Structural Influence on the Thermal Conversion of Self‐Catalyzed HfB2/ZrB2 Sol–Gel Precursors by Rapid Ultrasonication of Oxychloride Hydrates

Sol–gel precursors to HfB₂ and ZrB₂ are processed by high‐energy ultrasonication of Hf,Zr oxychloride hydrates, triethyl borate, and phenolic resin to form precipitate‐free sols that turn into stable gels with no catalyst addition. Both precursor concentration and structure (a sol or a gel) are found to influence the synthesis of the diboride phase at high temperature. Decreasing sol concentration increases powder surface area from 3.6 to 6.8 m²/g, whereas heat‐treating a gel leads to residual oxides and carbides. Particles are either fine spherical particles, unique elongated rods, and/or platelets, indicating particle growth with directional coarsening. Investigation of the conversion process to ZrB₂ indicates that a multistep reaction is likely taking place with: (1) ZrC formation, (2) ZrC reacts with B₂O₃ or ZrC reacts with B₂O₃ and C to form ZrB₂. At low temperatures, ZrC formation is limiting, while at higher temperatures the reaction of ZrC to ZrB₂ becomes rate limiting. ZrC is found to be a direct reducing agent for B₂O₃ at low temperature (~1200°C) to form ZrB₂ and ZrO₂, whereas at high temperatures (~1500°C) it reacts with B₂O₃ and C to form pure ZrB₂.     

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.     

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.     

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.     

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.     

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.     

In situ synthesis,physical and mechanical properties of ZrB2–ZrC–WB composites

In this study, two composition ZrB₂–ZrC–WB composites were synthesized by reactive hot-pressing of Zr + B₄C + WC powder mixtures at 1900 °C. The microstructure of the resulting composites was characterized by a combination of scanning electron microscopy and X-ray diffraction. It is seen that highly-dense ZrB₂–ZrC–WB composites with a homogenous fine-microstructure were obtained after the sintering. The mechanical behavior of the composites was evaluated using by testing under four-point bend testing at room and high temperatures. The results show that the high-temperature strength of the ZrB₂–ZrC–WB composites was substantially improved, compared to ZrB₂–ZrC-based composites without WB. In addition, the elastic properties, electrical conductivity, hardness and fracture toughness of the composites were measured at room temperature. The results reveal that these properties were comparable to those of ZrB₂–ZrC-based composites without WB.     

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.     

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.     

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.     

Carbothermal synthesis of zirconium diboride (ZrB2) whiskers

Abstract

In the present investigation, carbothermal synthesis technique is used for the production of ZrB₂ whiskers. The synthesis is carried out by heating the mixture of ZrB₂, H₃BO₃ and carbon black over the temperature range of 1300 to 1700°C in argon atmosphere. Different elements such as Ni, Co and Fe are tested for their role as catalysts. The synthesised powder contains ZrB₂ as the major phase with minor phases of ZrC and B₄C. Whisker yield is found to be low at lower temperatures (<1500°C) and then increases with the pyrolysis temperature. The Ni addition seems more effective as a catalyst than Co or Fe. Shorter length whiskers are found in the case of Co catalyst, whereas use of Fe catalyst shows whisker with rod shape and a special bird's nest type whiskers. The electron microscope study of whisker reveals the presence of various defects.     

Effect of Si3N4 Addition on Compressive Creep Behavior of Hot‐Pressed ZrB2–SiC Composites

Compressive creep studies have been carried out on hot‐pressed ZrB₂–SiC (ZS) and ZrB₂–SiC–Si₃N₄ (ZSS) composites in air under stress and temperature ranges of 93–140 MPa and 1300°C–1425°C, respectively for time durations of ≈20–40 h. The results of these studies have shown the creep resistance of ZS composite to be greater than that of ZSS. As the temperature is increased from 1300°C to 1425°C, the stress exponent of ZS decreases from 1.7 to 1.1, whereas that of ZSS drops from 1.6 to 0.6. The activation energies for these composites have been found as ≈95 ± 32 kJ/mol at temperatures ≤1350°C, and as ≈470 ± 20 kJ/mol in the range of 1350°C–1425°C. Studies of the postcreep microstructures using scanning and transmission electron microscopy have shown the presence of glassy film with cracks at both ZrB₂ grain boundaries and ZrB₂–SiC interfaces. These results along with calculated values of activation volumes suggest grain‐boundary sliding as the major damage mechanism, which is controlled by O^2? diffusion through SiO₂ at ≤1350°C, and by viscoplastic flow of the glassy interfacial film at temperatures ≥1350°C. Studies by transmission electron microscopy have shown formation of crystalline precipitates of Si₂N₂O near ZrB₂–SiC interfaces in ZSS tested at ≥1400°C, which along with stress exponent values <1 suggests that grain‐boundary sliding involving solution‐precipitation‐type mechanism is operative at these temperatures.     

