Mechanical properties of polymer matrix composites at 77 K and at room temperature after irradiation with 6Co 7-rays

S. Egusa and M. Hagiwara

Japan Atomic Energy Research Institute, Takasaki Radiation Chemistry Research Establishment, Takasaki-shi, Gunma 370-12, Japan

Received 27 March 1986

Ten different polymer matrix composites were irradiated with 6Co y-rays at room temperature, and were examined with regard to the mechanical properties at 77 K and at room temperature. The radiation-induced degradation of these composites is observed much more significantly in the ultimate strength and in the shear modulus than in the Young's modulus. The radiation resistance of these composites depends primarily on the radiation resistance of matrix resins, which increases in the order diglycidyl ether of bisphenol A < tetraglycidyl diaminodiphenyl methane < Kerimid 601. Comparison of the mechanical properties tested at 77 K and at room temperature demonstrates that the extent of radiationinduced decrease in the composite strength is appreciably greater in the 77 K test than in the room temperature test. Interpretation of these results is based on the competition between the two opposing effects due to the hardness and brittleness of matrix resins.

Keywords: mechanical properties; polymers; irradiation

Polymer matrix composites are anticipated to be used as mechanical supporters and as electrical and thermal insulators in the construction of superconducting magnets for fusion reactors ~,2. This is because these organic materials are superior to inorganic materials in terms of cost and processing~. The use of polymer matrix composites, however, may be restricted by the radiation resistance of these materials. From this point of view, several studies have been reported on the mechanical and electrical properties of polymer matrix composites irradiated at low temperatures. Coltman and Klabunde irradiated epoxy and polyimide matrix composites at 4.9 K and performed the mechanical tests at 77 or 300 K4,s. Takamura and Kato irradiated samples at 5 K and carried out the mechanical tests at 4.2 or 77 K without warm-up to room temperature~. Hurley et al. 7, Weber et al. 8, and Yamaoka et al. 9 made fast-neutron irradiations of composites at low temperatures of 5-77 IC All of these studies are very useful as sources of design data for fusion magnets. At present, however, it is unknown to what extent the temperature during irradiation influences the extent of radiation damage in composites. It is also unknown to what extent the temperature during mechanical tests influences the observable decrease in the composite strength after irradiation. The elucidation of these problems will be very useful for furthering the fundamental understanding of the degradation behaviour of polymer matrix composites to be used in fusion magnets. In the present work, mechanical testing of l0 different polymer matrix composites was carried out at 77 K and at room temperature after irradiation with nCo
0011-2275/86/070417-06 $03.00 1986 Butterworth ~ Co (Publishers) Ltd.

y-rays at room temperature. This study revealed that the extent of radiation-induced decrease in the composite strength is appreciably greater in the 77 K test than in the room temperature test. The present Paper mainly describes the dose dependence of the mechanical properties such as Young's modulus, shear modulus and ultimate strength. Possible mechanisms for the enhanced extent of composite degradation in the 77 K test are also presented. A later Paper will describe the influence of irradiation temperature (5 K and room temperature) on the extent of radiation damage in composites ~.

Experimental
Materials The 10 different polymer matrix composites studied in the present work are shown in Table 1. The glass/epoxy [(I) and (II)], carbon/epoxy, glass/polyimide, and carbon/ polyimide composites were prepared by Sumitomo Bakelite Co., Ltd (Japan). The alumina/epoxy composite was especially prepared by Sumitomo Kagaku Co., Ltd (Japan). The matrix resin in the glass/epoxy (I), carbon/ epoxy, and alumina/epoxy composites is Sumiepoxy ELM-434 (tetraglycidyl diaminodiphenyl methane, T G D D M ) cured with diamino diphenyl sulphone (DDS), and the matrix resin in the glass/epoxy (II) composite is Epikote 1001 (diglycidyl ether of bisphenol A, DGEBA) cured with diamino diphenyl methane (DDM). The matrix resin in the glass/polyim~de and carbon/polyimide composites is polyaminobismaleimide (Kerimid 601). The reinforcing fillers used in these composites are E-glass fibre cloth (Kanebo KS-1210) treated with

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Polymer matrix composites: S. Egusa and M. Hagiwara

