Reactive laser synthesis of ultra-high-temperature ceramics HfC, ZrC, TiC, HfN, ZrN, and TiN for additive manufacturing

Ultra-high-temperature ceramics (UHTCs) are optimal structural materials for applications that require extreme high temperature resilience (Mp > 3000 degrees C), resistance to chemically aggressive environments, wear, and mechanical stress. Processing UHTCs with laser-based additive manufacturing (AM) has not been fully realized due to a variety of obstacles. In this work, selective laser reaction sintering techniques (SLRS) were investigated for the production near net-shape UHTC ceramics such as HfC, ZrC, TiC, HfN, ZrN, and TiN. Specifically, group IV transition metal and metal oxide precursor materials (<44 mu m) were chemically converted and reaction-bonded into layers of UHTCs using single-step selective laser processing in 100 vol% CH4 or NH3 gas that might be compatible with prevailing powder bed fusion techniques. Conversion of either metals (Hf, Zr and Ti) or metal oxides (HfO2, ZrO2, and TiO2) particles was first investigated to examine reaction mechanisms and volume changes associated with SLRS of single-component precursor systems. SLRS processing of metal or metal oxide alone produced near stoichiometric UHTC phases and yields up to >99.9 wt% total for carbides and nitrides and during the rapid reactive in-situ processing scheme. However, for single-phase feedstocks, gas-solid reactivity induced volumetric changes (correlated with the stochiometry of the rocksalt-type UHTC carbide and nitride products) resulted in residual stresses and cracking in the model-AM product layer. To mitigate conversion-induced stresses of single-phase precursors, composite metal/metal oxide precursors were employed to compensate for the volume changes of either the metal (which expands during conversion) or the metal oxide precursor (which contracts). While conversion of the optimized composite materials produced HfC layers with as little as +0.9% volume change, results indicated interparticle adhesion must be optimized to obtain robust UHTC-AM layers. Computational models of carbon and nitrogen diffusion in host transition metal lattices corroborated experimental results where a progressive particle conversion might inhibit interparticle diffusion unless laser processing parameters are carefully optimized to favor reaction bonding over discrete particle conversion. While this method presents a host of processing considerations, we demonstrate how this reactive approach may be viable for the AM of numerous UHTC materials that are not readily produced using current methods.