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UNIVERSITY OF CALIFORNIA LOS ANGELES

ZrB2-Based Composites for Ultra-High-Temperature Applications

A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Materials Science and Engineering By

Do Hwan Chung

2010

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© copyright by Do Hwan Chung 2010 .

Suneel Kodambaka ^ ^ ^ Daniel Yang " //£ V /0#/<o ta Jdnn/Ming Yafid Committee/Chair University of California.The dissertation of Do Hwan Chung is approved. Los Angeles 2010 .

my mother. in . my wife.Dedicated to my father. and my two sons.

............1 Introduction 1.....2 Experimental procedure...........................16 29 Chapter 3 ZrB2-nano SiC ceramics ..TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES ACKNOWLEGEMENTS VITA PUBLICATIONS ABSTRACT Chapter 1 Ultra-high-temperature ceramics 1.....1 Materials 3... ...2.....................2 Applications of ultra-high-temperature ceramics References Chapter 2 Literature survey of ultra-high-temperature ceramics 2...........................................................1 Introduction...............................2 Elastic property measurements 35 38 IV .................3 Mechanical properties of ZrB2-SiC ceramics 2.................2 Oxidation mechanism of ZrB2-SiC ceramics 2.................35 3.............32 Abstract 3...5 Liquid phase sintering References vii xi xii xiv xvi xvii 1 1 2 7 8 8 9 12 14 .32 34 3..2.1 Selection of ultra-high-temperature ceramics 2........4 Spark plasma sintering 2................................

..3..2..93 ..91 4....119 V .1 Densities.1 Materials 4.........1.4 Micropillar compression test 3....2 Elastic moduli..4 Electrical conductivity .....2..2.....3 Micropillar compression test of ZrB2-nano SiC composite materials 3......2 Elastic moduli.. and fracture toughness measurements 4..... hardness.3 Results and discussion 3...3 Mechanical properties 3................ Conclusion References .2.......3..3 Thermal conductivity 38 40 40 40 43 45 47 72 74 74 76 78 78 79 80 81 82 ........3........82 85 87 4.2 Elastic moduli...........4 Conclusion References Chapter 4 Multiphase ZrC-ZrB2-SiC ceramics Abstract 4....3....4...3. and microstructures 3...5 Micropillar compression tests of ZrC-ZrB2-SiC composites ...3....... hardness and fracture toughness 3..2.3 Results and discussion 4.4 Micropillar compression test 4.....3....3... Experimental procedures 4. hardness..89 4....3 Thermal and electrical conductivity measurements 4....... phases....... phases........ and microstructures 4...2.... Introduction 4..2.. and fracture toughness 4...........1 Densities..3.....

2.1 Fabrication 5.2 Phase analysis. and porosity measurements 5.1 Density.1 Introduction 5. hardness.2 Experimental procedures 5.3 Elastic properties.2.3 Results and discussion 5.3. and phase 5.4 Microstructure observations 5. and fracture toughness 5.3.2 Elastic moduli.2.Chapter 5 SCS 9afiber-reinforcedZrB2-RB(Reaction-bonded) SiC composite Abstract 5. and fracture toughness measurements 5. hardness.3 Microstructural analysis 5.4 Conclusion References Chapter 6 Conclusions 121 121 123 124 124 125 126 126 128 128 129 130 132 146 148 vi . porosity.3. density.2.

................... Schematic of the SPS process [19] Figure 2-7.59 vii .. Typical TEM microstructures of each sample .... Belly-down attitude during re-entry 5 6 Figure 2-1.... Re-creation of the Shockwave during re-entry Figure 1-2... Several materials with melting temperatures approaching or above 3000°C [1] Figure 2-2....... Typical SiC grain locations in ZrB2-SiC composite ..LIST OF FIGURES Figure 1-1..... Microstructure of ZrB2-SiC ceramics [17] Figure 2-6..58 Figure 3-6.. Basic mechanism of spark plasma sintering [20] Figure 2-8..... Classification of ceramic nanocomposites 23 24 25 26 27 28 54 Figure 3-2........... Typical FE-SEM images of each sample 55 56 Figure 3-4.57 Figure 3-5. X-ray diffraction patterns of each composite material (a) ZSN-0 (b) ZSN-5(c)ZSN-10(d)ZSN-20(e)ZSN-30 Figure 3-3. ZrB2-SiC phase diagram [12] 21 22 Figure 2-3............. The cross-sectional microstructure of ZrB2-SiC ceramics [13] Figure 2-5.. (a) unoxidized ZrB2-SiC (b) the initial response during heating (c) evolution as the temperature approaches 1500°C (d) steady state at 1500°C [13] Figure 2-4... The change of average grain size of each component.. Three different steps of liquid phase sintering by Kingery Figure 3-1.. The schematic diagram of a proposed oxidation mechanism for ZrB2-SiC ceramics.

. ZSN-5....Figure 3-7.. ZSN-20 61 Figure 3-9....... height change relation by micropillar compression test for ZSN-5 66 Figure 3-14...... TEM microstructural images of ZSN-10 by the micropillar compression test (a) Whole TEM laminar (b) Dislocations (c) Stacking fault 70 Figure 3-18.. Fabricated micropillar of ZSN-0.. The TEM image and EDX result of second phase. and ZSN-10 63 64 Figure 3-12. The change of hardness and fracture toughness of ZrB2-nano SiC composite with SiC content 62 Figure 3-10..... height change relation by micropillar compression test for ZSN-10 Figure 3-15.... Typical interface between ZrB2 grain and SiC grain (ZSN-5: HRTEM image) 60 Figure 3-8. B)x.... TEM microstructural images of ZSN-0 by the micropillar compression test (a) Whole TEM laminar (b) Stacking fault (c) dislocation 69 Figure 3-17. Zr(0... ZSN-10 micropillar (a) before and (b) after compression 67 68 Figure 3-16.. Typical cracking pattern of ZrB2-SiC composites (ZSN-0. Stress vs......... ZSN-10. and ZSN-20) Figure 3-11. in ZrB 2 grain. height change relation by micropillar compression test for ZSN-0 65 Figure 3-13. Stress vs.71 viii ... Fracture surface images of ZSN-5 by the micropillar compression test (a) Fracture surface of whole micropillar (b) Intragranular fracture (c) Intergranular fracture . Stress vs....

Current versus voltage measured at room temperature for the ZrC-ZrB2-SiC composites Figure 4-9. Typical TEM images for the ZZS-1 composite Figure 4-5. (f) ZZS-6.... strain (%) curve of ZZS-2 micropillar Figure 4-12. (e) ZZS-5.. Typical TEM images of interphase interface between (a) SiC and ZrE$2 and (b) ZrB 2 and ZrC Figure 4-7.... Stress vs.. Stress vs.... . Intragranular fracture surface of ZZS-2 micropillar Figure 4-14..... Intragranular fracture surface of ZZS-1 micropillar Figure 4-13. (a) ZZS-1... Stress vs. Typical TEM images for the ZZS-2 composite 102 103 104 105 Figure 4-6. ZZS-3. X-ray diffraction patterns for each sample..... (h) ZZS-8 Figure 4-3... strain (%) curve of ZZS-6 micropillar 108 109 110 Ill 112 113 114 Figure 4-15.. Detailed dimensions of SCS 9a fiber-reinforced composites for fracture toughness 135 ix ..... Typical cracking behavior of ZrC-ZrB2-SiC composites 106 107 Figure 4-8. 117 Figure 4-18.. ZZS-6. Fabricated micropillar of ZZS-1. Typical examples of recorded shrinkage curves during the SPS cycle for ZZS-2..... Dimensional and shape change of ZZS-6 micropillar 116 Figure 4-17.. strain (%) curve of ZZS-1 micropillar Figure 4-11... strain (%) curve of ZZS-7 micropillar. Stress vs..... (d) ZZS-4..Figure 4-1...... ZZS-2. Typical cracking behavior of ZZS-7 micropillar. Typical TEM images of ZZS-6 micropillar after compression stress.... Typical FE-SEM images for the ZrEb-ZrC-SiC composites Figure 4-4.. and ZZS-5 101 Figure 4-2.... and ZZS-7 Figure 4-10. (b) ZZS-2........ (c) ZZS-3. (g) ZZS-7...118 Figure 5-1. 115 Figure 4-16.

. 138 Figure 5-5. 142 Figure 5-9. The FE-SEM image of the interface between fiber and matrix 143 Figure 5-10. (a) Carbon coating layer of the fiber (b) ZrE$2 grain (c) ZrB2 and SiC agglomerate (d) ZrB2 and SiC grains 145 x . Whole cross section view of SCS 9a fiber-reinforced composite 139 140 Figure 5-7. Typical TEM microstructures and SAED (Selected Area Electron Diffraction) of the composite 144 Figure 5-11. Typical TEM microstructural images and EDS results of the interface between the fiber and the matrix. FE-SEM images of SCS 9a fiber-reinforced composite. Typical FE-SEM images of cracks inside and outside the composite . (b) Cross-sectional view 136 Figure 5-3.. FE-SEM images of SCS 9a fiber-reinforced composite fracture Figure 5-6. Typical X-ray diffraction pattern of SCS 9a fiber-reinforced ZrB2-RB SiC composite 137 Figure 5-4. (a) Top surface view.Figure 5-2. 141 Figure 5-8. Typical indentation mark and cracking pattern of SCS 9a fiber composite. FE-SEM images of residual carbon from reaction bonding and EDS result.

....4... min) Table 3-1..........45 in sample names are starting SiC particle size of micron) 19 Table 2-2........ Thermal properties measured at room temperature for the ZrC-ZrB2-SiC composites 99 Table 4-6..... 45.. C... 100 Table 5-1. B: ZrB2 starting powder size...... 1. °C.. 1000K...... ZrC.... Physical and mechanical properties of ZrB2-SiC ceramics with different hot pressing time and temperature [18] (A... Compositions of each sample Table 3-2... and 180: time. and 2000K [12] 134 xi .. Hardness and fracture toughness of ZrB2-nano SiC composites materials 5 3 Table 4-1.. ZrC. and SiC for ZrC-ZrB2-SiC composies Table 4-4. Average grain sizes of ZrB2-nano SiC composite materials Table 3-4. The measured grain size of each component ZrB2. Elastic properties of ZrB2-nano SiC composite materials 20 49 50 51 52 Table 3-5... Physical and mechanical properties with reducing SiC particle size of ZrB2-SiC ceramics [17] (10..... Densities and elastic properties of ZrC-ZrB2-SiC composites 95 96 Table 4-3......... 1950.. Hardness and fracture toughness of ZrB2-ZrC-SiC composites 97 98 Table 4-5.. B: 2um....7. A: 6um....... and B4C at 298K... 90.............LIST OF TABLES Table 2-1. 0.. Gibbs free energy of formation of ZrB2. Compositions of ZrC-ZrB2-SiC composites Table 4-2.. Densities of each sample Table 3-3... Electrical properties measured at room temperature for the ZrC-ZrB2-SiC composites..... 0. 1850. and 2050: temperature.

Without your help and support. Narottam P. but also to help organize my research in a comprehensive means. who introduced me to the field of ultra-high-temperature ceramics and who has guided my doctoral studies all the way.ACKNOWLEGEMENTS This research is supported by the National Aeronautics and Space Administration (NASA) Glenn Research Center in Cleveland Ohio. it would have been impossible for me to complete this dissertation. Bansal is the program manager. and Professor Jenn-Ming Yang for the satisfaction of this dissertation. I would like to give my thanks to all of the committee members. Professor Daniel Yang. both in the scientific field and in daily life. and I have immeasurably treasured your advice and guidance. I wish to express my deepest gratitude to professor Jenn-Ming Yang. advisor. I would like to thank you for supporting and encouraging me throughout these years. I am especially grateful for your great ability not only to share your academic knowledge. Your door has always been open. I also want to thank my father and mother for struggling with all the accompanying difficulties so that I could concentrate on my work and smoothly finish xii . Your incredible enthusiasm and optimistic dedication to science has impressed me deeply. Professor Suneel Kodambaka.

my studies abroad. Your endless support and understanding are my driving force. Last but not least, I would like to express my deepest gratitude to my life partner, Min Jung, who is the light of my life. Thank you so much for our ten-year journey together, for all the tears and happiness we have had together, and also for your endless support, encouragement and love. With you, life will never be boring. All my friends are of great importance to me. All of you enrich my life and make it more colorful and joyful. All those wonderful times are unforgettable and highly appreciated. I wish to thank all of you as much as I can. I cherish your friendship and consideration.

Xlll

VITA 1992-1995 Completion of two school years in Chemistry Daejeon University Daejeon, Korea (R.O.K.) 1993-1994 Military Service, Korea (R.O.K.) Corporal, Army 1996-1998 Bachelor of Science in Chemistry Sejong University Seoul, Korea (R.O.K.) 1999-2000 Bachelor of Science in Ceramic Engineering Yonsei University Seoul, Korea (R.O.K.) 2001-2002 Master of Science in Ceramic Engineering

Seoul, Korea (R.O.K.) >003~2004 Master of Science in Chemical Engineering and Materials Science University of Southern California

Los Angeles, CA, USA 2005-2010 Doctor of Philosophy in Materials Science and Engineering University of California, Los Angeles Los Angeles, CA, USA

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[3] Kihyun Yoon. Do Hwan Chung. Kihyun Yoon.PUBLICATIONS [1] Seung Hyun Lee. Byungduk Yang. Journal of the European ceramic society. Volume 28. Do Hwan Chung. (2010). Jaehyuk Jang. forthcoming. ppl279-1285. Jenn-Ming Yang. Preparation and characteristics of PTFE (Polyteterafluoroethylene) composites for microwave circuit board. Journal of the Korean ceramic society. Ho Sung Lee. Ta)/CrTi bilayer thin films during sputter-deposition. Do Hwan Chung. Mechanical and physical behavior spark plasma sintered ZrC-ZrB2-SiC composites. Korea Patent. Yutaka Kagawa. Jongheui Kim. Manufacturing method of PTFE composite board. Application number 1020020078716. [4] Jo Jung. pp735-738. [2] Shu-Qi Guo. and Joon Keun Park. Toshiyuki Nishimura. XVI . Volume 40. (2003). (2002). Current applied physics. and Byungduk Yang. (2008). In-situ surface stress and magnetic properties of the CoCrX(X=Pt. Dohwan Chung.

micron-sized particles. and continuous fibers were used as reinforcement. 2010 Professor Jenn-Ming Yang. Three major investigations were conducted in this dissertation. Various forms of SiC including nano-sized particles. Los Angeles. Spark plasma xvii . microstructure.ABSTRACT OF THE DISSERTATION ZrB2-Based Composites for Ultra-High-Temperature Applications by Do Hwan Chung Doctor of Philosophy in Materials Science and Engineering University of California. Chair This dissertation presents an investigation into the processing. the effect of incorporating nano-sized SiC particles into ZrB2 was investigated. and mechanical behavior of ZrB2-based composites for ultra-high-temperature applications. First.

Micropillar compression test was also conducted. The fracture toughness of composite was measured to be four times higher than that of matrix materials. Elastic modulus. In addition. However. extensive matrix cracking was observed due to mismatch in thermal expansion coefficient between the fiber and xviii . The detailed microstructure of the composite was analyzed using transmission electron microscope. The composite was consolidated by conventional hot pressing method. It was found that the fracture toughness of ternary ZrC-ZrB2-SiC ceramics is comparable to that of the ZrB2 ceramics and ZrB2-SiC ceramics. The fully densed ceramics were prepared by spark plasma sintering. micropillar compression tests revealed information about typical longitudinal cracking behavior and generation of stacking faults. The chemical reaction between fiber and matrix materials was not observed based on thermodynamic calculation and TEM microstructural analysis. The third part of this dissertation focused on studying the effect of incorporating continuous SiC fibers on the microstructure and properties of ZrB2. The second study focused on the ternary ZrC-ZrB2-SiC ceramics. hardness.sintering was used to consolidate nano-sized SiC/ZrB2 composite. thermal conductivity. fracture toughness. and electrical conductivity of ternary ZrC-ZrB2-SiC ceramics were measured. It was found that incorporation of nano-sized SiC effectively hindered the grain growth of ZrB2.

the challenge and future research needs in developing ultra-high-temperature ceramics are discussed. XIX .matrix. Finally.

