Surface energies in high-entropy carbides with variable carbon stoichiometry

The carbon vacancy in high-entropy carbides (HECs) has a significant impact on their physical and chemical properties, yet relevant studies have still been relatively few. In this study, we investigate the surface energies of HECs with variable carbon vacancies through first-principles calculations. The results show that the surface energy of the (1 0 0) surface of the stoichiometric HECs is significantly lower than that of (1 1 1) surface. With the decrease in carbon stoichiometry, the surface energies of both (1 0 0) and (1 1 1) surfaces increase gradually, which is mainly due to the weakening of covalent bonding and the decrease of metal Hirshfeld-I (HI) charges. However, the surface energy of (1 0 0) surface increases more quickly than that of (1 1 1) surface and will exceed that of (1 1 1) surface when the carbon stoichiometry decreases to a certain extent, which is primarily attributed to the greater decrease rate of metal HI charges of (1 0 0) surface.     

Elemental analysis of cemented carbides by calibration-free portable laser-induced breakdown spectroscopy

The process of cemented carbides manufacturing requires rapid and field elemental analytical techniques to control and evaluate the properties of products. Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) is such a potential elemental analytical technique. In this work, a portable LIBS instrument combined with a CF method was developed for the analysis of cemented carbides. Three batches of cemented compact carbides without reference samples were analyzed. Qualitative and quantitative analysis of the samples were achieved by using the portable LIBS instrument combined with CF method. To validate the analysis results, X-ray fluorescence spectrometry (XRF) was used to analyze the samples as well. The results of CF-LIBS agreed well with the results of XRF, with relative errors between ?29.53 and 24.70%. The results demonstrated that the portable LIBS instrument combined with CF method was capable for direct and rapid analysis without any need of standard measurements. Notably, with the portable LIBS instrument combined with CF method, acceptable accuracy could be obtained, which is promising for practical field applications.     

A first-principles investigation on mechanical and metallic properties of titanium carbides under pressure

The titanium carbides are potential candidates to achieve both high hardness and refractory property. We carried out a structural search for titanium carbides at three pressures of 0 GPa, 30 GPa and 50 GPa. A phase diagram of the Ti-C system at 0 K was obtained by elucidating formation enthalpies as a function of compositions, and their mechanical and metallic properties of titanium carbides were investigated systematically. We also discussed the relation of titanium concentration to the both mechanical and metallic properties of titanium carbides. It has been found that the average valence electron density and tractility improved at higher concentrations of titanium, while the degree of covalent bonding directionality decreased. To this effect, the hardness of titanium carbide decreases as the content of titanium increases. Our results indicated that the titanium content significantly affected the metallic properties of the Ti-C system.     

In-situ observation of interaction between precipitates and austenite during δ→γ phase transformations

The δ-ferrite to γ-austenite phase transformation in duplex stainless steels was observed using ultra high-temperature confocal laser scanning microscope, and the orientation relationship between the γ phase, and precipitate is discussed. Owing to mutual promotion action, the γ phase was observed at δ/δ grain boundary at the beginning of δ-ferrite→γ-austenite transformation, followed by two-dimensional γ-phase growth at the same speed (0.625?µm?s^?1) along the grain boundary and into the δ grain matrix. The γ-phase growth rate decreases to 0.244?µm?s^?1 when precipitate stops growing. In the process of grain growth at high temperature, the precipitated pinning grain boundary will slow the movement speed of the grain boundary.

The mutual promotion action leads to preferential nucleation of the γ phase, and the nucleation and growth of the austenite also promoting the growth of MnS the growth.     

Effect of residual excess carbon on the densification of ultra-fine HfC powder

The residual carbon content of ultra-fine hafnium carbide (HfC) powder was controlled by the optimization of the synthesis process, and the effect of residual carbon on the densification of HfC powder was analyzed. The amount of residual carbon in the HfC powder could be reduced by the de-agglomeration of HfO₂ powder before the carbo-thermal reduction (CTR) process. The average particle size of HfO₂ powder decreased from 230 to 130 nm after the de-agglomeration treatment. Ultra-fine (d₅₀: 110 nm) and highly pure (metal basis purity: >99.9 % except for Zr) HfC powder was obtained after the CTR at 1600 °C for 1 h using the C/Hf mixing ratio of 3.3. In contrast, the C/Hf ratio increased to 3.6 without the de-agglomeration treatment, indicating that a large amount of excess carbon was required for the complete reduction of the agglomerated HfO₂ particles. HfC ceramics with high relative density (>98 %) were obtained after spark plasma sintering at 2000 °C under 80 MPa pressure when using the HfC powder with low excess carbon content. In contrast, the densification did not complete at a higher temperature (2300 °C) and pressure (100 MPa) when the HfC powder contained a large amount of residual carbon. The results clearly indicated that residual carbon suppressed the densification of HfC powder in case the carbide powder had low oxygen content, and the residual carbon content could be controlled by the optimization of the synthesis process. The average grain size and Vickers hardness of the sintered specimen were 6.7(±0.7) μm and 19.6 GPa, respectively.     

