FIG. 5—Comparison of critical strain energy release rates.
parison, the figure also shows the performance of the 5208 epoxy resin. Fig-
ure 4 shows a comparison of the wet 177°C (350°F) stress-strain behavior of
T300-6K/V378A and T300-3K/5208, illustrating the degree of environmental
improvement achieved by V378A. These tests, all performed after saturating
in 75 percent relative humidity, involved rapid heating of the gage section
with hot air blowers. Weight measurements conducted before and after heat-
ing verified that this procedure helped to assure retention of moisture during
the test. Specimens were coupons 2.54 by 22.9 cm (1 by 9 in.) loaded at 2.5
mm/min (0.1 in./min), and each had one transverse and two axial strain
gages. Each specimen was cut from a (±45)2S laminate.
The target for Gic of 0-deg lamina was met only by V378A and XE-716-3.
However, tests of C6000/X108-55B initially gave high but erratic results.
Two additional panels of this material were made and tested, and each pro-
duced consistent but below-target results. Figure 5 summarizes the Gu test
results, which were obtained with a nontapered, double cantilevered beam
test procedure developed at the Fort Worth Division.
A review of all of the screening results was conducted. Of the eight mate-
rials evaluated, it was determined that only T300-6K/V378A graphite/
polyimide material met all of the established criteria. Each of the other mate-
rials failed at least two of the screening requirements.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
28 COMPOSITES FOR EXTREME ENVIRONMENTS
the problem of high resin at the center, nor did reductions in laminate thick-
ness to 40 plies.
To investigate the cause of this flow problem. General Dynamics re-
quested Rheometric test data on V378A from U.S. Polymeric. As illustrated
in Fig. 6, the data show that the viscosity of V378A is much higher than the
normal 5208 epoxy purchased by General Dynamics. In addition, a short
flow period was indicated by Fisher-Johns "gel time" data, as shown in Fig.
7. To combat the effects of these characteristics, a hold in the cure cycle was
established near and on the low-temperature side of the point of minimum
viscosity, in order to allow the longest time for resin flow. However, this
cycle did not result in sufficient bleeding, even with 40-ply laminates.
General Dynamics approached a solution to the bleeding problem in two
different ways. Experiments were conducted to determine the feasibility of
100
l«
1
<9
10
in 110
TENKRATUDE I t l
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
McKAGUE ON NEW COMPOSITE MATRIX 29
150 /
/
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
30 COMPOSITES FOR EXTREME ENVIRONMENTS
when the pressure inside the bubble exceeds the sum of the autoclave pres-
sure and the restraint provided by the resin-to-gas surface tension;* that is
P ^ 7 : 5 ) > Po + 6ag,iT,Xydr, (1)
where
Pg = gas bubble pressure,
Po = autoclave pressure,
Ogi = resin-gas surface tension,
5max = maximum nucleation site size,
T = temperature,
S = gas concentration, and
X = degree of resin advancement.
Based upon Eq 1, the low-temperature dwell in the V378A cure cycle may be
the major factor in avoiding bubble growth. Because the 80°C (176°F) dwell
is 50°C (122°F) lower than the epoxy-cycle dwell temperature, the driving
force to enlarge a bubble is reduced significantly.
'Carter, H. G., General Dynamics, Fort Worth, Tex., private communication, Feb. 1980.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
McKAGUE ON NEW COMPOSITE MATRIX 31
Concluding Remarks
U.S. Polymeric's T300-6K/V378A, a graphite-fiber-reinforced modified
bis-maleimide, has met all of the screening criteria established by General
Dynamics for an improved composite material in advanced aircraft applica-
tions. When both V378A and epoxy have been saturated in 75 percent rela-
tive humidity, V378A has better retention of its mechanical properties upon
exposure to 177°C (350°F) heat. The dry Tg of V378A measured by ther-
momechanical analysis (TMA) is approximately 300°C (570°F) when post-
cured 4 h at 245°C (475°F), followed by another hour at 288°C (550°F). De-
spite this high Tg, the material exhibits a ±45 tension strain-to-failure,
comparable to that of epoxies.
Of equal or greater importance, the T300-6K/V378A material offers a
significant improvement over epoxies in terms of thick-laminate processibil-
ity. Laminates in the 60 to 90-ply thickness range can be cured without voids/
porosity even when laid up in high humidity. This provides major cost bene-
fits through reduction of component rejections and scrappage. Furthermore,
V378A has emerged as the first practical true-net-resin graphite/thermoset
prepreg, thereby providing further manufacturing cost savings through the
avoidance of bleeder materials and associated labor charges.
Because of these processing advantages and improved properties, T300-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
32 COMPOSITES FOR EXTREME ENVIRONMENTS
A cknowledgments
The materials screening and processing investigations reported in this
paper were funded entirely by General Dynamics as an Independent Re-
search and Development (IRAD) task. The author acknowledges the work
and ideas of J. D. Reynolds, M. S. Williams, and J. H. Fruit with thanks and
appreciation.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
S. C. Kmz^
Thermomechanical Characterization
of Graphlte/Polyimide Composites
ABSTRACT: The stiffness, strength, and shear properties of three polyimide resins
(NR-150B2, PMR-15, and CPl-2237) combined with three different moduli graphite
fibers (C-6000, F-5A, and GY-70) have been determined in the temperature range 20
to 371°C (68 to 700°F). Flexural test results from the various unidirectional composites
show that stiffness retention with increasing temperature is affected only by the thermal
integrity of the polyimide matrix. No loss in modulus occurs up to 316°C (600°F) for
the PMR-15 and CPl-2237 based composites [T, = 377°C (710°F)] or to 260°C (500°F)
for the NR-150B2 based material [Tg = 349°C (660°F)], with any of the three fibers. In
contrast, both flexure and shear strengths show fiber-dependent behavior, irrespective
of the matrix resin, with increasing temperature. The higher modulus fiber composites
(F-5A, GY-70) undergo little strength change up to 343°C (650°F). Composite strengths
of the lower modulus fibers (C-6000), however, degrade by as much as 50 percent over
the same temperature range. Thermal-oxidative stability of the various graphite fibers,
and its effect on interfacial strength degradation, are considered primary causes for the
fiber-type dominated strength behavior. In general, strength retention appears directly
related to degree of graphitization (modulus) of the fibers. The accumulated mechani-
cal property data, some previously unknown, are correlated with microstructural fea-
tures such as fiber-matrix adhesion, porosity, and processing defects. This study of a
family of graphite/polyimide composites provides a basis for selecting a high tempera-
ture, structural weight-saving material.
33
Materials
Three types of graphite fibers with a range of modulus (E) values were
selected to produce composite laminates: Celion C-6000 [E = 234
GPa(34 X 10* psi); Celanese Structural Composites], Fortafil F-5A
[£ = 331 GPa(48 X 10* psi); Great Lakes Carbon Corp.], and Celion GY-70
[£ = 517 GPa(75 X 10* psi); Celanese]. The three polyimides chosen as ma-
trices were NR-150B2 (Du Pont Co.) and two versions of PMR resins, PMR-15
(Composites Horizons) and CPI-2237 (Ferro Corp.), prepared by the indi-
vidual composite prepreggers based on the original NASA-Lewis formulation
[10]. Thesd fibers and resins were incorporated into prepreg material, and
subsequently into unidirectional composite laminates by commercial manu-
facturers in the combinations shown in Table 1. In the instances where fiber
sizing was necessary to ease prepreg fabrication (for example, C-6000/
NR-150B2), the only sizing used was the matrix polyimide resin itself; in no
case were fibers sized with epoxy resin.
All eight graphite/polyimide systems in Table 1 were compression molded.
Although the exact cure cycle for the NR-150B2 material manufactured by
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 35
m
"O <N 00 O Tf VO O
o O o —^ O O O
-H -H -H +1 -H +1 -H
^^ 0^ ? V~i r^ r-; OO 0\
fn f*i Tt rn rS TT •—
r^ • * (N rt O ro rn o
ri ^ O —' rs O —: ^
-H -H -H 41 +1 +1 -H HH
—1 oo o fS oo ^ 1^ ro
u o —J wS (3\ vS VO rn P^
1
<N
o o o oo
3 GO OO
m
oo
o o o o o o o o o o
0
-H »0 <N CS - ^ —
O O
OS "O 0 \ t
O
- ^ —.
0
s
<1 o> <n pvj ^ ON vo s o -H r-> f n o \ ^
m ( S ^ »n
00 •<1- ON NO
r s »n r-( s o f s • n <N <n (N »n c s >ri (N »n (N W1
p - 00 »n ON ^ ^ Q r - o \ - ^ -H Q NO 00 ON v ^
f*^ m "O 00 r f »n 00 —« r - -H r ^ S t ^ O 1^ - ^
f*! r ^ f*^ t ^ r ^ r ^ m r- m r-
f*^ \ 0 f*^ \ 0 f/l \ 0
I
0 o o o
w w S X X X
I u
4) -—V « ^—^
•^
00 >
• ••« •
00 >
•2 a -2 5 -s
,.
V}
U
M
V
M
M
U
M
(A
U
tfl 0 o o
o c -a c -o a a. o. a
u c4 u a c E E E
E
I o
O
00
u "O 4> "O
f- 5 I- S W
u V] u 1/3
O
c
U
0
c
U
\
o
c
U
\
o
c O
d.
0 s-
o
u
•
o 0 0 o
a, 1 0 '1 0 .§ N
N u
2
u •c • 0c
(-a \ := ^ .-= o 0 o
X X X
s-i & l = >
asdss
u da d 0
u
0
a
o
Q. a
O
o
U
0
1
£ U J3 U §
£ £ u U
E
o
E
o
u
E
o
U LJU i
b
>-
< "r
V >-
6 o u o
< •^ • o o •
o
a
E
o
u
OL.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
36 COMPOSITES FOR EXTREME ENVIRONMENTS
Testing
All of the composite laminates had unidirectional (0°) fiber orientation
and were obtained from the manufacturers as 2.54 mm (0.1 in.) thick panels.
The desired mechanical properties to be measured were: fiexural modulus, E,
fiexural strength, a/, and apparent interlaminar shear strength, T. Test spec-
imens were machined from the panels in accordance with the ASTM Tests for
Fiexural Properties of Plastics and Electrical Insulating Materials [D 790-71
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 37
(1978)] for the flexural modulus and flexural strength determinations, and
with the ASTM Test for Apparent Interlaminar Shear Strength of Parallel
Fiber Composites by Short Beam Method (D 2344-76) for the shear strength.
Span-to-depth ratios (where specimen depth equaled panel thickness) of 40:1,
16:1, and 4:1 were used for measuring flexural modulus, flexural strength,
and short beam shear strength, respectively.
The three types of flexural tests were performed in a floor model Instron at
room temperature [20 to 22°C (68 to 72°F)] and at the intervals 121°C
(250°F), 204°C (400°F), 260°C (500°F), 288°C (550°F), 316°C (600°F), 343°C
(650°F), and 371°C (700°F). Elevated temperature testing was done in an
oven, in air environment, which could be maintained within ±1°C (±2°F).
The specimens were allowed approximately 15 min to thermally equilibrate
after the desired oven temperature had been reached. A minimum of five test
specimens were used to determine a given property at a given temperature.
0 100 200 300 400 100 " f C 300 400 200 300
-\~r "\
-•-.
-*—r»^.
./- \ '9 -~ ^"
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
38 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 39
100 200 300 400 0 100 T'^ 300 400 0 100 200 300
•» "
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
40 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 41
c^ m ^H 1 ^ W-) r-
o *- cs (s rn >n '<*' -^
II I I I I
o
a.
E
o
U
_ \o «o 00 r-«oo
(N '— CN > 0 TJ- •*
++ + 1 11
-^••B o <on
g <ri m
Z i& « S eu
Z a, U
o js U C
•J •^ o o W1 ( ^ 0>
^ tn c~ o -^ —
^
V
j= U tu
i-S
r^ ff^ vo
-I
n
<
8 8
a
o
X
M
<
o PL,
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
42 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 43
Structure-Property Interactions
Fracture Surface Characterization—Evidence to support the postulated ef-
fects of fiber/interface degradation and resin postcure on elevated tempera-
ture properties can be obtained from fracture surfaces of flexural test speci-
mens. Figure 4 shows scanning electron micrographs comparing room
temperature and 343°C (650°F) fracture behavior of three fiber types in a
PMR-15 matrix (see Fig. 2). An obvious feature in Fig. 4a is that the pulled-
out C-6000 fiber lengths protruding from the surfaces are significantly longer
for a specimen tested at 343°C (650°F) than at 22°C (72°F). This suggests,
according to composite fracture theory [16], that either a toughness increase
or an interface breakdown occurs with increasing temperature. Comparison
of areas (A) under the actual load (/*)-deflection (d) curves for the respective
composites indicates a marked drop in toughness at the high temperature.
Thus, the greater lengths of exposed fibers point to a loss in fiber-matrix ad-
hesion, in agreement with the experimental shear data. In contrast, the P-d
curves for both F-5A and GY-70 composites in Figs. 4b and 4c, respectively,
FIG. 4a—Comparison of room temperature and 343°C (dSVF) fracture behavior of PMR-15
composites containing C-6000 fibers. The pulled-out fiber lengths on the fracture surfaces indicate
fiber-matrix bond integrity: areas (A) under the load {P)-deflection (d) curves reflect composite
fracture toughness.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
44 COMPOSITES FOR EXTREME ENVIRONMENTS
F 5A / PMR 15
(b)
72 F 650 F
•
1/
P /
/A, / A,
Aa-161%A,
FIG. 4b—Comparison of room temperature and 343°C (6S(fF) fracture behavior of PMR-15
composites containing F-SA fibers. The pulled-out fiber lengths on the fracture surfaces indicate
fiber-matrix bond integrity; areas (A) under the load (P)-defiection (d) curves reflect composite
fracture toughness.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 45
QY70/PI^15
(c)
Aj»120% A,
FIG. 4c—Comparison of room temperature and 343°C (650f'F) fracture behavior ofPMR-15
composites containing GY-70 fibers. The pulled-out fiber lengths on the fracture surfaces indicate
fiber-matrix bond integrity; areas (A) under the load (Vydeflection (d) curves reflect composite
fracture toughness.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
46 COMPOSITES FOR EXTREME ENVIRONMENTS
d—
A,-83% A,
FIG. 5a—Comparison of room temperature and 316°C (600^1^ fracture behavior ofNR-150B2
composites containing C-6000 fibers.
A2*81%A,
FIG. 5b—Comparison of room temperature andilS'C (fiOCPF) fracture behavior ofNR-150B2
composites containing GY-70fibers.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 47
NR 150B2
f-ISOfim-l
(a)
PMR 15
(b)
FIG. 6b—Optical micrographs of PMR-15 polyimide resin based composites. Note porosity lev-
els and uniformity of fiber bundle compaction and fiber distribution.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
48 COMPOSITES FOR EXTREME ENVIRONMENTS
CR 2237
l_150^m-f
(C)
FIG. 6c—Optical micrographs of CPI-2237 polyimide resin based composites. Note porosity
levels and uniformity of fiber bundle compaction and fiber distribution.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 49
FIG. 7—Optical (a) and scanning electron (b) micrographs showing voids within and between
fiber bundles in GY-70/NR-150B2 (ii) composite.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
50 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 51
example, oxygen, moisture). Fig. 10 shows cored C-6000 fibers which were
found clustered among normal ones in an NR-150B2 composite. Their origin
and effect on mechanical properties are not known, but they serve to illustrate
one of the many variations reported [5] in graphite fiber uniformity. Finally,
an example of a nonoptimum microstructure, typically associated with pro-
cessing ultrahigh performance materials, is shown in Fig. 11. Incorporation
of GY-70 fibers into an NR-150B2 resin results in extensive fiber-to-fiber
contact due to the bilobal nature of the fibers. Relatively little fiber-matrix
interlocking is observed, compared, for example, to C-6000 fibers in PMR-15
in Fig. 4a, revealing the characteristic poor adhesion property of GY-70
fibers.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
52 COMPOSITES FOR EXTREME ENVIRONMENTS
FIG. 11 —Scanning electron micrographs of G Y- 70/NR- 150B2 composite fracture surface. Note
the frequent occurrence offiber-to-fiber packing contact and poor fiber-matrix adhesion.