Table 1
Polymer matrix composites studied Reinforcing fillera E-glass clothb E-glass clothb E-glass clothc E-glass clothc Carbon cloth d Alumina fibree E-glass clothb E-glass cloth c S-2 glass clothf Carbon cloth d Matrix resing (60) TGDDM/DDS (55) DGEBA/DDM (50) DGEBA/DICY (52) DGEBA/DDS (56) TGDDM/DDS (55) TGDDM/DDS (62) Kerimid 601 (58) Kerimid 601 (60) Kerimid 601 (62) Kerimid 601

Composite Glass/epoxy (I) Glass/epoxy (11) G-10CR G-11CR Carbon/epoxy Alumina/epoxy Glass/pelyimide Spaulrad Spaulrad S Carbon/polyimide

cross-head speed of 0.6 m m m i n - ' . The load was applied in the direction normal to the laminate planes of the specimen.
Results

E-glass fibre composites

The Young's (tensile) and shear moduli were determined by performing the three-point bend test at span lengths 0f 60, 40 and 20 m m for each specimen, and by solving the simultaneous equations which were derived from 1.5 ~

aValues in parentheses indicate the volume fraction of fibres (%) bplain woven E-glass fabric having 5 3 / 4 8 yarns per 25 mm in the warp/fill direction. Each yarn is composed of ~ 2 0 0 fibres having a diameter of 7.36 p.m Cplain woven E-glass fabric having 4 2 / 3 2 yarns per 25.4 mm in the warp/fill direction dplain woven carbon fabric having 22.5 yarns per 25 mm in both directions. Each yarn is composed of ~,1000 fibres having a diameter of 8 p,m ~Uniaxial alumina fibre having a diameter of 9 #m fSatin woven S-2 glass fabric -I-GDDM=tetraglycidyl diaminodiphenyl methane; DGEBA= diglycidyl ether of bisphenol A; DDS=diamino diphenyl sulphone; DDM=diamino diphenyl methane; DICY---dicyanodiamide

/' =

0.3(qh) ] e bC

(1)

where: A is the deflection; P is the applied load; 1 is the span length; b is the specimen width; h ~is the specimen depth (thickness); E is the Young's modtllus; and G is the shear modulus. The complete details of the procedure are described elsewhere ~6. The ultimate strength of the composite was calculated from ~s

oc. = 3ef(l/h)12bh

(2)

where trcu is the ultimate strength andPf is the applied load at failure.

T-glycidoxypropyltrimethoxysilane, carbon fibre cloth (Torayca No. 6142) treated with an epoxy sizing agent, and Sumitomo's uniaxial alumina fibre with no surface treatment". Further details of these fillers are given in

40
Q.
L~
~

I
O"

I
0

35
0 -0-0-0

Table 1. The G-10CR, G-11CR, Spaulrad, and Spaulrad S composites were obtained from Spaulding Fibre Company, Inc. (USA). The matrix resin in G-10CR is a solid D G E B A epoxy cured with dicyanodiamide, and the matrix resin in G-11CR is a liquid DGEBA epoxy cured with DDS 'z. For both of these composites, the reinforcing filler is E-glass fibre cloth treated with T-aminopropyltriethoxysilane. The matrix resin in the Spaulrad and Spaulrad S composites is Kerimid 601. The reinforcing filler used in Spaulrad is E-glass fibre cloth, while the filler used in Spaulrad S is S-2 glass fibre cloth. The 1.6-3.2 m m thick laminate sheets of these ten types of composites were cut in the warp direction, thus obtaining rectangular specimens of dimensions 6.4 m m z 70 m m x (1.6-3.2) mm. Irradiations and mechanical tests
6Co T-ray irradiations were made in air at ambient temperature with an exposure rate of 2.0 106 roentgen h-L The exposure rate was determined by using a cobalt glass dosimeter ~3. The absorbed dose in matrix resin of a composite was calculated by using conversion factors of 0.00933 and 0,00922 Gy roentgen-' for the epoxy and polyimide matrix composites, respectively. These conversion factors were evaluated from 0.0087 times the ratio of the n u m b e r of electrons per gram in the matrix resin and in air". The mechanical properties were examined by performing three point bend tests for the warp direction of reinforcing fabrics. The bend rig was specially constructed so that the tests could be made at the span lengths of 60, 40 and 20 mm, at liquid nitrogen temperature as well as at room temperature. The radius of the loading and support noses was 3 mm. This bend rig was used with a mechanical test machine, Shimadzu Servopulser Model EHF-UC5-10L. All measurements were conducted at a

