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At least 1,279 records · Page 71

Quantitative Prediction of Perovskite Stability Using Accelerated Testing and Machine Learning

PV technologies based on hybrid perovskites offer the potential for reducing solar cell costs, but they are particularly vulnerable to degradation by environmental factors such as moisture, oxygen, and illumination. Commercialization will require not only stable materials and device architectures but also accelerated testing protocols and models that can predict degradation from the accelerated testing data. Here, we report results from in situ photoluminescence (PL) and photoconductivity (PC) measurements during perovskite degradation with simultaneous optical transmittance (Tr) measurements or reflected dark field (DF) imaging. From PL, PC, Tr, and DF, we determine (respectively) the steady-state quasi-Fermi level splitting, the mean effective carrier diffusion length, the extent of conversion of perovskite to higher bandgap degradation products, and the extent of scattering from domains with different orientation or composition, all as a function of time during degradation. Simultaneous measurement of PL-PC-Tr or PL-PC-DF on perovskite absorbers in an environmental chamber over a wide range of humidity, oxygen, temperature, and illumination levels yields a rich data set. We use machine learning to develop a model that accurately predicts (within 10%) the time for the diffusion length to decrease to 85% of its initial value. The model takes the environmental conditions and the first few measurements from the PL-PC-Tr or PL-PC-DF experiment as input. Thus, the model provides a framework to interpret the results of accelerated testing of absorber materials. One of the dominant features in the model of degradation for CH 3 NH 3 PbI 3 is the initial rate at which transmittance increase. For devices with opaque contacts, the pixel-averaged rate of change of the intensity in dark-field images can be used in place of transmittance. Results are also presented on full PV devices with in-situ current-voltage (JV) measurements. Here, the data from simultaneous PL-DF-JV under environmental stresses reveal intimate connection between degradation and shunts and provide a framework to extend accelerated testing to devices. Further, the presentation reveals underlying universal behavior in degradation pathways over a broad range of environmental stresses and perovskite compositions.

14 SOLAR ENERGY↗

Stellarator Theory and Non-Axisymmetric Shaping (Final Technical Report)

Divertors are a critical concept for all magnetically confined fusion systems. The W7-X stellarator has an island divertor as do many of the privately funded stellarator reactor designs, but non-resonant divertors have many advantages, which are defined in the paper OSTI ID: 3021689, “Stellarators with enhanced tritium confinement and edge radiation control” and discussed in OSTI ID: 3021687, 3021688, 3021692, and 3021695. The three basic advantages are: (1) Resilience, the location at which the diverted plasma reaches the walls is insensitive to plasma conditions, unlike island divertors. (2) The width of the region at the plasma edge that flows into the divertor has a controllable width. It can be made sufficiently broad to avoid neutrals impending on the plasma from charge exchanging with high energy plasma particles. The resulting high energy neutrals erode the walls. (3) The controllable width and confinement of non-resonant divertors allow high-Z impurities to be added. The shortness of their confinement time limits their diffusion into the plasma interior. High-Z impurity radiation at the plasma edge seems the only way to sufficiently spread the outcoming power over the walls. The lack of experiments is a major impediment to application of non-resonant divertors, although the small experiment STAR_LITE is being built at Hampton University to study them.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Understanding NBI heating and fueling in LTX-β tokamak

