Novel Synthesis of ZrB2 Powder Via Molten‐Salt‐Mediated Magnesiothermic Reduction

Zirconium diboride (ZrB₂) powder was synthesized at a low temperature via a molten‐salt‐mediated reduction route using ZrO₂, Na₂B₄O₇ and Mg powders as starting raw materials. By using appropriately excessive amounts of Mg and Na₂B₄O₇ to compensate for their evaporation losses, ZrO₂ could be completely converted into ZrB₂ after 3 h at 1200°C. In addition, the formation of undesirable Mg₃B₂O₆ could be effectively avoided. As‐prepared ZrB₂ powders were phase pure, 300–400 nm in size and generally well dispersed. SEM images showed that to a large extent the reactively formed ZrB₂ retained the morphology and size of the starting ZrO₂. The salt melt formed from MgCl₂ and Na₂B₄O₇ at test temperatures is believed to be responsible for the reduced synthesis temperature and good dispersion of the final ZrB₂ product powder.     

Preparation and properties of dense ZrB2 composite reinforced by elongated SiC and Al3BC3 grains

Dense ZrB₂-SiC-Al₃BC₃ ultra-high temperature ceramic composite was fabricated by hot pressing sintering at 1900°C for 1 hour under a pressure of 20 MPa using Zirconium diboride (ZrB₂) as the raw material and a powder mixture of SiC, B₄C, Al, and carbon as the sintering additive. Al and B₄C underwent in situ reaction with carbon powder to produce Al₃BC₃, which promoted the densification of ZrB₂ ceramic. SiC grains were found to be elongated during sintering. The ZrB₂-SiC-Al₃BC₃ composite exhibited excellent mechanical properties, such as high flexural strength of 589 ± 147 MPa and fracture toughness of 7.81 ± 1.09 MPa m^1/2. Oxidation behavior of the ZrB₂-SiC-Al₃BC₃ composite was studied in air at 1500°C for 1 hour. A continuous layer of oxides consisting of a mixture of SiO₂, Al₂SiO₅, and Al₂O₃ was formed on the surface of the ZrB₂-SiC-Al₃BC₃ composite. This layer of oxides efficiently prevented oxygen from diffusing into the specimens during oxidation, which improved the oxidation resistance of the ZrB₂ ceramics.     

Zirconium diboride-mullite composite form mineral: Combustion synthesis,consolidation, characterizations and properties

Zirconium diboride-mullite composite powder was synthesized in-situ by combustion in argon of a zircon sand/B₂O₃/Al reactant system in a 3 : 3: 10 M ratio. Zircon sand with a particle size less than 45 μm was activated by high-energy milling for 360 min. The optimum reactant system included the addition of 0.01 mol of Si. The product of the synthesis of this system contained 34 wt% ZrB₂ and 50 wt% mullite. The obtained zirconium diboride-mullite powder was consolidated by hot pressing at 25 MPa in an argon environment, ramping at 10 °C/min to 1,450, 1550 and 1650 °C and holding for 60 min. The sintered composite hot-pressed at 1650 °C had a density of 3.39 g/cm³, flexural strength of 153.25 ± 1.19 MPa, hardness of 10.66 GPa and fracture toughness of 4.23 MPa.m^1/2. The flexural strength and hardness of the composite was significantly influenced by the grain size of the reinforced ZrB₂. The predominantly intergranular fracture observed in surface micrographs confirmed the high toughness of the composite. The coefficient of thermal expansion of the product hot-pressed at 1650 °C was 6.53 × 10⁻⁶/°C: much lower than reported coefficients of existing Al₂O₃, ZrO₂ ZrB₂, and ZrB₂–SiC refractory ceramics.     

