B-C-N 固溶体包覆 cBN 的高温高压制备与表征

立方氮化硼（cBN）是已知硬度仅次于金刚石的超硬材料，在含铁簇元素材料 的切、磨、削等加工中有着不可替代的作用。然而，cBN 的硬度只有金刚石的一半， 其加工效率和使用寿命较低。考虑到 cBN 与金刚石在晶体结构与原子共价键半径 的近亲关系，可通过在 cBN 表层包覆碳类材料，经高温高压固溶强化处理，形成 硬度更高和热稳定性更好的 B-C-N 壳层包覆 cBN 材料，增强其机械性能与化学惰性，从而提高其加工效率与使用寿命。 本工作使用 Kawai 型大腔体压机装置，以不同粒度的 cBN 粉末和石墨烯粉末 作为主要原料，研究了制备聚晶 cBN 及 B-C-N 固溶体包覆 cBN 材料的高温高压 合成技术与方法。主要研究内容包括：1）聚晶 cBN 材料的设计和表征，探讨在各 种压力合成条件下温度对烧结体特性的影响，为对比研究 B-C-N 型固溶体壳层奠 定了试验基础和理论依据。2）以相同的 cBN 初始材料，按照一定比例混合化学活 性更好的石墨烯，通过控制温度、压力条件，制备不同的 B-C-N 固溶体包覆 cBN 的样品，通过对其性能表征，研究了压力、温度、组分对 B-C-N 固溶体包覆 cBN 烧结体性能的影响，并与纯的聚晶 cBN 烧结体性能进行了对比研究。本文主要得 到了以下结论： 1. 选择合适的原材料是得到优良 B-C-N 固溶材料的必要前提。本文对 cBN 的 原材料及粒度的影响进行了探讨，发现在采用的两种不同的 cBN 原材料，A 型 cBN 粉末粒度分布集中，颗粒大小均匀，更适合用于 cBN 基超硬材料的高温高压合成。 2. 在不同压力和温度条件下合成的聚晶 cBN 材料表现出不同的性质。1）通过 对比实验，发现在合成压力高于 16 GPa 的条件下，当合成温度高于 1600 °C 时， 聚晶 cBN 才能烧结成块，并且随着温度的上升，颗粒的晶界会模糊，晶粒也会长 大，在合成条件为 18 GPa、2000 °C 时，合成的聚晶 cBN 外观呈现半透明状，在 该条件下合成了高纯度的烧结完好的聚晶 cBN。2）压力的升高抑制了晶粒的长大， 同时增加了晶粒间的位错和缺陷的产生，同时温度的上升使其显微结构明显致密 化，18 GPa、2 000 °C 样品的维氏硬度达到了 45 GPa，相比单晶 cBN 硬度 30 GPa 有很大提升。 3. 在高压下碳原子固溶到 cBN 中形成 B-C-N 固溶体与温度正相关。1）研 究发现在相同压力下随着温度越高，越有利于碳原子溶解到金刚石中：温度超过 2 000 °C 时晶界中会产生石墨烯转变的金刚石，当温度持续上升，金刚石在拉曼和 X-ray 图谱中峰值减弱，当到达 2 300 °C 时消失，同时材料外观由不透明的深 色转变为半透明，金刚石中的碳原子固溶到 cBN 晶格中，导致了 cBN 的晶格明显 减小，符合 Vegard’s law。2）由于固溶强化作用，随着温度上升带来的固溶度的提 高，样品硬度和热稳定性有一定提升，18 GPa、2300 °C 样品小加载时维氏硬度高 达 90 GPa，大加载时稳定在 60 GPa，相比聚晶 cBN 硬度 45 GPa 有显著提高；热稳 定性由原料 cBN 的 1073 °C 提高到了 1180 °C，比聚晶 cBN 的 1130 °C 有提高。

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