Composites Science and Technology 68 (2008) 30333040

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Composites Science and Technology

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Effect of thermal exposure on strength of ZrB2-based composites with nano-sized SiC particles
Shu-Qi Guo a,*, Jenn-Ming Yang b, Hidehiko Tanaka c, Yutaka Kagawa a,d
a

Composites and Coatings Center, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan Department of Materials Science and Engineering, University of California, Los Angeles, CA 90095-1595, USA c Nano Ceramic Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan d Research Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan
b

a r t i c l e

i n f o

a b s t r a c t
The effect of oxidation exposure on the room-temperature exural strength of ZrB2-based composites with nano-sized and micron-sized SiC particles was investigated. The composites were densied by vacuum hot-pressing at 2000 C for 60 min under a uniaxial pressure of 30 MPa. The exural strength of asreceived composites and after exposure in air at 1400 C for 10 h was measured using the four-point bending test. The results show that the presence of intergranular and intragranular nano-sized SiC particles imparts a better oxidation resistance and improves the exural strength of single-phase ZrB2 and ZrB2 ceramics with micron-sized SiC. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 26 March 2008 Received in revised form 12 June 2008 Accepted 17 June 2008 Available online 1 July 2008 Keywords: Zirconium diboride Nano SiC particles Thermal exposure Flexural strength

1. Introduction Diborides and carbides of zirconium (ZrB2 and ZrC) have extremely high melting points (>3000 C), high thermal and electrical conductivities, chemical inertness against molten metals, and great thermal shock resistance [1,2]. The unique combinations of mechanical and physical properties make them attractive candidates for structural applications at ultra-high temperatures. As a result, ZrB2 and ZrC ceramics are being considered for a variety of high-temperature thermomechanical structural applications, including furnace elements, plasma-arc electrodes, rocket engines and thermal protection structures for leading-edge parts on hypersonic re-entry space vehicles at over 1800 C [16]. However, the use of those single-phase materials for high temperature structural applications is limited by the poor oxidation and ablation resistance as well as poor damage tolerance. The composite approach has been successfully adopted in order to improve the oxidation and ablation resistance of single-phase ceramics. For example, the addition of a second phase, such as SiC to ZrB2 results in a composite with improved strength, better oxidation, thermal shock and ablation resistance [2,712]. The improvement of oxidation and ablation resistance is believed to arise from the formation of a coherent passivating oxide scale on the surface. Furthermore, the addition of SiC also limits the grain

growth during densication and improves the sinterability of ZrB2. Thus far, micron-sized and ultra-ne SiC particles were added to the ZrB2 for most of the studies reported in the literature [9,10]. The SiC particles tend to be dispersed along the grain boundaries of ZrB2 (intergranular phase). It had been recently demonstrated that some SiC grain growth occurred during hot-pressing of ZrB2SiC composites [13,14]. Furthermore, the exural strength of the composite decreased substantially as the average size of SiC grains increased from $1.2 to 3.1 lm. Zhu et al. [14] also suggested that the largest SiC grains in the microstructure acted as the critical aws causing the failure of the composite. Hence, it was concluded that smaller SiC grain sizes would result in higher strength for ZrB2SiC composites. Very recently, Hwang et al. [15] reported that the incorporation of nano-sized SiC particles improved the oxidation resistance of ZrB2 ceramics. However, the retained fracture strength of nano-sized SiCZrB2 ceramics after oxidation exposure at high temperature is not well-known. In the present study, the effects of oxidation exposure on the room-temperature exural strength of hot-pressed ZrB2 composites with nano-sized and micron-sized SiC particles were examined in air at 1400 C, for up to 10 h. 2. Experimental procedure The starting powders used in this study were: ZrB2 powder (Grade F, Japan New Metals, Tokyo), average particle size %2.1 lm, nano b-SiC powder (Sumitomo Osaka Cement Co. Ltd.,

* Corresponding author. Tel.: +81 (0)29 859 2223; fax: +81 (0)29 859 2401. E-mail address: GUO.Shuqi@nims.go.jp (S.-Q. Guo). 0266-3538/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2008.06.021

