Critical Factors Dictating Reversibility of the Zinc Metal Anode
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Ma, Lin↗
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Critical fields of liquids of liquid superconducting metallic hydrogen
Liquid metallic hydrogen, in a fully dissociated state, is predicted at certain densities to pass from dirty to clean and from type II to type I superconducting behavior as temperature is lowered.
Jaffe, J.↗
Heterolytic Hydrogen Activation: Understanding Support Effects in Water–Gas Shift, Hydrodeoxygenation, and CO Oxidation Catalysis
Identifying the role of oxide supports in transition metal catalysis is critical toward our understanding of heterogeneous catalysis. The water-gas shift (WGS) reaction is a prototypical example where oxide support dictates catalytic activity, yet the cause for this remains uncertain. Herein, we show that a single descriptor—the equilibrium constant for hydroxyl formation—relates the WGS turnover frequency across disparate oxide supports. The dissimilar equilibrium constant, or oxophilicity, between early and late transition metals exemplify the utility of metal-support interfacial sites to circumvent adsorption-energy scaling restrictions, thereby providing bifunctional gains for the WGS reaction class. In relation, the equilibrium constant for hydroxyl formation is equivalent to the equilibrium constant for the formal heterolytic dissociation of hydrogen, and therefore, reflects the ability of the metal-support interface to participate in hydrogen heterolysis. The ubiquitous coexistence, yet divergent chemical behavior of homo- and heterolytically activated hydrogen renders oxide support identity central toward our understanding of hydrogenation catalysis. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and performed at the Environmental Molecular Sciences Laboratory in (EMSL), which is a DOE Office of Science User Facility located at the Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility. N.N. would like to thank Oliver Y. Gutierrez for critical feedback during the final stage of manuscript preparation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomic dynamics of gas-dependent oxide reducibility
Understanding oxide reduction is critical for advancing metal production, catalysis and energy technologies. Although carbon monoxide (CO) and hydrogen (H 2 ) are widely used reductants, the mechanisms by which they work are often presumed to be similar, both involving lattice oxygen removal. However, because of growing interest in replacing CO with H 2 to lower CO 2 emissions, distinguishing gas-specific reduction pathways is critical. Yet, capturing these atomic-scale processes under reactive gas and high-temperature conditions remains challenging. Here we use environmental transmission electron microscopy, which is capable of real-time, atomic-resolution imaging of gas–solid redox reactions to directly visualize the gas-dependent oxide reduction dynamics in NiO. We show that CO drives surface nucleation and the growth of metallic Ni islands, leading to self-limiting surface metallization. Conversely, H 2 activates a coupled surface-to-bulk transformation, where protons from dissociated H 2 infiltrate the oxide lattice to promote the inward migration of surface-generated oxygen vacancies and enabling bulk metallization. By contrast, oxygen vacancies formed by CO remain confined near the surface, where they rapidly form a metallic Ni layer that inhibits further reduction. Furthermore, these results reveal distinct atomistic pathways for CO and H 2 and provide insights that may guide metallurgical processes and catalyst design.
36 MATERIALS SCIENCE↗
Conservation of Strategic Aerospace Materials (COSAM)
Research efforts to reduce the dependence of the aerospace industry on strategic metals, such as cobalt (Co), columbium (Cb), tantalum (Ta), and chromium (Cr), by providing the materials technology needed to minimize the strategic metal content of critical aerospace components for gas turbine engines are addressed. Thrusts in three technology areas are identified: near term activities in the area of strategic element substitution; intermediate-range activities in the area of materials processing; and long term, high risk activities in the area of 'new classes' of high temprature metallic materials. Specifically, the role of cobalt in nickel-base and cobalt-base superalloys vital to the aerospace industry is examined along with the mechanical and physical properties of intermetallics that will contain a minimum of the stragetic metals.
