A blend composed of an ethynyl terminated aspartimide (brittle component) and an ethynyl terminated arylene ether oligomer (tough component) was thermally cured to yield a resin which underwent preliminary evaluation to determine the potential for use in structural applications on aerospace vehicles. The blend exhibited good compression moldability, allowing for fabrication of neat moldings, adhesive specimens and composites at temperatures of 250 C under a pressure of 1.4 MPa (200 psi). Neat resin moldings and adhesive specimens provided relatively high mechanical properties. Composite specimens provided promising results in spite of fiber misalignment, fiber washout, and a small amount of panel warpage

Connell, John W.

Hergenrother, Paul M.

English

NASA Technical Reports Server

N93-$0842
PRELIMINARY PROPERTIES OF A RESIN FROM ETHYNYL TERMINATED MATERIALS
Paul M. Hergenrother and John W. Connell
Materials Division
NASA Langley Research Center
Hampton, VA
SUMMARY
A blend composed of an ethynyl terminated aspartimide (brittle component) and an ethynyl
terminated arylene ether oligomer (tough component) was thermally cured to yield a resin which underwent
preliminary evaluation to determine the potential for use in structural applications on aerospace vehicles.
The blend exhibited good compression moldability, allowing for the fabrication of neat resin moldings,
adhesive specimens and composites at temperatures of 250°C under a pressure of [ 1.4 MPa (200 psi)].
Neat resin moldings and adhesive specimens provided relatively high mechanical properties. Composite
specimens provided promising results in spite of fiber misalignment, fiber washout and a small amount of
panel warpage.
INTRODUCTION
As part of a NASA program to develop technology on high performance/high temperature structural
resins, particularly composite matrices, the chemistry and properties of blends of ethynyl (acetylenic)
terminated materials are under investigation (ref. 1-6). Specifically, low molecular weight diethynyl
compounds such as ethynyl terminated aspartimides (ETA), are mixed with ethynyl terminated arylene ether
oligomers (ETAE) of different molecular weights. The number average molecular weights (Mn) ranged
from 3000 to 12,000 g/mole. The ETA served as the brittle thermosetting component while the ETAE was
the tough linear component.
Various blends have been prepared and subsequently thermally cured under different conditions to
deter,nine the effect of composition and crosslink density on final resin properties. The objective was to
obtain materials with good compression moldability and cured neat resins and composites with a favorable
combination of mechanical properties at temperatures as high as 177°C. The work reported herein concerns
the chemistry and the mechanical and physical properties of one of these blends.
EXPERIMENTAL
Ethynyl Terminated Aspartimide
The ethynyl temlinated aspartimide was prepared from the reaction of N,N-bismaleimido-4,4,'-
diphenyhnethane and 3-ethynylaniline as previously reported (ref. 1). The aspartimide was obtained in the
form of a tan solid as a mixture of d, 1 and meso stereoisomers, mp 104-110°C.
Ethynyl Terminated Arylene Ether Oligomer
The ethynyl terminated arylene ether oligomers was prepared following a known procedure (ref. 2)
by reacting 4,4'-dichlorobenzophenone with a calculated excess of 9,9-bis(4-hydroxyphenyl)fluorene to
afford a hydroxy terminated oligomer with Mn of - 8000 g/mole. The hydroxy terminated oligomer was
subsequently end-capped with 4-ethynylbenzoyl chloride. The ETAE oligomer had an inherent viscosity of
0.29 dL/g and initial glass transition (Tg) of 238°C. The 300°C cured resin exhibited a Tg of 248°C.
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Blend
The blend was prepared by dissolving an equal weight of each component in 1,4-dioxane to yield
clear solutions. To isolate the blend, the solution was added to water in a high speed blender. The solid
was collected, washed with water and stage-dried to 100°C under vacuum. These powders were used to
prepare moldings and films. The blend had an initial Tg of 140°C and the cured resin exhibited a Tg of
245°C, fracture toughness (KIc) of [1.57 MPa m 1/2 (1425 psi in 1/2)] and a coefficient of thermal expansion
(23 to 200°C) of 36.8 ppm/°C.
