Phase stability,mechanical and thermodynamic properties of (Hf,Zr, Ta,M)B2 (M= Nb,Ti, Cr,W) quaternary high-entropy diboride ceramics via first-principles calculations

As the high-entropy design concept applied to the diboride ceramic system, high-entropy diboride ceramics with a wide range of composition control, is expected to become a new high-performance material for extreme high-temperature environments. Herein, the effects of four transition metal elements (Nb, Ti, Cr, W) on the phase stability and properties of (Hf, Zr, Ta)B₂-based high-entropy diboride ceramics are systematically investigated via the first-principles calculations. All components were identified as thermodynamically, mechanically and dynamically stable from enthalpy of formation, elastic and phonon spectrum calculations. Among these, compared with the (Hf, Zr, Ta)B₂ ceramics, the addition of Nb and Ti on the metal sublattice is beneficial to improve the mechanical properties of ceramics, including Young's modulus, hardness and fracture toughness, while the introduction of Cr and W weakens the strength of covalently and ionic bonds inside the material, reducing its mechanical properties. The predicted thermophysical properties show that the high-entropy diboride ceramics containing Nb and Ti have better high-temperature comprehensive performance, including higher Debye temperature, thermal conductivity and lower thermal expansion characteristics, which is conducive to the application in extreme high-temperature environments. This research will provide important guidance for the design and development of new high-performance high-entropy diboride ceramics.     

Hot-corrosion of refractory high-entropy ceramic matrix composites synthesized by alloy melt-infiltration

Carbon fiber-containing refractory high-entropy ceramic matrix composites (C/RHECs) were fabricated through a reaction with carbon powders, transition metal carbides, and Zr–Ti alloys as a novel heat resistant material used for components of hypersonic vehicles cruising at Mach 7–10. With the infiltration of alloys at 1750 °C into a composite preform containing carbon and carbide powders for 15 min, a high-entropy matrix was successfully formed in situ. Arc-jet tests were conducted in the temperature range of 1800–1900 °C. Results showed the formation of an oxidized region composed of complex oxides, such as (Zr, Hf)O₂, (Nb, Ta)₂(Zr, Hf)₆O₁₇, (Zr, Hf)TiO₄, and Ti(Nb, Ta)₂O₇, with an average thickness of ~600 μm, under which an unoxidized region remained. The porous oxidized region resulted from the evolution of CO_(g) during oxidation, while a dense oxide region formed as the outermost region. This indicates that the dense oxide region acted as a barrier to oxygen diffusion for the unoxidized region during oxidation.     

Synthesis of rare earth containing single-phase multicomponent metal carbides via liquid polymer precursor route

Novel high-entropy carbide ceramics (HEC) containing rare earth metals, namely (Ti, Zr, Hf, Ta, La, Y)C, (Ti, Zr, Hf, Ta, Nb, La, Y)C, and (Ti, Zr, Hf, Ta, Nb, Mo, W, La)C were prepared with single-phase structure by polymer precursor method. Controlled co-hydrolysis and polycondensation of equiatomic metal-containing monomers were conducted successively, followed by blending allyl-functional novolac resin as carbon source, and the polymer precursors were obtained as clear viscous liquid solutions. The single-phase formation possibility was theoretically analyzed from the aspects of size-effect parameter δ of the designed compositions. All as-obtained ceramics possessed single face-centered-cubic structure of metal carbides and high-compositional uniformity from nanoscale to microscale. The (Ti, Zr, Hf, Ta, Nb, Mo, W, La)C ceramic powder pyrolyzed at 1800°C exhibited low-oxygen impurity content of 1.2 wt%. Thus, multicomponent high-entropy carbide nanoceramics with over five metal elements containing even rare earth element were firstly synthesized and characterized.     

