纳米碳化钒/碳化铬复合粉末的微波辅助高能球磨合成及其应用

以微米级氧化钒(V2O5)、氧化铬(Cr2O3)和纳米碳黑为原料，采用机械合金化及微波辅助加热法制备了纳米碳化钒/碳化铬复合粉末。利用XRD、XPS、TG-DSC、SEM、TEM和BET对产物进行了分析表征。结果表明，：纳米碳化钒/碳化铬复合粉末的最佳合成条件为：碳的质量分数为35%，反应温度为900℃，保温时间为1h。在该条件下的反应产物主要由V3Cr2C5、Cr2VC2和Cr3C2组成，颗粒为球形或类球形，分散性较好，无明显团聚现象，平均颗粒尺寸约为50nm，复合粉末的比表面积为115.53m2/g。添加纳米碳化钒/碳化铬复合粉末可以提高陶瓷结合剂cBN磨具的力学性能和磨削效率，降低磨具的损耗，并且对磨具具有减摩作用。     

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.     

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.     

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 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.     

退火工艺对采暖系统用耐沟状腐蚀钢带性能的影响

通过对耐沟状腐蚀现象的研究,结合生产设备能力,设计了6种成分钢带和6种退火工艺。借助光学显微镜、扫描电镜、拉伸试验、中性盐雾试验等手段,研究了采暖系统用耐沟状腐蚀钢带生产过程中冷轧退火工艺对其性能的影响。结果发现:低于Ac₁温度(650、700 ℃)的退火不可能改变原来冷轧铁素体晶界的遗传结构,冷轧α相的再结晶长大不充分,碳化物的聚合和长大过程也不充分;当退火温度达到Ac₁左右(750 ℃),由于碳元素的固溶加剧,导致α相再结晶和析出物的聚合长大,得到极优的延展性,对深冲非常有利;退火温度位于Ac₁~Ac₃之间(850 ℃),发生α→γ相再结晶,可以取得最好的软化效果。对于含Ti的试验钢,随着退火温度的降低,其塑性应变比r值呈下降趋势。Cr的加入不利于耐沟状腐蚀性能,但是Al的加入有利于耐沟状腐蚀性能。采用两段式退火工艺进行工业化生产,可以得到外观和性能优良的采暖系统用耐沟状腐蚀产品。     

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.     

High-entropy boride–carbide ceramics by sequential boro/carbothermal synthesis

A dual-phase high-entropy boride (HEB)/carbide (HEC) ceramic with a fine grain size was synthesized by a sequential boro/carbothermal process. In the first step, an Hf–Nb–Ta–Ti–Zr-containing carbide was synthesized by a carbothermal reduction of oxides followed by the reaction of the carbide with B₄C and ZrH₂ to convert part of the carbide to boride. The resulting composition was ∼29 vol% HEB with an average grain size of ∼1.1 μm. Solid solution formation occurred at the densification temperature of 1900°C resulting in a relative density higher than 99%. The Vickers hardness was 26.5 ± 1.4 GPa. This is the first report of synthesizing dual-phase boride–carbide high-entropy ceramics from carbothermally synthesized, HEC powders.