Electrical and thermophysical properties of ZrB2 and HfB2 based composites

Electrical resistivities, thermal conductivities and thermal expansion coefficients of hot-pressed ZrB₂–SiC, ZrB₂–SiC–Si₃N₄, ZrB₂–ZrC–SiC–Si₃N₄ and HfB₂–SiC composites have been evaluated. Effects of Si₃N₄ and ZrC additions on electrical and thermophysical properties of ZrB₂–SiC composite have been investigated. Further, properties of ZrB₂–SiC and HfB₂–SiC composites have been compared. Electrical resistivities (at 25 °C), thermal conductivities (between 25 and 1300 °C) and thermal expansion coefficients (over 25–1000 °C) have been determined by four-probe method, laser flash method and thermo-mechanical analyzer, respectively. Experimental results have shown reasonable agreement with theoretical predictions. Electrical resistivities of ZrB₂-based composites are lower than that of HfB₂–SiC composite. Thermal conductivity of ZrB₂ increases with addition of SiC, while it decreases on ZrC addition, which is explained considering relative contributions of electrons and phonons to thermal transport. As expected, thermal expansion coefficient of each composite is reduced by SiC additions in 25–200 °C range, while it exceeds theoretical values at higher temperatures.     

Volatility diagram of ZrB2‐SiC‐ZrC system and experimental validation

A volatility diagram of zirconium carbide (ZrC) at 1600, 1930, and 2200°C was calculated in this work. Combining it with the existing volatility diagrams of ZrB₂ and SiC, the volatility diagram of a ternary ZrB₂‐SiC‐ZrC (ZSZ) system was constructed in order to interpret the oxidation behavior of ZSZ ceramics. Applying this diagram, the formation of ZrC‐corroded and SiC‐depleted layers and the oxidation sequence of each component in ZSZ during oxidation and ablation could be well understood. Most of the predictions from the diagrams are consistent with the experimental observations on the oxidation scale of dense ZrB₂‐SiC‐ZrC ceramics/coatings after oxidation at 1600°C or ablation at 1930 and 2200°C. The reasons for the discrepancy are also briefly discussed.     

Microstructural characterization of ZrB2–SiC based UHTC tested in the MESOX plasma facility

Microstructures were investigated for ZrB₂–SiC and ZrB₂–HfB₂–SiC ultra high temperature ceramics that were subjected to a high temperature plasma environment. Both materials were tested in the MESOX facility to determine the recombination coefficient for atomic oxygen up to 1750 °C in subsonic air plasma flow. Surfaces were analyzed before and after testing to gain a deeper insight of the surface catalytic properties of these materials. Microstructural analyses highlighted oxidation induced surface modification. Oxide layers were composed of silica with trace amounts of boron oxide and zirconia if the maximum temperature was lower than about 1550 °C and zirconia for higher temperatures. The differences in the oxide layer composition may account for the different catalytic behavior. In particular, the presence of a borosilicate glass layer on the surface of ZrB₂–SiC materials guarantees atomic oxygen recombination coefficients that are relatively lower than the coefficients measured when only zirconia is present. The oxidation processes of ZrB₂–HfB₂–SiC materials, associated with catalytic tests carried out up to 1550 °C, lead to the formation of hafnia as well as silica, and zirconia. The higher recombination coefficients measured in the case of ZrB₂–HfB₂–SiC materials can be correlated with the presence of hafnia which is probably characterized by higher catalytic activity compared to zirconia. In any case, the investigated materials demonstrate a low catalytic activity over the inspected temperature range with maximum values of recombination coefficients close to 0.1.     

