Hydrogen is known to embrittle austenitic stainless steels, which are widely used in high-pressure hydrogen storage and delivery systems, but the mechanisms that lead to such material degradation are still being elucidated. The current work investigates the deformation behavior of single crystal austenitic stainless steel 316L through combined uniaxial tensile testing, characterization and atomistic simulations. Thermally precharged hydrogen is shown to increase the critical resolved shear stress (CRSS) without previously reported deviations from Schmid's law. Molecular dynamics simulations further expose the statistical nature of the hydrogen and vacancy contributions to the CRSS in the presence of alloying. Slip distribution quantification over large in-plane distances (>1 mm), achieved via atomic force microscopy (AFM), highlights the role of hydrogen increasing the degree of slip localization in both single and multiple slip configurations. The most active slip bands accumulate significantly more deformation in hydrogen precharged specimens, with potential implications for damage nucleation. For 〈110〉 tensile loading, slip localization further enhances the activity of secondary slip, increases the density of geometrically necessary dislocations and leads to a distinct lattice rotation behavior compared to hydrogen-free specimens, as evidenced by electron backscatter diffraction (EBSD) maps. The results of this study provide a more comprehensive picture of the deformation aspect of hydrogen embrittlement in austenitic stainless steels.
Warecki, Zoey; Ferrari, Victoria C.; Robinson, Donald A.; Sugar, Joshua D.; Lee, Jonathan; Ievlev, Anton V.; Kim, Nam S.; Stewart, David M.; Lee, Sang B.; Albertus, Paul; Rubloff, Gary; Talin, A.A.
We show that the deposition of the solid-state electrolyte LiPON onto films of V2O5 leads to their uniform lithiation of up to 2.2 Li per V2O5, without affecting the Li concentration in the LiPON and its ionic conductivity. Our results indicate that Li incorporation occurs during LiPON deposition, in contrast to earlier mechanisms proposed to explain postdeposition Li transfer between LiPON and LiCoO2. We use our discovery to demonstrate symmetric thin film batteries with a capacity of >270 mAh/g, at a rate of 20C, and 1600 cycles with only 8.4% loss in capacity. We also show how autolithiation can simplify fabrication of Li iontronic transistors attractive for emerging neuromorphic computing applications. Our discovery that LiPON deposition results in autolithiation of the underlying insertion oxide has the potential to substantially simplify and enhance the fabrication process for thin film solid state Li ion batteries and emerging lithium iontronic neuromorphic computing devices.
A previous SAND report, SAND2020-11353 described the basic metallurgical and surface roughness properties of additively manufactured Ti-64 material made using a powder bed fusion process. As part of that work, material was post-processed using a hot isostatic press (HIP) to densify and heat treat the material. This report is meant as an addendum to the original report and to provide specific data on material processed with HIP. The main focus of this report is to show the effects of HIP on the m
Non-stoichiometric perovskite oxides have been studied as a new family of redox oxides for solar thermochemical hydrogen (STCH) production owing to their favourable thermodynamic properties. However, conventional perovskite oxides suffer from limited phase stability and kinetic properties, and poor cyclability. Here, we report a strategy of introducing A-site multi-principal-component mixing to develop a high-entropy perovskite oxide, (La1/6Pr1/6Nd1/6Gd1/6Sr1/6Ba1/6)MnO3 (LPNGSB_Mn), which shows desirable thermodynamic and kinetics properties as well as excellent phase stability and cycling durability. LPNGSB_Mn exhibits enhanced hydrogen production (?77.5 mmol moloxide?1) compared to (La2/3Sr1/3)MnO3 (?53.5 mmol moloxide?1) in a short 1 hour redox duration and high STCH and phase stability for 50 cycles. LPNGSB_Mn possesses a moderate enthalpy of reduction (252.51-296.32 kJ (mol O)?1), a high entropy of reduction (126.95-168.85 J (mol O)?1 K?1), and fast surface oxygen exchange kinetics. All A-site cations do not show observable valence changes during the reduction and oxidation processes. This research preliminarily explores the use of one A-site high-entropy perovskite oxide for STCH.