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Osaka, Japan), average particle size %30 nm and oxygen of 0.38 wt.%; and a-SiC powder (GC#2000, Showa Denko K.K, Tokyo, Japan), average particle size %6.4 lm and oxygen of 0.29 wt.%. In order to examine the effects of nano-particle content as well as starting particle size on strength, ve batches of powder were prepared, four of them containing nano b-SiC powder of 5, 10, 15 and 20 vol.%, respectively, the fth one containing 20 vol.% large a-SiC powder. In addition, the single-phase ZrB2 powder was prepared to compare the effect of SiC addition on exural strength. Compositions of the ZrB2-based composites with SiC are listed in Table 1. The powder mixtures were ball-milled using SiC milling media and ethanol under 200 rpm for 24 h, and the resulting slurry was then dried under magnetic stirring to avoid sedimentation. Before sintering, the dried mixtures were sieved through a metallic sieve with 60-mesh screen size. The obtained powder mixtures were hot-pressed (FVHP-1-3, Fuji Electric Co. Ltd., Tokyo, Japan) in the graphite dies under a pressure of 30 MPa under vacuum in tablets 21 mm 25 mm 3.5 mm in size. Powder compacts were heated under vacuum of $7.0 103 Pa to 2000 C with a heating rate of 50 C/min under an uniaxial pressure of 30 MPa. After hot-pressing at 2000 C for 60 min, the temperature was decreased to 500 C with a heating rate of 20 C/min, and then the sample was cooled to 25 C (room temperature) in the furnace. The load was removed when the die temperature dropped below 1750 C. The densities, q, of the hot-pressed composite compacts were measured by the Archimedes method with distilled water as the medium. The grain size, d, was determined by measuring the average linear intercept length, dm, of the grains in FE-SEM images of sintered composites, according to the relationship of d = 1.56dm which was given by Mendelson [16]. Test specimens with dimensions of 25 mm 2.5 mm 2 mm were cut from the sintered ZrB2SiC composites plates. All the specimens were ground with an 800-grit diamond wheel, and the tensile surfaces for the bend test were polished with diamond paste up to 0.5 lm. The edges of the specimen were then chamfered at 45. In addition, in order to examine strength retention of the sintered materials after exposure in air at a high temperature, the specimens were exposed in air at 1400 C. The surfaces of the specimens were ultrasonically cleaned in acetone and kept in an oven with a constant temperature of 100 C prior to oxidation exposure. The specimens were exposed to dry air at 1400 C, for up to 10 h. The 1400 C oxidation exposures were conducted in an electronic furnace (Model SSFT-1520, Nikkato Co. Ltd., Tokyo, Japan). The specimens were supported on high purity Al2O3 knifeedged xtures during oxidation exposure. The fracture strengths of the as-sintered and post-oxidized specimens were determined using the four-point exure test at room temperature (inner span 10 mm, outer span 20 mm). The bending test was performed using an universal testing system (Autograph Model AG-50KNI, Shimadzu Co. Ltd., Kyoto, Japan) with a constant crosshead speed of 0.5 mm/min. At least three specimens were used for each measurement. After the bending test, the fracture surfaces of the specimens were examined by