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.     

SPS densification and microstructure of ZrB2 composites derived from sol–gel ZrC coating

A technique for densifying ultra high temperature ceramic composites while minimising grain growth is reported. As-purchased ZrB₂ powder was treated with a zirconia-carbon sol–gel coating. Carbothermal reduction at 1450 °C produced 100–200 nm crystalline ZrC particles attached on the surface of ZrB₂ powders. The densification behaviour of the sol–gel coated powder was compared with both the as-purchased ZrB₂ and a compositionally similar ZrB₂–ZrC mixture. All three samples were densified by spark plasma sintering (SPS). The ZrB₂ reference sample was slow to densify until 1800 °C and was not fully dense even at 2000 °C, while the sol–gel modified ZrB₂ powder completed densification by 1800 °C. The process was studied by ram displacement data, gas evolution, SEM, and XRD. The sol–gel coated nanoparticles on the ZrB₂ powder played a number of important roles in sintering, facilitating superior densification by carbothermal reduction, nanoparticle coalescence and solid-state diffusion, and controlling grain growth and pore removal by Zener pinning. The sol–gel surface modification is a promising technique to develop ultra-high temperature ceramic composites with high density and minimum grain growth.     

Synthesis of ZrB2–ZrC hybrid powders via boro-carbothermal reduction of ZrO2 by B4C and carbon black

ZrB₂–ZrC hybrid powders were synthesized by a novel two-step reduction on basis of ZrO₂ + B₄C + C→ ZrC + ZrB₂ + CO reaction in Ar atmosphere, using ZrO₂, B₄C, and carbon black powders as starting materials. Thermodynamics of relevant reactions were evaluated. Effects of excess additions of B₄C and C on phase constituents were investigated. Morphology and chemistry of the powder products were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and transmission electron microscopy (TEM). The results showed that ZrB₂–ZrC hybrid powders with no obvious impurity content could be obtained after heating at 1350 °C for 1 h followed by further reaction at 1700 °C for 1 h with 16 wt% B₄C + 8 wt% C excess addition. Relative contents of the ZrB₂: ZrC phase in the product powders could be conveniently regulated by varying the B₄C and C content in the starting compositions. The resultant powders had good oxidation resistance with an oxidation activation energy value of 433 kJ/mol. Good sinterability of the powder products was demonstrated by hot pressing at 1950 °C for 60min under 30 MPa pressure, which resulted in fully dense ZrB₂–ZrC composite ceramics with Vickers hardness value larger than 18.3 ± 0.6 GPa.     

Microstructural development during spark plasma sintering of ZrB2–SiC–Ti composite

The present study investigates the effect of Ti addition on the microstructure development and phase evolution during spark plasma sintering of ZrB₂–SiC ceramic composite. A ZrB₂–20?vol% SiC sample with 15?wt% Ti was prepared by high-energy milling and spark plasma sintering at 2000?°C for 7?min under 50?MPa. The X-ray diffraction test, microstructural studies and thermodynamic assessments indicated the in-situ formation of several compounds due to the chemical reactions of Ti with ZrB₂ and SiC. The Ti additive was completely consumed during the sintering process and converted to the ceramic compounds of TiC, TiB and TiSi₂. In addition, another refractory phase of ZrC was also formed as a result of sidelong reaction of ZrB₂ and SiC with the Ti additive.     

