J. Am. Ceram. Soc.

, 83 [9] 2330 32 (2000)

journal
Reactive Hot Pressing of ZrB2SiC Composites
Guo-Jun Zhang, Zhen-Yan Deng, Naoki Kondo, Jian-Feng Yang, and Tatsuki Ohji*
National Industrial Research Institute of Nagoya, Nagoya, Aichi 463-8687, Japan A ZrB2SiC composite was prepared from a mixture of zirconium, silicon, and B4C via reactive hot pressing. The three-point bending strength was 506 43 MPa, and the fracture toughness was 4.0 MPam1/2. The microstructure of the composite was observed via scanning electron microscopy; the in-situ-formed ZrB2 and SiC were found in agglomerates with a size that was in the particle-size ranges of the zirconium and silicon starting powders, respectively. A model of the microstructure formation mechanism of the composite was proposed, to explain the features of the phase distributions. It is considered that, in the reactive hot-pressing process, the B and C atoms in B4C will diffuse into the Zr and Si sites and form ZrB2 and SiC in situ, respectively. Because the diffusion of Zr and Si atoms is slow, the microstructure (phase distributions) of the obtained composite shows the features of the zirconium and silicon starting powders. I. Introduction produce TiB2Ti(C,N)SiC ternary composites10 and in-situformed TiB2-toughened SiC.11 In the present study, the following reaction will be used to prepare ZrB2SiC composite: 2Zr Si B4C 3 2ZrB2 SiC (1)

The volume contents of the composite formed from the abovementioned reaction are 74.85 vol% ZrB2 and 25.15 vol% SiC. The theoretical density of the composite, according to the rule of mixtures, is 5.37 g/cm3. This processing can avoid the effect of the oxidation of fine ZrB2 powder on the sintering in the conventional processing. In this communication, the manufacturing process, mechanical properties, and microstructure of the composite will be reported preliminarily.

II.

Experimental Procedure

(ZrB2) is a hexagonal crystal of the AlB2 type and is similar to titanium diboride (TiB2). ZrB2 has a high melting point (3040C), high hardness (22 GPa), high electrical conductivity (9.2 106 cm), and good corrosion resistance. ZrB2 is wetted but not attacked by molten metals; thus, it has been used as molten-metal crucibles, HallHeroult cell cathodes, and thermowell tubes for steel refining.1 The flexural strength and fracture toughness of ZrB2 ceramics are 200 375 MPa and 4 5 MPam1/2, respectively. The density of ZrB2 is 6.09 g/cm3, and the thermal expansion coefficient is 5.5 106 K1.1 ZrB2 powder can be manufactured via the reaction of elemental zirconium and boron or via the reaction of ZrO2 with carbon and B4C or with carbon and B2O3.1,2 ZrB2 ceramics usually are produced via hot pressing or presureless sintering from ZrB2 powder. However, the mechanical properties and oxidation resistance of monolithic ZrB2 ceramics are not satisfactory for applications such as thermowell tubes. Thus, some components are added to form ZrB2-based ceramic composites. For example, the addition of SiC will improve the oxidation resistance,3,4 the addition of BN will improve the thermal shock property, and the addition of B4C will increase the hardness and toughness.4 ZrB2ZrC and LaB6ZrB2 eutectic composites with high mechanical properties were prepared via directional solidification.5,6 Johnson et al.7 developed a method to prepare ZrB2ZrCzirconium composites with homogeneously distributed platelet-shaped ZrB2. TiB2SiC composites have been prepared from a mixture of TiH2, silicon, and B4C,8,9 and this in-situ reaction has been used to
IRCONIUM DIBORIDE

The starting powders were zirconium, silicon, and B4C; the characteristics of the powders are listed in Table I. The stoichiometric powders, according to reaction (1), were mixed in propanol with ZrO2(Y2O3) balls for 24 h in a plastic bottle and then dried. The composite was produced via reactive hot pressing in a graphite die with a BN coating at a temperature of 1900C under a pressure of 30 MPa for 60 min in an argon atmosphere. The dried mixed powder was placed into a cold graphite die and loaded to 3 MPa before the temperature was increased. Reaction (1) is exothermic, with a large enthalpy of reaction; therefore, a slow heating rate (10C/min) was adopted to prevent the reaction from becoming self-sustaining. To prevent the molten silicon from moving out of the die at high temperatures, the application of pressure was begun at 1550C and gradually increased to 30 MPa before the temperature reached a value of 1900C. The obtained product, 25 mm in diameter and 5 mm thick, was cut into specimens and then ground with diamond wheel (800 grit size) along the longitudinal direction of the specimens. Phase composition was determined via X-ray diffractometry (XRD) using CuK radiation. The density was tested using the waterdisplacement method. The three-point bending strength was measured on bars with dimensions of 2.5 mm 3 mm 20 mm (four edges were beveled using 1500 grit SiC abrasive paper); the span was 16 mm, and the crosshead speed was 0.5 mm/min. The strength data were an average of five measurements. The fracture toughness was measured via the indentation method, using a load of 5 kg, according to Japanese Industrial Standard JIS R 1607.12 The calculation formula is K IC 0.026

