Top-Down Reactive Approach for the Synthesis of Disordered ZrN Nanocrystalline Bulk Material from Solid Waste

Transition metal nitrides possess superior mechanical, physical, and chemical properties that make them desirable materials for a broad range of applications. A prime example is zirconium nitride (ZrN), which can be obtained through different fabrication methods that require the applications of high temperature and pressure. The present work reports an interesting procedure for synthesizing disordered face centered cubic (fcc)-ZrN nanoparticles through the reactive ball milling (RBM) technique. One attractive point of this study is utilizing inexpensive solid-waste (SW) zirconium (Zr) rods as feedstock materials to fabricate ZrN nanopowders. The as-received SW Zr rods were chemically cleaned and activated, arc-melted, and then disintegrated into powders to obtain the starting Zr metal powders. The powders were charged and sealed under nitrogen gas using a pressurized milling steel vial. After 86 ks of milling, a single fcc-ZrN phase was obtained. This phase transformed into a metastable fcc-phase upon RBM for 259 ks. The disordered ZrN powders revealed good morphological characteristics of spherical shapes and ultrafine nanosize (3.5 nm). The synthetic ZrN nanopowders were consolidated through a spark plasma sintering (SPS) technique into nearly full-density (99.3% of the theoretical density for ZrN) pellets. SPS has proven to be an integral step in leading to desirable and controlled grain growth. Moreover, the sintered materials were not transformed into any other phase(s) upon consolidation at 1673 K. The results indicated that increasing the RBM time led to a significant decrease in the grain size of the ZrN powders. As a result, the microhardness of the consolidated samples was consequently improved with increasing RBM time.