My work on the contract DE-SC=0023274 (July, 2022 - July, 2025) was focused on understanding the plasma fueling by NBI. On Dec. 1998 with Sergei Krasheninnikov (UCSD, San Diego, CA) we initiated the Li Wall Fusion (LiWFusion) as a new concept of magnetic fusion [1]. The new 1 2 plasma 3 4 5 6 2.1 Overview of rate coefficients, mean-free paths λH0 , and diffusions coefficients 6 2. GSV code for ⟨σv⟩ analysis of NBI fueling concept was a reaction of the lack of luck of tokamak fusion with QDT = 1 on TFTR and JET. We recognized the edge plasma cooling by recycling to be the route reason of the tokamak problems on the way to burning plasma. LiWFusion relies on plasma pumping by a lithium layer on the inner walls of the plasma chamber, combined with the plasma heating and fueling by the Neutral Beam Injection (NBI). These two innovations eliminate the route problem of the tokmak fusion. The concept became theoretically mature in 2006. In 2012, the technology of continuously Flowing Liquid Lithium (24/7-FLiLi) was invented by me for the future implementations of the LWFusion concept. At the same time, my every presentation on LiWFusion to International Symposium on Lithium Applications since 2010 was objected by some person with words “Everybody since the 1970s knows that plasma fueling by NBI is impossible”. I dropped the name of the author of this objection and ignored his views. My work on the current grant on NBI fueling of LTX-β not only clarified the issue but resolved it in an astonishing way. The NBI fueling was fully understood (thus humiliating the current dogmatic fusion community). The new future of LTX-β dedicated for decades to Li in tokamaks, as well as of the entire magnetic fusion program was envisioned, in sharp contrast with the fallure of OFES in the post-TFTR era of 21st century.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Focused Ion Beam Tomography of Alloy 617 Corroded in Molten Chloride Salt

Materials qualification of reactor structural materials is a critical step in rapid implementation of advanced nuclear reactor technologies, particularly to assess the corrosion performance in these designs. Accelerated qualification of reactor structural materials requires incorporating powerful computational toolsets, such as phase field modelling in the Multiphysics Object-Oriented Simulation Environment (MOOSE) framework, to predict the evolution of structural materials due to corrosion. Accordingly, computational toolsets will require experimental data generated at appropriate length scales to validate accuracy. Focused ion beam (FIB) provides a high degree of control over manipulation of materials for analytical purposes, including capturing data on the evolution in the microstructure and elemental composition of materials at the mesoscale, an appropriate length scale for phase field modelling of intergranular diffusion phenomena using the MOOSE framework. For instance, the FEI Helios G4 UX dual beam plasma FIB microscope at the Irradiated Materials Characterization Laboratory (IMCL) is capable of backscatter diffraction (EBSD) and energy-dispersive x-ray spectroscopy (EDS) documenting the evolution in the microstructure and elemental composition, respectively. The Helios can perform EDS and EBSD three-dimensionally (3D) using tomography, which is then combined using different software packages to visualize 3D volumes correlating elemental composition to microstructural data. The purpose of this investigation was to develop a streamlined characterization and data processing workflow for 3D tomography studies on the FEI Helios G4 plasma FIB. The investigation is segmented into three parts: 1) Optimizing the data collection workflow, 2) identifying appropriate data processing and visualization software (i.e. DREAM.3D, MIPAR, and VGStudioMax), and 3) establishing an infrastructure for public release. The optimization of the data collection workflow is in collaboration with members of the U220 department to setup formal training on the tomography operation of the G4, through ThermoFisher Scientific, and exploring DREAM.3D, MIPAR, and VGStudioMax data processing/visualization software packages. VGStudioMax currently demonstrates the most promise for future use. Optimization of the data collection and processing workflow is still ongoing. A collaboration with INL High Performance Computing (HPC) established an open-source license for expediting the public release of FIB tomography datasets through HPC. FIB tomography data generated by the G4 will provide comprehensive data for validating 3D phase field mesoscale modelling tools within the MOOSE framework for accelerated qualification of reactor structural materials.

Copeland-Johnson, Trishelle↗

Effect of water droplet growth dynamics on electrode current in fuel-cell catalyst layers

Fuel cells are a promising next-generation energy-conversion technology designed to replace internal combustion engines in transportation applications. However, much work remains to optimize them. Operation at high humidities causes liquid water droplet formation on Pt catalyst particles during oxygen reduction, potentially impeding reactant arrival to the reactive electrode. In this work, four different cases of water droplet growth in fuel-cell catalyst layers are considered: pinned or advancing droplets on a bare Pt surface, advancing droplets on a Nafion film, and water-layer growth in carbon nanopores. Transient drop growth is captured with a combination of mass, species mass, and momentum balances, and the subsequent limiting current is determined via oxygen diffusion and Tafel kinetics. Further, water droplets are found not to be mass-transfer limiting due to the relatively large liquid-gas area compared to the Pt nanoparticle. Mass-transfer-limited behavior is calculated in carbon nanopores.