Films
Thin films [approximately 0.127 mm (5 mils thick)] of the blend were prepared by melt pressing
powders of the blend at [6.7 to 10.3 MPa (1 to 1.5 Ksi)] for 0.5 h at 250°C. The film specimens [5.1 cm x
0.63 cm x 0.013 cm (2 in x 0.25 in x 0.005 in)] were bent back upon themselves to place the rounded
portion under stress and immersed in hydraulic fluid (Chevron Hyjet IV) for 24 h and in chloroform for 1 h
to determine sensitivity towards these solvents.
Molded Specimens
Powdered blend was compression-molded by heating to 200 ° and then 250°C, each for 0.5 h under
[1.4 MPa (200 psi)] in a stainless steel mold. Miniature compact tension specimens [1.6 cm x 1.6 cmx
0.95 cm thick (0.62 in x 0.62 in x 0.375 in thick)] were machined from the moldings and subsequently
tested to determine fracture toughness (KIc, critical stress intensity factor) according to ASTM E399 using
four specimens per test.
Flat moldings [7.6 cmx 7.6 cm x 0.18 cm (3.0 in x 3.0 in x 0.070 in)] were prepared by
compression-molding the powdered blend using the conditions described above. Dogbone specimens [6.35
cmx 0.92 cm x 0.18 cm (2.5 in x 0.375 x 0.070 in)] were machined from the moldings and subsequently
tested to determine neat resin tensile properties according to ASTM D638 using four specimens per test.
Adhesive Specimens
Adhesive tape was prepared by multiple coating of 112-E glass (A-1100 finish) with a 1,4-dioxane
solution (- 30% solids content) of the blend and subsequently stage dried to 100°C for 1 h after each coat.
The final volatile contents of the tapes were less than 1%. Standard adhesive specimens [bond area 2.54 cm
(1.00 in) wide x 1.27 cm (0.5 in) overlap)] using titanium (Ti, 6A1-4V) adherends with a Pasa Jell 107
(Products Research and Chemical Corp., Semco Div.) surface treatment were fabricated using conditions
similar to those described for the molded specimens. The Ti adherends were initially primed with a dilute
1,4-dioxane solution (- 5% solid content) of the blend and subsequently dried at 100°C for 1 h. Tensile
shear specimens were tested according to ASTM D 1002 using four specimens per test condition.
Composite Specimens
Prepreg was prepared by using a 25% solid solution of the blend in 1,4-dioxane to coat unsized AS-
4 (12K tow) carbon/graphite fiber on a drum winding machine. The solutions had Brookfield viscosities of
- 400 centipoise at 23°C. After drying the prepreg to a final temperature of 100°C for 1 hour, the volatile
content was - 1% (determined by heating a weighed piece of prepreg for 1 hour at 300°C). Unidirectional
and cross-ply laminates were fabricated in a stainless steel mold by heating to 200°C and then 250°C for 0.5
hour each under [1.4 MPa (200 psi)]. In some cases the panels were postcured by heating at 250°C for 2
hours under [1.4 MPa (200 psi)]. After ultrasonic scanning to detect voids, the panels were cut into
specimens and tested for various properties according to ASTM procedures. Fracture energy was
determined by testing double cantilever beam specimens according to a previously reported method (ref. 7).
Tensile, flexural and short beam shear properties were determined according to ASTM D-3518, D-790, and
D-2344 respectively.
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Radiation Exposure
Electron beam radiation exposure was performed on composite and neat resin test specimens. The
specimens were exposed to 1 MeV electrons using a Radiation Dynamics, Inc., Dynamitron Model 1000/10
accelerator. The samples were mounted side by side on a temperature-controlled aluminum plate positioned
in the uniform area of the electron beam. The absorbed dose and dose rate were calculated from current flux
levels monitored with a Faraday cup mounted in the exposure area of the aluminum plate. The Faraday cup
was calibrated through the use of National Bureau of Standards calibrated polymeric dosimeter films. The
exposure chamber operated at a pressure of 2 x 10 -7 torr and the temperature of the specimens did not
exceed 40°C. The materials received doses of 5.5 x 108 rads and 1.0 x 109 rads at a dose rate of 5 x 107
rads/h without interruption. After exposure the specimens were stored in a desiccator until tested.
