CARBON-CARBON COMPOSITES UNIDIRECTIONALLY REINFORCED WITH CARBON AND GRAPHITE FIBERS

Institut fiir Chemische Technik der Universitat Karlsruhe,

(Keceiued 13 August 1971) Abstract-A study was performed on unidirectional fiber reinforced composites, prepared by the wet-winding technique using thermosetting resins or pitch as binder. In the case of pitch binder, gas pressure was applied during the baking process for obtaining higher coking values at fast heating rates. Usually, as a result of the shrinkage of the thermosetting resin during carbonization, the structural integrity of a composite is damaged. It is demonstrated that such damage can be avoided by the use of binder materials exhibiting a wide temperature range of plasticity. Carbon-carbon composites reinforced by Thornel 50 graphite fibers were prepared with pitch as matrix precursor. Superior mechanical properties as compared with those of the multiple impregnated carbon-carbon composites made with resin were already found without impregnation, even at bulk densities below 1.3 g/cm. A subsequent pitch impregnation and recarbonization resulted in an increase of the flexural and interlaminar shear strength. With 36 per cent Thornel 50 fiber and two pitch imprecations, a carbon-carbon composite of 14X g/cm bulk density with Hexural strength of 79 x IO" psi and interlaminar shear strength of 3.1 X 103 psi was obtained. 1. INTRODUCTION 2. THE DIFFICU~T~ES MATRIX SHRINKAGE THERMOSETTING CAUSED BY WHEN USING BINDERS

E. FITZER

and B. TERWI~SCH

Karlsruhe,

Germany

Carbon-carbon composites are actually artificial carbons with carbon fibers as filler material. It is well known that the strength of polycrystalline carbons is strongly inlluenced by the binder bridges between the filler particles, that is by the structure and morphology of the binder carbon and by the adhesion between the filler-carbon and the binder-carbon. Therefore, the selection of the binder and the control of the pyrolysis process are considered as key points in the fabrication of high-quality artificial carbons as well as of carbon-carbon composites. ~nidirectionaIly reinforced composites were prepared by wet-winding technique, using thermosetting polymers or pitch as matrix precursors. Commercially available carbon and graphite yarns such as the carbon fiber VYB, the graphite fiber WYB and Thorne125 and 50 were employed.

It has been shown previously[l, 2] that severe shrinkage problems arise by the use of thermosetting polymers as matrix raw material. The diagrams in Fig. 1 present the behavior of non-reinforced thermosetting polymers during pyrolysis, according to Fitzer and Burger [l]. The curves of weight loss and shrinkage indicate the temperature interval between 300 and 600C as the main degradation range, and the strongest influence on the composite integrity can be expected at these temperatures. The maximum tensile strength of 17,000 psi was found for the non-reinforced carbon matrix after heat treatment to 1200C. The weight losses of the composites are due to the matrix portion. However, the linear bulk shrinkage in fiber direction is

E. FITZER

and

B. IERWIESCH

230

500

750

,000

1230

Temperature. "C

Fig. 2. Bulk properties at room temperature of carbon fiber reinforced polymers after gradual degradation. I PH-VYB; II EO-VYB; 111 PH-Thornel 25; IV PH-Thornel 50; (I, III) precalculated values.

I
0

I
400

I
800 C

Izoo

Temperature,

Fig. 1. Bulk properties at room temperature of thermosetting resins after gradual degradation. FA furfurylalcohol resin; PH phenolic resin; EO epoxy resin. to be smaller than 1 per cent. Therefore, the mechanical bulk properties of the composites are dominated by this hindered matrix shrinkage in fiber direction. Figure 2 shows the strength behavior of the fiber reinforced composites (I-IV) after stepwise carbonization as full lines. All measurements were made at room temperature. The strength of the matrix alone (PH) and of the hypothetical properties of the composites calculated from the undamaged fiber and the matrix strengths (I and III) found

according to the mixture rule, are included for comparison. Although these calculated values are nearly reached after curing, the composites exhibit a progressive reduction in strength with increasing pyrolysis treatment. In the case of the low module fiber (I and II in Fig. 2) the strength of the composite drops below the strength of the nonreinforced matrix. With the high modulus fibers Thornel 25 and Thornel 50 (III and IV), a minor decrease of the tensile strength is observed, and a bulk strength of the composite more than twice that of the nonreinforced carbonized matrix was obtained. However, this value is only a small part (approx. 30 per cent) of the calculated strength. Obviously, not only the matrix but also the fibers are damaged by the hindered matrix shrinkage during the carbonization. It may not be generally known that thermosetting polymers allow a limited plastic deformation up to 500C during the pyrolysis, as illustrated in Fig. 3, but this deformation

CARBON-CARBON
Pretreated up to

COMPOSITES
Polished surface Thornel 25. PH VYB-PH

385

210C

305oc

R&l
After 400C at

F&r After up heat to treatment IOOOC

curly 110C

(a)

(b)

Cc)

515T

Fig. 4. Schematic

of model shapes made from phenolic resin and carbon and graphite fibers.

