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At least 253 records · Page 14

Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte

Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.

Wang, Yixian [Materials Science and Engineering Pr↗

In Situ High-Temperature TEM Observation of Inconel Corrosion by Molten Chloride Salts with N 2 , O 2 , or H 2 O

Here, in situ transmission electron microscopy (TEM) diffraction and imaging techniques are used to monitor and quantify corrosion of Inconel-625 by pure molten chloride salts (MgCl 2 – NaCl – KCl) at 500 °C–800 °C in 1.0 atm inert N 2 or pure O2, or by salts which are controllably hydrated in a high vacuum chamber. The isothermal corrosion rate R in inert N 2 increases from 203 ± 30 μ m year –1 at 700 °C to 463 ± 30 μ m year –1 at 800 °C. An oxygen ambient causes a six-fold increase to R = 1261 ± 170 μ m year –1 at 700 °C. Salt hydration dramatically accelerates corrosion to R > 3 × 10 5 μ m year –1 at 700 °C while it leads to a more moderate R = 95 ± 20 and 486 ± 30 μ m year –1 at 500 °C and 600 °C, respectively. These isothermal corrosion rates indicate that the molten chloride corrosion is significantly accelerated by salt hydration at temperatures above 600 °C, where corrosion is aggravated by increased generation and solubility of corrosive HCl gases. Hence, to reduce rate of corrosion it is important to both avoid incorporation of H 2 O into the system at each stage and ensure proper flushing of the system before increasing the temperature beyond 600 °C. Compositional analysis of the corroded cells indicate that corrosion in O 2 ambient is dominated by oxidation of metals by O 2 gas dissolved in the chloride melt, but corrosion in H 2 O ambients is caused by chlorination of metals by dissolved HCl gas and MgOH + ions. So, to reduce rate of corrosion, steps should be taken to tailor chloride melt compositions that has low solubility for HCl and O 2 . All of our corroded samples exhibit passive-protective oxide layers of Cr, Mg, and Ni. In addition, distinct volatile compounds of Ni, Mo and Cr involving NiCl 2 , (Na,K) 2 MoO 4 and CrO 2 (OH) 2 are detected in N 2 , H 2 O, and O 2 ambients, respectively. We believe that corrosion acceleration can be minimized by minimizing formation of volatile by-products or promoting reactions that could convert these volatile compounds to solid phases, as these volatile compounds led to destruction of protective oxide layers.

14 SOLAR ENERGY↗

Understanding oxidation of Fe-Cr-Al alloys through explainable artificial intelligence

Abstract The oxidation resistance of FeCrAl based on alloying composition and oxidizing conditions is predicted using a combinatorial experimental and artificial intelligence approach. A neural network (NN) classification model was trained on the experimental FeCrAl dataset produced at GE Research. Furthermore, using the SHapley Additive exPlanations (SHAP) explainable artificial intelligence (XAI) tool, we explore how the NN can showcase further material insights that are unavailable directly from a black-box model. We report that high Al and Cr content forms protective oxide layer, while Mo in FeCrAl creates thick unprotective oxide scale that is vulnerable to spallation due to thermal expansion. Graphical abstract

Materials Science↗

Conceptual design of HFIR irradiation experiment for material compatibility study on liquid Sn divertor

Liquid Sn is one of the promising coolants for liquid surface divertor concept of fusion reactors. However, the compatibility between liquid Sn and structural materials is an important issue that has to be addressed, because liquid Sn is extremely corrosive to steels at high temperatures. The corrosion may be mitigated when a protective Al2O 3 layer is formed on the surface of alumina forming steels. However, the effect of neutron irradiation on the integrity of protective layer is not made clear so far. Japan and US joint research project “FRONTIER” started in 2019 to investigate the material compatibility under neutron irradiation. The purpose of the present study is to develop the conceptual design of the irradiation test capsule which enables material compatibility tests for the alumina forming steels - liquid metal systems under neutron irradiation in the High Flux Isotope Reactor at Oak Ridge National Laboratory, TN, USA. The three dimensional drawing of capsule structure was then developed. The validity of the material selections for the capsule design was investigated by means of corrosion tests of SiC, Si3N4, Ti, and Mo in liquid Sn at 773 K for 262 hr.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Depth Profiling Analysis of Aluminum Oxidation During Film Deposition in a Conventional High Vacuum System

The oxidation of aluminum thin films deposited in a conventional high vacuum chamber has been investigated using x-ray photoelectron spectroscopy (XPS) and depth profiling. The state of the Al layer was preserved by coating it with a protective MgF2 layer in the deposition chamber. Oxygen concentrations in the film layers were determined as a function of sputter time (depth into the film). The results show that an oxidized layer is formed at the start of Al deposition and that a less extensively oxidized Al layer is deposited if the deposition rate is fast. The top surface of the Al layer oxidizes very quickly. This top oxidized layer may be thicker than has been previously reported by optical methods. Maximum oxygen concentrations measured by XPS at each Al interface are related to pressure to rate ratios determined during the Al layer deposition.