Conclusions
Modulus retention to temperatures between 260°C (500°F) and 316°C
(600°F) is not a limiting factor for structural application of graphite/
polyimide composites. Flexural and shear strengths at 316°C (600°F), how-
ever, are moderately to severely reduced from room temperature values, de-
pending on the fiber type. The highest modulus fibers appear to be the most
oxidation resistant, and produce the most thermally stable composites. Con-
versely, the lower modulus fibers suffer thermal degradation, made apparent
by a predominantly interfacial composite failure mode at the higher temper-
atures. Despite thermal losses in both flexural and shear strength, C-6000
composites retain consistently higher values than other higher modulus
composites, at any given temperature. The presence of voids, significant in
number and size, is expected to contribute to fiber oxidative attack as well as
long-term oxygen and moisture absorption. The family of graphite/polyimide
composites investigated shows potential for both stiffness and strength criti-
cal applications, providing their thermal stability and micromechanical
properties are considered in design.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
KUNZ ON GRAPHITE/POLYIMIDE COMPOSITES 53
Acknowledgments
This work was supported by the U. S. Department of Energy (DOE) under
Contract DE-ACO4-76-DP00789. G. E. VanTine, J. E. Perea, and N. H. Hall
performed the experiments for this study. Technical review of the manuscript
by A. K. Miller, K. Hirschbuehler, and F. P. Gerstle is gratefully
acknowledged.
References
[7] Petker, I. and Stern, B. A., 23rd National SAMPE Symposium and Exhibition. Society for
the Advancement of Material and Process Engineering, May 1978, p. 775.
[2] Lottridge, L., 25th National SAMPE Symposium and Exhibition, Society for the Advance-
ment of Material and Process Engineering, May 1980, p. 765.
[i] Gibbs, H. H., Wendt, R. C , and Wilson, F. C , Polymer Engineering and Science, Vol. 19,
No. 5, April 1979, p. 342.
[<| Delvigs, P., Alston, W. B., and Vannucci, R. D., 24th National SAMPE Symposium and
Exhibition, Book 2, Society for the Advancement of Material and Process Engineering,
May 1979, p. 1053.
[5] McMahon, P. E., 23rd National SAMPE Symposium and Exhibition, Society for the
Advancement of Material and Process Engineering, April 1978, p. 150.
[5] Scola, D. A., 22nd National SAMPE Symposium and Exhibition, Society for the Advance-
ment of Material and Process Engineering, April 1977, p. 238.
[7] Gibbs, H. H., 21st National SAMPE Symposium and Exhibition, Society for the Advance-
ment of Material and Process Engineering, April 1976, p. 592.
[S] Sheppard, C. H., "Development and Demonstration of Manufacturing Processes for
Fabricating NTS Graphite/PMR-15 Polyimide Structural Elements," First Quarterly Prog-
ress Report, Nov. 1977, Contract NASl-15009 of Boeing Aerospace Co., Seattle, Wash.
98124; National Aeronautics and Space Administration, Langley Research Center,
Hampton, Va. 23665.
[9] Sheppard, C. H., Hoggatt, J. T., and Hunter, A. B., llth National SAMPE Technical
Conference, Society for the Advancement of Material and Process Engineering, Nov. 1979,
p. 40.
[iO] Serafmi, T. T., "Processable High Temperature Resistant Polymer Matrix Materials,"
NASA Technical Memorandum 71682, 1975.
[11] Serafmi, T. T., "Status Review of PMR Polyimides," NASA Technical Memorandum
79039, 1979.
[12] Cavano, P. J., "Resin/Graphite Fiber Composites," NASA Report CR-134727, Dec. 1974.
[13] Cavano, P. J., "Second Generation PMR Polyimide/Fiber Composites," NASA Report
CR-159666, Oct. 1979.
[14] Haynes, W. M. and Tolbert, T. L., Journal of Composite Materials, Vol. 3, Oct. 1969, p. 709.
[IS] Goan, J. C. and Prosen, S. P., Interfaces in Composites, ASTM STP 452, American Society
for Testing and Materials, 1969, p. 3-26.
[16] Kelly, A., Proceedings, The Royal Society, London, Vol. A 319, 1970, p. 95.
[17] Vannucci, R. D., "Effect of Processing Parameters on Autoclaved PMR Polyimide
Composites," NASA Technical Memorandum 73701, 1977.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
M. D. Campbell^ and D. D. Burleigh^
' Physicist, General Dynamics Convair Division, San Diego, Calif. 92138.
54
Test Materials
Measurements were made on two materials, each in a [0,45,90,135]g quasi-
isotropic layup and in a unidirectional layup.
The HTS/PMR 15 panels were furnished to the program by the National
Aeronautics and Space Administration (NASA) Langley Research Center.
The HTS/NR 150B2 panels were fabricated by General Dynamics Convair
Division. As a check of laminate quality, resin content and tensile strength
were measured for both layups of both materials. Results are shown in
Table 1.
!asiiMie««
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
56 COMPOSITES FOR EXTREME ENVIRONMENTS
Test Methods
Thermal Conductivity
Due to the high anisotropy of the graphite/polyimide composites, two dif-
ferent methods were used in measuring the conductivity. For the X (0° fiber
direction) direction, the cut-bar (comparative) method was used (Fig. 2).
Measurements in the Y (90° fiber direction) and Z (through-thickness) direc-
tions were made on a guarded-hotplate (absolute) apparatus covered by the
ASTM Test for Steady-State Thermal Transmission Properties by Means of
the Guarded Hot Plate (C 177-76) (Fig. 3).
Cut-Bar Method
In the cut-strip/cut-bar technique (Fig. 2), a test stack is built up from al-
ternate pieces of a standard material and the unknown specimen. One end of
the stack has an electrical heater; the other end has an electrical heater plate
built on top of a heat sink which may be cooled with liquid nitrogen (LN2),
water, or air. The use of these cooling media coupled with the use of various
insulating plates between the plate heater and the heat sink allow us to vary
the mean test temperature from 100 to 600 K. Two thermocouples are
TABLE;I—Test matrix.
X Y Z X Y Z
UNI I 1 2 2
ISO 1 ... 1 2 ... 2 2 2
NOTE—A similar set was tested for both HTS/PMR 15 and HTS/NR 150B2. Numbers indicate
specimen quantities. Temperature extremes are: 116 and 588 K.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 57
RADUTKM SWELDS
mounted in each segment of the stack and the entire assembly is radiation
shielded. A bell jar is placed over the assembly and tests may be run in vacuum
or a variety of gaseous environments.
Measurements are made by establishing the desired mean temperature and
a temperature differential of 10 to 25 K across the stack with the two heaters.
When equilibrium is reached, the temperature differences across the specimen
and the standard references are recorded. Thermal conductivity then is cal-
culated using the relationship:
K, = Kr ATs/AT, • X./X, • As/A,
where
Kx = thermal conductivity of unknown,
Ks = thermal conductivity of standard,
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
58 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 59
For the Z direction measurements, 100-mm (4-in.) test discs were cut from
the as-received sheet without disturbing the surfaces. For the Y direction
measurements, 32 strips approximately 100 by 4 mm (4 X 5/32 in.) were cut,
with the 4 mm (5/32 in.) dimensions in the Y direction. These were then bonded
with NR 150B2 resin to form a plate with the laminate Y direction oriented
through the thickness. The test discs were then cut from these plates. The
resin film has a thermal conductivity similar to the matrix in the laminates
and amounted to less than 1 percent of the total area; therefore, it should not
significantly influence the test results.
Thermal conductivity data were taken at mean temperatures of approxi-
mately 116,180,245,310,375,440,505, and 569 K. Accuracy of both methods
is within ±10 percent.
Thermal Expansion
All expansion measurements were made using a modified Leitz push-rod
dilatometer covered in principle by the ASTM Test for Linear Thermal
Expansion of Rigid Solids with a Vitreous Silica Dilatometer [E 228-71
(1979)]. All specimens were vacuum-dried prior to test to eliminate the pos-
sibility of length changes resulting from moisture content changes during the
expansion test. The specimen was maintained in a dry helium atmosphere
while under test. The apparatus was calibrated using an NBS-certified fused-
silica standard. Accuracy over the full temperature range is better than
±7 X 10"' m/m. This is a mean coefficient of thermal expansion (CTE) un-
certainty of ±0.016 X 10'' m/m/K over 472 K. Data were taken in the fol-
lowing temperature sequence: 297, 116, 176, 236, 297, 347, 397, 447, 497,
547, 588, 297, 116, 588, and 297 K.
Specific Heat
Specific heats were measured using a DuPont 910 Differential Scanning
Calorimeter. Using an NBS-certified synthetic sapphire standard, uncertain-
ties were less than ± 2 percent. A test specimen approximately 1 X 6 mm in
diameter was used. Test specimens were vacuum-dried prior to test. For this
program, data were taken and specific heats of each specimen calculated at
116, 180,245, 310,375,440,505, and 588 K, and plotted against temperature.
Emittance
Total hemispherical emittance was obtained by measuring spectral reflec-
tivity and using X -I- ex = 1, where X = spectral reflectivity, the fraction of
light being reflected, and ex = spectral emissivity, the fraction of light being
emitted.
Spectral reflectivity measurements were made at ambient from 2.5 to 30 jitm
using an ellipsometer. The emittance, e, was then calculated at ambient and
588 K.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
60 COMPOSITES FOR EXTREME ENVIRONMENTS
Test Results
Thermal Conductivity
Test results for each specimen were plotted against mean specimen
temperature and best-fit quadratics drawn through the data. These curves
are shown in Fig. 4 through 7. Representative data are in Table 3.
Since the fiber was the same in both cases and the resins were generically
identical, it was expected that both materials would have nearly the same
thermal conductivities. This was the case in the directions where the matrix
dominated; that is, Y direction of unidirectional laminates (Fig. S) and Z di-
rection for isotropic laminates (Fig. 7). Conductivity in the former was
slightly higher, the result of fibers in the prepreg lamina crossing each other
and providing higher conduction paths across the ply than those provided by
the matrix alone.
Results differed significantly, however, for the directions where the fiber
properties dominate. Near room temperature, values for the HTS/PMR 15
specimens were higher than the HTS/NR 150B2 specimens by a factor of 2
to 3 in the X direction of unidirectional (Fig. 4) and isotropic (Fig. 6) lami-
nates. The reason for this is not clear. In these measurements the fibers
should be carrying most of the heat and in both cases the fibers are the same
type (HTS). The resins are different but are generically the same; their con-
ductivities should be almost identical. This should be a very small contribu-
tion to the overall conductivity in any case. If there were significant differences
between the fibers used for the two different composites, it would be expected
that the thermal expansion and tensile strength data would also be different.
This is not so, however.
The only observed differences between the two composites are the relatively
high porosity of HTS/NR 150B2 and the higher resin content of
j 1 .:
0
-
-
HTS/PMR15
HTS/NR 150B2
1 ; I 1 r
]
1 ;
j i y^ •
B/" y "i j
!
1 • I
'
V^
•i
so 100 ISO 200 350 300 3S0 400 4S0 500 S50 SOO
TEMPERfllURE IKI
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 61
1 1 -
1 - HTS/PMR15
0 - HTS/NR1S0B2
' ^--^
1 ^^-^ a ^^
a
-
i
50 100 ISO 20C 250 300 350 400 450 500 550 600
TEMPERATURE IK I
FIG. 5—Thermal conductivity. UNI Y comparison {hot plate).
- HTS./PMR15
0 - HTi>/NR150e2
* •
y
L/\ ^
/"
1 i
SO 100 150 200 250 300 3S0 400 450 SX 550 600
TEllPERflTURE IKl
FIG. b—Thermal conductivity, ISO X comparison (cut bar).
ij • HT >/PMR15
0 - HT »/NR150 B2
r:=»T«
:^
! „ - -
:^S^
--TT-r-n --n-r-n
50 100 150 2X 250 30C 350 400 450 SOO 550 600
TEMPERRTURE IK)
FIG. 7—Thermal conductivity, ISO Z comparison (hot plate).
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
62 COMPOSITES FOR EXTREME ENVIRONMENTS
•o •o • o
E i4
•o • t~
o »
•* • —
•* • •»
d • d
— ^ \ o ^o <ri (N
C8 O c
*~ C"
o o o
\ V \ ^
c <N ^ w-1 «t ,
r^ «ri o r^ I
u « C ; OO 00 m ^ ,
d d o p,
U o I I I T.
B
a
S
o
. <r> . o\ . o
.-1
ea
<•
H
• QO
J= «
^^ 3
•o
c0
u
N N
Z Z Z O O O O
en W5
D D
I
fS <N
lo
a:
o
• ^
"O
mi
OB
o
"^
i 03
o
Su oi:
S OS as :s 0£
c 0. Z
•V z •X NZ
• ^ 0. z
12 X
H M
H
(/}
H
X X X X X
X X
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 63
HTS/PMR 15. Voids in the matrix and lack of matrix-fiber contact would be
expected to affect the measurements of unidirectional laminates in the Y di-
rection, and the voids should reduce the Z direction conductivity of isotropic
laminates by a percentage near their volume percentage in the specimen.
These measurements were in fairly good agreement, however, which indicates
that the difference in void and resin content do not have a significant effect
on the conductivity in these directions.
In measuring conductivity in the X-direction, it is important that the heat
be carried uniformly throughout the cross-section. For this to occur, the heat
must be introduced uniformly into the end of the specimen; that is, into the
ends of the fibers. This is difficult to ensure. For all fibers to be involved
equally in the heat transfer, the matrix must convey heat among the fibers.
The matrix conductivity is low and if it is further reduced by a high void vol-
ume, then little heat may be transferred to those fibers insulated from the
heat source. This would result in the total area of the cross-section involved
in heat transfer being considerably smaller than anticipated, and would yield
a proportionally lower number.
It is assumed, then, that the differences observed are caused by faulty heat
transfer in the HTS/NR 150 composite due to discontinuities and that the
higher values measured for HTS/PMR 15 are more representative of both
materials.
Thermal Expansion
As a graphite fiber-reinforced organic matrix composite is heated, the
negative CTE fiber tends to contract, while the positive CTE matrix tends to
expand. The resulting length of the composite is dependent on many factors,
most of which are subject to variations from laminate to laminate and from
point to point within a laminate.
CTE's (Al/1/degree) are not constant. In fact, they may not even vary
smoothly. For this reason, it is not appropriate to quote a value for the CTE
of a composite except when referring to a narrow, specific temperature range.
It is more appropriate to present data graphically in the form of Al/1 ver-
sus temperature so that the thermal strain from point to point can be seen
(Figs. 8 through 23). The lines connecting the individual Al points are straight
lines and do not necessarily represent specimen behavior between the dis-
crete points.
For comparison purposes, CTE values for each specimen are given in
Table 3. Since the results often varied from cycle to cycle, they are only rep-
resentative values to indicate the gross behavior of the specimen.
Unidirectional—The combination of the negative CTE fiber and the posi-
tive CTE resin produced very low expansion in the X direction of both uni-
directional materials. Here, the full extent of thefibersis exhibited. During the
initial thermal cycle both materials had slope sign changes from minus to
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
64 COMPOSITES FOR EXTREME ENVIRONMENTS
— 1
lO
2*"^^-^ i.ri3
^-^—f.
^^T" r"^'^
1
J'
plus in the 400 to 450 K range. Slopes ranged from approximately —0.4 X 10"*
m/m/K to +6 X 10'' m/m/K for the PMR 15 specimens, and from - 5 X 10"'
m/m/K to + 0.5 X 10"' m/m/K for the NR 150 specimens.
Both materials showed a tendency to change length on succesive thermal
cycles. Differences between values at 300 K were as great as 2 X 10"* m/m
for the NR 150 specimens (Figs. 10 and 11). With the exception of the final
cycle on specimen L2499, this scatter was roughly half for the PMR 15 spec-
imens (Figs. 8 and 9). This indicates that a permanent length change has
taken place which could be caused by microcracking, post-curing of the
resin, or a complex stress relaxation.
In the Y direction of the unidirectional laminates where the matrix CTE
dominates, the matrix differences are evident (Figs. 12 through 15). CTE's
? « - ^ _ ^ A
t.S"
'•^•fe-J * Jl 10 II
IZ.K
~**
~~-~~^_^
It
•d -'
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 65
iV
" • - ^ • ^
13"^^^^ ^"^
IZ,I&
^ - ^ • .
• . . .
• • • '
2 ' J, L
1,5
-1 0
t'"*'^ 7 - o
-1 5:^^ M •^ s
a: -I
1?
I-.
