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At least 361 records · Page 20

A Progress Report for a 44-month Aging Study on Nitroplasticizer (NP) Stability – Summary of KF and TGA Results

In the past few years, a 44-month long aging experiment was conducted under various aging conditions. The properties of aged nitroplasticizer (NP) samples were analyzed using Fourier transform infrared spectroscopy, Karl Fischer (KF) titration, thermogravimetric analysis (TGA), liquid chromatography tandem quadrupole time of flight mass spectrometry, and ion chromatography. In this progress report, complete KF and TGA results are reported and discussed.

36 MATERIALS SCIENCE↗

A mechanistic model for creep and thermal aging in Alloy 709

This report describes a physics-based model for creep and thermal aging in Alloy 709. Alloy 709 is an advanced austenitic alloy, targeted for use in future Sodium Fast Reactors (SFRs) and other advanced reactors. The material has superior high temperature properties compared to currently qualified 316 and 304 stainless steels. However, the available creep and thermal aging test database for Alloy 709 is significantly more limited compared to the historical materials. The physics-based model developed here is one way to accelerate the qualification of the material by providing more accurate long-term predictions for creep properties and thermal aging, compared to current empirical time-extrapolate techniques. The crystal plasticity finite element model is used to predict the deformation and failure of alloy 709. The same setup for the CPFE model is used in both the baseline model calibration process and the simulation campaigns for parameter inference. Specific constitutive choices are made for Alloy 709 to capture the primary deformation mechanisms. The dislocation creep formulation developed by Hu and Cocks is extended to account for coupled precipitation formation and the grain boundary cavitation model developed by Sham, Needleman, et al. is used to model grain boundary cavitation-induced failure. A novel update algorithm is proposed to render the semi-discrete constitutive update for the Sham-Needleman model unconditionally stable. A progressive calibration approach is adopted based on the observations that several types of material responses can be effectively decoupled. A surrogate model is trained based on full-fledged CPFE simulations to accelerate the forward model evaluations, and stochastic variational inference (SVI) is used to calibrate the unknown microstructural model parameters. The calibrated mechanistic model is used to predict the long-term creep life of Alloy 709, and the predictions are compared against classical empirical approaches.

36 MATERIALS SCIENCE↗

LLNL FY23 Aging and Lifetimes Exit Criteria: Milestone 8650, GC #4

Silicone rubbers are important materials within the complex and are used in various applications due to wide operating temperatures, favorable aging characteristics, and chemical inertness. However, silicone rubbers are susceptible to degradation in the presence of acid or base. The goal of the project is to design outgassing vessels to probe material degradation byproducts from additively manufactured (AM) silicones compressed against Arrhenius base under dry (sub 100 ppm moisture) environments. The overarching goal of this task is to develop a mechanistic understanding of degradation from experimental data that will be used to inform predictive lifetime and aging models. An outgassing chamber for multi-material compressive aging was designed. The chamber consists of a stainless-steel enclosure, which is hermetically sealed once AM silicone samples are compressed against Arrhenius base pellets in compression rigs (Fig. 1). Outgassing chambers, compression rigs, and accessories were procured, arrived onsite, and received surface treatments. Outgassing of degradation byproducts will be monitored over 12 weeks at 35 °C and 70 °C.

36 MATERIALS SCIENCE↗

Fast Semi-automated Filtration Method for Non-targeted LC-QTOF Data of Aged Nitroplasticizer Samples

A full dataset of aged nitroplasticizer (NP) is composed of more than 2000 unique mass-to-charges (m/z) when combining the non-targeted data obtained from both positive and negative electrospray ionization modes in time-of-flight mass spectrometry. Therefore, manual processing of these data often takes days, weeks, or even months to scrutinize for mechanistic insights. To effectively extract meaningful signals that represent vital degradation intermediates in the early NP degradation mechanism, a semi-automated postprocessing workflow for data filtering, tailored to the aging experiment of NP, has been developed. The automated portion of this workflow is written in a Python code (using pandas, numpy, and matplotlib libraries), which removes more than 65% of potential false signals within seconds via four threshold-based adjustable filters: signal sensitivity, coefficient of variation, number of measurements, and retention time variability. As for the manual portion, a pattern-based inspection method is employed to reduce another 23% or more false positives, which greatly simplifies data visualization and results in less than 3% of potential candidate m/z needing in-depth data interpretation. As a positive control, known compounds are verified. Using this semi-automated data reduction method, the amount of time required is reduced to a matter of hours for data filtering in the non-targeted datasets of aged NP, which saves more time and effort for compound identification.