Kim, Jongmin↗

NASA Technologies that Benefit Society

Applications developed on Earth of technology needed for space flight have produced thousands of spinoffs that contribute to improving national security, the economy, productivity and lifestyle. Over the course of it s history, NASA has nurtured partnerships with the private sector to facilitate the transfer of NASA-developed technology. For every dollar spent on research and development in the space program, it receives back $7 back in the form of corporate and personal income taxes from increased jobs and economic growth. A new technology, known as Liquid-metal alloy, is the result of a project funded by NASA s Jet Propulsion Lab. The unique technology is a blend of titanium, zirconium, nickel, copper and beryllium that achieves a strength greater than titanium. NASA plans to use this metal in the construction of a drill that will help for the search of water beneath the surface of Mars. Many other applications include opportunities in aerospace, defense, military, automotive, medical instrumentation and sporting goods.Developed in the 1980 s, the original Sun Tigers Inc sunlight-filtering lens has withstood the test of time. This technology was first reported in 1987 by NASA s JPL. Two scientists from JPL were later tasked with studying the harmful effects of radiation produced during laser and welding work. They came up with a transparent welding curtain that absorbs, filters and scatters light to maximize protection of human eyes. The two scientists then began doing business as Eagle Eye Optics. Each pair of sunglasses comes complete with ultraviolet protection, dual layer scratch resistant coating, polarized filters for maximum protection against glare and high visual clarity. Sufficient evidence shows that damage to the eye, especially to the retina, starts much earlier than most people realize. Sun filtering sunglasses are important. Winglets seen at the tips of airplane wings are among aviations most visible fuel-saving, performance enhancing technology. Aerodynamics centers on two majors forces-lift and drag. Lift enables the plane to fly and drag is the resistance encountered while moving through the air. The air coming off the end of a standard wing, in a vortex, causes significant drag and turbulence, forcing the spacing between takeoffs. A Langley engineer for NASA published finding in 1976 and verified by test in 1977 that winglets produce a 7 percent increase in lift-drag ratio with a 20 percent decrease in drag. This configuration reduces emissions, allows for greater range and carry more payload and the planes fly more quietly. Winglet technology has saved 2 billion gallons of jet fuel worldwide in 2010. Aerogel represents what technology experts believe to be the best insulation material ever invented. It is very light, flexible and can withstand temperatures of minus 3000 deg F. Aerogel products will be found in everything from clothing, to building insulation to space vehicles. Corpo Nove incorporated the Spaceloft version of the NASA-developed aerogel material into this jacket which was test during an Antarctic expedition.

Griffin, Amanda↗

Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO 2 overlayers

Ultra-thin film coatings are used to protect semiconductor photoelectrodes from the harsh chemical environments common to photoelectrochemical energy conversion. These layers add contact transfer resistance to the interface that can result in a reduction of photoelectrochemical energy conversion efficiency of the photoelectrode. Here, we describe the concept of a partial protection layer, which allows for direct chemical access to a small fraction of the semiconductor underlayer for further functionalization by an electrocatalyst. The rest of the interface remains protected by a stable, inert protection layer. CuO is used as a model system for this scheme. Atomic layer deposition (ALD)-prepared TiO 2 layers on CuO thin films prepared from electrodeposited Cu 2 O allow for the control of interfacial morphology to intentionally expose the CuO underlayer. The ALD-TiO 2 overlayer shrinks during crystallization, while Cu 2 O in the underlayer expands during oxidation. As a result, the TiO 2 protection layer cracks to expose the oxidized underlying CuO layer, which can be controlled by preceding thermal oxidation. Furthermore, this work demonstrates a potentially promising strategy for the parallel optimization of photoelectrochemical interfaces for chemical stability and high performance.