^ -2 It'
ISO-]
100-
50- ?# =•
2 7
i-S"
0-
_^^^^%
3
<i
-100-
200 300 400 500 Sm
TEMP K L2502 N2554 1-27-78
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
66 COMPOSITES FOR EXTREME ENVIRONMENTS
(.S
«.,/<5
^
H»
i^^"^^
^s^
X
15
1'
HJ. 7
i.J.IS
1 3 ^ ^ ^ *<
lab-
(5
lA
•^^r f^
• ^ — i * ^ ^^^ >,^.I2.H(,
175-
0 100 3 0 0 9 0 0 4 0 0 5 0 0 6 0 0 7 0 3 1
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 67
were approximately 24 X 10'' m/m/K for the PMR 15 and 16 X 10"* m/m/K
for the NR 150 specimens, respectively.
Scatter in the Al data for the PMR 15 specimens was nearly twice as great
as for the NR 150 specimens, which had lower resin content. It is possible
that the high void content prevents microcracking.
Quasi-isolropic—The longitudinal (X) CTE of a quasi-isotropic laminate
should be more positive than that of a unidirectional laminate of the same
fiber and matrix. This was observed for both materials, with the CTE of the
quasi-isotropic being positive over the entire temperature range, rather than
negative at the low end and slightly positive at the high end as were the uni-
directional layups (Figs. 8 through 11 and 16 through 19).
Expansion of the PMR 15 specimens was considerably greater than that
of the NR 150B2 specimens, with the former yielding slopes in the order of
/
A
^
— 2
T
' |>
5
1 3^
^^* /
//
^ * \ y ^
13
/
lU
/
/•^ ,s
'•*
^/
3^
' >
/
i
laT^ . •- «
"
6-
a 100 200 300 100 500 soo TOO aoo
FIG. n—Thermal expansion. HTS/PMR 15. ISO. X.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
68 COMPOSITES FOR EXTREME ENVIRONMENTS
IJ
II
^ 2
K
9
A -5
-— 1
2
H
/ ^
11 ^ -— ^
Ifc
y
? 2-
J
'<^ "
5*/^
- fr-J
^
i
.-> >^ y
J
_—-—Sirf
:J^
lb
"
0.8 to 1.7 X 10"' m/m/K and the latter 0.3 to 1.2 X 10"* m/m/K. These
values are indicative of the higher resin content in the PMR 15 specimens;
the difference in the expansion values is of the same order of magnitude as
the difference in resin content.
Both materials exhibited a large amount of scatter in Al/1 over the thermal
cycles.
Net length changes at ambient temperatures were approximately 2 X 10"*
m/m for the NR 150B2 and 4 X 10"" m/m for the PMR 15. Both NR 150B2
specimens produced about the same resuhs. Results for the two PMR 15
specimens were different from each other both in shapes of the Al/1 curves
and total change in length from 113 to 588 K.
It is assumed generally that the CTE's in the Y and Z directions of a uni-
directional laminate are the same since no fibers run in either of these direc-
tions. In reality, the lack of perfect alignment of the fibers in the preprcg
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 69
Specific Heat
Specific heat results for both materials are plotted in Fig. 24. The curves
are best-fit quadratics. Representative data are in Table 3.
Although the fiber is the same in both materials (HTS), the resins are suf-
l<
Aji<
IS
\%.\\
l'^
1)
I&
It
•'y 10
•-*5=r-i^ A \ ^ 9
f^~~7
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
70 COMPOSITES FOR EXTREME ENVIRONMENTS
_ ^^
13
IJ"
- 100 /
// „
/j^ ^
T
, S
11.H,*
2*^—'
1}
Emittance
Emittance results for both materials are given in Table 3. In all cases,
values for the HTS/NR 150B2 specimens were slightly higher than those for
the HTS/PMR 15 specimens. Emittance data at 589 K, for both materials,
are approximately 3 percent higher than those at 300 K.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CAMPBELL AND BURLEIGH ON THERMOPHYSICAL PROPERTIES 71
: 1 1
a - HTS/PMH15
0 - HTS/NR150B2
''X
Conclusions
Thermal Conductivity
Thermal conductivities of HTS/PMR 15 and HTS/NR 150B2 are very
similar in matrix-dominated directions (Z and Y directions of isotropic
laminates).
Significant differences between the two materials were observed in fiber-
dominated directions (X direction of both unidirectional and isotropic lami-
nates). It is suspected that the differences resulted from the higher void con-
tent of the HTS/NR 150B2 affecting the accuracy of the measurement. The
values were expected to be the same as those for HTS/PMR 15.
Thermal Expansion
Scatter was high and reproducibility was poor for both materials, leading
to the conclusion that laminate quality was not optimum in either case.
Higher expansion of the PMR 15 laminates in all except the X direction of
the unidirectional laminate (where the fibers dominate) was assumed to be
the result of higher resin content.
Specific Heat
Differences between specific heats for the two materials were expected,
due to differences in structures of the resins and in laminate resin contents.
Values for the HTS/PMR 15 specimens were consistently higher than those
for the HTS/NR 150B2 specimens, with the difference being approximately
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
72 COMPOSITES FOR EXTREME ENVIRONMENTS
4 percent at 300 K. This correlates with the higher resin content of these spec-
imens since the specific heat of the resin is higher than that of the fiber.
Emitiance
Values for the HTS/NR 150B2 specimens were approximately 4 percent
higher than those for HTS/PMR 15. In both cases, 589 K results were ap-
proximately 3 percent higher than the results at 300 K.
Acknowledgments
The work was sponsored by NASA Langley Research Center under
Contract No. NAS-1-15103, monitored by R. K. Clark.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
D. P. Garber,^ D. H. Morris.^ andR. A. Everett, Jr?
REFERENCE: Garber, D. P., Morris, D. H., and Everett, R. A., Jr., "Elastic Proper-
ties and Fracture Behavior of Graphite/Polyimide Composites at Extreme Tempera-
tures," Compositesfor Extreme Environments, ASTMSTP 768, N. R. Adsit, Ed., Amer-
ican Society for Testing and Materials, 1982, pp. 73-91.
ABSTRACT: The influence of elevated and cryogenic temperatures on the elastic mod-
uli and fracture strengths of several Celion 6000/PMR-15 laminates was measured.
Tests were run at -157, 24 (room temperature), and 316°C (-250, 75, and 600°F).
Both unnotched and notched laminates were tested. Several failure criteria, developed
to predict the uniaxial fracture strength of epoxy laminates, were used to predict the
fracture strength of polyimide laminates.
Lamina elastic moduli were measured at each temperature by testing unnotched
[0]8, [90]i, and [±45]2i laminates. The measured values were used with classical lami-
nate theory to predict the elastic constants in [0/45/90/—45],, [0/45/90/-45]2.,
[45/0/-45/0],, and [45/90/-45/90], laminates. With few exceptions, the predictions
agreed with the moduli measured experimentally. As for the ultimate tensile strength,
although the 8-ply and 16-ply quasi-isotropic laminates were about equally strong at
elevated temperature, their respective strengths diverged at the lower temperatures.
The 8-ply laminates lost strength as the temperature decreased, whereas the 16-ply
laminates became stronger.
The notched laminates had layups of [±45]2., [0/45/90/-45],, and [45/0/-45/0]..
The measured moduli, the ultimate strengths, and the point stress or average stress cri-
terion of Nuismer and Whitney were combined to calculate the characteristic lengths
associated with each criterion. Characteristic lengths were compared to determine the
effect of temperature.
' Materials engineer, Kentron International, Inc., NASA Langley Research Center, Hampton,
Va. 23665.
^Associate professor. Department of Engineering Science and Mechanics, Virginia Polytechnic
Institute and State University, Blacksburg, Va. 24061.
' Aerospace engineer. Structures Laboratory, U.S. Army Research and Technology Labora-
tories (AVRADCOM), NASA Langley Research Center, Hampton, Va. 23665.
73
Test Procedures
Tension and fracture tests were performed at 316, 24, and —157°C (600,
75, and —250°F). An environmental chamber, which was small enough to
permit the specimens to be gripped outside the chamber, was used to control
the test temperature. The maximum variation in temperature was ±5°C
(±9°F) at elevated and cryogenic temperatures. Heat was provided by elec-
trical resistance elements, and cooling was provided by liquid nitrogen.
All tests were performed at a constant cross-head speed. For tension tests
the cross-head speed was 0.0008 mm/s (0.002 in./min), and for fracture tests
it was 0.002 mm/s (0.005 in./min). For all experiments the test section within
the environmental chamber was 203 mm (8 in.). It took approximately 1 h to
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 75
reach 316°C (600°F), and 15 min to reach -157°C (-250°F). Specimens were
allowed to soak at temperature for 10 to 15 min before being tested. Loads
were measured with a load cell that was thermally isolated from the test
specimens.
Average longitudinal and transverse strains for tension tests were measured
by foil strain gages that retained accuracy over the range of temperatures in
this study. The accuracy and repeatability of the gages for determining elas-
tic modulus has been established by Chapman [1].* Except where noted, ul-
timate strains were not measured due to gage failures. Strains were not mea-
sured for the fracture tests.
Results
The resuhs of the unnotched tension tests are summarized in Tables 1 and
2. Three replicate tests were performed at each temperature for each lami-
Unnotched
Specimen Tensile
Temperature, Thickness, Strength, £x, G,2,
Laminate deg C (deg F) mm (in.) MPa (ksi) GPa (Msi) Vxy GPa (Msi)
'En.
'Ell.
''Calibration error.
*The italic numbers in brackets refer to the list of references appended to this paper.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
76 COMPOSITES FOR EXTREME ENVIRONMENTS
2 g ?; g
u o. O
_ VO _, —
r^ •*
''I
• O o
a
X
U4
I III " ^ f^
S
l^—'
Tf
^ "O —' >r»
o ' 5 ^ OO
<N - " <N —
ill oS-5r5'nS^S'^o=>o-:SrS»!o°i».o
-^ (-^ "^ r^ -^ (-i <N , i *^ Q "^ « ^^ iri "^ (
I I ^ I I I I I I
^
? I
.1
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 77
nate, except where noted. Results presented in this paper are average values
of the replicate tests. In most cases, data values were within a few percent of
the average values presented in this paper. The principal exception occurred
in the data for the [90]8 laminate. For this laminate, the tensile strength at
elevated temperature varied almost 30 percent from the average. As men-
tioned previously, it was not possible to determine ultimate tensile strains in
many cases, due to failure of the gages from either adhesive failure or gage
tearing at high strains.
Lamina constants £11, £22, and 1*12 were determined from tests of the unidi-
rectional laminates, and Gn was determined from tests of the [±45] lami-
nates using Rosen's method [2]. The results appear in Table 1. Laminate
constants for unnotched tension specimens were determined experimentally
for the other laminates, and compared with laminate analysis calculations
based on experimental lamina constants (Table 2). As would be expected,
good agreement was obtained.
The results of the notched tension tests are summarized in Table 3. Three
replicate tests were performed at each temperature for each laminate, except
where noted. Results presented in this paper are average values of the repli-
cate tests. The test data were correlated using the Nuismer and Whitney
point stress and average stress criteria [i]. Each criterion yields a characteris-
tic distance, which appears in the table. More will be said about this distance
in a later section.
Discussion
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
78 COMPOSITES FOR EXTREME ENVIRONMENTS
Notched
Specimen Specimen Hole Tensile Characteristic Distance
Temperature, Width, Thickness, Diameter, Strength,
deg C (deg F) mm (in.) mm (in.) mm (in.) MPa (ksi) do mm (in.) flo mm (in.)
0/45/90/-45].
316 100 1.09 25.4 199 3.07 7.47
(600) (3.94) (0.043) (1.00) (28.8) (0.121) (0.294)
100 1.09 9.53 281 2.57 7.82
(3,94) (0.043) (0.375) (40.7) (0.101) (0.308)
100 1.07 4.76 297 1.50 4.80
(3.93) (0.042) (0.188) (43.1) (0.059) (0.189)
100 1.09 1.59 342^ 0.79 3.18
(3.94) (0.043) (0.063) (49.6) (0.031) (0.125)
24 100 1.09 25.4 175 3.07 7.47
(75) (3.95) (0.043) (1.00) (25.4) (0.121) (0.294)
100 1.12 9.53 234 2.21 6.38
(3.95) (0.044) (0.375) (34.0) (0.087) (0.251)
100 1.07 4,76 274 1.70 5.82
(3.95) (0.042) (0.188) (39.7) (0.067) (0.229)
100 1.07 1.59 310* 0.86 3.78
(3.93) (0.042) (0.063) (44.9) (0.034) (0,149)
50.8 1.17 4.76 259 1.47 4,72
(2.00) (0.046) (0.188) (37.6) (0.058) (0.186)
25.4 1.14 4.76 228 1.12 3.20
(1.00) (0.045) (0.188) (33.0) (0.044) (0.126)
19.1 1.14 4.76 222 1.14 3.30
(0.752) (0.045) (0.188) (32.2) (0.045) (0.130)
-157 100 1.07 25.4 217 8.10 26.4
(-250) (3.94) (0.042) (1.00) (31.3) (0.319) (1.04)
100 1.09 9.53 279* 6.10 29.2
(3.95) (0.043) (0.375) (40.5) (0.240) (1.15)
100 1.12 4.76 290° 3.56 18.9
(3.95) (0.044) (0.188) (42.0) (0.140) (0.744)
100 1.09 1.59 324-^ 12.24 424'
(3.93) (0.043) (0.063) (47.0) (0.482) (16.7)
[45/0/-45/0].
316 63.2 1.17 25.4 298 3.02 8.08
(600) (2.49) (0.046) (1.00) (43.2) (0.119) (0.318)
63.2 1.17 9.53 476 2.49 8.31
(2.49) (0.046) (0.375) (69.0) (0.098) (0.327)
63.2 1.09 4.76 503 1.37 4.80
(2.49) (0.043) (0.188) (72.9) (0.054) (0.189)
63.2 1.09 1.59 684' 2.36 20.7'
(2.49) (0.043) (0.063) (99.2) (0.093) (0.815)
24 63.2 1.17 25.4 274 2.64 6.81
(75) (2.49) (0.046) (1.00) (39.7) (0.104) (0.268)
63.5 1.14 9.53 423 1.96 6.07
(2.50) (0.045) (0.375) (61.4) (0.077) (0.239)
63.2 1.09 4.76 467 1.22 4.09
(2.49) (0.043) (0.188) (67.7) (0.048) (0.161)
63.2 1.12 1.59 542 0.66 2.62
(2.49) (0.044) (0.063) (78.6) (0.026) (0.103)
50.8 1.09 4.76 465 1.24 4.09
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 79
TABLE 3 Continued
Notched
Specimen Specimen Hole Tensile Characteristic Distance
Temperature, Width, Thickness, Diameter, Strength,
deg C (deg F) mm (in.) mm (in.) mm (in.) MPa (ksi) rf„ mm (in.) Oo mm (in.)
[±45]2,
316 100 86.2 e e
1.17 25.4
(600) (3.95) (0.046) (1.00) (12.5)
100 1.27 9.53 104
(3.95) (0.050) (0.375) (15.0)
100 1.22 4.76 114
(3.95) (0.048) (0.188) (16.5)
100 1.22 1.59 115
(3.95) (0.048) (0.063) (16.7)
24 100 1.14 25.4 118 e e
(75) (3.95) (0.045) (1.00) (17.2)
100 1.24 9.53 127
(3.95) (0.049) (0.375) (18.4)
100 1.22 4.76 151
(3.95) (0.048) (0.188) (21.9)
100 1.27 1.59 160
(3.95) (0.050) (0.063) (23.2)
50.8 1.24 4.76 136
(2.00) (0.049) (0.188) (19.7)
25.4 1.22 4.76 116
(1.00) (0.048) (0.188) (16.8)
18.9 1.24 4.76 103
(0.746) (0.049) (0.188) (14.9)
-157 100 1.22 25.4 125 e e
(-250) (3.96) (0.048) (1.00) (18.2)
100 1.12 9.53 151
(3.95) (0.044) (0.375) (21.9)
100 1.24 4.76 174
(3.95) (0.049) (0.188) (25.3)
100 1.24 1.59 174
(3.95) (0.049) (0.063) (25.2)
[0/45/90/-45] .
316 63.5 2.36 4.76 328 1.85 6.68
(600) (2.50) (0.093) (0.188) (47.5) (0.073) (0.263)
24 63.2 2,41 4.76 319 1 40 4. 37
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
80 COMPOSITES FOR EXTREME ENVIRONMENTS
TABLE 3 Continued
Notched
Specimen Specimen Hole Tensile Characteristic Distance
Temperature, Width, Thickness, Diameter, Strength,
deg C (deg F) mm (in.) mm (in.) mm (in.) MPa (ksi) dc mm (in.) a^ mm (in.)
