Materials Science and Engineering A 520 (2009) 158161

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Materials Science and Engineering A

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Processing and mechanical properties of short bers/Si3 N4p reinforced BaOAl2 O3 2SiO2 ceramic matrix composites
Jingmei Ma, Feng Ye , Limeng Liu, Haijiao Zhang
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, PR China

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a b s t r a c t
Dense short silicon carbide (SiCsf ) and carbon bers (Csf ) reinforced BaAl2 Si2 O8 (BAS) glass-ceramic composites with silicon nitride were fabricated by hot-pressing technique. The phase characterization, microstructure, mechanical properties and fracture behavior of the composites were investigated by Xray diffraction, scanning electron microscopy, transmission electron microscopy and three-point bending tests. The results showed that short silicon carbide and carbon bers disperse homogeneously in BAS matrix, and had good chemical compatibility with the glass-ceramic matrix. The addition of Si3 N4 could successfully eliminate the microcracks in the BAS matrix induced by the thermal mismatch between the ber and matrix. Both the added short bers could effectively reinforce the BAS glass-ceramic by the associated toughening mechanisms such as crack deection, ber bridging and pullout effects. 2009 Elsevier B.V. All rights reserved.

Article history: Received 10 November 2008 Received in revised form 6 May 2009 Accepted 16 June 2009 Keywords: Barium aluminosilicate Carbon bers Silicon carbide bers Short-ber composites Mechanical properties

1. Introduction Barium aluminosilicate (BaAl2 Si2 O8 or BAS) glass-ceramic is worthy of consideration as a matrix material with application in high temperature structure material due to its high melting temperature of 1760 C, excellent oxidation resistance, low coefcient of thermal expansion of 2.29 106 / C up to 1000 C and good dielectric property [1,2]. However, the pure BAS ceramic matrix exhibits relatively low mechanical properties with reported exural strength of 80 MPa and fracture toughness of 1.8 MPa m1/2 [3], which limits its use in many structural applications. Over the past years, various kinds of reinforcements, such as particulate [4,5], whisker [69], platelet [10,11] and continuous ber [12,13] have been introduced to improve the mechanical properties of BAS glassceramic. Continuous ber reinforced composites exhibit superior properties compared with the monolithic BAS matrix [1416]. The high strength and modulus of the bers can provide superior mechanical properties and prevent catastrophic brittle failure in composites. While improvements in mechanical properties have been demonstrated, ease of producibility and low cost has been sacriced. Short ber reinforced composites have drawn much attention due to their adaptability to conventional manufacturing techniques, low cost of fabrication and inner oxidation protection [1719]. Our previous work showed that short carbon ber reinforced BAS

glass-ceramic matrix composites could be successfully prepared by hot-pressing and the obtained composites exhibited high exural strength and fracture toughness [20]. However, the large thermal expansion mismatch between BAS and bers resulted in a large number of microcracks in the matrix, which deteriorated the mechanical properties of the composites. The microcracks caused by the thermal mismatch must be avoided to further improve the mechanical performance of the composites. In this study, short silicon carbide and carbon bers reinforced BAS glass-ceramic composites were fabricated by hot-pressing. The role of incorporation of Si3 N4 into BAS matrix on eliminating the microcracks caused by the thermal mismatch was investigated. The effect of bers on the microstructure and mechanical performance of the composites were also discussed.
2. Experimental procedure The materials used in this study were BAS glass-ceramic composites reinforced with 20 vol% short bers (Csf or SiCsf ) and 30 vol%Si3 N4 . High purity powders of BaCO3 , Al2 O3 and SiO2 were used for forming BAS. The silicon carbide bers (NUDT, Changsha, China) with an average diameter of 12 m and carbon bers (TX-3, Carbon Co., Ltd., Jilin, China) with an average diameter of 7 m were cut to a length of 24 mm as reinforcements. Starting powders were Si3 N4 (E10grade, UBE Industries Ltd., Japan), Al2 O3 (gradeA16SG, Alcoa), BaCO3 (99.9% grade, Rare Metallic Co.,Ltd., Japan) and SiO2 (99.9% grade, Rare Metallic Co.,Ltd., Japan). When calculating the overall compositions, 2.38 wt%SiO2 (according to manufacturers specications) on the surface of Si3 N4 powder was taken into account. The detailed compositions of the investigated composites are listed in Table 1. The matrix powders (BaCO3 , Al2 O3 , SiO2 and Si3 N4 ) were mixed by ball milling for 24 h in ethanol with silicon nitride balls as the mixing media. At the same time, the short bers (Csf or SiCsf ) were ultrasonically dispersed into ethanol. The welldispersed solutions of short bers were added to the above solution. The mixed

