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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Thermal stability of additively manufactured austenitic 304L ODS alloy

Thermal stability and high-temperature mechanical properties of a 304L austenitic oxide dispersion strengthened (ODS) alloy manufactured via laser powder bed fusion (LPBF) are examined in this work. Additively manufactured 304L ODS alloy samples were aged at temperatures of 1000, 1100, and 1200 °C for 100 h in an argon atmosphere. Microstructure characterization of LPBF 304L ODS alloy before and after the thermal stability experiments revealed that despite the annihilation of dislocations, induced cellular substructure by the LPBF process was partially retained in the ODS alloy even after aging at 1200 °C. The size of Y-Si-O nanoparticles after aging at 1200 °C increased from 25 to 50 nm. EBSD analysis revealed that nanoparticles retained the microstructure of LPBF 304L ODS and hindered recrystallization and further grain growth. At 600 °C and 800 °C, the yield stress of the 290 and 145 MPa were measured, respectively, which are substantially higher than 113 MPa, and 68 MPa for 304L at the same temperatures. Furthermore, the creep properties of LPBF 304L ODS alloy were evaluated at a temperature of 700 °C under three applied stresses of 70, 85, and 100 MPa yielding a stress exponent (n) of ~7.7; the minimum creep rate at 100 MPa was found to be about two orders of magnitude lower than found in the literature for wrought 304L stainless steel.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Boride-based Ceramic Super-high Temperature Thermocouples in Harsh Environments (Final Scientific/Technical Report)

An electromotive force (emf) can be generated along a temperature gradient between the cold end and hot end of a thermoelectric material, termed the Seebeck effect. Based on the Seebeck effect, metallic alloys have been extensively employed to detect temperatures for centuries, named thermocouples. However, commercially available thermocouple alloys suffer from limitations, such as oxidation, chemical degradation, and poor long-term stability under high-temperature harsh environments. This DOE-funded project aimed to develop high-temperature, chemically tolerant thermocouples suitable for operation in extreme environments relevant to semiconducting thermoelectric materials. The research focused on boride-based semiconducting thermoelectric compounds as candidates for next-generation thermocouples with enhanced oxidation resistance, chemical stability, and thermal robustness under conditions representative of charcoal-fired electricity facilities. During the funded years, boride materials were synthesized using an arc-plasma technique under ambient air and argon atmospheres, enabling scalable and cost-effective production compared with conventional boride fabrication methods. The synthesized borides were processed into nanostructured powders, followed by consolidation into dense bulk materials using a spark plasma sintering (SPS) bottom-up approach. Comprehensive characterization was performed, including microstructural analysis, electrical transport measurements, and optical and thermal property evaluation. Both p-type and n-type boride electric legs were fabricated and integrated into boride-based thermocouples. The thermal and irradiation stabilities of the boride nanomaterials and bulk thermoelectric materials were systematically evaluated to assess suitability for long-term operation in harsh environments. Additionally, 12 students were broadly hands-on trained spanning the full research workflow, including word processing and technical editing (e.g., LATEX for manuscript and poster preparation), data collection and analysis (using Python and related libraries and hardware interfaces), sample preparation (including arc-plasma synthesis and spark plasma sintering), and advanced characterization techniques (such as X-ray diffraction, UV–vis spectroscopy, electron microscopy, differential thermal analysis (DTA), and Seebeck coefficient measurements, etc). Overall, this project demonstrated the feasibility of boride-based thermoelectric materials as durable high-temperature thermocouples, providing a promising pathway toward robust temperature sensing technologies aligned with DOE energy infrastructure and extreme-environment monitoring needs.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2026

Mechanistic origin of solvent-dependent thermal stability in sodiated Sn anodes for sodium-ion batteries

