Thermophysical Properties of ZrB2 and ZrB2–SiC Ceramics

Thermophysical properties were investigated for zirconium diboride (ZrB₂) and ZrB₂–30 vol% silicon carbide (SiC) ceramics. Thermal conductivities were calculated from measured thermal diffusivities, heat capacities, and densities. The thermal conductivity of ZrB₂ increased from 56 W (m K)⁻¹ at room temperature to 67 W (m K)⁻¹ at 1675 K, whereas the thermal conductivity of ZrB₂–SiC decreased from 62 to 56 W (m K)⁻¹ over the same temperature range. Electron and phonon contributions to thermal conductivity were determined using electrical resistivity measurements and were used, along with grain size models, to explain the observed trends. The results are compared with previously reported thermal conductivities for ZrB₂ and ZrB₂–SiC.     

Fabrication and Characterization of ZrB2-Based Ceramic Using Synthesized ZrB2–LaB6 Powder

ZrB₂–LaB₆ powder was obtained by reactive synthesis using ZrO₂, La₂O₃, B₄C, and carbon powders. Then ZrB₂–20 vol% SiC–10 vol% LaB₆ (ZSL) ceramics were prepared from commercially available SiC and the synthesized ZrB₂–LaB₆ powder via hot pressing at 2000°C. The phase composition, microstructure, and mechanical properties were characterized. Results showed that both LaB₆ and SiC were uniformly distributed in the ZrB₂ matrix. The hardness and bending strength of ZSL were 17.06±0.52 GPa and 505.8±17.9 MPa, respectively. Fracture toughness was 5.7±0.39 MPa·m^1/2, which is significantly higher than that reported for ZrB₂–20 vol% SiC ceramics, due to enhanced crack deflection and crack bridging near SiC particles.     

Properties of a Pressureless-Sintered ZrB2–MoSi2 Ceramic Composite

A ZrB₂-based composite was fully densified by pressureless sintering at 1850°C with addition of 20 vol% MoSi₂. The microstructure was very fine, with mean dimensions of ZrB₂ grains around 2.5 μm. The four-point flexural strength in air was in excess of 500 MPa up to 1500°C.     

Microstructure and Properties of Spark Plasma-Sintered ZrO2–ZrB2 Nanoceramic Composites

In a recent work, ¹ we have reported the optimization of the spark plasma sintering (SPS) parameters to obtain dense nanostructured 3Y-TZP ceramics. Following this, the present work attempts to answer some specific issues: (a) whether ZrO₂-based composites with ZrB₂ reinforcements can be densified under the optimal SPS conditions for TZP matrix densification (b) whether improved hardness can be obtained in the composites, when 30 vol% ZrB₂ is incorporated and (c) whether the toughness can be tailored by varying the ZrO₂–matrix stabilization as well as retaining finer ZrO₂ grains. In the present contribution, the SPS experiments are carried out at 1200°C for 5 min under vacuum at a heating rate of 600 K/min. The SPS processing route enables retaining of the finer t -ZrO₂ grains (100–300 nm) and the ZrO₂–ZrB₂ composite developed exhibits optimum hardness up to 14 GPa. Careful analysis of the indentation data provides a range of toughness values in the composites (up to 11 MPa·m^1/2), based on Y₂O₃ stabilization in the ZrO₂ matrix. The influence of varying yttria content, t -ZrO₂ transformability, and microstructure on the properties obtained is discussed. In addition to active contribution from the transformation-toughening mechanism, crack deflection by hard second phase brings about appreciable increment in the toughness of the nanocomposites.     

Oxidation Resistance of Fully Dense ZrB2 with SiC, TaB2, and TaSi2 Additives

Specimens of ZrB₂ containing various concentrations of B₄C, SiC, TaB₂, and TaSi₂ were pressureless-sintered and post-hot isostatic pressed to their theoretical densities. Oxidation resistances were studied by scanning thermogravimetry over the range 1150°–1550°C. SiC additions improved oxidation resistance over a broadening range of temperatures with increasing SiC content. Tantalum additions to ZrB₂–B₄C–SiC in the form of TaB₂ and/or TaSi₂ increased oxidation resistance over the entire evaluated spectrum of temperatures. TaSi₂ proved to be a more effective additive than TaB₂. Silicon-containing compositions formed a glassy surface layer, covering an interior oxide layer. This interior layer was less porous in tantalum-containing compositions.     

