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At least 397 records · Page 22

Suppressing Atmospheric Degradation of Sulfide-Based Solid Electrolytes via Ultrathin Metal Oxide Layers

Sulfide-based solid-state electrolytes (SSEs) are promising materials with superior Li-ion conductivity; however, their poor atmospheric stability limits commercial manufacturing at scale. Here, we investigate the impact of ultrathin metal oxide layers deposited via atomic layer deposition (ALD) on the stability of Li 6 PS 5 Cl (LPSCl). Al 2 O 3 layers grown directly on LPSCl particles significantly stabilize the surface chemistry and Li-ion transport properties relative to uncoated material upon exposure to both an ambient atmosphere (22% relative humidity, RH) and humidified O 2 (100% RH). Detailed investigations indicate that coatings impede the surface and bulk degradation kinetics of exposed materials, even for coatings as thin as ∼1 Å. Furthermore, this suggests that stabilization is due to more than just a physical barrier. Shifts in valence band edge positions of coated LPSCl indicate that ALD coatings alter the surface electronic structure and resulting oxidation tendency of underlying LPSCl, suggesting new avenues to improving the environmental stability of sulfide SSEs.

Atmospheric chemistry↗

The Dynamical Role of Optical Phonons and Sublattice Screening in a Solid-State Ion Conductor

Solid-state electrolytes (SSEs) require ionic conductivities that are competitive with liquid electrolytes to realize applications in all-solid-state batteries. Although candidate SSEs have been discovered, the underlying mechanisms enabling superionic conduction (>1 mS cm –1 ) remain elusive. In particular, the role of ultrafast lattice dynamics in mediating ion migration, which involves couplings between ions, phonons, and electrons, is rarely explored experimentally at their corresponding time scales. To investigate the complex contributions of coupled lattice dynamics on ion migration, we modulate the charge density occupations within the crystal framework and then measure the time-resolved change in impedance on picosecond time scales for a candidate SSE, Li 0.5 La 0.5 TiO 3 (LLTO). Upon perturbation, we observe enhanced ion migration at ultrafast time scales. The respective transients match the time scales of optical and acoustic phonon vibrations, suggesting their involvement in ion migration. We further computationally evaluate the effect of a charge transfer from the O 2p to the Ti 3d band on the electronic and physical structure of LLTO. We hypothesize that the charge-transfer excitation distorts the TiO 6 polyhedra by altering the local charge density occupancy of the hopping site at the migration pathway saddle point, thereby causing a reduction in the migration barrier for the Li + hop. We rule out the contribution of photogenerated electron carriers and laser heating. Overall, our investigation introduces a new spectroscopic tool to probe fundamental ion hopping mechanisms transiently at ultrafast time scales, which has previously only been achieved in a time-averaged manner or solely via computational methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Anthropogenic Aerosol Transport on Cloud Condensation Nuclei Activity During Summertime in Qilian Mountain, in the Northern Tibetan Plateau

Here in this study, we conducted field campaigns at two mountain-top observatories on the Qilian Mountains (QLM) in the northeastern Tibetan Plateau of China, which plays a vital role in sustaining water resources for the downstream arid and semi-arid regions. The two observatories, Waliguan Baseline Observatory (WLG) and Laohugou station (LHG), are situated on the eastern and western edge of the QLM, respectively. The objectives of this study were to examine the properties of atmospheric aerosols, CCN concentrations (NCCN) at varying supersaturation levels (SS = 0.2%–1.0%), and the hygroscopic nature of aerosols in the QLM, especially during the formation of orographic cloud. Notably, the average aerosol concentration and N CCN was approximately 2–3 factors higher at WLG compared to LHG. The chemical compositions of aerosols were primarily dominated by sulfate and organic aerosol (OA) at these two sites. A very high hygroscopicity parameter of aerosol calculated using chemical composition was observed at these two sites (0.37 ± 0.03 at LHG vs. 0.30 ± 0.04 at WLG). Enhanced aerosol loading episodes impacted by anthropogenic emission were observed at these two sites. Exploration on high-loading cases at each site, we found that the CCN activity was dominated by aerosol size, but the chemical processes of aerosol during the formation of orographic cloud could also be important in CCN activity, especially for low SS conditions. These findings collectively underscore the significant impact of anthropogenic air plumes on CCN concentrations in the QLM and their potential influence on precipitation patterns.