In situ studies of oxidation of ZrB2 and ZrB2–SiC composites at high temperatures

High temperature oxidation of ZrB₂ and the effect of SiC on controlling the oxidation of ZrB₂ in ZrB₂–SiC composites were studied in situ, in air, using X-ray diffraction. Oxidation was studied by quantitatively analyzing the crystalline phase changes in the samples, both non-isothermally, as a function of temperature, up to ～1650 °C, as well as isothermally, as a function of time, at ～1300 °C. During the non-isothermal studies, the formation and transformation of intermediate crystalline phases of ZrO₂ were also observed. The change in SiC content, during isothermal oxidation studies of ZrB₂–SiC composites, was similar in the examined temperature range, regardless of sample microstructure and composition. Higher SiC content, however, markedly retarded the oxidation rate of the ZrB₂ phase in the composites. A novel approach to quantify the extent of oxidation by estimating the thickness of the oxidation layer formed during oxidation of ZrB₂ and ZrB₂–SiC composites, based on fractional conversion of ZrB₂ to ZrO₂ in situ, is presented.     

SiC Depletion in ZrB2–30 vol% SiC at Ultrahigh Temperatures

The formation of a porous SiC‐depleted region in ZrB₂–SiC due to active oxidation at ultrahigh temperatures was characterized. The presence/absence of SiC depletion was determined at a series of temperatures (1300°C–1800°C) and times (5 min–100 h). At T < 1627°C, SiC depletion was not observed. Instead, the formation of a ZrO₂ + C/borosilicate oxidation product layer sequence was observed above the ZrB₂–SiC base material. At T ≥ 1627°C, SiC was depleted in the ZrB₂ matrix below the ZrO₂ and borosilicate oxidation products. The SiC depletion was attributed to active oxidation of SiC to form SiO(g). The transition between C formation in ZrO₂ (T < 1627°C) and SiC depletion in ZrB₂ (T ≥ 1627°C) is attributed to variation in the temperature dependence of thermodynamically favored product assemblage influenced by the local microstructural phase distribution. The growth kinetics of the SiC depletion region is consistent with a gas‐phase diffusion‐controlled process.     

Oxidation and recession of plain weave carbon fiber reinforced ZrB2-SiC-ZrC in oxygen–hydrogen torch environment

The oxidation and recession of four plain weave carbon fiber reinforced ZrB₂-SiC-ZrC composites with different matrix compositions were compared with those of a plain weave carbon fiber reinforced ZrB₂-SiC matrix composite. These composites were fabricated using a silicon melt infiltration method. The composite with the higher ZrC content also formed ZrSi₂ in the matrix instead of residual silicon. The composites were oxidized at 1700 and 1800 °C in an oxygen–hydrogen torch environment. The oxides consisted of ZrO₂ and SiO₂, which formed on the surface of all samples. Carbon fiber at the surface was lost due to oxidation. The recession resistance of ZrB₂-SiC-ZrC matrix composites remained constant at 1700 °C, even if the matrix composition varied, while the resistance at 1800 °C increased with the matrix of ZrC and ZrSi₂. The ZrB₂-SiC-ZrC matrix composite with the higher ZrC and ZrSi₂ compositions formed a sintered ZrO₂-rich layer, which was denser than the ZrO₂-SiO₂ and improved the recession resistance.     

Effect of LaB6 addition on compressive creep behavior with simultaneous oxide scale growth of spark plasma sintered ZrB2-SiC composites

A study has been carried out to examine the effect of LaB₆ addition on the compressive creep behavior of ZrB₂-SiC composites at 1300–1400°C under stresses between 47 and 78 MPa in laboratory air. The ZrB₂-20 vol% SiC composites containing LaB₆ (10% in ZSBCL-10 and 14% in ZSBCL-14) besides 5.6% B₄C and 4.8% C as additives were prepared by spark plasma sintering at 1600°C. Due to cleaner interfaces and superior oxidation resistance, the ZSBCL-14 composite has exhibited a lower steady-state creep rate at 1300°C than the ZSBCL-10. The obtained stress exponent (n ∼ 2 ± 0.1) along with cracking at ZrB₂ grain boundaries and ZrB₂-SiC interfaces are considered evidence of grain boundary sliding during creep of the ZSBCL-10 composite. However, the values of n ∼ 1 and apparent activation energy ∼700 kJ/mol obtained for the ZSBCL-14 composite at 1300–1400°C suggest that ZrB₂ grain boundary diffusion is the rate-limiting mechanism of creep. The thickness of the damaged outer layer containing cracks scales with temperature and applied stress, indicating their role in facilitating the ingress of oxygen causing oxide scale growth. Decreasing oxidation-induced defect density with depth to a limit of ∼280 μm, indicates the predominance of creep-based deformation and damage at the inner core of samples.