Electrophoretic deposition of ZrB2 coatings in NaCl-KCl-AlF3 melt containing synthesized ZrB2 nanoparticles

A novel method for preparation of ZrB₂ coatings has been proposed by combination of molten salt synthesis of ZrB₂ nanoparticles and subsequent electrophoretic deposition of the as-synthesized ZrB₂ nanoparticles in the same molten system in this paper. Nanoscale ZrB₂ particles have been produced by borothermal reduction of ZrO₂ in NaCl-KCl-AlF₃ melt at 980°C. Then electrophoretic deposition of the as-synthesized ZrB₂ nanoparticles has been achieved in the resulting molten suspension at a reduced temperature of 900°C, yielding relatively dense ZrB₂ coatings on graphite substrates with a thickness of around 25 μm. Moreover, the effect of different cell voltages ranging from 0.8 V to 1.4 V (i.e., electric field 0.4–0.7 V/cm) on the prepared ZrB₂ coatings has been investigated. Finally, during the tests at 600°C–800°C in air, ZrB₂ coatings deposited at a cell voltage of 1.2 V have exhibited good high-temperature oxidation resistance.     

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.     

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.     

Oxidation resistance and microstructure evolution of ZrB2–SiC–La2O3/SiC dual-layer coating on siliconized graphite at 1800 °C under low air pressures

The oxidation behaviors of a ZrB₂–SiC–La₂O₃/SiC dual-layer coating on siliconized graphite at 1800 °C under low air pressures (50, 5 and 0.5 kPa) were investigated. The results showed that with the decrease of air pressure, the oxidation kinetics of the coated samples changed from parabolic weight gain to linear weight loss. A protective oxide scale consisted of ZrO₂ and SiO₂ with La dispersed was formed on the coating surface after oxidation in 50 kPa air. The oxide scale formed in 5 kPa air was full of bubbles. Only porous ZrO₂ layer was left on the coating surface after oxidation in 0.5 kPa air. At 1800 °C, the active oxidation of SiC occurred and gaseous SiO formed at the coating/oxide interface. The surface volatilization of SiO became severe with the decrease of air pressure, resulting in the presence of non-protective oxide scale.     

Determination of Retained B2O3 Content in ZrB2‐30 vol% SiC Oxide Scales

The composition of the borosilicate glass layer formed during oxidation of ZrB₂‐30 vol% SiC was determined to elucidate the extent of B₂O₃ retention in the oxide during high‐temperature oxidation. Oxidation was conducted in stagnant air at 1300°C, 1400°C, and 1500°C for times between 100 and 221 min. Specimens were characterized using mass change and scanning electron microscopy. After oxidation, the borosilicate glass layer was dissolved from the specimens sequentially with deionized H₂O and HF acid, to analyze the glass composition using inductively coupled plasma optical emission spectrometry. It was found that the average B₂O₃ content in the glass scale ranged from 23 to 47 mol%. Retained B₂O₃ content in the bulk of the glass decreased with increasing temperature, confirming increased volatility with temperature. Boron depth profiles were also obtained in the near surface region using X‐ray photoelectron spectroscopy and energy dispersive spectroscopy. The measured B concentrations were used to estimate the B₂O₃ concentration profile and B diffusion coefficients in the borosilicate glass. Implications for the ZrB₂‐SiC oxidation process are discussed.     

Oxidation of zirconium diboride with niobium additions

Oxidation of ZrB₂ ceramics containing Nb additions at 1500 °C resulted in the formation of a two-layer oxide scale. The outer surface was partially covered by a glassy layer containing B₂O₃ with smaller amounts of Nb and Zr oxides dissolved into it. With increasing exposure time, evaporation of B₂O₃ from the outer layer resulted in precipitation of oxide particles in the receding glassy phase. Between the outer layer and the unoxidized (Zr,Nb)B₂ was a porous layer that consisted of particles containing Zr, Nb, and O. The formation of Nb₂Zr₆O₁₇ was observed in the porous oxide layer. Since this compound is solid at the oxidation temperature, liquid phase sintering of the ZrO₂ scale was not possible. However, dissolution of Nb into B₂O₃ increased the stability of the liquid/glassy layer, which acted as a barrier to the transport of oxygen at higher temperatures compared to the scale formed on nominally pure ZrB₂.     

