Fine-grained dual-phase high-entropy ceramics derived from boro/carbothermal reduction

In the current work, fine-grained dual-phase, high-entropy ceramics (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)B₂-(Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C with different phase ratios were prepared from powders synthesized via a boro/carbothermal reduction approach, by adjusting the content of B₄C and C in the precursor powders. Phase compositions, densification, microstructure, and mechanical properties were investigated and correlated. Due to the combination of pinning effect and the boro/carbothermal reduction approach, the average grain size (～0.5?1.5 μm) of the dual-phase high-entropy ceramics was roughly one order of magnitude smaller than previously reported literature. The dual-phase high-entropy ceramics had residual porosity ranging from 0.3 to 3.2 % upon sintering by SPS and the material with about 18 vol% boride phase exhibited the highest Vickers hardness (24.2±0.3 GPa) and fracture toughness (3.19±0.24 MPam^1/2).     

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.     

Synthesis,microstructure and mechanical properties of high-entropy (VNbTaMoW)C5 ceramics

High-entropy ceramics (HEC) with a fixed composition of (VNbTaMoW)C₅ were prepared by spark plasma sintering (SPS) from 1500 °C to 2200 °C. XRD, TEM, HRTEM, SAED and EDX were used to investigate effects of the sintering temperatures on compositional homogeneity, constituent phases and microstructure of the HECs. The results showed that single-phase HEC formed at a temperature as low as 1600 °C while ultimate elemental distribution homogeneity could be obtained at 2200 °C. Elemental distribution homogenization was accompanied by microstructural coarsening and oxide impurities aggregating at grain boundaries as temperature increased. SPS at 1900 °C for 12 min could yield uniform HECs (VNbTaMoW)C₅ with Vickers hardness, nanohardness, fracture toughness and Young’s modulus reaching 19.6 GPa, 29.7 GPa, 5.4 MPa m^1/2 and 551 GPa, respectively. The resultant HECs showed excellent wear resistance when coupled with WC at room temperature.     

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.     

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.     

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.     

Influence of vanadium content on the microstructural evolution and mechanical properties of (TiZrHfVNbTa)C high-entropy carbides processed by pressureless sintering

A series of (TiZrHfVNbTa)C high-entropy ceramics with different vanadium contents have been fabricated by pressureless sintering at 2300 °C–2500 °C for 1 h, utilizing self-synthesized carbide powders obtained by carbothermal reduction. The addition of vanadium is beneficial to promote densification process and refine grain, as well as facilitate the homogeneous distribution of metal elements. The distribution of pores is also modified, almost entirely existing at grain boundary, and the integral mechanical properties achieve optimization. However, excess adding vanadium does not favor forming a single-phase (TiZrHfVNbTa)C high-entropy ceramic. The optimal (TiZrHfVNbTa)C high-entropy ceramic sintered at 2300 °C possesses a high relative density of 97.5 % and homogeneous microstructure with small grain size of 1.2 μm. The flexural strength and Vickers hardness reach 473 MPa and 24.9 GPa, respectively. This work has established a cost-effective and convenient preparation of novel (TiZrHfVNbTa)C high-entropy carbide ceramics.     

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.     

Microstructure and mechanical properties of spark plasma sintered TiB2 ceramics combined with a high-entropy alloy sintering aid

A high-entropy alloy (HEA), CoCrFeNiMn_0.5Ti_0.5, is used as a sintering aid for the densification of TiB₂ sintered by spark plasma sintering. The HEA content in the starting TiB₂-HEA mixture is varied from 0 to 10?wt-%. The microstructure and mechanical properties of the sintered samples are analysed and the optimum HEA content of 10% is found for the preparation of the TiB₂-HEA ceramics, allowing combining high mechanical properties (Vickers hardness of 2174.64?HV and flexural strength of 427.69?MPa) and high relative density of 99.1%.     

Microstructure and mechanical properties of B4C based ceramics with Fe3Al as sintering aid by spark plasma sintering

B₄C based ceramics were fabricated with different Fe₃Al contents as sintering aids by spark plasma sintering at relatively low temperature (1700 °C) in vacuum by applying 50 MPa pressure and held at 1700 °C for 5 min. The effect of Fe₃Al additions (from 0 to 9 wt%) on the microstructure and mechanical properties of B₄C has been studied. The composition and microstructure of as-prepared samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe microanalyzer (EPMA) equipped with WDS (wavelength dispersive spectrometry) and EDS. The mixtures of B₄C and Fe₃Al underwent a major reaction in which the metal borides and B₄C were encountered as major crystallographic phases. The sample with 7 wt% of Fe₃Al as a sintering aid was found to have 32.46 GPa Vickers hardness, 483.40 MPa flexural strength, and 4.1 MPa m^1/2 fracture toughness which is higher than that of pure B₄C.     

