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.     

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.     

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.     

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.     

Preparation of SiC from acid‐leached coal gangue by carbothermal reduction

For the comprehensive utilization of coal gangue, acid‐leached coal gangue was used as silicon source and part of carbon source, low ash anthracite and degreasing cotton were added respectively as supplementary carbon source, SiC and SiC fiber were prepared by carbothermal reduction method accordingly. The results show that the main components in leached coal gangue are amorphous SiO₂ and carbon, which are suitable for the synthesis of SiC as raw materials. The synthesis temperature and holding time have important influence on the synthesis of SiC, and the optimum synthesis parameters for SiC are at 1550°C for 4 hours; under this condition, the yield of SiC is 78.27%, and the specific surface area is 6750 cm²/g. The results show that the resulting products are essentially composed of β‐SiC with a minor amount of α‐SiC. Besides, based on the carbon fiber transformation method, SiC fiber was prepared by using leached coal gangue and degreasing cotton as raw materials. Therefore, it can be concluded that leached coal gangue is a very effective and inexpensive source for preparing SiC, and more importantly, this work has important economic and social significance to realize waste recycling and control pollution.     

Influence of rare earth Tb4O7 addition on the densification,abrasion resistance and microstructure of alumina ceramics

This study aimed to improve the purity and performance of alumina ceramics used as ball milling media. High-alumina ceramics (>?96?wt% Al₂O₃), with high densification and excellent abrasion resistance, were fabricated by the cold isostatic pressing method. The effects of adding the rare earth Tb₄O₇ on the densification, abrasion resistance, crystalline phase, micro-morphology and grain size of the ceramics were studied. The experiment results showed that the densification and abrasion resistance of the samples increased with Tb₄O₇ addition. The sample with 0.8?wt% Tb₄O₇ sintered at 1625?°C exhibited the best performance, with a linear shrinkage, relative density and abrasion rate of 22.28%, 95.70% and 0.103‰^, respectively. The abrasion resistance improved by 27.5% compared with the sample without Tb₄O₇. X-ray diffraction analysis indicated that the primary phases of the samples were corundum, spinel, CaAl₁₂O₁₉ and α-quartz, and a small quantity of Tb₃Al₅O₁₂ was generated when more than 0.4?wt% Tb₄O₇ was added. Furthermore, some Mg²⁺ and Ca²⁺ ions in the liquid phases dissolved into Tb₃Al₅O₁₂ crystalline grains during the sintering process, which enhanced the grain boundary cohesion of the materials. Scanning electron microscopy indicated that the existence of Tb₃Al₅O₁₂ at grain boundaries reduced the average size of the corundum grains. This helped transform inter-granular fractures into trans-granular fractures, thereby improving the abrasion resistance of the ceramic materials.     

Effect of the addition of polyvinylpyrrolidone as a pore-former on microstructure and mechanical strength of porous alumina ceramics

The effect of the solvent on the properties of porous alumina ceramics was studied when polyvinylpyrrolidone (PVP) was used as an organic pore-former. In particular, porous alumina ceramics were produced by dry-pressing of mixed PVP–alumina powder; the mixing of PVP and alumina powder was achieved via ball milling using water or acetone as solvent, or dry ball milling. Due to the different solubility of PVP in water and acetone, porous alumina ceramics with different pore structures and mechanical properties were obtained. Because of its cylindrical pores being aligned to some extent, the sample prepared using acetone as solvent exhibited the highest bending strength (140.2 MPa) and Young's modulus (57.4 GPa), which were 1.6 times and 3.4 times higher compared to that prepared without PVP. Moreover, the addition of PVP via wet ball milling led to more uniform dispersion of PVP in alumina, hence limiting the grain growth during sintering process and increasing the grain bonding.     

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.     

Mechanical behaviour of reaction processed SiC ceramics from artificial precursor from plant

Mechanical behaviour of SiC ceramics synthesized from two artificial precursors from plants – coir fibreboard and bamboo pulp fibreboard – was studied and the mechanical properties – flexural strength, Young's modulus, fracture toughness and hardness – of the ceramics synthesized from the two kinds of artificial precursors were compared. The effect of processing of the artificial precursors, as reflected in the microstructure of the ceramics synthesized from them, was taken into consideration in the analysis of the mechanical property data; these data could also be possible to be explained by the empirical models of fracture mechanics. The results of the study established the possibility of application of the investigated SiC materials as structural ceramics.     

