Metal hydrides can store hydrogen isotopes with high volumetric density. In metal tritides, tritium beta decay can result in accumulation of helium within the solid, in some cases exceeding 10 at.% helium after only 4 years of aging. Helium is insoluble in most materials, but often does not readily escape, and instead coalesces to form nanoscale bubbles when helium concentrations are near 1 at.%. Blistering or spallation often occurs at higher concentrations. Radioactive particles shed during this process present a potential safety hazard. This study investigates the effects of high helium concentrations on erbium deuteride (ErD2), a non-radioactive surrogate material for erbium tritide (ErT2). To simulate tritium decay in the surrogate, high doses of 120 keV helium ions were implanted into ErD2 films at room temperature. Scanning and transmission electron microscopy indicated spherical helium bubble formation at a critical concentration of 1.5 at.% and bubble linkage leading to nanoscale crack formation at a concentration of 7.5 at.%. Additionally, crack propagation occurred through the nanocrack region, resulting in spallation extending from the implantation peak to the surface. Electron energy loss spectroscopy was utilized to confirm the presence of high-pressure helium in the nanocracks, suggesting that helium gas plays a predominant role in deformation. This work improves the overall understanding of helium behavior in ErD2 by using modern characterization techniques to determine: the critical helium concentration required for bubble formation, the material failure mechanism at high concentration, and the nanoscale mechanisms responsible for material failure in helium implanted ErD2.
The performance of solid-state electrochemical systems is intimately tied to the potential and lithium distributions across electrolyte-electrode junctions that give rise to interface impedance. Here, we combine two operando methods, Kelvin probe force microscopy (KPFM) and neutron depth profiling (NDP), to identify the rate-limiting interface in operating Si-LiPON-LiCoO2 solid-state batteries by mapping the contact potential difference (CPD) and the corresponding Li distributions. The contributions from ions, electrons, and interfaces are deconvolved by correlating the CPD profiles with Li-concentration profiles and by comparisons with first-principles-informed modeling. We find that the largest potential drop and variation in the Li concentration occur at the anode-electrolyte interface, with a smaller drop at the cathode-electrolyte interface and a shallow gradient within the bulk electrolyte. Correlating these results with electrochemical impedance spectroscopy following battery cycling at low and high rates confirms a long-standing conjecture linking large potential drops with a rate-limiting interfacial process.
Structural alloys may experience corrosion when exposed to molten chloride salts due to selective dissolution of active alloying elements. One way to prevent this is to make the molten salt reducing. For the KCl + MgCl2 eutectic salt mixture, pure Mg can be added to achieve this. However, Mg can form intermetallic compounds with nickel at high temperatures, which may cause alloy embrittlement. This work shows that an optimum level of excess Mg could be added to the molten salt which will prevent corrosion of alloys like 316 H, while not forming any detectable Ni-Mg intermetallic phases on Ni-rich alloy surfaces.
The passivation of polycrystalline nickel surfaces against hydrogen uptake by oxygen is investigated experimentally with low energy ion scattering (LEIS), direct recoil spectroscopy (DRS), and thermal desorption spectroscopy (TDS). These techniques are highly sensitive to surface hydrogen, allowing the change in hydrogen adsorption in response to varying amounts of oxygen exposure to be measured. The chemical composition of a nickel surface during a mixed oxygen and hydrogen exposure was characterized with LEIS and DRS, while the uptake and activation energies of hydrogen on a nickel surface with preadsorbed oxygen were quantified with TDS. By and large, these measurements of how the oxygen and hydrogen surface coverage varied in response to oxygen exposure were found to be consistent with predictions of a simple site-blocking model. This finding suggests that, despite the complexities that arise due to polycrystallinity, the oxygen-induced passivation of a polycrystalline nickel surface against hydrogen uptake can be approximated by a simple site-blocking model.
This project focused on providing a fundamental physico-chemical understanding of the coupling mechanisms of corrosion- and radiation-induced degradation at material-salt interfaces in Ni-based alloys operating in emulated Molten Salt Reactor(MSR) environments through the use of a unique suite of aging experiments, in-situ nanoscale characterization experiments on these materials, and multi-physics computational models. The technical basis and capabilities described in this report bring us a step closer to accelerate the deployment of MSRs by closing knowledge gaps related to materials degradation in harsh environments.