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10 2 0 3 0 4 0 5 0 6 0 7 0
Absorbed Dose

B090100
(HGy}

Figure 1 Plot of Young's modulus v e r s u s absorbed dose in the matrix for the E-glass fibre composites tested at (a) room temperature and (b) 77 K. O, TGDDM/DDS; e , polyimide; D, G-11CR; I , DGEBA/DDM; ~ , G-IOCR. (Only the matrix resin is indicated to designate the composite, except for G-IOCR and G-11CR)

418

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Polymer matrix composites: S. Egusa and M. Hagiwara

The Young's modulus measured at room temperature and at 77 K is plotted in Figures la and b, respectively, as a function of absorbed dose in the matrix. The Young's modulus for each unirradiated specimen is seen not to differ strikingly among the five types of E-glass fibre composites in both the room temperature and 77 K tests. Comparison of the room temperature and 77 K data points, on the other hand, reveals that the Young's modulus at 77 K is ~ 18% higher than that at room temperature for all the unirradiated specimens shown in Figure 1. Following irradiation the Young's modulus measured at room temperature (Figure la) is observed to scarcely decrease up to I00 M G y for all the composites except G-10CR. The Young's modulus measured at 77 K (Figure lb), on the other hand, is seen to decrease significantly with increasing dose for the G-10C1L G - I 1 C R and glass/epoxy ( D G E B A / D D M ) composites. For the glass/epoxy ( T G D D M / D D S ) and glass/polyimide composites, however, such a decrease in the Young's modulus is quite small or practically nil within the dose range covered in the present work. The shear modulus measured at room temperature and at 77 K is plotted in Figures 2a and b, respectively, as a function of absorbed dose in the matrix. AlthoughFigure2 shows some data scatter, it is seen that the shear modulus at 77 K is = 3 times higher than that at room temperature for all the Unirradiated specimens except the polyimide 4"0~1
/

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. . .

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....

20

....

30

40

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Absorbed

60 70 80 Dose (HGy)

90

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.~..=E__.,r . . . . . . . ~

Figure 3 Plot of ultimate strength v e r s u s absorbed dose in the matrix for the E-glass fibre composites tested at (a) room temperature and (b) 77 K. Key to symbols as for Figure 1. (Only the matrix resin is indicated to designate the composite, except for G-IOCR and G-11CR)

,~ ~.o0.5 - (a)

I
0

n
10

I
20

~
go

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100

30 40 50 60 70 80 Absorbed Dose (MGy)

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20

30 40 50 60 70 80 Absorbed Dose (MGy)

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Figure 2 Plot of shear modulus v e r s u s absorbed dose in the matrix for the E-glass fibre composites tested at (a) room temperature and (b) 77 K. Key to symbols as for Figure I. (Only the matrix resin is indicated to designate the composite, except for G-10CR and G-11CR)

matrix composite. Following irradiation the shear modulus measured at room temperature (Figure 2a) appears to increase at first and then decreases with increasing dose for the G-11CR and glass/epoxy (DGEBAJDDM) composites, suggesting the possibility of cross-linking reactions taking place in the matrix resin at low doses. For the glass/epoxy ( T G D D M / D D S ) and glass/polyimide composites, an incubation dose is observed before the shear modulus begins to decrease. The shear modulus for G-10CR seems to decrease monotonously with dose. The shear modulus measured at 77 K (Figure 2b), in contrast, is seen to decrease monotonously with increasing dose for all the composites. The ultimate strength measured at room temperature and 77 K is plotted in Figures 3a andb, respectively, as a function of absorbed dose in the matrix. Each data point indicates the average value of three failure tests made at the span length of 20 ram, and the error bar shows the standard deviation. A missing error bar means that the deviation is too small to be shown. The ultimate strength for unirradiated specimens is seen to be the lowest for the glass/polyimide composite and the highest for the glass/ epoxy ( T G D D M / D D S ) composite in both the room temperature and 77 K tests. Comparison of the room temperature and 77 K data points, however, shows that the ultimate strength at 77 K is ~ 2 times higher than at room temperature for all the unirradiated specimens shown in Figure 3. Following irradiation the ultimate strength