eld emission scanning electron microscopy (FE-SEM, S-4800, Hitachi High-Technologies Corporation, Tokyo, Japan). 3. Results and discussion 3.1. Microstructures Typical microstructural features of the single-phase ZrB2 and ZrB2-based composites with nano- and micron-sized SiC observed under FE-SEM are shown in Fig. 1. The microstructure of the singlephase ZrB2 consists of the equiaxed ZrB2 and some pores (dark contrast). Most of the pores are presented at multiple-grain pockts. On the other hand, the general microstructures of the ZrB2-based composites with nano- and micron-sized SiC are similar, consisting of the equiaxed ZrB2 (grey contrast) and SiC (dark contrast) grains. The measured average grain sizes of the ZrB2 and SiC are listed in Table 1. In the case of the single-phase ZrB2, the average grain size of ZrB2 is $6.1 lm, which is signicantly higher than the starting powder ($2.1 lm). Apparently, grain growth occurred during hot-pressing. The average grain size of ZrB2 in the composite with 5 vol.% nano-sized SiC particle is similar to that in the single-phase ZrB2. This means that the 5 vol.% nano-sized SiC addition is insufcient for hindering the grain growth of ZrB2 phase during sintering. However, the average grain size of ZrB2 in the composites with 1020 vol.% nano-sized SiC particle is in the range of 4.54.2 lm which is smaller that in the single-phase ZrB2. This indicated that 10 vol.% or more SiC addition is sufcient for hindering the grain growth of ZrB2 during the sintering. In addition, for the ZrB2-based composite with micron-sized SiC, the grain size of ZrB2 is measured to be 5.4 lm which is larger that of the composite with nano-sized SiC particle. This implies that the nano-sized SiC is more effective for hindering the grain growth of ZrB2 than micro-sized SiC. The average grain size of the coarse SiC was reduced from 6.0 to 1.6 lm after sintering. Apparently, the mixing process is effective in reducing the size of SiC particles. However, the average size of SiC in the ZrB2 composites with nano-sized SiC is $0.8 lm, which is substantially higher than that of the starting powder ($30 nm). The mixing process employed was not effective in breaking apart the agglomeration of nano-sized SiC particles. As a result, clusters of nano-sized SiC particles were fused together during hot-pressing to form SiC particles with submicron in diameter. Occasionally, several nano-sized SiC particles can be observed within the ZrB2 grains. As a result, a more effective mixing/dispersion technique to break apart the agglomeration nano-sized SiC particles needs to be developed to uniformly disperse the nano-sized SiC particles. The measured densities and relative densities for the various ZrB2SiC composite materials are also summarized in Table 1. It is evident that single-phase ZrB2 has the lowest density ($91%). The low relative density is expected due to its strong covalent bond and low self diffusion [11]. Melendez-Martinez et al. [17] reported a nal density of 86.5% for a single-phase ZrB2 densied under a pressure of 30 MPa at 1900 C for 30 min. Higher density can be achieved through optimizing the temperature, pressure, time, additives and particle sizes of the staring materials. In the present

Table 1 Compositions, true densities, relative densities and grain size of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles Materials Compositions (vol.%) ZrB2 ZSN-0 ZSN-5 ZSN-10 ZSN-15 ZSN-20 ZSM-20 100 95 90 85 80 80 SiC 0 5 10 15 20 20 Nano Nano Nano Nano Micron 6.09 5.95 5.80 5.66 5.52 5.52 5.51 5.69 5.65 5.46 5.37 5.42 90.4 95.6 97.4 96.5 97.3 98.2 SiC grade Theoretical density (g/cm3) Measured density (g/cm3) Relative density (%TD) Average grain size (lm) ZrB2 6.1 2.2 5.9 1.4 4.5 1.6 4.4 1.7 4.2 1.9 5.4 1.6 SiC 0.8 0.4 0.8 0.4 0.9 0.5 0.9 0.5 1.6 0.6

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Fig. 1. Typical FE-SEM micrographs of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles; (a) ZSN-0, (b) ZSN-10, (c) ZSN-20 and (d) ZSM-20.

study, the relative densities exceeding 95% are obtained for the ZrB2 powder with nano-sized particles, which is signicantly higher than that of the single-phase ZrB2 powder. It is evident that the addition of nano-sized SiC has a similar effect in improving the sinterability of ZrB2. Improvement of the sinterability of ZrB2 due to ultra-ne SiC addition is documented in literatures. Monteverde [9] showed that ZrB2 with 10 vol.% ultra-ne SiC (d90 = 0.8 lm) achieved full density by vacuum hot-pressing at 1900 C for 20 min. Hwang et al. [15] showed that the sinterability of ZrB2 was signicantly improved by addition of nano-sized SiC and the improvement was enhanced with SiC amount as well as with reducing SiC starting-powder size. Zhu et al. [14] also showed that smaller starting SiC particle sizes led to improved densication. This improvement of densication is due to the formation of intergranular liquid phases during hot-pressing, assisting in densication at lower temperatures. Similar cause is expected in the present studied ZrB2 with nano- and micron-sized SiC starting powders. However, the highest relative density is not obtained in the ZrB2 with nano-sized SiC particle, but in the ZrB2 with micron-sized SiC particle. This probably is associated with the agglomeration nano-sized SiC particles which lead to the formation of submicron SiC (Table 1), in turn resulting in reduced improvement in densication of ZrB2 with nano-sized SiC particles. 3.2. Oxidation Fig. 2 shows typical examples of X-ray diffraction patterns of the single-phase ZrB2 and ZrB2-based composites with nano- and micron-sized SiC before and after 10 h of oxidation exposure at 1400 C. Before oxidation exposure (Fig. 2a), only ZrB2 phase was detected in the single-phase ZrB2, while ZrB2 and SiC phases were present in the ZrB2 with nano- and micron-sized SiC. Although a grain-boundary phase is reported in ZrB2-based composites with SiC particles [15], a trace amount of the secondary crystalline phase was not detected in any instance. In addition, the peak intensities of ZrB2 phase decreased with SiC addition, and the intensities were stronger for the ZrB2 with micron-sized SiC than for that with nano-sized SiC. This indicated that the amount of SiC particles in per unit area is higher in the ZrB2 with nano-sized SiC than in that