Chong, Lina; Gao, Guoping; Wen, Jianguo; Li, Haixia; Xu, Haiping; Green, Zach; Sugar, Joshua D.; Kropf, A.J.; Xu, Wenqian; Lin, Xiao M.; Xu, Hui; Wang, Lin W.; Di Liu, Jia
Discovery of earth-abundant electrocatalysts to replace iridium for the oxygen evolution reaction (OER) in a proton exchange membrane water electrolyzer (PEMWE) represents a critical step in reducing the cost for green hydrogen production. We report a nanofibrous cobalt spinel catalyst codoped with lanthanum (La) and manganese (Mn) prepared from a zeolitic imidazolate framework embedded in electrospun polymer fiber. The catalyst demonstrated a low overpotential of 353 millivolts at 10 milliamperes per square centimeter and a low degradation for OER over 360 hours in acidic electrolyte. A PEMWE containing this catalyst at the anode demonstrated a current density of 2000 milliamperes per square centimeter at 2.47 volts (Nafion 115 membrane) or 4000 milliamperes per square centimeter at 3.00 volts (Nafion 212 membrane) and low degradation in an accelerated stress test.
Wexler, Robert B.; Sai Gautam, Gopalakrishnan; Bell, Robert T.; Shulda, Sarah; Strange, Nicholas A.; Trindell, Jamie T.; Sugar, Joshua D.; Nygren, Eli; Sainio, Sami; McDaniel, Anthony H.; Ginley, David; Carter, Emily A.; Stechel, Ellen B.
Modeling-driven design of redox-active off-stoichiometric oxides for solar thermochemical H2 production (STCH) seldom has resulted in empirical demonstration of competitive materials. We report the theoretical prediction and experimental evidence that the perovskite Ca2/3Ce1/3Ti1/3Mn2/3O3 is synthesizable with high phase purity, stable, and has desirable redox thermodynamics for STCH, with a predicted average neutral oxygen vacancy (VO) formation energy, Ev = 3.30 eV. Flow reactor experiments suggest potentially comparable or greater H2 production capacity than recent promising Sr-La-Mn-Al and Ba-Ce-Mn metal oxide perovskites. Utilizing quantum-based modeling of a solid solution on both A and B sub-lattices, we predict the impact of nearest-neighbor composition on Ev and determine that A-site Ce4+ reduction dominates the redox-activity of Ca2/3Ce1/3Ti1/3Mn2/3O3. X-ray absorption spectroscopy measurements provide evidence that supports these predictions and reversible Ce4+-to-Ce3+ reduction. Our models predict that Ce4+ reduces even when it is not nearest-neighbor to the VO, suggesting that refinement of Ce stoichiometry has the possibility of further enhancing performance.
Engineering the transition metal dichalcogenide (TMD)-metal interface is critical for the development of two-dimensional semiconductor devices. By directly probing the electronic structures of WS2-Au and WSe2-Au interfaces with high spatial resolution, we delineate nanoscale heterogeneities in the composite systems that give rise to local Schottky barrier height modulations. Photoelectron spectroscopy reveals large variations (>100 meV) in TMD work function and binding energies for the occupied electronic states. Characterization of the composite systems with electron backscatter diffraction and scanning tunneling microscopy leads us to attribute these heterogeneities to differing crystallite orientations in the Au contact, suggesting an inherent role of the metal microstructure in contact formation. We then leverage our understanding to develop straightforward Au processing techniques to form TMD-Au interfaces with reduced heterogeneity. Our findings illustrate the sensitivity of TMDs’ electronic properties to metal contact microstructure and the viability of tuning the interface through contact engineering.
Hydrogen produced through low-temperature water electrolysis using anion exchange membranes (AEM) combines the benefits of liquid-electrolyte alkaline electrolysis and solid-polymer proton exchange membrane electrolysis. The anion conductive ionomers in the oxygen-producing anode and hydrogen-producing cathode are a critical part of the three-dimensional electrodes. The ionomer in the hydrogen-producing cathode facilitates hydroxide ion conduction from the cathode catalyst to the anode catalyst, and water transport from the anode to the cathode catalyst through the AEM. This ionomer also binds the catalyst particles to the porous transport layer. In this study, the cathode durability was improved by use of a self-adhesive cathode ionomer to chemically bond the cathode catalyst particles to the porous transport layer. It was found that the cathode ionomers with high ion exchange capacity (IEC) were more effective than low IEC ionomers because of the need to transport water to the cathode catalyst and transport hydroxide away from the cathode. The cathode durability was improved by using ionomers which were soluble in the spray-coated cathode ink. Optimization of the catalyst and ionomer content within the cathode led to electrolysis cells which were both mechanically durable and operated at low voltage.
