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.     

Synthesis of Hf6Ta2O17 superstructure via spark plasma sintering for improved oxidation resistance of multi-component ultra-high temperature ceramics

Ultra-high temperature ceramics (UHTCs) have shown aspiration to overcome challenges in the thermal protection system (TPS) by designing new materials referred to as multi-component UHTCs (MC-UHTCs) in the compositional space. MC-UHTCs have shown remarkable improvement in oxidation resistance due to the formation of the Hf₆Ta₂O₁₇ superstructure during plasma exposure. Herein, the Hf₆Ta₂O₁₇ superstructure is synthesized via a solid-state reaction between HfO₂ and Ta₂O₅ powder mixtures during spark plasma sintering (SPS). The compositions chosen are 50 vol% of HfO₂ -50 vol% of Ta₂O₅ (50HO-50TO) and 70 vol% of HfO₂ -30 vol% of Ta₂O₅ (70HO-30TO). The phase quantification via Rietveld analysis showed Hf₆Ta₂O₁₇ as a principal phase with some residual Ta₂O₅ phase in both the samples. The high-temperature thermal stability of the samples was evaluated using high-velocity plasma jet exposure for up to 3 min. 50HO-50TO was able to withstand the intense plasma condition, which is attributed to the higher content of the Hf₆Ta₂O₁₇ phase (～84%) and lower strain in the Ta₂O₅ phase. The augmentation in the Hf₆Ta₂O₁₇ phase to 94.7% (in 50HO-50TO) post plasma exposure has been attributed to the invariant transformation from a liquid state to Hf₆Ta₂O₁₇ at temperatures >2500 °C during testing. The mechanical integrity is elucidated from the insignificant change in the hardness ～13.3 GPa before and 11.2 GPa after plasma exposure of the 50HO-50TO sample. As a result, the Hf₆Ta₂O₁₇ superstructure's thermo-mechanical stability suggests developing novel oxidation-resistant MC-UHTCs in compositional space for reusable space vehicle applications.     

Production and characterization of spark plasma sintered (Ti,Nb)B2 solid solutions with graphene nanoplatelets and hexagonal boron nitride

For this study, (Ti,Nb)B₂ solid solutions were consolidated by spark plasma sintering. In addition, (Ti,Nb)B₂ with graphene nanoplatelets (GNPs) and hexagonal boron nitride (h-BN) were produced to evaluate the potential of the new structural materials. The phase formation, microstructure, mechanical properties, oxidation resistance and room temperature reflectance, and absorbance features of (Ti,Nb)B₂ were investigated. X-ray diffraction and Transmission electron microscopy observations showed that a complete solid solution phase was formed when the samples were sintered at 1850 °C for 5 min under 50 MPa. Ti_0.75Nb_0.25B₂ exhibited a relative density of ～98.6%, a hardness of ～20.5 GPa, and an indentation fracture toughness of ～3.4 MPa·m^1/2. It was found that the presence of 1 vol% h-BN as an additive enhanced the hardness (～10%) and fracture toughness (～30%) of Ti_0.75Nb_0.25B₂ by activating toughening mechanisms. The GNP added Ti_0.75Nb_0.25B₂ proved to have better oxidation resistance and optical absorbance than the other materials used in the study.     

The microstructure,formation mechanism and sintering characteristics of Al2O3/ZrO2 supersaturated solid solution powders

In this study, the Al₂O₃/ZrO₂ supersaturated solid solution powders with different ZrO₂ contents were successfully synthesized by a novel combustion synthesis combined with water cooling (CS-WC) method. The solid solubility and formation mechanism of solid solution under the extremely non-equilibrium solidification condition were discussed in details. The ultra-high cooling rate greatly improves the solubility limit of Al₂O₃ in ZrO₂. When ZrO₂ content is 30 mol%, the Al₂O₃ has been almost dissolved into the ZrO₂ lattice. The formation mechanism of solid solution can be attributed to solute interception caused by the huge degree of supercooling. During the sintering process, the solid solution powders precipitate ZrO₂ particles and the Al₂O₃ matrix, which forms a fine and uniform nanostructure. Due to the synergistic effect of t-m phase transformation toughening and ZrO₂ nanoparticles toughening, the Al₂O₃/ZrO₂ nanoceramics exhibit excellent mechanical properties when ZrO₂ contents are at the range of 25–37 mol%.     

