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

The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle–plastic deformation transition temperature were determined for HfB₂, HfC_0·98, HfC_0·67, and HfN_0·92 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 HfC_0·98 to 1100°C for HfC_0·67 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.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

High‐temperature mechanical behavior of ZrB2‐based composites with micrometer‐ and nano‐sized SiC particles

Using micrometer‐ and nano‐sized SiC particles as reinforcement phase, two ZrB₂‐SiC composites with high strength up to 1600°C were prepared using high‐energy ball milling, followed by hot pressing. The composite microstructure comprised finer equiaxed ZrB₂ and SiC grains and intergranular amorphous phase. The temperature dependency of flexure strength related to the initial particle size of SiC. In the case of micrometer‐sized SiC, the high‐temperature strength was improved up to 1500°C compared to room‐temperature strength, but the strength degraded at 1600°C, with strength values of 600‐770 MPa. In the case of nano‐sized SiC, the enhanced high‐temperature strength was observed up to 1600°C, with strength values of 680‐840 MPa.     

Oxidation Behavior of Hot Pressed ZrB2‐ZrC‐SiC Ceramic Composites

Dense ZrB₂‐SiC ceramics containing 40 vol% ZrC particles are fabricated via hot pressing method. Then the sintered ceramics are oxidized in air up to 1500°C, and the oxidation kinetics of the ceramic composites is deduced in combination with the reacted fraction curves. As indicated by the experimental results, the oxidation kinetics changes from reaction‐controlled process to diffusion‐controlled one with increasing of oxidation temperature. In addition, the oxidation kinetics parameters are obtained, which indicates that the oxidation resistance decays at elevated temperatures. Furthermore, the evolution of surface morphology and oxide scale during oxidation process is clarified.     

Ultra‐High Temperature Mechanical Properties of a Zirconium Diboride–Zirconium Carbide Ceramic

The mechanical properties of a ZrB₂‐10 vol% ZrC ceramic were measured up to 2300°C in an argon atmosphere. Dense billets of ZrB₂‐9.5 vol% ZrC‐0.1 vol% C were produced by hot‐pressing at 1900°C. The ZrB₂ grain size was 4.9 μm and ZrC cluster size was 1.8 μm. Flexure strength was 695 MPa at ambient, decreasing to 300 MPa at 1600°C, increasing to 345 MPa at 1800°C and 2000°C, and then decreasing to 290 MPa at 2200°C and 2300°C. Fracture toughness was 4.8 MPa·m^½ at room temperature, decreasing to 3.4 MPa·m^½ at 1400°C, increasing to 4.5 MPa·m^½ at 1800°C, and decreasing to 3.6 MPa·m^½ at 2300°C. Elastic modulus calculated from the crosshead displacement was estimated to be 505 GPa at ambient, relatively unchanging to 1200°C, then decreasing linearly to 385 GPa at 1600°C, more slowly to 345 GPa at 2000°C, and then more rapidly to 260 GPa at 2300°C. Surface flaws resulting from machining damage were the critical flaw up to 1400°C. Above 1400°C, plasticity reduced the stress at the crack tip and the surface flaws experienced subcritical crack growth. Above 2000°C, microvoid coalescence ahead of the crack tip caused failure.     

Elevated Temperature Strength Enhancement of ZrB2–30 vol% SiC Ceramics by Postsintering Thermal Annealing

The mechanical properties of dense, hot‐pressed ZrB₂–30 vol% SiC ceramics were characterized from room temperature up to 1600°C in air. Specimens were tested as hot‐pressed or after hot‐pressing followed by heat treatment at 1400°C, 1500°C, 1600°C, or 1800°C for 10 h. Annealing at 1400°C resulted in the largest increases in flexure strengths at the highest test temperatures, with strengths of 470 MPa at 1400°C, 385 MPa at 1500°C, and 425 MPa at 1600°C, corresponding to increases of 7%, 8%, and 12% compared to as hot‐pressed ZrB₂–SiC tested at the same temperatures. Thermal treatment at 1500°C resulted in the largest increase in elastic modulus, with values of 270 GPa at 1400°C, 240 GPa at 1500°C, and 120 GPa at 1600°C, which were increases of 6%, 12%, and 18% compared to as hot‐pressed ZrB₂–SiC. Neither ZrB₂ grain size nor SiC cluster size changed for these heat‐treatment temperatures. Microstructural analysis suggested additional phases may have formed during heat treatment and/or dislocation density may have changed. This study demonstrated that thermal annealing may be a useful method for improving the elevated temperature mechanical properties of ZrB₂‐based ceramics.     