25 ENERGY STORAGE↗

The effect of ion pairing on speciation and transport in ion exchange membranes at varying hydration levels: A four-state model

Understanding ion pairing in ion exchange membranes (IEMs) is essential for advancing IEM applications in energy and environmental technologies. Here, this study introduces a four-state molecular dynamics model to quantify speciation and transport within Nafion-117, specifically examining the role of ion pairing in monovalent and divalent counterions (NaCl, Na 2 SO 4 , and MgSO 4 ). By analyzing radial distribution functions (RDFs) and molecular snapshots, we distinguish ion pairing modes and classify counterions into four states: condensed counterion, condensed ion pair, free ion pair, and free counterion. A key finding is that while divalent counterions (e. g., Mg 2+ ) maintain stable speciation across hydration levels, monovalent counterions (e.g., Na + ) show notable speciation shifts with hydration. Both monovalent and divalent counterions are not diffusive when condensed onto the polymer (sorbed to membrane functional groups). In contrast, free counterions are diffusive across all hydration levels. To evaluate the overall diffusivity of counterions, four-state fractions and diffusivities are computed, each contributing to counterion transport. The condensed/free ion speciation for multivalent sulfate salts aligns with previous revisions to the Donnan-Manning framework that include ion pairing, thereby validating its relevance to established membrane theories. The four-state model's diffusivity results support several current ion exchange assumptions, including that the condensed counterions are immobile, while uncondensed counterions are mobile. The four-state model offers insights into contact ion pairing within IEMs, highlighting its potential even when undetected in aqueous solution experiments. This work advances the theoretical understanding of counterion speciation in IEMs while identifying model limitations that suggest avenues for refinement, such as distinguishing water-mediated ion pairs between fully hydrated ions.

Ion exchange membranes↗

Modeling of the Influence of a Damaged Thermally Grown Oxide (TGO) Layer in an Environmental Barrier Coating System

Environmental barrier coatings (EBC) are an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. EBCs are susceptible to a number of failure modes including oxidation/delamination, recessions, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object impact damage in a combustion environment. Spallation of environmental barrier coating (EBC), induced by a thermally grown oxide (TGO) layer, is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from a silicon carbide (SiC) based substrate itself. The TGO layer evolves (i.e., thickness increases with time) as water vapor and oxygen gradually diffuse through the EBC, and the EBC spalls off once the TGO layer reaches some critical thickness. The critical thickness of the TGO layer for failure is in the range of 20-30 microns, but it can vary due to exposure temperature, microstructure etc. Current work at NASA Glenn Research Center, under the Revolutionary Tools and Methods (RTM) subproject is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. The effect of damage in the TGO layer on the resulting stress states is also assessed both in uniform and non-uniform TGO layers.

Mital, Subodh K.↗

Effect of sucrose on the oxidation-reduction conditions and retention of rhenium during vitrification of low-activity waste

Technetium speciation and solubility during nuclear waste vitrification are affected by oxygen partial pressure in the melt. Thus, reducing agents such as sucrose, which are routinely added to nuclear waste feeds to repress foaming, can significantly affect the volatilization of Tc and increase its retention in glass. Using Re as a surrogate for Tc, we measured the effect of sucrose addition to two low-activity waste melter feeds on the Re retention, oxygen partial pressure, and iron redox as functions of temperature. As expected, Re retention in glass increased as the sucrose content increased. Furthermore, this is attributed to sucrose reaction with nitrates and nitrites in the feed. Destruction of nitrates and nitrites reduces the salt phase fraction and thus likely promotes Re diffusion into the glass-forming melt. In agreement with available literature, we discuss that a modest increase in the sucrose content (compared to current practice) can significantly improve the Tc retention without reducing Fe 2+ to metal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Role of edge-localized neoclassical tearing modes in quiescent H-mode plasmas in the DIII-D tokamak

