Materials Letters 62 (2008) 43604362

Contents lists available at ScienceDirect

Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Effect of graphite ake on the mechanical properties of hot pressed ZrB2SiC ceramics
Xinghong Zhang, Zhi Wang , Xin Sun, Wenbo Han, Changqing Hong
Center for Composite Materials, Harbin Institute of Technology, Harbin 150001, PR China

a r t i c l e

i n f o

a b s t r a c t
A ZrB2 ceramic containing 20 vol.% SiC and 10 vol.% graphite ake (ZrB2SiCG) was fabricated by hot pressing. It was shown that the fracture toughness was improved due to the introduction of graphite ake, whereas the exure strength and hardness decreased slightly. The fracture toughness of ZrB2SiCG composite was 6.1 0.3 MPam1/2, which was much higher than that of monolithic ZrB2, ZrB2SiC composite and similar ZrB2SiCC composite. The toughening mechanisms are crack deection and branching as well as stress relaxation near the crack tip. The results here pointed to a potential method for improving fracture toughness of ZrB2-based ceramics. 2008 Elsevier B.V. All rights reserved.

Article history: Received 2 June 2008 Accepted 19 July 2008 Available online 24 July 2008 Keywords: ZrB2SiC Graphite ake Microstructure Mechanical properties

1. Introduction Zirconium diboride (ZrB2) based ultrahigh temperature ceramics (UHTCs) were developed in the 1960s. Up to now, it is known that the addition of appropriate amounts of SiC to these materials improves their oxidation resistance and mechanical properties [14]. However, unsatisfactory fracture toughness is still the obstacle for UHTCs to be used widely, especially for applications in severe environments. Some studies [5,6] have shown substantial improvement in fracture toughness and resistance to slow crack growth by the introduction of whiskers into the ceramic matrix. Recently, however, there has been an increasing awareness of the health hazards associated with the manufacture of whisker containing materials [7]. A current solution to this problem is replacement of the whiskers by ultrane, single crystal, disc-shaped particles, such as SiC akes. Flakes may have the same potential as whiskers for improvement in toughness by crack bridging and deection [8]. Further, the graphite ake is an attractive material for high temperature applications due to its high strength, high modulus, layered structure that allows for self-lubrication, excellent thermal shock resistance, and high fracture toughness [9,10]. These properties make it widely used for metal matrix composites [11]. Nevertheless, up to date, there are only a few papers devoted to the study on ZrB2 matrix composites toughened by the graphite ake. In this paper, we have fabricated ZrB220 vol.% SiC composite toughened by 10 vol.% graphite ake (ZrB2SiCG) by hot pressing.

The effect of graphite ake on the microstructure and mechanical properties is analyzed. 2. Experimental Commercially available ZrB2 powder (2 m, N 99.5%, Northwest Institute for non-ferrous metal research, China), SiC (1 m, N 99.5%, Weifang Kaihua Micro-powder Co., Ltd., China.) and the graphite ake (mean diameter and thickness are 15 m and 1.5 m, respectively, N 99%, Qingdao Tiansheng Graphite Co., Ltd., China) were used as raw powders. The powder mixtures of ZrB2 plus 20 vol.% SiC plus 10 vol.% graphite ake were ball-mixed for 10 h in a polyethylene bottle using ZrO2 balls and ethanol as the grinding media. After mixing, the slurry was dried in a rotary evaporator and screened. The resulting powder mixtures were hot pressing at 1900 C for 1 h under a uniaxial load of 30 MPa in Ar atmosphere. The microstructural features of the hot pressed composite were observed by scanning electron microscopy (SEM, FEI Sirion, Holland) with simultaneous chemical analysis by energy dispersive spectroscopy (EDS, EDAX Inc). The phase composition was determined by X-ray diffraction (XRD; Rigaku, Dmax-rb, CuKa = 1.5418 ).The bulk density of the specimens was measured by the Archimedes method. Flexural strength () was tested in three point bending on 3 mm by 4 mm by 36 mm bars, using a 30 mm span and a crosshead speed of 0.5 mmmin 1. Each specimen was ground and polished with diamond slurries down to a 1 m nish. The edges of all the specimens were chamfered to minimize the effect of stress concentration due to machining aws. Hardness (Hv 1.0) was measured by Vickers' indentation with a 9.8 N load applied for 15 s on polished sections. Fracture toughness (KIC) was evaluated by a single-edge notched beam test with a 16 mm span and a crosshead