Pursuing enhanced oxidation resistance of ZrB2 ceramics by SiC and WC co-doping

The oxidative degradation of ZrB₂ ceramics is the main challenge for its extensive application under high temperature condition. Here, we report an effective method for co-doping suitable compounds into ZrB₂ in order to significantly improve its anti-oxidation performance. The incorporation of SiC and WC into ZrB₂ matrix is achieved using spark plasma sintering (SPS) at 1800?°C. The oxidation behavior of ZrB₂-based ceramics is investigated in the temperature range of 1000?°C–1600?°C. The oxidation resistance of single SiC-doped ZrB₂ ceramics is improved due to the formation of silica layer on the surface of the ceramics. As for the WC-doped ZrB₂, a dense ZrO₂ layer is formed which enhances the oxidation resistance. Notably, the SiC and WC co-doped ZrB₂ ceramics with relative density of almost 100% exhibit the lowest oxidation weight gain in the process of oxidation treatment. Consequently, the co-doped ZrB₂ ceramics have the highest oxidation resistance among all the samples.     

Preparation of highly porous ZrB2/ZrC/SiC composite monoliths using liquid precursors via direct drying process

We developed a simple liquid precursor method for the syntheses of porous ZrB₂/ZrC/SiC composite monoliths. Furfuryl alcohol (FA), zirconium n-butoxide, tetraethyl orthosilicate and boric acid are used as the raw materials. By combining the polymerization of FA and gelation of inorganic sols, porous hybrid monoliths are prepared by direct drying the wet gels. The inorganic and organic polymers possibly form interpenetrated network which provides the robustness for the wet gel to withstand the severe changes during dessication. When heat-treated at 1600 °C, hybrid gels are converted into porous ZrB₂/ZrC/SiC monoliths. The microstructure of the ZrB₂/ZrC/SiC monoliths can be easily tailored by controlling the synthesis conditions. The porosities of the ZrB₂/ZrC/SiC monoliths can be tuned around 74.3–81.6%, while the average pore diameters can be tuned ranging from 1.0 to 8.5 μm with pretty narrow distribution. The compressive strengths of such highly porous ceramics are in the range of 1.2–1.9 MPa.     

Ablation resistance of SiC‐modified ZrC coating prepared by SAPS for SiC‐coated carbon/carbon composites

This study evaluated the ablation resistance of ZrC/SiC coating for carbon/carbon (C/C) composites at different temperatures and heat fluxes, which improved the researches on ultra‐high temperature oxidation of ZrC/SiC system. Results showed that the protection of coating depended on temperature and heat flux. Ablation test for 120 seconds under heat flux of 2.4 MW/m² at 2270°C revealed a good ablation resistance, with the linear ablation rate reduced by 96.4% and the mass gain rate increased by 383.3% compared with those of pure ZrC coating. The good ablation resistance was attributed to the formation of dense oxide scale surface. SiC could improve the compactness of the oxide scale at this temperature by forming SiO₂. A dense scale could not form at 2105°C after ablation for 120 seconds, resulting in a dissatisfactory ablation resistance of the coating. After ablation for 120 seconds at 1738°C, the coating was integrated due to the protection of glassy SiO₂ encapsulated ZrO₂. The coating could not resist the strong shear force from the flame at heat flux of 4.2 MW/m² and was severely damaged after ablation for 60 seconds.     

Solidification of welded SiC–ZrB2–ZrC ceramics

A silicon carbide‐based ceramic, containing 50 vol% SiC, 35 vol% ZrB₂, and 15 vol% ZrC was plasma arc welded to produce continuous fusion joints with varying penetration depth. The parent material was preheated to 1450°C and arc welding was successfully implemented for joining of the parent material. A current of 138 A, plasma flow rate of ~1 L/min or ~0.5 L/min, and welding speed of ~8 cm/min were utilized for repeated joining, with full penetration fusion zones along the entire length of the joints. Solidification was determined to occur through the crystallization of β‐SiC (3C), then the simultaneous solidification of SiC and ZrB₂, and lastly through the simultaneous solidification of SiC, ZrB₂, and ZrC through a ternary eutectic reaction. The ternary eutectic composition was determined to be 35.3 ± 2.2 vol% SiC, 39.3 ± 3.8 vol% ZrB₂, and 25.4 ± 3.0 vol% ZrC. A dual fusion zone microstructure was always observed due to convective melt pool mixing. The SiC content at the edge of the fusion zone was 57 vol%, while SiC content at the center of the fusion zone was 42 vol% although the overall SiC content was still nominally 50 vol% throughout the entire fusion zone.     