Oxygen diffusion mechanisms during high‐temperature oxidation of ZrB2‐SiC

Oxygen diffusion mechanisms during oxidation of ZrB₂‐30 vol% SiC were explored at temperatures of 1500°C and 1650°C using an ¹⁸O tracer technique. Double oxidation experiments in ¹⁶O₂ and ¹⁸O₂ were performed using a modified resistive heating system. A combination of scanning electron microscopy, energy‐dispersive spectroscopy, and time‐of‐flight secondary ion mass spectrometry was used to characterize the borosilicate and ZrO₂ oxidation products. Oxygen exchange with the borosilicate network was observed to occur quickly at the oxygen‐borosilicate surface at both 1500°C and 1650°C, while evidence of oxygen permeation was only observed at 1650°C for short time (<1 min) exposures. At longer times, >5‐9 min, complete oxygen exchange throughout both the borosilicate glass and ZrO₂ was observed at both temperatures preventing identification of the oxygen transport mechanisms, but demonstrating that oxygen transport is rapid in both oxide phases.     

Critical oxidation behavior of Ta-containing ZrB2 composites in the 1500–1650 °C temperature range

The microstructure evolution of ZrB₂ hot pressed with 15 vol% TaSi₂ was studied in the as-sintered state and after oxidation for 15 min at 1500 and 1650 °C in stagnant air. In the pristine material, the original ZrB₂ nuclei are surrounded by a mixed (Zr,Ta)B₂ solid solution. Refractory Ta-compounds are located at triple junctions and wetted grain boundaries are distinctive of this ceramic. After oxidation, the solid solution evolves into ZrO₂ grains encasing intragranular nano-structured TaB₂ particles. Here we show that the operating limit temperature of this composite is related to the critical oxidation of TaB₂ to Ta₂O₅ above 1600 °C, accompanied by large volume expansion and local liquid formation, which ruptures the ZrO₂ grains and structure.     

Carbothermal production of ZrB2–ZrO2 ceramic powders from ZrO2–B2O3/B system by high-energy ball milling and annealing assisted process

Zirconium diboride (ZrB₂)-zirconium dioxide (ZrO₂) ceramic powders were prepared by comparing two different boron sources as boron oxide (B₂O₃) and elemental boron (B). The production method was high-energy ball milling and subsequent annealing of powder blends containing stoichiometric amounts of ZrO₂, B₂O₃/B powders in the presence of graphite as a reductant. The effects of milling duration (0, 2 and 6 h), annealing duration (6 and 12 h) and annealing temperature (1200–1400 °C) on the formation and microstructure of ceramic powders were investigated. Phase, thermal and microstructural characterizations of the milled and annealed powders were performed by X-ray diffractometer (XRD), differential scanning calorimeter (DSC) and transmission electron microscope (TEM). The formation of ZrB₂ starts after milling for 2 h and annealing at 1300 °C if B₂O₃ is used as boron source and after milling for 2 h and annealing at 1200 °C if B is used as boron source.     

UO2 + 5 ​vol% ZrB2 nano composite nuclear fuels with full boron retention and enhanced oxidation resistance