In this report, we investigate the thermal reduction of the octahedral perovskite BaCe0.25Mn0.75O3(BCM) using in situ electron energy loss spectroscopy (EELS) in an aberration-corrected transmission electron microscope (TEM). The 12R-polytype of BCM is known to demonstrate high solar thermochemical hydrogen production capacity. In situ EELS measurements show that Mn is the active redox cation in BCM, undergoing thermal reduction from Mn4+to Mn3+during heating to 700 °C inside the TEM under a high vacuum. The progressive reduction of Mn4+during oxygen vacancy (Ov) formation was monitored as a function of temperature. Additionally, atomic-resolution scanning transmission electron microscopy identified two different types of twin boundaries present in the oxidized and reduced form of 12R-BCM, respectively. These two types of twin boundaries were shown, via computational modeling, to modulate the site-specific Ovformation energies in 12R-BCM. It is concluded that these types of atomic defects provide sites more energetically favorable for Ovformation during thermal reduction.
A direct comparison between electron transparent transmission electron microscope (TEM) samples prepared with gallium (Ga) and xenon (Xe) focused ion beams (FIBs) is performed to determine if equivalent quality samples can be prepared with both ion species. We prepared samples using Ga FIB and Xe plasma focused ion beam (PFIB) while altering a variety of different deposition and milling parameters. The samples' final thicknesses were evaluated using STEM-EELS t/λ data. Using the Ga FIB sample as a standard, we compared the Xe PFIB samples to the standard and to each other. We show that although the Xe PFIB sample preparation technique is quite different from the Ga FIB technique, it is possible to produce high-quality, large area TEM samples with Xe PFIB. We also describe best practices for a Xe PFIB TEM sample preparation workflow to enable consistent success for any thoughtful FIB operator. For Xe PFIB, we show that a decision must be made between the ultimate sample thickness and the size of the electron transparent region.
The resurgence of interest in a hydrogen economy and the development of hydrogen-related technologies has initiated numerous research and development efforts aimed at making the generation, storage, and transportation of hydrogen more efficient and affordable. Solar thermochemical hydrogen production (STCH) is a process that potentially exhibits numerous benefits such as high reaction efficiencies, tunable thermodynamics, and continued performance over extended cycling. Although CeO2 has been the de facto standard STCH material for many years, more recently 12R-Ba4CeMn3O12 (BCM) has demonstrated enhanced hydrogen production at intermediate H2/H2O conditions compared to CeO2, making it a contender for large-scale hydrogen production. However, the thermo-reduction stability of 12R-BCM dictates the oxygen partial pressure (pO2) and temperature conditions optimal for cycling. In this study, we identify the formation of a 6H-BCM polytype at high temperature and reducing conditions, experimentally and computationally, as a mechanism and pathway for 12R-BCM decomposition. 12R-BCM was synthesized with high purity and then controllably reduced using thermogravimetric analysis (TGA). Synchrotron X-ray diffraction (XRD) data is used to identify the formation of a 6H-Ba3Ce0.75Mn2.25O9 (6H-BCM) polytype that is formed at 1350 degrees C under strongly reducing pO2. Density functional theory (DFT) total energy and defect calculations show a window of thermodynamic stability for the 6H-polytype consistent with the XRD results. These data provide the first evidence of the 6H-BCM polytype and could provide a mechanistic explanation for the superior water-splitting behaviors of 12R-BCM.
Low-Z nanocrystalline diamond (NCD) grids have been developed to reduce spurious fluorescence and avoid X-ray peak overlaps or interferences between the specimen and conventional metal grids. Here, the low-Z NCD grids are non-toxic and safe to handle, conductive, can be subjected to high-temperature heating experiments, and may be used for analytical work in lieu of metal grids. Both a half-grid geometry, which can be used for any lift-out method, or a full-grid geometry that can be used for ex situ lift-out or thin film analyses, can be fabricated and used for experiments.