Thermophysical and mechanical properties of novel high-entropy metal nitride-carbides

In this work, a novel (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)(N_0.5C_0.5) high-entropy nitride-carbide (HENC-1) with multi-cationic and -anionic sublattice structure was reported and their thermophysical and mechanical properties were studied for the first time. The results of the first-principles calculations showed that HENC-1 had the highest mixing entropy of 1.151R, which resulted in the lowest Gibbs free energy above 600 K among HENC-1, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)N high-entropy nitrides (HEN-1), and (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy carbides (HEC-1). In this case, HENC-1 samples were successfully fabricated by hot-pressing sintering technique at the lowest temperature (1773 K) among HENC-1, HEN-1 and HEC-1 samples. The as-fabricated HENC-1 samples showed a single rock-salt structure of metal nitride-carbides and high compositional uniformity. Meanwhile, they exhibited high microhardness of 19.5 ± 0.3 GPa at an applied load of 9.8 N and nanohardness of 33.4 ± 0.5 GPa and simultaneously possessed a high bulk modulus of 258 GPa, Young's modulus of 429 GPa, shear modulus of 176 GPa, and elastic modulus of 572 ± 7 GPa. Their hardness and modulus are the highest among HENC-1, HEN-1 and HEC-1 samples, which could be attributed to the presence of mass disorder and lattice distortion from the multi-anionic sublattice structure and small grain in HENC-1 samples. In addition, the thermal conductivity of HENC-1 samples was significantly lower than the average value from the “rule of mixture” between HEC-1 and HEN-1 samples in the range of 300-800 K, which was due to the presence of lattice distortion from the multi-anionic sublattice structure in HENC-1 samples.     

A facile pathway to prepare molybdenum boride powder from molybdenum and boron carbide

Molybdenum boride is an ideal hard and wear-resistant material. In this study, a new method is proposed for preparing molybdenum boride, by which Mo first reacts with B₄C to generate the mixture of molybdenum boride and C, and then the product is decarburized by molten Ca to generate CaC₂. Pure molybdenum boride could be obtained after acid leaching to remove the by-product CaC₂. According to the experimental and thermodynamic calculation results, it is concluded that the single-phase MoB could be successfully prepared, while Mo₂B, Mo₂B₅, and MoB₄ could not be synthesized by this method. Moreover, it was found that the particle size of finally prepared MoB is determined by particle size of raw Mo powder. The residual carbon content of the product could be decreased to 0.10 wt% after first reaction at 1673 K for 6 hours and then decarburization reaction at 1673 K for 6 hours.     

Effect of S on H-induced grain-boundary embrittlement in γ-Fe by first-principles calculations

The effect of interstitial impurities (H and S) on the atomic, electronic structure, and mechanical properties of the γ-Fe Σ5 (021) grain boundary (GB) was investigated via first-principles calculations. H atoms act as an intergranular embrittler in the Σ5 GB due to a reduction in the charge density between the Fe atoms connected to the grains, whereas H and S co-segregation produces more pronounced embrittlement behavior, resulting in intergranular fracture. The S-induced embrittlement plays a crucial role in the H and S segregation, due to a combination of the structural and chemical effects. The fracturing of Σ5 GB due to S and H segregation is a two-step process. The first step is the breaking of Fe–Fe bonds in the GB, followed by the breaking of the remaining Fe–S bonds in the second step, resulting in the complete separation of the two grains. Moreover, the S atom can slightly compensate for the embrittlement induced by H, because some of the Fe atoms that obtain electrons from the S atoms can provide more electrons to the H atoms, and thus, they can compensate for the electrons that must be acquired from other Fe atoms. We call this “the electrons compensating effect” and this effect is helpful in the design and alloying of steels that are resistant to H embrittlement.     

稀土优化WC—Co硬质合金强韧性机理

探讨了稀土强化ＷＣ－Ｃｏ硬质合金的机理。结果表明，适量添加稀土氧化物或混合稀土氧化物均能有效提高ＷＣ－Ｃｏ硬质合金的强韧性；稀土能明显提高ＷＣ－Ｃｏ合金制品的表面宏观压应力：鉴于未加稀土的普通ＷＣ－Ｃｏ合金室温下ｈｃｐ型γ相的固有比例通常就很少，加稀土阻止γ相的ｆｃｃ→ｈｃｐ相变对合金强韧性的优化作用甚微；稀土氧化物对ＷＣ－８Ｃｏ硬质合金显微结构无明显影响，也不引起钨溶质对γ相的附加固溶强化效果。