6 30C

7OOT

Pyrolyzed

under

flexural

load

up

to

700

Fig. 5. Plastic deformation during pyrolysis under flexural load of thermosetting resin pre-heat treated without load up to various temperatures.

cannot prevent damage to the bulk integrity caused by the matrix of the composite shrinkage. Efforts were made to overcome this shrinkage problem by a reduction of the wetting of the fiber and consequently by a reduced bonding between the fiber and the matrix. For this purpose composites with a very low fiber content were prepared, in consequence of which the embedded monofilaments are isolated from each other. This permits a free expansion and shrinkage of the matrix perpendicular to the fiber direction. Thin plates with a thickness in fiber direction of approximately 1 mm were cut from these composites and carbonized up to 1000C. The effect of adhesion between fiber and matrix is shown schematically in Fig. 4. In the case of the smooth graphite fiber Thornel 25, the plate remained undamaged after final carbonization because of a weak

bonding, whereas the matrix of the plates with carbon fibers VYB was split perpendicular to the fiber direction because of the excellent bonding between matrix and the non-graphitized fiber. The primary shrinkage results in a diminution of the plate thickness and leads in both cases to a partial uncovering of the embedded fibers. The typical surface structure of such test specimens after the heat treatment as shown in the scanning micrographs (Fig. 5) is caused by the embedded fibers, which obstruct the thickness shrinkage of the plates. In the case of composites with a greater thickness in fiber direction, as shown in Fig. 6, the increased total shrinkage during carbonization not only causes cracks in the resulting carbon matrix Wt.- also a breakage of the high-strength Thornel50 fibers. 3. IMPREGNATION OF COMPOSITES WITH RESIN AS MATRIX PRECURSOR According to our investigations, two alternative ways seem feasible for the preparation of carbon-carbon composites having high strength combined with high interlaminar shear strength: (1) Stepwise filling of the primarily formed cracks by impregnation and recarbonization, when thermosetting resins are used as matrix precursor;

(: ZKRON

Vol. IO, No. 4-B

:m
(2) Using

E. FITZER

and B. TERWIESCI-1

a matrix precursor exhibiting a wide temperature range of plasticity during the pyrolysis and perhaps a subsequent densifkation by impregnation.

It can be recognized
process pensive. is very Contrary to

that this

the

impregnation and the exuse

time-consuming process, promises binder

of a thermoplastic

a good

As impregnation agent for the composites with thermosetting polymers as binder, a solution of phenolic resin was used. After each impregnation the samples were heated to 90C in order to evaporate the solvent and to precure the resin. After each fourth impregnation the resin was cured up to 110C and carbonized up to 1100C. Figure 7 illustrates the increase of weight and of flexural strength as a result of such repeated impregnation treatments. As can be seen, the flexural strength is not significantly increased before the second impregnation cycle and saturation seems to be reached after the fourth impregnation. More data on the effect of multiple impregnations are compiled in Table 1, and compared
with selected data taken from the literature.

Impregnation

Crmg2to I 10C I ___I__I__, I 2

Degradation to

3-3
IIOOC

4 4

Fig. 7. Increase otweight and flexural strength of carbon-carbon composites made from phenolic resin and Thornel 50 in dependence of the impregnation treatment. carbon-carbon Youngs modulus (10 psi) 9.8 10.0 10.9 composites Flexural strength (lo psi) < 1.6 Interlaminar shear strength (IO psi) < 0~01 0.28
(().(j(j):k

Table 1. Values of resin-bonded Matrix raw material PH PH PH PH PH PH PH IH PH

Selected

impregnated Tensile strength (lo psi) 41 11 46 5I 58 57

Fiber Thornel25 Thorne125 Thornel25 Thorne125 Thornel 50 Thornel 50 Thornel 50 Thornel50 Thornel 50
1ilmQure

Treatment non-impregnated 4 X impr., 1 X pyrol. 8 X impr., 2 X pyrol. 12 X impr., 3 X pyrol. non-impregnated 4 X impr., 1 X pyrol. 8 X impr., 2 X pyrol. 12 X impr., 3 X pyrol. 16 X impr., 4 X pyrol.

II.5 I.1 26.2 _ 6.1

41 2.6 _ 1X 46 4!) I7 1x

(1.18) (0.16)* (().;>,5 ):: (().<)) ( 1.94) :i:

il

( 1.18)
I.78 1.72

unknown PH PH Kcsill IH

d&7. unknown VYR CY-2 <Carborundum Morganite I Morganite I

unknown [3] 3 X impr.. 3 X pyrol[4 ] 3 x impr., 3 x pyrol[4] with pyrolytic carbon [5] repeated impregn. and [6] pyrol.