with micron-sized SiC. After oxidation exposure (Fig. 2b), only ZrO2 phase was detected for all the compositions materials. The peak intensities of the ZrO2 phase were the strongest in the single-phase ZrB2. Furthermore, the intensities were stronger for the ZrB2 with micron-sized SiC than for the ZrB2 with nano-sized SiC as well as they weakened with amount of nano-sized SiC particles. This implies that addition of SiC particles improved oxidation resistance of the single-phase ZrB2. This improvement was better in the ZrB2 ceramics with nano-sized SiC than in the ZrB2 with micronsized SiC and it was enhanced with amount of nano-sized SiC. These XRD analyses indicated that the single-phase ZrB2 and ZrB2-containing nano- and micron-sized SiC particles were oxidized to form the ZrO2 phase on the surfaces of specimens when they were exposed to 1400 C in dry air. Fig. 3 showed the appearances of the hot-pressed ZrB2SiC composites before and after the oxidation exposure. Before oxidation exposure, all the specimens were almost the same color. After oxidation exposure, however, the color of single-phase ZrB2 turned white with clear cracking on the surface. At high-magnication image (Fig. 4a), no distinct difference was observed on the oxidized surface. This shows that the oxidized surface consists of singlephase ZrO2. It is well-known that the single-phase ZrB2 was oxidized to form ZrO2 and B2O3 when ZrB2 was exposed to elevated temperature in air [7,18]. Thus, in the present study, when the single-phase ZrB2 was exposed to air at 1400 C, the ZrB2 was oxidized to the ZrO2 and B2O3 phases according to following reaction

5 ZrB2 O2 ! ZrO2 B2 O3 : 2

Although the B2O3 liquid layer presents an effective barrier to the transport of oxygen below 1100 C, at 1400 C and above, the rate of vaporization of B2O3 is comparable to the rate of formation [7]. Thus, only ZrO2 was presented for the single-phase ZrB2 after oxidation exposure. In addition, some cracks were observed on the oxidized surface (indicated by arrows in Fig. 4a). Cracking was induced by the volume expansion of the ZrO2 phase (typically 35 vol.%), which was produced during exposure through the phase transformation of tetragonal to the monoclinic phase upon cooling from exposure temperature to room temperature.

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ZrB2

SiC

ZrO2

ZSN-0 ZSN-0
Intensity (a.u.) Intensity (a.u.)

ZSM-20

ZSM-20

ZSN-20

ZSN-20

20

30

40

50

60

70

80

20

30

40

50

60

70

80

2 (degree)

2 (degree)

Fig. 2. Typical examples of X-ray diffraction patterns of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles; (a) before and (b) after oxidation exposure.

Fig. 3. Typical macroscopic appearances of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles before and after oxidation exposure.

On the other hand, the color of ZrB2-based composites with nano- and micron-sized SiC particles turned black (Fig. 3b), with a transparent glassy lm on the surfaces of the oxidized specimens. In particular, the color of the ZrB2-based composites with nanosized SiC particles is darker than that of the ZrB2-based composites with micron-sized SiC, which is a clear indication that more SiC and ZrB2 particles remained intact (without being oxidized) after oxidation exposure. Under SEM image (Fig. 4b), the oxidized surface of ZrB2 with SiC showed a distinctly difference with the sin-

gle-phase ZrB2: some white particles embedded in the background. The EDX analysis of the oxidized surfaces showed that the light places were rich in Zr and the background was rich in Si, with a high concentration of O (Fig. 5). The EDX results indicated that the oxidized surface of ZrB2-based composites with SiC consists of silica glass background and some ZrO2 particles embedded it. It is known that the ZrB2 and SiC were oxidized simultaneously to form ZrO2, B2O3 and silica glass when the ZrB2-containing SiC composition was exposed to air at high temperature [7,19]. Our