Understanding the thermal stability of high-energy density alloy anodes is critical for the safe deployment of sodium-ion batteries (SIBs). Here, accelerating rate calorimetry (ARC), post-mortem characterizations, and density functional theory (DFT) calculations are combined to understand the thermal reactivity of fully sodiated Sn, Sn-hard carbon (HC) blends, and HC anodes in carbonate- and ether-based electrolytes. ARC measurements show that propylene carbonate (PC) causes earlier self-heating rate (SHR) onset and higher reactivity than tetraethylene glycol dimethyl ether (TEGDME), indicating inferior thermal stability. Sodiated Sn exhibits better thermal stability than sodiated HC, while Sn-HC blends show intermediate behavior that improves with increasing Sn content. Post-ARC analyses reveal desodiation of Na15Sn4 to metallic Sn with particle coalescence, whereas Sn-HC blends and HC retain finer morphologies. PC promotes Sn oxidation to SnO, while TEGDME suppresses oxide formation; NaPF6-containing electrolytes additionally form NaF. DFT calculations show that PC adsorption lowers Na extraction energy and enhances interfacial electronic interactions, facilitating Na release and reductive decomposition. These results establish a direct correlation between solvent-dependent reaction pathways and thermal stability in SIB alloy anodes.

Accelerating rate calorimetry↗
DOE OSTI2021

Thermal Conductivity Measurement of Microstructure in Irradiated Materials

Argonne National Laboratory is establishing additional capabilities for advanced techniques for accelerated experiment-based fuel material screening. A key supporting element is expanded capabilities for the characterization of irradiated samples, including establishment of the capability to measure irradiated fuel thermal conductivity at the micro-scale level. Argonne is collaborating with the University of Illinois at Urbana-Champaign (UIUC) to adopt the suspended bridge method to measure thermal conductivity of radiation-induced microstructures in nuclear materials directly. The initial phase of work to support thermal conductivity measurements of microstructure in irradiated materials at Argonne has been executed, and is summarized here. This report is intended to serve as a status update for this activity, summarizing work completed in FY20.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Design, Analysis, Comparison, and Experimental Validation of Insulated Metal Substrates for High-Power Wide-Bandgap Power Modules

Direct bonded copper (DBC) substrates used in power modules have limited heat spreading and manufacturing capability due to ceramic properties and manufacturing technology. The ceramic and copper bonding is also subject to high mechanical stress due to coefficient of thermal expansion mismatch between the copper and the ceramic. For wide-bandgap (WBG) devices, it is of interest exploring new substrate technologies that can overcome some of the challenges of direct bonded copper substrates. In this technical paper, the design, analysis, and comparison of insulated metal substrates (IMSs) for high-power wide-bandgap semiconductor-based power modules are discussed. This paper starts with technical description and discussion of state-of-the-art DBC substrates with different ceramic insulators such as aluminum nitride (AlN), Al 2 O 3 , and Si 3 N 4 . Next, an introduction of IMSs and their material properties, and a design approach for SiC (silicon carbide) metal-oxide-semiconductor field-effect transistor (MOSFET)-based power modules for high-power applications is provided. The influence of dielectric thickness on the power handling capability of the substrate are also discussed. The designed IMS and DBC substrates were characterized in terms of steady-state and transient thermal performance using finite element simulation. Finally, the performance of the IMS and DBC are validated in an experimental setup under different loading and cooling temperature conditions. We report the simulation and experimental results showed that the IMS can provide high steady-state thermal performance for high-power modules based on SiC MOSFETs. Furthermore, the IMS provided enhanced transient thermal performance, which provided a reduced junction temperature when the module is operated at low fundamental output frequencies in traction drive systems.

42 ENGINEERING↗
DOE OSTI2024

Multimodal Approach Reveals the Symmetry-Breaking Pathway to the Broken Helix in EuIn 2 ⁢As 2

Understanding and manipulating emergent phases, which are themes at the forefront of quantum-materials research, rely on identifying their underlying symmetries. This general principle has been particularly prominent in materials with coupled electronic and magnetic degrees of freedom, in which magnetic order influences the electronic band structure and can lead to exotic topological effects. However, identifying symmetry of a magnetically ordered phase can pose a challenge, particularly in the presence of small domains. Here we introduce a multimodal approach for determining magnetic structures, which combines symmetry-sensitive optical probes, scattering, and group-theoretical analysis. We apply it to EuIn 2 ⁢As 2 , a material that has received attention as a candidate axion insulator. While first-principles calculations predict this state on the assumption of a simple collinear antiferromagnetic structure, subsequent neutron-scattering measurements reveal a much more intricate magnetic ground state characterized by two coexisting magnetic wave vectors reached by successive thermal phase transitions. The proposed high- and low-temperature phases are a spin helix and a state with interpenetrating helical and Néel antiferromagnetic order termed a “broken helix,” respectively. Employing a multimodal approach, we identify the magnetic structure associated with these two phases of EuIn 2 ⁢As 2 . We find that the higher-temperature phase is characterized by a variation of the magnetic moment amplitude from layer to layer, with the moment vanishing entirely in every third Eu layer. The lower-temperature structure is similar to the broken helix, with one important difference: Because of local strain, the relative orientation of the magnetic structure and the lattice is not fixed. Consequently, the symmetry required to protect the axion phase is not generically protected in EuIn 2 ⁢As 2 , but we show that it can be restored if the magnetic structure is tuned with uniaxial strain. Finally, we present a spin Hamiltonian that identifies the spin interactions that account for the complex magnetic order in EuIn 2 ⁢As 2 . Our work highlights the importance of a multimodal approach in determining the symmetry of complex order parameters.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Corrosion and Mechanical Durability Testing in High Temperature Molten Sulfur (CRADA Final Report)