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Polymer matrix composites: S. Egusa and M. Hagiwara

measured at room temperature (Figure 3a) decreases monotonously with increasing dose for G-10CR and G-11CR, while for the glass/epoxy (TGDDM/DDS, DGEBA/DDM) composites the ultimate strength begins to decrease only after an incubation dose of 10-20 MGy. For the glass/polyimide composite, even an increase in the ultimate strength is observed in the dose range up to 50 MGy. The ultimate strength measured at 77 K (Figure 3b), however, is seen to decrease monotonously with increasing dose for all the composites except the glass/ epoxy (DGEBA/DDM) composite. For this epoxy composite, an incubation dose of ~ 10 MGy is observed before the ultimate strength begins to decrease. The radiation resistance of these composites is seen to increase in the order G-10CR < glass/epoxy (DGEBA/DDM) ~ G - I 1 C R < glass/epoxy (TGDDM/DDS) < glass/ polyimide composites in both the 77 K and room temperature tests (Figure 3). This order of radiation resistance holds also for the Young's and shear moduli ( see Figures I and2), no matter what the temperature of the mechanical test. 2400 2000 ~O B 0
,,oo -

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~o
"...........

cO
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12OOlooo 800 I 400 200 0/I

I I I

i
--ii----.___tl__ .__n__~ {~I I 1 [ I I

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60 80 100 t20 140 160 IBO Absorbed Dose (MGy) Figure 5 Plot of ultimate strength versusabsorbed dose in the matrix for the TGDDM/DDS epoxy matrix composites tested st 77 K. O, Alumina/epoxy; ~, glass/epoxy; II, carbon/epoxy 120011 -~ ! t00 ~-o I I I I I I I I I

20

40

Alumina, carbon and S-2 glass fibre composites

The Young's modulus measured at 77 K is plotted in

.,o00
900
,~

Figure 4 as a function of absorbed dose in the matrix for

the alumina/epoxy, carbon/epoxy, carbon/polyimide, Spaulrad and Spaulrad S composites. The Young's modulus is seen to be much higher for the alumina/epoxy composite compared with the other composites. This result is most likely ascribed to a difference in the form of reinforcing fillers, i.e. the uniaxial form of alumina fibres and the woven fabric form of the other fibres. Following irradiation the Young's modulus of these composites is seen to remain unchanged even after irradiation up to 180 MGy. The ultimate strength of these composites measured at 77 K is plotted as a function of absorbed dose in the matrix inFigures 5 and6.Figure5 includes also the plot for the glass/epoxy (TGDDM/DDS) composite for comparison. The ultimate strength ofunirradiated specimens in Figure 5 is seen to be strikingly high for the alumina/ epoxy composite, but comparatively low for the carbon/ epoxy composite. The strikingly high strength of the alumina/epoxy composite may be ascribed to the same
120

i,
_

""" ....---.

a00
700

soo

"'

500

.....
o .... :5 .... o----_ -

~, 400 300 S 200

100 0

I 0

I 20

I 40

I I I I I 60 80 100 t20 140 Ahsor'bed Dose [MGy)

I t60

I t80

Figure 6 Plot of ultimate strength v e r s u s absorbed dose in the matrix for the polyimide matrix composites tested at 77 K. r-I, Spaulrad S; O, Spaulred; ~ , carbon/polyimide

110 100 - o - -
-90 80 0

"~

~= 70 60 -~--nn--m--m--nm~m ",Z.. 0 = 50 " ...... o .... ~ ~' 40

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factor as described above for the Young's modulus of this composite. Following irradiation the ultimate strength is seen to decrease monotonously with increasing dose at almost the same rate for the alumina/epoxy and glass/ epoxy composites. For the carbon/epoxy composite, however, the dose dependence of the strength is quite different from that for the alumina or glass fibre composite. The ultimate strength begins to decrease only after an incubation dose of ~ 60 MGy, and levels off at doses of 100 MGy or above. For the carbon/polyimide, Spaulrad and Spaulrad S composites, Figure 6 indicates that the ultimate strength of unirradiated specimens does not differ strikingly among these composites. Following irradiation the ultimate strength is seen to decrease monotonously with increasing dose at almost the same rate for these polyimide matrix composites.
Discussion