UHTC–carbon fibre composites: Preparation,oxyacetylene torch testing and characterisation

Current generation carbon–carbon (C–C) and carbon–silicon carbide (C–SiC) materials are limited to service temperatures below 1800 °C and materials are sought that can withstand higher temperatures and ablative conditions for aerospace applications. One potential materials solution is carbon fibre-based composites with matrices composed of one or more ultra-high temperature ceramics (UHTCs); the latter are intended to protect the carbon fibres at high temperatures whilst the former provides increased toughness and thermal shock resistance to the system as a whole. Carbon fibre–UHTC powder composites have been prepared via a slurry impregnation and pyrolysis route. Five different UHTC compositions have been used for impregnation, viz. ZrB₂, ZrB₂–20 vol% SiC, ZrB₂–20 vol% SiC–10 vol% LaB₆, HfB₂ and HfC. Their high-temperature oxidation resistance has been studied using a purpose built oxyacetylene torch test facility at temperatures above 2500 °C and the results are compared with that of a C–C benchmark composite.     

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.     

Thermo-mechanical simulation of ultrahigh temperature ceramic composites as alternative materials for gas turbine stator blades

The efficiency of the Bryton cycle strongly depends on the maximum temperature of the cycle. However, restrictions on metallurgical problems deprive engineers from the benefit of high temperatures. Ultrahigh temperature ceramics can be considered in such cases, instead of traditional materials like M152 superalloy. In this study, SiC reinforced HfB₂ and ZrB₂ ultrahigh temperature ceramics were proposed as gas turbine stator blades. The heat transfer and stress-strain equations were solved numerically by the finite element method to obtain temperature and stress distributions. The results showed that the maximum thermal stress occurs in vicinity of the cooling ducts where the temperature gradient is maximum. The maximum displacements of 1.2 mm (for HfB₂–SiC) and 1.14 mm (for ZrB₂–SiC) occur in the upper wall. It can be noticed that the ZrB₂–SiC made blade showed lower maximum stress and displacement than those for the HfB₂–SiC made one, as a result of lower expansion coefficient of ZrB₂–SiC system. The addition of SiC to monolithic HfB₂ and ZrB₂ ceramics decreases their thermal conductivity and following that, the temperature uniformity in blades reduces. Although the thermal stresses and the probability of failure in these stator blades enhance, the ZrB₂–SiC material presented the best performance among the other investigated samples. Both Coulomb-Mohr and Von Mises failure analyses were employed. It was understood that both blades made of HfB₂–SiC and ZrB₂–SiC composites simply withstand the applied stresses with the safety factors of about 1.5.     

In-situ synthesis of ultra-fine ZrB2–ZrC–SiC nanopowders by sol-gel method

ZrB₂–ZrC–SiC nanopowders with uniform phase distribution were prepared from cost-effective ZrOCl₂·8H₂O by a simple sol-gel method. The synthesis route, ceramization mechanism and morphology evolution of the nanopowders were investigated. ZrB₂–ZrC–SiC ceramic precursor can be successfully obtained through hydrolysis and condensation reactions between the raw materials. Pyrolysis of the precursor was completed at 650 °C, and it produced ZrO₂, SiO₂, B₂O₃ and amorphous carbon with a yield of 39% at 1300 °C. By heat-treated at 1500 °C for 2 h, highly crystallized ZrB₂–ZrC–SiC ceramics with narrow size distribution were obtained. With the holding time of 2 h, both the crystal size and the particle size can be refined. Further prolonging the holding time can lead to serious particles coarsening. Studies on the microstructure evolution of the generated carbon during the ceramic conversion demonstrates the negative effect of the ceramic formation on the structure order improvement of the carbon, due to the large amount of defects generated in it by the boro/carbothermal reduction reactions.     

Oxidation of HfB2–SiC ceramics under static and dynamic conditions

The kinetics and the mechanism of oxidation of ceramics based on HfB₂ and SiC, manufactured by elemental self-propagating high-temperature synthesis followed by hot pressing were investigated. The synthesis product contained HfC_(x) and HfO₂ as impurity phases. Depending on the ratio between the main components, the samples were characterized by high structural and chemical homogeneity, porosity of 3–6 vol%, hardness up to 29 GPa, bending strength of 500–600 MPa, fracture toughness of 5.6–8.9 MPa × m^1/2, and thermal conductivity of 86.0–89.7 W/(m × K). The oxidation was performed under static conditions at 1650 °C and upon exposure to a high-enthalpy gas flow. A dense layer consisting of HfO₂/HfSiO₄ grains formed on the surface of the ceramics during both oxidation conditions; the space between the grains was filled with amorphous SiO₂–B₂O₃. The best heat resistance was observed for the ceramics with 16 wt% SiC for static conditions and 8 wt% SiC for gas-dynamic conditions.     