Other Characterization
Differential Scanning Calorimetry (DSC) was performed at a heating rate of 20°C/min with the Tg
taken at the inflection point of the AT versus temperature curve after heating the sample to 300°C and
quenching. Coefficient of thermal expansion (CTE) measurements were performed on a DuPont 9900
Computer/Fhermal Analyzer at a heating rate of 5°C/min over the temperature range of 25-200°C using an
expansion probe.
RESULTS AND DISCUSSION
Although a number of different ETAs have been reported (ref. 1), the ETA in figure 1 was selected
for this study because of the following factors. It is easy to synthesize and it exhibited a favorable
combination of highly desirable processing properties such as low and broad melting range, low melt
viscosity, and a wide range between the melting and curing temperatures. In addition, it cures to provide a
material with relatively high solvent resistance and tensile modulus.
The ETAE was selected from a variety of candidates on the basis of compatibility with the ETA and
providing a cured material with a relatively high Tg: The blend was readily prepared by dissolving an equal
quantity of each component in 1,4-dioxane. A port_on of the solution was poured into water to precipitate a
solid for characterization and neat resin molding studies. The remaining solution was used to prepare
adhesive tape and prepreg.
The initial neat resin properties of the cured blend and those after exposure to various conditions are
presented in table 1. The initial properties after a 0.5 hr cure at 250°C under [ 1.4 MPa (200 psi)} are
respectable and suggest that this material should perform well as a composite matrix. The room temperature
tensile properties were essentially unchanged after processing for 2 hr at 250°C. The tensile modulus of 3.6
GPa should be adequate to support the composite reinforcement filaments under compressive loading,
thereby inhibiting microbuckling of the fibers. Upon exposure, the Tgand tensile modulus increased with a
decrease in the elongation. This is due to further cure that resulted inhigher crosslink density.
The Ti to Ti tensile shear strengths are given in table 2. The initial strengths at 23 and 150°C are
relatively good whereas the initial 177°C value was low, presumably due to inadequate cure. After aging
specimens for 650 hr at 200°C in air, further cure occurred that is reflected in a lower 23°C strength and a
significantly higher 177°C value. In essence, after exposure for 650 hr at 200°C in air, the 23, 150 and
177°C values are essentially the same (within the scatter normally obtained for tensile shear specimens).
Small flat composites were fabricated from solution-coated drum-wound prepreg using unsized AS-
4 fiber. No work was conducted to optimize prepreg preparation or composite processing conditions. The
initial laminates exhibited problems frequently associated with the use of drum-wound prepreg. These
include fiber misalignment, non-uniform resin content and areas of poor fiber wetting. In addition, the
cured composites exhibited fiber washout and a small amount of warpage. Further work will be performed
in an attempt to correct these problems. The preliminary laminate properties are presented in table 3. In
421
spite of the quality of the laminates, promising mechanical properties were obtained. The retention of
flexural strength and modulus at 150 and 177°C after a cure for 2 hr at 250°C under [1.4 MPa (2(X) psi)] is
particularly noteworthy. It appears that a 2 hr cure at 250°C is necessary to develop useable properties at
177°C. In addition, fracture energy of [438 J/m 2 (2.5 in lb/in2)] is an acceptable value.
CONCLUSIONS
A blend of an ethynyl containing aspartimide and an ethynyl terminated arylene ether oligomer (Mn N
8000 g/tool) was prepared, characterized and evaluated as a composite matrix. The material performed well
despite problems associated with prepreg quality. Further efforts will be expended to overcome these
shortcomings.
REFERENCES
1. P.M. Hergenrother, S. J. Havens and J. W. Connell, Polym. Prepr. 27(2), 408 (1986)
2. J.W. Connell, R. G. Bass and P. M. Hergenrother, Sci. Adv. Matl. Proc. Eng. Series 33, 251
(1988)
3. J.W. Connell and P. M. Hergenrother, Intl. SAMPE Tech. Conf. Series 21, 1029 (1989)
4. J.W. Connell, P. M. Hergenrother and S. J. Havens High Perf. Polym. J. 1(2), 119 (1989)
5. P.M. Hergenrother, J. W. Connell and S. J. Havens U.S. Pat. 4,889,912 (1989) to NASA
6. J.W. Connell, R. G. Bass and P. M. Hergenrother U.S. Pat. 4,861,882 (1989) to NASA
7. J.M. Whitney, C. E. Browning and W. J. Hoogsteden, Reinf. Plast. Composites, 1, 297 (1982)
o o
II _CH2_ i]
0 0
Ethynyl Terminated Aspartimide (ETA)
O o
C-O 0 0 0 O-C
HC _-C C =CH
Ethynyl Terminated Arylene Ether Oligomer (ETAE Mn~ 8000 g/mol, n = ~15)
Figure 1. Chemical structure of blend components.