Effect of tantalum solid solution additions on the mechanical behavior of ZrB2

Mechanical properties and microstructure were compared for zirconium diboride and two zirconium diboride solid solutions containing 3 and 6 at% tantalum diboride. X-ray diffraction indicated that the ceramics were nearly phase-pure and that tantalum dissolved into the ZrB₂ lattice to form (Zr,Ta)B₂ solid solutions. Microstructural analysis indicated that samples achieved nearly full relative density with average grain sizes that ranged from 3?5 μm. The three compositions had similar values of Young’s modulus (510?531 GPa), shear modulus (225?228 GPa), Vickers hardness (15.2–16.4 GPa), and flexural strength (391?452 MPa). Fracture toughness ranged from 2.6 to 3.7 MPa m^1/2 and with increasing tantalum content, the fracture mode changed from predominantly intergranular to predominantly transgranular. Diboride solid solution materials had comparable properties to the single metal diboride, but differences in microstructure, secondary phases, and strain state among the three ceramics partially obscured the actual effects of the solid solution on fracture behavior.     

Preparation of (Tb1-xLux)2O3 transparent ceramics by solid solution for magneto-optical application

Novel (Tb_1-xLu_x)₂O₃ magneto-optical transparent ceramics were prepared through a solid-solution method via vacuum pre-sintering followed by hot isostatic pressing (HIP). The Lu-containing samples were solid-solution phases between Tb₂O₃ and Lu₂O₃, which effectively stabilized the phase transition of Tb₂O₃ during the sintering process. A typical component of (Tb_1-xLu_x)₂O₃ ceramic with x = 0.5 was selected to study the densification behavior and microstructure evolution in detail. The polished (Tb_0.5Lu_0.5)₂O₃ ceramics with a thickness of 3 mm vacuum pre-sintered at 1700 °C under 1.0 × 10^?3 Pa combined with HIP post-treatment at 1600 °C showed good magneto-optical property. The Verdet constant measured at 633 nm was -224.33 rad·T^?1 m^?1, 30% higher than that of Tb₃Al₅O₁₂ (TAG). However, the in-line transmittance was 73.6% at 633 nm, lower than that of TAG. The (Tb_1-xLu_x)₂O₃ ceramics will be a promising material for Faraday devices after further improving the optical quality.     

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.     

Synthesis and spark plasma sintering of sub-micron HfB2: Effect of various carbon sources

The present work describes a simple process to synthesise HfB₂ powder with sub-micron sized particles. Hafnium chloride and boric acid were used as the elemental sources whilst several carbon sources including sucrose, graphite, carbon black, carbon nanotubes and liquid and powder phenolic resin were used. The carbon sources were characterised using thermogravimetric analysis and transmission electron microscope. The mechanism by which the structure of the carbon source used, affects the size and morphology of the resultant HfB₂ powder was studied; the HfB₂ powders were characterised using X-ray diffraction and scanning and transmission electron microscopy. The powder synthesised using powder phenolic resin had a surface area of 21 m² g⁻¹ and a particle size distribution between 30 and 150 nm. This was sintered using SPS to a relative density of 94% of theoretical density (TD) at 2100 °C and 50 MPa pressure without the help of any sintering aids.     