The overall goal of the project is to explore and identify suitable candidate materials for high-temperature molten sulfur thermal energy storage (TES) operating up to a maximum temperature of 400°C–420°C for industrial process heat applications. A detailed corrosion and strength analysis of coupons subjected to long-term thermal testing in molten sulfur will be conducted to characterize the fundamental corrosion mechanism, corrosion rates, and mechanical durability. The results from the project contribute to the engineering design of sulfur TES systems with desired longevity and lower construction and maintenance costs. The research outcome benefits the TES research and development community by providing detailed corrosion and degradation information for more effective engineering design of the molten sulfur TES containment. It improves the diversity and reliability of the renewable technologies available for the U.S. industries and U.S. power grid.

14 SOLAR ENERGY↗
DOE OSTI2023

FWP FEAA149: “Next Generation Environmental Barrier Coatings”

Environmental barrier coatings (EBCs) are required coatings for utilization of SiC/SiC ceramic matrix composite (CMC) components in gas turbines, where the EBC represents the life-limiting factor for such components. EBC/CMC systems have shown success in aero-engine applications with increased turbine inlet temperatures and improved efficiencies, which are achieved through higher temperature stability, lower density, and decreased reliance on cooling air compared to traditional superalloys. While industrial gas turbines (IGTs) do not currently utilize SiC/SiC CMCs, the current shift towards low-carbon or carbon-free fuel sources for power generation could result in a need for EBC/CMC components with higher temperature capabilities. In this work, three tasks were outlined to improve understanding of EBC lifetimes to encourage use in IGTs with carbon-free fuel such as hydrogen: 1. Define the bond coating oxidation kinetics and EBC failure criteria, 2. Measure thermal expansion coefficients of each layered material, and 3. Perform advanced characterization and modeling to assess EBC lifetimes. Cyclic steam oxidation tests were conducted on various EBC/Si/SiC chemistries and EBC/SiC architectures to define substrate oxidation kinetics and EBC failure modes. An open-source code was developed to quantify the undulating thermally grown oxide thickness with thousands of measurements from specimen cross-section images. Bond coating oxidation kinetics were determined and used to develop a kinetic and thermodynamic model for predicting EBC lifetimes. High-temperature Raman spectroscopy was utilized for determining the SiO 2 thermally grown oxide phase transformation as the life-limiting feature for EBCs. Model efforts supported the claim that the SiO 2 phase transformation causes elevated stress during thermal cycling with associated cracking that decreases the adhesion strength of the EBC, eventually resulting in coating spallation. The finite element model subroutine will be made publicly available upon internal review. Further development of an EBC lifetime model for IGTs involves definition of a critical SiO 2 thickness for EBC spallation and must also consider both environmental (gas velocity, pressure, etc.) and specimen (EBC dopants, layer architectures, etc.) effects into predicted bond coating oxidation kinetics for long-lifetime components.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Narrow-Channel, Fluidized Beds for Effective Particle Thermal Energy Transport and Storage