Corresponding author. Tel.: +86 45186413921; fax: +86 45186413922. E-mail address: yf306@hit.edu.cn (F. Ye). 0921-5093/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2009.06.029

J. Ma et al. / Materials Science and Engineering A 520 (2009) 158161 Table 1 Compositions, relative density and phase assemblages of the investigated materials. Material Composition (vol%) Si3 N4 BAS 20Csf /BAS 20Csf 30SN/BAS 20SiCsf 30SN/BAS Csf 20 20 20 SiCsf BAS 100 80 50 50 99 98 97 99 Relative density (%) Phase assemblage

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30 30

Hexacelsian Hexacelsian Hexacelsian, -Si3 N4 , -Si3 N4 Hexacelsian, -Si3 N4 , -Si3 N4

solutions were further mixed by ball milling for 4 h. The slurries were dried and aggregates were dispersed by hand as required. The dried blends were then hotpressed in graphite dies at 1600 C for 1 h under a pressure of 20 MPa in a nitrogen atmosphere into disks of 50 mm diameter and 6 mm thickness. To reveal the reinforcing effects of short bers and Si3 N4 , pure BAS glass-ceramic and 20 vol%Csf /BAS were also fabricated using the same sintering process. The densities of the samples were measured by Archimedes method in distilled water at 20 C. Crystalline phases of the produced composites were characterized by X-ray diffraction (XRD). Quantitative analysis of -Si3 N4 and -Si3 N4 phase content was determined by comparing the peak intensity ratios [21] The fracture toughness and the exural strength of the composites were measured in air at room temperature. Flexural strength measurements were performed on bar specimens (3 mm 4 mm 36 mm) using a three-point bend xture with a span of 30 mm. Fracture toughness measurements were performed on single-edgenotch beam specimens (SENB 2 mm 4 mm 30 mm) with a span of 16 mm, and a half-thickness notch was made using a 0.33 mm thick diamond-wafering blade. At least six specimens were tested for each test condition. Fracture surface of the bending test specimens and crack propagation path produced by Vickers indenter on the composites were examined by scanning electron microscopy (SEM). The microstructures of the composites were also characterized by transmission electron microscopy (TEM). Thin foil specimens taken normal to the hot-pressing axis were prepared by dimpling and subsequent ion beam thinning.

Fig. 1. XRD patterns of the investigated composites (a) 20SiCsf 30SN/BAS; (b) 20Csf 30SN/BAS.

3.2. Microstructure Fig. 2 demonstrates the typical microstructures of investigated composite after sintering. Both of the SiCsf and Csf are homogeneously dispersed in continuous BAS matrix, as shown in Fig. 2a and Fig. 2b, indicating that ultrasonic dispersion together with wet ball milling is a successful method for bers dispersion, which could effectively prevent the bers from aggregating. But the length of bers is only a few 100 m, which is much shorter than the original length. It is due to the impingement among bers and hence resulting in bers fracturing during ball mixing and hot-pressing process. No apparent cracks were found in the BAS matrix. However, for the composites without addition of Si3 N4 , the thermal mismatch between the carbon bers and the matrix always results in transverse microcracks in the matrix [20]. It reveals that addition of Si3 N4 to BAS matrix supplies a promising route for eliminating microcracking in carbon ber reinforced BAS composites by strengthening the BAS matrix. The typical TEM micrographs showing the ber/matrix interface region of the composites are presented in Fig. 3. It could be seen that the Csf and SiCsf have a good bond with the BAS matrix grains

3. Results and discussion 3.1. Densication and phase characterization After sintering at 1600 C for 1 h in a nitrogen atmosphere, the silicon carbide and carbon bers reinforced composites were densied to 99% and 97% of the theoretical density, respectively. It indicates that BAS could effectively wet the bers and Si3 N4 particles, and promote the densication. The typical XRD patterns taken from the polished surfaces for the composites are shown in Fig. 1. Only three crystalline phases were identied in the investigated composites, i.e. untransformed -Si3 N4 , -Si3 N4 and hexacelsian. No celsian was detected in this composite. Apparently, it is due to the sluggish kinetics of hexacelsian to celsian phase transformation [22]. Quantitative phase analysis of the Si3 N4 phase showed that the fractions of in both the composites are about 43.24%, indicating that the low sintering temperature (1600 C) could not realize the complete -Si3 N4 to -Si3 N4 phase transformation.