The boron isotope (¹⁰B) can be used as a neutron absorber in UO₂ to control the reactivity of nuclear fuel pellets, however, the boron source can react with oxygen source in UO₂ to form B₂O₃ that vaporize readily at temperatures above 1200 °C. Unfortunately, the sintering of UO₂ fuel requires hours holding at high temperature (>1700 °C), resulting in an inevitable B loss during sintering and unpredictable B concentration in final product. It is challenging to incorporate boron through a conventional sintering method. In this work, we demonstrated that spark plasma sintering (SPS), a field assisted sintering technology, can effectively densify UO₂ ​+ ​5 ​vol% ZrB₂ composite fuel pellets by rapid consolidation at 1600 °C for a short duration of 5 min under an applied pressure of 40 MPa. Thermogravimetric analysis (TGA) measurements confirm that ZrB₂ is fully retained inside the composite fuel pellets. Inside the composite fuel pellets, nano sized ZrB₂ particles are uniformly distributed along the grain boundaries of the UO₂ matrix. The ZrB₂ particle transforms to a glassy B₂O₃ phase covering the sample surface and grain boundaries of UO₂ matrix after a simple post-sintering annealing at 1000 °C in flowing Argon gas for 4 h. The formed glassy B₂O₃ slows down the diffusion of oxygen ions and postpones the onset temperature for oxidation of UO₂ from 400 °C to 550 °C. This study demonstrates the capability of SPS, an advanced fuel manufacturing technique, to achieve a full retention of ZrB₂ in UO₂ oxide fuel and increase oxidation resistance through a simple post-sintering annealing. The reported work holds great engineering potential for development of advanced oxide fuel for nuclear application.     

High-strength ZrB2-based ceramics prepared by reactive pulsed electric current sintering of ZrB2–ZrH2 powders

Fully densified ZrB₂-based ceramic composites were produced by reactive pulsed electric current sintering (PECS) of ZrB₂–ZrH₂ powders within a total thermal cycle time of only 35 min. The composition of the final composite was directly influenced by the initial ZrH₂ content in the starting powder batch. With increasing ZrH₂ content, ZrB₂–ZrO₂, ZrB₂–ZrB–ZrO₂ and ZrB₂–ZrB–Zr₃O composites were obtained. The ZrB₂–ZrB–ZrO₂ composite derived from a 9.8 wt% ZrH₂ starting powder exhibited an excellent flexural strength of 1382 MPa combined with a Vickers hardness of 17.1 GPa and a fracture toughness of 5.0 MPa m^1/2. The high strength was attributed to a fine grain size and the removal of B₂O₃ through reaction with Zr. Higher ZrH₂ content starting powders were densified through solution-reprecipitation resulting in the formation of coarser angular ZrB₂–ZrB composites with a Zr₃O grain boundary phase with a fracture toughness of 5.0 MPa m^1/2 and an acceptable strength in the 852–939 MPa range.     

Particle refinement of ZrB2 by the combination of borothermal reduction and solid solution

Flexible synthesis of ultra‐fine ZrB₂ powders was achieved by borothermal reduction in a mixture of ZrO₂, boron, and TiO₂. Without TiO₂ additive, coarse ZrB₂ powders with particle size of 0.81 μm were obtained, presumably due to good wettability and solubility of ZrB₂ in the byproduct B₂O₃. It was found that the particle growth of ZrB₂ was effectively inhibited by the solid solution of TiB₂ (≥1 mol%). The refinement mechanism was that the solid solution of in situ formed TiB₂ presumably lowered the wettability and solubility of ZrB₂ in the B₂O₃ liquid and significantly inhibited the coarsening of ZrB₂. The average particle size of resulting powders decreased to 0.37 μm with the addition of 10 mol% TiO₂.     

Oxidation behavior of ZrB2-SiC-ZrC at 1700 °C

The oxidation behaviors of four compositions of ZrB₂-SiC-ZrC and one composition of ZrB₂-SiC were studied at 1700 °C in air and under low oxygen partial pressure. Volatility diagrams for ZrB₂-SiC-ZrC and ZrB₂-SiC were used to thermodynamically elucidate the oxidation mechanisms. SiO₂ and ZrO₂ layers formed on the surfaces of ZrB₂-SiC-ZrC and ZrB₂-SiC oxidized at 1700 °C. A SiC-depleted layer only formed on the surface of the ZrB₂-SiC oxidized under low oxygen partial pressure. The oxide layer thickened with increasing ZrC volume content during oxidation in air and under low oxygen partial pressure. The ZrB₂-SiC-ZrC oxide surface exploded in air when the ZrC volume content was more than 50%. Under low oxygen partial pressure, the oxide surfaces of all the ZrB₂-SiC-ZrC specimens bubbled.     