Colorado School of Mines (Mines) led this program in collaboration with Sandia National Laboratories (Sandia) to characterize narrow-channel fluidized beds of aluminosilicate particles – supplied by Carbo Ceramics – as a means for releasing high-temperature thermal energy in particle heat exchangers and for capturing concentrated solar energy in indirect particle receivers. Single-channel, heat transfer experiments at Mines and reduced-order 1-D models and 3-D two-fluid, CFD models explored many aspects of counterflow, bubbling fluidized beds (net downward particle flow and upward gas flow) for enhancing particle-wall heat transfer at elevated temperatures. Results at Mines on single-channel test sections consistently showed that mild bubbling fluidization increases particle-wall heat transfer coefficients (h T,w ) regularly by more than 4.0x over h T,w values without fluidization at similar conditions (mean particle diameter d p , bed depth Δz b , and bed particle temperatures T p ). Insights from lab-scale tests and modeling studies provided Nusselt number correlations for h T,w and informed the design and fabrication (by Vacuum Process Engineering) of a nominal 40-kWth, particle-sCO 2 plate heat exchanger (HX) with 12 parallel narrow-channel, fluidized beds bounded by stainless-steel walls with embedded microchannels for high-pressure sCO 2 flows. Tests of the 40-kW th HX at the particle-sCO 2 HX test stand at Sandia's National Solar Thermal Test Facility (NSTTF) were limited, due to HX design, to particle inlet temperatures T p,in ≤ 520°C with maximum sCO 2 outlet temperatures T sCO2,out ≈ 440°C, which are well below design conditions for a primary HX in a sCO 2 power cycle for a Gen-3 concentrating solar power (CSP) plant. Total heat transfer $\dot{Q}_{HX}$ remains relatively constant with increased fluidization for fixed particle and sCO 2 inlet conditions because higher h T,w due to fluidization is offset by increased axial dispersion, which suppresses temperature differences between the particles and sCO 2 in the counterflow configuration. The axial dispersion reduces the effective overall heat transfer coefficient U based on T p,in to values around 200 W m -2 K -1 .

14 SOLAR ENERGY↗
DOE OSTI2020

Thermal transport across nanoscale damage profile in sapphire irradiated by swift heavy ions

In this work, we studied the degradation of thermal conductivity in single crystal sapphire (α-Al 2 O 3 ) irradiated by 167 MeV Xe swift heavy ions (SHIs) over the multiple fluences in the range of 10 12 –10 14 ions/cm 2 . Thermal conductivity was measured primarily in the cross-plane direction using a noncontact ultrafast optical pump-probe technique called picosecond time domain thermoreflectance (TDTR). Multiple samples with variable ion fluences allowed us to probe distinct regions resulting from different regimes of microstructure evolution caused by electronic energy loss. By tuning the penetration depth of the thermal waves using different modulation frequencies, two regions with distinct conductivities were identified and the values of which were found to be consistent with phonon-mediated thermal transport models while the microstructure was confirmed by electron microscopy characterization. These damaged regions were determined to be a several micrometer thick ion track region and several tens of nanometer-thick amorphous layer present only above 5.0 × 10 13 ions/cm 2 . These results demonstrate the applicability of TDTR to resolve thermal transport behavior in SHI irradiated oxides having nonhomogeneous damage profile on a nanometer scale. The presented approach facilitates future studies aiming at resolving the impact of distinct damage resulting from electronic and nuclear stopping regimes under irradiation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Techno-economic feasibility of borehole thermal energy storage system connected to geothermal heat pumps for seasonal heating load of two buildings in Fairbanks, Alaska

Borehole thermal energy storage (BTES) is an effective solution for managing imbalanced heating and cooling loads in cold regions. This study evaluated the long-term feasibility of a BTES system in the Fairbanks area, Alaska, through building energy modeling, resource characterization, and numerical modeling. The system was designed to store waste heat from a nearby coal power plant during summer and provide thermal energy during winter to geothermal heat pumps supplying heating loads in two buildings. Heating load profiles were modeled for the buildings using EnergyPlus, and the results indicated the annual heating load was 5.6 times greater than the cooling load. 40 borehole heat exchangers were pre-designed approximately 100 m away from the two buildings in terms of land availability and regulatorily optimized depth. The 20-year performance of the designed BTES system under two operational scenarios—one with a 5-year preheating period and one without—was numerically modeled using subsurface temperature and properties characterized through the literature review and thermal response tests. Both scenarios demonstrated that the BTES has the capacity to fully cover the heating loads in the two buildings throughout the 20-year lifetime. Production temperatures at central wells were 33 % higher on average than at outer wells in both scenarios. The 5-year preheating period increased subsurface and extraction temperatures, and correspondingly annual average and total thermal energy production was higher for 8 years than in the scenario without the preheating period. These results highlight the long-term reliability and sustainability of the BTES system in meeting heating demands over its lifetime, with the preheating period offering potential performance improvements. Implementing the BTES system in cold regions with high heating demand, such as Fairbanks, Alaska, could provide a long-term, sustainable energy solution for managing imbalanced heating and cooling loads.