Fig. 2. SEM micrographs of the investigated composites (a) 20Csf 30SN/BAS; (b) 20SiCsf 30SN/BAS.

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Fig. 3. TEM micrographs of the investigated composites (a) 20SiCsf 30SN/BAS; (b) diffraction pattern of the hexacelsian BAS; (c) 20Csf 30SN/BAS.

Fig. 4. Mechanical properties of the investigated composites (a) exural strength, (b) fracture toughness.

without obvious interfacial reaction or amorphous layer, indicating no chemical reaction between the ber and the matrix during composite processing. Microdiffraction analyses from the BAS matrix in the composites conrm that they are crystallized hexacelsian BAS (Fig. 3c), which is consistent with the XRD results. 3.3. Mechanical properties The mechanical properties of the investigated are shown in Fig. 4. Incorporation of short bers (Csf or SiCsf ) to BAS obviously increased the exural strength and fracture toughness of BAS glassceramic matrix. The exural strength and fracture toughness of (20 vol%SiCsf + 30 vol%Si3 N4 )/BAS composite reach 296.63 MPa and 4.48 MPa m1/2 , increasing 271% and 149% compared to the pure BAS

matrix, respectively. For (20 vol%Csf + 30 vol%Si3 N4 )/BAS composite, they are 216.2MPa and 3.27MPa m1/2 , increasing 171% and 82%, respectively. The increase in strength of the composites is undoubtedly due to the good interfacial bonding between ber and BAS, which can effectively realize the load to transfer from BAS matrix to ber. Fig. 4 also reveals that the effect of Si3 N4 on the mechanical properties of short carbon bers reinforced BAS composite. The introduction of Si3 N4 provides an excellent method of overcoming thermal mismatch between the carbon bers and the BAS matrix, eliminating microcracks and hence improving the strength. The fracture behavior of the investigated composites can be demonstrated clearly by SEM observing the fracture surfaces and the indentation crack propagation paths of the composites, as shown in Fig. 5 and Fig. 6. For carbon ber reinforced compos-

Fig. 5. Fracture surfaces of the investigated composites (a) 20Csf 30SN/BAS; (b) 20SiCsf 30SN/BAS.

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Fig. 6. SEM photographs of indentation crack propagation paths in the investigated composites: (a) 20Csf 30SN/BAS; (b) 20SiCsf 30SN/BAS.

ite, the crack always propagates along Csf /BAS interface (Fig. 5a) and extensive ber pullout is observed on the fracture surface (Fig. 6a), indicating the strong interaction between the propagation crack and the microstructure during the fracturing, and resulting in toughening behavior. However, for silicon carbide ber reinforced composite, the pullout length of ber is much shorter than that of carbon ber composite (Fig. 5b) and even some cracks propagates across SiCsf instead of deection along the SiCsf /BAS interface (Fig. 6b). The different fracture mode between the two investigated composites is due to their interfacial characterization. In the investigated Csf reinforced composites, the radial thermal expansion coefcient of carbon ber between room and 900 C is about 8 12 106 C1 , which is slightly higher than that of the BAS matrix (8 106 C1 ). It will result in a trend for bers debonding during cooling, and hence promote crack deection during fracturing. But, for the SiCsf reinforced composites, the thermal expansion coefcient of SiC ber (3.4 106 C1 ) is lower than that of BAS matrix (8 106 C1 ). During cooling from high temperature, signicant radial compressive stresses build up because the matrix shrinks more round the SiC bers, which will inhibit the interfacial debonding and crack deection. It is expected to further improve the mechanical properties of SiCsf /BAS composites by optimizing the interfacial characterization. 4. Conclusion Dense short silicon carbide and carbon bers reinforced BAS glass-ceramic composites with silicon nitride were fabricated by hot-pressing technique. Both of the bers have a good chemical compatibility with BAS glass-ceramic matrix and display good strengthening and toughening effects. The introduction of Si3 N4 provides an excellent method of overcoming thermal mismatch between the carbon bers and the BAS matrix by strengthening the

BAS matrix and hence eliminating microcracks in matrix induced by thermal mismatch. A radial compressive stress on the bers in silicon nitride ber composite causes large intercal frictional stress between the ber and the matrix, which results in a limited amount of ber pullout. Acknowledgement This work was supported by Excellent Youth Foundation of Heilongjiang Province of China. References
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