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

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

High-entropy materials have attracted considerable interest due to the combination of useful properties and promising applications. Predicting their formation remains the major hindrance to the discovery of new systems. Here we propose a descriptor-entropy forming ability-for addressing synthesizability from first principles. The formalism, based on the energy distribution spectrum of randomized calculations, captures the accessibility of equally-sampled states near the ground state and quantifies configurational disorder capable of stabilizing high-entropy homogeneous phases. The methodology is applied to disordered refractory 5-metal carbides-promising candidates for high-hardness applications. The descriptor correctly predicts the ease with which compositions can be experimentally synthesized as rock-salt high-entropy homogeneous phases, validating the ansatz, and in some cases, going beyond intuition. Several of these materials exhibit hardness up to 50% higher than rule of mixtures estimations. The entropy descriptor method has the potential to accelerate the search for high-entropy systems by rationally combining first principles with experimental synthesis and characterization.

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High-entropy high-hardness metal carbides discovered by entropy descriptors

Results. The incidence rate of significant non-cardiac occlusive stenotic lesions in patients with coronary artery disease (CAD), who had to undergo CABG, was 15,84 %. Simultaneous revascularization of coronary and non-coronary arteries was performed in 2,46 % of patients with CAD and PolyVD and multi-stage surgical proced ures were chosen in other cases. Conclusions. The outcomes of CAD surgical treatment were improved in this group of patients due to the implementation of a mul-

Федеральное государственное бюджетное учреждение «Научно-исследовательский институт комплексных проблем сердечно-сосудистых заболеваний» Сибирского отделения Российской академии медицинских наук, Кемерово, Россия

Ultra-high temperature ceramics: Materials for extreme environments

Hypersonic flight involves extremely high velocities and gas temperatures with the attendant necessity for thermal protection systems (TPS). New high temperature materials are needed for these TPS systems. A systematic investigation of the thermodynamics of potential materials revealed that low oxidation rate materials, which form pure scales of SiO2, Al2O3, Cr2O3, or BeO, cannot be utilized at temperatures of 1800°C (and above) due to disruptively high vapor pressures which arise at the interface of the base material and the scale. Vapor pressure considerations provide significant insight into the relatively good oxidation resistance of ZrB2- and HfB2-based materials at 2000°C and above. These materials form multi-oxide scales composed of a refractory crystalline oxide (skeleton) and a glass component, and this compositional approach is recommended for further development. The oxidation resistance of ZrB2-SiC and other non-oxide materials is improved, to at least 1600°C, by compositional modifications which promote immiscibility in the glass component of the scale. Other candidate materials forming high temperature oxides, such as rare earth compounds, are largely unexplored for high temperature applications and may be attractive candidates for hypersonic TPS materials.

Oxidation-based materials selection for 2000°C + hypersonic aerosurfaces: Theoretical considerations and historical experience

The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle–plastic deformation transition temperature were determined for HfB2, HfC0·98, HfC0·67, and HfN0·92 ceramics. The oxidation resistance of ceramics in the ZrB2–ZrC–SiC system was characterized as a function of composition and processing technique. The thermal conductivity of HfB2 exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2·5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC0·98 to 1100°C for HfC0·67 ceramics. The transition temperature of HfB2 was 1100°C. The ZrB2/ZrC/SiC ceramics were prepared from mixtures of Zr (or ZrC), SiB4, and C using displacement reactions. The ceramics with ZrB2 as a predominant phase had high oxidation resistance up to 1500°C compared to pure ZrB2 and ZrC ceramics. The ceramics with ZrB2/SiC molar ratio of 2 (25 vol% SiC), containing little or no ZrC, were the most oxidation resistant.

Mechanical, Thermal, and Oxidation Properties of Refractory Hafnium and zirconium Compounds

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

A model for the oxidation of ZrB2, HfB2 and TiB2

The thermal conductivity, thermal expansion, Young's Modulus, flexural strength, and brittle-plastic deformation transition temperature were determined for HfB2, HfC0.98, HfC0.67, and HfN0.92 ceramics. The mechanical behavior of αHf(N) solid solutions was also studied. The thermal conductivity of modified HfB2 exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2.5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC0.98 to 1100°C for HfC0.67 ceramics. The transition temperature of HfB2 was 1100°C. Pure HfB2 was found to have a strength of 340 MPa in 4 point bending, that was constant from room temperature to 1600°C, while a HfB2 + 10% HfCx had a higher room temperature bend strength of 440 MPa, but that dropped to 200 MPa at 1600°C. The data generated by this effort was inputted into finite element models to predict material response in internally heated nozzle tests. The theoretical model required accurate material properties, realistic thermal boundary conditions, transient heat transfer analysis, and a good understanding of the displacement constraints. The results of the modeling suggest that HfB2 should survive the high thermal stresses generated during the nozzle test primarily because of its superior thermal conductivity. The comparison the theoretical failure calculations to the observed response in actual test conditions show quite good agreement implying that the behavior of the design is well understood.

Mark M. Opeka

Papers

Oxidation-based materials selection for 2000°C + hypersonic aerosurfaces: Theoretical considerations and historical experience

Mechanical, Thermal, and Oxidation Properties of Refractory Hafnium and zirconium Compounds

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

A model for the oxidation of ZrB2, HfB2 and TiB2

Designing for ultrahigh-temperature applications: The mechanical and thermal properties of HfB2, HfcX, HfNX and αHf(N)