This paper reviews the crystal chemistry, synthesis, densification, microstructure, mechanical properties, and oxidation behavior of zirconium diboride (ZrB2) and hafnium diboride (HfB2) ceramics. The refractory diborides exhibit partial or complete solid solution with other transition metal diborides, which allows compositional tailoring of properties such as thermal expansion coefficient and hardness. Carbothermal reduction is the typical synthesis route, but reactive processes, solution methods, and pre-ceramic polymers can also be used. Typically, diborides are densified by hot pressing, but recently solid state and liquid phase sintering routes have been developed. Fine-grained ZrB2 and HfB2 have strengths of a few hundred MPa, which can increase to over 1 GPa with the addition of SiC. Pure diborides exhibit parabolic oxidation kinetics at temperatures below 1100°C, but B2O3 volatility leads to rapid, linear oxidation kinetics above that temperature. The addition of silica scale formers such as SiC or MoSi2 improves the oxidation behavior above 1100°C. Based on their unique combination of properties, ZrB2 and HfB2 ceramics are candidates for use in the extreme environments associated with hypersonic flight, atmospheric re-entry, and rocket propulsion.

Refractory Diborides of Zirconium and Hafnium

Macroporous ceramics with pore sizes from 400 nm to 4 mm and porosity within the range 20%–97% have been produced for a number of well-established and emerging applications, such as molten metal filtration, catalysis, refractory insulation, and hot gas filtration. These applications take advantage of the unique properties achieved through the incorporation of macropores into solid ceramics. In this article, we review the main processing routes that can be used for the fabrication of macroporous ceramics with tailored microstructure and chemical composition. Emphasis is given to versatile and simple approaches that allow one to control the microstructural features that ultimately determine the properties of the macroporous material. Replica, sacrificial template, and direct foaming techniques are described and compared in terms of microstructures and mechanical properties that can be achieved. Finally, directions to future investigations on the processing of macroporous ceramics are proposed.

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Processing Routes to Macroporous Ceramics: A Review

Thermal Conductivity of Polymer-Based Composites: Fundamentals and Applications

Zirconium diboride (ZrB 2 ) and ZrB 2 ceramics containing 10, 20, and 30 vol% SiC particulates were prepared from commercially available powders by hot pressing. Four-point bend strength, fracture toughness, elastic modulus, and hardness were measured. Modulus and hardness did not vary significantly with SiC content. In contrast, strength and toughness increased as SiC content increased. Strength increased from 565 MPa for ZrB 2 to >1000 MPa for samples containing 20 or 30 vol% SiC. The increase in strength was attributed to a decrease in grain size and the presence of WC.

High-Strength Zirconium Diboride-Based Ceramics

Seven equimolar, five-component, metal diborides were fabricated via high-energy ball milling and spark plasma sintering. Six of them, including (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)B2, (Hf0.2Zr0.2Ta0.2Mo0.2Ti0.2)B2, (Hf0.2Zr0.2Mo0.2Nb0.2Ti0.2)B2, (Hf0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2, (Mo0.2Zr0.2Ta0.2Nb0.2Ti0.2)B2, and (Hf0.2Zr0.2Ta0.2Cr0.2Ti0.2)B2, possess virtually one solid-solution boride phase of the hexagonal AlB2 structure. Revised Hume-Rothery size-difference factors are used to rationalize the formation of high-entropy solid solutions in these metal diborides. Greater than 92% of the theoretical densities have been generally achieved with largely uniform compositions from nanoscale to microscale. Aberration-corrected scanning transmission electron microscopy (AC STEM), with high-angle annular dark-field and annular bright-field (HAADF and ABF) imaging and nanoscale compositional mapping, has been conducted to confirm the formation of 2-D high-entropy metal layers, separated by rigid 2-D boron nets, without any detectable layered segregation along the c-axis. These materials represent a new type of ultra-high temperature ceramics (UHTCs) as well as a new class of high-entropy materials, which not only exemplify the first high-entropy non-oxide ceramics (borides) fabricated but also possess a unique non-cubic (hexagonal) and layered (quasi-2D) high-entropy crystal structure that markedly differs from all those reported in prior studies. Initial property assessments show that both the hardness and the oxidation resistance of these high-entropy metal diborides are generally higher/better than the average performances of five individual metal diborides made by identical fabrication processing.

https://escholarship.org/content/qt99m7h5w8/qt99m7h5w8.pdf

High-Entropy Metal Diborides: A New Class of High-Entropy Materials and a New Type of Ultrahigh Temperature Ceramics.

