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

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Silicon nitride has been researched intensively, largely in response to the challenge to develop internal combustion engines with hot-zone components made entirely from ceramics. The ceramic engine programs have had only partial success, but this research effort has succeeded in generating a degree of understanding of silicon nitride and of its processing and properties, which in many respects is more advanced than of more widely used technical ceramics. This review examines from the historical standpoint the development of silicon nitride and of its processing into a range of high-grade ceramic materials. The development of understanding of microstructure–property relationships in the silicon nitride materials is also surveyed. Because silicon nitride has close relationships with the SiAlON group of materials, it is impossible to discuss the one without some reference to the other, and a brief mention of the development of the SiAlONs is included for completeness.

Silicon Nitride and Related Materials

Handbook of SiC properties for fuel performance modeling

Humankind's aerospace aspirations are placing unprecedented demands on vehicle propulsion systems. Advanced structural ceramics are playing a key role in addressing these challenges.

Advanced structural ceramics in aerospace propulsion.

Among the ultra-high temperature ceramics (UHTC) are a group of materials consisting of zirconium diboride or hafnium diboride plus silicon carbide, and in some instances, carbon. These materials offer a good combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTCperform well in the environment for such applications, i.e. air at low pressure. The purpose of this study was to examine three of these materials under conditions more representative of a propulsion environment, i.e. higher oxygen partial pressure and total pressure. Results of strength and fracture toughness measurements, furnace oxidation, and high velocity thermal shock exposures are presented for ZrB2 plus 20 vol.% SiC, ZrB2 plus 14 vol.% SiC plus 30 vol.% C, and SCS-9a SiC fiber reinforced ZrB2 plus 20 vol.% SiC. The poor oxidation resistance of UHTCs is the predominant factor limiting their applicability to propulsion applications. # 2002 Elsevier Science Ltd. All rights reserved.

Evaluation of ultra-high temperature ceramics foraeropropulsion use

3000°C. That's not just hot ... it's EXTREMELY hot. It is above the melting or decomposition temperatures for most of the materials known to man. But in the world of extreme environment engineering, it is just a baseline.

https://www.electrochem.org/dl/interface/wtr/wtr07/wtr07_p30-36.pdf

UHTCs: Ultra-High Temperature Ceramic Materials for Extreme Environment Applications

The oxidation kinetics of CVD SiC were monitored by thermogravimetric analysis (TGA) in a 50% H2O/50% O2 gas mixture flowing at 4.4 cm/s for temperatures between 1200 and 1400 C. Paralinear weight change kinetics were observed as the water vapor oxidized the SiC and simultaneously volatilized the silica scale. The long-term degradation rate of SiC is determined by the volatility of the silica scale. Rapid SiC surface recession rates were estimated from these data for actual aircraft engine combustor conditions.

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Paralinear Oxidation of CVD SiC in Water Vapor

Chemically vapor deposited silicon carbide (CVD SiC) was oxidized at temperatures of 1000°-1400°C in H2O/O2 gas mixtures with compositions of 10-90 vol% water vapor at a total pressure of 1 atm. Additional experiments were conducted in H2O/argon mixtures at a temperature of 1100°C. Experiments were designed to minimize impurity and volatility effects, so that only intrinsic water-vapor effects were observed. The oxidation kinetics increased as the water-vapor content increased. The parabolic oxidation rates in the range of 10-90 vol% water vapor (the balance being oxygen) were approximately one order of magnitude higher than the rates that were observed in dry oxygen for temperatures of 1200°-1400°C. The power-law dependence of the parabolic oxidation rate on the partial pressure of water vapor at all temperatures of the study indicated that the molecular species was not the sole rate-limiting oxidant. The determination of an activation energy for diffusion was complicated by variations in the oxidation mechanism and oxide-scale morphology with the partial pressure of water vapor and the temperature.

Variation of the Oxidation Rate of Silicon Carbide with Water‐Vapor Pressure

Several compositions of ZrB2- and HfB2-based Ultra-High Temperature Ceramics (UHTC) were oxidized in stagnant air at 1627°C in ten minute cycles for times up to 100 min. These compositions include: ZrB2-20 vol% SiC, HfB2-20 vol% SiC, ZrB2-20 vol% SiC-20 vol% TaSi2, ZrB2-33 vol% SiC, HfB2-20 vol% SiC-20 vol% TaSi2, and ZrB2-20 vol% SiC-20 vol% TaC. The weight change due to oxidation was recorded. The ZrB2-20 vol% SiC-20 vol% TaSi2 composition was also oxidized in stagnant air at 1927°C and in an arc jet atmosphere. Samples were analyzed after oxidation by X-ray diffraction, field emission scanning electron microscopy, and energy dispersive spectroscopy to determine the reaction products and to observe the microstructure. The ZrB2-20 vol% SiC-20 vol% TaSi2 showed the lowest oxidation rate at 1627°C, but performed poorly under the more extreme tests due to liquid phase formation. Effects of Ta-additions on the oxidation of the diboride-based UHTC are discussed.

Elizabeth J. Opila

Papers

Evaluation of ultra-high temperature ceramics foraeropropulsion use

UHTCs: Ultra-High Temperature Ceramic Materials for Extreme Environment Applications

Paralinear Oxidation of CVD SiC in Water Vapor

Variation of the Oxidation Rate of Silicon Carbide with Water‐Vapor Pressure

Oxidation of ZrB2- and HfB2-based ultra-high temperature ceramics: Effect of Ta additions