14 SOLAR ENERGY↗

Engineering Surface Architectures for Improved Durability in III–V Photocathodes

GaInP2 has shown promise as the wide bandgap top junction in tandem absorber photoelectrochemical (PEC) water splitting devices. Among previously reported dual-junction PEC devices with a GaInP 2 top cell, those with the highest performance incorporate an AlInP 2 window layer (WL) to reduce surface recombination and a thin GaInP2 capping layer (CL) to protect the WL from corrosion in electrolytes. However, the stability of these III-V systems is limited, and durability continues to be a major challenge broadly in the field of PEC water splitting. This work provides a systematic investigation into the durability of GaInP 2 systems, examining the impacts of the window layer and capping layer among single junction pn-GaInP 2 photocathodes coated with an MoS 2 catalytic and protective layer. The photocathode with both a CL and WL demonstrates the highest PEC performance and longest lifetime, producing a significant current for >125 h. In situ optical imaging and post-test characterization illustrate the progression of macroscopic degradation and chemical state. The surface architecture combining an MoS 2 catalyst, CL, and WL can be translated to dual-junction PEC devices with GaInP 2 or other III-V top junctions to enable more efficient and stable PEC systems.

08 HYDROGEN↗

Self-healing electrode protection in electrochemical cells

Articles and methods for protection of electrodes in electrochemical cells, including protective material precursor layers for use in electrode protective structures, are provided. Certain embodiments relate to electrode protective structures that comprise protective material precursor layers that, upon direct contact with a liquid electrolyte, cause a reaction product to form between the material of the precursor layer and a component of the electrolyte.

36 MATERIALS SCIENCE↗

Study of the effects of gaseous environments on sulfidation attack of superalloys

Studies were conducted to examine the effect of the gaseous corrodents NaCl, HCl, and NaOH on the high temperature oxidation and Na2SO4-induced corrosion behavior of the alumina former NiAl, the chromia former Ni-25 wt.% Cr, elemental Cr, and the superalloy B-1900. Experiments were conducted at 900 and 1050 C in air in the presence and absence of the gaseous corrodents. Effects involving both reaction rates and microstructural changes in oxide morphology were observed due to the presence of these corrodents at levels anticipated to be present in operating industrial and marine gas turbines. The effect of gaseous NaCl, HCl, and possibly NaOH on NiAl in simple oxidation was to remove aluminum from below the protective alumina layer and to simultaneously weaken the adherence of the protective alumina oxide scale to the substrate. The aluminum removed from below the oxide scale was redeposited on its surface as alpha-Al2O3 whiskers. With respect to the chromia formers, gaseous NaCl and HCl promoted breakaway oxidation kinetics and changes in the microstructures of the oxide scales.

Smeggil, J. G.↗

Reformulation of Oxide Growth Equations for Oxidation of Silicon Bond Coat in Environmental Barrier Coating Systems

The formulation of Deal and Grove for the oxidation of silicon and the growth of a silica layer is revisited to include the effects of a protective coating layer. The linear-parabolic equation of the form x_o^2+Ax_o=Bt is still applicable, but the expressions for the constants A and B must be modified to account for the coating. The modified expression for A is a linear function of the coating thickness. The expression for B is modified by the relative solubility of the outer coating layer. The modified expressions are applied to assess recently published experimental results for the oxidation of a silicon bond coat in an environmental barrier coating (EBC). Conclusions are drawn regarding the diffusivity and solubility of oxidants in the EBC top coating.

Sullivan, Roy M.↗

Issues and Consequences of Atomic Oxygen Undercutting of Protected Polymers in Low Earth Orbit

Hydrocarbon based polymers that are exposed to atomic oxygen in low Earth orbit are slowly oxidized which results in recession of their surface. Atomic oxygen protective coatings have been developed which are both durable to atomic oxygen and effective in protecting underlying polymers. However, scratches, pin window defects, polymer surface roughness and protective coating layer configuration can result in erosion and potential failure of protected thin polymer films even though the coatings are themselves atomic oxygen durable. This paper will present issues that cause protective coatings to become ineffective in some cases yet effective in others due to the details of their specific application. Observed in-space examples of failed and successfully protected materials using identical protective thin films will be discussed and analyzed. Proposed approaches to prevent the failures that have been observed will also be presented.

