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.     

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.     

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.     

Laser Sintering of UltraPure SiO2 Crucibles

The present work introduces the laser sintering as a novel and cost-effective production process for ultrapure quartz glass crucibles. By employing CO₂ laser systems, providing a power output of up to 12 kW, large SiO₂ crucible preforms are sintered to graded structures with no contamination and without any change in geometry.     

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.     

Plastic Deformation of ZrB2 Single Crystals

The active slip planes, the Burgers vector, and the critical resolved shear stress to induce macroscopic deformation in ZrB₂ single crystals were determined. Room-temperature microhardness indentation and high-temperature uniaxial compression loadings were used to induce deformation. Slip occurred in a close-packed α direction on prismatic planes at room temperature and on the basal plane at high temperatures. The high-temperature yield stress and yield drop are discussed in terms of a Widmanstaetten-type precipitate observed in the crystals.     

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.     

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.     

Three-Dimensional Laser Surface Sintering of SiO2 Green Bodies

The present work presents first results obtained with a new semi-solid freeform fabrication technique for ceramic products. It is a combination of three-dimensional (3D) surface milling and laser surface sintering (3D-LSS). By using the 3D-LSS technique, complex-shaped vitreous silica prototypes with high durability have been constructed.     

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.     

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.     

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.     

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.     

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.     

Strength, Fracture Mode, and Thermal Stress Resistance of HfB2 and ZrB2

Zirconium diboride and hafnium diboride were fabricated by hot-pressing at 1800°C and 120,000 psi. Bend strengths were measured on the fully dense materials from 25° to 1400° C in an argon atmosphere. These diboride compounds do not exhibit any gross plastic flow in the temperature range studied. The bend strengths go through a maximum between 700° and 1000°C and vary from 39,000 to 68,000 psi for HfB₂ and 30,000 to 56,000 psi for ZrB₂. The maxima in strength correspond to maxima in the fraction of transgranular fracture. The bend strength and room-temperature elastic modulus measurements were combined with available thermal conductivity and expansion data to calculate thermal stress resistance parameters. Under steady-state heat flow conditions, the calculated thermal stress resistance parameters of the borides are higher than those calculated for other refractory compounds.     

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.     

Reaction Sintering of ZnO-AI2O3

The reaction sintering of equimolar mixtures of ZnO and A1₂O₃ powders was investigated as a function of primary processing parameters such as the temperature, heating rate, green density, and particle size. The powder mixtures were prepared by two different methods. In one method, the ZnO and A1₂O₃ powders were ball-milled. In the other method, the ZnO powder was chemically precipitated onto the A1₂O₃ particles dispersed in a solution of zinc chloride. The sintering characteristics of the compacted powders prepared by each method were compared with those for a prereacted, single-phase powder of zinc aluminate, ZnAl₂O₄. The chemical reaction between ZnO and A1₂O₃ occurred prior to densification of the powder compact and was accompanied by fairly large expansion. The mixing procedure had a significant effect on the densification rate during reaction sintering. The densification rate of the compact formed from the ball-milled powder was strongly inhibited compared to that for the single-phase ZnAl₂O₄ powder. However, the densification rate of the compact formed from the chemically precipitated mixture was almost identical to that for the ZnAl₂O₄ powder. The difference in sintering between the ball-milled mixture and the chemically precipitated mixture is interpreted in terms of differences in the microstructural uniformity of the initial powder compacts resulting from the different preparation procedures.     

Initial Sintering of MnXO-Al2O3

Effects of manganese oxide on the initial sintering kinetics of compacts of 5-μ diameter alumina were studied by isothermal shrinkage measurements from 1450° to 1650°C. The observed rates were characterized by assuming a volume-diffusion mechanism. Variations in sintering rate with both oxygen partial pressure in the furnace and impurity concentration, as well as the observed activation energy, indicated oxygen-ion diffusion was the rate-limiting step during densification.