. but several significant challenges remain in the use of UHTCs. Research on UHTCs was started to meet the need for high-temperature materials that would allow the development of maneuverable hypersonic flight vehicles. and these materials have not yet to be widely implemented [2]. monatomic oxygen) [1]..g. Some of the earliest work on UHTCs was conducted by the company ManLab in the early 1960s. under a research program funded by the Air Force Materials Lab (AFML) [3. above 2400 °C) and in reactive atmospheres (e. In addition.4].1 Introduction Ultra-high-temperature ceramics (UHTCs) are a family of compounds that are chemically and physically stable at high temperatures (e. UHTCs are ideal for thermal protection systems. they are very hard.Chapter 1 Ultra-high-temperature ceramics 1. intermittent research has made some progress. have good wear resistance. Because of these characteristics. and relatively high thermal conductivities (compared to other ceramic materials).g. Since then. As the interest in monolithic UHTCs has l . UHTCs are famous for possessing some of the highest melting temperatures of known materials. especially those that require chemical and structural stability at extremely high operating temperatures [2]. mechanical strength.

To reduce the large amount of heat generated. the vehicle re-enters 2 .2 Applications of ultra-high-temperature ceramics One application of UHTCs is the hypersonic flight vehicle whose speed begins at four to five times the speed of sound (Mach 4 or 5). which produces a surface temperature of about 1400 °C. propulsion system components. blunt edged designs are employed.risen again in the early 1990s. windows. To take a full advantage of this effect. which produce the re-creation of the blunt-body shock wave that develops during re-entry. high costs of raw materials have led to many new investigations into different methods of fabricating UHTCs. the materials of this vehicle should be sustainable for several hundreds of hours in this temperature range and in an oxidizing atmosphere. such as reactive hot pressing and pressureless sintering by liquid infiltration and reaction [5.6]. The current desired speed of this vehicle is Mach 6. 1. The maximum temperature of the nose cone and the leading edges of the wings is about 1650 °C during re-entry. UHTCs with improved mechanical and thermal properties are required for hypersonic flight vehicle parts such as airframe components. In addition. engine cowls. and control surfaces [1]. A second application of UHTCs is the orbital/re-entry vehicle.

and control surfaces. a thermal protection system. the vehicles with sharp leading edges and trailing edges enable an increased abort-to-land window on launch. Propulsion systems can include air-breathing engines such as turbines. windows. Improved materials are needed for leading and trailing edges. As result of these drawbacks of blunt body design. rocket motors have a very limited life expectancy because of the extreme 3 . Rocket motors are currently the focus because they have a significant opportunity for UHTCs. The ability to fly faster at any given altitude also increases the cross-range for landing. However. other hot structure components. respectively. Thus. and scramjets. which improve aerodynamic performance by allowing for laminar flow over control surfaces. A final application is the propulsion system. The first problem is limited maneuverability which is from a narrow 'abort-to-land' window at launch and limited cross-range on re-entry. ramjets.the atmosphere with a belly-down attitude. However. the future re-entry vehicles should be employed with sharp leading edges and trailing edges. the blunt edged design of the vehicle give two major problems. The second major problem is communication blackout period which is due to barrier layer between shockwave and blunt body described in figure 1-1. The re-creation of shockwave and belly-down attitude is shown in figure 1-1 and 1-2.

4 .temperatures (over 3000 °C) and highly reactive environment (dissociating materials). but how long it will last before failure. Therefore. the main interesting point in these applications is not whether a material will fail.

-3r * "SSfe Sb Figure 1-1. Re-creation of the Shockwave during re-entry 5 .•I .

Figure 1-2. Belly-down attitude during re-entry 6 .

S. [3] Kaufman.References [1] William G. [4] Clougherty. E. Z. J. Kim. 1968 Research and development of refractory oxidation resistant diborides AFML-TR-68-190. D. E. T. T. Matt Gasch. V. E. Yang J.. ManLabs Inc. [2] 5309-5315. 1966 Investigation of boride compounds for very high temperature applications RTD-TRD-N63-4096.. Kondo. Kalish. 1994 Fabrication and microstructural evaluation of ZrB2/ZrC/Zr composites by liquid infiltration J. [6] Zhang. NASA technical report ARC-E-DAA-TN486. [5] Woo. Ceram. H. V. and Clougherty. L. N. Mat. [83] 2330-2332. and Mairead Stackpoole. Fahrenholtz and Gregory E. and Ohji. [2] Sylvia Johnson. ManLabs Inc. 7 ... Am. 2009 Assessment of the state of the art of ultra high temperature ceramics. C. and Kang. E. S. and Peters. K. G. Hilmas 2004 Draft of NSF-AFOSR Joint Workshop on Future Ultra-High Temperature Materials. 2002 Reactive hot pressing of ZrB-2-SiC composites. Sci. Part III. Soc. Deng.

1 Selection of ultra-high-temperature ceramics The several materials with melting temperatures approaching or above 3000 °C include several oxides. However. carbides. moduli. The oxides are reasonable to consider for use in oxidizing environments. Applications I mentioned above will involve exposure to oxidizing fuels or aero heating so that all non-oxide materials will undergo oxidation to form some combination of solid. fabricability. such as high melting point. In the case of real engineering applications. and gaseous reaction product. thermal conductivity. borides. and nitrides listed have similar properties. but these materials are not suitable for those application because of poor thermal shock resistance due to high thermal expansion and low thermal conductivity [2]. carbides. high melting temperature is not the only criterion for materials selection. the borides tend to have higher thermal conductivity compared to carbides and nitrides. strength at room temperature or elevated temperature.Chapter 2 Literature survey of ultra-high-temperature ceramics 2. and cost are more important properties to determine optimal materials. carbides. density. Several borides. and nitrides of group IV and V elements are most suitable for these applications. nitrides. and refractory metals listed in figure 2-1 [1]. All borides. and hardness due to strong covalent bonding. Oxidation resistance. thermal expansion. 8 . liquid.

which give them better thermal shock resistance and make them the most ideal for many high temperature applications [3,4,5]. Among the borides in figure 2-1, ZrE$2 and HfB2 have received the most attention because their oxidation resistance is superior to the other borides, due to the stability of ZrC>2 and HfC^ scales that form on these materials at elevated temperatures in oxidizing environments [1]. In addition, the combination of other refractory phases such as SiC or MoSi2 improves the strength and oxidation resistance [6]. In this study, ZrB2-based ceramics and ZrB2-based ceramic composites will be discussed.

2.2 Oxidation mechanism of ZrB2-SiC ceramics All the advantages mentioned above of borides (especially ZrB2 and HfB2) are leading many researchers to investigate various properties. Even though the oxidation mechanism is beyond the scope of this research, it will be discussed in detail in this chapter since oxidation resistance of these materials is very important as well as others and the most widely studied recently. Pure ZrB2 crystal oxidized to Z1O2 crystal and B2O3 liquid in air between 700-1100 °C. Parabolic (diffusion controlled) kinetics are observed because it is weight gain stage due to formation of B2O3 and Zr0 2 and kinetics are controlled by

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the transport of oxygen through B2O3 [7]. The oxidation rate increases para-linearly because overall rate of mass change is a combination of weight gain due to formation of B2O3 and ZrC>2 and weight loss due to volatilization of B2O3 between 1100-1400 °C [8,9]. Above 1400 °C, the rate of evaporation of B2O3 is greater than its rate of production, leaving a non-protective porous ZKD2 scale, which is unfavorable for the applications. In these temperature ranges, rapid linear kinetics were observed because mass gain due to formation of ZrC>2 is much greater than mass loss due to consumption of ZrB2 [10]. However, the oxidation resistance of ZrB2 was improved by the addition of SiC due to the formation of silica-rich scales on surfaces above 1100 °C. As the volatility of SiC>2 scales is lower than that of B2O3 scales, diffusion controlled kinetics was observed in these temperature ranges [6, 11]. William G. Fahrenholtz, et al. proposed oxidation mechanisms of ZrB2-SiC ceramics to several steps up to 1500 °C. The first step is the so-called unoxidized ZrB2-SiC stage. In this stage, SiC particles are uniformly dispersed in a ZrB2 matrix and solid solution is not expected because the solid solution limit for each component is low, shown in the ZrB2-SiC phase diagram in figure 2-2 [12, 13]. The second step is the initial response during heating below -1200 °C and the main oxidation

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mechanism is the oxidation of ZrB2 with reaction (1) in this stage. The parabolic kinetics can be observed due to hindering of oxygen diffusion through the scale composed of B2O3, ZrC>2, and SiC particles, which do not oxidize significantly. The third step is evolution as the temperature approaches 1500 °C. In this stage, the composition of the scale changes significantly from B2O3, ZrC>2, and SiC to ZrC>2 and Si02 because oxidation of SiC is the dominant oxidation with reaction (2) and B2O3 start evaporating in this temperature range. Compared to pure ZrB2 kinetics in this temperature range, parabolic kinetics can also be achieved by the SiC^-based scale rather than B203-based scale. The last step is steady state at 1500 °C. The most important characteristics of this stage are the generation of SiC depleted layer between unoxidized ZrB2-SiC layers and a Zr02+Si02 layer and SiC<2 rich layer on the top surface. The thickness of these two layers continuously increases because the source of Si is the active oxidation of SiC, due to the low oxygen partial pressure in the SiC depleted layer. Figure 2-3 shows the schematic diagram of a proposed oxidation mechanism and figure 2-4 shows the oxidized cross sectional microstructure of ZrB2-SiC ceramics [13]. As the temperature increases, the pressure in the SiC depleted region will increase until it is high enough to rupture the scale or cause failure at one of the

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these processing conditions normally produce coarsening of the final microstructures. ZrB2(cr) + 5/202(g) -»• Zr02(cr) + B203(1) SiC(cr) + 3/202(g) -> Si02(l) + CO(g) Reaction (1) Reaction (2) 2.interfaces in the layered structure.3 Mechanical properties of ZrB2-SiC ceramics As ZrB2 have high melting temperature and strong covalent bond characteristics.013 X 105 Pa. 12 . the densification of ZrB2 powders requires very high temperature (2100-2300 °C) and pressure-assisted sintering procedures [15]. which is estimated to occur at -1775 °C [14]. This leads to degradation in the mechanical properties such as hardness and strength [16]. which leads to the formation of microcracks due to thermal expansion mismatch during cooling. but large amount of work has not been carried out to improve mechanical properties and to understand fracture mechanism scientifically in ambient temperature or high temperature. A lot of research related to high temperature properties such as oxidation resistance and thermal shock resistance with various processing and combination of additives have resulted in many achievements. However. This may occur when the total pressure in the SiC depleted region reaches -1.

and time are listed in table 2-2. et al. The mechanical properties (including physical properties) are listed in table 2-1 and typical microstructures of ZrB2-SiC ceramics with four different SiC starting powder size from lOum through 0. The reduction of SiC grain size leads to an increase in relative density. hardness. et al.45um are shown in figure 2-5.Sumin Zhu. but no effect with reduction of SiC grain size are found on the modulus. three different hot pressing temperatures. ZrB2 and SiC grain sizes increase. and flexural strength. Modulus and hardness are not related to the hot pressing temperature and time [18]. B: 2um). As the hot pressing temperature and time increase. but fracture toughness and flexural strength decrease. 13 . and fracture toughness [17]. The results from the these two recent works indicate that SiC starting powder size and sintering temperature and time play an important role in promoting physical and mechanical properties of ZrB2-SiC ceramics. researched the effect of hot pressing time and temperature on the microstructure and mechanical properties of ZrB2-SiC. studied the influence of silicon carbide particle size on the microstructure and mechanical properties of ZrB2-SiC ceramics. Poisson's ratio. The physical and mechanical properties of ZrB2-SiC ceramics with two different starting powder sizes of ZrB2 (A: 6um. Alireza Rezaie.

Powders are placed in a graphite die and heating is affected by passing through the die and sample if the sample is conductive while a pressure is applied on the powder. At the same time.2. resulting in a sintered compact of over 99% density. The basic mechanism of neck formation by spark plasma is shown in figure 2-7. Since only the surface temperature of the particles rises rapidly by self-heating. This causes evaporation and melting on the particle surfaces. The schematic SPS process is shown in figure 2-6 [19].4 Spark plasma sintering Spark plasma sintering (SPS) is one of the powder consolidation methods with applied pressure and pulsed DC current simultaneously. local high temperature states of several to tens of thousands of degrees centigrade are generated momentarily. These necks gradually develop and plastic transformation progresses during sintering. a precision sintered compact is manufactured in a shorter time. and necks are formed around the area of contact between particles [20]. bulk fabrication 14 . An electrical discharge process takes place on a microscopic level and accelerates material diffusion. Therefore. When a spark discharge appears in a gap or at the contact point between particles. particle growth of the starting powder materials is controlled. Sintering is realized by subjecting the green body to arc discharges generated by pulsed DC current.

The plasma is proposed to cause a cleansing effect on the surface of the particles. (d) selective control of the density in specified regions. the most important difference is the fast heating rate to as high as 1000 °C. the die and sample are heated by Joule heating from a current passing through them if the sample is conducting by the SPS method. In contrast. (b) the absence of sintering aids. (f) single step sintering-bonding. However. leading to sintering enhancement [19]. (c) improving bonding strength between particles and (d) controlling phase 15 . The advantages of the SPS method are: (a) low power consumption (approximately one-fifth of Hot Pressing). in addition to providing heat. (c) control of the thermal gradient (for functional graded materials (FGMs)). (b) consolidating amorphous materials. (e) accurate control of the porosity. The short sintering time is particularly suitable for: (a) preserving initial powder grain size or nanostructure. Compared to conventional hot pressing methods.of particles with amorphous structure and nano-crystallization formation are now possible without changing their characteristics [21]. (g) particle surface cleaning. (h) high heating rate and (i) near-net-shape capability. Typically. the sample and the die are heated by radiation from an enclosing furnace in the hot-pressing method. the pulsed DC current has been assigned another role: that of creating plasma.

SPS is the most promising consolidation method for ultra-high-temperature ceramics which require high temperature with fast heating rate and pressure to maintain fine microstructure. rearrangement. [24]. 2. Many improvements of mechanical and physical properties of materials by SPS method were reported from the researchers who investigated ultra-high temperature ceramics. The liquid can be present during the entire sintering process or during a specific stage of the sintering cycle. takes place right after liquid phase forms with 16 .5 Liquid phase sintering Liquid phase sintering (LPS) is a sintering process that involves liquid and solid particles. They are two basic methods to obtain liquid phase: (i) Using mixed powders of differing characteristics. Figure 2=8 shows the three steps of liquid phase sintering process by Kingery. and (ii) Taking advantage of the interaction between two or more components or from the formation of a eutectic liquid [23]. Therefore. et al. The first step. According to Kingery's model. the liquid phase sintering process has three different steps that may in certain cases be partly overlapped.reactions or decomposition (in the case of composites) [22].