422
Prope W
Tg, °C
Tensile St., MPa (Ksi)
Tensile Mod., GPa (Ksi)
Elong. (break), %
KIc, MPa m 1/2(psi in 1/'2)
GIc, Jim 2 (in lb/in 2)
Coef. Therm. Expansion,
ppm/°C
0.5 hr @ 250°C/200 psi
245
93.1 (13.5)
3.6 (525)
2.6
1.57 (1425)
675 (3.8)
36.8
Table 1 - Neat Resin Propcrties
Cure and/or Exposure Conditions
0.5 hr @ 250°C_00 psi
650 hr @ 200°C. air
254
95.8 (13.9)
0.5 hr @ 250oC/200 psi
1 X 109 Rads (electron beam
exposure)
254
76.5 (11.1)
2 hr @ 250°C/200 psi
249
89.0 (12.9)
3.9 (569)
2.4
34.7
3.9 (571)
2.0
3.55 (515.5)
2.6
Table 2 - Ti to Ti Tensile Shear Strengths
Test Condition
23°C
23°C after 650 hr @ 200°C, air
150°C
150°C after 650 hr@ 200°C, air
177°C
177°C after 650 hr @ 200°C, air
Strength, MPa (psi) [failure mode]
22.8 (3300) (cohesive)
17.9 (2600) (mixed)
17.2 (2500) (cohesive)
20.5 (2975) (mixed)
8.3 (1200) (thermoplastic)
18.6 (2700) (mixed)
423
_ooerrv
Tensile St., MPa (Ksi)
Tensile Mod., GPa (Msi)
Tensile Strain, %
Hexural St., MPa (Ksi)
Hexural Mod., GPa (Msi)
Hexural St., MPa (Ksi)
Hexural Mod., GPa (Msi)
Flexural St., MPa (Ksi)
Hexural Mod., GPa (Msi)
Hexural St., MPa (Ksi)
Flexural Mod., GPa (Msi)
Hexural St., MPa (Ksi)
Flexural Mod., GPa (Msi)
Short Beam Shear St., MPa (Ksi)
Fracture Energy (Glc), J/m 2
(in lb/in 2)
Table 3 - Preliminary Unidirectional Larrunate Properties
Cure and Exposure
Conditions Resin Content, % 23
2 hr @ 250°C/1.4 MPa 35 1917 (278)
121 (17.6)
1.33
0.5 hr@ 250°C/1.4 MPa 36 1613 (234)
106 (15.4)
0.5hr@250°C/1.4MPa 36 1530 (222)
650hr@200°C, air 99.3 (14.4)
0.5 hr@250°C/1.4MPa 36 1661 (241)
1X 109 rads 108 (15.6)
2 hr@250°C/1.4MPa 33 1517 (220)
104 (15.1)
2 hr@250°C/1.4MPa 33 1483 (215)
500hr@200°C, air
102.7 (14.9)
0.5 hr@250°C/1.4MPa 38 74.5 (10.8)
2 hr @ 250°C/1.4 MPa 36 438 (2.5)
Test Temperature, °C
15___Q 17.__5.7
1737 (252)
139 (2O.2)
1.21
683 (99)
60.0 (8.7) --
1323 (192) 1214 (176)
104 (15.1) 89.6 (13.0)
1131 (164)
90.3 (13.1)
1462 (212) 1359 (197)
100 (14.5) 97.2 (14.1)
1290 (187) 1124 (163)
97.2 (14.1) 90.3 (13.1)
32.4 (4.7) 29.0 (4.2)
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Preliminary properties of a resin from ethynyl terminated materials

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