E 1/ 2 P 1/ 2 a C 3/ 2

(2)

R. W. Ricecontributing editor

Manuscript No. 189035. Received October 6, 1999; approved April 24, 2000. This work has been conducted as special research (KYOU-SOU TOKKEN) supported by AIST, MITI, Japan. *Member, American Ceramic Society.

where P is the indentation load, a the half length of the indent, C the half length of the crack, and E the elastic modulus of the composite. E is calculated from the elastic moduli of the components (EZrB2 450 GPa and ESiC 414 GPa), according the rule of mixtures. The hardness data and toughness data were an average of ten measurements. Scanning electron microscopy (SEM) was performed to observe the microstructure of the composite. 2330

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Communications of the American Ceramic Society Table I. Characteristics of the Starting Powders

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Starting powder

Particle size (m)

Chemical composition

Manufacturer

Zirconium Silicon B4C

43 10 1

98% pure; impurities include 0.02% Al, 0.1% Ca, 0.06% Fe, 1% Hf, 0.1% Mg, and 0.08% Ti 99.9% pure; impurities include 0.001% Ca, 0.008% Cr, 0.03% Fe, and 0.004% Ni 75% boron, 20%25% carbon

High Purity Chemicals, Saitama, Japan High Purity Chemicals, Saitama, Japan Denki Kagaku Kogyo Co., Ltd., Tokyo, Japan

III.

Results and Discussion

According to the XRD pattern, only ZrB2 and SiC phases are present in the obtained composite, which shows that the reaction occurred during the reactive hot-pressing process and is in accordance with reaction (1). This observation means that the ZrB2SiC composite can be produced through this in-situ reaction and the volume contents of ZrB2 and SiC also can be adjusted by adding ZrB2 or SiC powder to the mixed reactant powders. The characteristics of the synthesized composite are listed in Table II. The relative density of the composite is considerably high, and it is believed that the relative density can be improved through optimization of the processing, such as via adjustment of the hot-pressing temperature and hold time. The bending strength of the composite is 506 43 MPa, which is 2 times higher than that of conventional monolithic ZrB2 ceramics with a grain size of several tens of micrometers.1,4 The difference in grain size would be one of the main reasons for the improved strength of the present composite. In addition, for a particulate composite, particle bridging would work when a propagating crack meets the secondary-phase particles and improves the strength of the composite.13 In the present case, the SiC and ZrB2 can be treated as the secondary-phase particles and the matrix, respectively. In addition, for in-situ composites, the interfaces between the component phases generally are cleaner and stronger than those of the conventionally processed composites.11,14,15 Such phenomena also should exist in the in-situ ZrB2SiC composite and lead to a considerably high bending strength. The fracture toughness of the composite is somewhat less than that of monolithic ZrB2 ceramics. This phenomenon is suggested to be related to the thermal expansion coefficients of ZrB2 and SiC (ZrB2 5.5 106 K1 and SiC 4.0 106 K1, respectively). According to the calculation method that was proposed by Taya et al.,16 the calculated average residual stresses for the ZrB2 matrix and SiC particles in the composite are 152 MPa (tensile) and 452 MPa (compressive), respectively. (In the calculation, the parameters are set as follows: Poissons ratios of ZrB2 0.25 for ZrB2 and SiC 0.14 for SiC, and the temperature range over which stresses are not relieved by plastic deformation is T 1200 K.) That is, the existence of the tensile stress in the ZrB2 matrix will reduce the toughening effect by the particle bridging of the SiC particles. An approximate calculation, according to the Taya group, shows that the reduction in the fracture toughness that is caused by the existence of the tensile stress in the ZrB2 matrix is 0.45 MPam1/2. Figure 1 shows the microstructure of the composite. The particle size of SiC is generally 3 m, whereas that of ZrB2 is larger and in the range of 310 m. These pictures indicate that the

Fig. 1. SEM micrographs of the ZrB2SiC composite ((a) polished surface and (b) fracture surface); the white phase is ZrB2, and the dark gray phase is SiC.

Table II. Characteristics of the Reaction-Synthesized ZrB2SiC Composite

Property Value

Phase composition, via XRD Relative density (percentage of theoretical density) Bending strength Fracture toughness Vickers hardness Grain size

ZrB2 and -SiC 97.67% 506 43 MPa 4.0 MPam1/2 21.0 GPa SiC, 3 m; ZrB2, 310 m

distributions of the in-situ-formed ZrB2 and SiC phases in the composite are not homogenous on a microscale level. That is, the ZrB2 phase generally gathers together to form larger agglomerates, and in these agglomerates, the particle size of ZrB2 is large. The SiC phase also gathers together to form agglomerates, but the sizes of these agglomerates are smaller than those of the ZrB2 phase. The sizes of the agglomerates of ZrB2 and SiC are in the particle size ranges of the starting powders of zirconium and silicon, respectively, when the data from Table I are compared with Fig. 1. This observation suggests that such phase distributions are related to the particle size of the starting powders. Figure 2 shows the formation mechanism of this composite in the reactive hotpressing process. Figure 2 shows that, in the reactive hot-pressing process, the B and C atoms in B4C will diffuse into the Zr and Si sites, respectively, and then form ZrB2 and SiC in situ. Because the diffusion of Zr and Si atoms is slow, the formed agglomerates of synthesized ZrB2 and SiC possess the features of the starting