The fabrication of long-lived electrical contacts to thermoelectric Bi2Te3-based modules is a challenging problem due to chemical incompatibilities and rapid diffusion rates. Previously, technical guidance from SAND report 2015-7203 selected electroplated Au as the preferred method for fabrication of long-lived contacts because of concerns that the grain structure of sputtered/physical vapor deposited (PVD) Au contacts can evolve during aging. We have re-evaluated PVD Au contacts and show that they are appropriate for long-life service. We measure grain size and morphology at different aging times under accelerated temperature gradient conditions, and we show that the PVD Au contacts are stable and remain relatively unchanged. The PVD Au fabricated here is not subject to the deterioration observed in the previous report.
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 study 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.
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.
Multiple experimental configurations for performing nanoscale orientation mapping are compared to determine their fidelity to the true microstructure of a sample. Transmission Kikuchi diffraction (TKD) experiments in a scanning electron microscope (SEM) and nanobeam diffraction (NBD) experiments in a transmission electron microscope (TEM) were performed on thin electrodeposited hard Au films with two different microstructures. The Au samples either had a grain size that is >50 or <20 nm. The same regions of the samples were measured with TKD apparatuses at 30 kV in an SEM with detectors in the horizontal and vertical configurations and in the TEM at 300 kV. Under the proper conditions, we demonstrate that all three configurations can produce data of equivalent quality. Each method has strengths and challenges associated with its application and representation of the true microstructure. The conditions needed to obtain high-quality data for each acquisition method and the challenges associated with each are discussed.
The thermodynamic stability and melting point of magnesium borohydride were probed under hydrogen pressures up to 1000 bar (100 MPa) and temperatures up to 400 °C. At 400 °C, Mg(BH4)2 was found to be chemically stable between 700 and 1000 bar H2, whereas under 350 bar H2 or lower pressures, the bulk material partially decomposed into MgH2 and MgB12H12. The melting point of solvent-free Mg(BH4)2 was estimated to be 367-375 °C, which was above previously reported values by 40-90 °C. Our results indicated that a high hydrogen backpressure is needed to prevent the decomposition of Mg(BH4)2 before measuring the melting point and that molten Mg(BH4)2 can exist as a stable liquid phase between 367 and 400 °C under hydrogen overpressures of 700 bar or above. The occurrence of a pure molten Mg(BH4)2 phase enabled efficient melt-infiltration of Mg(BH4)2 into the pores of porous templated carbons (CMK-3 and CMK-8) and graphene aerogels. Both transmission electron microscopy and small-angle X-ray scattering confirmed efficient incorporation of the borohydride into the carbon pores. The Mg(BH4)2@carbon samples exhibited comparable hydrogen capacities to bulk Mg(BH4)2 upon desorption up to 390 °C based on the mass of the active component; the onset of hydrogen release was reduced by 15-25 °C compared to the bulk. Importantly, melt-infiltration under hydrogen pressure was shown to be an efficient way to introduce metal borohydrides into the pores of carbon-based materials, helping to prevent particle agglomeration and formation of stable closo-polyborate byproducts.
Noble gases are generated within solids in nuclear environments and coalesce to form gas stabilized voids or cavities. Ion implantation has become a prevalent technique for probing how gas accumulation affects microstructural and mechanical properties. Transmission electron microscopy (TEM) allows measurement of cavity density, size, and spatial distributions post-implantation. While post-implantation microstructural information is valuable for determining the physical origins of mechanical property degradation in these materials, dynamic microstructural changes can only be determined by in situ experimentation techniques. We present in situ TEM experiments performed on Pd, a model face-centered cubic metal that reveals real-time cavity evolution dynamics. Observations of cavity nucleation and evolution under extreme environments are discussed.