The edge-harmonic oscillations (EHOs) in standard quiescent H-mode (QH-mode) plasmas in DIII-D are consistent with edge-localized neoclassical tearing modes (NTMs) based on nonlinear two-fluid MHD simulations. Using kinetic equilibria constrained by edge profile measurements, the MHD simulations show that the n = 1 NTM and its harmonics can be destabilized at the pedestal top of QH-mode plasma by the edge bootstrap current. The simulations further show that the unstable NTMs can saturate either at small (<2% ψ N ) or large (>4% ψ N ) island width depending on the magnitude of the edge bootstrap current, where ψ N is the normalized radius in poloidal flux. The onset of the EHO also results in a prompt decrease in the pedestal width and height, consistent with simulation results for the onset of the NTM at the top of the QH-mode pedestal. This suggests that the avoidance of edge-localized modes (ELMs) in QH-mode can be attributed to the enhanced local transport induced by the NTM that is sufficient to prevent the expansion of the pedestal to an unstable width, analogous to the mechanism explored for ELM suppression by resonant magnetic perturbations. Nonlinear MHD simulations scanning the E × B frequency and the ratio of parallel and perpendicular thermal diffusivity (χ | /χ ⊥ ) at the pedestal top show that edge-localized NTMs are destabilized for conditions of high E × B frequency, high pedestal temperature, and low pedestal density, qualitatively consistent with experimental conditions required for observing the EHO.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A quasilinear operator retaining magnetic drift effects in tokamak geometry

The interaction of radio frequency waves with charged particles in a magnetized plasma is usually described by the quasilinear operator that was originally formulated by Kennel and Engelmann (Phys. Fluids vol. 9, 1966, pp. 2377-2388). In their formulation the plasma is assumed to be homogenous and embedded in a uniform magnetic field. In tokamak plasmas the Kennel-Engelmann operator does not capture the magnetic drifts of the particles that are inherent to the non-uniform magnetic field. To overcome this deficiency a combined drift and gyrokinetic derivation is employed to derive the quasilinear operator for radio frequency heating and current drive in a tokamak with magnetic drifts retained. The derivation requires retaining the magnetic moment to higher order in both the unperturbed and perturbed kinetic equations. The formal prescription for determining the perturbed distribution function then follows a novel procedure in which two non-resonant terms must be evaluated explicitly. The systematic analysis leads to a diffusion equation that is compact and completely expressed in terms of the drift kinetic variables. The equation is not transit averaged, and satisfies the entropy principle, while retaining the full poloidal angle variation without resorting to Fourier decomposition. As the diffusion equation is in physical variables, it can be implemented in any computational code. In the Kennel-Engelmann formalism, the wave-particle resonant delta function is either for the Landau resonance or the Doppler shifted cyclotron resonance. In the combined gyro and drift kinetic approach, a term related to the magnetic drift modifies the resonance condition.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Silicene, Siloxene, or Silicane? Revealing the Structure and Optical Properties of Silicon Nanosheets Derived from Calcium Disilicide