Liquid organic hydrogen carriers such as alcohols and polyols are a high-capacity means of transporting and reversibly storing hydrogen that demands effective catalysts to drive the (de)hydrogenation reactions under mild conditions. We employed a combined theory/experiment approach to develop MOF-74 catalysts for alcohol dehydrogenation and examine the performance of the open metal sites (OMS), which have properties analogous to the active sites in high-performance single-site catalysts and homogeneous catalysts. Methanol dehydrogenation was used as a model reaction system for assessing the performance of five monometallic M-MOF-74 variants (M = Co, Cu, Mg, Mn, Ni). Co-MOF-74 and Ni-MOF-74 give the highest H2 productivity. However, Ni-MOF-74 is unstable under reaction conditions and forms metallic nickel particles. To improve catalyst activity and stability, bimetallic (NixMg1-x)-MOF-74 catalysts were developed that stabilize the Ni OMS and promote the dehydrogenation reaction. An optimal composition exists at (Ni0.32Mg0.68)-MOF-74 that gives the greatest H2 productivity, up to 203 mL gcat-1 min-1 at 300 °C, and maintains 100% selectivity to CO and H2 between 225-275 °C. The optimized catalyst is also active for the dehydrogenation of other alcohols. DFT calculations reveal that synergistic interactions between the open metal site and the organic linker lead to lower reaction barriers in the MOF catalysts compared to the open metal site alone. This work expands the suite of hydrogen-related reactions catalyzed by MOF-74 which includes recent work on hydroformulation and our earlier reports of aryl-ether hydrogenolysis. Moreover, it highlights the use of bimetallic frameworks as an effective strategy for stabilizing a high density of catalytically active open metal sites. This journal is
The surfaces of textured polycrystalline N-type bismuth telluride and P-type antimony telluride materials were investigated using ex situ photoelectron emission microscopy (PEEM). PEEM enabled imaging of the work function for different oxidation times due to exposure to air across sample surfaces. The spatially averaged work function was also tracked as a function of air exposure time. N-type bismuth telluride showed an increase in the work function around grain boundaries relative to grain interiors during the early stages of air exposure-driven oxidation. At longer time exposure to air, the surface became homogenous after a ∼5 nm-thick oxide formed. X-ray photoemission spectroscopy was used to correlate changes in PEEM imaging in real space and work function evolution to the progressive growth of an oxide layer. The observed work function contrast is consistent with the pinning of electronic surface states due to the defects at a grain boundary.
Austenitic stainless steels are used extensively in harsh environments, including for high-pressure gaseous hydrogen service. However, the tensile ductility of this class of materials is very sensitive to materials and environmental variables. While tensile ductility is generally insufficient to qualify a material for hydrogen service, ductility is an effective tool to explore microstructural and environmental variables and their effects on hydrogen susceptibility, to inform understanding of the mechanisms of hydrogen effects in metals, and to provide insight to microstructural variables that may improve relative performance. In this study, hydrogen precharging was used to simulate high-pressure hydrogen environments to evaluate hydrogen effects on tensile properties. Several austenitic stainless steels were considered, including both metastable and stable alloys. Room temperature and subambient temperature tensile properties were evaluated with three different internal hydrogen contents for type 304L and 316L austenitic stainless steels and one hydrogen content for XM-11. Significant ductility loss was observed for both metastable and stable alloys, suggesting the stability of the austenitic phase is not sufficient to characterize the effects of hydrogen. Internal hydrogen does influence the character of deformation, which drives local damage accumulation and ultimately fracture for both metastable and stable alloys. While a quantitative description of hydrogen-assisted fracture in austenitic stainless steels remains elusive, these observations underscore the importance of the hydrogen-defect interactions and the accumulation of damage at deformation length scales.
The effects of internal hydrogen on the deformation microstructures of 304L austenitic stainless steel have been characterized using electron backscattered diffraction (EBSD), transmission Kikuchi diffraction (TKD), high-resolution scanning transmission electron microscopy (HRSTEM), and nanoprobe diffraction. Samples, both thermally precharged with hydrogen and without thermal precharging, were subjected to tensile deformation of 5 and 20 pct true strain followed by multiple microscopic interrogations. Internal hydrogen produced widespread stacking faults within the as-forged initially unstrained material. While planar deformation bands developed with tensile strain in both the hydrogen-precharged and non-precharged material, the character of these bands changed with the presence of internal hydrogen. As shown by nanobeam diffraction and HRSTEM observations, in the absence of internal hydrogen, the bands were predominantly composed of twins, whereas for samples deformed in the presence of internal hydrogen, ε-martensite became more pronounced and the density of deformation bands increased. For the 20 pct strain condition, α'-martensite was observed at the intersection of ε-martensite bands in hydrogen-precharged samples, whereas in non-precharged samples α'-martensite was only observed along grain boundaries. We hypothesize that the increased prevalence of α'-martensite is a secondary effect of increased ε-martensite and deformation band density due to internal hydrogen and is not a signature of internal hydrogen itself.
