过渡金属钒硼化合物的高温高压合成与表征

      过渡金属钒硼化合物因晶体结构和成键方式的多样性展现出丰富的物 理和化学性能。然而，该体系存在多种物相，各物相间的形成能差异小， 为制备纯相材料带来了挑战。理论研究表明，钒硼体系中的单硼化钒（VB） 具备成为硬质陶瓷材料的潜力，但 VB 与 V₃B₄、V₅B₆ 形成能相近，合成纯 相的难度较大，导致其力学、电学和热学等性质的研究工作稀少且零散。

      本研究采用 V 和 B 粉为初始材料在高温高压下成功制备了高纯的 VB， 同时探究了工艺参数对合成的影响，最终发现温度对 VB 的合成起到决定性 作用，能够克服形核势垒，促使反应快速进行。最后对其物相、力学、电 学和热稳定性等性质进行了系统研究。热学分析表明，VB 的氧化起始温度 高达 950 °C，较之相同结构的硼化物，具有最高的热稳定性，可能归因于 B-B 键高的键和能与表层快速形成 B₂O₃ 氧化膜阻挡进一步氧化的共同作用。 维氏硬度结果表明，VB 的本征硬度为 17.2 GPa。经过高压细晶强化后，VB 的平均晶粒尺寸从约 24 μm 减小到约 8 μm，减小了 67%。得益于晶界效应， VB 强化后的硬度高达 22.3 GPa，较之前提高约 29%，高于目前所有相同结 构单硼化物及国产商用碳化钨的硬度（~18.5 GPa）。第一性原理计算显示， VB 具有较高的剪切模量（G: 233 GPa）、弹性模量（B: 272 GPa）以及较 低的泊松比（ν: 0.17）。其理想剪切强度 τ 和理想拉伸强度 σ_t 分别为 40.0 GPa 和 41.3 GPa，高于同结构的 NbB（τ: 30.0 GPa，σ_t：22.4 GPa）与 TaB （τ: 33.0 GPa，σ_t: 21.7 GPa）。因此 VB 的高硬度特性得益于其高的剪切模 量、弹性模量、理想剪切和拉伸强度以及低的泊松比。高压低温（2-300 K） 电输运结果表明，VB 在 5 GPa 室温下的电导率为 0.7 μΩ m，与金属钒的电 导率（0.2 μΩ m）相近，展现出优异的导电性能。此外，我们首次利用 V 和 VB₂ 作为前驱体成功合成了高纯的 VB，其本征硬度可达 20.5 GPa。

      综上，我们利用高温高压的方法合成了一种兼具高硬度、 高热稳定性 和优异导电性能的硬质陶瓷材料--VB，可能具有潜在的工业用途。

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