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Fig. 4. SEM images of oxidized surfaces of the hot-pressed single-phase ZrB2 and ZrB2-based composite with 20 vol.% nano-sized SiC particles; (a) ZSN-0 and (b) ZSN20.

experimental results indicated that the oxidation of ZrB2 and SiC might be occurring for the studied material during the oxidation exposure. Moreover, the weight gain after oxidation in the ZrB2 with nano-sized SiC particles decreased with increasing amount of SiC particle (Table 2). Furthermore, the weight gain after oxidation exposure in the ZrB2-based composite with 20 vol% nano-sized SiC particles is lower than that with 20 vol% micron-sized SiC particles. It is evident that the ZrB2-based composites with nano-sized SiC particles exhibited a better oxidation resistance than that with micron-sized SiC particles. Better oxidation resistance due to addition of nano-sized SiC particles is documented in literature. Hwang et al. [15] revealed that SiC grain-size reduction result in improved oxidation resistance in ZrB2-based ceramics with SiC. This improvement is attributed the formation of the protective silicarich glass layer on the surface of the ZrB2-based composites with nano-sized SiC during the earlier stage of oxidation, as a result of an increase in the ZrB2/SiC interface length per unit area of exposed-surface and a decrease in the spacing between SiC particles with increasing amount of SiC particles or reducing SiC starting size. Similar cause is expected in the nano-sized SiC-containing ZrB2 ceramics investigated in this study. 3.3. Flexural strength Table 2 also lists the exural strengths of the single-phase ZrB2 and ZrB2-based composites with nano- and micron-sized SiC particles measured by four-point bending test before and after oxida-

Fig. 5. Elemental composition maps of oxidized surface of the hot-pressed ZrB2based composite with 20 vol.% nano-sized SiC particles.

Table 2 Weight gain and exural strength of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles before and after 10 h of oxidation exposure at 1400 C in dry air Materials Total weight gain (mg/cm2) 4-Point exural As-received ZSN-0 ZSN-5 ZSN-10 ZSN-15 ZSN-20 ZSM-20 24.01 7.11 6.94 5.31 4.66 11.02 457 58 549 49 524 63 714 59 608 93 531 10 Strength (MPa) Post-exposed 141 21 635 15 610 83 718 82 700 41 506 19

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tion of 10 h at 1400 C. Before oxidation exposure, the single-phase ZrB2 has the lowest exural strength (457 MPa). This may be due to the presence of $10% porosity. The exural strength of the ZrB2based composites with nano-sized SiC particles is signicantly higher than that of the single-phase ZrB2. The ZrB2-based composite with 15 vol.% nano-sized SiC has the highest exural strength of 714 MPa. It is also clear that the exural strength of ZrB2-based composite with 20 vol.% nano-sized SiC is higher than that with 20 vol.% micron-sized SiC. This veries an earlier study that smaller SiC grain sizes would result in higher strength for ZrB2SiC composites [14]. After oxidation exposure, the exural strength of single-phase ZrB2 dropped sharply from 457 MPa to 141 MPa, which corresponds to $70% reduction. In contrast, the exural strength of ZrB2-based composites with nano-sized SiC particles increased signicantly except for the composite with 15 vol.% SiC in which its exural strength retained almost constant. The exural strength of the ZrB2-based composite with micron-sized SiC particles decreased after oxidation, however. The fracture surfaces of the hot-pressed ZrB2 and ZrB2-based composites with nano- and micron-sized SiC are observed under SEM, which examples are shown in Fig. 6. A typical intergranular fracture mode was observed in the single-phase ZrB2 as shown in Fig. 6a. For the ZrB2-based composites with nano-sized SiC particles (Fig. 6b), both ZrB2 and SiC grains exhibited typical intragranular fracture characteristics. SiC particles were located along the grain boundaries (intergranular). In addition, high-magnication SEM images shown in Fig. 6c revealed that some nano SiC particles were observed within ZrB2 grains (intragranular) as indicated by arrows in Fig. 6c. Niihara [20] reported that the strength of a ceramic could be enhanced substantially through the incorporation of nano-particles within the grains (intragranular nanocomposites). For the ZrB2-based composite with micron-sized SiC (Fig. 6d), the fracture surface of ZrB2 and SiC also exhibited a typical intragranular feature. The large SiC particles were observed at the multipleZrB2 grains pockets as indicated by arrows in Fig. 6d. As a result, the nano-sized SiC particles are more effective in enhancing the strength of the ZrB2 ceramic than that derived from micron-sized SiC particles.