54 ENVIRONMENTAL SCIENCES↗

Velocity Dependence of Rate‐And‐State Friction in Granular Fault Gouge and Implications for Slow‐Slip Events

Abstract The standard rate‐and‐state friction (RSF) has extensively captured frictional behaviors, but it fails to explain the velocity dependence of frictional stability transition and widespread slow‐slip events (SSEs) in experiments and nature adequately. An alternative microphysical Chen‐Niemeijer‐Spiers (CNS) model can well describe the velocity dependence of frictional behaviors of granular gouges. Using the original CNS model, standard RSF parameters can be quantified microphysically. However, some micro‐parameters are not easy to estimate quantitatively, making it difficult to extrapolate to natural and experimental conditions. Here, we simplify the microphysically‐derived RSF parameters including direct effect a , evolution effect b , and critical slip distance D c , as well as equivalent values ( a eq , b eq , and D eq ). The simplified friction parameters directly illustrate their velocity dependence, namely the essentially constant a , a eq , and D c , negatively velocity‐dependent b and b eq , as well as varying D eq for different laws. They are roughly consistent with experimental results in various fault gouges. A modified CNS model is further derived from the original CNS model, establishing a direct link between the standard RSF and CNS models. The modified CNS model exhibits virtually identical frictional behaviors to the original CNS, but differs from the standard RSF at large velocity perturbations. Moreover, the linearized stability analysis indicates that the critical stiffness for the modified CNS model is velocity‐dependent. Compared with the standard RSF, the modified CNS model not only explains the velocity dependence of frictional stability transition, but also exhibits a more gradual transition for SSEs with a broader range of stiffness ratios.

Geochemistry & Geophysics↗

Corrosion interactions between stainless steel and lead vanado-iodoapatite nuclear waste form part II

This paper studied the release of iodine from lead vanado-iodoapatite (I-APT, Pb 9.85 (VO 4 ) 6 I 1.7 ), a potential nuclear waste form for the radioactive waste element of I-129, which can be enhanced when crevice corrosion of stainless steel (SS) occurring nearby. Reference corrosion studies of I-APT were performed in different bulk solutions including DI water, 0.6 M and 6 M NaCl, and 0.1 M HNO 3 without metal crevice corrosion interactions. The localized enrichment of Cl – , one of the major consequences of SS crevice corrosion, was found to be the decisive factor that led to the enhanced release of iodine. A surface alteration layer consisting of a mixture of nanocrystalline I-APT and Cl-rich apatite (Cl-APT) formed on I-APT surface. Meanwhile, large Cl-APT crystals formed at the crevice mouth on the I-APT surface. This study reveals a new near-field corrosion mechanism for ceramic waste forms when they are exposed to aggressive local corrosive conditions created by the electrochemical reactions of nearby metals. The insight gained in this study could be beneficial for a more accurate prediction of waste form degradation.

36 MATERIALS SCIENCE↗

Kinetic analyses for solid-state phase transition of metastable amorphous-AlO x (2.5 < x ≤ 3.0) nanostructures into crystalline alumina polymorphs