15 GEOTHERMAL ENERGY↗
DOE OSTI2024

Connecting radiation-driven changes in structural, thermal, and mechanical properties in several medical device polymers

Stemming from security threats and shortages in supply, a recent push has emerged to develop alternatives to radioisotope Cobalt-60 gamma radiation for sterilization of polymeric medical products, including electron beam (e-beam) and X-ray machine-based sources. However, before large-scale implementation, the effects of these non-isotope-based methods must be thoroughly investigated from several perspectives, involving their potential detrimental effects on the structural, thermal, and mechanical properties of polymers in medical devices. This paper investigates such effects in commonly used medical device polymers, including polypropylene homopolymer (PPH), polyolefin elastomer (POE), low-density polyethylene (LDPE), acrylonitrile butadiene styrene (ABS), and chlorobutyl rubber (CIIR). To connect radiation-driven changes in polymer structural and thermal properties and corresponding changes in mechanical properties, several characterization techniques were utilized, including gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). We found that the tensile strength of X-ray irradiated PPH, as well as X-ray, e-beam, and gamma irradiated CIIR decreases due to chain scission, which is corroborated by GPC and DMA. The GPC results of LDPE suggest chain scission, but interestingly without a corresponding decline in tensile strength. By comparison, POE and ABS appear to undergo further crosslinking with increasing irradiation dose, which generally strengthens them. Importantly, in the vast majority of the cases, there were small to no changes in properties upon changing radiation technologies (at a given dose), i.e., no radiation source dependence. However, in a few specific cases, radiation method dependencies did arise, for instance, in terms of the molecular weight of PPH being significantly increased upon X-ray irradiation, while the melting temperature, glass transition temperature, and elongation at break reduced compared to gamma. Overall, this study provides valuable insight into radiation-driven chemical and structural changes in polymers that produce changes in physical and functional properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes

One of the most challenging aspects of developing high-energy lithium-based batteries is the structural and (electro)chemical stability of Ni-rich active cathode materials at thermally-abused and prolonged cell cycling conditions. Here, we report in situ physicochemical characterizations to improve the fundamental understanding of the degradation mechanism of charged polycrystalline Ni-rich cathodes at elevated temperatures (e.g., ≥ 40 °C). Using multiple microscopy, scattering, thermal, and electrochemical probes, we decouple the major contributors for the thermal instability from intertwined factors. Our research work demonstrates that the grain microstructures play an essential role in the thermal stability of polycrystalline lithium-based positive battery electrodes. We also show that the oxygen release, a crucial process during battery thermal runaway, can be regulated by engineering grain arrangements. Furthermore, the grain arrangements can also modulate the macroscopic crystallographic transformation pattern and oxygen diffusion length in layered oxide cathode materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Scintillation properties of diamond powders and feasibility of using them in thermal neutron detectors

Diamond offers unique properties for radiation detection, including high radiation hardness, very low gamma sensitivity, and fast response. Conventional diamond detectors rely on charge collection, but this approach requires ultra-pure single crystals and suffers from radiation-induced degradation. Here, in this work, we demonstrate an alternative approach using diamonds as scintillators for detection of charged particles and thermal neutrons. Prototypes were fabricated from commercially available diamond powders bonded to glass substrates and coupled with 6 LiF converters and silicon photomultipliers (SiPMs) and conventional PMTs. We characterized their scintillation properties under alpha particle excitation, x-ray photoluminescence, and thermal neutrons. The tryout detectors exhibit strong scintillation light signals, nanosecond-scale response times, and neutron detection efficiencies up to approximately 14 %, evaluated by comparison to conventional 3 He detector with known efficiency. These results demonstrate the feasibility of cost-effective, lightweight and robust diamond scintillation detectors for applications in space and planetary science, nuclear security, safeguards and environmental monitoring requiring efficient, robust, gamma-blind neutron detectors.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Optical bistability in PECVD silicon-rich nitride