Effects of Sc2O3 sintering aid for the densification and mechanical properties of SiC–ZrB2 composites

This study examined the effects of a Sc₂O₃ sintering aid on the density, microstructure and mechanical properties of SiC–5 vol% ZrB₂ composites prepared by hot-pressing. Microstructural studies showed that the addition of Sc₂O₃ not only caused a decrease in the hot-pressing temperature from 1950 to 1750 °C by liquid phase sintering, but also resulted in the formation of crystalline Sc₄Zr₃O₁₂ at the grain boundaries via a reaction with ZrO₂ on the surface of the ZrB₂ powder. The addition of Sc₂O₃ produced a fine-grained microstructure with a 43% (430→615 MPa) and 20% (3.6→4.3 MPa m^1/2) increase in flexural strength and fracture toughness, respectively, compared to the SiC–ZrB₂ composite without Sc₂O₃.     

A novel strategy for synthesizing porous ZrB2-SiC ceramics via boro/carbothermal reaction process templated pore-forming approach

In this work, pure ZrB₂-SiC composite powders were obtained using ZrO₂, SiO₂, B₄C and carbon black as raw materials via a boro/carbothermal reduction (BCTR) reaction process at 1500 °C for 2 h in vacuum condition. Based on this finding, porous ZrB₂-SiC ceramics were in-situ synthesized via a novel and facile boro/carbothermal reaction process templated pore-forming (BCTR-TPF) method. The phase composition, linear shrinkage, and pore size distribution were also methodically studied. Results show that the porous ZrB₂-SiC ceramics with controllable porosity of 67–78%, compressive strength of 0.2–9.8 MPa and thermal conductivity of 1.9–7.0 W·m⁻¹K⁻¹ can be fabricated by varying of ZrO₂ and B₄C particle sizes. The formation of ZrB₂ grains was controlled via solid-solid and solid-liquid-solid growth mechanisms, the growth process of SiC grains was mainly regulated by solid-solid, vapor-vapor and vapor-solid growth mechanisms during the overall synthesis process. Finally, the pore-forming mechanism of porous samples prepared via the BCTR-TPF method was gases combined with template pore-forming mechanism, i.e., B₄C and carbon black acted as pore-forming templates, and gaseous products generated in the BCTR reaction were also applied as gas pore-forming agent.     

Evolution of structure during the oxidation of zirconium diboride–silicon carbide in air up to 1500 °C

The structures that developed as dense ZrB₂–SiC ceramics were heated to 1500 °C in air were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction. The oxidation behavior was also studied using thermal gravimetric analysis (TGA). Below 1200 °C, a protective B₂O₃-rich scale was observed on the surface. At 1200 °C and above, the B₂O₃ evaporated and the SiO₂-rich scale that formed was stable up to at least 1500 °C. Beneath the surface, layers that were rich in zirconium oxide, and from which the silicon carbide had been partially depleted, were observed. The observations were consistent with the oxidation sequence recorded by thermal gravimetric analysis.     

Production of Al2O3‐Stabilized Tetragonal ZrO2 Nanoparticles for Thermal Barrier Coating

Al₂O₃‐stabilized tetragonal ZrO₂ nanoparticles were obtained through hot‐air spray pyrolysis and characterized after postsynthesized treatments. The produced nanoparticles were 26 nm in size with surface area of 59 m²/g. A multilayer thermal barrier coating of nanostructured Al₂O₃‐ZrO₂‐embedded silicate was applied to the mild steel (EN3) specimen using spin‐coating technique and characterized comprehensively employing X‐ray diffraction and scanning electron microscope. The Al₂O₃‐stabilized ZrO₂ with silicate matrix facilitates the formation of zirconium silicate nanostructured surface‐protective coating on EN3 specimen. The Al₂O₃‐ZrO₂/SiO₂ matrix‐based hybrid inorganic coating shows effective thermal barrier for EN3 after firing at a high temperature of 600°C.