Solid-solid phase change materials (SS-PCMs) hold promise for energy storage/dissipation in batteries and energetic materials. Yet, phase change kinetics for SS-PCMs undergoing metastable to semi-stable/stable phase transformations remain relatively ill-studied because trapping metastable phases remain challenging. Recently, we demonstrated the kinetic entrapment and stabilization of a highly disordered and amorphous Al-oxide phase m-AlO x @C (x~2.5-3.0) via laser ablation synthesis in solution (LASiS). We report here, to our knowledge, the first chemical kinetics analysis for S-S phase transition of the m-AlO 3 @C nanocomposites (< 5–8 nm sizes) into semi-stable equilibrium alumina phases (θ/γ-Al 2 O 3 ) via disproportionation reaction, while releasing excess trapped gases. Our results indicate the atomic density of the AlO 3 structures to be ~5–10 times less than that of the final Al 2 O 3 phases, which led to the hypothesis of a volume shrinkage process during their phase transition. Temperature-dependent X-ray diffraction studies reveal the high-temperature phase transition for m-AlO 3 → θ/γ-Al 2 O 3 to follow contracting volume kinetics model, thereby validating our earlier hypothesis. Using the geometric volume contraction model, reaction kinetics analyses from Arrhenius plots reveal the activation energy barrier for the phase transition to be ~270±11 kJ/mol. This makes the activation energy barrier nearly identical to the oxidation of micron-sized Al particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Domain wall enabled steep slope switching in MoS2 transistors towards hysteresis-free operation

Abstract The device concept of ferroelectric-based negative capacitance (NC) transistors offers a promising route for achieving energy-efficient logic applications that can outperform the conventional semiconductor technology, while viable operation mechanisms remain a central topic of debate. In this work, we report steep slope switching in MoS 2 transistors back-gated by single-layer polycrystalline PbZr 0.35 Ti 0.65 O 3 . The devices exhibit current switching ratios up to 8 × 10 6 within an ultra-low gate voltage window of $$V_{{{\mathrm{g}}}} = \pm \! 0.5$$ V g = ± 0.5 V and subthreshold swing (SS) as low as 9.7 mV decade −1 at room temperature, transcending the 60 mV decade −1 Boltzmann limit without involving additional dielectric layers. Theoretical modeling reveals the dominant role of the metastable polar states within domain walls in enabling the NC mode, which is corroborated by the relation between SS and domain wall density. Our findings shed light on a hysteresis-free mechanism for NC operation, providing a simple yet effective material strategy for developing low-power 2D nanoelectronics.

36 MATERIALS SCIENCE↗

Self-replenishing Ni-rich stainless-steel electrode toward oxygen evolution reaction at ampere-level

In the past few decades, tremendous attention has been devoted to enhancing the activity of oxygen evolution reaction (OER) catalysts for hydrogen production, while the cost and long-term stability of catalysts, which can play an even more important role in industrialization, have been much less emphasized. Herein, we engineered an OER electrode from abundant stainless steel (SS) via facile approaches, and the obtained electrode consists of a Ni-rich oxide surface layer with a Fe-rich metal substrate. An outstanding activity was observed with an overpotential of 316 mV at 100 mA cm −2 in 1 M KOH electrolyte. Additionally, an electrode self-replenishing concept is proposed in which a Ni-rich catalyst layer can be regenerated from a metallic substrate due to the difference in diffusion and dissolution rates of metal oxides/hydroxides, and this regeneration is validated by various characterizations. A recorded degradation rate of 0.012 was observed at 1000 mA cm −2 for 1000 h. The facile engineering of OER electrodes from SS combined with the self-replenishing catalyst can potentially address the cost, activity, and long-term stability barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A review of composite solid-state electrolytes for lithium batteries: fundamentals, key materials and advanced structures

All-solid-state lithium ion batteries (ASSLBs) are considered next-generation devices for energy storage due to their advantages in safety and potentially high energy density. As the key component in ASSLBs, solid-state electrolytes (SSEs) with non-flammability and good adaptability to lithium metal anodes have attracted extensive attention in recent years. Among the current SSEs, composite solid-state electrolytes (CSSEs) with multiple phases have greater flexibility to customize and combine the advantages of single-phase electrolytes, which have been widely investigated recently and regarded as promising candidates for commercial ASSLBs. Based on existing investigations, herein, we present a comprehensive overview of the recent developments in CSSEs. Initially, we introduce the historical development from solid-state ionic conductors to CSSEs, and then summarize the fundamentals including mechanisms of lithium ion transport, key evaluation parameters, design principles, and key materials. Finally, four main types of advanced structures for CSSEs are classified and highlighted according to the recent progress. Moreover, advanced characterization and computational simulation techniques including machine learning are reviewed for the first time, and the main challenges and perspectives of CSSEs are also provided for their future development.

