Synthesis of rod-like ZrB2 crystals by boro/carbothermal reduction

Rod-like ZrB₂ crystals were synthesized at 1600 °C in Ar atmosphere by boro/carbothermal reduction using ZrOCl₂⋅8H₂O, B₄C and carbon powders as raw materials. The optimum molar ratio of raw materials required to form pure ZrB₂ grains was found to be 2: 1.2: 3. With increase in temperature and subsequent heat preservation stage, ZrB₂ powders grew into a rod-like morphology along the c axis. The rod-like ZrB₂ grains obtained at 1600 °C have diameters of 0.5–3 μm and high aspect ratios of >8. Effects of molar ratio of raw materials, heating temperature and holding time on the phase composition and final morphology were investigated. Growth mechanism of rod-like ZrB₂ grains was also analyzed.     

ZrB2–SiC–G Composite Prepared by Spark Plasma Sintering of In‐Situ Synthesized ZrB2–SiC–C Composite Powders

To avoid introduction of milling media during ball‐milling process and ensure uniform distribution of SiC and graphite in ZrB₂ matrix, ultrafine ZrB₂–SiC–C composite powders were in‐situ synthesized using inorganic–organic hybrid precursors of Zr(OPr)₄, Si(OC₂H₅)₄, H₃BO₃, and excessive C₆H₁₄O₆ as source of zirconium, silicon, boron, and carbon, respectively. To inhabit grain growth, the ZrB₂–SiC–C composite powders were densified by spark plasma sintering (SPS) at 1950°C for 10 min with the heating rate of 100°C/min. The precursor powders were investigated by thermogravimetric analysis–differential scanning calorimetry and Fourier transform infrared spectroscopy. The ceramic powders were analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The lamellar substance was found and determined as graphite nanosheet by scanning electron microscopy, Raman spectrum, and X‐ray diffraction. The SiC grains and graphite nanosheets distributed in ZrB₂ matrix uniformly and the grain sizes of ZrB₂ and SiC were about 5 μm and 2 μm, respectively. The carbon converted into graphite nanosheets under high temperature during the process of SPS. The presence of graphite nanosheets alters the load‐displacement curves in the fracture process of ZrB₂–SiC–G composite. A novel way was explored to prepare ZrB₂–SiC–G composite by SPS of in‐situ synthesized ZrB₂–SiC–C composite powders.     

Synthesis and growth behavior of micron-sized rod-like ZrB2 powders

Using ZrOCl₂·8H₂O, Na₂B₄O₇·10H₂O and C₁₂H₂₂O₁₁ as raw materials, micron-sized rod-like ZrB₂ powders were prepared via a molten-salt-mediated carbothermal reduction from chemically homogenous precursors obtained by sol-gel method. The effects of Zr/B/C molar ratio, firing temperature, holding time and molten salt on the composition of products have been investigated, respectively. Pure micron-sized ZrB₂ powders with controllable rod-like morphology were obtained at 1400 °C for 4 h holding with Zr/B/C of 1/5/5 in presence of molten salt, which has a diameter of 1–2 µm and aspect ratios of 3–10. The investigation of growth behavior showed that at the first stage, nano-size ZrB₂ columns grew along the c-axis with ZrC_x thin film on their top as “active-site”. Then, with consuming ‘active sites’, ZrB₂ columns started to grow in diameter direction, and finally small columns merged into a larger rod.     

Highly-efficient preparation of anisotropic ZrB2–SiC powders and dense ceramics with outstanding mechanical properties

Highly-dense ZrB₂–SiC ceramics with excellent mechanical properties including Vickers hardness of 24.5 GPa and fracture toughness of 4.8 MPa/m^1/2 were successfully prepared, by spark plasma sintering of the raw powders synthesized by a novel molten-salt and microwave co-assisted boro/carbothermal reduction (MSM-BCTR) method. Compared with the processing conditions required for synthesizing ZrB₂–SiC by conventional reduction method, the present MSM-BCTR method possessed a variety of significant merits including the smaller material cost, lower processing temperature (1200°C), and remarkably higher efficiency (soaking time as short as 20 minutes). More importantly, the ZrB₂–SiC powders, resultant from MSM-BCTR treatment, were verified to have single-crystalline nature and uniform well-grown anisotropic morphologies (rod-like ZrB₂ and sheet-like SiC) as well as great potential in promoting the mechanical properties of their bulk counterparts. This great achievement was mainly ascribed to the specific MSM-BCTR conditions characterized by microwave heating and molten-salt medium.     