"One specimen.
*Not used in plot.
'Two specimeiis.
''Four specimens.
'Nuismer-Whitney model not applicable.
-'^AU specimens failed at grip.
'Two specimens failed at grip.
* One specimen failed at grip.
100 15
TENSILE
MODULUS, Msl
GPa [i)5/n/-i|5/0]. 10
50 [o/is/goz-iB],
[0/II5/90/-15] 2s
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 81
°F
-200 200 600
2000
1 1 1 1
1500
tOlg " 200
TENSILE
STRENGTH, 1000 - - ksl
MPa
[W/OZ-HS/Olj
100
500 ____[0/i|5/90/-H5]2s
u—^— "
_ o — — •—
-
[0/l(5/90/-45]5
0 1 1 , 1 1 1
-200 0 200 too
TEMPERATURE, °C
2 Msl
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
82 COMPOSITES FOR EXTREME ENVIRONMENTS
°F
-200 200 500 30
200 1 • ' • - " . - , , _ — , . ,
-——_____U5/90/-U5/90]5
150-
TENSILE
STRENGTH, 100
MPa
^"""^^^^^^^^^^^^^S^ 15 ksl
[^^§f8
50
1 1 1 r , 0
-200 0 200 ilOO
TEMPERATURE, °C
FIG. 4—Tensile strength versus temperature for matrix-dominated laminates.
1.0
.6
POISSON'S
RATIO
/[0/i45/90/-'45]5
[0/i45/90/-'*5],
[it5/90/-i(5/90]^
[90]o
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 83
300
- 10
NOTCHED
STRENGTH, 200
ksl
MPa
HOLE D1A>1ETER
o 1.6 mm (1/16 In) 20
o M.8 iTin (3/lb In)
100
6. 9.5 mm (3/8 In)
O 25.t mm (1 In)
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
84 COMPOSITES FOR EXTREME ENVIRONMENTS
500
SO
100-
NOTCHED
STRENGTH, ksl
NPO
1)0
HOLE DIAMETER
20C- 1.6 nri ( 1 / 1 6 I n )
i|,8 nm (3/16 In)
9.5 inn (3/8 In)
25.1 m (1 In)
-200 2!5!r too
TEMPERATURE, °C
FIG. 1—Notched strength versus temperature for the [45/0/-45/0], laminates, width = 65.4
mm (2.5 in.).
150
20
NOTCHED
STRENGTH, 100 HOLE DIAMETER ksl
HPO 0 1.6ran(1/16 In)
a 1.8 mm (3/16 In)
a 9,5ran(3/8 In) 10
50 O 25.1)ran(1 In)
FIG. 8—Notched strength versus temperature for the [±4S]2s laminates, width = 102 mm (4.0
in.).
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 85
400
56
300 [0/15/90/-H5]5
NOTCHED
- 42
STRENGTH, ksl
HPa
200-
28
[tl.5]2s
n
100- 14
1 1
1 1 1 J 1 1 1
20 40 60 100
WIDTH, mn
FIG. 9—Notched strength versus width at room temperature for a fixed/law size at 4.8 mm
(3/16 in.).
where the specimens passed through the oven wall. This suggests that [±45]
specimens should be tested in a different manner.
Despite the uncertainty as to the location of failure initiation, the data
shown in Fig. 8 clearly indicate the existence of a notch effect which is
temperature dependent. As would be expected for a matrix-dominated lami-
nate, both strength and the apparent notch effect decrease with increasing
temperature.
Figure 9 shows the effect of width on notched strength for afixedflaw size
and temperature. For all three laminates there is little width effect for plates
wider than S1 mm (2 in.); that is, plates with a hole diameter to width ratio
less than 0.094 may be treated as infinite plates. As mentioned previously, no
tests were conducted on 102 mm (4 in.) plates for the [45/0/—45/0]s lam-
inate. It should be noted that all data points in Fig. 9 are the average of three
identical tests.
Failure Model
Figures 10 and 11 compare the experimental notched strengths with
strengths predicted by the Nuismer and Whitney point stress and average
stress models [3]. The point stress model states that failure of a notched ten-
sion specimen will occur when the stress at some distance, do, ahead of the
notch equals the unnotched tensile strength. In equation form, this failure
criterion is
ON
-^=2[2 + C' + 3C- (KT' - 3)(5C* - 74')]-'
Oo
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
86 COMPOSITES FOR EXTREME ENVIRONMENTS
1.0,-
^ 316°C (600°F)
o 2i)°C (75°F)
O -157°C (-250°F)
NOTCHED
TENSILE
STRENGTH
UNNOTCHED
TENSILE ^ yO^ = 5,8 m (0.23 in)
STRENGTH ,t - CURVES FITTED ONLY
TO DATA AT 2lt°C
AND 316°C
_L.
0.1 0.2 0.3 0.1
HOLE DIAMETER
WIDTH
where { = R/{R + do), ON" is the failure stress for a notched infinite plate, Oo
is the unnotched tensile strength, KT° is the orthotropic stress concentration
factor for an infinite width plate, and R is hole radius. The infinite plate
notched strength is found by multiplying the experimentally determined
notched strength for a finite width plate by a finite width correction factor
o 2H°C (75°F)
D -157°C (-250°F)
NOTCHED
TENSILE
STRENGTH
UNNOTCHED ,ag = 1.6 mm (0.18 In)
TENSILE
STRENGTH
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 87
The average stress model states that failure of a notched specimen will
occur when the average stress over some distance ahead of the notch, Oo,
equals the unnotched tensile strength. This failure criterion may be written
where { = R/{R + Oo)- The distance do and a<, are called characteristic
distances.
It is apparent from Fig. 10 that one value offloor do gives fair predictions
of the notched strength of the [0/45/90/—45], laminate for both room and
elevated temperature. These characteristic distances were found using the
appropriate failure criterion, the unnotched strength, and the experimentally
determined notched strengths. The values of Oo and do are average values for
all data at the two temperatures and various hole sizes. The average stress
criterion gives slightly better results than the point stress criterion. Average
values of ao and do also were determined from the cryogenic temperature
data for this laminate. Due to uncertainty in data from both notched and
unnotched tests, however, curves for these values are not shown in the figure.
As shown in Fig. 11, the notched strengths of [45/0/—45/0], laminates at
all three temperatures can be predicted fairly well using one value of Oo or do.
Again, the average stress criterion gives a slightly better fit.
However, as shown in Fig. 12, the fracture data for the matrix-dominated
[±45] laminate cannot be correlated using the Nuismer-Whitney model [5].
For this laminate, notched strengths greater than unnotched strength were
1.5r
e D
1.0
NOTCHED
TENSILE
STRENGTH
UNNOTCHED A 316°C (600°F)
TENSILE
STRENGTH g 5 o 2«°C (75°F)
D-157°C (-250°F)
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
88 COMPOSITES FOR EXTREME ENVIRONMENTS
AVG, PT,
STRESS STRESS
• oCltS/OZ-IS/Olj. H = en mil (2,5 In)
• D [0/115/90/-1)5],, , W = 102 mm (11.0 In)
CHARACTERISTIC
DISTANCE, H
mn
0 200
TEMPERATURE, °C
FIG. 13—Characteristic distance versus temperature for the [45/0/~45/0], and [0/45/-
90/-45]2, laminates.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 89
1.0
20
CHARACTERISTIC
DISTANCE,
nm
0.5 In.
10
^ a
AVG. PT.
STRESS STRESS
• o [W/OZ-aS/Olj, W= 6i| rm ( 2 . 5 In)
CHARACTERISTIC
DISTANCE, t
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
90 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GARBER ET AL ON GRAPHITE/POLYIMIDE COMPOSITES 91
References
[/] Chapman, A. J., "Graphite/Polyimide Tension Tests at Elevated and Cryogenic Tempera-
tures," NASA Conference Publication 2079, National Aeronautics and Space Administra-
tion, Langley Research Center, Hampton, Va., 1979.
[2] Rosen, B. W., Journal of Composite Materials, Vol. 6, Oct. 1971, pp. 552-554.
[3] Nuismer, R. J. and Whitney, J. M., in Fracture Mechanics of Composites, ASTM STP 593,
American Society for Testing and Materials, 1975, pp. 117-142.
[4] Morris, D. H. and Hahn, H. T., Journal of Composite Materials, Vol. 11, April 1977, pp.
124-138.
[5] Yeow, Y. T., Morris, D. H., and Brinson, H. F., Experimental Mechanics, Vol. 19, No. 1,
Jan. 1979, pp. 1-8.
[5] Morris, D. H. and Hahn, H. T., in Composite Materials: Testing and Design (Fourth Confer-
ence), ASTM STP 617, American Society for Testing and Materials, 1977, pp. 5-17.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Atmospheric and Extroatmospheric
Environments
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
E. E. Morris^
ABSTRACT: Studies showing higli tensile strength, low thermal conductivity, and ade-
quate fatigue strength capabilities in conjunction with low resin outgassing properties
of S-901 Tiber glass with SCI REZ 080 and 081 epoxy resins has resulted in use of fila-
ment wound tension straps, struts, and conical shells as thermal isolators in several
high-performance cryogenic applications. These thermal isolator structures and their
use in the following cryogenic systems are discussed in this paper: hydrogen and oxy-
gen dewars for space shuttle, helium tank for the infra-red astronomy satellite, space-
craft refrigerators, and infrared telescope. Mechanical and thermo-physical properties
of the composite laminates are presented.
95
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 97
OXYGEN TANK
DENSITY PROBE-
HEATER ASSEMBLY-
- PRESSURE
VESSEL
, SUPPORTS
QUANTITYA
r^^^^^TiT J^ [&L^^^ \
SIGNAL \
CONDITIONER^
>—MOUNTING TRUNNION
celeration loads. Total static supported weight is about 408 kg (900 lb) for
the oxygen tank and 82 kg (180 lb) for the hydrogen tank.
The straps, made from unidirectional windings of Owens-Corning S-901
glass fiber roving impregnated with SCI REZ 081 epoxy resin, are shown in
Fig. 2. They have high strength-to-density and strength-to-thermal conduc-
tivity ratios at ambient and cryogenic temperatures. Oxygen pressure vessel
thermal isolator support straps measure 25.4 cm (10 in.) long with 3.18-cm
(1.25-in.) -diameter load pin, and 0.26-cm (0.10-in.) -thick by 0.89-cm (0.35-
in.) -wide legs. The hydrogen tank straps are 30.5 cm (12 in.) long with 3.18-cm
(1.25-in.) -diameter load pin and 0.20-cm (0.08-in.) -thick by 0.76-cm (0.30-in.)
-wide legs.
The strap and inner pressure vessel support assembly is shown in Fig. 3;
the outer vacuum shell is added to complete the dewar assembly. Qualifica-
tion testing of the PRSA assemblies has been completed successfully, includ-
ing critical vibration and thermal tests. So effective is the combined insulat-
ing characteristics of the hydrogen tank that it would take 63 days for the 20
K (—423°F) hydrogen to evaporate in a filled PRSA tank.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
98 COMPOSITES FOR EXTREME ENVIRONMENTS
IIHI
(IR). The low temperature reduces thermal background noise to low levels so
that the IR detectors are more sensitive. Telescope cooling is achieved using
cryogenic super critical helium stored in a toroidal main cryogen tank, which
is in turn supported with S-901 glass/SCI REZ 080 resin unidirectional
thermal isolation straps. Figure 4 shows the general arrangement of IRAS,
and Fig. 5 shows the straps with metal load pin spools installed. Nine 30.5-
cm (12-in.)-long straps are used in the IRAS to support the cryogen tank and
its contents, and to provide thermal isolation sufficient for a one-year mis-
sion in space with active helium cooling. The IRAS recently passed its vibra-
tion qualification testing successfully.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 99
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
100 COMPOSITES FOR EXTREME ENVIRONMENTS
wllian EMU
Thermal
Isolator
Straps
of Saturn and its rings. The near infrared mapping spectrometer of the Gali-
leo spacecraft to Jupiter also will use small filament wound straps to hold an
infrared detector array and to align it. One side of the array is a black radia-
tor, radiating into space to achieve very low array temperatures (70 to 80 K)
for maximum resolution and efficiency. The straps limit heat flow to the ra-
diator to permit low temperature. Another similar current application of the
S-901 glass/SCI REZ 080 straps is in the thematic mapper instrument of the
Landsat D spacecraft.
Another important class of instruments utilizing the filament wound
thermal isolators is cryogenic refrigerators, typified by the High Energy As-
tronomy Observatory (HEAO) cryogenic ammonia and methane refrigera-
tor systems. These are employed in the gamma ray spectrometer to maintain
the necessary low temperature.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 101
m-
FIG. 5—IRAS cryogenic tank support straps.
Typical
Total Inside Pin Diameter, Width, Thickness, Cross-Sectional Breaking Load,
Length, in. in. in. in. Area, in.^ lb
NOTE—Conversion factors: 1 in. = 2.54 cm,; 1 in.^ = 6.452 cm^ 1 lb = 0.454 kg.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
102 COMPOSITES FOR EXTREME ENVIRONMENTS
^vy 3 HHI
^A^
A' iT^a'l-^'MiT^iiP"
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 103
Filament
Ultimate strength, psi 650 000
Elastic modulus, psi 12.4 X 10'
Density, lb/in.' 0.088
Composite
Filament fraction in composite, volume percent 67
Density, lb/in' 0.072
Longitudinal modulus, psi
350° F 8.3 X 10'
75°F 8.3 X 10'
-320°F 9.1 X 10'
Longitudinal tensile ultimate strength, psi
350°F 174 000
75°F 220 000
-320° F 275 000
Coefficient of thermal expansion, in/in, °F
75 to -320°F 1.6 X 10"'
75 to 350°F 1.4 X 10"'
Note—Conversion factors: 1 psi = 703.1 kg/m'; 1 lb/in.' = 27 680 kg/m'; °C = 5/9 (°F - 32);
1 in. = 2.54 cm.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
104 COMPOSITES FOR EXTREME ENVIRONMENTS
Acceptance Testing
In addition to dimensional inspection, straps often are given acceptance
tests, which include proof loading and spring constant determination. In
some applications, the spring constants strap-to-strap must be within a very
close tolerance range, and straps are segregated into matched sets. Some
straps, for example, the PRSA straps, are strain gaged on each leg and each
part is individually calibrated as a spring; strain gage output, extensometer
output, and load pin-to-load pin displacement are measured as a function of
load, and must be within specified limits. Usually, lot acceptance witness
specimens are subjected to destructive fatigue and static testing in order to
certify a production lot.
Static Strength
Delivered strap static strength at room temperature is a function of strap
geometry, specifically the load pin diameter-to-leg thickness ratio, D/t. A
preliminary design curve for nominal strap strength at ambient temperature
is shown in Fig. 8, based on more than 100 tests. Delivered strength is higher
for "thinner" composites, while "thick" composites result in lower strength,
as might be expected.
Composite strength increases considerably in going from ambient to cry-
ogenic temperatures (about 25 to 35 percent). However, most applications
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 105
with which we are familiar have a "warm" strap end, so that the higher
strength associated with cryogenic temperature exposure is not used to ad-
vantage in hardware design.
AL/Lp
in which P is the tensile load, A is twice the cross section area of one leg (2
IVt), and AL is the axial deflection between load pin centers. From this rela-
tionship, it is obvious that the straps have an apparent modulus less than
theoretical, with short straps having large pin diameters yielding the lowest
values.
Since the straps are preloaded in tension to prescribed levels in each spe-
cific application, precise knowledge of their spring constant is essential.
Strap spring constant (K) is defined by the relationship
K = P/AL
As previously mentioned, normal strap acceptance test procedure is to
measure spring constant for each strap produced over the load range of
interest.
Thermal Conductivity
Precise thermal conductivity measurements have been made on S-901
glass/SCI REZ 080 straps by the National Bureau of Standards over the
temperature range 2 to 280 K (—456 to 45°F). Results are shown in Fig. 9*.
