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Materials Data on UI4 by Materials Project

UI4 crystallizes in the monoclinic C2/c space group. The structure is one-dimensional and consists of two UI4 ribbons oriented in the (0, 0, 1) direction. U4+ is bonded to six I1- atoms to form edge-sharing UI6 octahedra. There are a spread of U–I bond distances ranging from 2.88–3.13 Å. There are two inequivalent I1- sites. In the first I1- site, I1- is bonded in a single-bond geometry to one U4+ atom. In the second I1- site, I1- is bonded in an L-shaped geometry to two equivalent U4+ atoms.

36 MATERIALS SCIENCE↗

Unconventional Pathways to Carbide Phase Synthesis via Thermal Decomposition of UI 4 (1,4-dioxane) 2

UI4(1,4-dioxane) 2 was subjected to laser-based heating-a method that enables localized, fast heating (T > 2000 °C) and rapid cooling under controlled conditions (scan rate, power, atmosphere, etc.)-to understand its thermal decomposition. A predictive computational thermodynamic technique estimated the decomposition temperature of UI 4 (1,4-dioxane) 2 to uranium (U) metal to be 2236 °C, a temperature achievable under laser irradiation. Dictated by the presence of reactive, gaseous byproducts, the thermal decomposition of UI 4 (1,4-dioxane) 2 under furnace conditions up to 600 °C revealed the formation of UO 2 , UI x , and U(C 1–x O x ) y , while under laser irradiation, UI 4 (1,4-dioxane) 2 decomposed to UO 2 , U(C 1–x O x ) y , UC 2–z O z , and UC. Despite the fast dynamics associated with laser irradiation, the central uranium atom reacted with the thermal decomposition products of the ligand (1,4-dioxane = C 4 H 8 O 2 ) instead of producing pure U metal. In conclusion, the results highlight the potential to co-develop uranium precursors with specific irradiation procedures to advance nuclear materials research by finding new pathways to produce uranium carbide.

36 MATERIALS SCIENCE↗