Additive manufacturing (AM) includes a diverse suite of innovative manufacturing processes for producing near-net shape components, typically from powder or wire feedstock. Reported mechanical properties of AM materials vary significantly depending on the details of the manufacturing process and the characteristics of the processing defects (namely, lack of fusion defects). However, an excellent combination of strength, ductility, and fracture resistance can be achieved in AM-type 304L and 316L austenitic stainless steels by minimizing processing defects. It is important to recognize that localized solidification processing during AM produces microstructures more analogous to weld microstructures than wrought microstructures. Consequently, the mechanical behavior of AM austenitic stainless steels in harsh environments can diverge from the performance of wrought materials. This report provides an overview of the fracture and fatigue response of type 304L materials from both directed energy deposition and powder bed fusion techniques. In particular, the mechanical performance of these materials is considered for high-pressure hydrogen applications by evaluating fatigue and fracture resistance after thermally precharging test specimens in high-pressure gaseous hydrogen. The mechanical behaviors are considered with respect to previous reports on hydrogen-assisted fracture of austenitic stainless steel welds and the unique characteristics of the AM microstructures. Fatigue crack growth can be relatively insensitive to processing defects, displaying similar behavior as wrought materials. In contrast, fracture resistance of dense AM austenitic stainless steel is more consistent with weld metal than with compositionally similar wrought materials. Hydrogen effects in the AM materials generally are more severe than in wrought materials but are comparable to measurements on welded austenitic stainless steels in hydrogen environments. Although hydrogen-assisted fracture manifests differently in welded and AM austenitic stainless steel, the fracture process appears to have a common origin in the compositional microsegregation intrinsic to solidification processes.
Tensile properties, fatigue crack initiation, fatigue crack growth rate, and fatigue life are evaluated in 304L austenitic stainless steel fabricated by directed energy deposition (DED). Large lack of fusion (LoF) defects (often >1 mm in length) significantly reduce ultimate tensile strength and ductility, as well as accelerate fatigue crack initiation and reduce fatigue life. In comparison, small spherical defects (<100 μm in diameter) have less effect on tensile and fatigue properties. Fatigue crack growth rate is less severely affected by defects than other properties, showing only local acceleration in the proximity of LoF defects. Therefore, shorter fatigue life is attributed to the role of LoF defects on facilitating fatigue crack initiation and to a lesser extent fatigue crack propagation. Additionally, the fatigue life can be normalized for defects by considering their effect on ultimate tensile strength, suggesting that in the limit of low defect population, the fatigue strength of additively manufactured stainless steel is similar to conventional wrought materials.
The US Department of Energy's Office of Nuclear Energy is interested in developing supercritical carbon dioxide (sCO2) power cycles that can achieve higher cycle efficiencies and lower costs than the traditional steam Rankine cycles. For the application of an sCO2 energy conversion system with a Very High Temperature Gas Reactor (VHTGR), turbine inlet temperatures over 850°C may be required. Consequently, it is necessary to demonstrate structural materials, including turbine inlet piping, that can be code certified at operating temperatures up to 900°C at sCO2 pressures up to 42 MPa (6100 psi). There are very few metal alloys that retain their strength at these high temperatures, and that are chemically compatible with sCO2.
Microstructures and mechanical properties are evaluated in austenitic stainless steel structures fabricated by directed energy deposition (DED) considering the effects of applied loading orientation, build geometry, and distance from the deposition baseplate. Locations within an as-deposited build with different thermomechanical history display different yield strength, while those locations with similar history have approximately the same yield strength, regardless of test specimen orientation. Thermal expansion of deposited material near the baseplate is inhibited by the mechanical constraint imposed by the baseplate, promoting plastic deformation and producing a high density of dislocations. Concurrently, high initial cooling rates decrease away from the baseplate as the build is heated, causing an increased spacing of cellular solidification features. An analysis of strengthening mechanisms quantitatively established for the first time the important strengthening contribution of high dislocation densities in the materials (166–191 MPa) to yield strength that ranged from 438 to 553 MPa in the present DED fabricated structures. A newly adopted mechanistic relationship for microsegregation strengthening from the literature indicated an additional important contribution to strengthening (123–135 MPa) due to the cellular solidification features. These findings are corroborated by the measured evolution of microstructure and hardness caused by annealing the DED material. These results suggest that the mechanical properties of deposited austenitic stainless steels can be influenced by controlling thermomechanical history during the manufacturing process to alter the character of compositional microsegregation and the amount of induced plastic deformation.