* Hust, J. G. and Arvidson, J. M., "Thermal Conductivity of Glass Fiber/Epoxy Composite
Support Bands for Cryogenic Dewars," Report 275.03-78-2, National Bureau of Standards,
Feb. 1978.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
106 COMPOSITES FOR EXTREME ENVIRONMENTS
"- /
•
SO
/ -
60
- / -
^ 40 - / ^ ,
1
3
^
_ ^ y^ •
>
- -
-0 /
0
U
H 10 - / -
R
- / -
6
y -
4 7 ,, 1 1 1 J 1 1 1
, , 1 1 1 1 1 1 1 1
,
ar "1 (, 8 10 . 20 40 60 80 100 200 400
Outgassing
Standard evaluations performed to assess vacuum compatibility of com-
posite materials for spacecraft applications include determination of vacuum
weight loss and volatile condensable material (VCM). These tests have been
established as a screening procedure for nonmetallics considered for use in
NASA spacecraft. The criteria used for selection are that a maximum of 1.0
percent weight loss and a maximum of 0.10 percent VCM are permitted as a
result of a 24 h pulverized material bakeout at 125°C (257°F) in a
<6.6661 X 10'' Pa (<5 X 10"' torr) test chamber with VCM collected on a
25°C (77°F) substrate.
The Jet Propulsion Laboratory performed tests of SCI REZ 080 and SCI
REZ 081 epoxy following their procedure for vacuum outgassing of poly-
mers (micro-VCM technique) with acceptable results, as shown in Table 3.
Material
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 107
Mran. R - O.OS
Fatigue
Ambient and cryogenic temperature fatigue tests have been performed on
thermal isolator suspension straps under several programs. Results obtained
are similar to characteristics determined for glass/epoxy flat laminates.
The National Bureau of Standards (NBS) conducted fatigue tests at room
temperature and 4 K (-452°F) on SCI fabricated S-901 glass/SCI REZ 080
filament wound support straps.'' Room temperature fatigue data are shown
in Fig. 10, where the maximum fatigue stress is plotted as a function of the
static strength. Fatigue data obtained at liquid helium temperature are added
to the room temperature data in Fig. 11. These data clearly demonstrate a su-
perior fatigue resistance at 4 K (—452°F), about an order of magnitude
greater than at 295 K (72°F). Although a reliable S-N curve at 4 K (-452°F)
could not be constructed without more extensive data, it appears that the
stress level required for failure at a specified number of cycles may approach
twice the value required at room temperature. The improvement in fatigue
resistance at 4 K (—452°F) exceeds that which might be predicted based on
scaling the fatigue stress levels to account for the increase in static strength
alone.
' Tobler, R. L. and Read, D. T., "Fatigue Resistance of a Uniaxial S-Glass/Epoxy Composite
at Room and Liquid Helium Temperatures," National Bureau of Standards, 1976.
' Hofer, K. E. and Olsen, E. M., "An Investigation of Fatigue and Creep Properties of Glass
Reinforced Plastics for Primary Aircraft Structures," Report M6104, Illinois Institute of Tech-
nology Research Institute, April 1967.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
108 COMPOSITES FOR EXTREME ENVIRONMENTS
295«K, Mean
Fatigue Cycles. N
QQ O
Fatigue Cyclee. N
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
MORRIS ON CRYOGENIC DEWARS AND INSTRUMENTS 109
Conclusion
Materials, processes, and design data have been developed for composite
thermal isolators, and these cryogenic structures have been used successfully
for a range of sophisticated spacecraft applications. With increasing use and
cost of cryogens, new trends are expected in the use of composites with cryo-
gens for industrial products, in addition to space applications.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
C. L. Leung^
110
ing electrons [7].^ These may acquire sufficient energy to be removed from
the macromolecular chain to form ionic systems. These electrons also may
be excited to higher nonbonding energy levels, forming radicals. These ionic
and radical species then may react with the surrounding materials to form
new chemical species.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
112 COMPOSITES FOR EXTREME ENVIRONMENTS
that the bulk properties of the composites will be essentially equal to that at
a lOOO-km altitude. Therefore, the vacuum chosen (10"' to 10"' torr) in the
laboratory is sufficiently small that reducing it even more would have essen-
tially no effect on results obtained during the irradiation exposure.
When cured, epoxy resins are above average in radiation resistance in
comparison with other thermosetting resins [2]; this is very likely due to their
rigidity and aromatic content. Of itself, the chemical composition of a par-
ticular resin influences its resistance to radiative degradation. For example,
when irradiated with -y radiation, glycidyl amine resins cured with aromatic
diamine-based hardener were found to show little deterioration of flexural
strength at doses up to 10'° rads, while the glycidyl ether/aromatic diamine
system shows a 50 percent reduction in flexural strength at about 4 X lO'
rads [5].
The presence of graphite fibers is likely to affect the photochemical behav-
ior of the matrix material. Besides being conductors for free electrons, graphite
fibers may transfer the absorbed radiation energy back into the polymer,
thereby promoting degradation. Graphites and carbons as a class are more
susceptible to property changes from irradiation than other inorganic ceramic
oxides, such as beryllium oxide, alumina, and silica. It has been reported [2]
that the chemical reactivity of graphite is increased in the presence of radia-
tion, mainly by oxidation in the presence of carbon dioxide, oxygen, water
vapor or all three. These oxidation products may consist of reactive species
which are retained on the fiber surface and then interact with the matrix poly-
mer, affecting the bonding between the fiber-matrix interface.
Experimental
A 48-ply unidirectionally reinforced composite panel (Fiberite 934 rein-
forced with Union Carbide T300 graphite fibers) was fabricated and cured
by standard production procedures. The cured composite has a fiber volume
Vf = 0.60 and a volume fraction of voids Vy < 0.01.
For short beam interlaminar shear tests, specimens 0.015 m long and 0.004
m wide were cut with a diamond cutoff wheel to a thickness of 0.002 m.
Thin plate specimens for moisture absorption measurements were cut to
provide dimensions of length by width by thickness of (20 by 5 by 1) X 10"' m.
Figure 1 details the specimen orientation which exposes the interlaminar,
transfibrous, and translaminar faces, respectively, as the major exposed
areas (80 percent of total area) in moisture absorption measurements [6].
In studying the dynamic mechanical properties of the composites by the
Rheovibron, fiexural specimen geometry was used, as discussed by Massa
and coworkers [7,8]. This specimen geometry recently has been successfully
used in studying environmental effects on the mechanical properties of
graphite/epoxy composites [P, 10]. A schematic of the flexural specimen as-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
LEUNG ON SPACE ENVIRONMENTAL EFFECTS 113
Interlaminar surface (i - 3)
Transfi&rous surface {i » 1)
TA
fT TransTaminar surfaca ( i = 2}
FIG. 1—Specimen orientation and geometry for kinetics of absorption in interlaminar, transfi-
brous, and translaminar directions of uniaxial reinforced composite (layers represent plies and dots
fiber ends).
sembly is shown in Fig. 2. The specimens, in the form of rods, were ma-
chined to about 0.0015 m in diameter.
Specimens for interlaminar shear, dynamic mechanical, and moisture dif-
fusion measurements were inserted in small vials. For irradiation under
vacuum, the vials were evacuated to about 10"' torr, and then sealed. High
temperature irradiation was achieved by placing the vials inside a thermo-
statted dewar which was regulated at 100°C.
Irradiation was achieved by a Co-60 source having a flux rate of 2.57 X lO'
rads/h. For both the evacuated and open vials, four different dosage levels
were used: 4.4 X lO', 8.8 X 10\ 1.4 X 10*, 3.2 X 10* rads. Both room
temperature and 100°C were used during irradiation. The highest dosage level
(3.2 X 10* rads) is equivalent to the total radiation received in three years in
a geosynchronous orbit.
After the appropriate radiation dosages were received, the vials were
broken, and the specimens were stored in a dry desiccator until use.
Interlaminar shear (short beam) strengths were measured on a three-point
loading device. Moisture diffusion measurements were measured by immersing
the specimens in water at 75°C, and periodically weighing the moisture up-
take. Glass transition and tan 6 measurements were obtained on a Rheovibron
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
114 COMPOSITES FOR EXTREME ENVIRONMENTS
°V = in vacuum.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
LEUNG ON SPACE ENVIRONMENTAL EFFECTS 115
RADS (X10'|
changed and even decreased slightly. Reference to Fig. 1 shows that the major
diffusion paths for the interlaminar and translaminar surfaces are through
the matrix resin, and that for the transfibrous surface it is through the fiber-
matrix interface. Therefore, the data in Table 1 suggest that while y radiation
damaged the matrix resin (by microcracking, perhaps), it improved the
matrix-fiber interaction, and thus lowered the moisture diffusivity along the
matrix-fiber interface.
0 260
4.4 X 10' 231 230 236 235
8.8 X 10' 230 230 239 230
1.4 X 10' 234 235 240 238
3.2 X 10' 225 238 237
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
116 COMPOSITES FOR EXTREME ENVIRONMENTS
_I 1 1 I 1 I L — I 1 1 i 1—
to 12 14 ie IS 20 22 24 20 2> » 32
RADS (Xio'l
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
LEUNG ON SPACE ENVIRONMENTAL EFFECTS 117
A cknowledgments
This research was performed under Rockwell International's Independent
Research and Development Program. The technical assistance of G. Lind-
berg and L. Bivins is greatly appreciated.
References
[/] Kusy, R. P., Macromolecules, Vol. 9, 1976, p. 791.
[2] King, R. W., Broadway, N. J., Mayer, R. A., and Palinchak, S. in Effects of Radiation on
Materials and Components, J. F. Kircher and R. W. Bowan, Eds., Rheinhold, New York,
1964, Chapter 3.
[3] Morgan, J. T. and Stapleton, G. B., "Post Irradiation Mechanical Properties of Radiation
Resistance Cast Epoxy Resin Systems," Report RL-75-136, Science Research Council,
Chilton, England, July 1975.
[4] Brown, G. L., Thomasson, J. F., and Kurland, R. M., National Society for the Advance-
ment of Material and Process Engineering Symposium Exhibition Proceedings, Vol. 24,
No. 2, 1979, pp. 1021-1031.
[J] Haskins, J. F. and Holmes, R. D., "Advanced Composites Design Data for Spacecraft
Structural Applications," AFML-TR-79-4208, Air Force Materials Laboratory, March
1980.
[5] Leung, C. C , Dynes, P. T., and Kaelble, D. H. in Nondestructive Evaluation and Flaw Crit-
icalityfor Composite Materials, ASTM STP 696, American Society for Testing and Mate-
rials, 1979, pp. 298-315.
[7] Massa, D. J., Journal of Applied Physics, Vol. 44, No. 6, 1973, pp. 2595-2600.
[8] Massa, D. J., Flick, J. R., and Petrie, S. E. B., American Chemical Society, Division of
Organic Coatings and Plastics Chemistry, Preprints, Vol. 35, 1975, pp. 371-376.
[9] Kaelble, D. H., "Nondestructive Test for Strength Degradation in Composites, First Year
Report," Contract F33615-74-C-5180, Advanced Research Projects Agency, Arlington,
Va., and Air Force Materials Laboratory, Wright Patterson Air Force Base, Ohio, Sept.
1975, pp. 232-250.
[70] Dynes, P. J. and Kaelble; D. H., Journal of Applied Polymer Science, Vol. 22, 1978, pp.
837-840.
[11] Kenyon, A. S. and Nielson, L. E., Journal of Macromolecular Science, Chemistry, Vol. A3,
No. 2, 1969, pp. 275-295.
[12] Raff, R. A. F. and Subramanian, R. B., Journal of Polymer Science, Vol. 15, 1971, pp.
1535-1537.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
p. Shyprykevich^ and W. Walter^
' Project engineer. Advanced Composites, Grumman Aerospace Corp., Bethpage, N.Y. 11714.
^Technical specialist. Structural Mechanics, Grumman Aerospace Corp., Bethpage, N.Y.
11714.
118
FIBERGLASS/EPOXY
GRIPPERPADt4)
BONDED TO SPECIMEN
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
120 COMPOSITES FOR EXTREME ENVIRONMENTS
were 8-ply, Type I (0/±45/90)., Type II, (0/±45/0)., and 16-ply, Type III,
[(0/±45/90)s]2, and Type IV [(0/±45/0)s]2. Types I and III were used to
monitor static tensile strength. Types II and IV monitored static compressive
strength. The tension specimens were quasi-isotropic laminates which have
been widely used in other generic studies. The compressive specimens were
similar to the tension specimens, except that the 90-deg plies were replaced
by 0-deg plies to induce matrix-type failure in compression.
Hercules AS/3501-5A graphite/epoxy prepreg was the material, and all
panels were made from the same batch. The laminates were cured using a 1 h
hold at 107°C under vacuum plus 585 kPa, followed by 1 h at 177°C under
585 kPa pressure. The laminates were cooled down slowly to minimize micro-
cracking. The panels were then oven postcured for 8 h at 177°C.
The cured panels were ultrasonically and dimensionally inspected. Next,
the panels were sawed into plates sufficiently large to produce 15 to 25 test
specimens and the same number of 5.0 by 2.4 cm associated travelers. These
travelers were cut from the specimens after the fiberglass tabs were bonded
to the specimens. The edges of the specimen (two sides) and travelers (four
sides) were ground to final dimensions. The fabrication process was com-
pleted by drilling holes in both the specimens and travelers, and locally spot-
facing the travelers for accurate thickness measurements. After dimensional
and visual inspection and installation of the boh, each specimen and the as-
sociated traveler were packaged in sealed bags.
Test Procedures
The static tests were performed on a universal testing machine of the
constant-rate-of-head movement type. The test load was applied in accord-
ance with the standard practice of 0.13 cm/min. Strain measurements were
made on a representative number of specimens using two resistance strain
gages adhesively bonded in back-to-back fashion on the faces of the speci-
mens, centered between the tab and the center hole.
The tension tests were performed using the methods currently practiced by
industry and described in the U. S. Air Force Guide for Advanced Compos-
ites. The specimens were gripped and an axial load applied until failure
occurred.
The compressive tests were performed using an Illinois Institute of Tech-
nology Research Institute (IITRI) compression tool modified to accomodate
the 2.54-cm-wide specimens. The fixture incorporates a gripping arrange-
ment similar to (reversed) that used for tension testing, thereby introducing
load from the grip to the specimen by shear rather than by end loading. Buck-
ling was observed by strain gage reading during initial tests of Type II (8-ply)
specimens. Therefore, a Teflon-faced fixture for supporting this specimen
along its edges was designed, fabricated, and used. The unloaded bolt in the
center of the specimen for both 8 and 16-ply specimens was used as a contact
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 121
WET BULB
THEBMISTOB 30 T/C SPECIMENS
INEACHMFR
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
122 COMPOSITES FOR EXTREME ENVIRONMENTS
Moisture Uptake
The test moisture gains are plotted in Figs. 4 and 5 for the temperate and
tropical storage conditions. Figures 4 and 5 also include analytical weight
gain predictions based on "virgin" (constant) material diffusion characteris-
tics. The virgin material predictions were calculated by a finite-difference
formulation of Fickian diffusion equation* with equilibrium moisture con-
EXPOSURE. MONTHS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 123
EXPOSURE, MONTHS
where Z)„ = 11.657. The boundary conditions were daily variations for each
month.' The band in the analytical predictions is the result of the drying ef-
fect of the weekly supersonic flight. The seasonal effect is evident for the
temperate environment. When the analysis was continued beyond the
15-month duration shown in Figs. 4 and 5 the predicted equilibrium mois-
ture contents were 1.17 and 0.52 percent for the tropical and temperate loca-
tions, respectively.
For the tropics (solid symbols in Figs. 4 and 5) the average moisture gains
were much greater than the predicted initial analysis. Furthermore, equilib-
rium moisture level was not reached, even for the 8-ply specimens, making
moisture levels predictions for 20-year aircraft life uncertain. The divergence
of the analysis from the test data occurred quite early, before the end of the
2-month period. The test moisture gains (2.5 to 3.0 percent) after 15 months
of tropical exposure were much greater than the 1.86 percent saturation level
at 100 percent relative humidity assumed for this material system.
For the temperate environment, moisture gains of the specimens are
shown in Figs. 4 and 5 by open symbols. A moisture equilibrium level was
reached at about 1 percent for the 8-ply specimens. This is approximately
double the value that was predicted by analysis. Some of the discrepancy be-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
124 COMPOSITES FOR EXTREME ENVIRONMENTS
tween test and analysis was attributed to the malfunctions of the wet bulb
sensor in the test apparatus. For example, between days 160 and 185 several
exposures to 100 percent relative humidity at temperatures of 10 to 24°C (the
equivalent of rainy days) caused a noticeable increase in moisture absorbed
in the specimens. Two flights were applied during this period, and the re-
sponse of the specimens was affected by this experience. However, the corre-
lation between test and analysis for the temperate environment is much better
than for the tropical environment. The moisture uptake trends between test
and analysis are similar including the effect of seasonal variations of relative
humidity in the exposure cycle, especially noticeable for the 8-ply specimens.