36 MATERIALS SCIENCE↗

Accelerated Aging Scoping Study of Additively Manufactured Coupons

Additive manufacturing (AM) is a relatively new technological advancement that allows for rapid prototyping, development of intricate shapes, and reduction in manufacturing time. The materials of interest for this project are Ultem 1010, ABS M30, FDM Nylon 12, PC, and PPSF. However, little is known regarding the aging behavior of these AM materials. The limited aging study outlined herein was designed to compare the chemical, physical, and mechanical properties of AM parts as they experience accelerated aging at 70 °C for a total of 24 weeks. In general, ABS M30 stood out as it appeared to undergo chemical and physical changes leading to increase in density and an overall more brittle material, making this commonly used material not attractive for long-term use.

36 MATERIALS SCIENCE↗

Early Stages of Age Hardening in U-6%Nb: An Energy Barrier Hypothesis for Twin Reorientation

It is well known that age hardening occurs in U-6%Nb (Ref. 1-9). Figure 1 shows that increases in hardness occur at aging temperatures up to ~400°C, and overaging occurs above ~450°C. Overaging occurs by cellular decomposition of the αʺ b martensite, similar to overaging reactions in other uranium alloys. But the mechanism of age hardening remains elusive, particularly in its early stages.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

MOSAIC: An Effective FFT-based Numerical Method to Assess Aging Properties of Concrete

As the nuclear fleet in the United States ages and subsequent license renewal applications grow, the prediction of concrete durability at extended operation becomes more important. To address this issue, a Fast-Fourier Transform (FFT) method is utilized to simulate aging-related degradation of concrete within the Microstructure Oriented Scientific Analysis of Irradiated Concrete (MOSAIC) software. MOSAIC utilizes compositional phase maps to simulate damage from radiation-induced volumetric expansion (RIVE), applied force, creep, and thermal expansion. This compositional detail allows each mineral in the microstructure to be assigned specific material properties, allowing the simulation to be as accurate and representative as possible. The principal goal of MOSAIC is to simulate the effects of nonlinear aging mechanisms occurring in nuclear concrete on the macroscopic mechanical properties, using only the aggregate microstructure compositional information as a starting point. Here, several realistic example simulations are shown to demonstrate the utility and uniqueness of the MOSAIC software.

36 MATERIALS SCIENCE↗

Battery data integrity and usability: Navigating datasets and equipment limitations for efficient and accurate research into battery aging

A tremendous commitment of resources is needed to acquire, understand and apply battery data in terms of performance and aging behavior. There are many state of performance (SOP) and state of health (SOH) metrics that are useful to guide alignment of batteries to end-use, yet how these metrics are measured or extracted can make the difference between usable, valuable datasets versus data that lacks the necessary integrity to meet baseline confidence levels for SOP/SOH quantification. This work will speak to 1) types of data that support SOP and SOH evaluations on mechanistic terms, 2) measurement conditions needed to assure high data integrity, 3) equipment limitations that can compromise data high fidelity, and 4) the impact of cell polarization on data quality. A common goal in battery research and field use is to work from a data platform that supports economical paths of data capture while minimizing down-time for battery diagnostics. An ideal situation would be to utilize data obtained during normal daily use (“pulses or cycles of convenience”) without stopping the daily duty cycles to perform dedicated SOP/SOH diagnostic routines. However, difficulties arise in trying to make use of daily duty cycle data (denoted as cycle-by-cycle, CBC) that underscores the need for standardization of conditions: temperature and duty cycles can vary over the course of a day and throughout a week, month and year; polarization can develop within an immediate cycle and throughout successive cycles as a hysteresis. If CBC data is envisioned as a data source to determine performance and aging trends, it should be recognized that polarization is a frequent consequence of CBC and thus makes it difficult to separate reversible and irreversible components to metrics such as capacity loss and resistance increase over aging. Since CBC conditions can have a major impact on data usability, we will devote part of this paper to CBC data conditioning and management. Differential analyses will also be discussed as a means to detect changing trends in data quality. Our target cell chemistries will be lithium-ion types NMC/graphite and LMO/LTO.

