Laser-Induced Thermal Decomposition of Uranium Coordination Compounds with Non-oxidic Ligands to Produce Nitride and Carbide Materials.

The production of ceramics from uranium coordination compounds can be achieved through thermal processing if an excess amount of the desired atoms (i.e., C or N), or reactive gaseous products (e.g., methane or nitrogen oxide) is made available to the reactive uranium metal core via decomposition/fragmentation of the surrounding ligand groups. Here, computational thermodynamic approaches were utilized to identify the temperatures necessary to produce uranium metal from some starting compounds─UI4(TMEDA)2, UCl4(TMEDA)2, UCl3(pyridine)x, and UI3(pyridine)4. Experimentally, precursors were irradiated by a laser under various gaseous environments (argon, nitrogen, and methane) creating extreme reaction conditions (i.e., fast heating, high temperature profile >2000 °C, and rapid cooling). Despite the fast dynamics associated with laser irradiation, the central uranium atom reacted with the thermal decomposition products of the ligands yielding uranium ceramics. Residual gas analysis identified vaporized products from the laser irradiation, and the final ceramic products were characterized by powder X-ray diffraction. The composition of the uranium precursor as well as the gaseous environment had a direct impact on the production of the final phases.

Electrochemical Performance of Polymer-Derived Silicon-Oxycarbide/Graphene Nanoplatelet Composites for High-Performance Li-Ion Batteries.

Amorphous polymer-derived silicon-oxycarbide (SiOC) ceramics have a high theoretical capacity and good structural stability, making them suitable anode materials for lithium-ion batteries. However, SiOC has low electronic conductivity, poor transport properties, low initial Couloumbic efficiency, and limited rate capability. Therefore, there is an urgent need to explore an efficient SiOC-based anode material that could mitigate the abovementioned limitations. In this study, we synthesized carbon-rich SiOC (SiOC-I) and silicon-rich SiOC (SiOC-II) and evaluated their elemental and structural characteristics using a broad spectrum of characterization techniques. Li-ion cells were fabricated for the first time by pairing a buckypaper composed of carbon nanotubes with SiOC-I or SiOC-II as the anode. When mixed with graphene nanoplatelets, the SiOC-II/GNP composites exhibited improved electrochemical performance. High specific capacity (average specific capacity of 744 mAh/g at a 0.1C rate) was achieved with the composite anode (25 wt % SiOC-II and 75% GNP), which was much better than that of monolithic SiOC-I, SiOC-II, or GNPs. This composite also exhibited excellent cycling stability, achieving 344 mAh/g after 260 cycles at a 0.5C rate and high reversibility. The enhanced electrochemical performance is attributed to better electronic conductivity, lower charge-transfer resistance, and short ion diffusion length. Due to their superior electrochemical performance, SiOC/GNP composites with CNT buckypaper as a current collector can be considered a promising anode material for LiBs.

Unconventional Pathways to Carbide Phase Synthesis via Thermal Decomposition of UI4(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 UI4(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 UI4(1,4-dioxane)2 under furnace conditions up to 600 °C revealed the formation of UO2, UIx, and U(C1-xOx)y, while under laser irradiation, UI4(1,4-dioxane)2 decomposed to UO2, U(C1-xOx)y, UC2-zOz, 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 = C4H8O2) instead of producing pure U metal. 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.

In situ chemical functionalization of gallium nitride with phosphonic acid derivatives during etching.

In situ functionalization of polar (c plane) and nonpolar (a plane) gallium nitride (GaN) was performed by adding (3-bromopropyl) phosphonic acid or propyl phosphonic acid to a phosphoric acid etch. The target was to modulate the emission properties and oxide formation of GaN, which was explored through surface characterization with atomic force microscopy, X-ray photoelectron spectroscopy, photoluminescence (PL), inductively coupled plasma-mass spectrometry, and water contact angle. The use of (3-bromopropyl) phosphonic acid and propyl phosphonic acid in phosphoric acid demonstrated lower amounts of gallium oxide formation and greater hydrophobicity for both sample sets, while also improving PL emission of polar GaN samples. In addition to crystal orientation, growth-related factors such as defect density in bulk GaN versus thin GaN films residing on sapphire substrates were investigated as well as their responses to in situ functionalization. Thin nonpolar GaN layers were the most sensitive to etching treatments due in part to higher defect densities (stacking faults and threading dislocations), which accounts for large surface depressions. High-quality GaN (both free-standing bulk polar and bulk nonpolar) demonstrated increased sensitivity to oxide formation. Room-temperature PL stands out as an excellent technique to identify nonradiative recombination as observed in the spectra of heteroepitaxially grown GaN samples. The chemical methods applied to tune optical and physical properties of GaN provide a quantitative framework for future novel chemical and biochemical sensor development.