Pressureless sintering of high-entropy boride ceramics

High-entropy boride ceramics were densified by pressureless sintering. Green densities of the ceramics varied by composition with the highest green density of 53.6 % for (Hf, Nb, Ta, Ti, Zr)B₂. After pressureless sintering, relative densities up to ∼100 % were obtained for (Cr, Hf, Ta, Ti, Zr)B₂ and (Hf, Ta, Ti, V, Zr)B₂. Two compositions, (Hf, Ta, Ti, W, Zr)B₂ and (Hf, Mo, Ti, W, Zr)B₂ contained secondary phases and did not reach full density. All compositions had average grain sizes less than 10 µm and less than 2 vol % of residual B₄C. This is the first report of conventional pressureless sintering of high-entropy boride ceramics powder compacts without evidence of liquid phase formation.     

A novel strategy for rapid fabrication of continuous carbon fiber reinforced (TiZrHfNbTa)C high-entropy ceramic composites: High-entropy alloy in-situ reactive melt infiltration

For the first time, dense continuous carbon fiber (C_f) reinforced (TiZrHfNbTa)C high-entropy ceramic (C_f/HEC) composites were rapidly prepared via in-situ reactive melt infiltration (RMI). A TiZrHfNbTa high-entropy alloy served as the cation source and carbon in C_f reinforced carbon matrix (C_f/C) preforms served as the anion source, and a (TiZrHfNbTa)C high-entropy ceramic phase with a near equimolar ratio was successfully formed. The results revealed that most of the TiZrHfNbTa high-entropy alloy reacted with the carbon matrix, and the harvested C_f/HEC composites exhibited an excellent bending strength (612.6 MPa) and low ablation rates. High reaction rates caused by ultra-high temperature and homogeneous distribution of elements in the high-entropy TiZrHfNbTa alloy significantly reduced the difference in reactivity with C among Ti, Zr, Hf, Nb, and Ta are considered to be the reasons for successful formation of (TiZrHfNbTa)C high-entropy ceramic with a near equimolar ratio in C_f/HEC composites.     

Compositional disorder and sintering of entropy stabilized (Hf,Nb,Ta,Ti,Zr)B2 solid solution powders

Entropy-stabilized (Hf,Nb,Ta,Ti,Zr)B₂ solid solution powders produced by a carbo/boro-thermal reduction followed by solid solution formation were first analysed by synchrotron radiation x-ray diffraction, and their long range periodicity (i.e. lattice parameters) as well as the micro-strain intended as lattice disorder were quantitatively determined. A model to describe the micro-strain was proposed. The as-synthesized (Hf,Nb,Ta,Ti,Zr)B₂ solid solution powders were then hot-pressed at 2200 K and 50 MPa until near full densification was achieved. The hot-pressed material had a residual micro-porosity of 1.3 vol.% and consisted of a (Hf,Nb,Ta,Ti,Zr)B₂ ceramic matrix, 0.3-1 μm grain size range, and of a residual 10 vol.% B₄C particulate component, grain size in the range 0.2-2 μm. B₄C was a side product of the former synthesis and, after hot-pressing, remained trapped along the grain boundaries of the primary (Hf,Nb,Ta,Ti,Zr)B₂ solid solution ceramic matrix. Micro-hardness HV_0.2 = 22.7 ± 1.9 GPa for 1.96 N applied force was measured.     

Oxyacetylene ablation of (Hf0.2Ti0.2Zr0.2Ta0.2Nb0.2)C at 1350 − 2050 °C

Ablation resistance of a multi-component carbide (Hf_0.2Ti_0.2Zr_0.2Ta_0.2Nb_0.2)C (HTZTNC) was investigated using an oxyacetylene flame apparatus. When the surface temperature of the HTZTNC was below 1800 °C, (Nb, Ta)₂O₅, (Hf, Zr)TiO₄, and (Hf, Zr)O₂ were found to be the main oxidation products, while at higher temperature, formation of (Hf, Zr, Ti, Ta, Nb)O_x was favored and its content gradually increased with the increase in ablation temperature. Based on the ablation results and thermodynamic simulation analysis, a possible ablation mechanism of HTZTNC was proposed. Active oxidation of TiC and outward diffusion of TiO were demonstrated to occur during the ablation process, which constitute the critical steps for the ablation of HTZTNC. These results can contribute to the design of ablation resistant ultra-high-temperature ceramics.     