Additive manufacturing (AM) offers the potential for increased design flexibility in the low volume production of complex engineering components for hydrogen service. However the suitability of AM materials for such extreme service environments remains to be evaluated. This work examines the effects of internal and external hydrogen on AM type 304L austenitic stainless steels fabricated via directed-energy deposition (DED) and powder bed fusion (PBF) processes. Under ambient test conditions, AM materials with minimal manufacturing defects exhibit excellent combinations of tensile strength, tensile ductility, and fatigue resistance. To probe the effects of extreme hydrogen environments on the AM materials, tensile and fatigue tests were performed after thermalprecharging in high pressure gaseous hydrogen (internal H) or in high pressure gaseous hydrogen (external H). Hydrogen appears to have a comparable influence on the AM 304L as in wrought materials, although the micromechanisms of tensile fracture and fatigue crack growth appear distinct. Specifically, microstructural characterization implicates the unique solidification microstructure of AM materials in the propagation of cracks under conditions of tensile fracture with hydrogen. These results highlight the need to establish comprehensive microstructure-property relationships for AM materials to ensure their suitability for use in extreme hydrogen environments.
This SAND report fulfills the final report requirement for the Born Qualified Grand Challenge LDRD. Born Qualified was funded from FY16-FY18 with a total budget of ~$13M over the 3 years of funding. Overall 70+ staff, Post Docs, and students supported this project over its lifetime. The driver for Born Qualified was using Additive Manufacturing (AM) to change the qualification paradigm for low volume, high value, high consequence, complex parts that are common in high-risk industries such as ND, defense, energy, aerospace, and medical. AM offers the opportunity to transform design, manufacturing, and qualification with its unique capabilities. AM is a disruptive technology, allowing the capability to simultaneously create part and material while tightly controlling and monitoring the manufacturing process at the voxel level, with the inherent flexibility and agility in printing layer-by-layer. AM enables the possibility of measuring critical material and part parameters during manufacturing, thus changing the way we collect data, assess performance, and accept or qualify parts. It provides an opportunity to shift from the current iterative design-build-test qualification paradigm using traditional manufacturing processes to design-by-predictivity where requirements are addressed concurrently and rapidly. The new qualification paradigm driven by AM provides the opportunity to predict performance probabilistically, to optimally control the manufacturing process, and to implement accelerated cycles of learning. Exploiting these capabilities to realize a new uncertainty quantification-driven qualification that is rapid, flexible, and practical is the focus of this effort.
This work proposes a finite element (FE) analysis workflow to simulate directed energy deposition (DED) additive manufacturing at a macroscopic length scale (i.e. part length scale) and to predict thermal conditions during manufacturing, as well as distortions, strength and residual stresses at the completion of manufacturing. The proposed analysis method incorporates a multi-step FE workflow to elucidate the thermal and mechanical responses in laser engineered net shaping (LENS) manufacturing. For each time step, a thermal element activation scheme captures the material deposition process. Then, activated elements and their associated geometry are analyzed first thermally for heat flow due to radiation, convection, and conduction, and then mechanically for the resulting stresses, displacements, and material property evolution. Simulations agree with experimentally measured in situ thermal measurements for simple cylindrical build geometries, as well as general trends of local hardness distribution and plastic strain accumulation (represented by relative distribution of geometrically necessary dislocations).
Directed energy deposited (DED) and forged austenitic stainless steels possess dissimilar microstructures but can exhibit similar mechanical properties. In this study, annealing was used to evolve the microstructure of both conventional wrought and DED type 304L austenitic stainless steels, and significant differences were observed. In particular, the density of geometrically necessary dislocations and hardness were used to probe the evolution of the microstructure and properties. Forged type 304L exhibited the expected decrease in measured dislocation density and hardness as a function of annealing temperature. The more complex microstructure–property relationship observed in the DED type 304L material is attributed to compositional heterogeneities in the solidification microstructure.
