Materials Science and Engineering A 387389 (2004) 845851

Mechanical properties and microstructure of carbon bre reinforced carbon materials produced by chemical vapour inltration
R. Ermel, T. Beck , O. Vhringer
Institute of Materials Science and Engineering I, University of Karlsruhe (TH), Kaiserstr. 12, D-76131 Karlsruhe, Denmark Received 25 August 2003; received in revised form 25 November 2003

Abstract Correlations between mechanical properties, bre architecture, matrix texture and fracture behaviour of carbon bre reinforced carbon CFC-materials produced by chemical vapour inltration are investigated using results from tensile and four-point-bending tests, polarized light microscopy and scanning electron microscopy. Mechanical testing was performed at temperatures from 20 up to 1600 C. Samples were tested in the as-received state and after heat treatment at T = 2200 C. The heat treatment leads to an increasing Youngs modulus and brittleness, which corresponds with an increasingly distinct layer structure of high textured matrix carbon. A rise of test temperature up to 1400 C also leads to a larger Youngs modulus and increasing brittleness. However, at T = 1600 C the material shows a pronounced pseudoductile behaviour. Scanning electron micrographs show in this case a lot of concentric cracks between the sublayers of the high textured matrix. The fracture behaviour is explained by a multiple delamination between these layers. 2004 Elsevier B.V. All rights reserved.
Keywords: Carbon/carbon-composites; Fracture behaviour; High-temperature properties; Tensile test; Four-point-bending test; Microstructure

1. Introduction High strength at temperatures up to 1800 C and a good chemical resistance in neutral and reducing environments are outstanding properties of carbon bre reinforced carbon (CFC). The capability to pseudoductile fracture behaviour in the case of an appropriate bre architecture and matrix texture predestinates CFC as a material for components, which undergo extremely high thermal and mechanical loadings. Pseudoductile behaviour of such a composite consisting of two brittle components occurs if an appropriate strength of the brematrix interface results from the manufacturing process. Then, matrix initialized cracks deect at the brematrix interfaces and a locally limited debonding between bres and matrix takes place and the bres will bridge the crack. Additionally, bre fracture during further loading can cause so-called bre-pullout, consuming additional energy for crack propagation [13]. The fracture toughness of CFC can be further increased if the crack deection occurs not only at brematrix interCorresponding author. Tel.: +49-721-608-4159; fax: +49-721-608-7451. E-mail address: tilmann.beck@mach.uni-karlsruhe.de (T. Beck). 0921-5093/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2003.12.075

face but also in the matrix itself [4]. This behaviour requires a matrix consisting completely, or at least partially, of high textured pyrolytic carbon, which is deposited in concentric layers around the bre. Tests on chemical vapour inltrated (CVI) bre-felts show, that a material with a larger volume fraction of high textured matrix shows a more pronounced pseudoductility than composites with medium or low textured matrices [5]. The CVI process can be described as follows: methane diffuses into the bre-preform, where it cracks into hydrogen and elementary carbon and latter is deposited on the surface of the bres until the bre structure is completely densied. Because of an exact understanding of the CVI process [6,7], it is possible to produce a composite of high density within a time of a few days. The parameters of the inltration process must be optimized to get a complete densication combined with the desired texture of the carbon matrix [8]. This work presents the results of four-point-bending and tensile tests at temperatures from 20 up to 1600 C on two different CVI-CFC-materials. Some specimens were heat treated at T = 2200 C after manufacturing which results in a weak partial graphitization of the high textured pyrolytic matrix carbon. Fractographic investigations with SEM and a microstructure analysis with polarized light microscopy

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Fig. 1. Microstructure of CVI-CFC.

(PLM) are used for the interpretation of the results of mechanical testing.

2. Experimental details 2.1. Investigation of the microstructure

extinction angle of polarized light characterizes the texture of pyrolytic carbon, so that a separation in isotropic (ISO), low (LT), medium (MT) und high textured (HT) carbon is possible [9]. Fig. 1 shows an example of a carbon bre surrounded by matrix-layers with different textures. 2.2. Mechanical testing

The investigation of the microstructure is carried out by polarized light microscopy (PLM) on specimens cut perpendicular to the bre direction. The measurement of the

Mechanical testing of the CFC-samples is performed on an electromechanical testing machine. Because of the sus-

Fig. 2. Material 1: UD- and bre-felt-layers (a) and material 2: 2D-0/0/90/90 (b).