Influence of CeO2 addition on the microstructure and mechanical properties of Zirconia-toughened alumina (ZTA) composite prepared by spark plasma sintering

In this study, zirconia-toughened alumina (ZTA) samples with different amounts of CeO₂ were prepared by the spark plasma sintering method. The phase composition and microstructure of the samples were examined by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The addition of CeO₂ results in grain refinement and density increase; moreover, CeO₂ stabilises the high-temperature metastable phase. As the amount of CeO₂ reaches 7 wt%, a new CeAl₁₁O₁₈ phase appears. The Vickers hardness, modulus, and fracture toughness of the samples depend to a large extent on the grain size, relative density, and existence of the second phase. Among the composites, that with 5 wt% CeO₂ shows the best performance with the highest values of relative density, Vickers hardness, and fracture toughness: 96.51%, 1688 HV, and 9.91 MPa.√m, respectively.     

Processing and mechanical properties of B4C-SiCw ceramics densified by spark plasma sintering

Homogenous distribution of whiskers in the ceramic matrix is difficult to be achieved. To solve this problem, B₄C-SiC_w powder mixtures were freeze dried from a slurry dispersed by cellulose nanofibrils (CellNF) in this work. Dense B₄C ceramics reinforced with various amounts of SiC_w up to 12 wt% were consolidated by spark plasma sintering (SPS) at 1800 °C for 10 min under 50 MPa. During this process, CellNF was converted into carbon nanostructures. As iron impurities exist in the starting B₄C and SiC_w powders, both thermodynamic calculations and microstructure observations suggest the dissolution and precipitation of SiC_w in the liquids composed of Fe-Si-B-C occurred during sintering. Although not all the SiC_w grains were kept in the final ceramics, B₄C-9 wt% SiC_w ceramics sintered at 1800 °C still exhibit excellent Vickers hardness (35.5 ± 0.8 GPa), flexural strength (560 ± 9 MPa) and fracture toughness (5.1 ± 0.2 MPa·m^1/2), possibly contributed by the high-density stacking faults and twins in their SiC grains, no matter in whisker or particulate forms.     

Sintering behavior and mechanical properties of Ta4HfC5-based composites with ZrB2 additive

Ta₄HfC₅ powder was synthesized using TaCl₅, HfCl₄ and phenolic resin as raw materials. Then, Ta₄HfC₅–10 vol% MoSi₂ ceramics and Ta₄HfC₅–10 vol% MoSi₂ with different proportions of ZrB₂ (10 – 30 vol%) ceramics were sintered by spark plasma sintering. Zr atoms substituted Ta and Hf atoms in Ta₄HfC₅ during the sintering process at 2000 °C. The sintering behavior and microstructure evolution upon the ceramics are discussed. The mechanical properties of the composites were improved compared to the pure Ta₄HfC₅ ceramics. The hardness of Ta₄HfC₅–MoSi₂ with 30 vol% ZrB₂ increased from around 10 GPa to almost 13 GPa, the flexural strength increased from around 245–435 MPa, and the fracture toughness increased from 2.56 ± 0.12 MPa?m^1/2 to 4.46 ± 0.20 MPa?m^1/2.     

Microstructure and mechanical properties of SiC-SiC joints joined by spark plasma sintering

The development of reliable joining technology is of great importance for the full use of SiC. Ti₃SiC₂, which is used as a filler material for SiC joining, can meet the demands of neutron environment applications and can alleviate residual stress during the joining process. In this work, SiC was joined using different powders (Ti₃SiC₂ and 3Ti/1.2Si/2C/0.2Al) as filler materials and spark plasma sintering (SPS). The influence of the joining temperature on the flexural strength of the SiC joints at room temperature and at high temperatures was investigated. Based on X-ray diffraction and scanning electron microscopy analyses, SiC joints with 3Ti/1.2Si/2C/0.2Al powder as the filler material possess high flexural strengths of 133 MPa and 119 MPa at room temperature and at 1200 °C, respectively. The superior flexural strength of the SiC joint at 1200 °C is attributed to the phase transformation of TiO₂ from anatase to rutile.     

Enhancement mechanical properties of in-situ preparated B4C-based composites with small amount of (Ti3SiC2+Si)

B₄C-based composites were synthesized by spark plasma sintering using B₄C、Ti₃SiC₂、Si as starting materials. The effects of sintering temperature and second phase content on mechanical performance and microstructure of composites were studied. Full dense B₄C-based composites were obtained at a low sintering temperature of 1800 °C. The B₄C-based composite with 10 wt% (TiB₂+SiC) shows excellent mechanical properties: the Vickers hardness, fracture toughness, and flexural strength are 33 GPa, 8 MPa m^1/2, 569 MPa, respectively. High hardness and flexural strength were attributed to the high relative density and grain refinement, the high fracture toughness was owing to the crack deflection and uniform distribution of the second phase.     