The elimination of porosity takes place as the system minimizes its surface energy. so that the large grains grow at the expense of the small grains. This establishes a concentration gradient in liquid phase. if the transport is confined by interfacial dissolution or precipitation. The final step is microstructure coarsening and solid-state sintering. because small grains are more soluble that large grains. The atoms can be transported from small grains to large grains by diffusion. This process relies strongly on two critical steps: dissolution of solid into the liquid and diffusion through the liquid. The rate and extent of shrinkage depend upon the viscosity and quantity of liquid phase formed and on its wetting properties [25].rapid partial densiflcation due to the capillary force exerted by the wetting liquid on the surface of solid particles. The most favorable features for rearrangement are: (i) a homogeneous distribution of a congruently melting liquid that wets the particles present. the so-called solution precipitation step. (iii) a large solubility ratio. (ii) the solid particles are soluble in the liquid. the process is reaction-controlled [26-28]. this process is diffusion-controlled. If the transport is limited by mass transfer from the source to the sink. The second step. A solid 17 . This process is coarsening or ripening. occurs due to a difference in solubility. The two driving forces of this step are the reduction of interfacial energy and the capillary force.

18 . The densification rate is greatly decreased during this part of the sintering cycle [29]. In this case. although microstructure coarsening continues by diffusion.skeleton is formed. the residual pores will enlarge if they contain entrapped gas that results in swelling. The rigidity of the solid skeleton hinders further rearrangement. and grain coalescence occurs.

5±0.9 98.0 K K (MPa m1'2) 4.7.0±0. 19 . 0.6±0.15 0.3±2 9 2.1 <r(MPa) 389±45 805±"1 83"±116 909±136 0 16 0. 1. 0.45 1.45 in sample names are starting SiC particle size of micron).3 4." 1.4 19.5±0.-1 ZSO.6±0.2±0.T 99.16 ZS0.4.4 Table 2-1.3±0.1±1.Matei isil ZS10 ZS1. Physical and mechanical properties with reducing SiC particle size of ZrB2-SiC ceramics [17] (10.-! Relativedensit} (%) 9".8 Avei age SiC gi nin size (Jim) 6.6 20.7 V E (GPvl) 4"9±5 509±3 515±7 520+- HV0.2 (GPa) 1".0 19.7±1.15 0.3±0.4 98.2 4.1±0.1 4.

and 2050: temperature.0 Ave SIC grain size (um) 1.1 3.2 ± 1.0 ± 0.0 4. 1850.5 ± 2.m. Physical and mechanical properties of ZrB2-SiC ceramics with different hot pressing time and temperature [18] (A.5 ± 0. B: ZrB2 starting powder size.3 ± 0.7 ± 3.2 ± 0.5 ± 1.5 ± 1.7 ± 1. 45.2 <r(MPa) 888 ± 151 770 ± 133 720 ± 38 1063 ± 91 1060 ± 59 854 ± 88 850 ± 100 804 ± 73 Table 2-2.9 2.0 ± 0.7 ± 1. 1950. B: 2(4.3 1.0 3.8 2.8 3.3 3.3 ± 0.8 2.3 5. and 180: time.1 ± 1.2 5.5 3.3 ± 1. A: 6um.2 2.m 1 : ) 3.Sample A-1850-45 A-1950-45 A-2050-45 B-1850-45 B-1950-45 B-2050-45 B-2050-90 B-2050-180 AveZrB : grain size (um) 2.1 ± 1.5 ± 0.2 4.2 ± 0.7 2.5 2.7 ± 0.0 ± 0. min) 20 .0 E (GPa) 503 ± 6 501 ± 1 503 ± 1 516+3 507 ± 3 505 + 2 508 ± 4 505 ± 1 H (GPa) 22 ± 2 22 ± 2 23 ± 2 20 ± 2 22 ± 2 23 ± 1 22 ± 1 22 ± 1 K I C (MP a .8 ± 2.1 4.2 4.1 4.9 ± 0. °C.6 1.2 ± 0.4 4. 90.5 ± 0.

Several materials with melting temperatures approaching or above 3000 °C[1] 21 .Metals Oxides Borldes Carbides Nitrides Material Family Figure 2-1.

2600 I \ 2400 \ \ \\ \ / ' (77%) I iM 2270° 2200 J I I L__J 20 2000 J 0 2rB2 L 40 j Mol % I 60 i L_J H 1 100 SiC Figure 2-2.3200 "I s 3050° 1 T 1 r 3000 \ \ \ Liquid L 2760°/I H 2800 r / . ZrB2-SiC phase diagram [12] 22 .

|~ Si02 ZrO 2 + S I 0 2 ZrB 2 (SiC-depIeted) ZrB 2 + SiC MrMMOT itei«MMfr A f t 11a Figure 2-3. (a) unoxidized ZrB2-SiC (b) the initial response during heating (c) evolution as the temperature approaches 1500 °C (d) steady state at 1500 °C [13].?v-** v 7". 23 .> 2 r B 2 + SIC ZK>2 + B2O3 + SiC ZrBrSiC ^-ZrO^SlOa > ZrBrSiC 9EL '-1* .'~.v*™ • . The schematic diagram of a proposed oxidation mechanism for ZrB2-SiC ceramics. •7"r*.

Depleted of SiC • ZrB2-SiC Figure 2-4. The cross-sectional microstructure of ZrB2-SiC ceramics [13] 24 .SiO.

Figure 2-5.45 25 .4 (c) ZS0.7 (d) ZS0. Microstructure of ZrE$2-SiC ceramics [17] (a) ZSIO (b) ZS1.

Pressure control Power Supply Figure 2-6. Schematic of the SPS process [19] 26 .

Basic mechanism of spark plasma sintering [20]. 27 .Applied Pressure Particle Electron Flow Generation of Spark Impact Diffusion Bonding Plastic Deformation Particle Applied Pressure Figure 2-7.

28 . Three different steps of liquid phase sintering by Kingery (I) Rearrangement (II) Solution-precipitation (III) Microstructure coarsening and solid state sintering.Figure 2-8.

electrochem. P. Proa. (1991) Engineering properties of borides ASTM Engineered materials handbook. A. Phy. J. R. Am. Less-Common Metals. p787-803 [5] Guillermet. (1992) Ultra high temperature assessment study. graham (1971) Thermogravimetric study of the oxidation of ZrB 2 in the temperature range of 800-1500 °C..Opeka. Monteverde. Conf. J. Soc. Trans. H. J. 118 [7] pi 195-1199. [8] W. C. [10] A. J. Vol. Graham. [231] p423-431 [6] W. Inst. L. Tripp and H. and Kerans. R. C. F.Opila. Fahrenholtz. J. L.. Chamberlain.. C. M. Davis. 150 [11] p552-559. Issue 5. Zaykoski (2007) Refractory diborides of zirconium and hafnium J. Vol 4-Ceramics and glasses. Soc. Bellosi (2003) Oxidation of ZrB2-based ceramics in dry air J. A. and I. [9] F. Technical chairman. Wuchina. G. p30-36 [3] Courtright. Irving and I. Schneider. W. and Grimvall. W. and G. 1 [2] 29 . S. Worsley (1968) Oxidation of titanium diboride and zirconium diboride at high temperatures. Hilmas. H. Ceramic Bulletin 52(8) p612-616 [7] R. Talmy. Talmy (2007) UHTCs: Ultra-high temperature ceramic materials for extreme environment applications. pl347-1364 [2] E.ceramic matrix composites AFWAL-TR-91-4061 Wright Patterson Air Force Base Ohio [4] Culter. G. The electrochemical society Interface. A.References [1] William G. Electrochem. and H. Fahrenholtz. A. E. H. E. Soc. Graham (1973) Effect of an SiC addition of the oxidation of ZrB 2 .90. Tripp. Gregory E. Katz. G (1991) Phase stability properties of transition metal diborides Am. Inna G. Fahrenholtz. Hilmas. Ceram. Oxidation of ZrB2-SiC ceramics under atmospheric and reentry conditions Refractory Appl. 16 [2] pl03-l 12. C. and James A.. E. C.

Inorg. 25 [10] pl487-1489.. Sci. and E. I. Fahrenholtz. Opeka. Mater. Mater. 90 [1] pl43-148 [14] M. Am. Neorg. Hoffman. Bull. [11] H. Fahrenholtz. Soc. (2007) Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride-silicon carbide ceramics. Bull.. Talmy. 42 p2735-2744. A. Mater. Ceram. Hilmas. [19] Z. and J. [12] S. (Engl Transl. J. [20] K. G. Tripp (1971) Microstructural features of oxide scales formed on zirconium diboride materials pp35-48 in Ceramics in severe environments: Materials Science Research. Yang. Mater. Sci. E. S.pl-8. H. Munir. Ceram.25 [10] pi752-1755. W. C. G. Ceram. and W. 41. (2004) Oxidation-based materials selection for 2000 °C+ hypersonic aerosurfaces: Theoretical considerations and historical experience.. Ohyanagi. Graham. J. E. Mroz. A. and G. [16] C.. M. [17] Sumin Zhu. Lu. G. Kvernes. (2008). A. (1995). International Materials Review. 27 p2077-2083. Moroshkina. (2007) Effect of hot pressing time and temperature on the microstructure and mechanical properties of ZrB2-SiC. 76 [12] p51-56. (2006) The effect of electric field and pressure on the synthesis and consolidation of materials: A review of the spark plasma sintering method. I. J. Am. (2007) Thermodynamic analysis of ZrB2-SiC oxidation: Formation of a SiC-depleted region. Sci. Titanium diboride. and M. Mater. Soc. Zaykoski. S. Akad. [18] Alireza Rezaie. C. [13] W. Nauk ASSR. [15] K. Ordanyan. Dmitriev. H. W. 39 [19] p5887-5904. Ceram. Am. Upadhya. (1997) Materials for ultra high temperature structural applications. J. J. J. Fahrenholtz. Sintering of nanoceramics. U. Davis. Soc. Hilmas. and G. Anselmi-Tamburini. Soc. M. G. (1989) Izv. Euro. and W.). I. A. P. p763-777.. 53 [1] p21-38 30 . 74 [6] pl58-159.

. 31 . [26] I. J. Yoshio Sakka. pi-24 [23] R. Acta metallurgica 20 p61-71 [29] W. German.com/e_htm/whatsps_e_htm/whatsps4_e. K. Wagner. Plenum press. Phy 30 p301-306 [25] W. Kingery (1959) Densification during sintering in the presence of a liquid phase. electrochem. Ardell (1971) Effect of volume fraction on particle coarsening. Technol. Huppmann and H. App. J. (1985) Liquid phase sintering. 2nd edition. Phy. Theoretical consideration. M. scm-sps. 053001. J. Introduction to ceramics. Chapter 10. D. Kingery. H. [28] A. 10. Sci. Theory..[21 ] http ://www. Chem. Vol23. Bowen. and Giovanni Maizza (2009) Electrical current activated/assisted sintering (ECAS): a review of patents 1906-2008. Acta Metallurgica. I. 19 p35-50 [27] C. New York and London [24] W.htm [22] Salvatore Grasso. and V. Mater. Wiley Interscience. R. Riegger (1975) Modeling of rearrangement processes in liquid phase sintering.. M. Uhlmann (1976). J. Slyozov (1961) The kinetics of precipitation from supersaturated solid solutions. Lifshitz. Soli. and D. D. Adv. J. p965-971. 65p581-591. (1961) Theory of precipitate change by redissolution. V.

each phase of ZrB2 and SiC were confirmed by SAED (Selected Area Electron Diffraction) and a second phase. The presence of intergranular and intragranular SiC improves the sinterability and limits the grain growth of ZrB2 effectively until 10 vol% of nano-sized SiC particles. The elastic constants of the composites were measured using an ultrasonic technique. The hardness of composites was increased with an increase of nano-sized SiC content. The microstructure of the as-consolidated composites was examined by field emission scanning electron microscopy and transmission electron microscopy. Zr(0. The composites were consolidated by spark plasma sintering. but the fracture toughness was not related to the content of SiC. was found due to a large amount of heat during spark plasma sintering. In addition. whereas the hardness and fracture toughness of the composites were determined using an indentation measurement. However. B)x. the grain size of SiC increased with an increase of nano-sized SiC content due to agglomeration by the mixing process. The applied stress to micropillars of ZrB2 nano-sized SiC 32 .Chapter 3 ZrB 2 -nano SiC ceramics Abstract The microstructure and mechanical properties of ZrB2 composites with nano-sized SiC particles were examined.

composites produced many dislocations and stacking faults. 33 .

high electrical and thermal conductivities. However.3. Sumin Zhu. 4]. In addition. SiC is the most widely studied by many researchers. et al. in the range from 0.1 Introduction Zirconium diboride and hafnium diboride have extremely high melting temperatures (>3000 °C). high chemical stability. reported the influence of SiC initial particle size. the introduction of these second phases improves the mechanical properties due to a liquid phase sintering effect [3. Among the second phases. The smaller SiC particle sizes led to improved densification. finer grain 34 . resistance to erosion/corrosion. leaving behind a non-protective porous Zr0 2 layer [2]. the second phase such as SiC and MoSi2 were introduced due to the generation of a borosilicate diffusion barrier layer above 1000 °C. and rocket propulsion systems [1]. To overcome the poor oxidation resistance of these diborides. on the microstructure and mechanical properties of ZrB2-SiC ceramics. atmospheric re-entry vehicle. and good mechanical properties which make them suitable for ultra-high-temperature applications such as hypersonic flight vehicle. use of those single phase ceramics materials for these applications has limitations because a passive layer composed of B 2 0 3 start evaporating above 1000 °C.45urn to 10um.

2 Experimental procedure 3. Thirdly. 3. Osaka. inter/intragranular nanocomposites can take both effects mentioned above. nano-sized SiC particles were used to improve the mechanical and physical properties of ZrB2-SiC ceramics and spark plasma sintering was used to take an effect of nanocomposites as mentioned above.1 Materials The starting powders used in this study were: ZrB2 powder (Grade F. Japan). nano/nano composites can have superplasticity due to grain boundary sliding [7]. and higher strength [5].2. Tokyo). average particle size ~30 nm and oxygen 35 . In this study. Lastly. proposed three different types of ceramic nanocomposites shown in figure 3-1 [6]. Firstly. et al. Japan New Metals. intergranular nanocomposites can improve creep resistance due to grain boundary pinning effect. Niihara. However. Ltd.. the introduction of nano-sized SiC starting powder into ZrE$2 ceramics was not studied widely yet by researchers until present. Secondly. average particle size -2. higher hardness.1 um and nano p-SiC powder (Sumitomo Osaka Cement Co. intragranular nanocomposites can improve transgranular fracture toughness and strength.sizes.

. and the resulting slurry was then dried under magnetic stirring to avoid sedimentation. Japan). four batches of powder were prepared. The load was removed when the die temperature dropped below 1000°C with a cooling rate 36 . The sintering was performed at 1900 °C for 3 min under an external pressure of 50MPa in an argon atmosphere. The powder mixture was put into graphite die lines with graphite foil and densified using spark plasma sintering (SPS-1030. the single-phase ZrB2 powder was prepared to compare the effect of SiC addition on mechanical properties. The temperature of the sample was automatically raised to 600"C. Tokyo. The pressure was applied at room temperature and held constant until the end of the sintering cycle. respectively. Compositions of the ZrE$2-based composites with SiC are listed in Table 3-1.%. Before sintering. the dried mixtures were sieved through a metallic sieve with 60-mesh screen size. and then was monitored by an optical pyrometer through a hole opened in the die and automatically regulated to the final sintering temperature with heating rate of ~300°C/min. In addition. Ltd. containing nano (3-SiC powder of 5. In order to examine the effects of nano-particle content as well as starting particle size.38 wt.content of 0.%. The powder mixtures were ball-milled using SiC milling media and ethanol under 200 rpm for 24 h. 10. 20 and 30 vol. Sumitomo Coal Mining Co.

