Iodine-Based Sensitization of Copper Alloys to Enable Self-Terminating Etching for Support Removal and Surface Improvements of Additively Manufactured Components.

Advances in selective laser melting (SLM) of metals in the past two decades have made metals additive manufacturing more accessible for industrial adoption. Despite printing process improvements, post-processing of SLM components has not improved much, resulting in considerable costs, delay, and design limitations. Building upon recent advances in sensitization-based self-terminating etching processes, this work details a new set iodine-based sensitization and etching chemistries that simplify the post-processing of copper (Cu) alloy components fabricated using SLM. This work demonstrates that iodine can be used to "sensitize" the surface of copper alloy components to form soluble copper iodide salt that can be then dissolved in common solvents, such as acetonitrile. This process removes a predefined amount of material from all interior and exterior surfaces in a self-terminating manner, enabling facile removal of internal and external supports, removal of any trapped powder, and the smoothing of interior and exterior surfaces. We demonstrate this process on GRCop (Cu-chromium-niobium) alloys due to their widespread use by the rocket propulsion industry along with a demonstration in copper (110) for applications in heat exchangers and electromagnetic transmitters/receivers. Our results provide the first systematic study on the effect of iodization temperature and duration on the thickness of the iodide region in GRCop-84 components. Additionally, the surface roughness before and after each iodization-dissolution was also quantified for GRCop-84 and showed 70% reduction in Ra roughness from a high of 10 µm as-printed to a low of 3 µm after four iodization-dissolution cycles.

Synthesis and Surface Chemistry of 2D TiVC Solid-Solution MXenes.

MXenes are emerging two-dimensional (2D) materials for energy-storage applications and supercapacitors. Their surface chemistry, which determines critical properties, varies due to different synthesis conditions. In this work, we synthesized TiVC solid-solution MXenes by two different synthesis methods and investigated their surface functional groups. We performed etching of the TiVAlC MAX phase using two different solutions, a highly concentrated HF (50 wt % ≈ 29 M) and a mixture of LiF and HCl (1.9 M LiF/12 M HCl). Large-scale delamination of TiVCTx to produce single-flake suspension was achieved by further intercalation of the resultant MXene from LiF/HCl with tetrabutylammonium hydroxide (TBAOH). X-ray diffraction indicates a large interlayer spacing of 2.18 nm for TiVCTx MXene flakes. To investigate the structural stability and adsorption energy of different functional groups on TiVC MXenes, density functional theory (DFT) calculations were performed and supported with X-ray photoelectron spectroscopy (XPS) measurements. A higher concentration of ═O and a lower concentration of -F were achieved on the TiVC synthesized by LiF/HCl, both of which provide a more favorable surface chemistry for energy-storage applications. Our results provide the first systematic study on the effect of synthesis conditions on the surface chemistry of solid-solution TiVC MXenes.