Pressureless sintering and properties of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics: The effect of pyrolytic carbon

A novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy ceramic was successfully prepared by pressureless sintering at 2200 °C. With increasing content of resin-derived-carbon, the density, and mechanical and thermal properties increased up to a maximum content of 2～4 wt% resin addition, after which further addition was detrimental. All specimens showed high strength (≥347±36 MPa), with the highest value achieving 450±64 MPa, and fracture toughness significantly higher (>20 %) than those of the corresponding monocarbides and Ta_0.5Hf_0.5C, (Ta_1/3Zr_1/3Nb_1/3)C. The thermal conductivity was approximately equivalent to the lowest value of the corresponding mono-carbides, which was assumed to be due to the lattice distortion effect.     

A novel aerogels/porous Si3N4 ceramics composite with high strength and improved thermal insulation property

A novel ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite with high strength, low density, good dielectric properties and low thermal conductivity was synthesized by filling ZrO₂-SiO₂ aerogels into the porous Si₃N₄ ceramics through vacuum sol-impregnating. The effects of aerogels on the microstructure and properties of composite were discussed. The results show that aerogels could form a mesoporous structure and significantly decrease the thermal conductivity from 9.8 to 7.3 W m^?1 K^?1. Meanwhile, the density, mechanical and dielectric properties of the porous Si₃N₄ ceramics could not be affected after introducing ZrO₂-SiO₂ aerogels. The composite exhibits high porosity (62.6%), high flexural strength (53.86 MPa) and low dielectric constant (2.86). The ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite shows great potential as radome materials applied in the fields of aerospace.     

TiO2和CaO-Al2O3-SiO2复合烧结助剂对刚玉陶瓷烧结的影响

在以α-Al2O3为原料的刚玉陶瓷配料中,分别添加0、0.15%、0.30%、0.45%、0.60%的TiO2和0、0.5%、1.0%、2.0%、4.0%的CaO-Al2O3-SiO2(CAS)玻璃,共组合出25组试验配方,以150MPa压力干压成型为45mm×5mm×4mm的试样,烘干后以5℃.min-1的升温速率升至1550℃保温2h烧成,然后检测烧后试样的相对密度、常温抗折强度和断裂韧性,并用扫描电镜观察烧后试样的显微结构。结果表明:引入TiO2能显著提高刚玉陶瓷的烧结致密化速率,但是引起晶粒的异向生长和异常长大,并使其断裂方式以沿晶断裂为主,试样力学性能也普遍较低;引入少量的CaO-Al2O3-SiO2易引起样品反致密化,只有CaO-Al2O3-SiO2的引入量大于1.3%才能有效地促进刚玉陶瓷的烧结,并抑制由0.6%的TiO2引起的严重的晶粒异向生长和异常长大,使材料的断裂方式向穿晶断裂转变,并使其力学性能逐渐回升。     

Biomorphic silicon/silicon carbide ceramics from birch powder

A novel process has been developed for the fabrication of biomorphic silicon/silicon carbide (Si/SiC) ceramics from birch powder. Fine birch powder was hot-pressed to obtain pre-templates, which were subsequently carbonized to acquire carbon templates, and these were then converted into biomorphic Si/SiC ceramics by liquid silicon infiltration at 1550 °C. The prepared ceramics are characterized by homogeneous microstructure, high density, and superior mechanical properties compared to biomorphic Si/SiC ceramics from birch blocks. Their maximum density has been measured as 3.01 g/cm³. The microstructure is similar to that of conventional reaction-bonded silicon carbide. The Vicker's hardness, flexural strength, elastic modulus, and fracture toughness of the biomorphic Si/SiC were 19.6 ± 2.2 GPa, 388 ± 36 MPa, 364 ± 22 GPa, and 3.5 ± 0.3 MPa m^1/2, respectively. The outstanding mechanical properties of the biomorphic Si/SiC ceramics are assessed to derive from the improved uniform microstructure of the pre-templates made from birch powder.     

Novel high-entropy microwave dielectric ceramics Sr(La0.2Nd0.2Sm0.2Eu0.2Gd0.2)AlO4 with excellent temperature stability and mechanical properties

Novel high-entropy Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ ceramics with a layered perovskite structure have been prepared via the standard solid-state reaction method. The design of high-entropy improves the bond valence and subsequently optimizes the large negative temperature coefficient of resonant frequency (τ_f = ?32 ppm/°C) of the simple SrLaAlO₄ ceramics. Excellent temperature stability (τ_f = ?6 ppm/°C) together with a relative permittivity (ε_r) of 18.6 and a quality factor (Qf = 14,509 GHz) are obtained in Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ ceramics sintered at 1475 °C. It indicates that the present ceramics have great application prospects in passive microwave components such as resonators and filters. Meanwhile, significant improvements in compressive strength and strain are achieved, which are 1040 MPa and 15.7% for Sr(La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)AlO₄ compared to 583 MPa and 12% in SrLaAlO₄. The enhanced mechanical properties originate from the dislocation strengthening mechanism as the intertwining of interlayer lattices is revealed from the high-resolution transmission electronic micrographs.