Mechanical properties and grain orientation evolution of zirconium diboride-zirconium carbide ceramics

The effect of ZrC on the mechanical response of ZrB₂ ceramics has been evaluated from room temperature to 2000 °C. Zirconium diboride ceramics containing 10 vol% ZrC had higher strengths at all temperatures compared to previous reports for nominally pure ZrB₂. The addition of ZrC also increased fracture toughness from $～3\text{.5}\text{MPa}\sqrt{\text{m}}$ for nominally pure ZrB₂ to $～4\text{.3}\text{MPa}\sqrt{\text{m}}$ due to residual thermal stresses. The toughness was comparable with ZrB₂ up to 1600 °C, but increased to $4\text{.6}\text{MPa}\sqrt{\text{m}}$ at 1800 °C and 2000 °C. The increased toughness above 1600 °C was attributed to plasticity in the ZrC at elevated temperatures. Electron back-scattered diffraction analysis showed strong orientation of the ZrC grains along the [001] direction in the tensile region of specimens tested at 2000 °C, a phenomenon that has not been observed previously for fast fracture (crosshead displacement rate = 4.0 mm min^?1) in four point bending. It is believed that microstructural changes and plasticity at elevated temperature were the mechanisms behind the ultrafast reorientation of ZrC.     

Host lattice and solid solution formation in an octal-cation (NbTaZrTiHfVWMo)C high entropy carbide ceramic

High entropy carbide ceramics (HECCs) exhibit property peculiarity, such as higher hardness and higher toughness than conventional binary counterparts. The cation-sites of HECCs consist of 4 or more types of transitional metals with equiatomic ratios. Our work advocates that the individual constituent carbide in HECCs cannot be treated equally; instead, one serves as the host lattice and other metallic elements occupy its cation-site lattice substitutionally. urging sintering before the completion of solid solution, individual carbides tend to bind with each other to form a variety of intermediate products. Specifically, in the octal-cation (NbTaZrTiHfVWMo)C carbide, TaC serves as the host lattice and a few intermediate products, such as (Zr,Hf)C and (Ti,V,W,Mo)C, formed. A dense and single-phase carbide can be obtained through sintering at a low temperature of 2000°C and the so-obtained carbide has a nanohardness of 38.71 GPa and a fracture toughness of ∼ 4.67 MPa·m^1/2, outweighing a majority of the existing carbides.     

Synthesis of (Fe,Cr)2O3 solid solution pigment powders for ink application

Iron chromite pigment was synthesized via solution combustion using iron(III) nitrate nonahydrate and chromium(III) nitrate nonahydrate as starting materials, and glycine, urea, citric acid, and ethylene glycol as fuels. The effect of postheating temperature on the structure, microstructure, and chromatic properties of the synthesized powders was also studied. X-ray diffraction patterns showed that the as-synthesized powders were amorphous to crystalline FeCr₂O₄ phases, depending on fuel type. Moreover, regardless of the fuel type, postheating led to the d-space shift and oxidation and formation of (Fe,Cr)₂O₃ solid solution. Phase transformation of FeCr₂O₄ to (Fe,Cr)₂O₃ solid solution was observed at 500/750°C depending on the dominant phase present in the as-synthesized particles. Fourier transform infrared analysis illustrated a shift in the band position of octahedral M–O and tetrahedral M–O bonds due to the movement of Fe cations and the lattice shrinkage by increasing the postheating temperature. Moreover, scanning electron micrographs showed that Fe_0.7Cr_1.3O₃ semispherical fine particles consisted mainly of porous and spongy FeCr₂O₄ particles due to the oxidation and phase transformation during postheating. According to chromatic measurements, the ink prepared by using the powders synthesized in the presence of glycine and post-heated at 500°C showed reddish-brown color which could be considered a promising candidate for tile decoration application. Furthermore, rheology studies revealed that the prepared ink showed non-Newtonian shear thinning behavior.     

Synthesis and properties of (Hf1-xTax)C solid solution carbides

Thermodynamically stable (Hf_1–xTa_x)C (x?=?0.1–0.3) compositions were selected by First Principle Calculation and synthesized in nanopowders via high-energy ball milling and carbothermal reduction of commercial oxides at 1450?°C. The formation of a solid solution during powder synthesis was investigated. The solid solution carbide powders were sintered at 1900?°C by spark plasma sintering without a sintering aid. As a result, the (Hf_1–xTa_x)C solid solution carbides exhibited high densities, excellent hardness and fracture toughness (ρ: 98.7–100.0%, HVN: 19.69–19.98?GPa, K_IC: 5.09–5.15?MPa?m^1/2) compared with previously reported HfC and HfC–TaC solid solution carbides.     