A facile route for the synthesis of high-entropy transition carbides/borides at low temperatures

As the main candidates in the field of ultra-high temperature ceramics, high entropy carbides/borides (HECs/HEBs) have good oxidation resistance properties, high hardness, as well as excellent thermal and electrical conductivities, which are the focused points of research nowadays. In the current study, (Hf,Ta,Zr,Nb,Mo,Ti)C powders were successfully synthesized by a three-step process, including the mixing process of raw oxides and carbon black with spaying Fe(NO₃)₃ solution, carbothermal reduction and subsequent calcium posttreatment. For the preparation of (Hf,Ta,Zr,Nb,Mo,Ti)B₂ powders, during the calcium posttreatment process, equal stoichiometric ratio of B₄C was added for the purpose of boriding reaction. The relevant X-ray diffraction and SEM characterizations indicate the successful preparations of face-centered cubic HECs and hexagonal HEBs. However, slight Mo local segregation was found in the prepared (Hf,Ta,Zr,Nb,Mo,Ti)B₂ powders. The iron generated from Fe(NO₃)₃ promotes the solid solution process between monocarbides during the carbothermal reduction process via the dissolution-diffusion-precipitation mechanism. In the calcium posttreatment process, the liquid calcium ensures the boriding reaction take place at a low temperature. In addition, the residual carbon could be combined with calcium to generate CaC₂ which is easy to be removed by acid leaching, and meanwhile, the added Fe could also be finally eliminated to produce pure HEC/HEB powders. The current method does not require the long-time high energy ball milling of raw materials, but only simple and mild mixing is enough. Therefore, such a facile route has a great potential application prospect for industrially preparing high entropy phase powders in a large scale.     

Room-temperature mechanical properties of a high-entropy diboride

The mechanical properties of a (Hf,Mo,Nb,Ta,W,Zr)B₂ high-entropy ceramic were measured at room temperature. A two-step synthesis process was utilized to produce the (Hf,Mo,Nb,Ta,W,Zr)B₂ ceramics. The process consisted of a boro/carbothermal reduction reaction followed by solid solution formation and densification through spark plasma sintering. Nominally, phase pure (Hf,Mo,Nb,Ta,W,Zr)B₂ was sintered to near full density (8.98 g/cm³) at 2000°C. The mean grain size was 6 ± 2 µm with a maximum grain size of 17 µm. Flexural strength was 528 ± 53 MPa, Young's modulus was 520 ± 12 GPa, fracture toughness was 3.9 ± 1.2 MPa·m^1/2, and hardness (HV_0.2) was 33.1 ± 1.1 GPa. A Griffith-type analysis determined the strength limiting flaw to be the largest grains in the microstructure. This is one of the first reports of a variety of mechanical properties of a six-component high-entropy diboride.     

Medium-entropy (Ti,Zr, Hf)2SC MAX phase

Medium- and high-entropy alloys or ceramics for tuning the physicochemical properties of materials by the combination of multiple principal elements have received much interest. Herein, a medium-entropy (Ti, Zr, Hf)₂SC phase was synthesized attributing to the structural and chemical diversity of MAX phases. The crystal structure of (Ti, Zr, Hf)₂SC was determined by the Rietveld refinement of XRD, SEM, and atom-resolved TEM along with EDS elemental analysis. Phase evolution of X-ray diffraction patterns and TG/DSC curves were employed to reveal the synthesis mechanism of (Ti, Zr, Hf)₂SC from 2TiC–Zr–ZrC-2HfH₂-3.2FeS reactant system. The Vicker's hardness and the electrical resistivity of (Ti, Zr, Hf)₂SC were found higher than those of Ti₂SC, but the thermal conductivity of (Ti, Zr, Hf)₂SC was lower.     

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.     