Si-nanosheets (Si-NSs) have recently attracted considerable attention due to their potential as next-generation materials for electronic, optoelectronic, spintronic, and catalytic applications. Even though monolayer Si-NSs were first synthesized over 150 years ago via topotactic deintercalation of CaSi 2 , there is a lack of consensus within the literature regarding the structure and optical properties of this material. Herein, we provide conclusive evidence of the structural and chemical properties of Si-NSs produced by the deintercalation of CaSi 2 with cold (~–30 °C) aqueous HCl and characterize their optical properties. We use a wide range of techniques, including XRD, FTIR, Raman, solid-state NMR, SEM, TEM, EDS, XPS, diffuse reflectance absorbance, steady-state photoluminescence, time-resolved photoluminescence, and thermal decomposition; when they are combined together, these techniques enable unique insight into the structural and optical properties of the Si-NSs. Additionally, we support the experimental findings with density functional theory (DFT) calculations to simulate FTIR, Raman, solid-state NMR, interband electronic transitions, and band structures. We determined that the Si-NSs consist of buckled Si monolayers that are primarily monohydride terminated. We characterize the nanosheet optical properties, finding they have a band gap of ~2.5 eV with direct-like behavior and an estimated quantum yield of ~9%. Given the technological importance of Si, these results are encouraging for a variety of optoelectronic technologies, such as phosphors, light-emitting diodes, and CMOS-compatible photonics. Furthermore, our results provide critical structural and optical properties to help guide the research community in integrating Si-NSs into optoelectronic and quantum devices.

36 MATERIALS SCIENCE↗

Designing polymeric membranes with coordination chemistry for high-precision ion separations

State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ , and Mg 2+ . We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Environmental Protection Coating System for Refractory Metal Alloys (EPCS for RMAs)

As part of ARPA-E’s Ultra High Temperature Impervious Materials Advancing Turbine Efficiency (UITIMATE) program, this project aims to develop an environmental protection coating system (EPCS) for refractory metal alloys (RMAs) – which will provide radical improvement in long term protection for ultra-high temperature refractory metal components in harsh gas-turbine environments. The drive for higher fuel efficiency and higher core power of gas turbines used in electric power generation and in aircraft propulsion requires higher peak operation temperatures. The temperature capability of state-of-the-art materials cannot meet the new requirements. Refractory metal alloys have desirable capabilities for achieving the required peak temperatures, but most of them are subject to oxidation in the gas turbine environment. Thus, there is a strong need to develop novel environmental protective coatings that enable the refractory metals to operate in an ultra-high temperature engine environment. This project is composed of four major technical innovations that can provide a potentially transformational solution in providing environmental protection for refractory metal alloys over a wide range of temperature. 1) Multi-layer self-healing environmental barrier coating (EBC) that provides protection against combustion gas environment. 2) Oxidation resistant diffusion barrier (DB) on the alloy surface to enhance coating stability. 3) Synergistic integration of the multi-layer self-healing EBC with the diffusion barrier to extend coating life. 4) Guidance of physics-based modeling to accelerate coating development and optimization. Our team has successfully developed a multi-layer self-healing environmental protection coating system (EPCS) that can provide oxidation protection for commercially available molybdenum based refractory metal alloys over a wide temperature range of up to 1600 °C for fuel-efficient gas turbine applications. The team also developed a multi-layer high temperature coating design tool to accelerate coating development and optimization based on physics-based modeling. The team also engaged RTX business unite, notable Pratt and Whitney, for future commercialization of this technology. The successful completion of this Phase I effort led to the selection of performing Phase II of the program. In Phase II, the team plans to apply the EPCS in the protection of a newly discovered molybdenum-based metal alloy which has the potential of superior high temperature properties to the commercial products. Th coating will be evaluated under test conditions and environment that mimic gas turbine operation.

36 MATERIALS SCIENCE↗

Fast ionic conduction achieved through the design and synthesis of ceramic heterointerfaces