Cu掺杂对Ce-Zr-O2固溶体结构及催化性能的影响

用反相微乳法法制备掺杂Cu2 的Ce-Zr-O2固溶体,利用X-射线粉末衍射法(XRD)和扫描电镜(SEM)对其进行了表征。结果表明,Ce-Zr-O2固溶体掺杂Cu2 形成的Ce0.45Zr0.45Cu0.1O2具有与CeO2相似的立方晶型,经1 000℃高温处理后,此晶体结构未发生变化。与未掺杂Cu2 的Ce-Zr-O2固溶体相比较,Ce0.45Zr0.45Cu0.1O2对甲苯完全氧化反应具有较高的催化活性。当反应温度达到550℃时,甲苯蒸汽能够在Ce0.45Zr0.45Cu0.1O2催化作用下全部转化为CO2,显示了良好的低温燃烧催化性能。经800℃和1 000℃高温热处理,仍具有较好的耐热稳定性。     

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.     

High-temperature oxidation behavior of monolithic Zr3[Al(Si)]4C6 and its composite incorporating 30vol% ZrB2-SiC: Providing a basis for broadening the service temperature

To provide a basis for the high-temperature oxidation of ultra-high temperature ceramics (UHTCs), the oxidation behavior of Zr₃[Al(Si)]₄C₆ and a novel Zr₃[Al(Si)]₄C₆-ZrB₂-SiC composite at 1500 °C were investigated for the first time. From the calculation results, the oxidation kinetics of the two specimens follow the oxidation dynamic parabolic law. Zr₃[Al(Si)]₄C₆ exhibited a thinner oxide scale and lower oxidation rate than those of the composite under the same conditions. The oxide scale of Zr₃[Al(Si)]₄C₆ exhibited a two-layer structure, while that of the composite exhibited a three-layer structure. Owing to the volatilization of B₂O₃ and the active oxidation of SiC, a porous oxide layer formed in the oxide scale of the composite, resulting in the degradation of its oxidation performance. Furthermore, the cracks and defects in the oxide scale of the composite indicate that the reliability of the oxide scale was poor. The results support the service temperature of the obtained ceramics.     

Spark plasma assisted carbothermal reduction-nitridation synthesis of (Ti,W, Mo)(C,N)-(Ni,Co) powders

Ultrafine (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders were rapidly synthesized from various metal oxides, mainly anatase-TiO₂, by spark plasma assisted carbothermal reduction-nitridation (SPCRN) at low temperature. The phase evolution of the SPCRN reaction was investigated using X-ray diffraction (XRD) and the microstructure of the product powders was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). NiO, Co₃O₄ and MoO₃ were converted to Ni, Co and Mo₂C by CR reaction at temperatures below 900 °C. WO₃ was successively transformed from W₂C to WC by CR reaction up to 1100 °C. Finally, at up to 1350 °C, (Ti, W, Mo)(C, N) formed into the sequence of TiO₂, Ti₄O₇, Ti₃O₅, Ti(O, N), Ti(C, N), (Ti, W)(C, N) and (Ti, W, Mo)(C, N). The crystal structure of (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders was analyzed by the Rietveld method and transmission electron microscopy (TEM). The findings demonstrated that the pure (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders with grain size of below 0.5 µm were synthesized from metal oxides by SPCRN reaction at 1400 °C for 10 min.     

Microstructure and mechanical properties of Ti(C,N)-based cermets fabricated by in situ carbothermal reduction of TiO2 and subsequent liquid phase sintering

Ti(C,N)-based cermets were prepared by in situ carbothermal reduction of TiO₂ and subsequent liquid phase sintering in one single process in vacuum. The densification behavior, phase transformation, and microstructure evolution of the cermets were investigated by DSC, XRD, SEM, and EDX. The results showed that the carbothermal reduction of TiO₂ was completed below 1250 °C, and Ti(C,N)-based cermets with refined grains were obtained after sintered at 1400 °C for 1 h by this method. The hard phase of the cermets mainly exhibited white core/gray rim structure, in great contrast to the typical black core/gray rim structure of hard phase in traditional cermets. Ti(C,N)-based cermets prepared by this novel method showed excellent mechanical properties with a transverse rupture strength of 2516±55 MPa, a Rockwell hardness of 88.6±0.1 HRA, and a fracture toughness of 18.4±0.7 MPa m^1/2, respectively.     