Thermal and Electric Properties in Hot-Pressed ZrB2–MoSi2–SiC Composites

The thermal and electrical properties of MoSi₂ and/or SiC-containing ZrB₂-based composites and the effects of MoSi₂ and SiC contents were examined in hot-pressed ZrB₂–MoSi₂–SiC composites. The thermal conductivity and electrical conductivity of the ZrB₂–MoSi₂–SiC composites were measured at room temperature by a nanoflash technique and a current–voltage method, respectively. The results indicate that the thermal and electrical conductivities of ZrB₂–MoSi₂–SiC composites are dependent on the amount of MoSi₂ and SiC. The thermal conductivities observed for all of the compositions were more than 75 W·(m·K)⁻¹. A maximum conductivity of 97.55 W·(m·K)⁻¹ was measured for the 20 vol% MoSi₂-30 vol% SiC-containing ZrB₂ composite. On the other hand, the electrical conductivities observed for all of the compositions were in the range from 4.07 × 10–8.11 × 10 Ω⁻¹·cm⁻¹.     

Pressureless Sintering of ZrB2–SiC Ceramics

A pressureless sintering process was developed for the densification of zirconium diboride ceramics containing 10–30 vol% silicon carbide particles. Initially, boron carbide was evaluated as a sintering aid. However, the formation of a borosilicate glass led to significant coarsening, which inhibited densification. Based on thermodynamic calculations, a combination of carbon and boron carbide was added, which enabled densification (relative density >98%) by solid-state sintering at temperatures as low as 1950°C. Varying the size of the starting silicon carbide particles allowed the final silicon carbide particle morphology to be controlled from equiaxed to whisker-like. The mechanical properties of sintered ceramics were comparable with hot-pressed materials with Vickers hardness of 22 GPa, elastic modulus of 460 GPa, and fracture toughness of ∼4 MPa·m^1/2. Flexure strength was ∼460 MPa, which is at the low end of the range reported for similar materials, due to the relatively large size (∼13 μm long) of the silicon carbide inclusions.     

Effect of the Machining Method on the Catalycity and Emissivity of ZrB2 and ZrB2–HfB2-Based Ceramics

The emissivity and the catalytic efficiency related to atomic oxygen recombination were investigated experimentally in the range 1000–2000 K for ZrB₂ and ZrB₂–HfB₂-based ceramics. In order to evaluate the effect of the machining method, two series of samples, one prepared by electrical discharge machining and the other machined by diamond-loaded tools, were tested. High emissivity (about 0.7 at 1700 K) and low recombination coefficients (on average 0.08 at 1800 K) were found for all the materials. The experimental data showed an effect of the surface machining on the catalytic behavior only on the ZrB₂-based composite; conversely, small variations were found in the recombination coefficients of ZrB₂–HfB₂-based samples for the different machining processes. The surface finish affected the emissivity at lower temperatures in both compositions, with the effect becoming negligible at temperatures above 1500 K.     

Interface Crystallography and Structure in LaB6–ZrB2 Directionally Solidified Eutectics

Interfaces in LaB₆–ZrB₂ composites directionally solidified by a zone melting process were characterized by transmission electron microscopy (TEM). The nominal crystallographic orientation relationship between the two phases corresponded to a high-symmetry near-coincidence site lattice (NCSL). The small mistilt (2°–5°) from the high-symmetry orientation relationship was shown to result in an increased volume density of coincident sites. Furthermore, the dominant interface facet planes were predicted by the NCSL model. The configurations of interfacial misfit dislocations were analyzed by high-resolution TEM and showed a good agreement with predictions based on the displacement shift complete lattice and secondary original lattice (O2-lattice) models. These analyses suggested that interfaces were relaxed to relatively low-energy configurations.     

Reactive Hot Pressing of ZrB2–SiC Composites

A ZrB₂–SiC composite was prepared from a mixture of zirconium, silicon, and B₄C via reactive hot pressing. The three-point bending strength was 506 ± 43 MPa, and the fracture toughness was 4.0 MPa·m^1/2. The microstructure of the composite was observed via scanning electron microscopy; the in-situ -formed ZrB₂ and SiC were found in agglomerates with a size that was in the particle-size ranges of the zirconium and silicon starting powders, respectively. A model of the microstructure formation mechanism of the composite was proposed, to explain the features of the phase distributions. It is considered that, in the reactive hot-pressing process, the B and C atoms in B₄C will diffuse into the Zr and Si sites and form ZrB₂ and SiC in situ , respectively. Because the diffusion of Zr and Si atoms is slow, the microstructure (phase distributions) of the obtained composite shows the features of the zirconium and silicon starting powders.     