We present a study of optical bi-stability in a 3.02 refractive index at 1550nm plasma enhanced chemical vapor deposition (PECVD) silicon-rich nitride (SRN) film, as it pertains to bi-stable switching, memory applications, and thermal sensing applications. In this work we utilize an SRN ring resonator device, which we first characterize at low-power and then compare thermo-optic coefficients, (2.12 ± 0.125) × 10 −4 /°C, obtained from thermal-heating induced resonance shifts to optically induced resonance shifts as well as estimated propagation loss and absorption. We then measure the time response of this nonlinearity demonstrating the relaxation time to be 18.7 us, indicating the mechanism to be thermal in nature. Finally, we demonstrate bi-stable optical switching.

42 ENGINEERING↗
DOE OSTI2021

Global and local texture development during initial plastic deformation of cold-pilgered Zircaloy-4 tubing

In this work we present a thorough characterization of the texture development during the initial step of a cold pilgering process of a Zircaloy-4 TREX tube, on which the axial cross section is reduced by 80% over a 40cm length with an overall Q-ratio of 2.34, followed by a recrystallization thermal treatment. Texture across a tapered specimen representing this working zone was characterized by neutron diffraction and high energy synchrotron x-ray diffraction at 28 positions (4 locations along its length and 7 locations across its thickness with 0.3 mm spatial resolution), and on the deformed end after the thermal treatment. Results show that the starting material (TREX tube) presents a texture gradient through its wall thickness, with the c poles aligned to the hoop direction at the outer surface (with radial and hoop Kearns factors: f R =0.36, f H = 0.50), and gradually rotating around the axial direction to become a quasi-radial orientation (~35 o out of the radial direction) at the inner surface ( f R =0.43, f H =0.35). The overall texture becomes more radial due to the cold pilgering, but the texture gradient remains during the whole deformation process, being always more radial at the inner surface, ( f R =0.53, f H =0.37 at 80%) than at the outer surface ( f R =0.41, f H =0.50at 80%). The most remarkable changes in texture produced by the rolling process is a 30 o rotation of the grains around their c-axis, producing a marked increase of the <11 2 ¯ 0> // axial fiber texture at expenses of the original <10 1 ¯ 0> // axial fiber texture observed in the TREX tube. The observed changes in texture during deformation were correctly explained by visco-plastic self-consistent (VPSC) modelling. This was achieved after the inclusion of the basal <a> slip system, which plays a central role to explain the 30 o rotation around the c-axis during deformation. The texture evolution was correctly described after the inclusion of a drag effect to grain rotation due to the interaction with neighbouring grains. The through thickness texture differences are greatly reduced by the recrystallization thermal treatment, with similar Kearns factors at the inner surface ( f R =0.50, f H =0.28) and the outer surface ( f R =0.48, f H =0.39). The predominance of the <10 1 ¯ 0> // axial fiber texture is recovered after recrystallization.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mononuclear to Polynuclear U(IV) Structural Units: Effects of Reaction Conditions on U-Furoate Phase Formation

In this work, Uranium(IV) complexation by 2-furoic acid was examined to better understand the effects of ligand identity and reaction conditions on species formation and stability. Five compounds were isolated: [UCl 2 (2-FA) 2 (H 2 O) 2 ] n (1), [U 4 Cl 10 O 2 (THF) 6 (2-FA) 2 ]•2(THF) (2), [U 6 O 4 (OH) 4 (H 2 O) 3 (2-FA) 12 ]•7(THF)•(H 2 O) (3), [U 6 O 4 (OH) 4 (H 2 O) 2 (2-FA) 12 ]•8.76(H 2 O) (4), and [U 38 Cl 42 O 54 (OH) 2 (H 2 O) 20 ]•m(H 2 O)•n(THF) (5). The structures were determined by single crystal X-ray diffraction and further characterized by Raman, IR, and optical absorption spectroscopy. The thermal stability and magnetic behavior of the compounds were also examined. Variations in the synthetic conditions led to notable differences in the structural units observed in the solid state. At low H 2 O/THF ratios, a tetranuclear oxo bridged [U 4 O 2 ] core was isolated. Aging of this solution resulted in the formation a U 38 oxo cluster capped by chloro and water ligands. However, at increasing water concentrations only hexanuclear units were observed. In all cases, at temperatures of 100-120 °C, UO 2 nanoparticles formed.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