ZrB2 and SiC. The TEM samples used in this study were prepared by Focused Ion Beam (FIB Nova 600. OR) with tungsten probe tips and four fingers copper grid. The morphology of the composites was characterized by field emission scanning electron microscopy (FE-SEM. OR) with a EDAX Energy Dispersive X-ray spectrometer (EDS) and a Si/Li detector super ultrathln window. The grain size of each component. was measured directly from the FE-SEM images of sintered composites using image J software. FEI. Hillsboro.of~ 600 °C/min. ZEISS VP1550). Panalytical X'Pert Pro). ZSN-5. and the crystalline phases were identified by X-ray diffractometry (XRD. The sintered composite pellets were then polished with a diamond paste up to 0. ZSN-10. To investigate detailed microstructural information of sintered composites with 30nm SiC powders. The density of the sintered composite compacts was measured by Archimedes method with distilled water as a medium. 37 .0 mm. and ZSN-20 samples were observed by TEM (FEI-Philips CM300. randomly selected areas of ZSN-0. The final sintered specimen size was 10mm in diameter pellets with a thickness of ~2. five FE-SEM images were used for direct measurement within the range of 200-300 population. In order to estimate the average grain size of each component. Hillsboro.5um. FBI.

and V. Tektronix Inc. The details of calculations are listed below. Beaverton. shear modulus (G) and Poisson's ratio (v) were calculated using the longitudinal and transverse sound wave velocities measured in the composite specimens. OR USA) with a fundamental frequency of 20 MHz. J (1) < v ' G = pV. are determined by r. Young's modulus (E). 3. and V.2 v = — -1 2G (2) (3) where p is the true density. At.v2 V v .. V.=£ At. are the longitudinal and transverse sound wave velocities. V. V} . and A/. are the elapsed times between the pulse and the echo of the longitudinal and transverse waves. r E = pV2 3V2-4V2^ . The accuracy of the soundwave velocity measurement was better than 1%.2. respectively [8].2.3.3 Mechanical properties 38 . respectively. At. (4) where h is the specimen thickness.2 Elastic property measurements The elastic moduli measurements of the composites were performed using an ultrasonic technique (TDS 3052B.

Yokohama. of the composites were determined using an indentation technique. Hv. is obtained experimentally. The Palmqvist equation is listed below: KIC = r.5 from crack length measurement.. a. Akashi Co. H is the hardness (GPa). was calculated from H = 1854. c. et al. and c is the total length including crack length and half diagonal length (pm). Ltd.0122 for l/a ratio varying in the 39 . The hardness.4-^=-. and crack sizes. a is the half diagonal length (um). the Palmqvist equation was used in this study becuase the ratio of l/a were in the range of 0.(E/H)2/5P/(al m) (6) where E is the Young's modulus (GPa). For fracture toughness calculations. (where l=c-a). were measured using an optical microscope attached to an indenter. and 10 indents were made for each measurement. The indentation load of 49N was used.. The value of r\ was 0. r\. K\c. the coefficient.m).25-2. (7) In the earlier work from Niihara. The corresponding diagonals of the indentation. The indentation tests were performed on the polished surface of the specimens by loading with a Vickers microhardness indenter (AVK-A.0089 and 0. P is the indentation load (N). /is the crack length (|J.The hardness and fracture toughness. Japan) for 20 s in ambient air at room temperature.

1 Densities. We have chosen r|=0. and ZSN-10) were compressed by the depth of 500nm from the sample surface with the flat punch tip of a nanoindenter (MTS Nanoindenter/XP. and microstructures The measured densities and relative densities for various ZrB2-nano SiC 40 .2. The obtained micropillars of each sample (ZSN-0.3. MTS system. After compression tests. FEI. Applied stress and displacement of samples were recorded to identify events such as fracture and deformation.5. Eden Prairie MN). Hillsboro.5 and 1-2. phases.3 Results and discussion 3. 3.25-2.5. respectively [9]. 3. TEM laminar samples were prepared by the Focused Ion Beam if the critical dimensional changes of micropillars were not found.range of 0. Microstructural information of micropillars from the prepared TEM samples was investigated.0122 because all ratios of l/a were in the range of 1-2.4 Micropillar compression test To investigate deformation or fracture mechanism of ZrB2-SiC composites. micropillars with ~5um diameter and ~20um height were prepared by Focused Ion Beam (FIB Nova 600. OR) on the surface of composites. ZSN-5.

It is evident that single-phase ZrB2 has the lowest density (-96.1%). The low relative density of pure ZrB2 is due to its strong covalent bond and low self diffusion [10]. The average grain sizes of the ZrB2 and SiC are also listed in table 3-3 and the typical tendency of average grain size of each component is shown in 41 . Typical microstructural features of the ZrB2-SiC composites observed under FE-SEM are shown in figure 3-3. As the SiC content of each composite material increases. The intensity of SiC peaks are increased with increasing SiC content in the composite material. X-ray diffraction (XRD) patterns of each composite materials consolidated by SPS are shown in figure 3-2. consisting of the equiaxed ZrB2 (grey contrast) and SiC (dark contrast) grains. The general microstructures of the ZrB2-SiC composites are similar. Any other second phases were not found and both ZrB2 and SiC phases were confirmed by XRD in all samples.composites are summarized in table 3-2. ZrB2 and SiC peaks were detected in the other four samples (ZSN-5-ZSN-30). Only ZrB2 peaks are detected in ZSN-0. and densities of each sample slightly increase with increase of SiC content from 96. SiC improves sinterbility of composites more effectively due to the liquid phase sintering effect and hindrance of ZrB2 grain growth.1% to 98%.

2. and ZSN-30 are very similar and the average grain sizes of ZrB2 of those samples which originated from . proving that SiC hinders ZrB2 grain growth.7 um after ball milling and sintering. ZSN-20. It is due to the fact that the average grain sizes of ZrB2 of ZSN-10.figure 3-4. Phases 42 . which is significantly higher than the starting powder (2. which is substantially higher than that of the starting powder (-30 nm). the average grain size of SiC also increased with increasing SiC content from 1. the average grain size of ZrE$2 decreases with increasing SiC content until 10 vol% SiC composite materials. Apparently. As a result. However. More detailed microstructural images by TEM and selected area electron diffraction (SAED) of each sample (ZSN-0-ZSN-30) are shown in figure 3-5.60 um.02 urn. A more effective mixing/dispersion technique to break apart the agglomeration of nano-sized SiC particles needs to be developed to uniformly disperse the nano particles.07 to 1.1 um was measured to be -1. the grain growth of ZSN-0 occurred during spark plasma sintering. clusters of nano-sized SiC particles were fused together during spark plasma sintering to form SiC grains with a few microns in diameter. The average grain size of pure ZrB2 is -4. The mixing process employed was not effective in breaking apart the agglomeration of nano-sized SiC particles.1 urn). In addition. The average grain size of ZrB2 was not decreased further after 10 vol% SiC content.

2 Elastic moduli. The thicknesses of interfaces are 1~2 nm.and crystallographic directions of several grains in these images were confirmed by EDAX and electron diffraction patterns. hardness and fracture toughness The elastic constants measured in various ZrB2-SiC composites are listed in 43 .3. which suggests that nano-sized SiC particles were fused together during spark plasma sintering.B)x. The size of SiC grains increase from a few tens of nanometers to several micrometers. In addition. ZrB2 grains are dark contrast and SiC grains are grey contrast in all images (opposite to FE-SEM images). Most SiC grains are of one crystallographic orientation and a few SiC grains are of several crystallographic orientations in one grain. 3. a small SiC grain could be found in pure ZrB2 ceramic composite (ZSN-0). Typical interfaces between ZrB2 grains and SiC grains are shown in figure 3-7. a second phase. was found in ZSN-20 because large amount of heat during spark plasma sintering might be localized in ZrB2 grain (shown in figure 3-8). Zr(0. Most SiC grains are located in interfaces between ZrB2 grains and SiC grains or grainboundaries between ZrB2 grains. but a few SiC grains with the size of several nanometers (30nm ~ 80nm) are found in ZrB2 grains in ZSN-5 and ZSN-30 (shown in figure 3-6). At first. so those inter-phase interfaces between two components are well bonded to each other. this SiC grain might come from SiC milling media.

which is lower than that of zirconium diboride and silicon carbide agglomerate may cause detrimental effect to elastic properties of composites materials. The results indicated that Young's moduli of the ZrB2 composites with nano-sized SiC are not sensitive to the compositions. This effect is based on the basic rule of mixtures. However. Hardness and fracture toughness of ZrB2-SiC composites obtained from the indentation technique are also summarized in table 3-4. The Young's modulus of single-phase ZrB2 was measured to be -499 GPa. The samples with higher SiC content have the higher value of hardness because the hardness of 44 . which is lower than the results in the literature (22 GPa)[13]. ZSN-5 and ZSN-10 have the best elastic properties and ZSN-20 and ZSN-30 have the worst properties because the Young's modulus of silicon carbide is reported to be 415 GPa [12].table 3-4. The porosity of the ZSN-0 might not be a main reason for the low hardness value because the porosity value is -4%. which is slightly higher than that reported in the literature (489 GPa) [11]. the hardness in the ZrB2-nano SiC ceramic increased with an increase of SiC content (shown in figure 3-9). The hardness of single-phase ZrB2 was measured to be ~13 GPa. Among the five compositions. It is the reason that low bonding strength between ZrB2 grains to maintain coherent microstructure due to inherent ZrB2 characteristics such as strong covalent bond and low self-diffusion.

Ni. The results also indicated that fracture toughness of the ZrB2 composites with nano-sized SiC is not sensitive to the compositions shown in figure 3-9.SiC (32 GPa) [12] is higher than that of ZrB2 (22 GPa) [13]. 3. 3-13. The fracture toughness of all ZrB2-nano SiC composite were in the range of 6. and 3-14.3. ZSN-5. As a result. Cu. and ZSN-10 are shown in figure 3-12. A typical cracking pattern is shown in figure 3-10.m172 and these values cannot be compared to others because many studies for fracture toughness of ultra-high-temperature ceramics were conducted by methods.5 MPa. The study of micropillar or nanopillar compression tests about single crystal metal such as Au. ZSN-5.8-7. For the single-phase ZrB2 ceramic. respectively. and ZSN-10 are shown in figure 3-11.3 Micropillar compression test of ZrB2-nano SiC composite materials Fabricated micropillars of ZSN-0. The dimensions of micropillars in this figure vary due to different magnification in order to show the configuration of micropillars. the crack propagated primarily along ZrB2 phase boundaries but the crack in the ZrB2 nano-SiC composite propagated across the ZrB2 and SiC grains without being deflected along the grain boundaries of the SiC grains. and even Si had similar results to the 45 . the incorporation of nano-sized SiC did not impart additional resistance to crack propagation. The stress and strain (%) characteristics of ZSN-0.

The TEM images of ZSN-0 and ZSN-10 and the fracture surface of FE-SEM images of ZSN-5 are shown in figure 3-16. the micropillar of ZSN-5 was broken after the stress of ZSN-5 reached only -2. The maximum stress of pure ZrE$2 micropillar was 15.33 GPa) because the flat punch tip might be improper contact with the top surface of the micropillar so that it is slightly tilted in one direction (indicated with arrow in figure 3-15). lots of dislocations and small stacking faults were found 46 . but stacking faults went through whole lamella so that they were produced in compression stress. This stress-strain curve might be explained for production of stacking fault in ZSN-0.universal scaling law. and 3-18. respectively. which can be explained briefly that smaller micropillars or nanopillars have higher stresses [14. the maximum stress values of micropillar compression tests of pure ZrE$2 and ZrB2-SiC ceramics did not follow the universal scaling law.5 GPa. The dislocations might be produced during the milling process because they are very small and located inside of one grain. which is slightly higher than the normal microhardness test (~13GPa). It is interesting to note that the maximum stress of ZSN-10 was fairly low (-0. In the ZSN-10 TEM lamella. Several small dislocations and stacking faults which go through whole lamella were found in the ZSN-0 sample. 15]. several discrete regions are found in stress-strain curve in figure 3-12. Also.74 GPa. However. 3-17. And.

These sub-micron-sized particles were distributed primarily along the grain boundaries. As a result. The mixing process employed was not effective in breaking apart the agglomeration of nano-sized SiC particles. These two defects might also be produced by compression stresses because the stress-strain curve shape is an inward curve. perhaps some part of energy from the applied stress was used for the generation of dislocations and stacking faults. The hardness of ZrB2 with nano-sized SiC was increased with increase of 47 . Further improvement in properties may be achievable through a more uniform dispersion of SiC nano particles. clusters of nano-sized SiC particles were fused together during sintering to form SiC particles sub-micron in diameter.compared to ZSN-0 lamella. some nano SiC particles were embedded within the grains. However. which is the same result as the fracture surface reported [16]. The presence of intergranular and intragranular SiC improves the sinterability and limits the grain growth of ZrB2.4 Conclusion The processing and mechanical behaviors of single-phase ZrE$2 and ZrB2 with nano-sized SiC particles were investigated. 3. The fracture mode observed from ZSN-5 micropillar was mixed inter/intragranular fracture.

48 . was found in ZrB2 grain due to localized large amounts of heat during spark plasma sintering by the TEM investigation. B)x.SiC content. The applied stress to micropillars of ZrB2 nano-sized SiC composites produced lots of dislocations and stacking faults. The phase of ZrB2 and SiC in each composite was confirmed SAED and the second phase. Zr(0. but the fracture toughness of composites was not sensitive to composition.

Compositions (vol. Compositions of each sample SiC 100 95 90 80 70 0 5 10 20 30 49 .%) Samples ZrB2 ZSN-0 ZSN-5 ZSN-10 ZSN-20 ZSN-30 Table 3-1.

13 96.66 5.95 5.09 5.4 98.85 5.80 5.5 97.23 5.78 5.Samples Theoretical Density 3 Measured Density 3 Relative Density (%TD) (g/cm ) (g/cm ) ZSN-0 ZSN-5 ZSN-10 ZSN-20 ZSN-30 6. Densities of each sample 50 .52 5.1 97.37 5.1 97.0 Table 3-2.

51 .84 ZSN-10 1.02±1.07 Table 3-3. Average grain sizes of ZrB2-nano SiC composite materials.71±0.Materials Grain size of ZrB2 (urn) Grain size of SiC (u.39±0.76±0.86±0.31 N/A ZSN-5 2.82 ZSN-20 1.56 1.17±0.82 ZSN-30 1.m) ZSN-0 4.7 1.07±0.63 1.60±1.64±0.77 1.

15 ZSN-20 200 455 0. Elastic properties of ZrB2-nano SiC composite materials 52 .15 ZSN-10 223 513 0.14 ZSN-30 200 455 0.14 ZSN-5 225 517 0.14 Table 3-4.Elastic Properties Samples G (GPa) E (GPa) V ZSN-0 219 499 0.

30 ±1 7.19±0.79 7.m 1/2 ) ZSN-0 13±0.6 ZSN-20 17.59 7.63 ±0.65 6.71 7.47±0.Hardness Sample (GPa) Toughness (MPa.24 ZSN-30 20.52 Table 3-4.36±0.52 ZSN-5 16. Hardness and fracture toughness of ZrB2-nano SiC composites materials 53 .72 ±0.25±0.78±0.57 ZSN-10 17.64 ±0.

\ / • # /• ^ « V—/ y. ' • . 54 .Classification of ceramic nanocomposites.« / • \ a (a) Inter type (b) Intra type \ • / ^ — < • (c) Intra/inter type (d) Nano/nano type Figure 3-1.

I A 2000 WW •At M M mmmJjkm UM •n M 1000 L IIJLII Uw*» *mm* J M » L. 10 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 0 100 29(cfegTee) igure 3-2. X-ray diffraction patterns of each composite material (a) ZSN-0 (b) ZSN-5 (c) ZSN-10 (d) ZSN-20 (e) ZSN-30 55 .'aufcMi MMMMM tabnn I JL MKM •I.7000 6000 5000 T H 4000 CO • 2B 2 a " H & 3000 (e). f t An * > t I IMMW .

Typical FE-SEM images of each sample. 56 .Figure 3-3.

The change of average grain size of each component.5~ -#-ac E4 E ^^^ '55 N ^—^ -1 0 3C 2 • ^ J \ - T • • O 1 n i 2 ( • • i i i 0 10 20 30 vu %of ac Figure 3-4. 57 .