Pressureless Sintering of High-Density ZrB2–SiC Ceramic Composites

Ultra-high-temperature ceramic composites of ZrB₂ 20 wt%SiC were pressureless sintered under an argon atmosphere. The starting ZrB₂ powder was synthesized via the sol–gel method with a small crystallite size and a large specific surface area. Dry-pressed compacts using 4 wt% Mo as a sintering aid can be pressureless sintered to ∼97.7% theoretical density at 2250°C for 2 h. Vickers hardness and fracture toughness of the sintered ceramic composites were 14.82±0.25 GPa and 5.39±0.13 MPa·m^1/2, respectively. In addition to the good sinterability of the ZrB₂ powders, X-ray diffraction and scanning electron microscopy results showed that Mo formed a solid solution with ZrB₂, which was believed to be beneficial for the densification process.     

A Study of the Phase Relations of ZrO2–TiO2 and ZrO2–TiO2–SiO2

The phase relations of the systems ZrO₂–TiO₂ and ZrO₂–TiO₂–SiO₂ were investigated. X-ray diffraction techniques served as the principal means of analysis. The binary system ZrO₂–TiO₂ was found to be one of partial solid solutions with no intermediate compounds. A eutectic point was found to exist at 50 to 55 weight % ZrO₂ and 1600°C. A preliminary investigation of the ternary system ZrO₂–TiO₂–SiO₂, although not extensive, resulted in a better understanding of this system, with a fairly accurate location of some of its boundary lines. A eutectic point was located at 2% ZrO₂, 10% TiO₂, and 88% SiO₂ at approximately 1500°C.     

Properties of ZrB2–SiC Ceramics by Pressureless Sintering

Pressureless sintering was used to densify ZrB₂–SiC ultra-high temperature ceramics. The physical, mechanical, thermal, electrical, and high temperature properties were investigated. This comprehensive set of properties was measured for ZrB₂ containing 20 vol% SiC in which B₄C and C were used as the sintering aids. The three-point flexural strength was 361±44 MPa and the elastic modulus was 374±25 GPa. The Vickers hardness and fracture toughness were 14.7±0.2 GPa and 4.0±0.5 MPa·m^1/2 respectively. Scanning electron microscopy studies of the microstructure of ZrB₂–SiC showed that SiC particles were distributed homogenously in the ZrB₂ matrix with little residual porosity.     

Low-Fire Processing of ZrO2–SnO2–TiO2 Ceramics

Effects of a liquid-phase-sintering aid, BaCuO₂+ CuO (BCC), on densification and microwave dielectric properties of (Zr_0.8Sn_0.2)TiO₄ (ZST) ceramics have been investigated. The densification kinetics of ZST are greatly enhanced with the presence of 2.5–5 wt% BCC, but become retarded when the amount of BCC increases further. At a given BCC content, moreover, slower densification kinetics are observed with a larger particle size of ZST. The above results are attributed to a chemical reaction taking place at the interface of BCC/ZST during firing. The ZST dissolves into BCC, forming crystalline phases of ZrO₂, SnO₂, CuO, and BaTi₈O₁₆ which reduce the amount of BCC flux available for liquid-phase sintering. The crystallization kinetics become more significant, compared with densification kinetics, with increasing the amount of BCC and the particle sizes of ZST. For samples with 2.5–5 wt% BCC, a high relative sintered density is obtained at 1000°C and the resulting microwave ceramics have a dielectric constant and a value of Q at 7 GHz in the ranges of 35–38 and 2800–5000, respectively.     

In Situ Synthesis of Ultrafine ZrB2–SiC Composite Powders and the Pressureless Sintering Behaviors

Ultrafine ZrB₂–SiC composite powders have been synthesized in situ using carbothermal reduction reactions via the sol–gel method at 1500°C for 1 h. The powders synthesized had a relatively smaller average crystallite size (<200 nm), a larger specific surface area (∼20 m²/g), and a lower oxygen content (∼1.0 wt %). Composites of ZrB₂+20 wt% SiC were pressureless sintered to ∼96.6% theoretical density at 2250°C for 2 h under an argon atmosphere using B₄C and Mo as sintering aids. Vickers hardness and flexural strength of the sintered ceramic composites were 13.9±0.3 GPa and 294±14 MPa, respectively. The microstructure of the composites revealed that elongated SiC grain dispersed uniformly in the ZrB₂ matrix. Oxidation from 1100° to 1600°C for 30 min showed no decrease in strength below 1400°C but considerable decrease in strength with a rapid weight increment was observed above 1500°C. The formation of a protective borosilicate glassy coating appeared at 1400°C and was gradually destroyed in the form of bubble at higher temperatures.     