O HT I OPEN TEMPERATE |
a 127 C I SOLID TROPICAL I
• 4 6 8 10 12 14 16 I 4 6 8 10 12 14 16
EXPOSURE TIME. MONTHS EXPOSURE T I M E . MONTHS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 125
STATIC, D R Y , A V E OF 15
HT I OPEN TEMPERATE
127 C I SOLID TROPICAL
« E 400
GROSS
FAILING
STRESS,
MPa
•0 2 4 6 a 10 12 14 16 0 2 4 6 8 10 12 14
EXPOSURE TIME, MONTHS EXPOSURE TIME, MONTHS
FIBERGLASSTABS
T Y P I C A L F A I L U R E MODE
OF TYPE IV SPECIMENS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
126 COMPOSITES FOR EXTREME ENVIRONMENTS
(0, +45, OL
o KH
t
o <P
b-O-J *
03 04 05 08 10 12 16 IS ?0 32 34 36 38 30
MOISTURE CONTENT, % WEIGHT
FIG. 9—Compressive static strength as a function of moisture content, Type 11 specimen, RT.
ilarly, for the tropical environment, the equivalent background relative hu-
midity of 85 percent and flights would result in a moisture content of 1.17
percent.
The effect of real-time exposure with temperature spiking on room
temperature static residual compressive strength also can be deduced from
Figs. 9 and 10. In this case, the real-time data are compared to the precondi-
tioned data (square symbol).
Preconditioning specimens by constant background humidity and tempera-
ture is a simple laboratory method of obtaining desired moisture content
levels in graphite/epoxy laminates. Exposure times can be accelerated by in-
creasing ambient temperature and relative humidity. The specimens here
were preconditioned by two time-sequenced humidity levels at the same con-
c e o , +45, 0) l
00 <W,5
o %
0 0 2 04 0.6 0.8 10 1? \4 16 IB 30 23 34 36 ?8 30
MOISTUHE CONTENT I % W E I G H T I
FIG. 10—Compressive static strength as a function of moisture content. Type JV specimen. RT.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 127
(0, +45, 0 ) ,
prflp-l
04 06 OB 12 10 14 16 1.8 20 22 24 26 2.B
MOISTURE CONTENT, %WEIGHT
C(0. ± « , 0)^32
; 350
4-'
FIG. 12—Compressive static strength as a function of moisture content. Type IV specimen,
nrc.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
128 COMPOSITES FOR EXTREME ENVIRONMENTS
and 30 days for the 1.17 percent target moisture. The length of time at each
humidity level varied with specimen thickness and target moisture.
Figure 9 compares 8-ply static strength results of preconditioned speci-
mens with simulated real-time exposed specimens. It can be seen that at low
moisture levels (0.5 percent) temperature spiking had no effect, but at higher
moisture levels (1.2 percent) spiking reduced residual strength. These results
are reasonable, since spiking does not exceed the Tg at low moisture levels,
and no changes in material properties are expected. For the 16-ply specimens
(Fig. 10), the reduction of strength due to spiking at high moisture contents
is not as apparent as for the 8-ply specimens. This is probably due to the dif-
ferences in failure modes between the 8 and 16-ply specimens.
Compression Tests at 127°C—The. 8-ply 127°C residual strength data are
shown in Fig. 11. The static strength decreases monotonically with moisture
content without an apparent lower strength limit. The four low points be-
tween 2.6 and 2.8 percent moisture content represent the longest exposure
time, 15 months. Thus, it appears that exposure time or number of flights
with consequent Tg exceedances contribute to strength degradation.
Two strength levels are apparent for the 16-ply specimens (Fig. 12). The
two levels represent two distinct failure modes as revealed by examination of
failed specimens. As previously discussed, at low moisture contents with or
without spiking, the specimens failed by compressive crushing; at moisture
contents beyond 1.4 percent, the failure mode is local instability. The cause
of the shift in failure mode could be resin softening caused by moisture con-
tent, exposure time combined with spiking, or a synergistic effect of both.
Increase of moisture beyond 1.4 percent did not decrease further the residual
compressive strength.
By comparing the residual strengths of preconditioned specimens to real-
time specimens at the same moisture contents, the validity of simple acceler-
ated environmental experiments to simulate real-time exposure can be as-
sessed. Figures 11 and 12 show that strengths at low moisture content were
unaffected by whichever means the given moisture level was reached. At an
intermediate moisture content of 1.2 percent the strength of preconditioned
specimens appeared to be lower. This is the opposite of what was observed
for room temperature 8-ply specimens, as shown in Fig. 9. At high moisture
contents, the preconditioning method fails, since these moisture contents
cannot be obtained without temperature spiking and subsequent apparent
modification of the material diffusion and absorptivity characteristics.
It is difficult to separate the effects of moisture content and temperature
spiking on residual compressive strength. It may be possible in the future to
use a physical parameter such as Tg exceedance to characterize the complex
effects of real-time exposure. The number of T, exceedances are not uniform
through the thickness of the specimen; hence, a ply-by-ply strength analysis
will be required. This in itself is not intractable. However, the definition and
effects of Tg exceedances are not yet well characterized.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 129
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
130 COMPOSITES FOR EXTREME ENVIRONMENTS
1
As/A V = C2 ( 1 - +1
B2N + T)
where
Ds = value of diffusivity after A^ exceedances of Tg,
Dv = value of diffusivity before any exceedances of Tg,
B\, B2, C\, C2, = numerical coefficients,
N= number of exceedances of Tg,
As = value of absorption coefficient after A^ exceedances of Tg,
and
/4 V = value of absorption coefficient before any exceedances
ofTg.
The values of 5i, B2, Ci, and C2 were manipulated to try to obtain the best
correlation with accelerated environmental test data shown in Fig. 14. This
test attempted to reproduce the effects of the real-time tropical exposure by
maintaining a background of 85 percent relative humidity whenever the flight
profile, identical to real-time tests, was not applied. The test was performed
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 131
10 20 30 40 50 60 70
N - NUMBER OF EXCEEDANCES OF GLASS TF^ANSITION TEMPE TUHE
FIG. 15—Relationship between thermal spiking and moisture absorptivity for graphite/epoxy.
in the same apparatus as the real-time tests, except that the flight profile was
applied daily during the five-day workweek and the 85 percent relative hu-
midity was maintained by on-ofi' conditioning at a constant 60°C. On-off
conditioning to produce 85 percent relative humidity consisted of turning on
steam for 2 h of a 3-h total cycle. Because of the high background relative
humidity and peak flight temperature (127°C), enough T, exceedances
would occur to duplicate the effects of tropical exposure.
The two main criteria which judged the adequacy of the correlation were
the match of the predicted moisture level with the average test data and the
magnitudes of excursions due to thermal spikes. The test apparatus recorded
temperature and relative humidity histories were used as boundary conditions
for the analytical predictions, except that the peak temperature of the thermal
spike was the average of four specimens' thermocouple readings. The values
of coefficients which gave the best correlation were Bi = Ci = 0, Bi = 0.03,
and Ci = 8.5.
It was not necessary to vary the diffusion coefficient, and only the absorp-
tivity was changed as a result of Tg exceedance. This is somewhat surprising.
The Tg exceedances create microcracks in the matrix and matrix/fiber inter-
face, and one would expect the rate of moisture absorption to change with Tg
exceedance. It should be noted that the chosen values of coefficients are not
unique; a different set of coefficients with nonzero Bi and Ci could provide
an equally good correlation. The functional relationship is shown graphically
in Fig. 15. The correlation between the test data and analysis is excellent for
the 8-ply specimens shown in Fig. 14. For comparison, the analysis with con-
stant absorptivity coefficient also is shown in Fig. 14. As can be seen, the
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
132 COMPOSITES FOR EXTREME ENVIRONMENTS
- TROPICAL EXPOSURE
• TEMPERATE EXPOSURE
FIG. 16—Comparison of predictions and real-time test data for 8-ply specimens.
predictions using that analysis begin to diverge from the test data after about
30 days, and at 60 days have reached a possible equilibrium state not at all
consistent with the test data.
- TROPICAL EXPOSURE
_ _ . - TEMPERATE EXPOSURE
FIG. 17—Comparison of predictions and real-time test data for 16-ply specimens.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
SHYPRYKEVICH AND WOLTER ON AIRCRAFT STORAGE 133
variations: it is drier in the summer than in the winter. Only two exceedances
of Tg were noted by the analytical model, all due to equipment malfunctions.
A more severe test of the analytical model was provided by the tropical lo-
cation real-time test data. The correlation for the 8-ply specimens (Fig. 16) is
quite good. For the 16-ply specimens (Fig. 17) the predicted moisture gains
are lower than the test data. Better tuning of the model could result in better
correlation. However, it is not surprising that a transport model based on
diffusion, even with history-dependent properties, does not correlate per-
fectly since increases in absorptivity may be due to increased surface area
and capillarity. Another source of error is due to the fact that the empirical
coefficients of the model are based on test duration of 60 days and as such
may not be applicable to tests of longer duration. However, the model is
considerably more accurate than predictions based on virgin material moisture
absorption behavior, as shown in Figs. 16 and 17.
Conclusions
Real-time tests simulating a tropical environment with 127°C flight
temperatures, have demonstrated that graphite/epoxy material properties
are degraded beyond what was expected and shown for temperate exposure.
The degradation has been traced to exceedances of Tg and is manifested by
substantial increases in absorptivity of the material and consequent further
reductions in matrix-dependent strength properties.
To account for the increases in the material diffusion/absorption proper-
ties, a semiempirical model was developed based on Fickian moisture trans-
port, whereby the material absorptivity was increased according to the
number of Tg exceedances. Predictions using the adjusted properties matched
test results much better. A more refined analysis, perhaps accounting for the
amount of Tg exceedance, or other factors, is indicated. More work is needed
to understand the mechanisms of moisture transport, but the analysis per-
formed here points to a possible direction for material with Tg exceedance
history.
Exposure to extreme environment (ground storage with weekly supersonic
flight profile) does not reduce fiber-dominated properties, as evidenced by
residual static tensile strength. Static compressive strength is degraded by
such exposure, especially at 127°C. The strength reduction is related directly
to moisture content, irrespective whether the water is held by resin or in micro-
cracks. The largest compressive strength reduction (50 percent from dry
properties) occurred at 127°C, where for the thicker 16-ply specimens, resin
loss of capability for load transfer caused the failure mode to change from
overall laminate compressive failure to local instability.
Preconditioning or other accelerated environmental tests, if they are to be
successful in duplicating real-time extreme environment, must include means
to exceed Tg. The semiempirical Fickian diffusion model described in this
paper would be of great help in planning such experiments.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
134 COMPOSITES FOR EXTREME ENVIRONMENTS
A cknowledgments
The authors wish to acknowledge the support of Grumman's R. Price and
P. Palter for conducting the tests. The authors also would like to thank J. B.
Whiteside for advice and suggestions. This program was funded partially
by Air Force Flight Dynamics Laboratory (AFFDL) Contract No.
F33615-76-C-5234, monitored by E. Demuts, and Advanced Development
Departments' in-house funding.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Moisture Environments
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
R. C. Givler,^ J. W. Gillespie, Jr.,^ andR. B. Pipes^
Environmental Exposure of
Carbon/Epoxy Composite
l\/laterial Systems
' Graduate student, graduate student, and professor, respectively. Department of Mechanical
and Aerospace Engineering, Center for Composite Materials, University of Delaware, Newark,
Del. 19711.
137
(120 weave/3501-6)
(AS/3501-6)
symmetric
(Cb /0/45/-45/0/45/90/-45/0/45/-45/0) c
5
FIG. 1—Laminate stacking sequence.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GIVLER ET AL ON COMPOSITE MATERIAL SYSTEMS 139
KEY
o.
TEMPERATURE
SENSOR
L N , GAS INLET
door; as the door rotates to the dotted configuration (Fig. 2), the specimens
were transported from the heated chamber to the cooling chamber and, as
was the case in the undashed configuration, the chambers are thermal sealed
from one another.
A temperature sensor mounted in the vicinity of the specimens, in con-
junction with a Koenig-Pretempco temperature controller, regulated the
thermal cycle history. When the desired specimen temperature was achieved
in either chamber, the door rotated through an angle of ±90-deg, thus expos-
ing the specimens to the other chamber. In this manner, the laminates auto-
matically were thermally cycled.
Figure 3 illustrates a typical thermal cycling history with an average cy-
cling period of 37 min. The plotted temperature variation is that of the en-
vironment, with a maximum temperature gradient of 0.67°C/s. To deter-
mine the nature of the spatial temperature variation through the thickness of
the laminates, the Biot (Bi) number was calculated. It may be recalled that
the Bi number is the ratio of internal resistance to external resistance of heat
transfer, and its value was found to be
(1)
k
where
h = coefficient of heat transfer,
/ = thickness of the laminate, and
k = thermal conductivity of the laminate.
The implication of Eq 1 assures a uniform temperature distribution through-
out the laminate despite the varying surface temperatures. Thus, changes in
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
140 COMPOSITES FOR EXTREME ENVIRONMENTS
200 -I 1 r 1 — —1 1 1[ - • -f— —1 1 1 r-
190
n n
v
100 -
1 -
I
u
i 90
a
u
a.
Z
u
0
0.67-C/MC i
-90
THERMAL CYCLING
HISTORY
-100 t 1 1 1 1 1 1 1 1 ' • 1 1 1
20 30 4 0 90 60 70 ao 90 100 110 120 130 140 190
TIME , MINUTES
Experimental Program
The experimental program was divided into two segments. The first phase,
described here, was an investigation of the residual composite flexural
strength subsequent to thermal cycling. Five specimens were thermally
cycled for 0, 1, 10, 100, and 1000 cycles, respectively. Upon completion of the
thermal cycling, the specimens were tested in three-point bending to failure
at 177°C. The flexure specimen dimensions were 1.27 by 7.6 cm, while the
nominal 32-ply laminate thickness was 0.40 cm. The loading nose was ap-
plied adjacent to the glass cloth plies of the laminate shown in Fig. 1. Reac-
tion end points for the flexural test fixture were separated by a distance of
5.08 cm, yielding a span-to-depth ratio of 12.7.
Results of the residual flexural response of the cycled laminates are illus-
trated in Fig. 4. Each data point corresponds to the average value from five
tests, and the error bands represent one standard deviation in the experimen-
tal data. For purposes of comparison, the actual uncycled flexural strength
was recorded to be 542 MN/m^. The trend in the data indicates the normal-
izedflexuralstrength increases slightly with thermal cycling. This anomalous
behavior possibly may be explained in terms of the post-curing of the resin
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GIVLER ET AL ON COMPOSITE MATERIAL SYSTEMS 141
I 1
1.25
(>
t
1
• 1
.90
ALL TESTS AT I 7 7 ' C
•
LJOG ( T H E R M A L CYCLES)
ACTUAL STRENGTH
UNCYCUD STRENGTH
phase during thermal cycling with the effect of a slight increase of the glass
transition temperature of the matrix. The presence of transverse cracking (to
be discussed subsequently) offered no degradation in flexural strength, since
the thermal cracks were found only in the 90-deg and 45-deg layers, which
contribute little to laminate flexural strength.
The remaining phase of the experimental program examined the effect of
thermal cycling on compressive strength of the composite laminate. Com-
pression data for the laminate of Fig. 1 was generated via the Illinois Institute
of Technology Research Institute (IITRI) compression test and recorded at
room temperature. Standard specimen dimensions were maintained, which
yielded a gage section of 12.7 by 4.0 mm. All fractures appeared to be com-
pressive in nature as local instabilities in the test section were not observed.
The results of the compressive test may be examined in Fig. 5, where it is
shown that normalized compressive strength was not affected by thermal cy-
cling. Again, each data point of Fig. 5 represents the average value from five
tests, while the error bands signify one standard deviation in the data. It
should be noted that the uncycled strength corresponds to the strength of the
thermally uncycled laminates (653 MN/m^), which have been subjected to
one-half thermal cycle, that of curing the laminate. This strength value was
used for normalization purposes.
Perhaps the most informative observation to be made from this experi-
mental investigation was the presence of transverse cracking in the 90-deg
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
142 COMPOSITES FOR EXTREME ENVIRONMENTS
M } }
.50
NOTE: UNCYCUDSTRENOTHISTHATOF
THE CURED LAMINATE (WHICH
CORRESPONDS TO ONE - H A L F
CYCLE.)