Stephens, J. R.↗
Revealing Solvent-Assisted Li+ Transport in the Solid Electrolyte Interphase operando
The performance of energy-dense lithium metal batteries is critically influenced by the properties of the solid electrolyte interphase (SEI). Yet, progress in understanding this layer has been limited by the lack of accurate operando characterization because the SEI evolves dynamically during cycling. Here, we apply dynamic electrochemical impedance spectroscopy (dEIS) to resolve the real-time evolution of the SEI on lithium metal in ether-based electrolytes with varying degrees of fluorination. We find that faster stabilization of the compact SEI resistance correlates with improved passivation and higher Coulombic efficiency. Unexpectedly, compact SEI resistance correlates directly with Li+ solvation energy, revealing that weaker Li+ solvation increases not only bulk but also interphase resistance. These findings challenge the conventional view of the SEI as a purely solid-phase conductor and instead support a solvent-assisted Li+ transport mechanism within the compact SEI. This framework emphasizes the need to balance SEI ionic conductivity with the Li+ solvation environment to maximize lithium metal battery performance.
Sacci, Robert [ORNL] (ORCID:0000000200735221)↗
Breaking the Energy Barrier of Heavy Metal Ion Diffusion in Micropores with Mesoporous 3D Graphene for Fast and Efficient Cu2+ Removal
Efficient removal of heavy metals from water critically depends not only on adsorption capacity but also on ion diffusion kinetics and the associated energy barriers. In conventional carbon adsorbents, severe diffusion confinement within micropores restricts ion transport, resulting in sluggish adsorption kinetics and large apparent activation energies despite high specific surface areas. Here, we demonstrate that this fundamental limitation is overcome by engineering meso/macroporous architectures in the 3D graphene materials synthesized via our discovered alkali-metal reactions with\\\\r\\\\n2\\\\r\\\\nCO. The unique 3D graphene materials possess defect-rich graphene frameworks with interconnected meso/macroporous networks, exhibiting simultaneously high surface area and greatly enhanced meso/macropore volume that enable efficient access to adsorption sites. As a result, the Cu2+ adsorption on 3D graphene proceeds with very low activation energies (4.98 kJ mol–1), which is almost 4 times smaller than on activated carbon (23.1 kJ mol–1). This finding offers a promising platform for efficient and sustainable water purification.
25 ENERGY STORAGE↗
LUBRICATING PROPERTIES OF CERAMIC-BONDED CALCIUM FLUORIDE COATINGS ON NICKEL-BASE ALLOYS FROM 75 DEG TO 1900 DEG F
The endurance life and the friction coefficient of ceramic-bonded calcium fluoride (CaF2) coatings on nickel-base alloys were determined at temperatures from 75° to 1900° F. The specimen configuration consisted of a hemispherical rider (3/16-in. rad.) sliding against the flat surface of a rotating disk. Increasing the ambient temperature (up to 1500° F) or the sliding velocity generally reduced the friction coefficient and improved coating life. Base-metal selection was critical above 1500° F. For instance, cast Inconel sliding against coated Inconel X was lubricated effectively to 1500° F, but at 1600° F severe blistering of the coatings occurred. However, good lubrication and adherence were obtained for René 41 sliding against coated René 41 at temperatures up to 1900° F; no blisters developed, coating wear life was fairly good, and the rider wear rate was significantly lower than for the unlubricated metals . Friction coefficients were 0.12 at 1500° F, 0.15 at 1700° F, and 0.17 at 1800° and 1900° F. Because of its ready availability, Inconel X appears to be the preferred substrate alloy for applications in which the temperature does not exceed 1500° F. René 41 would have to be used in applications involving higher temperatures. Improved coating life was derived by either preoxidizing the substrate metals prior to the coating application or by applying a very thin (<0.0002 in.) burnished and sintered overlay to the surface of the coating. Preoxidation did not affect the friction coefficient. The overlay generally resulted i n a higher friction coefficient than that obtained without the overlay. The combination of both modifications resulted in longer coating life and in friction coefficients intermediate between those obtained with either modification alone.