The macroscopic fracture appearances and SEM micrographs of the fracture surfaces for the hot-pressed ZrB2-based composites with nano- and micron-sized SiC after being oxidized at 1400 C for 10 h are shown in Fig. 7. For single-phase ZrB2, only central part of specimen was not oxidized after the oxidation exposure (Fig. 7a), and two large cracks were extended through to near the unreacted ZrB2 (indicated by arrows). The large cracks led to a substantial reduction of the strength of ZrB2 after oxidation exposure. Under high-magnication SEM image (Fig. 7d), the unreacted ZrB2 showed typical intragranular fracture characteristics. This differed from the as-sintered ZrB2 which showed a typical intergranular fracture mode (Fig. 6a). For both the ZrB2-based composites with nano- and micronsized SiC (Fig. 7b and c), on the other hand, the observable oxidized reacted region are absent, as a result of improved oxidation resistance of ZrB2 through the addition of SiC particles. Although, for the ZrB2 with micro-sized SiC, the fracture originated from a defect at or near the surface (indicated by an arrow in Fig. 7b), the fracture origin was not distinguishable for the ZrB2 with nano-sized SiC (Fig. 7c). Higher-magnication SEM images, taken from the tensile surface of specimens, are shown in Fig. 7e and f, respectively. For the oxidized ZrB2-based composite with micron-sized SiC particles (Fig. 7e), a thicker glassy layer is observed and a defect was also observed at the interface between the oxide scale and bulk ZrB2 (indicated by an arrow). This revealed that the ZrB2 specimens with micron-sized SiC develop thick oxide scales that probably possess high level of defects, resulting in a lower strength after oxidation exposure. In contrast, for the oxidized ZrB2-based composites with nano-sized SiC particles (Fig. 7f), the thinner oxide scale was observed. The thin oxide scale of the ZrB2-based composites with nano-sized SiC is attributed to its better oxidation resistance than that with micron-sized SiC. Clearly, the formation of the thin oxide scale can heal the surface aws without creating new cracks and defects at the oxidized surface and play a signicant role in the strength improvement after oxidation exposure. Thus, the improvement of exural strength after oxidation exposure may be attributed to the formation of a thinner oxide scale which effectively alters the geometry of the surface defects [21], as a result of a

Fig. 6. Typical fracture surfaces of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles; (a) ZSN-0, (b) ZSN-15, (c) high-magnication of (b) and (d) ZSM-20.

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Fig. 7. Typical macro- and microscopic fracture appearances of the hot-pressed ZrB2-based composites with nano- and micron-sized SiC particles after oxidation exposure; (a), (d) ZSN-0, (b), (e) ZSM-20, (c), (f) ZSN-20.

better oxidation resistance of the ZrB2 with nano-sized SiC than that with micron-sized SiC. 4. Summaries The room-temperature exural strength of ZrB2-based composites with nano-sized SiC particles was investigated and compared to that with micron-sized SiC particles before and after oxidation exposure in dry air at 1400 C for 10 h. The strength for ZrB2 with nano-sized SiC particles is higher than that with micron-sized SiC particles. This is attributed to a more uniform dispersion of nano-sized SiC particles at grain boundaries and within the grains, whereas the micron-sized SiC particles are located at multiplegrain pockets. After oxidation exposure, the exural strength of ZrB2-based composites with nano-sized SiC particles increased. In particular, the exural strength signicantly increased for the composites containing 5, 10 and 20 vol.% nano-sized SiC particles. In contrast, the strength of the ZrB2-based composite with microsized SiC particles decreased after oxidation. The presence of intergranular and intragranular nano-sized SiC particles imparts a bet-