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Fig. 3. Stressstrain curve from tensile test at T = 20 C, surface and longitudinal strain-distribution of three states of this tensile test (a). Scanning electron micrograph of the corresponding fracture surface (b).

ceptibility of CFC against oxidation the tests at high temperatures are carried out in a vacuum chamber at an air-pressure of p < 108 bar. With inductive heating of the specimens test temperatures up to 1800 C can be reached. The crosshead speed for four-point-bending tests is 2.0 mm/min and for the tensile tests 0.5 mm/min. The integral strain is measured with a capacitive extensometer. Additionally an optical extensometer based on grey-scale-correlation-analysis allows for an integral as well as locally resolved determination of the strains even at the highest test temperatures [10].

2.3. Specimen geometry The bending samples have a size of L B H = 52 mm 6 mm 1.6 mm and the distances of the inner and the outer support are L0 = 20 mm and La = 45 mm, respectively. Assuming a linear elastic behaviour the ctitious bending strength R is calculated according to: 3Fm
La Li 2 BH2

= R

(1)

848 Table 1 Investigated materials Designation Preform Material 1 Material 2

R. Ermel et al. / Materials Science and Engineering A 387389 (2004) 845851

Preformmanufacturer

Fibre Fibre type volume ratio About 20% 22.5% HT HT

UD/felt layer Dunlop 2D-0/0/90/90 Sintec

using Fm as maximum load. The elastically calculated surface strain results from the deection between the inner supports. The gauge length of the tensile specimens is L0 = 15 mm with a cross-section of B H = 2 mm 3 mm.

bres are parallel (Fig. 2). The sequence of the layers of the specimens from material 1 are chosen in order to get UD-layers at both surfaces of the samples. Table 1 summarizes bre architecture, bre volume ratio and bre type. The parameters of the CVI-process are the same for both materials. Due to that, the matrix in both materials mostly consists of high textured pyrolytic carbon with a thin layer of low textured pyrolytic carbon around the bres. Material 1 is characterized by a density of = 1.82 g/cm3 and an open porosity of P = 7%, the respective values of material 2 are = 1.76 g/cm3 and P = 10%.

3. Materials The investigated CFC-materials consist of inltrated preforms with a different bre architecture (Fig. 2). Material 1 is made of two different layers, a unidirectional (UD) C-bre and a bre-felt layer. Material 2 consists of a two-dimensional preform with a sequence of the layers in 0 /0 /90 /90 direction. Within each layer, 80% of the bres are orientated in the main direction. The specimens are taken from the inltrated preform in such a way that the directions of the load-axis and -

Fig. 4. Comparison between t curves of heat treated and as-received specimens from tensile test (a) and four-point-bending test (b).

Fig. 5. SEM-pictures of fracture surfaces of material 1 in the as-received (a) and the heat treated state (b) after four-point-bending at T = 20 C.

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4. Results and discussion 4.1. Material 1 Under tensile loading material 1 in the as-received state shows a marked pseudoductile behaviour with pronounced bre-pullout as presented in a typical stressstrain curve and

the corresponding fracture surface for a test temperature of 20 C in Fig. 3. The fracture surface of four-point-bending specimens shows less pronounced bre-pullout compared with tensile specimens. Additionally, in Fig. 3a the surface and the local strain-distribution in longitudinal direction is represented in three states of the tensile test. Distinct concentrations of strain can be found at a relatively low total strain of t = 0.45% (phase 2) before a crack on the surface can be noticed. 4.2. Inuence of heat treatment An inuence of a heat treatment at T = 2200 C for 2 h can be seen in tensile as well as in four-point-bending tests (Fig. 4). In both cases the Youngs modulus increases slightly while the plastic strain to failure decreases. The inuence of the heat treatment is more pronounced in tensile tests. An increase of strength due to the heat treatment observed in tensile tests cannot be noticed in four-point-bending tests. The reason might be a larger scatter of the exural strength, caused by a different fracture behaviour. This can be seen in one case in which delamination of a large area between unidirectional and felt-layer superposes the inuence of brematrix delamination. The corresponding R R,t curve is marked by an arrow in Fig. 4b. An investigation of the fracture surfaces by SEM shows for the heat treated sample (Fig. 5b) a more distinct laminar structure of the high textured pyrolytic carbon, compared to the as-received state (Fig. 5a). In addition, the matrix is characterized by many cracks parallel to the layers. However, the extent of pullout of bres and matrix layers seems to be reduced by the heat treatment. PLM investigations did not show any change of the matrix texture due to the heat treatment. 4.3. Material 2 A comparison between the stressstrain behaviour of material 2 in tensile- and four-point-bending tests at T = 20 C

Fig. 6. Representative stressstrain curves for tensile and four-point-bending tests (a) and scanning electron micrographs of the fracture surface of four-point-bending (b) and tensile samples (c).