Nickel alloy↗
Lubricating Properties of Ceramic-Bonded Calcium Fluoride Coatings on Nickel-Base Alloys from 75 to 1900 deg F
The endurance life and the friction coefficient of ceramic-bonded calcium fluoride (CaF2) coatings on nickel-base alloys were determined at temperatures from 75 F to 1900 F. The specimen configuration consisted of a hemispherical rider (3/16-in. rad.) sliding against the flat surface of a rotating disk. Increasing the ambient temperature (up to 1500 F) or the sliding velocity generally reduced the friction coefficient and improved coating life. Base-metal selection was critical above 1500 F. For instance, cast Inconel sliding against coated Inconel X was lubricated effectively to 1500 F, but at 1600 F severe blistering of the coatings occurred. However, good lubrication and adherence were obtained for Rene 41 sliding against coated Rene 41 at temperatures up to 1900 F; no blisters developed, coating wear life was fairly good, and the rider wear rate was significantly lower than for the unlubricated metals. Friction coefficients were 0.12 at 1500 F, 0.15 at 1700 F, and 0.17 at 1800 F and 1900 F. Because of its ready availability, Inconel X appears to be the preferred substrate alloy for applications in which the temperature does not exceed 1500 F. Rene 41 would have to be used in applications involving higher temperatures. Improved coating life was derived by either preoxidizing the substrate metals prior to the coating application or by applying a very thin (less than 0.0002 in.) burnished and sintered overlay to the surface of the coating. Preoxidation did not affect the friction coefficient. The overlay generally resulted in a higher friction coefficient than that obtained without the overlay. The combination of both modifications resulted in longer coating life and in friction coefficients intermediate between those obtained with either modification alone.
Sliney, Harold E.↗
Development of Luminescent Materials and Instrumentation for Critical Mineral Discovery and Monitoring
Presentation discussing career paths in chemistry as well as how chemical research is applied to address real-world problems. Here, a variety of different materials (metal-organic frameworks, carbon dots, thin films, etc.) are used as luminescent sensors to detect trace quantities of economically critical metals, which are used in applications ranging from renewable energy to national defense. In an application particularly relevant to Western Pennsylvania, the sensor technologies are deployed in coal utilization byproducts including fly ash leachates and acid mine drainage. Taken together, this research presents an exciting path towards reducing the characterization costs associated with metals prospecting and process monitoring, facilitating domestic production of these metals.
analytical chemistry↗
Universal Behavior of a Cyclic Oxidation Model
A mathematical model has been generated to represent the iterative, discrete growth and spallation processes associated with cyclic oxidation. Parabolic growth kinetics (k(sub p)) over and a constant spall area (F(sub A)) were assumed, with spalling occurring interfacially at the thickest regions of the scale. Although most models require numerical techniques, the regularity and simplicity of this progression permitted an approximation by algebraic expressions. Normalization could now be performed to reflect all parametric effects, and a universal cyclic oxidation response was generated: W(sub u) = 1/2 {3J(sub u)(sup 1/2)+ J(sub u)(sup 3/2)} where W, is weight change normalized by the maximum and J(sub u) is the cycle number normalized by the number to reach maximum. Similarly, the total amount of metal consumed was represented by a single normalized curve. The factor [(S(sub c)-l)(raised dot)sqrt(F(sub A)k(sub p)DELTAt)] was identified as a general figure of merit, where S(sub c) is the mass ratio of oxide to oxygen and DELTAt is the cycle duration. A cyclic oxidation failure map was constructed, in normalized k(sub p)-F(sub A) space, as defined by the locus of points corresponding to a critical amount of metal consumption in a given time. All three constructions describe behavior for every value of growth rate, spall fraction, and cycle duration by means of single curves, but with two branches corresponding to the times before and after steady state is achieved.