I 2 3
LOG (THERMAL CYCLES)
ACTUAL STRENGTH
UNCYCLEOSTRENSTH
Theoretical Analysis
Laminated plate analysis was employed to predict the stress state within
the composite laminate. Special concern was given to determining correctly
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GIVLER ET AL ON COMPOSITE MATERIAL SYSTEMS 143
the stresses in the 90-deg and adjacent ±45-deg pHes to justify the presence
of transverse cracks in these pHes. The usual notation for a laminated plate
analysis is given in Fig. 8, (which is redrawn from Vinson and Chou^) and
the constitutive relation describing the laminate response is given in Eq 2
(2)
IM] L^IijJLJ
where
Aij = Y.(Qv)k(hk-hk-i) (3fl)
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
144 COMPOSITES FOR EXTREME ENVIRONMENTS
f. 15 -
0 1 2 3 4
Dij=l/3^iQy)k{hk'-hk-i') (3c)
and
Qv = in''[Q][n (4)
Here, f is defined to be the transformation matrix of the stress tensor be-
tween rotated reference frames, while ^* transforms the engineering strain
components accordingly.'
Since the desired temperature excursion was quite large, it is necessary to
include the temperature-dependent material property variation. Moduli vari-
ation (both shear and elongational) were taken as linear functions of
temperature. The specific numerical values for the carbon/epoxy system were
referenced in the Air Force design guide,* while suppliers' data were used for
temperature-dependent properties in the glass weave material system. These
property variations are incorporated into the analysis in the definition of the
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GIVLER ET AL ON COMPOSITE MATERIAL SYSTEMS 145
Ik
z*
- , K , "4
•
1^^^ .-
''o
^' X-<i)- ^<r'^^<P^
®
.^ <S> ^y<^^^
^^^<^
^ ®
ffl yy^
y
FIG. 8—Nomenclature for laminated plate analysis.
(5fl)
(1 — J'12»'2l)
EziiT)
222 (56)
(1 — J'12»'2l)
Qn — ^21 — . (5c)
(1 — I'l2J'2l)
where the coefficient of thermal expansion also has been permitted to vary
linearly with temperature. Owing to this linear temperature variation, Eq 6
may be rewritten simply as
Using Eq 7, one now may predict the stresses that arise from the thermal
excursion of the laminate specimens. The stress-free temperature was taken
to be 177°C so that thermal residual stresses resulted as the temperature de-
creased from this point. Figure 9 shows the variation of thermally induced
stresses in the 90-deg carbon/epoxy ply as predicted by Eq 7. Predicted
stresses have been normalized by the respective intrinsic material strengths,
also taken to vary with temperature.* The stresses superscripted with an aster-
isk denote the improved prediction of the stresses by allowing the coefficient
of thermal expansion to vary with temperature, as in Eq 6. Indeed, Fig. 9
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
146 COMPOSITES FOR EXTREME ENVIRONMENTS
-50 0 50 100
temperature (°C)
FIG. 9—Analytically predicted thermal stresses in the 90-deg carbon/epoxy laminae.
shows the transverse residual stresses to exceed those of the inherent material
strength in the 90-deg carbon/epoxy ply only when a is allowed to vary with
temperature.
Likewise, examining Fig. 10 in a similar manner would lead to the predic-
tion of transverse cracks to appear in the adjacent ±45-deg carbon/epoxy
plies. The stresses in the remaining glass and graphite plies were far below
the ultimate material strengths, and no thermally induced cracks were ob-
served in these plies.
Conclusions
It was found that thermal cycling of the hybrid
[OGL5/O/45/-45/O/45/9O/-45/O/45/-45/O].
laminate produced cracks in the 90-deg and adjacent ±4S-deg laminae. Lam-
inate analysis verified that indeed the thermal stresses induced by thermal
cycling exceeded the intrinsic strength of the 90-deg and adjacent ±45-deg
laminae. An average of 3 cracks per centimetre were observed in the un-
cycled (control) specimens due to curing alone. Crack densities were ob-
served to increase with thermal cycling to a maximum of 26 cracks per cen-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
GIVLER ET AL ON COMPOSITE MATERIAL SYSTEMS 147
50 100
temperature K)
FIG. 10—Analytically predicted thermal stresses in the ±45-deg carbon/epoxy laminae.
timetre subsequent to 1000 thermal cycles. It was expected that the interface
between the glass and carbon plies might be a site for delamination, due to
the gross mismatch of corresponding coefficients of thermal expansion.
However, this was not the case, as no glass/epoxy or carbon/epoxy dis-
bonds were observed subsequent to thermal cycling.
Compressive strength, measured at 21°C, revealed no significant change
after 1000 thermal cycles; thus, it appears thermal cycling has no effect upon
uniaxial compressive strengths for the laminate investigated.
Flexural strength, measured at 177°C, increased 29 percent after 1000
thermal cycles. A conservative argument would state that flexural strength
experienced no degradation due to thermal cycling.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
L. W. Rehfield.^ R. P. Briley.^ and S. Putter^
REFERENCE: Rehfield, L. W., Briley, R. P., and Putter, S., "Dynamic Tests of Graph-
ite/Epoxy Composites in Hygrothermal Environments," Composites for Extreme Envi-
ronments. ASTM STP 768, N. R. Adsit, Ed., American Society for Testing and Mate-
rials, 1982, pp. 148-160.
' Professor and visiting scholar, respectively. School of Aerospace Engineering, Georgia Insti-
tute of Technology, Atlanta, Ga. 30332.
^Senior engineer, McDonnell Douglas Astronautics Co., St. Louis, Mo. 63166.
148
Experimental Approach
Composite Test Specimens
Three composite graphite/epoxy panels of distinct layup have been manu-
factured by McDonnell Douglas Astronautics Co.-St. Louis from Narmco
5208/T300 unidirectional type. The layups are [0], [±45] and [0, -f-45, 90,
—45, 0, -l-45]s. They are each 12-plies thick and symmetric, and will be re-
ferred to as Type A, B, and C, respectively. Types A and B are limiting types
of fundamental interest, while C is representative of practical vehicle skin
panels. An approximate fiber volume fraction of 61.5 percent has been de-
termined by analysis of typical specimens. The specimens used in the earlier
study [7] came from these same panels also.
'The italic numbers in brackets refer to the list of references appended to this paper.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
150 COMPOSITES FOR EXTREME ENVIRONMENTS
Beam specimens were cut from the panels for environmental conditioning
and testing. [90] specimens are obtained from the Type A panel by cutting
normal to the fiber direction; these will be designated Type D specimens.
This type of specimen, added for this study, is also of fundamental interest.
Six specimens of each type were prepared. They are nominally 2.54 cm (1.00
in.) wide by 20.32 cm (8 in.) long. While actual thicknesses have been mea-
sured, a nominal thickness of 0.0137 cm (0.0054 in.) per ply has been used
throughout to analyze the test data; this value is based upon manufacturing
experience at the St. Louis McDonnell Douglas facility. Thickness mea-
surements performed also confirm this as a reasonable value.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
REHFIELD ET AL ON DYNAMIC TESTS OF GRAPHITE/EPOXY 151
Testing Technique
The vibration testing technique has been dictated by the need for simplic-
ity, repeatability and preservation of the environmental conditions. In order
to preserve the environmental states achieved for the composites by condi-
tioning in the water bath to the maximum extent, the excitation technique se-
lected for vibration testing is a transient one. The advantage obtained is a
short duration test. The beams are mounted in cantilever fashion in a fix-
ture with prescribed tip deflection. The tip suddenly is released, producing
transient response of the specimen that is dominated by the fundamental
mode of vibration. The fixture with a mounted beam specimen is shown in
Fig. 1. Response is sensed by an accelerometer mounted near the specimen
tip. A schematic of the experimental setup for the tests appears in Fig. 2.
The accelerometer signal is filtered through a low pass filter to minimize
the higher mode frequency content. The data are processed by means of a
Fourier analyzer. The analog to digital conversion capability of the analyzer
is all that is utilized. The low pass filter also serves to minimize aliasing er-
rors in the analog to digital conversion process. The digitized accelerometer
output is printed out, and the fundamental frequency and corresponding
damping coefficient determined by simple analyses. Frequency is determined
simply by counting the number of peak values contained in a suitably chosen
time interval. Values for the damping coefficient are obtained by the loga-
rithmic decay method.
Each test of an individual specimen in each environmental condition has
been repeated. This results in 12 data values (2 tests on each of 6 specimens)
for each environmental condition and for each of the 4 specimen types.
The large number of data values corresponding to each type of specimen
and environmental condition have been obtained to minimize the effects of
two factors. One is the variability found in even the highest quality compos-
ite material; it exceeds that of conventional "homogeneous" materials such
as metals. The second factor is associated with the difficulty of achieving
consistent clamping conditions in each of the tests. Elapsed time savings and
simplicity are achieved with cantilever tests; these advantages are believed to
outweigh the uncertainties associated with such things as uniform clamping
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
152 COMPOSITES FOR EXTREME ENVIRONMENTS
pressures and swelling strains. All these factors are dealt with in a practical
manner by repetition.
The prescribed initial tip deflections correspond to maximum strains at
the beams' fixed ends which are far less than the ultimate strains for the
material. For specimen Types A andC, a tip deflection of 0.34 cm (0.134 in.)
has been imposed. A value of 0.41 cm (0.161 in.) is applied to specimen
Types B and D. These selections insure that no damage results from the vi-
bration tests themselves. This is verified indirectly by repeatability of the test
results.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
REHFIELD ET AL ON DYNAMIC TESTS OF GRAPHITE/EPOXY 153
ACCELEROMETER
SPECIMEN
—I Ji.
FOURIER
PRINTER
ANALYZER
FIG. 2—Schematic diagram of the experimental setup for the vibration tests.
^-^Nf-7)^f-ferik (1)
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
154 COMPOSITES FOR EXTREME ENVIRONMENTS
L is the cantilever beam length, / i s the second moment of the cross sectional
area, m is the mass per unit length of the beam, and/i is the measured fun-
damental frequency in cycles per second. M, is an effective concentrated tip
mass that includes the effects of the accelerometer and accelerometer cable;
/, is the corresponding mass moment of inertia of the effective concentrated
tip mass about the beam neutral axis. The above equation is derived from a
Rayleigh quotient calculation for a simple cantilever beam with a tip mass.
The approximate vibration mode shape used is
A" is a coordinate measured from the fixed end of the beam. Damping is re-
ported as values for the damping coefficient as a percentage of the critical
values.
The values presented in Tables 1 and 2 are the means of 12 independent
experimentally determined values. Below each entry in parenthesis is the cor-
responding standard deviation expressed as a percent of the mean. This is a
convenient and concise way of presenting the experimental results.
Experimental Results
Table 1 contains the mean values of E/ calculated from measured mass,
geometric and fundamental frequency data for the specimens. Type A spec-
imens show a slight progressive increase in stiffness due to hygrothermal
conditioning; flexural response of these specimens is fiber controlled, so no
significant degradation was expected. Static data presented for AS/3501-5
graphite/epoxy from tension tests in the fiber direction [3,4] reflect a similar
slight increase in stiffness with hygrothermal conditioning. Type B and D
specimens show a decrease in stiffness with increased hygrothermal condi-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
REHFIELD ET AL ON DYNAMIC TESTS OF GRAPHITE/EPOXY 155
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
156 COMPOSITES FOR EXTREME ENVIRONMENTS
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
REHFIELD ET AL ON DYNAMIC TESTS OF GRAPHITE/EPOXY 157
<
O
K
UJ
D _
Q lij
li
O cc
o o
t- u.
z o
u z
o —
o
z
a.
s
<
TIP DEFLECTION/THICKNESS
deflections are used to establish the entries in Table 3. Cable damping has
been found to be insensitive to environmental conditions.
The damping coefficient for a specimen, ^s, is determined by adjusting the
measured damping coefficient, [,M, according to the following equation
CS^CM-{CA + CC) (4)
CA is obtained from Eq 3, Cc from Table 3, and average values of {M from
Table 2. Average specimen damping coefficients obtained in this manner are
presented in Table 4. This is a more useful form for the data.
A 54 0.227
B 25 0.193
C 44 0.265
D 27 0.176
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
158 COMPOSITES FOR EXTREME ENVIRONMENTS
CLEAN CONFIGURATION
0,3
_1_
0 02 0.4 0.6
_!_
0.8 10
TIP DEFLECTION/THICKNESS
FIG. 4—Damping tests on a Type B composite specimen in dry air at 25°C {77°F).
Remarks on Damping
Air and cable damping contributions are large. The former must be toler-
ated in environmental tests. The latter is present because the reliability and
suitability of transient response determination by accelerometer was desired.
Their magnitude tends to overshadow the intrinsic specimen damping in
fiber controlled modes of response for Type A and C specimens. The ad-
justed values of damping coefficient, therefore, should be viewed in this
light.
Some observations on the results in Table 4 deserve mention. First, except
for the 25°C (77°F), wet Type D specimen value, at the same temperature,
damping increases with moisture saturation for all specimen types.
Secondly, all specimen types show an immediate increase in damping with
hygrothermal conditioning. A reversal of trend occurs for Type B, C, and D
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
REHFIELD ET AL ON DYNAMIC TESTS OF GRAPHITE/EPOXY 159
Concluding Remarks
Considerable attention has been given to test conditions and testing tech-
nique. Since environmental effects are determined, vibration testing in a vac-
uum chamber could not be used. Damping contributions due to air and in-
strumentation wiring had to be evaluated in supplementary tests in order to
correct the experimental data obtained in the hot, moist environments.
The experimental results, after correction for the parasitic damping con-
tributions, produced no startling, unexpected findings. Matrix controlled
modes of response are the most affected by hygrothermal conditioning, and
stiffness reduction is likely to be the problem of most practical concern.
Since air and cable damping contributions are large, the adjustment
procedure, although rational, is not fully satisfactory. In particular. Type A
and C specimen adjusted damping coefficient values appear to be generally
higher than expected in the hot, moist cases. In connection with the current
experiments in progress to study frequency effects, specific attention will be
given to improving the means for determining damping. In particular, the
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
160 COMPOSITES FOR EXTREME ENVIRONMENTS
A cknowledgments
This work was sponsored by the U. S. Air Force Office of Scientific Re-
search under Grant AFOSR-73-2479 and Contract No. F49620-78-C-0085.
The composite test specimens were provided by the McDonnell Douglas
Corp.
References
[1] Maymon, G., Briley, R. P., and Rehfield, L. W. in Advanced Composite Materials—Envi-
ronmental Effects, ASTM STP 658, American Society for Testing and Materials, 1978, pp.
221-233.
[2] Briley, R. P., "Effects of Environmental Conditions on the Dynamic Behavior of Resin
Matrix Composites," Ph.D. thesis, Georgia Institute of Technology, Atlanta, Ga., 1981.
[3] Verette, R. M. and Labor, J. D., "Structural Criteria for Advanced Composites,"
AFFDL-TR-76-142, Vol. 1, Air Force Flight Dynamics Laboratory, Wright-Patterson
Air Force Base, Ohio, 1976.
[4] Browning, C. E., Husman, G. E., and Whitney, J. M. in Composite Materials: Testing and
Design (Fourth Conference), ASTM STP 617, American Society for Testing and Materials,
1977, pp. 481-496.
[5] Walter, G. A., "Special Problem Report for AE 8500," Georgia Institute of Technology,
Atlanta, Ga., 1976.
[6] Dugundji, J. in Proceedings of the Sixth Annual Mechanics of Composites Review, M.
Knight, Ed., AFWAL-TR-81-4001, Air Force Wright Aeronautical Laboratories, Wright-
Patterson Air Force Base, Ohio, 1981, pp. 70-73.
[7] Baker, W. E., Woolam, W. E., and Young, D., InternationalJournal of Mechanical Sci-
ences, Vol. 9, 1967, pp. 743-766.
[8] Lazan, B. J. in Structural Damping, J. E. Ruzicka, Ed., American Society of Mechanical
Engineers, New York, 1959, pp. 1-34.
[9] Lazan, B. J., Damping of Materials and Members in Structural Mechanics, Pergamon Press,
Elmsford, N. Y., 1968.
[/O] Kibler, K. G., "Time-Dependent Environmental Behavior of Graphite/Epoxy Compos-
ites," AFWAL-TR-80-4052, Air Force Wright Aeronautical Laboratories, Wright-Patter-
son Air Force Base, Ohio, 1980.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
L. L. Clements and P. R. Lee
' Research scientist. Advanced Research and Applications Corp., Sunnyvale, Calif. 94086.
Current affiliation: associate professor. Materials Engineering Department, San Jose State Uni-
versity, San Jose, Calif. 95192.
^Foothill/DeAnza Community College District in cooperation with NASA-Ames Research
Center, Moffett Field, Calif. 94035. Current affiliation: Chemical Systems Division, United
Technologies, Sunnyvale, Calif. 94086.