20

40

60

80

Absorbed

iO0 120 i4O t60 180 Dose (MGy)

Radiation resistance of polymer matrix composites

The comparison of mechanical properties shown in

Figure 4 Plot of Young's modulus v e r s u s absorbed dose in the matrix for the alumina, carbon, S-2 glass and E-glass fibre composites tested at 77 K. The epoxy resin in the alumina and carbon fibre composites is TGDDM/DDS. O, Alumina/epoxy; II, carbon/epoxy; <~, carbon/polyimide; O, Spaulrad; r-i, Spaulrad S

Figures 1-3 for irradiated composites demonstrates that

the ultimate strength and the shear modulus are much more sensitive to radiation than the Young's modulus in both the room temperature and 77 K tests. When these

420

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Polymer matrix composites: S. Egusa and M. Hagiwara

composites are irradiated, the radiation damage in the matrix resin as well as at the fibre-matrix interface will contribute to a decrease in the capacity of load transfer from the matrix to the fibre ~7, thus degrading the mechanical properties of composites. This will be the case particularly for the ultimate strength and the shear modulus because these properties are much more dependent on the properties of the matrix resin and the fibre-matrix interface than the Young's modulus is. When the type and content of reinforcing fillers are about the same, therefore, a difference in the radiation resistance of composites will be attributable mainly to a difference in the radiation resistance of the matrix resin and the fibrematrix interface. The dose dependence of the ultimate strength (Figure 3) or the shear modulus (Figure 2) demonstrates clearly that the radiation resistance of these composites increases in the order of G - 10CR < glass/epoxy (DGEBA/ DDM) ~ G-11CR < glass/epoxy (TGDDM/DDS) < glass/ polyimide composites. This result appears to be attributable mainly to a difference in the radiation resistance of matrix resins, because for all of these composites the reinforcing filler is E-glass fibre cloth with a comparable volume fraction of fibres (see Table 1). In a comparison between the G-10CR and G-11CR composites, therefore, it is concluded that a liquid DGEBA epoxy cured with DDS in G-11CR is more radiation resistant than a solid D G E B A epoxy cured with dicyanodiamide in G-10CR. Similarly, in a comparison among the glass/epoxy (DGEBA/DDM), glass/epoxy (TGDDM/DDS), and glass/polyimide composites, it is concluded that the radiation resistance of the matrix resin increases in the order D G E B A / D D M < T G D D M / D D S < polyimide. At the present stage, it is unknown to what extent the type of silane coupling agents or sizing agents for reinforcing fillers influences the radiation resistance of the composite. So far as the composites studied here are concerned, it seems reasonable to speculate that the influence of such agents is not so significant compared with that of matrix resins. This speculation is supported by the similarity of the dose dependence of ultimate strength between the glass/epoxy and alumina/epoxy composites shown in Figure 5. The matrix resins are the same type of T G D D M / D D S epoxy for both of these composites, but the surface treatment of reinforcing fillers is not the same. The above speculation is supported also by the similarity of the dose dependence of ultimate strength among the Spaulrad, Spaulrad S, and carbon/ polyimide composites shown inFigure 6. The matrix resins are all Kerimid 601 for these composites, but the reinforcing fillers are different from one another. These findings strongly suggest that the radiation resistance of polymer matrix composites is virtually determined by the type of matrix resin rather than the surface treatment of reinforcing fillers. These considerations and the dose dependence of composite strength shown in Figures 3, 4 and5 lead to a conclusion that the radiation resistance of matrix resins increases in the order DGEBA type epoxy < T G D D M type epoxy < Kerimid 601, no matter what type of hardener is involved. The comparatively low initial strength of the carbon/epoxy composite at 77 K (Figure 5) may be associated with a high state of internal shear stress in the composite. Such a stress will be generated at the fibrematrix interface during the cool-down to 77 K by a difference in the thermal expansion between the fibre and the matrix. The carbon fibres are, in fact, known to expand in the fibre digection while the epoxy resins contract on cooling TM.In the mechanical test at low temperatures, this stress is added to that generated by the applied load, thus decreasing the measured value of composite strength. However,the levelling off in the ultimate strength at doses of I> 100 MGy (Figure 5) may be associated with the load transfer capacity due to the friction shear stresses at the fibre-matrix interfacelL The contribution of the friction force mode to the total capacity of load transfer is known to be significant when the reinforcing filler is carbon fibres ~9. The friction force mode is considered to be much less sensitive to radiation compared with the chemical bond mode.