Oxidation behavior of ZrB2-SiC-ZrC in oxygen-hydrogen torch environment

The oxidation behavior of four ZrB₂-SiC-ZrC compositions with varying ZrC contents (20, 34, 50, and 64 vol.%) was compared to that of ZrB₂-SiC. The ceramics were oxidized at 1700 °C in an oxygen-hydrogen torch environment. The liquid oxide on the ZrB₂-SiC sample came off from the surface under such an environment. In contrast, the all ZrB₂-SiC-ZrC samples maintained the convex oxide on the surface, which consisted of ZrO₂ and SiO₂. The convex oxide of ZSZ with higher ZrC content was thicker, with the exception of ZrB₂-SiC-64vol.%ZrC sample. The ZrB₂-SiC-64vol.%ZrC sample formed a ZrO₂-rich layer, which was clearly denser than the ZrO₂-SiO₂. This densification was caused by ZrO₂-sintering, and it was specific behavior under the dynamic pressure.     

Densification and ablation behavior of ZrB2 ceramic with SiC and/or Fe additives fabricated at 1600 and 1800 °C

The effects of Fe and SiC additions on the densification, microstructure, and ablation properties of ZrB₂-based ceramics were investigated in this study. The sample powders were conventionally mixed by cemented carbide ball then sintered by spark plasma sintering. The ablation rates and behavior of the ceramics were investigated under an oxyacetylene torch environment at about 3000 °C. A sample with high relative density (96.3%), high flexural strength (415.6 MPa), and low linear ablation rate (−0.4 µm/s) was obtained via SPS at 1600 °C. Adding 4 vol% Fe was more beneficial to the density of ZrB₂ sintered at 1600 °C as compared to ZrB₂ sintered at 1800 °C. The ablation behavior and rates were similar among samples sintered at 1600 °C and 1800 °C.     

High‐Temperature Oxidation of ZrB2–SiC–AlN Composites at 1600°C

The effect of AlN substitution on oxidation of ZrB₂–SiC was evaluated at 1600°C up to 5 h. Replacement of ZrB₂ by AlN, with 30 vol% SiC resulted in improved oxidation resistance with a thinner scale and reduced oxygen affected area. On the other hand, substitution of AlN for SiC resulted in a deterioration of the oxidation resistance with an abnormal scale and significant recession. The effect of SiC content was also studied, and was found to be consistent with the literature for the composites without AlN additions. A similar effect was observed when AlN was added, with the higher SiC content materials showing improved oxidation resistance. X‐ray photoelectron spectroscopy showed the presence of Al₂O₃ and SiO₂ on the surface, which could possibly lead to a modification in the viscosity of the glassy oxide scale. Possibly, the oxidation behavior of ZrB₂–SiC composites can be improved with controlled AlN additions by adjusting the Al:Si ratios.     

Reactive Hot Pressing of ZrC–SiC Ceramics at Low Temperature

Composites of ZrC–SiC with relative densities in excess of 98% were prepared by reactive hot pressing of ZrC and Si at temperature as low as 1600°C. The reaction between ZrC and Si resulted in the formation of ZrC_1?x, SiC, and ZrSi. Low‐temperature densification of ZrC?SiC ceramics is attributed to the formed nonstoichiometric ZrC_1?x and Zr–Si liquid phase. Adding 5 wt% Si to ZrC, the three‐point bending strength of formed ZrC_0.8–13.4 vol%SiC ceramics reached 819 ± 102 MPa with hardness and toughness being 20.5 GPa and 3.3 MPa·m^1/2, respectively.     

Spark Plasma Sintering of Superhard B4C–ZrB2 Ceramics by Carbide Boronizing

A carbide boronizing method was first developed to produce dense boron carbide‐ zirconium diboride (“B₄C”–ZrB₂) composites from zirconium carbide (ZrC) and amorphous boron powders (B) by Spark Plasma Sintering at 1800°C–2000°C. The stoichiometry of “B₄C” could be tailored by changing initial boron content, which also has an influence on the processing. The self‐propagating high‐temperature synthesis could be ignited by 1 mol ZrC and 6 mol B at around 1240°C, whereas it was suppressed at a level of 10 mol B. B₈C–ZrB₂ ceramics sintered at 1800°C with 1 mole ZrC and 10 mole B exhibited super high hardness (40.36 GPa at 2.94 N and 33.4 GPa at 9.8 N). The primary reason for the unusual high hardness of B₈C–ZrB₂ ceramics was considered to be the formation of nano‐sized ZrB₂ grains.     