Banks, Bruce A.↗

Towards Risk-Informed Performance-Based Emergency Planning: Review of Regulation, Guidance, and Methods

At a fundamental level, nuclear facility safety is built upon the concept of defense-in-depth (DID), which entails multiple, independent layers of protection for public health and safety. Within the DID structure, emergency preparedness (EP) is the last layer of defense and provides reasonable assurance that adequate protective measures can and will be taken in the event of a radiological emergency. Over several decades, the EP regulatory framework has evolved in response to lessons learned from actual events, experience with maintaining and testing EP capabilities, and advances in a wide range of technologies. Furthering this evolution, recent developments in risk-informed performance-based (RIPB) design and licensing approaches provide an opportunity to leverage insights regarding the attributes of the specific facility and site to inform EP.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Superhydrophobic Post Treatment and Coating Extenders for Improved Asset Sustainability

Launch structures, hardware, and ground support equipment, at NASA's John F. Kennedy Space Center in Florida, are exposed to a highly corrosive natural coastal marine environment. In addition, during launches, rocket exhaust deposition is also highly corrosive. Superhydrophobic coatings are being considered for additional corrosion protection on existing structures to enhance corrosion resistance and add an additional layer of protection against harsh environmental elements. These coatings have come into their own recently, and are now being investigated as corrosion protective coatings due to their water repelling capability. These coatings can be used on existing coatings, newly coated materials, or used on bare substrates. The coatings are not suitable for permanent corrosion protection, but can be used where additional corrosion control is desired or only when temporary corrosion control is needed, such as in hardware sitting on a launch pad for 30-45 days prior to a launch. In this study, superhydrophobic coatings were applied on various coated and uncoated substrates and exposed to the spaceport environment for various times up to 60 days. This paper highlights the current results of the superhydrophobic coatings performance evaluated by X-ray photoelectron spectroscopy, and contact angle measurements.

Coating↗

Experimentally informed structure optimization of amorphous TiO 2 films grown by atomic layer deposition

Amorphous titanium dioxide TiO 2 (a-TiO 2 ) has been widely studied, particularly as a protective coating layer on semiconductors to prevent corrosion and promote electron–hole conduction in photoelectrochemical reactions. The stability and longevity of a-TiO 2 is strongly affected by the thickness and structural heterogeneity, implying that understanding the structure properties of a-TiO 2 is crucial for improving the performance. This study characterized the structural and electronic properties of a-TiO 2 thin films (~17 nm) grown on Si by atomic layer deposition (ALD). Fluctuation spectra V(k) and angular correlation functions were determined with 4-dimensional scanning transmission electron microscopy (4D-STEM), which revealed the distinctive medium-range ordering in the a-TiO 2 film. A realistic atomic model of a-TiO 2 was established guided by the medium-range ordering and the previously reported short-range ordering of a-TiO 2 film, as well as the interatomic potential. The structure was optimized by the StructOpt code using a genetic algorithm that simultaneously minimizes energy and maximizes the match to experimental short- and medium-range ordering. The StructOpt a-TiO 2 model presents improved agreements with the medium-range ordering and the k-space location of the dominant 2-fold angular correlations compared with a traditional melt-quenched model. The electronic structure of the StructOpt a-TiO 2 model was studied by ab initio calculations and compared to the crystalline phases and experimental results. Finally, this work uncovered the medium-range ordering in a-TiO 2 thin films and provided a realistic a-TiO 2 structure model for further investigation of structure–property relationships and materials design. In addition, the improved multi-objective optimization package StructOpt was provided for structure determination of complex materials guided by experiments and simulations.

36 MATERIALS SCIENCE↗

MoS2 interactions with 1.5 eV atomic oxygen

Exposures of MoS2 to 1.5-eV atomic oxygen in an anhydrous environment reveal that the degree of oxidation is essentially independent of crystallite orientation, and that the surface-adsorbed reaction products are MoO3 and MoO2. A mixture of oxides and sulfide exists over a depth of about 90 A, and this layer has a low diffusion rate for oxygen. It is concluded that a protective oxide layer forms on MoS2 on exposure to the atomic-oxygen-rich environment of LEO.

Martin, J. A.↗

Tempus Project (Final Report)

This final technical report tracks the accomplishments of the Tempus Project to the statement of project objectives and resulting deliverables. The objective of the Tempus project was to develop and demonstrate the capabilities of a secure, modular, and customizable time synchronization platform that provides layers of protection from GPS spoofing attacks and other vulnerabilities. These vulnerabilities present a challenge to power system operators utilizing GPS-based time synchronization, as time synchronization increasingly plays a critical role in the efficient and reliable operation of power systems. The Tempus project addressed these concerns through the development of a secure, customizable time synchronization platform. The Tempus platform applies a layered approach to time security that protects from manipulation of timing systems used by power utilities. The Tempus platform consists of a component framework utilizing modularized time sources and customizable manipulation detection algorithms. With multiple time sources, and comparisons between sources and tracking sudden or subtle changes to the timing phase and time information, the Tempus system can detect and mitigate compromised timing sources.

24 POWER TRANSMISSION AND DISTRIBUTION↗