The family of three-dimensional topological insulators opens new avenues to discover novel photophysics and to develop novel types of photodetectors. ZrTe5 has been shown to be a Dirac semimetal possessing unique topological, electronic, and optical properties. Here, we present spatially resolved photocurrent measurements on devices made of nanoplatelets of ZrTe5, demonstrating the photothermoelectric origin of the photoresponse. Because of the high electrical conductivity and good Seebeck coefficient, we obtain noise-equivalent powers as low as 42 pW/Hz1/2, at room temperature for visible light illumination, at zero bias. We also show that these devices suffer from significant ambient reactivity, such as the formation of a Te-rich surface region driven by Zr oxidation as well as severe reactions with the metal contacts. This reactivity results in significant stresses in the devices, leading to unusual geometries that are useful for gaining insight into the photocurrent mechanisms. Our results indicate that both the large photothermoelectric response and reactivity must be considered when designing or interpreting photocurrent measurements in these systems.
Directed energy deposition (DED) and forged austenitic stainless steels possess distinct microstructures, but may exhibit similar mechanical properties. In this study, annealing is used to evolve the microstructures of these materials, and scanning electron microscopy techniques are used to probe the similarities and differences of the microstructure-property relationships. A strong correlation between geometrically necessary dislocation (GND) density and hardness is observed for the forged material. Finally, a more complex relationship is observed in the DED material and is attributed to the thermally driven dissolution of the solidification microstructure.
Electrochemical atomic layer deposition (E-ALD) is a method for the formation of nanofilms of materials, one atomic layer at a time. It uses the galvanic exchange of a less noble metal, deposited using underpotential deposition (UPD), to produce an atomic layer of a more noble element by reduction of its ions. This process is referred to as surface limited redox replacement and can be repeated in a cycle to grow thicker deposits. It was previously performed on nanoparticles and planar substrates. In the present report, E-ALD is applied for coating a submicron-sized powder substrate, making use of a new flow cell design. E-ALD is used to coat a Pd powder substrate with different thicknesses of Rh by exchanging it for Cu UPD. Cyclic voltammetry and X-ray photoelectron spectroscopy indicate an increasing Rh coverage with increasing numbers of deposition cycles performed, in a manner consistent with the atomic layer deposition (ALD) mechanism. Cyclic voltammetry also indicated increased kinetics of H sorption and desorption in and out of the Pd powder with Rh present, relative to unmodified Pd.
Laser engineered net shaping (LENS) is an additive manufacturing process that presents a promising method of creating or repairing metal parts not previously feasible with traditional manufacturing methods. The LENS process involves the directed deposition of metal via a laser power source and a spray of metal powder co-located to create and feed a molten pool (also referred to generically as Directed Energy Deposition, DED). DED technologies are being developed for use in prototyping, repair, and manufacturing across a wide variety of materials including stainless steel, titanium, tungsten carbidecobalt, aluminum, and nickel based superalloys. However, barriers to the successful production and qualification of LENS produced or repaired parts remain. This work proposes a finite element (FE) analysis methodology capable of simulating the LENS process at the continuum length scale (i.e. part length scale). This method incorporates an element activation scheme wherein only elements that exceed the material melt temperature during laser heating are activated and carried through to subsequent analysis steps. Following the initial element activation calculation, newly deposited, or activated elements and the associated geometry, are carried through to thermal and mechanical analyses to calculate heat flow due to radiation, convection, and conduction as well as stresses and displacements. The final aim of this work is to develop a validated LENS process simulation capability that can accurately predict temperature history, final part shape, distribution of strength, microstructural properties, and residual stresses based on LENS process parameters.
The Enhanced Surveillance Sub-program has an annual NNSA requirement to submit a comprehensive report on all our fiscal year activities right after the start of the next calendar year. As most of you know, we collate all of our PI task submissions into a single volume that we send to NNSA, our customers, and use for other programmatic purposes. The functional objective of this report is to formally document the purpose, status, and accomplishments and impacts of all our work. For your specific submission, please follow the instructions described below and use the template provided. These are essentially the same as was used last year. We recognize this report may also include information on specific age-related findings that you will provide again in a few months as input to the Stockpile Annual Assessment process (e.g., in the submittal of your Component Assessment Report). However, the related content of your ES AR input should provide an excellent foundation that can simply be updated as needed for your Annual Assessment input.