Figure 3-5. Typical TEM microstructures of each sample. 58 .

Typical SiC grain locations in ZrB2-SiC composite 59 .Figure 3-6.

TJF" -*" •< Figure 3-7. Typical interface between ZrB2 grain and SiC grain (ZSN-5: HRTEM image) 60 .

Figure 3-8. in ZrB2 grain. The TEM image and EDX result of second phase. B)x. ZSN-2( 61 . Zr(0.

Q) CO 20 Q_ (I) (/) 10 (0 5 0 j _ 3 O _L J_ -1_ ZSN-0 ZSN-5 ZSN-10 ZSN-20 ZSN-30 Sample Figure 3-9.30 25 Hardness Toughness CM a. The change of hardness and fracture toughness of ZrB2-nano SiC composite with SiC content. 62 .

4-umV Figure 3-10. ZSN-10. ZSN-20). -•:. 63 .•¥ -.Bt * • . Typical cracking pattern of ZrB2-SiC composites (ZSN-0."•-**v.

ii7iiiiMiit:fffii Figure 3-11 Fabricated micropillar of ZSN-0.• 'f ?«•'*-" SI •iif^iBJnai. and ZSN-10 64 . ZSN-5.

16 14 . height change relation by micropillar compression test for ZSN-0 65 . Stress vs. 12 _ • ZSN-0 (GPa) / f Jr / V) 00 o 6 2 0 i ^r i i j i i 0 1 2 3 4 AL/LO (%) Figure 3-12.

5 •*™*>s • ZSN-5 C O Q- -r f i i i i • • 2.0 15 M 1 0 C D N ^ ^ <*> C D s_ CO / 0. height change relation by micropillar compression test for ZSN-5 66 .0 2.3.0 I 10 20 30 40 50 AL/L(%) Figure 3-13. Stress vs.5 0.

5 AL/L (%) Figure 3-14.20 0.0 0. ^ 0.35 0.05 0.0.15 - C D ^ co C O -t—> |D 0.5 2.5 1.30 0.10 !_ 0.25 s-^. height change relation by micropillar compression test for ZSN-10 67 .0 2.0 1. Stress vs.00 J 1 I I L C O 0.

ZSN-10 micropillar (a) before and (b) after compression 68 .Figure 3-15.

TEM microstructural images of ZSN-0 by the micropillar compression test (a) Whole TEM laminar (b) Stacking fault (c) dislocation 69 .Figure 3-16.

TEM microstructural images of ZSN-10 by the micropillar compression test (a) Whole TEM laminar (b) Dislocations (c) Stacking fault 70 .Figure 3-17.

Fracture surface images of ZSN-5 by the micropillar compression test (a) Fracture surface of whole micropillar (b) Intragranular fracture (c) Intergranular fracture 71 .Figure 3-18.

and Songhe Meng. E. Gregory E. Niihara. Am. H. E. and G. (1982). 72 . No5. (2007) Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride-silicon carbide ceramics. Hasselman. Soc.. ceramic nanocomposites. R. International materials reviews. 1 [2] pl-8. pi347-1364 [2] A. Hilmas. Ceram. J. SAND 2006-2925 [5] Sumin Zhu. Oxidation of ZrB2-SiC ceramics under atmospheric and reentry conditions Refractory Appl. [6] Koichi Niihara (1991) New design concept of structural ceramics. p l 3 4 6 .References [1] William G. G. Morena. Chamberlain. Mater. Mukhopadhyay and B. Trans. Inna G. Am. Tevet. P.90. W. Talmy. Elastic Moduli of Transparent Yttria. Lett. and D. 27 p2077-2083. Fahrenholtz. Ceram. Evaluation of KiC of brittle solids by the indentation method with low crack-to-indent ratios. Scripta Materialia 57. and James A. p825-828. Basu. Fahrenholtz. 82. p257-288. Erica Corral. 99. Ping Hu. [10]. pl36-144 [9] K. (1999). [4] Ronald Loehman. Consolidation-microstructure-property relations in bulk nanoceramics and ceramic nanocomposites: a review. Ceram. Fahrenholtz. and O. G. (2006) Ultra high temperature ceramics for hypersonic vehicle applications. Soc. L. [8] O. [3] Jiecai Han. J. The ceramic society of Japan. W. Hans Peter Dumm. (2007). Yeheskel. I . and Raj an Tandon. Issue 5. Sci. and G. Paul Kotula. Vol.. Soc. Zaykoski (2007) Refractory diborides of zirconium and hafnium J. Hilmas. p974-982 [7] A. Euro. Xinghong Zhang. (2007) Oxidation behavior of zirconium diboride-silicon carbide at 1800 °C. Hilmas. J. Vol52.

Science. Munro. p622-630. vol 26. Melandri. Dou and B. 7. Journal of physical and chemical reference data. (2000). Microstructure and Mechanical Properties of ZrB2-based Ceramics. p986-989. F. Derby. Man. J. Materials Park. D. 73 [6] p 141-142. Zirconium diboride. Bellosi. [11] R. Dennis M. [15] R. Materials properties of a sintered alpha-SiC. Bull. OH. Edited by S. Proc. Uchic. pp787-803. [14] Michael D. Development and characterization of metal diboride based composites toughened with ultra fine SiC particulates. vol 4. G. ASM International. Sci. (1997). and C. [12] R. 305. (1994). 9 [2]. (2009). Jeffrey N. Scripta materialia. (2004) Sample dimensions influence strength and crystal plasticity.. Monteverde. p524-527. Engineering properties of borides in ceramics and glasses: Engineered materials handbook. Am. 61. Morz. Schneider Jr. Florando.. A universal scaling law for the strength of metal micropillars and nanowires. (2005). [16] Frederic Monteverde and Alida Bellosi. 73 .[10] A. Mater. A. William D. Fabbriche. D. Nix. pl56-170. Cutler. Ceram. Dimiduk. [13] C. Soc. (1991). Solid state sciences. ppl 195-1203. J.

The applied stress to micropillar of ZrC-ZrB2-SiC 74 . thermal and electrical properties of ZrC-ZrB2-SiC multiphase composites were examined. The elastic moduli of the composites were measured using the longitudinal and transverse soundwave velocities measured.25 W (m K)'1.50 GPa. The thermal conductivities for the composites were in the range 38. On the other hand. The ranges of hardness and fracture toughness values were measured to be 18. respectively.69 to 6.79 to 21. The composites were consolidated by spark plasma sintering. respectively.916xl04 to 4.Chapter 4 Multiphase ZrC-ZrB 2 -SiC ceramics Abstract The effects of composition on mechanical.521xl04 (Q cm)"1.08 MPa m1/2. whereas the hardness and fracture toughness of the composites were determined using an indentation measurement. The electrical conductivities of the multiphase composites were in the range 0. The results indicated that the shear modulus was in the range 180 to 225 GPa and the Young's modulus was in the range 434 to 517 GPa. the thermal and electrical conductivities of the ZrC-ZrB2-SiC composites were measured at room temperature by a nanoflash technique and a current-voltage method. and 4. The microstructure of the as-consolidated composites was examined by field emission scanning electron microscopy and transmission electron microscopy.25 to 98.

composites produced long cracks from surface to bottom without deflecting along grain boundaries. .

The unique combinations of mechanical and physical properties make them attractive candidates for structural applications at ultra-high temperatures. and great thermal shock resistance [1-4]. high thermal and electrical conductivities. The improvement of oxidation and ablation resistance is believed to arise from the formation of coherent passivating oxide scales on the surface. the ZrC-ZrB2-SiC multiphase composite system has been demonstrated to have superior resistance to ablation or conversion than do the corresponding ZrB2/SiC composites under an arc-jet environment [8]. thermal shock and ablation resistance [5-8]. the addition of second phase such as SiC to ZrE$2 results in a composite with improvement of strength and better oxidation. The ZrB2-30ZrC-10SiC (vol %) composites have been successfully consolidated using both hot-pressing and spark plasma sintering [9. For example. the use of these single-phase ceramics materials for high-temperature structural applications is limited by their poor oxidation.1. A composite approach has been successfully adopted in order to improve the oxidation and ablation resistance of single-phase ceramics. More recently. thermal shock and ablation resistance as well as poor damage tolerance. Introduction Diborides and carbides of zirconium (ZrB2 and ZrC) have extremely high melting points (>3000 °C). chemical inertness against molten metals.4. However. 76 .

10]. Furthermore, this composite exhibited high strength with low scattering of strength up to 1500°C, these components are also both thermodynamically and chemically stable at high temperature because the intergranular reaction in the composite is absent [10]. However, the effects of separate components on mechanical, thermal and electrical properties of ZrC-ZrB2-SiC composites are not yet systematically studied. The compositional dependence of these properties is very important for designing ZrC-ZrB2-SiC composites in sustained thermomechanical applications. On the other hand, spark plasma sintering (SPS) is one of the most recent processing techniques developed for densifying ceramic materials, including poorly sinterable compounds [11, 12]. One advantage of SPS concerning ceramics is that the grain growth of starting materials is restricted, as a considerable shorter sintering time (within several minutes) is required compared to hot-pressing or hot isostatic pressing, thereby retaining the fine and homogenous grains. Another is to enhance densification of poorly sinterable ceramics, as a result of the spark discharge generated between powders as well as the presence of the electrical field under pulsed direct current. Previous studies in ZrB2-based ceramic materials showed that SPS enhanced densification and refined microstructure in very short processing cycles [10,

77

13]. This is attributable to the presence of the electrical field during SPS which caused faster diffusion due to the enhanced migration speed of ions [14]. In the present study, ZrC-ZrE^-SiC composites with different compositions were consolidated by spark plasma sintering. The effects on physical properties, mechanical properties with microstructural analysis, thermal properties, and electrical properties of ZrC-ZrB2-SiC composites are discussed in this chapter. In addition, fracture mechanisms based on micropillar compression test are presented.

4.2. Experimental procedures 4.2.1 Materials The starting powders used in this study were: ZrB2 powder (Grade F, Japan New Metals, Tokyo), average particle size —2.12 |im, ZrC powder (Grade F, Japan New Metals), average particle size «2.32 um; and a-SiC powder (Grade UF-15, H.C. Starek, Berlin, Germany), average particle size «0.5 jina. In order to examine the effect of composition on the mechanical, thermal and electrical properties, eight series of ZrC-ZrB2-SiC compositions were prepared in this study. These compositions are shown in table 4-1. The powder mixtures were wet-mixed using SiC milling media and ethanol for 24 h, and then dried in oven. Before sintering, the dried

78

mixtures were sieved through a metallic sieve with 60-mesh screen size. The powder mixture was put into a graphite die lines with graphite foil and densified using spark plasma sintering (SPS-1030, Simitomo Coal Mining Co. Ltd., Tokyo, Japan). The sintering was performed at 1950°C for 2 min under a pressure of 50 MPa in argon atmosphere. Changes in temperature and sintering displacement were recorded by a computer during the entire sintering process. Final sintered specimen size was 10 mm in diameter pellets with a thickness of -2.0 mm. After removing the surface of the sintered compact to avoid contamination from the graphite die, the densities of the sintered composite compacts were measured by the Archimedes method with distilled water as medium. X-ray diffraction (XRD) was used for crystalline phase identification of the composites. The grain size of each component, ZrB2, ZrC, and SiC, was measured directly from the field emission scanning electron microscopy (FE-SEM) images of sintered composites using image J software. In order to estimate the average grain size of each component, five FE-SEM images were used for direct measurement within the range of 200-300 population. Microstructure of the composites was observed by FE-SEM and transmission electron microscopy (TEM). 4.2.2 Elastic moduli, hardness, and fracture toughness measurements The elastic moduli measurements of the composites were performed using an

79

shear modulus.. of the composites was determined using an indentation technique. of the composites was measured on a disk-shaped specimen with a diameter of 10 mm and thickness of ~2 mm using the nanoflash technique (LFA447/2-4N. Klc. OR USA) with a fundamental frequency of 20 MHz. Yokohama. The flash source is a Xenon flash lamp operating in the wavelength range 80 . The corresponding diagonals of the indentation and crack sizes were measured using an optical microscope attached to the indenter. Akashi. The hardness and fracture toughness.2. The fracture toughness. Germany). and ten indents were made for each measurement. a. and Poisson's ratio. v.ultrasonic technique (TDS 3052B. Nanoflash. Japan) for 20 s in ambient air at room temperature. G. The details of calculations were listed in chapter 3.3 Thermal and electrical conductivity measurements The thermal diffusivity. Postfach. The indentation tests were performed on the polished surface of the specimens by loading with a Vickers microhardness indenter (AVK-A. KIC. Beaverton. E. Ltd.8 N was used. of composites were calculated from the Palmqvist equation [15]. were calculated using the longitudinal and transverse soundwave velocities measured in the composite specimens. NETZSCH-Geratebau GmbH. Co. Young's modulus. Tektronix Inc.. The indentation load of 9. 4.

kc. is determined from thermal diffusivity. Prior the measurements. A power supply (Model: 6220. the thermal conductivity of the composites. [16] kt=pCpa (1) where p is the density of the composites. Hillsboro. Cleveland. FEI. and density of the composites according to the following equation.2. 4. Also.of 0. Moreover. C . Keithley) were used to measure the IV characteristics of the samples. and a is the thermal diffusivity of the composites. USA) and digital multimeter (Model: 2182 Nanovoltmeter. was measured with alumina as the reference material.15 urn to 2 um.4 Micropillar compression test ZrC-ZrB2=SiC composites micropillars with ~5 um diameter and -20 um height were prepared by Focused Ion Beam (FIB Nova 600. Keithley. heat capacity. OR) on the surface of composites in order to investigate fracture behavior or effect of 81 . the heat capacity. the electrical conductivity measurements of the composites were performed using the four-wire probe at room temperature. Subsequently. the samples were coated with a colloidal graphite spray in order to enhance the absorption of the Xenon light pulse energy and the emission of IR radiation to the temperature detector. Ohio. All of the measurements were performed in ambient air at room temperature. Cp is the heat capacity of the composites.

and microstructures The shrinkage curves obtained during the SPS cycle for the various composite materials consolidated by SPS are shown in figure 4-1.compression stress on ZrC-ZrB2-SiC composites. ZZS-6. Eden Prairie MN). ZZS-2. The measurable shrinkage was observed at temperatures ranging from 1500 to 1600°C. depending upon the compositions. An optical microscope with high magnification (X 500) in the nanoindenter was used to place the flat punch tip precisely to avoid tilting the micropillars during compression. detailed microstructural observation of compressed micropillars was conducted by TEM. For examples. MTS system. phases. and ZZS-7) were compressed to the depth of 500 nm from the sample surface with the 10 \m\ diameter flat punch tip of a nanoindenter (MTS Nanoindenter/XP. Applied stress and displacement of samples were observed to identify events such as fracture and deformation.3. fracture surface.1 Densities. In addition. The shrinking behavior of ZrC-ZrB2-SiC (ZZS) is almost the same for the studied compositions regardless of component content. The prepared micropillars of each sample (ZZS-1. 4. or dimensional changes of micropillars were observed by FE-SEM after compression tests were finished. Cracks. the onset 82 .3 Results and discussion 4.

X-ray diffraction patterns for the various ZrC-ZrB2-SiC composite materials consolidated by SPS are presented in figure 4-2. The measured densities and relative densities for the various ZrC-ZrB2-SiC composite materials consolidated by SPS are summarized in table 4-2. This is attributed to the fact that the same shrinkage behavior was observed during SPS for all of the studied compositions. It is evident that all the composites were almost fully densified (relative density > 98%) and their relative density was almost the same regardless of composition. ZrC and SiC phases were detected in every case. all of the compositions showed almost the same shrinkage rate with time. Although the peaks of ZrB2. ~1550°C for ZZS-3. and ~1540°C for ZZS-5. The main part of the densification occurred within a period of ~2 min. This suggests that an intergranular reaction did not occur at the grain boundaries during sintering. only ZrB2. The theoretical densities of the composites were calculated according to the rule of mixtures. ~1580°C for ZZS-2. The 83 . whereas conventional hot-press typically required hours of densification at substantially higher temperatures to yield fully densified compacts. During subsequent densification. ZrC and SiC phases showed the different intensity with compositions.temperature of densification was determined to be ~1530°C for ZZS-1. Typical microstructural features of the ZrC-ZrB2-SiC composites observed under FE-SEM is shown in figure 4-3.