Effect of alloying elements on stacking fault energies and twinnabilities in high-entropy transition-metal carbides

Twinning is a fundamental mechanism behind the simultaneous increase in the strength and ductility of high-entropy alloys. Similar approaches may contribute to the remarkable improvements of the mechanical properties of high-entropy ceramics. In this study, the stacking fault energies (SFEs) and twinnabilities of a novel category of ZrNbTa-based high-entropy transition-metal carbides (HETMCs) are investigated in terms of their generalized stacking fault energy curves (γ-curves) via first-principle calculations. The γ-curves show that dislocation nucleation in ZrNbTa-based HETMCs occurs more easily than that of unary transition metal (TM, TM = Zr, Nb, Ta, Hf, Ti, V) carbides. When a pre-existing intrinsic stacking fault (ISF) is considered, C- vertices (TM- mirror) twinning fault (TF) more likely forms and TF may be more stable than ISF. The stable SFEs of C- vertices ISF and TF decrease with the addition of Hf, Ti, and V atoms to (ZrNbTa)C owing to the severe local lattice distortion. The calculated barrier energies and twinnabilities further indicate that twinning is possible for the selected ZrNbTa-based HETMCs. Theoretical twinnabilities (τ_a) decrease in the following sequence: (ZrNbTa)C > (ZrNbTaHfTi)C > (ZrNbTaHf)C > (ZrNbTaHfTiV)C. Thus, the addition of Hf, Ti, and V atoms to (ZrNbTa)C may decrease the twinning probability. This study may be used as a guide for the design of twinning-induced plasticity HETMCs with excellent mechanical properties.     

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.     

Fabrication of high-entropy carbide ceramics (Ti,Zr,Hf,Nb,Ta)C through low-temperature calcium-hydride reduction of oxides

High-entropy carbides (HECs) are paid great attention owing to superior properties, and various fabrication methods have been used to date to produce high-quality material. Here, a novel approach, in the case of HECs, is used to prepare powder and bulk (Ti,Zr,Hf,Nb,Ta)C: the calcium-hydride reduction (CHR) of oxides, followed by pressureless sintering (PS) and spark plasma sintering (SPS). The material obtained is characterized via TEM, SEM, and XRD. It has been shown that the CHR provides the formation of the nano-sized powder with a multiphase structure consisting of binary carbides. Subsequent PS and SPS lead to the formation of a single-phase structure; however, porosity differs significantly. As a bulk state, (Ti,Zr,Hf,Nb,Ta)C exhibits typical high hardness (20.4 GPa) and good fracture toughness (4.2 MPa∙m^1/2). The results have shown that calcium-hydride reduction process, with proper development, can provide a new cost-effective technology for the synthesis of nano and submicron powders of high-entropy carbides.     

Processing of dense high-entropy boride ceramics

Dense (Hf_0.2,Zr_0.2,Ti_0.2,Ta_0.2,Nb_0.2)B₂ high-entropy ceramics with high phase purity were produced by two-step spark plasma sintering of precursor powders synthesized by boro/carbothermal reduction of oxides. The reacted powders had low oxygen (0.404 wt%) and carbon (0.034 wt%) contents and a sub-micron average particle size (∼0.3 μm). Powders were synthesized by optimizing the excess B₄C content of the reaction mixture and densified by a two-step spark plasma sintering process. The relative density increased from 98.9% to 99.9% as the final sintering temperature increased from 2000 °C to 2200 °C. The resulting ceramics were nominally single-phase (Hf,Zr,Ti,Ta,Nb)B₂ with oxygen contents as low as 0.004 wt% and carbon as low as 0.018 wt%. The average grain size increased from 2.3 ± 1.2 μm after densification at 2000 °C to 4.7 ± 1.8 μm after densification at 2100 °C, while significant grain growth occurred during sintering at 2200 °C. The high relative densities, low oxygen and carbon contents, and fine grain sizes achieved in the present study were attributed to the use of synthesized precursor powders with high purity and fine particle size, and the two-step synthesis-densification process. These are the first reported results for dense high-entropy boride ceramics with high purity and fine grain size.     

