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.     

Solution-Based Synthesis of Submicrometer ZrB2 and ZrB2–TaB2

Zirconium diboride and a zirconium diboride/tantalum diboride mixture were synthesized by solution-based processing. Zirconium n -propoxide was refluxed with 2,4-pentanedione to form zirconium diketonate. This compound hydrolyzed in a controllable fashion to form a zirconia precursor. Boria and carbon precursors were formed via solution additions of phenol–formaldehyde and boric acid, respectively. Tantalum oxide precursors were formed similarly as zirconia precursors, in which tantalum ethoxide was used. Solutions were concentrated, dried, pyrolyzed (800°–1100°C, 2 h, flowing argon), and exposed to carbothermal reduction heat treatments (1150°–1800°C, 2 h, flowing argon). Spherical particles of 200–600 nm for pure ZrB₂ and ZrB₂–TaB₂ mixtures were formed.     

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.     

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.     

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.     

Oriented Structure and Crystallography of Directionally Solidified LaB6—ZrB2 Eutectic

Directional solidification of LaB₆—ZrB₂, by use of an electron beam heating technique, yielded oriented ZrB₂ fibers in a LaB₆ matrix. The average diameter of the ZrB₂ fibers was ∼0.2–1.2 µm, with fiber lengths up to 100 µm. Primary platelike LaB₆ dendrites formed upon the solidification of an ingot with a composition of LaB₆—18 wt% ZrB₂. LaB₆ was the first phase to nucleate when eutectic growth occurred, and ZrB₂ showed nonfaceted growth. For the ingot solidified with planar growth the orientation relations of the phases were as follows: growth direction, [001]_LaB6∥[00.1]_ZrB2; interfacial plane, (11.0)_LaB6∥(11.0)_ZrB2.     

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.     

Fabrication and Characterization of an Ultra-High-Temperature Carbon Fiber-Reinforced ZrB2–SiC Matrix Composite

A novel carbon fiber-reinforced ZrB₂–SiC matrix composite was fabricated by heaterless chemical vapor infiltration through infiltration of SiC matrix into a carbon fiber-ZrB₂ powder preform. The C/ZrB₂–SiC composite presented a flexural strength of 148 MPa, a fracture toughness of 5.6 MPa·m^1/2, and a good oxidation and ablation resistance.     

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.     

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.     

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.     

Joining of ZrB2-Based Ultra-High-Temperature Ceramic Composites to Cu–Clad–Molybdenum for Advanced Aerospace Applications

Three hot-pressed ZrB₂-based ultra-high-temperature ceramic composites (UHTCC), ZrB₂–SiC_p (ZS), ZrB₂–SiC_p–C (ZSC), and ZrB₂–SCS9A (SiC fiber)–SiC_p (ZSS), were joined to Cu–clad–Mo using AgCuTi brazes ( T _L∼1073–1173K) and Pd-base brazes ( T _L∼1493–1513K). More extensive chemical interactions occurred in Pd-base joints than in AgCuTi-base joints. The Pd-braze region displayed higher hardness in joints made using ZS than ZSS and ZSC. Residual stress calculations point toward negative strain energy up to ∼23% clad layer thickness because α_{Cu–clad–Mo}<α_ZS (α=coefficients of thermal expansion). Above this thickness, α_{Cu–clad–Mo}>α_ZS, strain energy is positive, and it increases with increasing thickness. Projected reductions in the thermal resistance highlight the benefits of joining the UHTCC to Cu–clad–Mo.     

Dispersion Behavior of ZrB2 Powder in Aqueous Solution

Dispersion conditions of ZrB₂ powder in water were investigated using poly(ethyleneimine) (PEI) as a dispersant. Pulverization of ZrB₂ powder to submicrometer size was difficult and a substantial amount of large particles remained after an intensive planatery milling for 72 h. The isoelectric point (IEP) of ZrB₂ powder was measured to be pH 5.8 by electrophoresis, which shifted to pH 6.2 after milling. The application of PEI changed the IEP of the boride slurry to ∼pH 11. Well-dispersed aqueous ZrB₂ slurries with a high solid loading (up to 45 vol%) were fabricated at pH 6.5–7.5 by the application of 1.5 wt% PEI.     

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.     

Reaction Processes and Characterization of ZrB2 Powder Prepared by Boro/Carbothermal Reduction of ZrO2 in Vacuum

The present work was concentrated mainly on the reaction processes of boro/carbothermal reduction (BCTR) of ZrO₂ with B₄C and carbon in vacuum, and characterization of morphology and sinterability of the obtained ZrB₂ powder. Combining the thermodynamic calculations, X-ray diffraction results, and the trend of furnace pressure with temperature during synthesis, a detailed explanation of the reaction processes of BCTR was developed. Most of the ZrB₂ particles obtained at 1650°C presented a nearly spherical morphology, whereas those synthesized at 1750°C showed a nearly columnar morphology with an increased size. Compared with the powder synthesized at 1750°C as well as the commercially additive-free powder used in the reported work, the ZrB₂ powder synthesized at 1650°C showed a better sinterability due to its smaller particle size and lower oxygen content.     

Transmission Electron Microscopy Characterization of Hot-Pressed ZrB2 with MoSi2 Additive

Microstructure of the hot-pressed ZrB₂ with MoSi₂ additive was investigated by transmission electron microscopy (TEM). The effect of MoSi₂ addition on the microstructure of the ceramic was assessed. For the pure ZrB₂, the microstructure consisted of the equiaxed ZrB₂ grains and a few elongated ZrB₂ grains. For the ZrB₂ with MoSi₂ additive, the microstructure consisted almost entirely of equiaxed ZrB₂ grains. A few dislocations were present in the ZrB₂ grains. In addition, high-resolution TEM observations showed that the intergranular amorphous phase was absent at two ZrB₂ grain boundaries in the ZrB₂ with MoSi₂ additive.     

The System KAlSiO4–Mg2SiO4–KAlSi2O6

Schairer's study (1954) on phase relations in the system KalSi₂O₆–Mg₂SiO₄–SiO₂ was extended to include the system KalSiO₄–Mg₂SiO₄–KalSi₂O₆. It is shown that this join is ternary; however, the relatively high vapor pressure of the condensed phases prohibits study by the usual quenching techniques. The apparent intersection of the (KalSiO₄–Mg₂SiO₄–SiO₃) join with the primary phase volume of spinel is attributed to loss of the alkali-silicate constituents by vapor transport. This results in the effective bulk composition being moved away from this join toward the primary phase volume of spinel in the system K₂O–MgO–Al₂O₃–SiO₂.     

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.