Fig. 7. Stressstrain curves for T = 20, 1100, 1400 and 1600 C.

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Fig. 8. SEM-pictures of fracture surfaces after four-point-bending tests at T = 1600 C (a) and at T = 20 C (b).

is presented in Fig. 6a. A larger plastic elongation is found in the tensile test. This agrees with SEM examinations of the fracture surface after tensile and bending tests which showed a larger extent of bre-pullout and delamination of matrix layers for tensile specimens (Fig. 6b and c). 4.4. Inuence of test temperature Four-point-bending tests were carried out at temperatures up to 1600 C. The resulting surface stressstrain curves are shown in Fig. 7 for temperatures of 20, 1100, 1400 and 1600 C. Youngs modulus increases slightly with temperature while the scatter of the strength values decreases with T. Up to T = 1400 C, all samples show a brittle fracture behaviour. However, at T = 1600 C the plastic fracture strain

of 0.3% is much higher than at lower T. An explanation is given by SEM-observation of the fracture surfaces at high magnication at which a high textured matrix streaked with a lot of concentric cracks can be detected (Fig. 8a). The surface is very rough while the surface of the samples tested at temperatures up to 1400 C is much smoother (Fig. 8b). Accordingly, delamination between matrix layers can explain the pseudoplastic behaviour at T = 1600 C. Fibre-pullout seems to be of subordinate signicance, because the fracture surfaces show a similar structure at all test temperatures. 5. Summary Two CVI-CFC materials with a different bre architecture but with mainly the same matrix texture were tested

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in four-point-bending and tensile tests at temperatures up to 1600 C. For both materials tensile loading led to a more pronounced pseudoductility and bre-pullout than four-point-bending tests. The consequence of heat treatment of material 1 at T = 2200 C after inltration is a slightly higher Youngs modulus and a lower plastic fracture strain than in as-received state. Scanning electron micrographs showed a more distinct layer structure of the high textured matrix and a smaller bre and matrix layer pullout in the case of heat treated specimens. A signicant change of the texture caused by heat treatment was not detected by PLM. Increasing test temperatures up to 1400 C lead to increasing Youngs modulus and a decreasing plastic fracture strain. However, an inuence of T 1400 C on the fracture surface and matrix microstructure cannot be noticed. Tests at T = 1600 C resulted in a relatively large plastic fracture strain of about 0.3%, due to an increasing number of concentric cracks within the high textured matrix. So, this pseudoplastic behaviour is attributed to delamination between matrix layers.

Acknowledgements The present study was performed in the Collaborative Research Center 551: Carbon from the gas phase. Financial support by the German Research Foundation (DFG) is gratefully acknowledged. The authors thank Prof. K.J. Httinger for the inltrated samples.

References
[1] G. Savage, CarbonCarbon Composites, Chapman & Hall, London, 1993. [2] S.-M. Oh, J.-Y. Lee, Carbon 27 (1989) 423. [3] A.G. Evans, D.B. Marshall, Acta Metall. 37 (1989) 2567. [4] B. Reznik, D. Gerthsen, Carbon 41 (2003) 57. [5] B. Reznik, M. Guellali, D. Gerthsen, R. Oberacker, M.J. Hoffmann, Mater. Lett. 52 (2002) 14. [6] K.J. Httinger, Chem. Vap. Deposit. 4 (1998) 151. [7] W.G. Zhang, Z.J. Hu, K.J. Httinger, Carbon 41 (2002) 2529. [8] W. Benzinger, K.J. Httinger, Carbon 37 (1999) 1311. [9] B. Reznik, K.J. Httinger, Carbon 40 (2002) 621. [10] GOM mbH, Aramis Verformungsmessung nach dem Rasterverfahren, Aramis, 2002, p. 4.7.3-2.