Phase stability,mechanical properties and melting points of high-entropy quaternary metal carbides from first-principles

With a combination of first-principles calculations and thermodynamics formalism of configurational mixing entropy, we have constructed three-dimensional phase diagram in terms of thermodynamic and structural parameters including the configurational mixing entropy and enthalpy, the temperature of the melting point, and the lattice constant difference of the constitute carbides for fifteen equiatomic quaternary high-entropy metal carbide (HEMC) ceramics of group IVB and VB refractory metals (RM = Ti, Zr, Hf, V, Nb, and Ta). We further predicted nine new HEMCs and provided an explanation for the existence of six experimentally realized quaternary HEMCs. In addition, our calculations of the melting points and mechanical properties show that the HEMCs have the unique properties of high hardness, high fracture toughness, and ultrahigh melting points. The computational procedure involved in this work may be used to design new high-entropy ceramics for specific applications.     

Microstructure and mechanical properties of multiwalled carbon nanotube toughened spark plasma sintered ZrB2 composites

ZrB₂ based composites containing 10 vol.-% carbon nanotubes (CNTs) are synthesised by spark plasma sintering at temperatures ranging from 1600 to 18008C and at an applied pressure of 25?MPa. The effects of sintering temperature on densification behaviour, microstructural evolutions and mechanical properties are presented. Results indicate that ZrB₂-CNT composites fabricated at 16508C have the optimal combination of dense microstructure and properties. The fracture toughness is sensitive to the temperature change and reaches 7.2?MPa m^1/2 for the CNT toughened ZrB₂ ceramics, which is higher than the measured result for monolithic ZrB₂ (3.3?MPa m^1/2). The crack deflection and CNT pullout are the dominant toughening mechanisms.     

Ultra high temperature high-entropy borides: Effect of graphite addition on oxides removal and densification behaviour

The introduction of 0.5–1.0 wt.% graphite to the powders prepared by Self-propagating High-temperature Synthesis (SHS) is found to be highly beneficial for the removal of oxide impurities (from 2.7-8.8 wt.% to 0.2–0.5 wt.%) during spark plasma sintering (1950°C/20 min, 20 MPa) of (Hf_0.2Mo_0.2Ta_0.2Nb_0.2Ti_0.2)B₂ and (Hf_0.2Mo_0.2Ta_0.2Zr_0.2Ti_0.2)B₂ ceramics. Concurrently, the consolidation level achieved is enhanced from about 92.5% and 88%, respectively, to values exceeding 97%. While a further increase of graphite slightly improves samples densification, final products become progressively richer of the unreacted carbon.It is assumed that graphite plays a double role during SPS, e.g. not only as a reactant during the carbothermal reduction of oxides contaminant, but also as lubricating agent for the powder particles. The latter phenomenon is likely the main responsible for the densification improvement when 3 wt.% or larger amounts of additive are used. Another positive effect is the crystallite size refinement of the high-entropy phases with the progressive abatement of oxides, to confirm that their presence promotes grain coarsening during the sintering process.     

Sintering behavior and mechanical properties of spark plasma sintering SiO2-MgO ceramics

SiO₂-MgO ceramics containing different weight fractions (0, 0.5, 1, 2, and 4 wt%) of SiO₂ powder were prepared by mixing nano MgO powder, and the powder mixtures were densified by spark plasma sintering (SPS). The effect of SiO₂ addition and SPS method on the sintering behavior, microstructure and mechanical properties were investigated. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The highest relative density, flexural strength and hardness of 2 wt% SiO₂-MgO ceramics reached 99.98%, 253.99 ± 7.47 MPa and 7.56 ± 0.21 GPa when sintered at 1400 °C by SPS, respectively. The observed improvement in the sintering behavior and mechanical properties are mainly attributed to grain boundary "strengthening" and intragranular "weakening" of the MgO matrix. Furthermore, the spark plasma sintering temperature could be decreased by more than 100 °C as compared with the HP method, SPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Microstructure,fracture behaviour and mechanical properties of conductive alumina based composites manufactured by SPS from graphenated Al2O3 powders

Conductive Al₂O₃/graphene composites were manufactured by SPS from Al₂O₃ powders coated with a few graphene layers. Composite powders with a total carbon content of 0.1, 0.6 and 1.0 wt. % were manufactured by chemical vapour deposition. The effect of the graphene content on the microstructure, mechanical and electrical properties of the compacts were studied. Graphene, homogenously located along the grain boundaries, dramatically hindered the Al₂O₃ grain growth. The continuous interconnected graphene network enhanced electrical properties, achieving percolation threshold as low as 0.6 wt. % of graphene. The content of 1 wt. % of graphene increased electroconductivity by 13 orders of magnitude as compared to the monolithic alumina. The indentation fracture toughness increased by 20 % in specimens with 0.6 wt. % graphene content as compared to pure alumina. The presence of 1.0 wt. % of graphene resulted in a slight decrease of elastic modulus and hardness, but strength decreased by 40 %.