Chemical process and solid solution formation in reactive hot pressed ZrB2–SiC ceramics doped with W

ZrB₂–SiC doped with W was prepared from a mixture of Zr, Si, B₄C and W via reactive hot pressing. The fully dense ZrB₂–SiC–WB–ZrC ceramic was obtained at 1900°C for 60 min under 30?MPa in an argon atmosphere. Reaction path and solid solution characteristics of the starting powders were studied through a series of pressureless heat treatment at temperatures between 700 and 1500°C. The solid solution phases of (Zr, W)B₂, (W, Zr)B and (Zr, W)C were formed directly by reactions between the precursors. Homogeneous distribution of solute atoms in solution and the solid solubilities were also studied.     

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.     

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.     

Spark-plasma sintering of ZrB2 ultra-high-temperature ceramics at lower temperature via nanoscale crystal refinement

We have explored the feasibility of reducing the spark-plasma-sintering (SPS) temperature of additive-free ZrB₂ ultra-high-temperature ceramics (UHTCs) via crystal size refinement of the starting powder down to the low nanoscale. We found that under otherwise the same SPS conditions (75 MPa pressure, and 100 °C/min heating ramp) nanoscale ZrB₂ can be densified at temperatures about 450 °C lower than for the typical micrometre and submicrometre ZrB₂ powders, and at least 250 °C below the ultra-fine powder temperature. Furthermore, the nanoscale crystal refinement also promotes the production of fine-grained ZrB₂ UHTCs. We also found that elimination of the B₂O₃ impurities plays an important role in the complete densification. The unequalled sinterability of the nanoscale ZrB₂ powders highlights the need to use high-energy ball-milling for the comminution of the typical commercially available ZrB₂ powders.     

Synthesis of ZrB2-SiC powders in one-step reduction process

ZrB₂-SiC composite powders were synthesized through one-step reduction process of ZrO₂, B₄C, carbon black, silicon or silica under flowing argon. Effects of B₄C contents, calcination temperatures and different silicon sources on the phase composition and morphology were investigated. Combining the X-ray diffraction (XRD) results and scanning electron microscope (SEM) images, the spherical ZrB₂-SiC powders ranging from 100?nm to 300?nm would be prepared with silicon at 1500?°C for 60?min when n(B)/n(Zr) was at 2.4. As using silica as the raw material, the obtained ZrB₂ and SiC particles in the powders exhibited different shapes and sizes. The SiC grains were uniformly formed among the ZrB₂ grains.     

Effect of processing parameters on the formation process of nano-sized ZrB2 powders by the high energy ball milling

ABSTRACT

Nano-sized ZrB₂ powders were synthesised using the high energy ball milling with ZrO₂ and B₂O₃ as raw materials and Mg as the reducing agent. The resulting powders were characterised by X-ray diffraction, scanning electron microscopy, laser particle size analysis, transmission electron microscopy, energy dispersive spectrometry, and X-ray photoelectron spectroscopy. The influence of the synthesis parameters, including the ratios of ZrO₂ to B₂O₃, milling medium, and reaction time, on the synthetic course of the ZrB₂ nanopowders were studied systematically. The mechanisms by which these parameters influence the synthetic course of and the resulting product quality are determined. Ultimately, the diameter of the resulting particles is about 200–400?nm, which are an agglomeration composed of many individual small particles with an average diameter of ～50?nm. In addition, the oxidation of ZrB₂ powders has also been studied.     

Low‐Temperature Rapid Synthesis of Rod‐Like ZrB2 Powders by Molten‐Salt and Microwave Co‐Assisted Carbothermal Reduction

A novel molten‐salt and microwave coassisted carbothermal reduction (termed as MSM‐CTR) method was developed to prepare ZrB₂ powders from raw materials of ZrO₂, B₄C, and amorphous carbon. The results indicated that the carbothermal reduction reaction for synthesizing ZrB₂ was initiated at the temperature as low as 1150°C, and phase pure ZrB₂ powders were obtained after only 20 min at 1200°C, which were significantly milder than that of the conventional CTR method as well as the modified CTR method even using active metal as additional reducing agents. More interestingly, the as‐obtained ZrB₂ powders consisted of well‐defined single‐crystalline nanorods, which had diameters of 40–80 nm and high aspect ratios of >10. These results demonstrated that the MSM‐CTR is a simple and efficient route for preparation of high‐quality ZrB₂ powders.     

Preparation and characterization of ultrafine ZrB2–SiC composite powders by a combined sol–gel and microwave boro/carbothermal reduction method

A combined sol–gel and microwave boro/carbothermal reduction technique was investigated and used to synthesize ultrafine ZrB₂–SiC composite powders from raw starting materials of zirconium oxychloride, boric acid, tetraethoxysilane and glucose. The effects of reaction temperature, molar ratios of n(B)/n(Zr) and n(C)/n(Zr+Si) on the synthesis of ultrafine ZrB₂–SiC composite powders were studied. The results showed that the optimum molar ratios of n(B)/n(Zr) and n(C)/n(Zr+Si) for the preparation of phase pure ultrafine ZrB₂–SiC composite powders were 2.5 and 8.0, respectively, and the firing temperature required was 1300 °C. This temperature was 200 °C lower than that require by using the conventional boro/carbothermal reduction method. Microstructures and phase morphologies of as-prepared ultrafine ZrB₂–SiC composite powders were examined by field emission-scanning electron microscopy (FE-SEM) and transmission electron microscope (TEM), showing that SiC grains were formed evenly among the ZrB₂ grains, and the grain sizes of ZrB₂ in the samples prepared at 1300 °C for 3 h were about 1–2 μm. The average crystalline sizes of these two phases in the as-prepared samples were calculated by using the Scherrer equation as about 58 and 27 nm, respectively.     

Synthesis of plate-like α-Al2O3 single-crystal particles in NaCl–KCl flux using Al(OH)3 powders as starting materials

Plate-like α-Al₂O₃ single-crystal particles were successfully synthesized in NaCl–KCl flux using Al(OH)₃ powders as starting materials, and the influence of pre-calcining of Al(OH)₃ powders on the phase formation and morphology of α-Al₂O₃ powders was focused. When Al(OH)₃ powders are used as starting materials, the synthesized product at 900 °C is mainly composed of α-Al₂O₃ and κ-Al₂O₃, and most synthesized particles show alveolate morphology. At 1100 °C, single-phase α-Al₂O₃ powders are developed, in which there are many aggregations of intensively bound plate-like particles. In contrast, using porous amorphous Al₂O₃ powders obtained by pre-calcining Al(OH)₃ powders at 550 °C for 3 h as the starting material, plate-like α-Al₂O₃ single-crystal particles can be well developed above 900 °C. The reason of the influence of pre-calcining of Al(OH)₃ powders on the phase formation and morphology of α-Al₂O₃ powders is also discussed in the paper.     

Effect of WSi2 addition on densification and properties of ZrB2

Abstract

Effect of WSi₂ addition on densification and properties of ZrB₂ has been investigated. Samples of the following composition with controlled addition of WSi₂ were prepared by hot pressing (1) ZrB₂, (2) ZrB₂+2·5%WSi₂, (3) ZrB₂+5%WSi₂ and (4) ZrB₂+10%WSi₂. Hot pressing of monolithic ZrB₂ at 1750°C resulted in achieving a density of only 80·1% ρ_th. Addition of WSi₂ enhanced the densification and resulted in near theoretical density. Microstructural investigations revealed the presence of reaction product containing Si and Zr. An increase in WSi₂ content led to an increase in hardness of the product. A slight increase in fracture toughness was observed with WSi₂ addition. Crack deflection was observed in the microstructure. Oxidation study of the composite samples revealed that the oxidised layer is not adherent and resulted in spallation at the end of the test.     

Low temperature synthesis of ZrB2-SiC powders by molten salt magnesiothermic reduction and their oxidation resistance

Herein, we prepare phase-pure ZrB₂-SiC composite powders by molten-salt-mediated reduction of ZrSiO₄/B₂O₃/activated carbon mixtures with Mg, showing that the phase composition and morphology of the above composites is influenced by firing temperature, B:Zr and C:Si molar ratios, and the amount of excess Mg. Notably, phase-pure ZrB₂-SiC powder with a ZrB₂:SiC weight ratio of ~75:25 could be obtained by 3-h firing at 1200?°C, i.e., at a temperature lower than that used for conventional carbothermal reduction by at least 200?°C. As-prepared ZrB₂-SiC composites exhibited grain sizes of several microns and comprised SiC nanoparticles well distributed in the ZrB₂ matrix. Finally, the oxidation activation energies of the prepared ZrB₂ and ZrB₂-SiC powders were determined as 326 and 381?kJ/mol, respectively, which demonstrated that the introduction of SiC improved the oxidation resistance of monolithic ZrB₂.     

ZrB2-MoSi2 ceramics: A comprehensive overview of microstructure and properties relationships. Part II: Mechanical properties

The mechanical behavior of ZrB₂-MoSi₂ ceramics made of ZrB₂ powder with three different particle sizes and MoSi₂ additions from 5 to 70 vol% was characterized up to 1500 °C. Microhardness (12–17 GPa), Young’s modulus (450–540 GPa) and shear modulus (190–240 GPa) decreased with both increasing MoSi₂ content and with decreasing ZrB₂ grain size. Room temperature fracture toughness was unaffected by grain size or silicide content, whilst at 1500 °C in air it increased with MoSi₂ and ZrB₂ grain size, from 4.1 to 8.7 MPa m^½. Room temperature strength did not trend with MoSi₂ content, but increased with decreasing ZrB₂ grain size from 440 to 590 MPa for the largest starting particle size to 700–800 MPa for the finest due to the decreasing size of surface grain pullout. At 1500 °C, flexure strength for ZrB₂ with MoSi₂ contents above 25 vol% were roughly constant, 400–450 MPa, whilst for lower content strength was controlled by oxidation damages. Strength for compositions made using fine and medium ZrB₂ powders increased with increasing MoSi₂ content, 250–450 MPa. Ceramics made with coarse ZrB₂ displayed the highest strengths, which decreased with increasing MoSi₂ content from 600 to 450 MPa.     

Synthesis of ZrB2/SiC composite powders by single-step solution process from organic–inorganic hybrid precursor

A precursor of a zirconium diboride/silicon carbide (ZrB₂/SiC) composite was synthesised via an organic–inorganic hybrid derived from gum karaya, tetraethyl orthosilicate, boric acid and zirconyl chloride starting materials. Fourier transform infrared spectroscopy of the as-synthesised dried hybrid revealed the formation of Si–O, Zr–O–C and B–O–B. X-ray diffraction revealed that the powder consists of only ZrB₂ and β-SiC. Scanning electron microscopy and TEM of the composite powders showed that SiC and ZrB₂ occurred in intimately mixed aggregates of spheroidal submicron sized particles for low (3M) boric acid concentration, while at high (5M) boric acid concentration, the two phases are larger with the ZrB₂ adopting a blocky, angular morphology (～10–30?μm long by 5?μm wide and thick), while the SiC remains spheroidal with ～1?μm diameter particles in 10–20?μm diameter aggregates. Thermogravimetry–differential thermal analysis with the help of X-ray diffraction analysis revealed that the formation temperature was low at 1275°C for ZrB₂ and 1350°C for the SiC with 40?wt-% yield.     

Zirconium diboride laminates for improved damage tolerance at elevated temperatures

The mechanical response was studied for dense laminates containing layers of ZrB₂ (~145 µm) and graphite—10 vol% ZrB₂ (~20 µm). Individual layers were formulated by mixing starting powders with thermoplastic polymers and pressing into sheets. Laminates were produced by stacking and warm pressing the sheets, debinding, and hot pressing at 2050°C, 32 MPa, in Ar. The laminates were fractured at temperatures up to 2000°C in Ar. Laminates exhibited room temperature flexure strength of 260 MPa, increasing to 300 MPa at 1600°C, and then decreasing to 160 MPa at 2000°C. Inelastic work of fracture was 0.6 kJ/m² at room temperature, reached a maximum of 1.3 kJ/m² at 1400°C, and reverted to linear elastic failure at 2000°C. During fracture, cracks were deflected at the interfaces between the strong ZrB₂ layers and the relatively weak C-ZrB₂ layers, which led to an increased inelastic work of fracture by more than an order of magnitude compared to conventional ZrB₂ ceramics. This study demonstrated that laminate architectures are a promising approach for improving the damage tolerance of ZrB₂-based ceramics at elevated temperatures.     

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.     

Microstructure and mechanical properties of reaction-hot-pressed zirconium diboride based ceramics

ZrB₂ ceramics were prepared by in-situ reaction hot pressing of ZrH₂ and B. Additions of carbon and excess boron were used to react with and remove the residual oxygen present in the starting powders. Additions of tungsten were utilized to make a ZrB₂-4 mol%W ceramic, while a change in the B/C ratio was used to produce a ZrB₂-10 vol% ZrC ceramic. All three compositions reached near full density. The baseline ZrB₂ and ZrB₂–ZrC composition contained a residual oxide phase and ZrC inclusions, while the W-doped composition contained residual carbon and a phase that contained tungsten and boron. All three compositions exhibited similar values for flexure strength (~520 MPa), Vickers hardness (~15 GPa), and elastic modulus (~500 to 540 GPa). Fracture toughness was about 2.6 MPa m^1/2 for the W-doped ZrB₂ compared to about 3.8 MPa m^½ for the ZrB₂ and ZrB₂–ZrC ceramics. This decrease in fracture toughness was accompanied by an observed absence of crack deflection in the W-doped ZrB₂ compared with the other compositions. The study demonstrated that reaction-hot-pressing can be used to fabricate ZrB₂ based ceramics containing solid solution additives or second phases with comparable mechanical properties.