25 ENERGY STORAGE↗

Compositional and structural control in LLZO solid electrolytes

Garnet-based solid-state electrolytes (SSEs) represent a promising class of materials for next-generation batteries with improved safety and performance. However, lack of control over the composition and crystal structure of the well-known Li 7 La 3 Zr 2 O 12 (LLZO) garnet material has led to poor reproducibility with a wide range of ionic conductivities reported in the literature. In this study, the role of precursor homogeneity in controlling the compositional and structural evolution of Al-doped LLZO is explored. A novel solution-based synthesis approach is employed to demonstrate enhanced atomic-scale mixing of the starting materials in comparison to conventional solid-state preparation methods. Through this technique, it is shown that the stability and formation temperature of the highly conductive cubic phase is directly impacted by the spatial distribution of the doping element and reactant species in the precursor mixture. Precursor homogeneity was also an important factor in mitigating the formation of unwanted secondary impurities. These findings can be used to guide the synthesis of SSEs with reproducible material characteristics and enhanced electrolytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Results from a new flowing liquid Li limiter with TZM substrate during high confinement plasmas in the EAST device

A third generation flowing liquid lithium (FLiLi) limiter with a substrate made of TZM, an alloy with >99% Mo, was fabricated by conventional manufacturing techniques. TZM has a high corrosion resistance, a high sputtering threshold, and a good wettability to Li, as compared to stainless steel (SS), which had been used as an FLiLi substrate surface in 2014 and 2016. The third generation FLiLi was inserted into the edge in EAST H-mode plasmas in an upper single-null configuration with an ion grad-B drift toward the upper divertor with a limiter temperature of 330–380 °C and an auxiliary heating power of about 2–8 MW. Analysis has shown that by using TZM FLiLi, fuel particle recycling continuously decreased and near-complete edge localized mode elimination was achieved in H-mode plasmas with RF-only heating. The main impurities during the initial FLiLi discharges were Mo, Fe, and W resulting from strong plasma interaction at the Mo plate side, the SS collector, and the upper W divertor. Plasma stored energy increased by about 10 kJ in subsequent FLiLi discharges due to decreased impurity radiation. Engineering analysis shows a uniform lithium flow with an ~80% Li coverage ratio on the limiter surface, similar to the second FLiLi, even though only one of two J × B pumps was functioning. Despite technical difficulties, the FLiLi gen.3 improved the overall plasma performance, providing support for flowing liquid Li plasma facing component applications in present and future devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Reduced scaling extended multi-state CASPT2 (XMS-CASPT2) using supporting subspaces and tensor hyper-contraction

We present a reduced scaling formulation of the extended multi-state CASPT2 (XMS-CASPT2) method, which is based on our recently developed state-specific CASPT2 (SS-CASPT2) formulation using supporting subspaces and tensor hyper-contraction. By using these two techniques, the off-diagonal elements of the effective Hamiltonian can be computed with only O(N 3 ) operations and O(N 2 ) memory, where N is the number of basis functions. Furthermore, this limits the overall computational scaling to O(N 4 ) operations and O(N 2 ) memory. Thus, excited states can now be obtained at the same reduced (relative to previous algorithms) scaling we achieved for SS-CASPT2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decay Dose Shielding Analysis with Hybrid Unstructured Mesh/Constructive Solid Geometry Monte Carlo Calculation and ADVANTG Acceleration