High temperature oxidation behavior of ZrB2-SiC added MoSi2 ceramics

In this paper, MoSi₂, MoSi₂-20?vol% (ZrB₂-20?vol% SiC) and MoSi₂-40?vol% (ZrB₂-20?vol% SiC) ceramics were prepared using pressureless sintering. The oxidation behaviors of these MoSi₂-(ZrB₂-SiC) ceramics were investigated at 1600?°C for different soaking time of 60, 180 and 300?min, respectively. The oxidation behaviors of the MoSi₂-(ZrB₂-SiC) ceramics were studied through weight change test, oxide layer thickness measurement, and microstructure analysis. Further investigation of the oxidation behaviors of the MoSi₂-(ZrB₂-SiC) ceramics was conducted at a higher temperature of 1800?°C for 10?min. The microstructure evolution of the ceramics was also analyzed. It was finally found that the oxidation resistance of MoSi₂ was improved by adding ZrB₂-SiC additives, and the MoSi₂-20?vol% (ZrB₂-20?vol% SiC) ceramic exhibited the optimal oxidation resistance behavior at elevated temperatures. From this study, it is believe that it can give some fundamental understanding and promote the engineering application of MoSi₂-based ceramics at high temperatures.     

Synthesis of ZrC–SiC Powders by a Preceramic Solution Route

Homogenous liquid precursor for ZrC–SiC was prepared by blending of Zr(OC₄H₉)₄ and Poly[(methylsilylene)acetylene]. This precursor could be cured at 250°C and converted into binary ZrC–SiC composite ceramics upon heat treatment at 1700°C. The pyrolysis mechanism and optimal molar ratio of the precursor were investigated by XRD. The morphology and elements analyses were conducted by SEM and corresponding energy‐dispersive spectrometer. The evolution of carbon during ceramization was studied by Raman spectroscopy. The results showed that the precursor samples heat treated at 900°C consisted of t‐ZrO₂ (main phase) and m‐ZrO₂ (minor phase). The higher temperature induced phase transformation and t‐ZrO₂ converted into m‐ZrO₂. Further heating led to the formation of ZrC and SiC due to the carbothermal reduction, and the ceramic sample changed from compact to porous due to the generation of carbon oxides. With the increasing molar ratios of C/Zr, the residual oxides in 1700°C ceramic samples converted into ZrC and almost pure ZrC–SiC composite ceramics could be obtained in ZS‐3 sample. The Zr, Si, and C elements were well distributed in the obtained ceramics powders and particles with a distribution of 100 ~ 300 nm consisted of well‐crystallized ZrC and SiC phases.     

High-temperature bending strength,internal friction and stiffness of ZrB2–20 vol% SiC ceramics

Dense ZrB₂–20 vol% SiC ceramics (ZS) were fabricated by hot pressing using self-synthesized high purity ZrB₂ and commercial SiC powders as raw materials. The high temperature flexural strength of ZS and its degradation mechanisms up to 1600 °C in high purity argon were investigated. According to the fracture mode, crack origin and internal friction curve of ZS ceramics, its strength degradation above 1000 °C is considered to result from a combination of phenomena such as grain boundary softening, grain sliding and the formation of cavitations and cracks around the SiC grains on the tensile side of the specimens. The ZS material at 1600 °C remains 84% of its strength at room temperature, which is obviously higher than the values reported in literature. The benefit is mainly derived from the high purity of the ZrB₂ powders.     

Effect of sintering temperature on electrical properties of SiC/ZrB2 ceramics

SiC/20?wt% ZrB₂ composite ceramics were fabricated via pressureless solid phase sintering in argon atmosphere at different temperature. The effect of sintering temperature on microstructure, electrical properties and mechanical properties of SiC/ZrB₂ ceramics was investigated. Electrical resistivity exhibits twice significant decreases with increasing sintering temperature. The first decrease from 1900?°C to 2000?°C is attributed to the obvious decrease of continuous pore channels in as-sintered materials. The second decrease from 2100?°C to 2200?°C results from the improvement of carbon crystallization and the disappearance of amorphous layers enveloping ZrB₂ grains. Additionally, the increase of sintered density with increasing temperature caused greatly advance of flexural strength, elastic modulus and Vickers hardness. But excessive temperature is detrimental to flexural strength because of SiC grain growth.     

High‐temperature tensile strength and fracture behavior of ZrB2‐SiC‐graphite composite

The tensile behavior of ZrB₂‐SiC‐graphite composite was investigated from room temperature to 1800°C. Results showed that tensile strength was 134.18 MPa at room temperature, decreasing to 50.34 MPa at 1800°C. A brittle‐ductile transition temperature (1300°C) of ZrB₂‐SiC‐graphite composite was deduced from experimental results. Furthermore, the effect of temperature on the fracture behavior of ZrB₂‐SiC‐graphite composite was further discussed by microstructure observations, which showed that tensile strength was controlled by the relaxation of thermal residual stress below 1300°C, and was affected by the plastic flow during 1300°C and 1400°C. At higher temperature, the tensile strength was dominated by the changes of microstructures.