ZrC (dark contrast).12 pm) and ZrC (-2. and that of SiC was in the range of 0. ZrC. such as ZrB2 particles for ZZS-2.99 to 1. the primary component in the composite. and SiC amounts are the same for this composition. ZrB2. and SiC) about ZrC-ZrB2-SiC composites was listed in the table 4-3. ZrC particles for ZZS-3.32 pm) but not helpful to reduce average grain size from small initial powders like SiC (-0. consisting of the equiaxed ZrB2 (grey contrast). however. respectively.04 um. ZrB2.75 um. ZrC (bright contrast). ZZS-6. For other compositions.39 um. and ZZS-7. and SiC particles for ZZS-5.59 to 1.25 to 1. In the case of the ZZS-1 composition. formed an interconnected skeleton structure with the other two components homogenously dispersed in it.general microstructures of the ZrC-ZrB2-SiC composites are similar. and ZZS-8. and SiC particles are homogenously and individually present in the isolated locations because the added ZrB2. and SiC (dark contrast) grains. The average grain size of ZrB 2 was in the range of 1. Typical TEM images for ZZS-1 and ZZS-2 are listed in figure 4-4 and figure 4-5. The average grain size of each component (ZrC. that of ZrC was in the range of 0. and 84 . It is noted that the milling process was effective to reduce initial powder size such as ZrB2 (-2. ZZS-4. ZrC. The contrast of each component grain is opposite that of each component grain in FE-SEM images: ZrB2 (grey contrast).5 um).

and their values are 180 GPa and 435 GPa.2 Elastic moduli. Phases and crystallographic information of all three components. respectively. and SiC-containing composition (ZZS-1). ZrC.3. In the case of the same volume percent of ZrB2. the shear and Young's moduli are 205 GPa and 477 GPa. Then. respectively. Any TEM interface images with high resolution mode could not be obtained due to large TEM lamellae thickness. Typical interphase interfaces between ZrB2-ZrC and ZrC-SiC are shown in figure 4-6. and fracture toughness The elastic moduli measured in the various ZrC-ZrB2-SiC compositions consolidated by SPS are listed in table 4-2. it is found that the shear and Young's moduli are related to component content. The lowest shear and Young's moduli were measured in the ZZS-3 composition.SiC (bright contrast). but decreased with increasing ZrC addition. but interphase interfaces were very sharp and narrow so that any second phase cannot be expected in the interfaces. In contrast. were confirmed by SAED. ZrC. and their values are 225 GPa and 517 GPa. 4. From this table. The highest shear and Young's moduli were measured in ZZS-2 composition. hardness. respectively. both the elastic moduli increased with increasing ZrB2 as well as SiC addition. and SiC. ZrB2. but no second phase was found inside the grains (compared to ZrE$2-nano sized SiC composites). Poisson's ratio remains almost 85 .

m1/2.constant for the studied compositions regardless of component content. The compositional dependence of hardness and fracture toughness may be associated with the complex residual stress state that develops during cooling from the processing temperature due to the thermal expansion mismatch among ZrE$2 (CTE: 6.3-3. The hardness and fracture toughness of the ZrC-ZrB2-SiC composites obtained from an indentation technique are summarized in table 4-4. The fracture toughness values of ZrB2-SiC (10-30 % SiC) composites were reported to be between 4.7 ppm/°C).51 GPa. Note that for the ZZS-5 composition the fracture toughness was not listed in this table because it is difficult to measure the crack length accurately. respectively.[17] and 3.69 to 6.m1/2 [8].5 ppm/°C).0-4. ZrB2 and SiC grains without being deflected along the grain boundaries. The fracture toughness of hot-pressed ZrE$2 .8 to 21. A typical cracking pattern is shown in figure 4-7.3 MPa. ZrC (CTE: 7. The crack propagated across the ZrC. The results indicated that both the hardness and fracture toughness of the composites are dependent on the composition.[18] respectively.m1/2.3 MPa. SiC was reported to be 2. Therefore.1 MPam1/2. and 4.1-5. the fracture toughness values of the ZrC-ZrB2-SiC 86 .1 ppm/°C) and SiC (CTE: 4.1 MPa. The ranges of hardness and fracture toughness values were measured to be 18.

The 87 .36 to 30. but increased with increasing SiC and ZrB2 additions.64 Wirf'K~'. ZrC. it is obvious that the heat capacity and the thermal diffusivity decreased with increasing ZrC amount. 4. showing a compositional dependence. in turn resulting in the lowest thermal conductivity in the studied compositions.5 to 0. In particular. the same volume percent of ZrB2. In the case of ZZS-1. and the calculated thermal conductivities of the various ZrC-ZrB2-SiC composites consolidated by SPS are summarized in table 4-5. the thermal conductivity measured was 72. This strong dependence of thermal diffusivity on composition suggests that the thermal conductivity of the ZrC-ZrB2-SiC composition is dominated by the heat flow in the composites. and SiC containing composition.3. thermal diffusivities.multiphase composites are comparable to that of the single-phase ceramics and ZrB2-SiC composites. The thermal diffusivity was in the range of 12.46 mm2 s"1.3 Thermal conductivity The measured heat capacities. From this table. It is evident that the compositional dependence is stronger for the thermal diffusivity than for the heat capacity. the ZZS-3 composition showed the low heat capacity as well as the lowest thermal diffusivity. The heat capacity was in the range of 0. The thermal conductivity then decreased with increasing amount of ZrC.62 Jg'K" .

thermal conductivity dropped from 72.64 Wirf'KT1 for the ZZS-1 composition to 38.25 Wm_1K~l for the ZZS-3 composition, for approximate loss of 50%. On the other hand, the thermal conductivity of the ZrC-ZrB2-SiC composites increases with increasing ZrB2 as well as of SiC amount. The improvement of thermal conductivity is more substantial for increasing SiC than for increasing ZrB2. The ZZS-5 composition, 50 vol.% SiC containing composite, showed the highest heat capacity as well as the highest thermal diffusivity, which in turn resulting in the highest thermal conductivity among all the materials. The thermal conductivity increased from 72.64 Wm^K"1 for the ZZS-1 composite to 92.85 WnT'K"1 for the ZZS-5 composition material, for approximate increase of 30%. It is known that the thermal conductivity of the composites is dependent on the thermal conductivity of the components and the interfacial thermal resistance of the grain boundaries. The thermal conductivity of SiC is higher than that of the ZrB2 and ZrC materials, [1, 19, 20] and ZrC has the lowest thermal conductivity among the ZrB2, ZrC, and SiC components [1, 19]. This implies that the increasing SiC and ZrB2 content should improve thermal conductivity of ZrC-ZrB2-SiC ceramics. Conversely, increasing ZrC content should decrease thermal conductivity. This effect is closely linked to the amount of SiC, ZrB2 and ZrC additions as well as to the distribution

88

because they influenced the heat flow resistance through the components and the interfaces. In the case of high ZrC-containing ZrC-ZrB2-SiC (ZZS-3, ZZS-4, and ZZS-8), the ZrC was the pristine phase and the other two phases (ZrB2 and SiC) were dispersed in it. This structure characteristic led to increased resistance for the heat flow through the components and their interfaces, compared to ZZS-1. This thermal resistance was enhanced with increasing amount of ZrC. In the case of high SiC or ZrB2-containing ZrC-ZrB2-SiC (ZZS-2, ZZS-5, ZZS-6, and ZZS-7), on the other hand, the ZrC particles were embedded in a SiC or ZrB2 matrix. This characteristic structure of SiC or ZrB2 particles formed in ZrC-ZrB2-SiC composites should enhance its heat transport capability, because it could provide a route of higher heat flow. In particular, SiC has the highest thermal conductivity among ZrB2, SiC and ZrC. Thus, in the present study, the addition of SiC or ZrB2 improved heat capacity as well as heat transport, resulting in high thermal conductivity. 4.3.4 Electrical conductivity In figure 4-8, the two examples of the current-voltage relations measured at room temperature for the various ZrC-ZrB2-SiC composites consolidated by SPS are presented. It is clear that the current increased linearly with voltage for every case, i.e. a linear relationship between current and voltage. This indicated that good ohmic

89

contacts have been realized between the measured composite samples and the electrode. Additionally, the slope of the current-voltage curve is related to the compositions: high ZrB2 content resulted in a lower slope. This indicated that the resistance is reduced with increasing ZrB2 in the ZrC-ZrB2-SiC compositions. The measured electrical resistivity and conductivity of the various ZrC-Z'rB2-SiC composites consolidated by SPS are summarized in table 4-6. The electrical conductivity of the ZrC-ZrB2-SiC composites was measure to be in the range of 0.916xl04 to 4.521xl04 Q ' W 1 . In the case of ZZS-1, 33.3 vol.% ZrB2-33.3 vol.% ZrC-33.3 vol.% SiC composite, the measured electrical conductivity was 1.606xl04 fr'cirf'. The electrical conductivity improved with ZrB2 addition. The highest electrical conductivity was measured in the ZZS-2 composition composite and the value was 4.521 xlO4 fT'cm"1. On the other hand, the electrical conductivity decreased with increasing ZrC and/or SiC contents. The lowest electrical conductivity was measured in the ZZS-4 composition composite. Although bulk ZrB2 and ZrC are located in the electrical conductivity range of conductors, the electrical conductivity of ZrC was significantly lower than that of ZrB2 [19]. Thus, the decrease in electrical conductivity due to ZrC addition is a result of the lower electrical conductivity of ZrC. In addition, it was found that the addition of SiC further reduced the electrical

90

This is because of high ZrB2 content for the former (30 vol. the electrical conductivities of all the ZrC-ZrB2-SiC composites investigated in this study are still within the range of conductors. respectively. ZZS-2. However. Although the high ZrC and/or SiC-containing ZrC-ZrB2-SiC composites exhibited lower electrical conductivity as compared with high ZrB2-containing composites. This indicated that ZrB2 addition is important for improving the electrical conductivity of ZrC-ZrB2-SiC composites.39 GPa for ZZS-2 shown in figure 4-10 and figure 4-11.% ZrB2).% SiC-containing composites. Both ZZS-1 and ZZS-2 micropillars did not follow the universal scaling law mentioned in chapter 3 and these two micropillars were broken at fairly low maximum stress with 4. but in the 30 vol. and ZZS-7 are listed in figure 4-9.3. 91 . ZZS-6.conductivity of the ZrC-ZrB2-SiC composites because SiC is a semiconductor.% ZrB2) compared with the latter (15 vol. Typical fracture surfaces of ZZS-1 and ZZS-2 micropillars were shown in figure 4-12 and figure 4-13.5 Micropillar compression tests of ZrC-ZrB2-SiC composites Typical FE-SEM images of fabricated micropillars about ZZS-1. electrical discharge machining can be used for all the ZrC-ZrB2-SiC composites. 4.% SiC-containing composite. the lowest electrical conductivity was not observed in the 50 vol. As a result.38 GPa for ZZS-1 and 1.

respectively. Several TEM microstructures are listed in figure 4-18.42 GPa. the micropillar of ZZS-6 was not broken. Most grains of both micropillars exhibited intragranular fracture behavior rather than intergranular fracture behavior. The micropillar was slightly tilted to one direction (indicated by arrow mark in the image). The image was captured right before complete fracture. but small dimensional and shape changes were noticed by FE-SEM images after applied compression stress in figure 4-16. respectively. However. The images taken after applied compression stress for the ZZS-7 micropillar are shown in figure 4-17. It is noted that the crack did not0 start from the bottom edge of the micropillar but from the top surface of the micropillar in the longitudinal direction. In these images. The dislocations were very small and located in one grain so that they were produced from the milling process.respectively.3 GPa and 4. but stacking faults might be produced by applied compression stress because stacking faults were connected through several grains. The stress-strain (%) curve of ZZS-6 and ZZS-7 are listed in figure 4-14 and figure 4-15. The maximum stress of ZZS-6 and ZZS-7 reached 3. 92 . These results were very similar to the ZSN system discussed in chapter 3. stacking faults and small dislocations were found in the number 1 area and the number 2 area in the TEM lamella. respectively.

4.4.1 MPa. Poisson's ratio was almost the same for all the studied compositions. respectively.8 to 21. Primary component phase formed a short net-like structure. and 4. depending on composition. but it increases with increasing SiC and/or ZrB2 content. (2) The shear modulus of the ZrC-ZrB2-SiC composites was in the range 180 to 225 GPa. and the other secondary phases were homogenously dispersed in it.m1/2. Conclusion (1) The ZrC-ZrB2-SiC composites were consolidated by SPS at 1950°C for 2 min under a pressure of 50 MPa. The ranges of hardness and fracture toughness values were measured to be 18.25 to 87. ZrC and SiC grains.59 Wm"'K"'. and the Young's modulus was in the range 434 to 517 GPa. The measured electrical conductivities were in the 93 .69 to 6.51 GPa. and the composites were almost fully dense regardless of composition. conversely. the electrical conductivity decreased with increasing SiC and/or ZrC content. The microstructure of the composites consisted of the equiaxed ZrB2. The measured thermal conductivities are in the range 38. (4) The electrical conductivities of the ZrC-ZrB2-SiC composites increased with increasing ZrB2 content. (3) The thermal conductivity of the ZrC-ZrB2-SiC composites decreases with increasing ZrC content. depending on component content.

916xl0 4 to 4. The longitudinal cracking behavior was observed in the ZZS-7 micropillar. respectively. (5) The applied compression stress to ZZS-1 and ZZS-2 micropiUars led to complete fracture with maximum stress of 4. In addition.521xl0 4 O ' W 1 .range 0. 94 .38 GPa and 1.39 GPa. stacking faults were generated by applied stress (by TEM investigation).

Compositions (Vol.%) Materials ZrB2 ZrC SiC ZZS-1 33.3 33. 95 .3 33. Compositions of ZrC-ZrB2-SiC composites.3 ZZS-2 70 15 15 ZZS-3 15 70 15 ZZS-4 15 55 30 ZZS-5 30 20 50 ZZS-6 55 15 30 ZZS-7 55 30 15 ZZS-8 30 55 15 Table 4-1.

16 0.05 5.85 6.01 5.65 4.8 98.06 Measured Density (g/cm3) 5.18 0.14 5.7 98.6 98.7 98.51 5.94 5. Densities and elastic properties of ZrC-ZrB2-SiC composites.18 0.51 5.86 5.17 0.1 98.44 5.18 0.70 5.5 99.44 5.17 0. 96 .5 98.5 Elastic Properties G (GPa) 205 225 180 192 206 215 211 196 E (GPa) 477 517 435 449 486 500 496 457 V 0.Theoretical Materials Density (g/cm3) ZZS-1 ZZS-2 ZZS-3 ZZS-4 ZZS-5 ZZS-6 ZZS-1 ZZS-8 5.93 6.16 0.17 Table 4-2.97 Relative Density (%TD) 98.76 6.

74±0.33±0.62 1.59±0.26 Table 4-3.30±0.61 1.78±0.The measured grain size of each component ZrB2.43 1.71±0.53±0.60 ZrC (um) 1.52 1. and SiC for ZrC-ZrB2-SiC composies 97 .Sample ZZS-1 ZZS-2 ZZS-3 ZZS-4 ZZS-5 ZZS-6 ZZS-7 ZZS-8 ZrB2 (um) 1.35±0.60 0.27±0.25±0.65 1.20±0.64±0.82±0.58±0.36±0.25 1.77 1.99±0.25 0.39±0.55 0.33±0.09±0.55 1.75±0.51 SiC (um) 0.04±0.41 1.36 0.54 1.31±0.48 1.61 1.49 1.31 0.26 0.36 0. ZrC.60±0.21±0.46 1.