Here, the target segments of the Oak Ridge National Laboratory Second Target Station (STS) neutron production facility become highly activated due to spallation reactions or nuclei transmutation by primary protons and emitted neutrons. Once the target segments are removed from their location within the core vessel, decay dose rates must be accurately quantified to determine the shielding configurations of remote-handling tools and transport casks and to aid in planning maintenance activities. For this analysis, we utilized a hybrid unstructured mesh (UM)/constructive solid geometry approach for calculating spallation products and neutron fluxes, activation calculations using the AARE package that includes the CINDER2008 activation code to calculate the decay photon source at different cooling times, and the ADVANTG code to accelerate the final decay photon transport calculation. Both Type 316 stainless steel (SS-316) and lead were investigated as candidates for shielding materials. The decay photon transport calculation through the thick SS-316 or lead shields exhibited between 25 and 30 orders-of-magnitude attenuations in the radial direction, depending on the shield. Such a difficult shielding calculation required advanced variance reduction. ADVANTG has some missing features, which limits its usability in spallation neutron source applications. It does not support volumetric sources created for MCNP6.2 UM capability. An approximate source was created for this problem. Not only was this approximate source needed for running the ADVANTG calculation to generate the weight windows, but also it was essential to develop source biasing (SB) parameters that were crucial for dramatically accelerating the decay photon transport in this problem. With this approximate source, the analysis was completed in a very reasonable computational time, and the design of the STS remote-handling equipment was finalized. This paper compares the efficiency of Monte Carlo simulations with different weight window and SB parameters calculated using different approximate ADVANTG calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Mitigated Dissimilar Mass Transfer with Aluminized RAFM Steels in Flowing PbLi at 650°C

To evaluate dissimilar material interactions in flowing eutectic Pb-16at. %Li between fusion-relevant materials and to establish a maximum operating temperature of future blanket designs, a series of thermal convection loop (TCL) experiments with flowing PbLi have been conducted. Following a 1000-h, 550°C to 650°C TCL experiment, a thin reaction product was observed on the surface of monolithic, high-purity SiC. To identify the source of the observed dissimilar material interaction and to understand the reaction kinetics, an identical 2000-h TCL exposure was conducted, but less reaction of the SiC specimen was observed. Characterization of the FeCrAlMo (alloy APMT) loop tubing and the PbLi-exposed austenitic stainless steel (SS) assembly parts suggested that the formation of the reaction layer on the surface of the PbLi-exposed SiC did not originate from the coated reduced activation ferritic martensitic (RAFM) steel, but from the dissolved loop materials (liquid metal exposed APMT tubing and type 316 SS fittings). Here, the results, after 2000 h, suggest that the dissimilar material reaction between the Al-coated RAFM steel and the SiC has very slow reaction kinetics within a temperature gradient of 550°C to 650°C.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

High-field side scrape-off layer density profile measurements and implications for high-field side LHCD coupling in DIII-D

The high-field side (HFS) scrape-off layer (SOL) is an often under-diagnosed region of tokamak plasmas. Situated in a region with favorable curvature, the HFS SOL has minimal turbulence-induced radial transport compared to the low-field side. Using profile reflectometry, the HFS SOL density profile is measured with high temporal resolution for a wide range of DIII-D plasma discharges for the first time. The magnetic configuration, particularly the location of the secondary separatrix (SS) largely determines the HFS SOL density profile. Additionally, density perturbations induced by edge-localized modes (ELMs) are observed in the HFS SOL, and the impact of ELMs on the SOL density profile is characterized for a range of magnetic configurations. It is found that ELM-induced HFS SOL perturbations are generally localized to within the SS and ELM-induced changes to the HFS wall density are minimized in near double-null configurations. The characterization of the HFS SOL density profile on DIII-D is crucial for the effective coupling of the planned HFS lower hybrid current drive (LHCD) launcher. Experimental HFS SOL measurements are used as input to full-wave simulations of LHCD coupling. Furthermore, this work simulates the effect of the magnetic configuration on LHCD coupling. It also simulates LHCD coupling in ELMs and high q min discharges. During such discharges, the LHCD coupling is predicted to be resilient to ELM-induced SOL density perturbations.

high-field side↗

Developing the hybrid scenario in DIII-D and KSTAR for W-compatible long-pulse operation