ter oxidation resistance and improves the exural strength of single-phase ZrB2 and ZrB2-based ceramics with micron-sized SiC. Further improvement in strength may be achieved through a more uniform dispersion of nano-sized SiC particles. Acknowledgements J.M.Y. gratefully acknowledges the support from NASA Glen Research Center. Dr. N. Bansal is the program manager. References
[1] Upadhya K, Yang JM, Hoffmann WP. Materials for ultrahigh temperature structural applications. Am Ceram Soc Bull 1997;76:516. [2] Fahrenholtz WG, Hilmas GE, Talmy IG, Zaykoski JA. Refractory diborides of zirconium and hafnium. J Am Ceram Soc 2007;90:134764. [3] Brown AS. Hypersonic designs with a sharp edge. Aerospace Am 1997;35:201. [4] Mroz C. Zirconium diboride. Am Ceram Soc Bull 1994;73:1412. [5] Norasetthekul S, Eubank PT, Bradley WL, Bozkurt B, Stucker B. Use of zirconium diboridecopper as an electrode in plasma applications. J Mater Sci 1999;34:126170.

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S.-Q. Guo et al. / Composites Science and Technology 68 (2008) 30333040 [14] Zhu S, Fahrenholtz WG, Hilmas GE. Inuence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboridesilicon carbide ceramics. J Eur Ceram Soc 2007;27:207783. [15] Hwang SS, Vasiliev AL, Padture NP. Improved processing and oxidationresistance of ZrB2 ultra-high temperature ceramics containing SiC nanodispersoids. Mater Sci Eng 2007;A464:21624. [16] Mendelson MI. Average grain size in polycrystalline ceramics. J Am Ceram Soc 1969;52:4436. [17] Melendez-Martinez JJ, Dominguez-Rodriguez A, Monteverde F, Melandri C, de Portu G. Characterization and high temperature mechanical properties of zirconium boride-based materials. J Eur Ceram Soc 2002;22:25439. [18] Tripp WC, Graham HC. Thermogravimetric study of the oxidation of ZrB2 in the temperature range of 800 C to 1500 C. J Electrochem Soc 1971;118:11959. [19] Monteverde F, Bellosi A. Oxidation of ZrB2-based ceramics in dry air. J Electrochem Soc 2003;150:B5529. [20] Niihara K. New design concept of structural ceramicsceramic nanocomposites. J Ceram Soc Japan 1991;99:97482. [21] Guo SQ, Hirosaki N, Yamamoto Y, Nishimura T, Mitomo M. Strength retention in silicon nitride ceramics with Lu2O3 additives after oxidation exposure in air at 1500 C. J Am Ceram Soc 2002;85:16079.

[6] Blum A, Ivanick W. Recent developments in the application of transition metal borides. Powder Met Bull 1956;7:758. [7] Tripp WC, Davis HH, Graham HC. Effect of an SiC addition on the oxidation of ZrB2. Am Ceram Soc Bull 1973;52:6126. [8] Opeka MM, Talmy IG, Wuchina WJ, Zaykoski J, Causey SJ. Mechanical, thermal, and oxidation properties of refractory hafnium and zirconium compounds. J Eur Ceram Soc 1999;19:240514. [9] Monteverde F. Benecial effects of an ultra-ne a-SiC incorporation on the sinterability and mechanical properties of ZrB2. Appl Phys A 2006;82:32937. [10] Monteverde F, Bellosi A. Development and characterization of metal-diboridebased composites toughened with ultra-ne-SiC particles. Solid State Sci 2005;7:62230. [11] Bellosi A, Monteverde F, Fabbriche DD, Melandri C. Microstructure and mechanical properties of ZrB2-based Ceramics. J Mater Process Manuf Sci 2000;9:15670. [12] Chamberlain AL, Fahrenholtz WG, Hilmas GE. High-strength zirconium diboride-based ceramics. J Am Ceram Soc 2004;87:11702. [13] Rezaie A, Fahrenholtz WG, Hilmas GE. Effect of hot pressing time and temperature on the microstructure and mechanical properties of ZrB2SiC. J Mater Sci 2007;42:273544.