Temperature dependence of composite degradation

The initial strength of E-glass fibre composites was found to increase by a factor of ~2 on cooling from room temperature to 77 K (Figure 3). This result can not be explained by the mechanical properties of E-glass fibres alone, because the increase in the strength of E-glass fibres is merely 40% on cooling from room temperature to 77 K2. According to the composite fracture behaviour described by the statistical accumulation of fib re fracture, the composite strength increases with a decrease in the ineffective fibre length, which is defined as the length at the broken fibre end over which the reinforcing effect is assumed to be absent2L The concept of the ineffective length is required even though the fibres may initially have been continuous. An expression for the ineffective length [see Equation (2.18) in Reference 21] indicates that this length increases in proportion to (Ef/Gm) 1/2, where Ef is the Young's modulus of the fibres and G m is the shear modulus of the matrix resins. If, therefore, the increase rate in hardness of the matrix resins on cooling is greater than that of reinforcing fillers, the resulting decrease in the Ef/G m ratio will lead to an increase in the composite strength. This idea appears to explain, at least partly, why the initial strength of E-glass fibre composites increases by a factor of ~ 2 on cooling to 77 K (Figure 3). The hardness of epoxy resin is, in fact, reported to increase by a factor o f ~ 3 on cooling from room temperature to 77 K2~. As to the dose dependence of composite strength, comparison of the room temperature and 77 K test data shown in Figures 1-3 reveals that the radiation-induced degradation is observed more appreciably with tests at 77 K than at room temperature. This tendency is seen most clearly for the ultimate strength shown in Figure 3. For the glass/epoxy (TGDDM/DDS) composite, for instance, the ultimate strength begins to decrease from the beginning of irradiation in the 77 K test, whereas in the room temperature test the strength begins to decrease only after an incubation dose of ~ 20 MGy. For the glass/polyimide composite, the ultimate strength decreases monotonously with increasing dose in the 77 K test, whereas in the room temperature test even an increase in the strength is observed in the dose range up to 50 MGy. For the other composites shown in Figure 3 also, it is seen that the extent of the composite degradation is appreciably greater in the 77 K test than in the room temperature test. All of these phenomena appear to be related to a decrease in toughness or an increase in brittleness of matrix resins on cooling to cryogenic temperatures. As pointed out by Kasen TM, such a decrease in toughness increases the notch sensitivity of matrix resins, thus causing the composites to become very sensitive to the presence of small flaws. As a result, this effect due to

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Polymer matrix composites: S. Egusa and M. Hagiwara

matrix brittleness tends to lower the composite strength at low temperatures, in contrast to the effect due to matrix hardness which tends to increase the composite strength at low temperatures. Then it is considered that the actual strength of polymer matrix composites is determined by the competition between the two opposing effects of matrix resins. For composites before irradiation, the effect due to matrix hardness will predominate at low temperatures, thus increasing the composite strength on cooling from room temperature to 77 K. For composites after irradiation, however, the main-chain scission reaction in matrix resins destroys the network structure of highly cross-linked polymers, and hence the effect due to matrix brittleness may become predominant at low temperatures, thus lowering the composite strength on cooling from room temperature to 77 K. When the mechanical test is performed at room temperature, therefore, the composite strength will be comparatively low before irradiation, and the decrease after irradiation will be relatively small, thus giving only a small drop in the composite strength after irradiation. When the test is made at low temperatures, the composite strength before irradiation is increased by the effect due to matrix hardness, while the decrease after irradiation is enhanced by the effect due to matrix brittleness, thus giving a large drop in the composite strength after irradiation. These considerations are, in fact, compatible with the experimental result that the extent of the radiation-induced decrease in the composite strength is appreciably greater in the 77 K test than in the room temperature test (Figure 3). opposing effects due to the hardness and brittleness of matrix resins.