Synthesis,characterization, and ceramization of a carbon-rich SiCw-ZrC-ZrB2 preceramic polymer precursor

A precursor (PBSZ) for SiC_w-ZrC-ZrB₂ hybrid powder was synthesized by chemical reaction of phenol, paraformaldehyde, zirconium oxychloride, boric acid and tetraethylorthosilicate. Results show that zirconium, silicon and boron atoms have been successfully introduced into the branched structure. Decomposition of PBSZ is completed at 800 °C, and it gives amorphous carbon, SiO₂, B₂O₃ and ZrO₂ with a yield of 38% at 1200 °C. During the pyrolysis process, ZrB₂ and SiC form at about 1500 °C, followed by the appearance of ZrC when the amount of B₂O₃ is limited. Highly crystallized ZrB₂–ZrC–C powder with ZrB₂ and ZrC grains evenly distributed in the carbon matrix together with randomly distributed SiC whiskers are obtained after heat-treated at 1800 °C. Further heated at 1900 °C, ZrB₂ and ZrC grains grow from 200 to 500 nm, while SiC whiskers show a much smaller diameter size and tend to grow on the ZrB₂–ZrC–C block surface. The morphology difference is caused by the larger gas supersaturation and accommodation coefficient of the pore channels on the block surface. In addition, defects of the carbon matrix are cumulated to the highest at 1500 °C and the structure-ordered carbon is obtained after heat treated at 1900 °C.     

A numerical approach to the heat transfer in monolithic and SiC reinforced HfB2, ZrB2 and TiB2 ceramic cutting tools

Cutting tools are widely used in industry and must be hard enough for machining processes, which should work appropriately at low temperatures to improve cutting speed and productivity. In this research, a numerical method was employed to calculate the temperature distribution in the cutting tools made of different diborides. Monolithic and SiC reinforced HfB₂, ZrB₂ and TiB₂ ceramics were selected for investigation and comparison studies. In this regard, 3-dimensional heat conduction equation was solved in a cutting tool with radiative, convective and heat flux boundary conditions by finite element method using COMSOL Multiphysics. This study clarifies that the maximum temperature in the tools made of ZrB₂ and TiB₂ among the monolithic ceramics is lower than that of HfB₂. Moreover, the temperature variation slope versus time is the highest in HfB₂. All composite materials reinforced with SiC showed lower maximum temperature than the monolithic ones. The thermal performance of TiB₂–SiC and ZrB₂–SiC composites was acquired to be better than that of the other investigated materials. The dominant heat transfer mechanism in the cutting tools was conduction.     

In situ synthesis of ZrB2–ZrC–SiC ultra-high-temperature nanocomposites by a sol–gel process

ABSTRACT

ZrB₂–ZrC–SiC is one of the ultra-high-temperature ceramic composites with excellent properties. In this research, high-purity ZrB₂–ZrC–SiC nanopowders were synthesised using a carbothermal reduction reaction at a relatively low temperature (1370°C) from cost-effective zirconium(IV) chloride by a sol–gel method. The effect of heat treatment temperature on the synthesis of ZrB₂–ZrC–SiC composite powder was studied. X-ray diffractometry results showed that the phases ZrB₂, β-SiC and ZrC were synthesised at 1370°C. The mean crystallite sizes for each of the phases were calculated using the Scherrer method. The specific surface area for the sample calcined at 1370°C was 81.479?m²?g^?1. SEM observation revealed that the particles had a size lower than 250?nm. Backscattered electron image and map analysis with scanning electron microscopy showed that a suitable phase homogeneity was achieved, as confirmed by energy-dispersive X-ray spectroscopy.     