Smialek, James L.↗
Material Interactions with Solar Wind Ion Environments
Solar wind composition is dominated by hydrogen (approx.96%) and helium (approx.3 to 4%) with a minor fraction (less than or equal to 1%) of heavy ions. Hydrogen (helium) ions impact spacecraft surfaces with energies from 0.5 to 5 keV (1.8 to 21 keV) due to variations in solar wind velocity from 300 km/s to 1000 km/sec with extremes of a few 10 s keV during periods of extremely high solar wind velocity exceeding 1000 km/sec. Mean impact energies are typically on the order of approximately 1 keV and 4 keV for hydrogen ions and helium ions, respectively. These energies are typically of the peak of the energy dependent light ion sputter yields for hydrogen and helium on many metals. In addition, light ions with kilovolt energies have been shown to produce blister (or exfoliation) damage to metal surfaces due to formation of high pressure gas bubbles within the materials when exposed to ion fluences on the order of 10(exp 16 to (10(exp 17 ions/sq cm. A number of spacecraft designs for current and future missions include gossamer polymer structures with thin metallic reflection coatings to shield instruments from the Sun or solar sail propulsion systems for use in a variety of locations in the inner solar system from 0.5 to 1 AU. In addition, there is interest in designing spacecraft for solar physics missions requiring operations as close to the Sun as 0.16 to 0.2 AU. Integrity of the metallic coatings is critical in many of these applications since degradation will result in modification of material thermal properties or exposure of polymers to solar UV photons which can compromise mission requirements. This paper will evaluate the relative contributions of sputtering and blister formation to material degradation in solar wind environments over a range of radial distances from the Sun to demonstrate where solar wind environments become important for materials selection. We will first review the physics and results from laboratory measurements of light ion sputtering, blistering, and exfoliation of metallic surfaces to establish the order of magnitude ion fluence required for significant surface damage. Solar wind ion fluence environments will then be evaluated due to variations in solar wind conditions as a function of solar cycle for varying distances from the Sun using models for radial variations in solar wind ion number density, temperature, and velocity to determine where sputtering and blistering is most likely to be an issue. Finally, ion fluence statistics for varying radial distances from the Sun will be shown to establish the mission duration and radial distances from the Sun where missions will encounter sufficient ion fluence to exhibit damage to metallic surfaces.
Minow, Joseph I.↗
NASA's activities in the conservation of strategic aerospace materials
The primary objective of the Conservation of Strategic Aerospace Materials (COSAM) Program is to help reduce the dependence of the United States aerospace industry on strategic metals by providing the materials technology needed to minimize the strategic metal content of critical aerospace components with prime emphasis on components for gas turbine engines. Initial emphasis was placed in the area of strategic element substinction. Specifically, the role of cobalt in nickel base and cobalt base superalloys vital to the aerospace industry is being examined in great detail by means of cooperative university-industry-government research efforts. Investigations are underway in the area of "new classes" of alloys. Specifically, a study was undertaken to investigate the mechanical and physical properties of intermetallics that contain a minimum of the strategic metals. Current plans for the much larger COSAM Program are also presented.
Stephens, J. R.↗
Engineering of Nanoscale Heterogeneous Transition Metal Dichalcogenide–Au Interfaces
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 WS 2 –Au and WSe 2 –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. Here 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.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Seeing in with X-rays: 4D Strain and Thermometry Measurements for Thermal-Mechanical Testing
Understanding temperature-dependent material decomposition and structural deformation induced by combined thermal-mechanical environments is critical for safety qualification of hardware under accident scenarios. Seeing in with X-rays elucidated the physics necessary to develop X-ray strain and thermometry diagnostics for use in optically opaque environments. Two parallel thermometry schemes were explored: X-ray fluorescence and X-ray diffraction of inorganic doped ceramics– colloquially known as thermographic phosphors. Two parallel surface strain techniques–Path-Integrated Digital Image Correlation and Frequency Multiplexed Digital Image Correlation–were demonstrated. Finally, preliminary demonstration of time-resolved digital volume correlation was performed by taking advantage of limited view reconstruction techniques. Additionally, research into blended ceramic-metal coatings was critical to generating intrinsic thermographic patterns for the future combination of X-ray strain and thermometry measurements.