Ablation properties of C/C-UHTCs and their preparation by reactive infiltration of K2MeF6 (Me = Zr,Ti) molten salt

Ultra-high temperature ceramic-modified C/C composites (C/C-UHTCs) were prepared by the reactive infiltration of K₂MeF₆ (Me = Zr, Ti) mixed with Si and Zr-Si powders. Molten salt infiltration can be divided into two stages: salt ion melt and Me-Si alloy melt. In the temperature range below 1400 °C, Zr and Si dissolve in the molten salt, are carried by the ion melt, and precipitate at the PyC interface to form carbides. Above 1400 °C, a large amount of molten salt volatilises and thermally decomposes. The Me-Si alloy forms a melt and infiltrates the C/C matrix, and finally forms C/C-ZrC-SiC, C/C-Ti₃SiC₂-SiC, and C/C-ZrC-TiC-SiC composites. The C/C-ZrC-SiC composite with the highest ZrC content exhibited the lowest mass rate (2.6 ± 0.02 mg/s) and linear ablation rate (0.82 ± 0.04 μm/s), which were reduced by 43.5 and 50.8 %, respectively, compared to the unmodified C/C-ZrC-SiC composite.     

Formation of (Al2OC)1−x(AlN)x solid solution starting from Al–Si–Al2O3 powder matrix at 1300°C in flowing nitrogen

(Al₂OC)_1−x(AlN)_x solid solution-reinforced Si–Al₂O₃ composite was successfully synthesized by designed heating of the Al–Si–Al₂O₃ composite to 580°C and held for 8 hours, followed by heating to 1300°C at a rate of 12°C/h in flowing nitrogen. The reaction mechanism is as follows: after the Al–Si–Al₂O₃ composite is heated to 580°C and held for 8 hours, an AlN cladding is formed on the surface of the Al powder, thus the composite is preconverted into (Al–AlN cladding structure)–Si–Al₂O₃ system. With increasing temperature, the AlN cladding ruptures and the reactive Al(l) flows out. The Al(l) preferentially undergoes active oxidation to form metastable Al₂O(g), which lowers P_O2 inside the composite and inhibits the active oxidation of Si. Moreover, ultrafine carbon is produced by the pyrolysis of the phenolic resin binder. Both metastable Al₂O(g) and ultrafine carbon are highly reactive. Therefore, under the induction of AlN and N₂, (Al₂OC)_1−x(AlN)_x solid solution is formed by the reaction which easily occurs at a relatively low temperature. In the presence of a large amount of Al₂O(g), the P_O2 in the composite does not satisfy the condition required for both Si nitridation and active oxidation, so the free Si remains stable in the composite, forming a metal-non-oxide-oxide composite. The cold crushing strength of the composites is up to 305 MPa, and the composites do not show hydration after 20 months of storage in the environment.     

Enhanced properties of solid solution (CeZr)O2 modified with metal oxides for catalytic oxidation of low-concentration methane

The solid solution (CeZr)O2 catalyst was synthesized, and it was modified with metal oxides by incipient impreg-nation. Morphology and structure were characterized by X-ray diffraction, transmission electron microscope, ni-trogen ad/desorption and H2-temperature program reduction techniques. The catalytic properties of methane oxidation were also investigated. The results showed that solid solution possessed a mesoporous structure and exhibited excellent catalytic performance. The activity of solid solution was improved effectively by nickel dop-ing, and the optimal loading is 15 wt%. The stability of (CeZr)O2 and modified (CeZr)O2 indicated that the struc-ture of pristine solid solution played a key role in promoting molecules diffusion and spatial confining oxide particle sintering.