Microwave Absorption of SiC/HfCxN1−x/C Ceramic Nanocomposites with HfCxN1−x‐Carbon Core–Shell Particles

The dielectric properties of high‐temperature stable single‐source precursor‐derived SiC/HfC_xN_1?x/C ceramic nanocomposites are determined by microwave absorption in the X‐band (8.2–12.4 GHz) at room temperature. The samples synthesized at 1700°C, denoted as SiC/5HfC_xN_1?x/C‐1700°C and SiC/15HfC_xN_1?x/C‐1700°C ceramics, comprising ≈ 1.3 and ≈ 4.2 vol% HfC_xN_1?x, respectively, show enhanced microwave absorption capability superior to hafnium‐free SiC/C‐1700°C. The minimum reflection loss of SiC/5HfC_xN_1?x/C‐1700°C and SiC/15HfC_xN_1?x/C‐1700°C are ?47 and ?32 dB, and the effective absorption bandwidth amount to 3.1 and 3.6 GHz, respectively. Segregated carbon, including graphitic carbon homogeneously dispersed in the SiC matrix and less ordered carbon deposited as a thin film on HfC_xN_1?x nanoparticles, accounts for the unique dielectric behavior of the SiC/HfC_xN_1?x/C ceramics. Due to their large reflection loss and their high chemical and temperature stability, SiC/5HfC_xN_1?x/C‐1700°C and SiC/15HfC_xN_1?x/C‐1700°C ceramics are promising candidate materials for electromagnetic interference applications in harsh environment.     

Effect of silicon/graphite ratio and temperature on oxidation protective properties of SiC/ZrB2–SiC coatings prepared by pack cementation

To investigate the silicon/graphite ratio and temperature on preparation and properties of ZrB₂–SiC coatings, ZrB₂, silicon, and graphite powders were used as pack powders to prepare ZrB₂–SiC coatings on SiC coated graphite samples at different temperatures by pack cementation method. The composition, microstructure, thermal shock, and oxidation resistance of these coatings were characterized and assessed. High silicon/graphite ratio (in this case, 2) did not guarantee higher coating density, instead could be harmful to coating formation and led to the lump of pack powders, especially at temperatures of 2100 and 2200 °C. But residual silicon in the coating is beneficial for high density and oxidation protection ability. The SiC/ZrB₂–SiC (ZS50-2) coating prepared at 2000 °C showed excellent oxidation protective ability, owing to the residual silicon in the coating and dense coating structure. The weight loss of ZS50-2 after 15 thermal shocks between 1500 °C and room temperature, and oxidation for 19 h at 1500 °C are 6.5% and 2.9%, respectively.     

Effect of ZrB2 content on the densification,microstructure, and mechanical properties of ZrC-SiC ceramics

ZrC ceramics containing 30 vol% SiC-ZrB₂ were produced by high-energy ball milling and reactive hot pressing. The effects of ZrB₂ content on the densification, microstructure, and mechanical properties of ceramics were investigated. Fully dense ceramics were achieved as ZrB₂ content increased to 10 and 15 vol%. The addition of ZrB₂ suppressed grain growth and promoted dispersion of the SiC particles, resulting in fine and homogeneous microstructures. Vickers hardness increased from 23.0 ± 0.5 GPa to 23.9 ± 0.5 GPa and Young’s modulus increased from 430 ± 3 GPa to 455 ± 3 GPa as ZrB₂ content increased from 0 to 15 vol%. The increases were attributed to a combination of the higher relative density of ceramics with higher ZrB₂ content and the higher Young’s modulus and hardness of ZrB₂ compared to ZrC. Indentation fracture toughness increased from 2.6 ± 0.2 MPa⋅m^1/2 to 3.3 ± 0.1 MPa⋅m^1/2 as ZrB₂ content increased from 0 to 15 vol% due to the increase in crack deflection by the uniformly dispersed SiC particles. Compared to binary ZrC-SiC ceramics, ternary ZrC-SiC-ZrB₂ ceramics with finer microstructure and higher relative densities were achieved by the addition of ZrB₂ particles.     