33 ZZS-5 20.61 ± 0. Hardness and fracture toughness of ZrB2-ZrC-SiC composites 98 .42 ZZS-7 19.04 ± 0.56 ± 1.37 ZZS-8 19.75 ZZS-2 21.63 ± 0.24 Table 4-4.40 ± 1.76 ± 0.78 5.96 6.51 ± 1.94 N/A ZZS-6 19.32 6.Sample Hardness (GPa) Toughness (MPa.m 1/2 ) ZZS-1 19.53 ZZS-3 19.75 5.10 ± 0.74 5.09 ± 0.40 ± 1.80 ± 0.69 ± 0.64 ± 0.26 ZZS-4 18.52 ± 0.00 4.21 5.20 ± 0.

53 23.1 ) a(mm2s_1) Thermal conductivity Kc (Wm-'K"1) ZZS-1 0.07 Table 4-5.69 85.25 ZZS-4 0.55 16.77 ZZS-5 0.Thermal Heat capacity Samples diffusivity Cpdg'K.20 89.33 49.54 27.62 30.51 12.73 ZZS-8 0.02 ZZS-1 0.50 16.46 92.58 22.85 ZZS-6 0.36 38. Thermal properties measured at room temperature for the ZrC-ZrE$2-SiC composites 99 .64 ZZS-2 0.64 73.63 ZZS-3 0.58 28.98 72.82 51.

606 ZZS-2 2.066 ZZS-4 10.207 ZZS-6 3.094 3.917 0.760 Table 4-6.916 ZZS-5 8. Electrical properties measured at room temperature for the ZrC-ZrB2-SiC composites .212 4.521 ZZS-3 9.682 1.384 1.Electrical Electrical conductivity Samples resistivity R(10"5Ocm) (lOtoW 1 ) ZZS-1 6.002 ZZS-7 3.282 1.333 3.231 ZZS-8 5.226 1.

2.0 <D O 03 CL . ZZS-3.«a 0. "l 1 1 1 1 1—I 1 1 1 1 1 ] 1 1—1 1" 2000 (a) E 1-5 E •4-j . Typical examples of recorded shrinkage curves during the SPS cycle for ZZS-2.. 101 . .5 Q 0 -I—I—I 1—I—I—I—1—I—I—1—1—I—I—I—I—I—I—1—I—I—I—I—1—I 1—I—I—I—I—u- 0 50 100 150 200 250 Sintering Time (second) 1000 300 Figure 4-1.1800 c f? 1. and ZZS-5.0 ~! 1—I 1 1 1 1 1 1 1 1—| 1 T .

. N N J| -J GO 8 « P 3 =r ^ N N GO 00 :f t f*" i ccr H T o --4 1? N N GO If fcz • *"- ^ ^^ ^ N N GO o IL r f— c c c c> x o to . N N i 5 ? P3 o o" 3 •a GO o :| •£> N N GO • 0\ <» ^^ o C/5 ro o Q. 'o 1 3 a.u) ro o CO X 1 *? ^ '/ i*.N N y GO • era' 31 c i Of 4^ "2 N N GO Intensity.f L S - 5 J S f (^ ? o to O . (a. a i C D (Q o C D C D CD f f -r i~ '.

5|ua «mmmM&¥mm«*^&vm Figure 4-3. Typical FE-SEM images for the ZrB2-ZrC-SiC composites 103 .

Typical TEM images for the ZZS-! composite 104 .Figure 4-4.

Typical TEM images for the ZZS-2 composite 105 .Figure 4-5.

>*~ " W i d C D ) Figure 4-6 Typical TEM images of interphase interface between (a) SiC and ZrB2 and (b) ZrB2 and ZrC 106 .

Typical cracking behavior of ZrC-ZrB2-SiC composites 107 .Figure 4-7.

> O 5 U -5 ^ — X < D O > -10 •ZZS-4 •ZZS-6 -15 -20 _j i—i i_ -150 -100 -50 0 50 100 150 Current (mA) Figure 4-8.20 —I—i—I—i—i—i—r- 15 10 .—s. Current versus voltage measured at room temperature for the ZrC-ZrB2-SiC composites 108 .

and ZZS-7 109 .Figure 4-9. ZZS-2. ZZS-6. Fabricated micropillar of ZZS-1.

strain (%) curve of ZZS-1 micropillar 110 . Stress vs.0 10 20 30 40 50 60 70 AL/L(%) Figure 4-10.

/ -H r— 0 10 20 30 Al_/L(%) 40 50 60 Figure 4-11. strain (%) curve of ZZS-2 micropillar 111 . .2 0.0 0.0 .2 (TJ Q_ • • • 1. . Stress vs.4 • ZZS-2 O </5 / 0.8 0.4 1. .6 0.1.

Intragranular fracture surface of ZZS-1 micropillar 112 .Figure 4-12.

Figure 4-13. Intragranular fracture surface of ZZS-2 micropillar 113 .

0 i #/ If /I /I H it / yj 0. Stress vs.20 Figure 4-14.0 2.5 0.5 3. strain (%) curve of ZZS-6 micropillar 114 .00 0.05 0.0 O "**-• w 1.15 0. 2.10 AL/L (%) / / 0.5 ^^ # • ZZS-6 S.3.5 w 0 i_ C 10 O 0.

10 0. strain (%) curve of ZZS-7 micropillar 115 .15 0.5 4 3 CO Q. CD </) w !_ -— * • CO <D 2 1 0 1 I I I L 0.20 0.25 AL/L (%) 0.30 Figure 4-15.05 0.00 0. Stress vs.

Dimensional and shape change of ZZS-6 micropillar 116 .Figure 4-16.

Typical cracking behavior of ZZS-7 micropillar 117 .* •_ » 2* Figure 4-17.

Figure 4-18. 118 . Typical TEM images of ZZS-6 micropillar after compression stress.

(1987). Monteverde. p32-40. Q. 73(6). P. On the preparation of bio-. Medri. (1998). 90(7). and W. Shen. Nishimura. (1994). nano. W.. Ablation resistant zirconium and hafnium ceramics.. Y. F. Use of zirconium diboride-copper as an electrode in plasma applications. Thermal and electric properties in hot-pressed ZrB2-MoSi2-SiC composites.. Mater. 7(3). [2] K. L.References [I] K. and A. Mroz. Sciti. Stucker. [6] A. 34(6). Upadhya. F. pi59-163. ZrB2 composite sintered materials. pl41-142. Bull. (2003). [4] O. P. Tanaka. Norasetthekul. Am.. White. 35(9). T. US Patent 4. 37(4). Aerospace Am.481. [II] M. Bozkurt. (2007). [7] C. p267-271. Bradley. Hypersonic designs with a sharp edge. 76(12). 3(1). Brown. Sci. Nygren. Eubank.. Eng.636. Bellosi. Am. p2255-2258. J. [5] J. A. Guo. J. Appl. J. Jpn. B. Bellosi. Soc. and D.750. Am. Bull. Ceram. T. Adv. Ceram. Comparison of ZrB2-ZrC-SiC composites fabricated by spark plasma sintering and hot pressing.. Kuwabara. (1997). p20-21.and structural 119 . Ceram. Bull. and Z.. [3] S. Bull.. [10] A. Balbo. Some characteristics and applications of ZrB 2 ceramics. Hoffmann. J. Int. pl261-1270. (2006). Soc. Zirconium diboride. Soc. (1999). [8] S. M. (2002). Yang. Kagawa. Mater. Soc. [9] V. and H.. Monteverde. p51—56. (2005). Fast densification of ultra-high temperature ceramics by spark plasma sintering. and L.450. Ceram. S. (1997). and B. Materials for ultrahigh temperature structural applications. Kida and Y Segawa. US Patent 5. Technol. Ceram. Kaufman. J.

. pl59-163. Palmqvist. [19] Manufactures Data. Arch Eisenhuettenwes. Am. Occurrence of Crack formation During Vickers Indentation as a Measure of the Toughness of Hard Materials. 120 . J. Japan New Metals Corporation Ltd. (1961). [12] M. Balbo. A.. Tokyo. G. Adv. Cheng. Comparison of ZrB2-ZrC-SiC composites fabricated by spark plasma sintering and hot pressing. and A. Boey.. Khor. Eng. H. [14] K. (1962). K. Phys. pl961-1963. 347. Butler. Sci. J. Soc. Bellosi. Eng. (1988). 14(2). Medri. Res.jp). Mater.co. Novel assemblies via spark plasma sintering. [18] H. 5(7). Flash method of determining thermal diffusivity. [17] F. J.. Yu. A. 67(12).7. pi679-1684.ceramics and composites by spark plasma sintering. Parker. A. Mater. p518-522. and G.p508-512. Ceram. Solid State Sci. C. P 629-633. Bellosi. p300-305. Beneficial effects of AIN as sintering aid on microstructure and mechanical properties of hot-pressed ZrB2. Monteverde. [20] Y.jnm. P.69. 5. [15] S. Jenkins. Zhou. Adv. (2005). Silic. p211-218. Eng.... F. and A. Takeda. 32(9). and Y. (2003). Monteverde. Bull. Abbott. J. 33. Sci. W. L.. L. Development of high-thermal-conductive SiC ceramics. Thermal conductivity and dielectric constant of spark plasma sintered aluminum nitride. (2004). Mater. [13] V. Low temperature sintering and elongated grain growth of 6H-SiC powder with AIB2 and C additives. Appl.. Japan (http://www. and Z. Nygren. Tanaka.. (1999). (2003). and F.. pl25—131. [16] W. Shen. Ind. heat capacity and thermal conductivity...

40% due to SiC reaction bonding process and the large cracks (including micro cracks were observed. and TEM analysis in the interface between the fiber and the matrix 121 . these are due to the thermal expansion mismatch between the fiber and matrix materials. The porosity was 10. SEM. the fracture toughness of the composite was improved compared to the fracture toughness of the matrix itself because of the effect of fibers. SCS 9a fiber-reinforced ZrB2-RB SiC composite was fabricated by hot pressing with reaction bonding process of SiC after tape casting with slurry and woven SCS 9a fibers. However. This high porosity and large cracks with micro cracks affected the hardness and fracture toughness of the composites. Density was measured by pycnometer and porosity was calculated from measured density. No chemical reaction was found by thermodynamical calculation.Chapter 5 SCS 9a fiber-reinforced ZrB 2 -RB(Reaction-bonded) SiC composite Abstract SCS 9a fiber-reinforced ZrB2-RB (Reaction-bonded) SiC composite was examined. At last. microstructural analysis was conducted by FE-SEM with EDS and TEM with EDS and SAED (Selected Area Electron Diffraction). Hardness and fracture toughness of matrix materials were measured by indentation technique. but fracture toughness of the composite was measured by four point bending method.

complex SiC structures such as twin boundaries and stacking faults were observed due to the reaction bonding process of SiC. . In addition.materials.

1 Introduction Zirconium diboride has a high melting temperature (>3000 °C). low-to-zero shrinkage capability. SiC fiber with low oxygen content and small diameter has good thermomechanical reinforcement capability [6]. which include low raw materials costs. However. making it promising candidate for ultra-high-temperature applications [1]. thermal shock resistance. resistance to erosion/corrosion. Thus. and glass-phase-free grain boundaries for many technical and high performance 123 . respectively [2. Addition of a silicon carbide to zirconium diboride enhances the oxidation resistance and limits the zirconium diboride grain growth due to borosilicate diffusion barrier and liquid phase sintering effect. near net-shape tailorability. chemical stability. Reaction bonding of ceramics has various advantages. 3]. Among various ceramic fibers for high temperature applications. high electrical and thermal conductivities.5. the incorporation of a fiber reinforcement phase into ZrB2-SiC ceramics is indispensible in order to improve fracture toughness. the use of ultra-high-temperature ceramics without reinforcements has limitations due to low fracture toughness and poor thermal shock resistance [4]. and good mechanical properties. as well as to lower the composite density [5].

SiC fiber-reinforced ZrB2-RB (Reaction Bonding) SiC composites were consolidated by a hot pressing method. and 84. However.2. the low-to-zero shrinkage capability makes most reaction forming techniques suitable for the fabrication of composites [7]. Levine. Si. Among these advantages. The flexural strengths of SiCfiber-reinforcedcomposites were 130 MPa. 5. studied ZrB2-SiC ceramics. ZrB2-SiC-C.1 Fabrication The starting powders used in this study were ZrB2.2 Experimental procedures 5.applications. and carbon powders and the fibers used in this study were SCS 9a fibers (Specialty Materials Inc. respectively.5 MPa at room temperature. and SiC fiber-reinforced ZrB2-SiC composites. 101 MPa. and 1327 °C. 124 . the composites were not separated into two separate pieces due to crack bridging by the fibers [8]. In this study. and microstructural analyses are discussed in this chapter. mechanical. 1127 °C. The physical. et al. Lowell. The flexural strength of composites were fairly low due to high porosity (up to 30%) from incomplete densification and large amount of micro cracks from the difference between coefficient of thermal expansion of matrix and that of fiber.

especially reaction-bonded SiC.55 °C/min and held for one hour. The simple equation is that porosity is (1-measured density/apparent 125 . The die was placed on a support fixture and loaded into an inert gas furnace. The first step to prepare composite billets with size of 10 cm by 7 cm was mixing the three powders to slurry state with composition of 20 vol% SiC and 80 vol% ZrE$2. The furnace was heated from room temperature to 525 °C at 0. which is composed of a 33 um carbon core and 46 um SiC outer layer.MA).2.3X10"3 Torr for 75min. and measured density by direct measurement from the pycnometer. and then the dried billet was trimmed and loaded into the hot pressing die. The prepared green billet was dried in oven at 110 °C.2 Phase analysis. No extrusion of fiber of matrix was observed upon removal from the die. The porosity was calculated from apparent density. and porosity measurements X-ray diffraction was used in order to confirm the crystalline phases. density. 5. The SCS 9a fibers were wound on the four-sided mandrel with eight-layer thickness to achieve 20 vol% SiC fiber content. The density of fabricated composite was measured directly by pycnometer with helium gas as a medium for accurate. The die was then loaded into the hot-press and processed at reaction bonding temperature (1450-1650 °C) and under a vacuum of 4. The wound fibers were coated with the matrix slurry by tape casting.

and the sharp edges were chamfered. All samples were polished with wet silicon carbide papers (grits 400.326[a/^]--L L_J L J l l35\a/W]2)\a/W](l-\a/W]} . and fracture toughness measurements Elastic properties could not be measured by ultrasonic technique due to difficulties in measuring the velocity of sound waves. five samples were cut from the composite billet. hardness.S 110" BW max L o V2 / J 3 [a I W f 2[l-a/W]3 (1) l3A9-0.density) X100 [9]. Hardness and fracture toughness of matrix materials were measured by microhardness tester as described in previous chapters. For density and porosity. Eden Prairie MN). The equations for calculations of fracture toughness are listed below and the detailed dimensional information is shown in figure 5-1. The load for measurement was 49N and ten tests were made in the matrix part. 600.9887-1. and 1200. • Iph f P \S .2.6S\a/W] + / = 1. successively) on all surfaces except end planes. 5.3 Elastic properties. Young's modulus was measured by nano-indentation technique (MTS Nanoindenter/XP. Ul ii_J £ 2 (2 ) {\ + [a/W] 126 . MTS system. The single edge pre-cracked beam tested in accordance with ASTM C 1421 [10] was used to determine the fracture toughness (KiPb) of SiC-fiber-reinforced ZrE$2-SiC composites with four test samples.