30

4.)

11
26 -

6.X
6.0 O-3W 32t

I YO-140
1!X

.()_I.,5

3.02

$No delamination. +Flexural modulus.

100 pm (a)

Fig. 5. Scanning micrographs of the model shapes after carbonization up to 1000C (a) carbon matrix-Thornel 25 (b) carbon matrix-VYB.

Fig. 6. Destruction of a carbon-carbon model composite made of phenolic resin and Thornel50, caused by the matrix shrinkage (a) total view (b) detail.

Fig.

11. Fracture surfaces of pitch-bonded carbon-carbon composites-(a) VYB-pitch (b) WYB-pitch.

Fig.

12. Micro-structure

of a pitch-bonded composite.

carbon-carbon

CARBON-CARBON

COMPOSITES

387

bonding carbon, structure

between without if the

primary damaging pyrolysis

and the

secondary composite of the

Influence pyrolys~ Heotlng of of rote: gas pitch IOC/mr pressure up to on 600C the

shrinkage

binder can be compensated by the formation of a porous carbon matrix comparable with that in classical carbon artifacts.
4. PREPARATION

AND PROPERTIES PITCH-BONDED CARBON-CARBON COMPOSITES the preparation with a plastic of matrix

OF

--______ sp 6,PC ---_____ sp 77oc SP 126Y

For three at

carbon-carbon precursor, pitches behavior by in shown Fig. 9. Influence of gas pressure on the pyrolysis of pitch up to 600C. Closed symbols-values from TGA; open symbols-values from pressure baking in an autoclave. Table 2. Characterization of the used pitches SP 65 Softening point (Kraemer-Sarnow) (C) 67 1.29 Density (g cmm3) 0.56 Sulfur (%) 30 Toluene insoluble (%) Temperature at 1000 CP (C) 139 Coke yield (%) 50 Elektrokemisk-method Ring furnace-method 63 SPSO SP 120 binder as is

composites (see Table

commercially atmospheric

available pressure analysis is shown coke

2) were used. The coking

studied

thermogravimetric Fig. 8. The coking ity to influence behavior apply

of gas pressure

on the

in Fig. 9. Because rates, pressure

of the improved baking

yield and the possibilused in the preparaprocess platewetFrom

high

heating

was preferably

tion of the composites. A flow diagram of the laboratory is given shaped composites winding in Fig. green were technique 10. In the prepared with molten first by step, unidirectionally

reinforced the pitch.

77 1.29 0.76 24 146 53 69

126 1.33 0.67 42 205 64 77

these plates samples were cut and compressed into bars. The pyrolysis was carried out in a gas autoclave min up to 600C. with a heating The pyrolysis rate of 10X/ was started

at

140

psi

nitrogen

pressure. increased up a to

During run,

the the

pyrolysis samples nitrogen Figure

the pressure were 11 heated shows

up to about 1000C under of

1000 psi. In a subsequent at atmospheric

pyrolysis pressure. fracture

surface

a carbon-carbon composite made with pitch as matrix raw material. Again, the influence
,: Heating rates 0 5oC/m,n

of the

the

fiber

surface carbon

on can The

the

bonding

with from

binder

be recognized excellent

these

micrographs.

adhesion

between the carbon matrix and VYB carbon fibers leads to a non-fibrous glasslike brittle
Temperature, OC

Fig. 8. Thermogravimetric analysis of three binder pitches.

fracture, contrary to that fiber-reinforced composites fibrous fracture.

of the WYB with a typical

388

E. FITZER

and

B. TERWIESCH

Fig. 10. Flow diagram of the laboratory process for making pitch-bonded carbon-carbon composites. The data on mechanical properties of the carbon-carbon composites prepared with pit.ch as binder and without any impregnation treatment are shown in Table 3. For better understanding, the bulk strength of the composites is additionally expressed in percentage of the strength of the fiber content, which has been used in the fabrication of the composites. This percentage can be regarded as a characteristic value for the amount of damage to the fibers, which is probably a breakage caused by the shrinkage stress [see Fig. 6(b)]. Up to 600C heat treatment temperature the fiber strength within the composites is largely retained for all fiber types, whereas after heat treatment to a final temperature of 1000C this retention is found only in the case of the graphitized fibers as reinforcement material. The carbon fiber VYB is considerably damaged by the matrix shrinkage similarly as in the case of resin binders. Composites, made of even the weak and non-expensive graphite fiber WYR, exhibit high values of tensile and flexural strength after baking up to lOOO*C, with the bulk density reaching only about 1.1 g/cm. More detailed experiments, which have not yet been completed, indicate that the carbon fiber volume content is of decisive influence on the bulk strength properties of the composites. The low fiber contents appears to improve the strength properties of the non-impregnated composites. It seems that a minimum distance between mono-