This report documents work that was performed under the Laboratory Directed Research and Development project, Science of Battery Degradation. The focus of this work was on the creation of new experimental and theoretical approaches to understand atomistic mechanisms of degradation in battery electrodes that result in loss of electrical energy storage capacity. Several unique approaches were developed during the course of the project, including the invention of a technique based on ultramicrotoming to cross-section commercial scale battery electrodes, the demonstration of scanning transmission x-ray microscopy (STXM) to probe lithium transport mechanisms within Li-ion battery electrodes, the creation of in-situ liquid cells to observe electrochemical reactions in real-time using both transmission electron microscopy (TEM) and STXM, the creation of an in-situ optical cell utilizing Raman spectroscopy and the application of the cell for analyzing redox flow batteries, the invention of an approach for performing ab initio simulation of electrochemical reactions under potential control and its application for the study of electrolyte degradation, and the development of an electrochemical entropy technique combined with x-ray based structural measurements for understanding origins of battery degradation. These approaches led to a number of scientific discoveries. Using STXM we learned that lithium iron phosphate battery cathodes display unexpected behavior during lithiation wherein lithium transport is controlled by nucleation of a lithiated phase, leading to high heterogeneity in lithium content at each particle and a surprising invariance of local current density with the overall electrode charging current. We discovered using in-situ transmission electron microscopy that there is a size limit to lithiation of silicon anode particles above which particle fracture controls electrode degradation. From electrochemical entropy measurements, we discovered that entropy changes little with degradation but the origin of degradation in cathodes is kinetic in nature, i.e. lower rate cycling recovers lost capacity. Finally, our modeling of electrode-electrolyte interfaces revealed that electrolyte degradation may occur by either a single or double electron transfer process depending on thickness of the solid-electrolyte-interphase layer, and this cross-over can be modeled and predicted.
Nanostructuring of thermoelectric materials is expected to enhance thermoelectric properties by reducing the thermal conductivity and improving the power factor from that of homogeneous bulk materials. In multiphase, nanostructured thermoelectric materials, an understanding of precipitation mechanisms and phase stability is crucial for engineering systems with optimal thermoelectric performance. In this presentation we will discuss our investigations of the morphological evolution, orientation relationship, and composition of Ag{sub 2}Te precipitates in PbTe using transmission electron microscopy (TEM) and atom probe tomography (APT). Annealing in the region of two phase equilibrium between Ag{sub 2}Te and PbTe results in the formation of monoclinic {beta}-Ag{sub 2}Te precipitates as determined by x-ray and electron diffraction studies. These precipitates are aligned to the PbTe matrix with an orientation relationship that aligns the Te sub-lattices in the monoclinic and rock salt structures. This relationship is the same as we have reported earlier for {beta}-Ag{sub 2}Te precipitates in rocksalt AgSbTe{sub 2}. Observations using TEM and APT suggest that the Ag{sub 2}Te precipitates initially form as coherent spherical precipitates which upon coarsening evolve into flattened semi-coherent disks along the <100>PbTe directions which is consistent with theoretical predictions for elastically strained precipitates in a matrix. Our HRTEM observations show that sufficiently small precipitates are coherently embedded, while larger precipitates exhibit misfit dislocations and multiple monoclinic variants to relieve the elastic strain. Analysis of the composition of both precipitate groups using APT indicates that the larger precipitates exhibit compositions close to equilibrium while the smaller nanoscale precipitates exhibit enhanced Pb compositions. This detailed analysis of the orientation relationship, morphology, composition, and coarsening behavior of embedded Ag{sub 2}Te precipitates may be helpful in understanding the precipitation mechanisms and microstructure of related thermoelectric materials, such as LAST.
The precipitation of Ag{sub 2}Te in a PbTe matrix is investigated using electron microscopy and atom probe tomography. We observe the formation of oriented nanoscale Ag{sub 2}Te precipitates in PbTe. These precipitates initially form as coherent spherical nanoparticles and evolve into flattened semi-coherent disks during coarsening. This change in morphology is consistent with equilibrium shape theory for coherently strained precipitates. Upon annealing at elevated temperatures these precipitates eventually revert to an equiaxed morphology. We suggest this shape change occurs once the precipitates grow beyond a critical size, making it favorable to relieve the elastic coherency strains by forming interfacial misfit dislocations. These investigations of the shape and coherency of Ag{sub 2}Te precipitates in PbTe should prove useful in the design of nanostructured thermoelectric materials.