To investigate detailed microstructural information of hot-pressed composites with SiC fibers. OR) with EDAX Energy Dispersive X-ray spectrometer (EDS) and Si/Li detector super ultrathin window. In addition. Thornwood NY). FEI. In order to estimate average crack density and average grain size of each component.2. OR) with tungsten probe tips and four fingers copper grid. fracture mechanism of matrix and composites were analyzed by FE-SEM images. The TEM samples used in this study were prepared by Focused Ion Beam (FIB Nova 600. 127 . Hillsboro. The crack density and grain size of each component were investigated by FE-SEM images with Image-J software. FEI.4 Microstructure observations In order to analyze the structural information of SiC fibers and matrix materials. Hillsboro. ten FE-SEM images were used. randomly selected areas of composites matrix and interface between SiC fibers and matrix were observed by TEM (FBI-Philips CM300.5. A total of 18 (6 X 3) pictures were taken of different areas with X 50 magnification so that all fiber layers structures should be included. The elemental analysis was conducted by FE-SEM with EDS for finding unknown elements in the composites. a whole cross sectional view of the composites was obtained by optical microscope with CCD camera (Carl Zeiss Microimaging Inc.

The measured density.4%. X-ray diffraction patterns for the composite consolidated by HP (Hot Press) are presented in figure 5-3. It is possible that the large amount of pores is from reaction-bonded SiC due to volume contraction after the reaction. the difference between 128 .3.09 g/cm3. and phase.98 g/cm3.3 Results and discussion 5. porosity. 4. The density of the composite is lower than that of two matrix ceramics because the density of the fiber (2. Although the peaks of ZrB2 and SiC phases showed the different intensity.8 g/cm3) is relatively lower than that of the other two components (ZrB2: 6.1 Density.85 g/cm3 and those of ZrC-ZrB2-SiC ceramics were in the range of 4.44 g/cm3. only ZrB2 and SiC phases were detected in the top surface of the composite and the cross section of the composite.13-5. .05 g/cm3. In addition.5. the apparent density.21 g/cm3).96 g/cm3. and 4. The porosity of the composite from direct calculation of densities was 10. which is higher than that of ZrB2-nano SiC ceramics and that of ZrC-ZrB2-SiC ceramics. The FE-SEM images of top surface view and cross sectional view are shown in the figure 5-2. SiC: 3.94-6. and the theoretical density of hot-pressed SCS 9a fiber-reinforced ZrB2-20 vol% SiC composites billet were 3. The measured densities of ZrB2-nano SiC ceramics were in the range of 5. respectively.

and fracture toughness The measured elastic modulus by nano indentation technique was 266±17 GPa. but porosity of sintered materials makes their mechanical and physical properties decrease exponentially [11].26 MPa-m1/2. One of the purposes of thefiber-reinforcedcomposite is to improve the fracture 129 . hardness.intensity of SiC peaks of the top surface of the composite and that of the cross section of the composite was found because SiC outer layers of the fibers make stronger SiC peaks. 5.89 GPa and 1.58±0.3. respectively. However. The cracks initiated from the corner of the diamond indentation pattern and propagated across the ZrB2 and SiC grains without being deflected along the grain boundaries of the ZrB2 grains and the SiC grains. we speculate that the small carbon core of the fiber could not be detected by X-ray diffraction. These values are also lower than that of ZrB2-nano SiC ceramics and that of ZrC-ZrB2-SiC ceramics due to the large amount of pores in the matrix part.44±0. which is lower than that of ZrB2-nano SiC ceramics and that of ZrC-ZrB2-SiC ceramics. It is difficult to compare with the other two ceramics due to the different fabrication methods and raw materials. The hardness and the fracture toughness for the matrix part were 7. Typical indentation marks and cracking patterns are shown in figure 5-4.2 Elastic moduli.

01 ±1. 5. The crack initiated from the edge of a pre-crack and several fibers were fractured. The composite structure is 8 layers with 0° 90° direction fiber arrays. Thus. four point bending test with pre-cracked beam was conducted for measurement of fracture toughness in order to confirm the effect of the fiber-reinforced composite. It is possible that fiber swimming occurred during fabrication. it is interesting to note that the composite beam did not separate into two separate pieces due to a crack bridging effect by the fibers.86 MPa-m1/2. However. However. Many large cracks and micro cracks were found inside and outside the composite. the fracture toughness of the composite was more than four times improved if compared to that of the matrix only. In addition. the array of fibers inside the composite was not straight compared to the first green billet. The fracture toughness was similar to the ZrC-ZrB2-SiC fracture toughness and lower than the ZrB2-nano SiC fracture toughness. The FE-SEM images of composite fracture are shown in figure 5-5.3 Microstructural analysis The whole cross section view of SiC fiber-reinforced composite is shown in figure 5-6. Delamination of composite was observed instead of a cut through the composite. Typical 130 .3. The measured fracture toughness of SiC-fiber-reinforced composite was 6.toughness of materials.

1000K. and 2000K) are listed in table 5-1. which is listed below. These carbon particles could be from residual carbon after reaction bonding of silicon and carbon. A FE-SEM image of the interface between fiber and matrix with high magnification (X 20000) is in figure 5-9. The black particles turned out to be carbon by EDS result with FE-SEM in figure 5-8. the 131 . In addition. These cracks are due to the matrix thermal expansion coefficient being greater than that of the fiber and thus leading to cracking upon cooling from the processing temperature [8]. the reaction between fiber and matrix was considered.FE-SEM images of the composite cracks are shown in figure 5-7. Based on basic calculations of Gibbs free energy for each component in reaction (1). 2ZrB2 + 2C -> 2ZrC + B4C Reaction (1) The standard Gibbs free energy of formation of each component in reaction (1) at different temperatures (298K. The most possible is between ZrB2 and carbon. The outer carbon coating layer of fiber and the ZrB2-SiC matrix part were well bonded to each other. small black particles were observed in the matrix part of the composite shown in figure 5-8. The crack density of the composite was l~3/mm2. The interface between SiC fiber and matrix material is critical for the fiber-reinforced composite in order to improve fracture toughness. but the size of most cracks was very large. First of all.

The detailed TEM microstructure images of interface between the fiber and the matrix are shown in figure 5-11. The desirable interface of the composite is not well-bonded interface with chemical reaction between the fiber and the matrix. As no complex structures were found in the ZrB2 grains. 5.189 kcal/mol. ZrB2 grain.reaction (1) has low possibility because the Gibbs free energy of reaction (1) is 42. The complex stacking faults were found in the region of part 2 and two twin boundaries were observed in the region of part 3 in figure 5-10. In addition. which is a positive value. ZrB2 and SiC agglomerate. the complex SiC grain structures could be from the reaction bonding process. The several regions in the interface part were confirmed by the EDS and diffraction. In order to analyze the detailed interface between the fiber and the matrix. TEM microstructures were investigated. Typical TEM microstructures and SAED (Selected Area Electron Diffraction) of ZrB2 and SiC grain are shown figure 5-10. it is noted that several SiC grains from the reaction bonding process have complex structures. which is not indicated in figure 5-11.4 Conclusion 132 . and ZrB2 with SiC grain were found in the interface without chemical reaction. It seems that only carbon coating layer of the fiber.

the fracture toughness of the composite itself was improved compared to the fracture toughness of matrix materials.40% porosity due to the SiC reaction bonding process and large cracks due to the thermal expansion mismatch of the fiber and the matrix materials. 133 . The SCS 9a fiber-reinforced ZrB2-RB SiC composite is a good approach for a composite with ultra-high temperature applications. but several processes are needed to improve the mechanical properties of the composite. and hence the low hardness and fracture toughness properties of the matrix. In addition. In addition.The SCS 9a fiber-reinforced ZrB2-RB SiC composite was investigated. complex SiC grain structures were observed. However. no chemical reaction was observed in the interface between the fiber and the matrix materials. Based on thermodynamical calculations with Gibbs free energies and TEM investigations with electron diffraction and EDS analysis. The microstructural analysis of the interface between the fiber and the matrix materials was conducted. such as twin boundary and stacking faults. The hot pressing method with reaction bonding of SiC resulted in 10. it is noted that the composite did not separate into two separate pieces by the four point bending test.

1000K.A G 298 A G IOOO A G 2000 (Kcal/mol) (Kcal/mol) (Kcal/mol) ZrB 2 -76.049 -73.782 -7. ZrC. 134 . Gibbs free energy of formation of ZrB2. C.713 -42.171 Table 5-1.225 -66.708 C 0 0 0 ZrC -46.194 -44.151 -8. and B4C at 298K.028 B4C -9. and2000K[12].

0 3 . Detailed dimensions of SCS 9a fiber-reinforced composites for fracture toughness. 135 .So = 40mm W = 4mm : a=2mm H B= 3mm .^ 4mm Si = 20mm 50mm Figure 5-1.

Figure 5-2. (b) Cross-sectional view. 136 . FE-SEM images of SCS 9a fiber-reinforced composite. (a) Top surface view.

. 1" •! 1 I i i • i i i i i i i 20 30 40 50 60 70 80 90 20 Figure 5-3. i 1 1 1?.. Typical X-ray diffraction pattern of SCS 9afiber-reinforcedZrB2-RB SiC composite 137 .10000 8000 6000 S il Cross section • • ZrB2 • SiC 4000 2000 0 _ • • • 1 • i i • 11 i * L i i 1A i 1 A i 20 30 40 50 60 20 70 80 90 100 12000 10000 8000 11 Top surface 11 •ZrB2 • SiC fr s = 6000 4000 2000 • 0 . i .i • • A .

Typical indentation mark and cracking pattern of SCS 9a fiber composite.n [*S/VJ ^ * i Figure 5-4. 138 .W^S ' $ & & & $ I r-v h ing patte.

139 ."<SS.J*£=£Z3»'V%3BB£. FE-SEM images of SCS 9afiber-reinforcedcomposite fracture. ?S: Figure 5-5. fes.* ^3L W. .

-Pf» **" ***« -^s^ifiS Figure 5-6. 140 . Whole cross-section view of SCS 9afiber-reinforcedcomposite.

Figure 5-7. Typical FE-SEM images of cracks inside and outside the composite 141 .

Figure 5-8. FE-SEM Images of residual carbon from reaction bonding and EDS result. 142 .

A a • " ' *-5 Figure 5-9. The FE-SEM image of the interface between fiber and matrix. 143 .

Figure 5=10 Typical TEM microstructures and SAED (Selected Area Electron Diffraction) of the composite 144 .

(c) ZrB2 and SiC agglomerate (d) ZrB2 and SiC grains. (a) Carbon coating layer of the fiber.Figure 5-11. (b) ZrB2 grain. Typical TEM microstructural images and EDS results of the interface between the fiber and the matrix. 145 .

M.90. Fabrication and characterization of an ultra high temperature carbon fiber-reinforced ZrB2-SiC matrix composite. Talmy. 22. Fahrenholtz. Ceram. Ceram. J. Ceram. Opeka.. (2004). Soc. Soc. Vol. Zaykoski. Paul Kotula. Hurst. Oxidation-based materials selection for 2000 °C + hypersonic aerosurfaces: Theoretical considerations and historical experience. Maclaren and sons 146 . Soc. Calculations in ceramics. p825-828. Halbig. A. G. and J. Inna G. 14. J. J. Dicarlo. Kiser. [7] Nils Calussen. of Euro. [3] Ronald Loehman. Am. and Raj an Tandon. Michael C. 90. and Dietmar Holtz. SAND 2006-2925 [4] M. Applied mathematics and computation. B. A. H. 39. [8] Stanley R. Talmy. Fracture mechanisms for SiC fibers and SiC/SiC composites under stress rupture conditions at high temperatures. [5] Sufang Tang. [9] R. (2002). Evaluation of ultra high temperature ceramics for aeropropulsion use. p2757-2767. Shijun Wang. Ping Hu. Sci. Suxing Wu. p3320-3322. Xinghong Zhang. [6] J. and Jonathan A. I. and Wenchuan Liu. (2004). Am. Hans Peter Dumm. Yun. Erica Corral. (2007). Scripta Materialia 57. (1994) Reaction bonding of aluminum oxide (RBAO) composites: Processing. James D. Radford. and Songhe Meng. Jingyi Deng. pl347-1364 [2] Jiecai Han. (2006) Ultra high temperature ceramics for hypersonic vehicle applications. and James A. Mater. M. Elizabeth J. and J. Zaykoski (2007) Refractory diborides of zirconium and hafnium J. J of Euro. Ceram. p97-109. Hilmas. Salem. Soc. Gregory E. Opila. p473-481. reaction mechanisms and properties. 152. p5887-5904. Mrityunjay Singh. Griffiths and C. (2007) Oxidation behavior of zirconium diboride-silicon carbide at 1800 °C. (1965). Issue 5.References [1] William G. [10]. Levine.

. London. Chase. Annual book of ASTM standards. (1999). Standard test method for the determination of fracture toughness of advanced ceramics at ambient temperatures. PA. Kovacik. V. American Society for Testing and Materials. England. JANAF thermochemical tables 147 . Chapter 4. (1974). 18. 01. [11] J. [10] ASTM C 1421-0lb. J. W.LTD. (1999). Sci. 15. West Conshohocken. [12] M. Master. pi007-1010. Correlation between Young's modulus and porosity in porous materials. Porous solids.

Chapter 2 An extensive and thorough literature survey of ultra-high-temperature ceramics were made in chapter two. At first. the requirements for each application were discussed. oxidation property and mechanical property. Two important properties of ZrB2-SiC ceramics. Lastly. liquid phase sintering mechanism was explained. Chapter 1 The ultra-high-temperature ceramics was defined and brief development history was explained. were explained with the limitation of current research from other studies. 148 . In addition. It can be concluded that ZrE$2-based composites are the most promising candidate materials for ultra-high-temperature applications. The spark plasma sintering was introduced with several advantages for nano and high temperature ceramics. the applications for ultra-high-temperature ceramics were introduced and then. how ZrB2-SiC ceramics were selected for ultra-high-temperature ceramics was explained. the investigation into ZrB2-based composites for ultra-high-temperature applications is summarized in this chapter with the conclusions of each previous research.Chapter 6 Conclusions In this dissertation.

In addition. The fully densed ceramics were prepared by the spark plasma sintering and liquid phase sintering effect. Zr(0. Spark plasma sintering and liquid phase sintering effect enabled ZrB2 nano-sized SiC ceramics to be fully dense. thermal conductivity. but the fracture toughness was not related to the compositions. The hardness of the ceramics was dependent on composition. B)x. Elastic modulus. Each phase ZrB2 and SiC grain was confirmed and the second phase. In addition. the produced dislocations and stacking faults were observed by the micropillar compression tests. hardness.Chapter 3 ZrE$2 nano-sized SiC ceramics were investigated in chapter three. micropillar compression tests gave information about typical longitudinal 149 . fracture toughness. was observed by the TEM microstructural analysis. Chapter 4 ZrC-ZrB2-SiC ceramics were investigated in chapter four. Incorporation of nano-sized SiC effectively hindered the grain growth of ZrB2. and electrical conductivity of ZrC-ZrB2-SiC ceramics decreased with increase of ZrC content in the studied composition range. but better dispersion process was needed to avoid the SiC agglomerates in the ceramics. The fracture toughness of ZrC-ZrB2-SiC ceramics was comparable with that of ZrB2 ceramics and that of ZrB2-SiC ceramics.

the fracture toughness of composite itself was four times higher than that of matrix materials. The prepared composite had high porosity and large amount of cracks and these results affected to the mechanical properties of composite.cracking behavior and generation of stacking faults. Chapter 5 SCS 9a fiber-reinforced ZrB2-RB SiC composite was investigated in chapter five. 150 . In addition. The chemical reaction between fibers and matrix materials was not observed based on thermochemical and TEM microstructural analysis. reaction-bonded SiC was observed to complex structures. However. The composite was consolidated with conventional hot pressing with reaction bonding of SiC.

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