filaments is necessary to ensure the presence of sufficient matrix material between the fibers to form strong carbon bridges between them. A typical structure is shown in Fig. 12. Higher fiber contents seem to cause the formation of cracks parallel to the fibers which necessitates a within the matrix, subsequent impregnation treatment. The best mechanical properties of non-impregnated carbon-carbon composites were found with low fiber contents (36 volume per cent) of the high quafity fiber Thornel 50. A flexural strength of 64 x lo psi was obtained in this case, although the bulk density is below l-3 g/cm 3. These values exceed those of the multiply impregnated and recarbonized composites with resin as matrix precursor. The superiority of a matrix with a wide temperature range of plasticity seems to be confirmed, although even with the pitch used by us, the matrix shrinkage problems arise in the case of too small distances between the single fibers. .A wide field of further research aimed at optimation of fiber/binder ratio with a variety of modified pitch binders is still before us. 5. IMPREGNATION OF PITCH-BONDED CARBON-CARBON COMPOSITES Although the best carbon-carbon composites without impregnation already show superior mechanical properties to the multi-impregnated resin-bonded ones, a further improvement by densification was found to be possible. The very low bulk density combined with the morphology of the binder bridges seems to be ideal for a subsequent impregnation treatment. Some preliminary results obtained by us are shown in Table 4. The greatest improvement is observed in those cases where the formation of cracks in the matrix during the carbonization was unavoidable, that is when the fiber content is high. Nevertheless, carbon-carbon composites with a relatively Iow fiber content of 36 vol.

Table 3. Values of pitch-bonded

carbon-carbon

composites without impregnation

treatment

Bulk density Treatment (g cmm3) 3.0 2.0 3.4 3.4 3.2 74 70 70 > 67 > 60 > 55 14 15 20 Tensile strength ( lo3 psi) Youngs modulus (10 psi)

Fiber

Fiber content (vol. 49L)

1)Strength of the contained fiber

Flexural sirength (105 psi)

Interlaminar shear strength (10 psi) 1.1 (PS) + 28 34 15 23 41 64 1.1 1.6 (l.O)? I.2 1.6 2.6 40 45 4

VYB VYB VYB ;f 12 moulded at 250C pyrolysed up to 600C pyrolysed up to 1000C moulded at 250C pyrolysed up to 600C pyrolysed up to 1000C 1.34 1.29 1.28 > 4g* > 47 > 47 1.27 1.14 1.10 34 32 32

moulded at 250C pyrolysed up to 600C pyrolysed up to 1000C

1.34 1.21 1.17

56 45 7

WYB WYB WYB

73

Ihornel50 Thornel50 Thornel50

36

*Fracture in the grip tNo delamination.

390

E. FITZER

and B. TERWIESCH carbon-carbon Youngs modulus ( 10fipsi) 3.2 3.4 20 20 composites Flexural strength (lo3 psi) 4 6 13 48 64 79 Interlaminar shear strength ( lo3 psi) (0.2) t

Table 4. Values of pitch-bonded Bulk density (g cme3) 1.17 1.39 1.10 1.40 1.28 1.48

Fiber VYB VYB WYB WYB Thornel50 Thornel50

Impregnationcycles

Tensile strength ( lo3 psi) 7 1 32 30 47* 46*

2-X 2X 2X

(0.5) 1(l.o)t 2.8 2.6 3.1

*Fracture in the grip. tNo delamination. per cent but with the high strength Thornel 50 fiber were obtained after two pitch impregnation and recarbonization cycles, with a bulk density of 1.48 g/cm3 and a flexural strength of 79 X IO3 psi. Despite the low adhesion between the carbon binder and the very smooth fiber surfaces, the interlaminar shear strength value of 3.1 x lo3 psi has to be considered as satisfactory. More additional information on the bonding conditions in such carbon-carbon composites are expected from results of further impi-egnation treatment and graphitization runs on these materials. REFERENCES 1. Fitzer E. and Biirger A., Int. Co@ on Carbon Fibers, their Composites and Applications, The Plastics Institute, London (1971). Paper 36. Terwiesch B., Fitzer E. and Biirger A., 161st. ACS-Meeting, Los Angeles 1971, Division of Organic Coatings and Plastics Chemistry, Vol. 31, p. 445. France L. L., Kachur V. and Hengstenberg T. F., SAMPE, 10, B-81 (1966). MacKay H. A., Report SC-RR-68-651 Sandia Laboratories, Albuquerque, New Mexico (1969). McLaughlin J. R., Nature, 227, 701 (1970). Newling D. 0. and Walker E. J., Int. ConJ Carbon Fibers, their Composites and Applications, The Plastics Institute, London (1971). Paper 37.

2.

3.
4. 5. 6.