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sizes were in the particle-size ranges of the zirconium and silicon starting powders. References
C. Morz, Zirconium Diboride, Am. Ceram. Soc. Bull., 73 [6] 14142 (1994). H. Zhao, Y. He, and Z. Jin, Preparation of Zirconium Boride Powder, J. Am. Ceram. Soc., 78 [9] 2534 36 (1995). 3 W. C. Tripp, H. H. Davis, and H. C. Graham, Effect of an SiC Addition on the Oxidation of ZrB2, Am. Ceram. Soc. Bull., 52 [8] 61216 (1973). 4 K. Sakai, Some Characteristics and Applications of ZrB2 Composite Ceramics, Ceram. Jpn., 24, 526 32 (1989). 5 C. C. Sorrell, H. R. Beratan, R. C. Bradt, and V. S. Stubican, Directional Solidification of (Ti,Zr) Carbide(Ti,Zr) Diboride Eutectics, J. Am. Ceram. Soc., 67 [3] 190 94 (1984). 6 C. M. Chen, W. C. Zhou, and L. T. Zhang, Oriented Structure and Crystallography of Directionally Solidified LaB6ZrB2 Eutectic, J. Am. Ceram. Soc., 81 [1] 237 40 (1998). 7 W. B. Johnson, A. S. Nagelberg, and E. Breval, Kinetics of Formation of a Platelet-Reinforced Ceramic Composite Prepared by the Directed Reaction of Zirconium with Boron Carbide, J. Am. Ceram. Soc., 74 [9] 2093101 (1991). 8 G. J. Zhang, Z. Z. Jin, and X. M. Yue, Reaction Synthesis of TiB2SiC Composites from TiH2-Si-B4C, Mater. Lett., 25, 97100 (1995). 9 G. J. Zhang, Z. Z. Jin, and X. M. Yue, Effects of Ni Addition on Mechanical Properties of TiB2/SiC Composites Prepared by Reactive Hot Pressing (RHP), J. Mater. Sci., 32, 209397 (1997). 10 G. J. Zhang, Z. Z. Jin, and Y. M. Yue, TiB2Ti(C,N)SiC Composites Prepared by Reactive Hot Pressing, J. Mater. Sci. Lett., 15, 26 28 (1996). 11 G. J. Zhang, X. M. Yue, Z. Z. Jin, and J. Y. Dai, In-Situ Synthesized TiB2 Toughened SiC, J. Eur. Ceram. Soc., 16, 409 12 (1996). 12 Testing Methods for Fracture Toughness of Fine Ceramics, Japanese Industrial Standard No. JIS R 1607, 1995. 13 T. Ohji, Y. K. Jeong, Y. H. Choa, and K. Niihara, Strengthening and Toughening Mechanisms of Ceramic Nanocomposites, J. Am. Ceram. Soc., 81 [6] 1453 60 (1998). 14 K. Niihara, New Design Concept of Structural CeramicsCeramic Nanocomposite, J. Ceram. Soc. Jpn., 99, 974 82 (1991). 15 N. Claussen, S. Wu, and D. Holz, Reaction Bonding of Aluminum Oxide (RBAO) Composites: Processing, Reaction Mechanisms and Properties, J. Eur. Ceram. Soc., 14, 97109 (1994). 16 M. Taya, S. Hayashi, A. S. Kobayashi, and H. S. Yoon, Toughening of Particulate-Reinforced Ceramic-Matrix Composite by Thermal Residual Stress, J. Am. Ceram. Soc., 73 [5] 138291 (1990).
2 1

Fig. 2. Microstructure formation mechanism of the ZrB2SiC composite in the reaction-synthesis process, depicting the transformation from (a) the powder compact to (b) the final microstructure of the composite.

powders. According to the above-described model, it is believed that a ZrB2SiC composite with a fine and homogeneous microstructure and better mechanical properties can be obtained using starting powders with a fine particle size. The results of this problem and the details of the phase-formation mechanism will be reported after future investigation. IV. Conclusions

A ZrB2SiC composite was prepared via reactive hot pressing of a mixture of zirconium, silicon, and B4C powders. The bending strength of the obtained composite was 506 43 MPa, and the fracture toughness measured by Vickers indentation technique was 4.0 MPam1/2. The microstructure of the composite possesses the features of the zirconium and silicon starting powders. A model was proposed to explain this characteristic of the microstructure. In the reactive hot-pressing process, B and C atoms will diffuse into the Zr and Si sites, respectively, and then form ZrB2 and SiC in situ. The diffusion of Zr and Si atoms was slow; therefore, the in-situ-formed ZrB2 and SiC were present in agglomerates whose