Energetics of La2O3–HfO2–SiO2 Glasses

A series of La₂O₃–HfO₂–SiO₂ glasses, approximately along the join 0.73SiO₂–0.27( x HfO₂–(1− x )La₂O₃), 0< x <0.3), was prepared using containerless processing techniques (aerodynamic levitation combined with laser heating in oxygen). The enthalpy of formation and enthalpy of vitrification at 25°C were obtained from drop solution calorimetry of these glasses and appropriate crystalline compounds in a molten lead borate (2PbO–B₂O₃) solvent at 702°C. The enthalpy of formation from crystalline oxides was exothermic and became less exothermic with increasing HfO₂ content. Heat contents were measured by transposed temperature drop calorimetry and depended linearly on the HfO₂ content. Differential scanning calorimetry showed that both the onset glass transition and the onset crystallization temperature of these glasses increased with increasing HfO₂ content. Upon slow cooling in air, the glasses crystallized to a mixture of baddeleyite, cristobalite, lanthanum disilicate, and hafnon.     

Phase Equilibria and Structural Species in NdCl3–NaCl, NdCl3–CaCl2, PrCl3–NaCl, and PrCl3–CaCl2 Systems

Equilibrium phase diagrams for the systems NdCl₃–CaCl₂ and NdCl₃–NaCl were determined by differential thermal analysis. A simple eutectic was observed at 59 ± 1 mol% CaCl₂ and 600°± 2°C in the NdCl₃–CaCl₂ system. A compound NaCl.3NdCl₃ which melts incongruently at 545°± 5°C to NdCl₃ and a liquid containing approximately 47 mol% NaCl, and a eutectic at 68 mol% NaCl and 439°± 2°C were found in the NdCl₃–NaCl system. On the basis of agreements between the activities calculated by the Clausius–Clapeyron equation and Temkin's model using the present data for the NdCl₃–CaCl₂ system and the literature data for the PrCl₃–CaCl₂ system, the melts in the former system consist of Nd³⁺, Ca²⁺, and Cl⁻ ions and in the latter system of Pr³⁺, Ca²⁺, and Cl⁻ ions. The above approach indicates the presence of Na⁺, Cl⁻, and NdCl^2-₅ ions in the NaCl-rich melts and Nd³⁺, Cl⁻, and NdCl⁻₄ in the NdCl₃-rich melts in the NdCl₃–NaCl system. Analogous ions were indicated in the melts of the PrCl₃–NaCl system.     

Immiscibility Area in the System TiO2–ZrO2–SiO2

A furnace for use in conjunction with the X-ray spectrometer was developed which was capable of heating small powdered specimens in air to temperatures as high as 1850°C. This furnace was also used for the heating and quenching of specimens in air from temperatures as high as 1850°C. An area of two liquids coexisting between 20 and 93 weight % TiO₂ above 1765°± 10°C. was found to exist in the system TiO₂–SiO₂, which is in substantial agreement with the previous work of other investigators. The area of immiscibility in the system TiO₂–SiO₂ was found to extend well into the system TiO₂–ZrO₂–SiO₂. The two liquids were found to coexist over a major portion of the TiO₂ (rutile) primary-phase area with TiO₂ (rutile) being the primary crystal beneath both liquids. The temperature of two-liquid formation in the ternary was found to fall about 80°C. with the first additions of ZrO₂ up to 3%. With larger amounts of ZrO₂ the change in the temperature of the boundary of the two-liquid area was so slight as to be within the limits of error of the temperature measurement. Primary-phase fields for TiO₂ (rutile), tetragonal ZrO₂, and ZrTiO₄ were found to exist in the system TiO₂–ZrO₂–SiO₂. SiO₂ as high cristobalite is known to exist in the system TiO₂–ZrO₂–SiO₂.     

Laser Sintering of ZrB2

Preliminary results about laser sintering of zirconium diboride (ZrB₂), a good ultra high-temperature ceramics candidate, are presented. In order to evaluate a suitable sintering method, single pulsed laser and a concentric dual laser system were carried out. Two different ZrB₂ powders having ∼15 and ∼2 μm particle size were assessed for sintering. Scanning electron microscopy images showed that the concentric dual laser sintered layer using ∼2 μm particle size of ZrB₂ had relatively smooth surface morphology. X-ray diffraction results confirmed that the sintered layer mainly retained the crystalline phases as the starting powder. In addition, the rapid cooling rate of laser sintering enabled the formation of needle-like nanostructures at the sintered surface.     

The ZrB2 Volatility Diagram

A volatility diagram was calculated for temperatures of 1000, 1800, and 2500 K to understand the oxidation of ZrB₂. Applying the diagram, it can be seen that exposure of ZrB₂ to air produces ZrO₂ (cr) and B₂O₃ (l) over the temperature range considered. The pressure of the predominant vapor species was predicted to increase from ∼10⁻⁶ Pa at 1000 K, to 344 Pa at 1800 K, and to ∼10⁵ Pa at 2500 K. Predictions were consistent with experimental observations that ZrB₂ exhibits passive oxidation below 1200 K, but undergoes active oxidation at higher temperatures due to B₂O₃ (l) evaporation.