Acknowledgements
The authors wish to express their appreciation to Dr J.R. Benzinger of Spaulding Fibre Company, Inc. for providing the G-10CR, G-11CR, Spaulrad and Spaulrad S composites, and to the staffof Sumitomo Kagaku Co., Ltd for preparing the alumina/epoxy composite. Thanks are also due to Dr C.E. Kabunde of Oak Ridge National Laboratory for valuable advice and suggestions on this work.

References
1 Brown, B.S. JNucl Mater (1981) 97 1 2 Abdou, M.A. JNucl Mater (1978) 72 147 3 Hay, R.D. and Rapperport, E.J. Oak Ridge National Laboratory Report ORNL/TM-2643 (1976) 4 Coltman, R.R., Jr and Kiabunde, C.E. JNuclMater (1981) 103 and 104 717 5 Coltman, R.R., Jr and Klabunde, C.E. J Nucl Mater (1983) 113 268 6 Takamura, S. and Kato, T. J Nucl Mater (1981) 103 and 104 729 and Adv Cryo Eng Mater (1984) 30 41 7 Hurley, G.F., Fowler, J.D. and Rohr, D.L Cryogenics (1983) 23 415 8 Weber, H.W., Kubasta, E., Steiner, W., Benz, H. and Nylund, K. J Nucl Mater (1983) 115 11 9 Yalnaoka, H., Miyata, K., Nakayama, Y. and Yoshida, H. in: Nonmetallic Materials and Composites at Low Temperatures Vol 3 (Eds Hartwig, G. and Evance, D.) Plenum Press, New York, USA. in press 10 Egusa, S., Kirk, M.A. and Birtcher, R.C.JNucl Mater submitted for publication 11 Abe, Y., Horikiri, S., Fujilnura, K., and lchiki, E. in: Progress in Science andEngineering of Composites (Eds Hayashi, T., Kawata, K. and Umekawa, S.) ICCM-IV, Tokyo, Japan (1982) 1427 12 Benzinger, J.R. Adv Cryog Eng Mater (1982) 28 231 13 Tanaka, R. and N akamura, Y. Radioisotopes (1.975) 24 I I 14 Spinks, J.W.T. and Woods, R.J. in: An Introduction to Radiation Chemistry John Wiley & Sons, New York, USA (1976) Ch 3 15 Zweben, C., Smith, W.S. and Wardle, M.W. in: Composite Materials." Testing and Design (Fifth Conference) (Ed Tsai, S.W.) American Society for Testing and Materials, ASTM STP 674 (1979) 228 16 Egusa, S., Kirk, M.A., Birtcher, R.C., Hagiwara, M. and Kawanishi, S. JNucl Mater (1983) 119 146 17 Chalnis, C.C. in: Composite Materials Vol 6 (Ed Plueddemann, E.P.) Academic Press, New York, USA (1974) Ch 2 18 Kasen, M.B. Cryogenics (1981) 21 323 19 Manocha, L.M. J Mater Sci (1982) 17 3039 20 Cameron, N.M. Glass Technol (1968) 9 14 21 Corten, H.T. in: Modem Composite Materials (Eds Broutman, L.J. and Krock, R.H.) Addison-Wesley Publishing Company, Massachusetts, USA (1967) Ch 2 22 Hartwig, G. and Knaak, S. Cryogenics (1984) 24 639

Conclusions
The present work has shown that the radiation-induced degradation of polymer matrix composites is reflected much more explicitly in the ultimate strength and in the shear modulus than in the Young's modulus. It was also suggested that the radiation resistance of these composites depends primarily on the radiation resistance of matrix resins rather than on the surface treatment of reinforcing fillers. The radiation resistance of matrix resins was found to increase in the order DGEBA type epoxy < T G D D M type epoxy < Kerimid 601, no matter what type of hardener was involved. Although the irradiation was carried out only at room temperature in the present work, the mechanical test made at room temperature and at 77 K demonstrated that the extent of the radiation-induced decrease in the composite strength is appreciably greater in the 77 K test than in the room temperature test. Interpretation of this result was based on the competition between the two

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Cryogenics 1986 Vol 26 July