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.     

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.     

Laser modified microstructures in ZrB2, ZrB2/SiC and ZrC

Microstructural evolution of spark plasma sintered ZrB₂, ZrB₂/20 vol.% SiC (ZS20) and ZrC ultra high temperature ceramics (UHTCs) during laser heating has been investigated. Laser heating at temperatures between 2000 and 3750 °C for up to 300 s, in air or vacuum, resulted in extensive bubble and crater formation on the surfaces of 10 mm diameter samples. However, even after exposure to ultra high temperatures, samples did not disintegrate. X-ray diffraction of exposed faces of ZrB₂ and ZS20 samples laser heated in air up to 2700 °C detected only crystalline zirconia. A wide range of morphologies, including nodules, needles, nanofibres and lamella, were observed. The surface of ZrC samples, laser heated in vacuum up to 3750 °C, were characterised by dendritic and eutectic morphologies. Other features associated with melting, such as solidification cracks and trapped porosity, were also observed. A complex array of mechanisms involving solid, liquid and vapour phases led to formation of these various morphologies including melting, oxidation, volatilisation and liquid flow     

Oxidation and cracking/spallation resistance of ZrB2–SiC–TaSi2–Si coating on siliconized graphite at 1500 °C in air

A ZrB₂–SiC–TaSi₂–Si coating on siliconized graphite substrate was prepared by a combination process of slurry brushing and vapor silicon infiltration. The high-temperature oxidation behavior and cracking/spallation resistance of the as-prepared coating were investigated in detail. It was revealed that the oxidation kinetics at 1500 °C in static air followed a parabolic law with a relatively low oxidation rate constant down to 0.27 mg/(cm²·h^0.5). The crack area ratio of the as-prepared coating was determined as 3.8 × 10⁻³ after severe thermal cycling from 1500 °C to room temperature for 20 times. Apart from the formation of ZrO₂ as skeleton phase with SiO₂ as infilling species, the good oxidation and cracking/spallation resistance of the coating also could be attributed to its unique duplex-layered structure, i.e., a dense ZrB₂–SiC–TaSi₂ major layer filled with Si and an outermost Si cladding top layer. Meanwhile, the strong adhesion strength of the SiC transition layer with the graphite substrate and the outer ZrB₂–SiC–TaSi₂–Si layer was a vital factor as well.     

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.     

Fabrication and properties of ZrB2–SiC–BN machinable ceramics

ZrB₂–SiC–BN ceramics were fabricated by hot-pressing under argon at 1800 °C and 23 MPa pressure. The microstructure, mechanical and oxidation resistance properties of the composite were investigated. The flexural strength and fracture toughness of ZrB₂–SiC–BN (40 vol%ZrB₂–25 vol%SiC–35 vol%BN) composite were 378 MPa and 4.1 MPa m^1/2, respectively. The former increased by 34% and the latter decreased by 15% compared to those of the conventional ZrB₂–SiC (80 vol%ZrB₂–20 vol%SiC). Noticeably, the hardness decreased tremendously by about 67% and the machinability improved noticeably compared to the relative property of the ZrB₂–SiC ceramic. The anisothermal and isothermal oxidation behaviors of ZrB₂–SiC–BN composites from 1100 to 1500 °C in air atmosphere showed that the weight gain of the 80 vol%ZrB₂–20 vol%SiC and 43.1 vol%ZrB₂–26.9 vol%SiC–30 vol%BN composites after oxidation at 1500 °C for 5 h were 0.0714 and 0.0268 g/cm², respectively, which indicates that the addition of the BN enhances oxidation resistance of ZrB₂–SiC composite. The improved oxidation resistance is attributed to the formation of ample liquid borosilicate film below 1300 °C and a compact film of zirconium silicate above 1300 °C. The formed borosilicate and zirconium silicate on the surface of ZrB₂–SiC–BN ceramics act as an effective barriers for further diffusion of oxygen into the fresh interface of ZrB₂–SiC–BN.