36 MATERIALS SCIENCE↗
The breakdown of both strange metal and superconducting states at a pressure-induced quantum critical point in iron-pnictide superconductors
Here we report the first observation of the concurrent breakdown of the strange metal (SM) normal state and superconductivity at a pressure-induced quantum critical point in Ca 10 (Pt 4 As 8 )((Fe 0.97 Pt 0.03 ) 2 As 2 ) 5 superconductor. We find that, upon suppressing the superconducting state, the power exponent (α) changes from 1 to 2, and the slope of the temperature-linear resistivity per FeAs layer (A $\Box$ ) gradually diminishes. At a critical pressure, A $\Box$ and superconducting transition temperature (T c ) go to zero concurrently, where a quantum phase transition from a superconducting state with a SM normal state to a non-superconducting Fermi liquid state occurs. Scaling analysis reveals that the change of A $\Box$ with T c obeys the relation of T c ~ (A $\Box$ ) 0.5 , similar to what is seen in other chemically doped unconventional superconductors. These results suggest that there is a simple but powerful organizational principle of connecting the SM normal state with the high-T c superconductivity.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Electrical Control of Magnetic Resonance in Phase Change Materials
Metal–insulator transitions (MITs) in resistive switching materials can be triggered by an electric stimulus that produces significant changes in the electrical response. When these phases have distinct magnetic characteristics, dramatic changes in the spin excitations are also expected. The transition metal oxide La 0.7 Sr 0.3 MnO 3 (LSMO) is a ferromagnetic metal at low temperatures and a paramagnetic insulator above room temperature. When LSMO is in its metallic phase, a critical electrical bias has been shown to lead to an MIT that results in the formation of a paramagnetic resistive barrier transverse to the applied electric field. Using spin-transfer ferromagnetic resonance spectroscopy, we show that even for electrical biases less than the critical value that triggers the MIT, there is magnetic phase separation, with the spin-excitation resonances varying systematically with applied bias. Therefore, voltage-triggered MITs in LSMO can alter magnetic resonance characteristics, offering an effective method for tuning synaptic weights in neuromorphic circuits.
36 MATERIALS SCIENCE↗
Effect of impurities on hydrogen defect stability and migration barrier in yttrium dihydride crystal
The impurity or alloying atoms in YH 2 can alter the local electronic structure and so the hydrogen defect stability, as well as the H migration barrier energy. Thus, DFT calculations were employed to determine the effect of foreign elements from alkali and alkaline earth metals to transition metals and one critical impurity element, O, on H vacancy stability and retention characteristics in YH2. Results revealed that alloying elements act as hydrogen vacancy sinks by reducing the vacancy formation energy at neighboring sites. The implantation of non-magnetic foreign elements (s1, s2, and d10 valence electrons) in hydrogen energy landscape was calculated to be minor; while the hydrogen vacancy formation energy was reduced from 1.37 eV to 1.00 eV, the migration energy barrier of hydrogen was increased from 0.87 eV to 1.15 eV for non-magnetic foreign elements. The migration energy barrier monotonically decreased with increasing d-shell occupancy, reaching as low as 0.4 eV for Cr, Mo(d4), and Fe (d4). Alloying with late transition metals (d8 and d9) moderately impacted the hydrogen vacancy formation. Finally, it was found to be O addition into the YH 2- lattice did not alter the energy landscape of hydrogen vacancies. Since alloyed YH 2 has not been studied extensively, this study provides an atomistic understanding how alloying elements and impurities trap vacancies and affects hydrogen mobility YH 2 . Meanwhile, the main findings of this study may serve as guidelines for introducing alloying elements in ZrH 2 as well.
08 HYDROGEN↗