Corresponding author. E-mail address: wangzhi1780@126.com (Z. Wang). 0167-577X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2008.07.027

X. Zhang et al. / Materials Letters 62 (2008) 43604362 3. Results and discussion 3.1. Microstructure

4361

Fig. 1. XRD spectrum of ZrB2SiCG composite.

speed of 0.05 mmmin 1 using 2 mm by 4 mm by 22 mm test bars, on the same jig used for the exural strength. All exural and fracture bars were cut with the tensile surface perpendicular to the hot pressing direction. A minimum number of six specimens were tested for each experimental condition.

An XRD spectrum obtained from the polished surface of the hot pressed ZrB2SiCG composite is shown in Fig. 1. Apparently, the phase analysis indicates the predominant phases for the as-sintered composite are ZrB2, SiC, graphite as well as a trace of ZrC. The formation of ZrC was attributed to the reaction of graphite with ZrO2, which was present as an impurity from grinding with ZrO2 media and/or as a surface oxide on the ZrB2 powders. Fig. 2 shows the polished and fractured surfaces of ZrB2SiCG composite. It can be found that the microstructure of ZrB2SiCG composite is characterized by the grey ZrB2, dark SiC, as well as the long and narrow dark graphite ake. Furthermore, the hot pressed ZrB2SiCG composite shows a preferred orientation of the graphite ake with its basal planes perpendicular to the hot pressing direction. The slots on the polished surface of ZrB2SiCG composite are the graphite, which reveals that signicant pullout of graphite occurred during the polishing process, indicating the weaker bonding within ZrB2SiCG composite due to the presence of soft graphite. Fig. 2B shows SEM image of the fractured surface of ZrB2SiCG composite. No porosity was obvious on the fracture surface. As with the polished surface, the graphite ake was observed. Voids that resulted from graphite ake pulling out were also detected. In addition, the microstructure of ZrB2SiCG composite is uniform. The mean grain sizes of ZrB2 and SiC were about 4 m and 2 m, respectively, and the graphite ake appears 12 m in thickness and ~ 15 m in diameter. Moreover, the mixed fracture mode, including both of transgranular and intergranular, was observed in the ZrB2SiCG composite. The typical crack propagation paths at the corners of indents during Vickers' hardness tests were presented in Fig. 3. EDS demonstrated that the spots (1 and 2) contained only carbon. When the crack interacted with the graphite ake, deection and branching were observed near the interface between the graphite and other phases. In addition, the crack propagation through the graphite ake is clearly observed for ZrB2SiCG composite. These were presumably attributed to both of the weaker bonding between graphite and other phases and the weaker lamination of graphite

Fig. 2. SEM images of polished (A) and fractured (B) surfaces of ZrB2SiCG composite.

Fig. 3. Typical micrograph of crack propagation on the polished surface of ZrB2SiCG composite.

4362 Table 1 Mechanical properties of ZrB2SiCG composite Fracture toughness (MPam1/2) 6.1 0.4 Flexural strength (MPa) 490.8 21.1