161
Physical properties
Filaments/fiber bundle 3000
Twist none
Filament density* 1.73 Mg/m'
Filament equivalent diameter* 6.9 urn
Mechanical properties
Minimum tensile strength 2660 MPa (385 ksi)
Average tensile modulus 200 to 240 GPa (32 to 35 msi)
Minimum average strain to failure 1.1%
"Dale Black, NARMCO Materials, Inc., Costa Mesa, Calif., June 1979,
'Not part of specification. Taken from Union Carbide Corporation product literature.
Experimental Procedure
Materials
The "T300/5208" graphite/epoxy composite was fabricated from prepreg
tape manufactured by NARMCO Materials, Inc., from Union Carbide Cor-
poration's Thornel 300 graphite fiber, and NARMCO's 5208 epoxy resin.
Table 1 gives the physical and mechanical properties of the WYP-30-1/0
(zero twist) grade of Thornel 300 fiber used in the prepreg. The NARMCO
5208 epoxy resin is one of several commercial epoxies based on the
TGDDM-DDS system, that is, the main constituents are tetraglycidyl 4,4'-
diaminodiphenyl methane epoxy (such as Ciba Geigy MY-720) cured with
4,4'-diaminodiphenyl sulfone (such as Ciba Geigy Eporal). The 5208 system
contains about 90 parts per hundred (pph) by weight of TGDDM, about 24
pph DDS, and about 10 pph of glycidyl ether of a bisphenol-A novolac
epoxy (Celanese SU-8).'
Specimen Fabrication
The specimens used in this study were fabricated for NASA-Ames by an
outside vendor. Large (approximately 1 m^) panels of the suitable lamination
sequence were prepared from one of two different batches of 0.3-m-wide
prepreg tape. These panels were cured in an autoclave held for 1/2 h at
' May, C. A., "Exploratory Development of Chemical Quality Assurance and Composition of
Epoxy Formulations," Technical Report AFML-TR-76-112, Air Force Materials Laboratory,
Dayton, Ohio, 1976.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CLEMENTS AND LEE ON QUALITY CONTROL VARIABLES 163
135°C and then 2 h at 180°C, under 700 kPa pressure. The average volume
percent fiber from these panels was determined to be 64.6 percent, with a
range of 64.3 to 64.8 percent. Next, vendor-fabricated tabs made from 0/90-
deg fiber glass fabric and epoxy resin were bonded to the panels. The tab ad-
hesive used for the panels made from prepreg Batch A was FM-143 adhesive
by 3M, cured for 1 h at 125°C and 50 psig. For the panels made from prepreg
Batch B, an unknown but reportedly comparable adhesive was used. Speci-
mens then were cut from the panels using a dry carborundum cut-off wheel.
The nominal configuration of these specimens was 12.7 mm wide, 1.2 mm
thick, with a gage length of 127 mm, and 60-mm-long fiber glass tabs.
The as-received specimens were found to suffer from numerous fabrica-
tion defects. Two problems were particularly troubling: extensive torn fibers
stuck out from the cut sides, and numerous edge delaminations extended
into the cut sides of specimens; and the composite itself, or the composite
plus the tabs, tended to be bowed. Because of our concern over these defects
and because of reproducibility problems in our preliminary results, most of
the specimens used in this study were subjected to extensive screening and
rework. This procedure involved screening the specimens and rejecting any
specimens that exhibited obvious bow or other irreparable defects. The spec-
imens were then reworked by wet-polishing sufficient material off both cut
sides to remove all detectable (at X30) torn or delaminated material. This
screening and rework procedure was done to bring all specimens up to the
quality outlined in the ASTM Test for Tensile Properties of Fiber-Resin
Composites (D 3039-76). The resulting width of these polished-edge speci-
mens ranged from 10 to 12 mm. The properties of unpolished = edge spec-
imens were also investigated. These specimens were screened for bow and for
edge defects. Only specimens without visually obvious edge delaminations
were retained.
In order to answer questions about the possible influence of degree of cure
upon 0-deg properties, some of the specimens were given a postcure of 2 h at
200°C, followed by a slow oven cool.
Environmental Conditioning
As-received specimens contained 0.15 to 0.45 percent moisture. Specimens
destined for mechanical testing were first dried in a vacuum desiccator at
100°C for 7 days, then held for at least 2 days under vacuum at room
temperature. Weight gain/loss studies (on dummy specimens, without tabs,
yet taken from the same panels) confirmed that this was sufficient time to en-
sure complete moisture removal from the specimens. Specimens to be tested
in the "dry" condition were left in a room-temperature vacuum desiccator
until being tested at the appropriate temperature and <5 percent relative
humidity. All specimens to be tested in the "wet" condition were placed,
after drying, in an environmental chamber at 60°C and approximately 100
percent relative humidity for at least 60 days. This process produced essen-
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
164 COMPOSITES FOR EXTREME ENVIRONMENTS
Mechanical Testing
Tension tests to failure were performed inside an environmental chamber
using a 10 000-kg-capacity servo-hydraulic mechanical testing machine. The
tensile grips were mounted to an alignment device consisting of a three-post
ball-bearing die set. This alignment device was mounted in turn to the hy-
draulic actuator and, through a universal joint, to the load cell and load
frame. Longitudinal strain was measured using an axial strain-gage exten-
someter; for many of the tests, transverse strain also was measured using a
diametral extensometer.
All tests were done at a constant elongation rate which resulted in an ac-
tual strain rate of 3 X 10"'i"'. Time to failure (at about 1 percent strain) was
approximately 5-1/2 min.
Experimental Matrix
The experimental conditions studied were as follows.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CLEMENTS AND LEE ON QUALITY CONTROL VARIABLES 165
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
166 COMPOSITES FOR EXTREME ENVIRONMENTS
100*«n—<*j f*—
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CLEMENTS AND LEE ON QUALITY CONTROL VARIABLES 167
(121 t ^ i ^
(6)T •
(17)
(ll)I^
(12) M1°
IITTJ
- • a -0% MOISTURE-
• o -2% MOISTURE
1 1 1 1
FIG. 2—Axial elastic modulus, Bu as a function of temperature at two different axial strains,
en, levels and moisture contents for Batch A specimens. {Error bar shows 95 percent confidence lim-
its. Numbers in parentheses are numbers of specimens.)
the phenomenon is that curved filaments in the composite straighten with in-
creased strain so that more filaments carry the applied load/ Another possi-
ble explanation is that there may be a strain-induced improvement in orien-
tation of the covalently bonded carbon platelets within the individual
filaments.'
Other findings on the behavior of f u were as follows.
In this case, the mean of the Batch A specimens is greater than that of Batch
B at the 95 percent confidence level.
3. There is a statistically significant temperature-induced increase in En
for dry specimens only. (See Fig. 2.) Since the axial thermal-expansion coef-
ficient of the fiber is negative (that is, the fiber contracts axially with in-
creased temperature), the increase in En is not surprising. However, it is not
clear why no such effect is seen for wet specimens.
4. There may be an effect of moisture upon £11, but such an effect is not
systematic. At 25°C and 0.1 percent strain, the mean £11 for the wet speci-
'Sendeckyj, G. P., Richardson, M. D., and Pappas, J. E. in Composite Reliability. ASTMSTP
580, American Society for Testing and Materials, 1976, pp. 528-546.
' M . K. Towne, Union Carbide Corp., Cleveland, Ohio, private communication, Oct. 1979.
^"N = number of specimens entering into statistics.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
168 COMPOSITES FOR EXTREME ENVIRONMENTS
mens is higher than that for the dry specimens to better than 95 percent con-
fidence. However, at 96°C and a strain of 0.5 percent, the mean £ii for the
wet specimens is lower than that for the dry specimens to better than 99 per-
cent confidence.
Determination of the major Poisson's ratio, v\2, was difficult since the di-
ametral extensometer slipped under many conditions. It was not possible to
get any good data on wet specimens, but the data obtained indicate no influ-
ence of any of the other variables upon vn- In particular, there appears to be
no influence of strain upon vn. The mean value of vn was 0.33 ± 0.01
{N= 14).
A very important finding of this study was the magnitude of the influence
of specimen quality upon 0-deg strength. Figure 3 compares 0-deg strength
as a function of temperature for polished-edge and unpolished-edge Batch A
specimens. As can be seen, the strength is significantly increased by the im-
proved specimen quality resulting from polished edges. It is also interesting
to compare these results with strengths of specimens previously rejected as
having irreparable defects:
0-deg Strength
The 0-deg strength of the good unpolished edge is no better than that of the
reject specimens. This finding confirms that the specimen preparation
procedure outlined in ASTM Method D 3039-76 is not overly conservative in
this case.
From Fig. 3, it also is seen that edge polishing produced a change in
strength behavior as a function of temperature. The 0-deg tensile strength of
dry polished-edge specimens increased significantly with an increase in
1800
• D -0% MOISTURE
• O -2% MOISTURE
FIG. 3—0-deg tensile strength as a function of temperature for polished-edge and unpolished-
edge Batch A specimens at two moisture contents.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CLEMENTS AND LEE ON QUALITY CONTROL VARIABLES 169
temperature, whereas the small increase in mean strength for dry unpolished-
edge specimens is not statistically significant. Moisture content, on the other
hand, had no statistically significant effect upon strength for Batch A speci-
mens whether they were edge polished or not. Unfortunately, we were unable
to get reliable strength data at 96°C wet because of end-tab failures. This was
because the additional moisture content we produced using the reverse
thermal effect, when combined with elevated temperature, caused tab failure
to occur before composite failure. (For Batch A specimens, the tabs them-
selves failed prior to composite failure, but for Batch B specimens, the tab
adhesive failed at very low loads.) Thus, our observations on the effect of
moisture content on strength are valid only at 25°C.
These findings are somewhat in disagreement with those of Lifshitz.'* Lif-
shitz studied unpolished-edge specimens and reported an effect of moisture
content on strength at both 25 and 96''C. Lifshitz's specimens, however, were
conditioned at 60°C and —100 percent relative humidity only. We suspect
that the additional moisture content we induced using the reverse thermal ef-
fect produced a degradation that cancelled any strength increase resulting
from nominally wet conditions alone. Lifshitz also reported a statistically
significant increase in strength with temperature for his unpolished-edge
specimens. However, his data compared only "room" and "wet" (without
reverse thermal effect) moisture conditions, whereas ours compares dry spec-
imens only.
Figure 4 illustrates the effect of prepreg batch upon 0-deg strength. The
mean strength at 25°C for wet Batch B specimens is less than that for dry
Batch B specimens at the 90 percent confidence level (but not at the 95 per-
cent confidence level). Far more clearly significant is the difference in
strength between Batch A and Batch B specimens at 96°C. As can be seen
from Fig. 4, the Batch B specimens are much weaker at this temperature. As
we have explained, we unfortunately were unable to fail the composite itself
at 96°C wet.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
170 COMPOSITES FOR EXTREME ENVIRONMENTS
£ 1600
S
• a -0% MOISTURE
• O - 2 % MOISTURE
60
T, C
FIG. 4—0-deg tensile strength as a function of temperature for polished-edge Batch A and Batch
B specimens at two moisture contents.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
CLEMENTS AND LEE ON QUALITY CONTROL VARIABLES 171
Conclusions
Our results demonstrate that the tensile properties of T300/5208 graph-
ite/epoxy composites are affected by various quality-control variables. Per-
haps the most important finding is the large effect of specimen quality
(preexisting torn fibers and edge delaminations, even if they are not easily
detectable) on strength. Another important finding is that strength and its
variation with temperature and moisture content can be influenced by pre-
preg batch-to-batch variations. These findings lead us to make three points
about studies of mechanical properties of graphite/epoxy. First of all, the
importance of careful specimen preparation technique cannot be overem-
phasized. The procedure outlined in ASTM Method D 3039-76 often is com-
promised in practice, but it is clear from our work that such a rigorous
procedure is justified. Second, the influence of preexisting flaws upon prop-
erties should be an integral part of any study of composite properties. And
third, the influence of such quality-control variables should be established,
or the variable itself carefully controlled, in any composite destined for ac-
tual service exposure.
Acknowledgment
Work for this project was performed at NASA-Ames Research Center,
Materials Science and Applications Office, Moffett Field, Calif., under Con-
tract NAS2-9989.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Summary
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
STP768-EB/Apr. 1982
Summary
The two most important findings at this conference were not what the
experimenters set out to prove. Shyprykevich and Wolter found that the ac-
celerated tests used to predict real time behavior of graphite/epoxy compos-
ites understated the effects. Meanwhile, Clements found what we already ex-
pected—that the quality of material and its preparation can have a larger
effect on the end properties than the deliberate exposures to harsh environ-
ments. The conclusion one would draw from this is that more studies of the
real life exposures are needed and that all investigators must take great care
in preparation of specimens and accurately report their test conditions.
The papers in this book have been divided into three sections. The first
deals with polyimide matrix composites, while the second and third sections
are concerned with epoxy matrix composites. Government restrictions pre-
vented the presentation of any work on metal matrix composites, even
though they are useful at some of the extreme conditions.
The polyimide matrix is useful at elevated temperatures up to 316°C
(600°F), while epoxies generally are useful to only half that temperature. The
results obtained by Serafini and Hanson clearly show that PMR-15 has a
useful life at the elevated temperature of up to 1000 h. The second paper, by
McKague, shows that a second class of polyimides is available. This class of
materials is more workable by people experienced with epoxies. The proper-
ties are superior to those of the epoxy composite at intermediate tempera-
tures [177°C (350°F)]. This makes them attractive for application on high
performance aircraft.
Kunz found that the more graphitic fibers (high modulus, lower strength)
were more stable in the polyimide resin composites. This confirms the find-
ing of Serafini and Hanson that the quality of the laminate (voids) had an ef-
fect on the susceptibility of the laminate to oxidation. The attempts to mea-
sure thermal conductivity and thermal expansion by Campbell and Burleigh
also were handicapped by the quality of the laminate.
The mechanical properties of similar polyimide matrix composites were
measured by Garber, Morris, and Everett. They found that the laminate
strength and modulus of fiber-dominated composites were not strong func-
tions of temperature in the range —157 to 316°C. The matrix-dominated
175
A^. R. Adsit
General Dynamics/Convair Division, San
Diego, Calif. 92138; symposium chairman
and editor.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
STP768-EB/Apr. 1982
Index
Failure, 85
Fatigue, 107
Absorbed moisture, 19
Fiber-matrix adhesion, 42
Adhesive, 163
Fickian diffusion, 129, 133
Aircraft, 118-134, 161
Filament wound composite, 95-109
AS carbon fibers, 120, 138, 154
Flaw, 85, 171
Autoclave, 29
Flexure properties, 8, 10,38, 52, 141,
147
B Fortafil fiber, 34
Beams {See Sandwich beams) Fracture, 43, 74, 87
M
Fabrication of composites, 6, 22, 36, Mechanical properties, 11, 24, 96,
119, 162 148
177
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Copyright' 1982 b y A S T M International www.astm.org
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
178 COMPOSITES FOR EXTREME ENVIRONMENTS
O
Tensile properties, 26, 74, 76, 86,
Outgassing, 106
124, 133, 168, 170
Oxidation resistance, 40, 52
Tg, 15,21,33,36, 115, 119, 129, 133,
141, 159
Thermal aging, 23
Photomicrograph, 11 Conductivity, 56, 60, 71, 105
PMR-15 polyimide, 6-19, 33, 55, 71, Cycle, 138-147
74,91 Degradation, 40
Poisson's ratio, 77, 168 Expansion, 59, 63, 71, 137, 145
Gravimetric analysis (TGA), 162
Isolate, 96, 102, 109
Spike, 8-19, 23-32, 126, 129, 131
Quality control, 161-171
Stress, 138, 146
Thermomechanical properties, 25, 33-
R
53
Radiative degradation, 111 Thermooxidative exposure, 6
Real time, 119, 124, 132 Stability, 10, 40, 42
Relative humidity, 150 Thermophysical, 54-72, 96
Residual stress, 137, 145 Thick laminate processing, 27
Resin Transverse cracking, 141, 146
934, 112 T 300 carbon fibers, 8-19, 22, 112,
3501, 120, 138, 154 149, 162
5208, 149, 162
U
Unnotched specimens, 74
Sandwich beam, 150-160 Strength, 90
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
INDEX 179
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.
Copyright by ASTM Int'l (all rights reserved); Tue Jan 17 20:03:14 EST 2012
Downloaded/printed by
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorized.