Microstructure and mechanical properties of high-entropy borides derived from boro/carbothermal reduction

Starting from metal oxides, B₄C and graphite, a suite of high-entropy boride ceramics, formulated (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)B₂, (Hf_0.2Zr_0.2Mo_0.2Nb_0.2Ti_0.2)B₂ and (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ derived from boro/carbothermal reduction at 1600 °C were fabricated by spark plasma sintering at 2000 °C. It was found that the synthetic high-entropy boride crystalized in hexagonal structure and the yield of the targeting phase was calculated to be over 93.0 wt% in the sintered ceramics. Benefitting from the nearly full densification (96.3% ˜ 98.5% in relative density) and the refined microstructure, the products exhibited the relatively high Vickers hardness. The indentation fracture toughness was determined to be comparable with the single transition metal-diboride ceramics. It should be noted that the formation of high-entropy boride ceramics were featured with the relatively high hardness at no expense of the fracture toughness.     

Synthesis of high-purity high-entropy metal diboride powders by boro/carbothermal reduction

Synthesis of high-purity high-entropy metal diboride powders is critical to implementing their extensive applications. However, the related studies are rarely reported. Herein we first theoretically studied the synthesis possibility of high-purity high-entropy diboride powders, namely (Hf_0.25Ta_0.25Nb_0.25Ti_0.25)B₂ (HTNTB), via boro/carbothermal reduction by analyzing the thermodynamics of the possible chemical reactions and then successfully synthesized the high-purity and superfine HTNTB powders via boro/carbothermal reduction for the first time. The as-prepared powders exhibited low-oxygen impurity content of 0.49 wt% and small average particle size of 260 nm. Meanwhile, they possessed good single-crystal hexagonal structure of metal diborides and high-compositional uniformity from nanoscale to microscale. This work will open up a new research field on the synthesis of high-purity high-entropy metal diboride powders.     

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.     

Preparation of tungsten diboride by a combination of boro/carbothermal reduction process and spark plasma sintering

Submicron tungsten diboride (WB₂) powder was successfully synthesized with the ratio of WO₃:B₄C:C = 2:1.1:5. The effects of carbon sources (carbon black or graphite) and heat treatment temperatures (1100, 1200, 1300 ℃) on the phase composition and microstructure of the as-synthesized WB₂ powder samples were studied. The results showed that ultrafine WB₂ powders with oxygen content of 1.65 wt% and 2.04 wt% were obtained by carbon black and graphite at 1300 ℃, respectively. The relatively density of the as-sintered WB₂ samples achieve ~ 91 % and ~ 87 % without any kind of sintering additive after spark plasma sintering at 1500 °C under 30 MPa for 10 min. The formation mechanism of the WB₂ powders synthesized by boro/carbothermal reduction was proposed and verified by thermodynamic calculation according to the phases present in the powder synthesized at different temperatures.     

Boro/carbothermal reduction co-synthesis of dual-phase high-entropy boride-carbide ceramics

Dense, dual-phase (Cr,Hf,Nb,Ta,Ti,Zr)B₂-(Cr,Hf,Nb,Ta,Ti,Zr)C ceramics were synthesized by boro/carbothermal reduction of oxides and densified by spark plasma sintering. The high-entropy carbide content was about 14.5 wt%. Grain growth was suppressed by the pinning effect of the two-phase ceramic, which resulted in average grain sizes of 2.7 ± 1.3 µm for the high-entropy boride phase and 1.6 ± 0.7 µm for the high-entropy carbide phase. Vickers hardness values increased from 25.2 ± 1.1 GPa for an indentation load of 9.81 N to 38.9 ± 2.5 GPa for an indentation load of 0.49 N due to the indentation size effect. Boro/carbothermal reduction is a facile process for the synthesis and densification of dual-phase high entropy boride-carbide ceramics with both different combinations of transition metals and different proportions of boride and carbide phases.     

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.     

First-principles prediction,fabrication and characterization of (Hf0.2Nb0.2Ta0.2Ti0.2Zr0.2)B2 high-entropy borides

The microstructure and mechanical properties of (Hf_0.2Nb_0.2Ta_0.2Ti_0.2Zr_0.2)B₂ high-entropy boride (HEB) were first predicted by first-principles calculations combined with virtual crystal approximation (VCA). The results verified the suitability of VCA scheme in HEB studying. Besides, single-phase (Hf_0.2Nb_0.2Ta_0.2Ti_0.2Zr_0.2)B₂ ceramics were successfully fabricated using boro/carbothermal reduction (BCTR) method and subsequent spark plasma sintering (SPS); furthermore, the effects of different amounts of B₄C on microstructure and mechanical properties were evaluated. Due to the addition of B₄C and C, all samples formed single-phase solid solutions after SPS. When the excess amount of B₄C increased to 5 wt%, the sample with fine grains exhibited superior comprehensive properties with the hardness of 18.1 ± 1.0 GPa, flexural strength of 376 ± 25 MPa, and fracture toughness of 4.70 ± 0.27 MPa m^1/2. Nonetheless, 10 wt% excess of B₄C coarsened the grains and decreased the strength of the ceramic. Moreover, the nanohardness (34.5–36.9 GPa) and Young's modulus (519–571 GPa) values with different B₄C contents just showed a slight difference and were within ranges commonly observed in high-entropy diboride ceramics.     

Dual-phase high-entropy ultra-high temperature ceramics

A series of dual-phase high-entropy ultra-high temperature ceramics (DPHE-UHTCs) are fabricated starting from N binary borides and (5-N) binary carbides powders. > ∼99 % relative densities have been achieved with virtually no native oxides. These DPHE-UHTCs consist of a hexagonal high-entropy boride (HEB) phase and a cubic high-entropy carbide (HEC) phase. A thermodynamic relation that governs the compositions of the HEB and HEC phases in equilibrium is discovered and a thermodynamic model is proposed. These DPHE-UHTCs exhibit tunable grain size, Vickers microhardness, Young’s and shear moduli, and thermal conductivity. The DPHE-UHTCs have higher hardness than the weighted linear average of the two single-phase HEB and HEC, which are already harder than the rule-of-mixture averages of individual binary borides and carbides. This study extends the state of the art by introducing dual-phase high-entropy ceramics (DPHECs), which provide a new platform to tailor various properties via changing the phase fraction and microstructure.     

Microstructure and mechanical properties of WB2–B4C composites fabricated by boro/carbothermal reduction and SPS

The phase composition, microstructure, and mechanical properties of the WB₂–B₄C composites fabricated by a combination of boro/carbothermal reduction and spark plasma sintering (SPS) method with WO₃, B₄C, and graphite as raw materials were investigated in this study. The experimental results showed that the relative density of the as-sintered WB₂–B₄C composites was ∼93.1% and ∼99.5%, respectively, after being SPS sintered at 1600°C under the applied load of 30 MPa for 10 min. Scanning electron microscope analysis showed that a network structure with WB₂ grains surrounded by B₄C grains was observed after sintering. Analyses of high-resolution TEM showed semi-coherent interface and lattice distortion transition region between WB₂ and B₄C grains. The Vickers hardness of WB₂–B₄C composite increased to 22.3 ± 0.9 GPa at 9.8 N owing to the fully dense, solid solution of C, and three-dimensional network structure. Moreover, the fracture toughness and flexural strength of WB₂–B₄C composite reach 6.04 ± 0.81 MPa m^1/2 and 750 ± 80 MPa, respectively, which could be attributed to the semi-coherent interface between WB₂ and B₄C grains.     

Rare-earth high-entropy aluminate-toughened-zirconate dual-phase composite ceramics for advanced thermal barrier coatings

Superb toughening is achieved by incorporating a secondary ferroelastic phase in high-entropy rare-earth zirconate 5RE₂Zr₂O₇ (HZ). Here, we report an enhancement of 64% in fracture toughness through the addition of 30mol% high-entropy rare-earth aluminate 5REAlO₃ (HA) to the HZ matrix (30HA). The aforementioned rare-earth elements RE are La, Sm, Eu, Gd, and Yb. The present dual-phase composite ceramic 30HA has a large fracture toughness of 2.77 ± 0.14 MPa m^1/2, along with excellent high-temperature phase stability, resulting in good usage for potential thermal barrier coating applications. Particularly, the fracture toughness of the dual-phase composite ceramics at first increases to a maximum and then drops suddenly, as the mole fraction of HA increases from 0 to 50%. A clear definition of fitting parameters and their physical significance is provided for a better interpretation of the experimental data. The present toughening mechanism sheds light on microstructure engineering in high-entropy ceramics for excellent mechanical properties.     

On the phase and grain boundaries in dual phase carbide/boride ceramics from micro to atomic level

The phase and grain boundary characteristics of recently developed fine-grained dual-phase high-entropy (Ti-Zr-Nb-Hf-Ta)C/(Ti-Zr-Nb-Hf-Ta)B₂ was investigated throughout all the accessible length scales using scanning electron microscopy (SEM), aberration-corrected scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS). The system exhibits relatively homogeneous grain size distribution where the average size is approximately 0.97 µm, with chemical composition (Ti_0.14 Zr_0.2 Nb_0.2 Hf_0.2 Ta_0.26)C + (Ti_0.38 Zr_0.18 Nb_0.22 Hf₀.₁₁₅ Ta_0.105)B₂. SEM analyses revealed no micro-crack formation and second – phase segregation at the boundaries or micro-pores at the triple – points. Investigation down to the sub-nanometer scale revealed that the phase and grain boundaries were typically clean and sharp with an indistinct 1 – 1.5 nm thin gradient of metallic elements at boride/boride and carbide/carbide interfaces. The sharp phase and grain boundaries do exhibit elemental enrichment from a trace amount of Fe being incorporated in interstitial positions of carbide and boride grains locally at boride/carbide boundaries or are present in boride and carbide grains in the form of continuous thin layer at boride/boride and carbide/carbide interfaces with the probably origin from starting powders.     

Low-temperature sintering of single-phase,high-entropy carbide ceramics

Dense (Hf, Zr, Ti, Ta, Nb)C high-entropy ceramics were produced by hot pressing (HP) of carbide powders synthesized by carbothermal reduction (CTR). The relative density increased from 95% to 99.3% as the HP temperature increased from 1750°C to 1900°C. Nominally phase pure ceramics with the rock salt structure had grain sizes ranging from 0.6 µm to 1.2 µm. The mixed carbide powders were synthesized by high-energy ball milling (HEBM) followed by CTR at 1600°C, which resulted in an average particle size of ~100 nm and an oxygen content of 0.8 wt%. Low sintering temperature, high relative densities, and fine grain sizes were achieved through the use of synthesized powders. These are the first reported results for low-temperature densification and fine microstructure of high-entropy carbide ceramics.     

Densification,microstructure, and mechanical properties of V-substituted HfB2-based ceramics

This study firstly developed Hf_1-xV_xB₂ (x = 0, 0.01, 0.02, 0.05) powders, which were derived from borothermal reduction of HfO₂ and V₂O₅ with boron. The results revealed that significantly refined Hf_1-xV_xB₂ powders (0.51 μm) could be obtained by solid solution of VB₂, and x ≥ 0.05 was a premise. However, as the content of V-substitution for Hf increased, Hf_1-xV_xB₂ ceramics sintered by spark plasma sintering at 2000 °C only displayed a slight densification improvement, which was attributed to the grain coarsening effect induced by the solid solution of VB₂. By incorporating 20 vol% SiC, fully dense Hf_1-xV_xB₂-SiC ceramics were successfully fabricated using the same sintering parameters. Compared with HfB₂-SiC ceramics, Hf_0.95V_0.05B₂-20 vol% SiC ceramics exhibited an elevated and comparable value of Vickers hardness (23.64 GPa), but lower fracture toughness (4.09 MPa m^1/2).     

Effect of Nb content on the phase composition,densification, microstructure,and mechanical properties of high-entropy boride ceramics

Dense high-entropy (Hf,Zr,Ti,Ta,Nb)B₂ ceramics with Nb contents ranging from 0 to 20 at% were produced by a two-step spark plasma sintering process. X-ray diffraction indicated that a single-phase with hexagonal structure was detected in the composition without Nb. In contrast, two phases with the same hexagonal structure, but slightly different lattice parameters were present in compositions containing Nb. The addition of Nb resulted in the presence of a Nb-rich second phase and the amount of the second phase increased as the Nb content increased. The relative densities were all >99.5 %, but decreased from ～100 % to ～99.5 % as the Nb content increased from 0 to 20 at%. The average grain size decreased from 13.9 ± 5.5 μm for the composition without Nb additions to 5.2 ± 2.0 μm for the composition containing 20 at% Nb. The reduction of grain size with increasing Nb content was due to the suppression of grain growth by the Nb-rich second phase. The addition of Nb increased Young’s modulus and Vickers hardness, but decreased shear modulus. While some Nb dissolved into the main phase, a Nb-rich second phase was formed in all Nb-containing compositions.     

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.     

Two-step synthesis process for high-entropy diboride powders

High-entropy diboride powders were produced by a two-step synthesis process consisting of boro/carbothermal reduction followed by solid solution formation. Nominally phase-pure (Hf,Zr,Ti,Ta,Nb)B₂ in a single-phase hexagonal structure had an average particle size of just over 400 nm and contained 0.3 wt% carbon and 0.3 wt% oxygen. The fine particle size was due to the use of high-energy ball milling prior to boro/carbothermal reduction, which led to a relatively low synthesis temperature of 1650°C. Oxygen and carbon contents were minimized by completion of the boro/carbothermal reduction reactions under vacuum. This is the first report of synthesis of a nominally phase pure high-entropy diboride powder from oxides using a two-step process.     

Phase evolution and microstructure characteristics during the carbothermal reduction of Hf(C,N,O) ceramics derived from a precursor

In this study, nanosized Hf(C,N,O) ceramics were successfully prepared from a novel precursor synthesised by combining HfCl₄ with ethylenediamine and dimethylformamide. Subsequently, the carbothermal reduction of these Hf(C,N,O) ceramics into hafnium carbide was investigated. The Hf(C,N,O) ceramics comprised Hf₂ON₂ and HfO₂ nanocrystals and amorphous carbon. Upon carbothermal reduction, conversion began at 1300 °C, when HfC first appeared, and continued to completion at 1500 °C, resulting in irregularly shaped crystallites measuring 50–150 nm. Upon increasing the dwelling time, the oxides were completely converted into carbides at 1400 °C. Furthermore, nitrogen was introduced into the reaction to catalyse the conversion of oxides into carbides considering the beneficial gas–solid reaction between CO and Hf₂ON₂. We expect that the ceramics prepared in this study will be suitable for the fabrication of high-performance composite ceramics, with properties superior to those of current materials.     

Boro/carbothermal reduction synthesis of uranium tetraboride and its oxidation behavior in dry air

Uranium tetraboride (UB₄) was successfully synthesized by boro/carbothermal reduction of UO₂ with B₄C and carbon as combined reduction agents under flowing argon. The effects of processing temperature and mole ratios of starting materials on phase evolution were studied. XRD results demonstrated that UB₄ was obtained with 3.75 mol% B₄C in excess based on the UO₂/B₄C/C molar ratios of 1:1:1 at 1500°C. SEM observation revealed that submicrometer-sized quasi-spherical UB₄ particles cemented together to be an aggregate. The laser particle size analysis showed that the particle size was in the range of 1-10 μm. The oxidation behavior of UB₄ was also investigated by TG and XRD. The oxidation of UB₄ started at about 500°C and it showed better oxidation resistance than other basic uranium nuclear fuels (UO₂, UC, UN and U₃Si₂). The oxidation chemical process of UB₄ was presented as a three-step process: (a) the formation of U₃O₈ and B₂O₃ oxidation products; (b) the formation of UB₂O₆ intermediate product by the interaction of U₃O₈ and B₂O₃; (c) the decomposition of UB₂O₆ to get U₃O₈.     

Improvement of sinterability and mechanical properties of ZrB2 ceramics by the modified borothermal reduction methods

Starting from ZrO₂ and boron (molar ratio: 1:4), four ZrB₂ powders were synthesized by borothermal reduction method, three of which were designed to introduce minor modifications by combining solid solution with Ti and/or water-washing. The sinterability, microstructures, mechanical properties and thermal conductivity were investigated. In comparison with the conventional borothermal reduction, the modified methods offered significant improvement in terms of densification of ZrB₂ ceramics, particularly the mixture that included water-washing. Owing to the refined particle size and boron residues, ZrB₂ ceramics from the modified borothermal reduction which included water-washing demonstrated nearly full densification, Vickers hardness of 14.0 GPa and thermal conductivity of 82.5 W/mK after spark plasma sintering at 2000 °C for 10 min. It was revealed that the properties of ZrB₂ ceramics could be enhanced utilizing the proposed minor modification, starting from the same raw materials and adopting the same sintering conditions.     

Highly transparent AlON ceramics sintered from powder synthesized by carbothermal reduction nitridation

Aluminum oxynitride (AlON) powders were synthesized by the carbothermal reduction and nitridation process using commercial γ-Al₂O₃ and carbon black powders as starting materials. And AlON transparent ceramics were fabricated by pressureless sintering under nitrogen atmosphere. The effects of ball milling time on morphology and particle size distribution of the AlON powders, as well as the microstructure and optical property of AlON transparent ceramics were investigated. It is found that single-phase AlON powder was obtained by calcining the γ-Al₂O₃/C mixture at 1550 °C for 1 h and a following heat treatment at 1750 °C for 2 h. The AlON powder ball milled for 24 h showed smaller particles and narrower particle size distribution compared with the 12 h one, which was benefit for the improvement of optical property of AlON transparent ceramics. With the sintering aids of 0.25 wt% MgO and 0.04 wt% Y₂O₃, highly transparent AlON ceramics with in-line transmittance above 80% from visible to infrared range were obtained through pressureless sintering at 1850 °C for 6 h.