X. Zhang et al. / Materials Letters 62 (2008) 43604362

Vickers' hardness (GPa) 10.7 0.9

Relative density (%) 99.7

[12]. It is believed that such interaction absorbs the energy of crack propagation during fracture and leads to the improved toughness [13]. 3.2. Mechanical properties Results of the mechanical properties (Vickers' hardness Hv 1.0, fracture toughness KIC, exural strength , relative density %) are listed in Table 1. The measured fracture toughness values ranged from 5.6 to 6.6 MPam1/2 (average value was 6.1 MPam1/2), which is higher than reported results of monolithic ZrB2 (2.3 3.5 MPam1/2), ZrB2SiC composites (4.04.5 MPam1/2) and similar ZrB2SiCC composites (3.4 MPam1/2) [14,16]. The increase in toughness may be due to the high aspect ratio of graphite ake and weaker interface bonding, which could enhance crack deection and branching as well as stress relaxation near the crack tip [8,17]. Although the introduction of graphite ake can increase fracture toughness, it can reduce exural strength and Vickers' hardness compared to ZrB2SiC. The results have reported that the hardness of a material with the addition of weak second phases, such as carbon/graphite, h-BN and pores generally decreased [14]. Accordingly, the reduction in hardness of ZrB2SiCG composite could be attributed to the existence of soft graphite, even though the volume content was only about 10 vol.%. The reduction in exural strength could be attributed to the weaker bonding within ZrB2SiCG composite [4] and lower load transfer due to the lower strength of the graphite ake as well as the akes acting as aws in composite. Furthermore, the strength of ZrB2-based ceramics is reported to be strongly dependent upon grain size [15,16]. Therefore, the character and size of graphite ake (especially in the diameter direction, 1020 m) in this work limited the exural strength compared to ZrB2SiC composites.

fracture toughness of ZrB2SiCG composite is 5.66.6 MPam1/2, which increased by approximately 74% compared to the reported toughness of monolithic ZrB2 (2.33.5 MPam1/2), 35% for ZrB2SiC composite (4.04.5 MPam1/2), and 78% for similar ZrB2SiCC composite (3.4 MPam1/2) produced by hot pressing. Both of the large aspect ratio and weaker interface bonding, which lead to the crack deection and branching as well as stress relaxation near the crack tip, contribute to the higher fracture toughness. Acknowledgments This work was supported by the National Natural Science Foundation of China (50602010), the Research Fund for the Doctoral Program of Higher Education (20060213031) and the Program for New Century Excellent Talents in University. References
[1] Chamberlain AL, Fahrenholtz WG, Hilmas GE, Ellerby DT. J Am Ceram Soc 2004;87:1170. [2] Monteverde F, Guicciardi S, Bellosi A. Mater Sci Eng, A 2003;346:310. [3] Monteverde F, Bellosi A. Solid State Sci 2005;7:622. [4] Singh M, Asthana R. Mat Sci Eng, A 2007;460461:153. [5] Zhang Xinghong, Xu Lin, Du Shanyi, Han Jiecai, Hu Ping, Han Wenbo. Mater Lett 2008;62:1058. [6] Sun Lan, Pan Jinsheng. Mater Lett 2002;53:63. [7] Barea R, Belmonte M, Osendi MI, Miranzo P. J Eur Ceram Soc 2003;23:1773. [8] Lenk R, Adler J. J Eur Ceram Soc 1997;17:197. [9] Liu Zhan Jun, Guo Quan Gui, Song Jin Ren, Liu Lang. Carbon 2007;45:146. [10] Zhu QS, Qiu XL, Ma CW. Carbon 1999;37:1475. [11] Siegrist ME, Amstad ED, Lfer JF. Intermetallics 2007;15:122836. [12] S. Balos, L. Sidjanin, doi:10.1016/j.jmatprotec.2008.02.015. [13] Faber KT, Evans AG. Acta Metall 1983;31:565. [14] Zhou XJ, Zhang GJ, Li YG, Kan YM, Wang PL. Mater Lett 2007;61:960. [15] Zhu SM, Fahrenholtz WG, Hilmas GE. J Eur Ceram Soc 2007;27:2077. [16] Rezaie A, Fahrenholtz WG, Hilmas Gr E. J Mater Sci 2007;42:2735. [17] Ngampungpis K, Kitamura T, Hirakata H. Eng Fract Mech 2008;75:1285.

4. Conclusion This study clearly showed that the addition of graphite ake into ZrB2-based UHTCs is a potential way to improve the fracture toughness, but by reducing the strength and hardness. The measured