Compositional pathways and anisotropic thermal expansion of high-entropy transition metal diborides

The recent discovery of high entropy transition metal diborides (HEBs) has sparked renewed interest in ultra-high temperature ceramics (UHTCs). Presently, transition metal (Me) oxides based boro-carbo/thermal reduction (BCTR) syntheses show great promise as relatively cheap production methods, but also may present limits to attain single phase pure HEBs. Herein, by selectively tuning the concentration of boron and carbon, the reducing agents of Me oxide mixture (Me = Ti, Ta, Nb, Zr and Hf), and exploiting high-resolution synchrotron X-ray powder diffraction, we first identified and quantified the formation of intermediate phases during the BCTR synthesis, with the ultimate intent to achieve a full dense (Ti,Ta,Nb,Zr,Hf)B₂ solid solution (SS). Additional insight was obtained by temperature dependent diffraction, which highlighted, for the first time in this class of materials, anisotropic thermal expansion, most likely at the origin of the SS micro-cracking, as was also observed by electron microscopy.     

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.     

Synthesis of all equiatomic five-transition metals High Entropy Carbides of the IVB (Ti,Zr, Hf) and VB (V,Nb, Ta) groups by a low temperature route

The six possible equiatomic five-transition metal High Entropy Carbides (HECs) of the IVB (Ti, Zr, Hf) and VB (V, Nb, Ta) groups of the periodic table, i.e., TiZrHfVNbC₅, TiZrHfVTaC₅, TiZrHfNbTaC₅, TiZrVNbTaC₅, TiHfVNbTaC₅ and ZrHfVNbTaC₅, were successfully obtained via a powder metallurgy route at room temperature, specifically, by one-step diffusion mechanosynthesis starting from the elemental constituents (using graphite as the carbon source). Three of those HECs, TiZrHfVTaC₅, TiZrVNbTaC₅ and ZrHfVNbTaC₅, were developed for the first time. Their development was possible without any subsequent thermal treatment, in contrast to the usual way (reactive sintering at 1800–2200 °C), and in a powder form, make them potential advanced raw ceramics for hard, refractory and oxidation resistance coatings or matrix phase composites.     

Effects of Ti,Y, and Hf additions on the thermal properties of ZrB2

Reactive hot pressing was utilized to synthesize and densify four ZrB₂ ceramics with impurity contents low enough to avoid obscuring the effects of dopants on thermal properties. Nominally pure ZrB₂ had a thermal conductivity of 141 ± 3 W/m K at 25 °C. Additions of 3 at% of Ti, Y, or Hf decreased the thermal conductivity by 20 %, 30 %, and 40 %, respectively. The thermal conductivity of (Zr,Hf)B₂ was similar to ZrB₂ synthesized from commercial powders containing the natural abundance of Hf as an impurity. This is the first study to demonstrate that Ti and Y additions decrease the thermal conductivity of ZrB₂ ceramics and report intrinsic values for thermal conductivity and electrical resistivity of ZrB₂ containing transition metal additions. Previous studies were unable to detect these effects because the natural abundance of Hf present masked the effects of these additions.     

Low-temperature sintered (Ti,Zr, Nb,Ta, Mo)C-based composites toughened with damage-free SiCw

The high sintering temperature would have a great tendency to damage the morphology and thus properties of the silicon carbide whisker (SiC_w) in high entropy carbide-silicon carbide whisker (HEC-SiC_w) composites, which, in turn, would impact the effectiveness of the operative toughening mechanisms. The objective of this study was to achieve full contributions to the toughening effects of SiC_w by preparing (Ti, Zr, Nb, Ta, Mo)C-SiC_w composites at low temperature (1600 ℃) using cobalt as additives. Results showed that the fracture toughness of the (Ti, Zr, Nb, Ta, Mo)C bulk reinforced with 20 vol% SiC_w and 5 vol% Co was 7.2 MPa?m^1/2, which was much higher than that of the (Ti, Zr, Nb, Ta, Mo)C bulk only sintered with 5 vol% Co (3.4 MPa?m^1/2). Meanwhile, it was also higher than that of the reported HEC-20 vol% SiC_w composite sintered at 2000 ℃ (4.3 MPa?m^1/2). For the fracture toughness of HEC-SiC_w composites, it was significantly increased by the introduction of damage-free SiC_w.