In this study, we report on the thermal conductivity of amorphous carbon generated in diamond via nitrogen ion implantation (N 3 + at 16.5 MeV). Transmission electron microscopy techniques demonstrate amorphous band formation about the longitudinal projected range, localized approximately 7 μm beneath the sample surface. While high-frequency time-domain thermoreflectance measurements provide insight into the thermal properties of the near-surface preceding the longitudinal projected range depth, a complimentary technique, steady-state thermoreflectance, is used to probe the thermal conductivity at depths which could not otherwise be resolved. Through measurements with a series of focusing objective lenses for the laser spot size, we find the thermal conductivity of the amorphous region to be approximately 1.4 W m-1 K-1, which is comparable to that measured for amorphous carbon films fabricated through other techniques.
To develop a fundamental understanding of dynamic strain aging, discovery experiments were designed and completed to inform the development of a dislocation based micromechanical constitutive model that will ultimately tie to continuum level plasticity and failure models. Dynamic strain aging occurs when dislocation motion is hindered by the repetitive interaction of solute atoms, most frequently interstitials, with dislocation cores. Initially, the solute atmospheres pin the dislocation core until the virtual force on the dislocation is high enough to allow glissile motion. At temperatures where the interstitials are mobile enough, the atmospheres can repeatedly reform, lock, and release dislocations producing a characteristic serrated flow curve. This phenomenon can produce unusual mechanical behavior of materials and changes in the strain rate and temperature responses. Detrimental effects such as loss of ductility often accompany these altered responses.
Digital computing is nearing its physical limits as computing needs and energy consumption rapidly increase. Analogue-memory-based neuromorphic computing can be orders of magnitude more energy efficient at data-intensive tasks like deep neural networks, but has been limited by the inaccurate and unpredictable switching of analogue resistive memory. Filamentary resistive random access memory (RRAM) suffers from stochastic switching due to the random kinetic motion of discrete defects in the nanometer-sized filament. In this work, this stochasticity is overcome by incorporating a solid electrolyte interlayer, in this case, yttria-stabilized zirconia (YSZ), toward eliminating filaments. Filament-free, bulk-RRAM cells instead store analogue states using the bulk point defect concentration, yielding predictable switching because the statistical ensemble behavior of oxygen vacancy defects is deterministic even when individual defects are stochastic. Both experiments and modeling show bulk-RRAM devices using TiO2-X switching layers and YSZ electrolytes yield deterministic and linear analogue switching for efficient inference and training. Bulk-RRAM solves many outstanding issues with memristor unpredictability that have inhibited commercialization, and can, therefore, enable unprecedented new applications for energy-efficient neuromorphic computing. Beyond RRAM, this work shows how harnessing bulk point defects in ionic materials can be used to engineer deterministic nanoelectronic materials and devices.
Austenitic stainless steel microstructures produced by directed energy deposition (DED)are analogous to those developed during welding, particularly high energy density welding. To better understand microstructural development during DED, theories of microstructural evolution,which have been established to contextualize weld microstructures, are applied in this study to microstructural development in DED austenitic stainless steels. Phenomenological welding models that describe the development of oxide inclusions, compositional microsegregation, ferrite,matrix austenite grains, and dislocation substructures are utilized to clarify microstructural evolution during deposition of austenitic stainless steels. Two different alloys, 304L and 316L, arecompared to demonstrate the broad applicability of this framework for understanding microstmctural development during the DED process. Despite differences in grain morphology and solidification mode for these two alloys (which can be attributed to compositional differences),similar tensile properties are achieved. It is the fine-scale compositional segregation and dislocation structures that ultimately determine the strength of these materials. The evolution of microsegregation and dislocation structures is shown to be dependent on the rapid solidification and thermomechanical history of the DED processing method and not the composition of the starting material.
The lower limit of metal hydride nanoconfinement is demonstrated through the coordination of a molecular hydride species to binding sites inside the pores of a metal-organic framework (MOF). Magnesium borohydride, which has a high hydrogen capacity, is incorporated into the pores of UiO-67bpy (Zr6O4(OH)4(bpydc)6 with bpydc2- = 2,2′-bipyridine-5,5′-dicarboxylate) by solvent impregnation. The MOF retained its long-range order, and transmission electron microscopy and elemental mapping confirmed the retention of the crystal morphology and revealed a homogeneous distribution of the hydride within the MOF host. Notably, the B-, N-, and Mg-edge XAS data confirm the coordination of Mg(II) to the N atoms of the chelating bipyridine groups. In situ 11B MAS NMR studies helped elucidate the reaction mechanism and revealed that complete hydrogen release from Mg(BH4)2 occurs as low as 200 °C. Sieverts and thermogravimetric measurements indicate an increase in the rate of hydrogen release, with the onset of hydrogen desorption as low as 120 °C, which is approximately 150 °C lower than that of the bulk material. Furthermore, density functional theory calculations support the improved dehydrogenation properties and confirm the drastically lower activation energy for B-H bond dissociation.