Long-pulse, high-performance operation with tungsten plasma-facing components is a crucial challenge for achieving steady-state (SS) goals in ITER and future fusion devices. This paper presents a joint international effort between the DIII-D and KSTAR tokamaks aimed at demonstrating the compatibility of the high q 95 ~ 6 hybrid scenario with a tungsten divertor and superconducting coils. A DIII-D hybrid scenario recipe is successfully tailored to KSTAR’s operational constraints, which facilitates cross-device studies. The results show successful 30 s long-pulse operation in KSTAR at a normalized beta (β N = 2.4) with a benign m/n = 4/3 mode and effective mitigation of tungsten accumulation. Despite this success, the KSTAR scenario exhibits a greater than 25% reduction in thermal confinement compared to the DIII-D reference. To investigate this discrepancy, we performed a predictive TGYRO validation study, which suggests that the difference is likely caused by a weaker temperature pedestal in the KSTAR discharge due to a higher and narrower density pedestal. In addition, such lower thermal confinement leads to higher impurity accumulation, possibly due to a change in neoclassical transport with increased inward pinch, which further degrades global confinement. We also report that stationary, long-pulse operation with sustained thermal confinement requires consistent fueling and wall conditioning. These findings highlight the importance of optimized fueling and real-time wall conditioning in achieving a high temperature pedestal and strong global confinement during stable long-pulse operation. We propose potential approaches toward fully SS, long-pulse operation, including real-time wall conditioning using an impurity dropper in KSTAR and future tokamaks.

DIII-D↗

Specifications and pre-production of n + -in-p large-format strip sensors fabricated in 6-inch silicon wafers, ATLAS18, for the Inner Tracker of the ATLAS Detector for High-Luminosity Large Hadron Collider

Abstract The ATLAS experiment is constructing new all-silicon inner tracking system for HL-LHC. The strip detectors cover the radial extent of 40 to 100 cm. A new approach is adopted to use p-type silicon material, making the readout in n + -strips, so-called n + -in-p sensors. This allows for enhanced radiation tolerance against an order of magnitude higher particle fluence compared to the LHC. To cope with varying hit rates and occupancies as a function of radial distance, there are two barrel sensor types, the short strips (SS) for the inner 2 and the long strips (LS) for the outer 2 barrel cylinders, respectively. The barrel sensors exhibit a square, 9.8 × 9.8 cm 2 , geometry, the largest possible sensor area from a 6-inch wafer. The strips are laid out in parallel with a strip pitch of 75.5 μm and 4 or 2 rows of strip segments. The strips are AC-coupled and biased via polysilicon resistors. The endcap sensors employ a “stereo-annulus” geometry exhibiting a skewed-trapezoid shapes with circular edges. They are designed in 6 unique shapes, R0 to R5, corresponding to progressively increasing radial extents and which allows them to fit within the petal geometry and the 6-inch wafer maximally. The strips are in fan-out geometry with an in-built rotation angle, with a mean pitch of approximately 75 μm and 4 or 2 rows of strip segments. The eight sensor types are labeled as ATLAS18xx where xx stands for SS, LS, and R0 to R5. According to the mechanical and electrical specifications, CAD files for wafer processing were laid out, following the successful designs of prototype barrel and endcap sensors, together with a number of optimizations. A pre-production was carried out prior to the full production of the wafers. The quality of the sensors is reviewed and judged excellent through the test results carried out by vendor. These sensors are used for establishing acceptance procedures and to evaluate their performance in the ATLAS collaboration, and subsequently for pre-production of strip modules and stave and petal structures.

Instruments & Instrumentation↗

Predicting the single-site and multi-site event discrimination power of dual-phase time projection chambers

Dual-phase xenon time projection chambers (TPCs) are widely used in searches for rare dark matter and neutrino interactions, in part because of their excellent position reconstruction capability in 3D. Despite their millimeter-scale resolution along the charge drift axis, xenon TPCs face challenges in resolving single-site (SS) and multi-site (MS) interactions in the transverse plane. In this paper, we build a generic TPC model with an idealized signal readout, and use Fisher Information (FI) to predict its theoretical capability of differentiating SS and MS events using the electroluminescence signal. We also demonstrate via simulation that, when only statistical photon noise is present, the theoretical limits can be approached with conventional reconstruction algorithms like maximum likelihood estimation, and with a convolutional neural network classifier. The implications of this study on future TPC experiments will be discussed.

Physics↗