High thermal conductive polyvinyl alcohol composites with hexagonal boron nitride microplatelets as fillers

A ZrB 2 -SiC composite was prepared from a mixture of zirconium, silicon, and B 4 C 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 ZrB 2 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 B 4 C will diffuse into the Zr and Si sites and form ZrB 2 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.

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 6 43 MPa, and the fracture toughness was 4.0 MPazm 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.

Reactive Hot Pressing of ZrB 2 -SiC Composites

The mechanical properties of Al2O3-based porous ceramics fabricated from pure Al2O3 powder and the mixtures with Al(OH)3 were investigated. The fracture strength of the porous Al2O3 specimens sintered from the mixture was substantially higher than that of the pure Al2O3 sintered specimens because of strong grain bonding that resulted from the fine Al2O3 grains produced by the decomposition of Al(OH)3. However, the elastic modulus of the porous Al2O3 specimens did not increase with the incorporation of Al(OH)3, so that the strain to failure of the porous Al2O3 ceramics increased considerably, especially in the specimens with high porosity, because of the unique pore structures related to the large original Al(OH)3 particles. Fracture toughness also increased with the addition of Al(OH)3 in the specimens with higher porosity. However, fracture toughness did not improve in the specimens with lower porosity because of the fracture-mode transition from intergranular, at higher porosity, to transgranular, at lower porosity.

Microstructure and Mechanical Properties of Porous Alumina Ceramics Fabricated by the Decomposition of Aluminum Hydroxide

Al 2 O 3 -based porous ceramics with high surface areas were fabricated by adding Al(OH) 3 to the starting powder, followed by pressureless sintering at temperatures >1100°C. Three types of starting powders were used in the present study: pure α-Al 2 O 3 , α-Al 2 O 3 + Al(OH) 3 , and α-Al 2 O 3 + ZrO 2 + Al(OH) 3 . The addition of Al(OH) 3 considerably increased the surface area of the porous Al 2 O 3 , and the addition of ZrO 2 further increased the surface area; a surface area as high as 36.39 m 2 /g was obtained, and the high surface area was retained at higher temperature. The pore size distribution of the specimens with high surface area was bimodal, with one peak at ∼100 nm and the other, which contributed most of the surface area, at ∼10 nm. X-ray analysis showed that in the sample with the fine pores and high surface area, there was θ-Al 2 O 3 phase produced by the decomposition of Al(OH) 3 , presumably because the phase transformation of θ-Al 2 O 3 to α-Al 2 O 3 was incomplete after low-temperature sintering. Moreover, the porous Al 2 O 3 with high surface area retained superior mechanical properties, attributed to the good sinterability of the fine α-Al 2 O 3 powder used in the present study. The sintered specimens could be large and designed to any shape, because pressureless sintering was used for fabrication. The present approach provides a new way of fabricating porous Al 2 O 3 ceramics that could be widely used as catalyst supports in industry, especially for high-temperature catalysis.

Guo-Jun Zhang

Papers

High thermal conductive polyvinyl alcohol composites with hexagonal boron nitride microplatelets as fillers

Reactive Hot Pressing of ZrB2–SiC Composites

Reactive Hot Pressing of ZrB 2 -SiC Composites

Microstructure and Mechanical Properties of Porous Alumina Ceramics Fabricated by the Decomposition of Aluminum Hydroxide

High-Surface-Area Alumina Ceramics Fabricated by the Decomposition of Al(OH)3