Lithium (Li) chloride and iron oxychloride (FeOCl), typically nonconductive, were combined to form a [Li 1+δ Cl] δ+ /[FeOCl] δ- heterointerface composite material (LFH), achieving ionic conductivities of >1 mS cm -1 . Analysis techniques (scanning transmission electron microscopy [STEM] and electron energy-loss spectroscopy [EELS]) indicated that the microstructure of LFH consisted of an amorphous LiCl-based shell surrounding a crystalline FeOCl-based core. Electrochemical measurements alongside solid-state 6,7 Li nuclear magnetic resonance (NMR) and molecular dynamic simulations revealed Li+ as the sole conductive species, with a diffusion barrier of ~0.25 eV. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) results further supported interstitial Li + diffusion at the heterointerface and within the LiCl phase, made possible by the heterointerface. Despite susceptibility to electronic conductivity, iron’s defects and multivalency (Fe³⁺, Fe²⁺) enable the Fe–O–Cl framework to accept Cl - , facilitating Li⁺ ionic conduction. Finally, a prototype solid-state cell (showing 97% Coulombic efficiency) demonstrated the viability of this heterointerface design for applications in energy storage.

36 MATERIALS SCIENCE↗

Neutron capture of UO 2 targets prepared by spin-coating assisted combustion synthesis

Two uranium dioxide (UO 2 ) targets of (414 ± 23) nm and (1092 ± 93) nm thicknesses were prepared on 6061 aluminum alloy and puratronic grade aluminum backing materials. The targets were deposited with a novel method combining spin coating and solution combustion synthesis (SCS). The target layers consisted of small (3–7 nm) UO 2 grains and uniformly distributed ultra-small (1–3 nm) pores. The prepared targets were tested at the Los Alamos National Laboratory’s LANSCE facility for neutron irradiation damage and suitability for neutron capture experiments. The samples showed no signs of target material loss after the irradiation. However, irradiation caused a significant increase in the grain size (4–10 nm), as well as upward mass diffusion and coalescence of the pores due to the thermal spikes. The magnesium in the aluminum 6061 alloy backing also diffused into the UO 2 layer during neutron irradiation. The structural changes in the target after the irradiation do not affect the data from neutron capture. As a result, the new method can be used more broadly to prepare other actinide targets for nuclear physics experiments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Tailoring the Structure of Carbon Molecular Sieves Derived from an Aromatic Polyamide

Energy-efficient and selective separation technologies are required to reclaim aqueous waste streams for reuse. Carbon molecular sieves (CMS) are one material capable of separating organic solvent and gaseous mixtures due to the presence of permanent, rigid, and molecular sieving pores and could potentially be used in aqueous separations. Here, a novel CMS material is derived from an aromatic polyamide precursor with tailored fabrication techniques. Structural characteristics of this CMS have been probed with various analyses and are potentially ideal for selective separations as adsorbents. In this work, elemental analyses provide insight about the potential chemical structures of CMS materials that result from degradation mechanisms. Gravimetric sorption data is used to estimate sorption, diffusion, and permeability selectivity with water and N, N-dimethylformamide. While challenges to the development and implementation of such carbonaceous materials remain, highly selective materials are critical starting points for enabling ultra-challenging separation processes of the future.

36 MATERIALS SCIENCE↗

Interfacial Reactivity-Triggered Oscillatory Lattice Strains of Nanoalloys

Understanding the structure evolution of nanoalloys under reaction conditions is vital to the design of active and durable catalysts. Herein, we report an operando measurement of the dynamic lattice strains of dual-noble-metal alloyed with an earth-abundant metal as a model electrocatalyst in a working proton-exchange membrane fuel cell using synchrotron high-energy X-ray diffraction coupled with pair distribution function analysis. Additionally, the results reveal an interfacial reaction-triggered oscillatory lattice strain in the alloy nanoparticles upon surface dealloying. Analysis of the lattice strains with an apparent oscillatory irregularity in terms of frequency and amplitude using time-frequency domain transformation and theoretical calculation reveals its origin from a metal atom vacancy diffusion pathway to facilitate realloying upon dealloying. This process, coupled with surface metal partial oxidation, constitutes a key factor for the nanoalloy's durability under the electrocatalytic oxygen reduction reaction condition, which serves as a new guiding principle for engineering durable or self-healable electrocatalysts for sustainable fuel cell energy conversion.

Wu, Zhi-Peng [State University of New York (SUNY),↗