25 ENERGY STORAGE↗

Relationship Between Filler Type, Thermomechanical Properties, and Aging of RTV Silicone Foams

Room-temperature vulcanizing (RTV) silicone foams are used in many industrial applications that require the material to perform over long time periods. However, mechanical properties tend to deteriorate when these foams age under a compressive load. The chemical aging is attributed to the presence of unreacted functional groups of the prepolymers, residues from acid, and catalytically active tin (II) species. Here, an optimized thermal treatment of an RTV foam that achieves completion of curing reactions and deactivation of reactive species is proposed. Foams that were thermally aged for three months under compressive load showed no signs of compression set, indicative of the effectiveness of the implemented post-curing approach. In addition, the effects of fillers (diatomaceous earth, fumed silica, and carbon nanofibers) on thermomechanical properties were investigated. Tensile strength, tear strength, and thermal conductivity increased when these fillers were added to the unfilled RTV formulation, with carbon nanofibers (CNFs) being the most effective filler. Rheological studies of RTV formulations indicated that 2.5 wt.% of CNFs is the upper limit that can be added to the RTV formulation.

36 MATERIALS SCIENCE↗

TOI-811b and TOI-852b: New Transiting Brown Dwarfs with Similar Masses and Very Different Radii and Ages from the TESS Mission

We report the discovery of two transiting brown dwarfs (BDs), TOI-811b and TOI-852b, from NASA’s Transiting Exoplanet Survey Satellite mission. These two transiting BDs have similar masses but very different radii and ages. Their host stars have similar masses, effective temperatures, and metallicities. The younger and larger transiting BD is TOI-811b at a mass of M {sub b} = 59.9 ± 13.0M {sub J} and radius of R {sub b} = 1.26 ± 0.06R {sub J}, and it orbits its host star in a period of P = 25.16551 ± 0.00004 days. We derive the host star’s age of 93{sub −29}{sup +61} Myr from an application of gyrochronology. The youth of this system, rather than external heating from its host star, is why this BD’s radius is relatively large. This constraint on the youth of TOI-811b allows us to test substellar mass–radius evolutionary models at young ages where the radius of BDs changes rapidly. TOI-852b has a similar mass at M {sub b} = 53.7 ± 1.4M {sub J} but is much older (4 or 8 Gyr, based on bimodal isochrone results of the host star) and is also smaller with a radius of R {sub b} = 0.83 ± 0.04R {sub J}. TOI-852b’s orbital period is P = 4.94561 ± 0.00008 days. TOI-852b joins the likes of other old transiting BDs that trace out the oldest substellar mass–radius evolutionary models where contraction of the BD’s radius slows and approaches a constant value. Both host stars have a mass of M {sub ⋆} = 1.32M {sub ⊙} ± 0.05 and differ in their radii, T {sub eff}, and [Fe/H], with TOI-811 having R {sub ⋆} = 1.27 ± 0.09R {sub ⊙}, T {sub eff} = 6107 ± 77 K, and [Fe/H] = + 0.40 ± 0.09 and TOI-852 having R {sub ⋆} = 1.71 ± 0.04R {sub ⊙}, T {sub eff} = 5768 ± 84 K, and [Fe/H] = + 0.33 ± 0.09. We take this opportunity to examine how TOI-811b and TOI-852b serve as test points for young and old substellar isochrones, respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Revisiting Newly Large Magellanic Cloud Age-gap Star Clusters

Recently, a noticeable number of new star clusters was identified in the outskirts of the Large Magellanic Cloud (LMC) populating the so-called star-cluster age gap, a space of time (∼4–12 Gyr) where the only known star cluster is up-to-date ESO 121-SC 03. We used Survey of the Magellanic Stellar History DR2 data sets, as well as those employed to identify these star-cluster candidates, to produce relatively deep color–magnitude diagrams (CMDs) of 17 out of 20 discovered age-gap star clusters with the aim of investigating them in detail. Our analysis relies on a thorough CMD cleaning procedure of the field-star contamination, which presents variations in its stellar density and astrophysical properties, such as luminosity and effective temperature, around the star-cluster fields. We built star-cluster CMDs from stars with membership probabilities assigned from the cleaning procedure. These CMDs and their respective spatial distribution maps favor the existence of LMC star field density fluctuations rather than age-gap star clusters, although a definitive assessment on them will be possible from further deeper photometry.

47 OTHER INSTRUMENTATION↗

Dilution impacts on smoke aging: evidence in Biomass Burning Observation Project (BBOP) data

Abstract. Biomass burning emits vapors and aerosols into the atmosphere that can rapidly evolve as smoke plumes travel downwind and dilute, affecting climate- and health-relevant properties of the smoke. To date, theory has been unable to explain observed variability in smoke evolution. Here, we use observational data from the Biomass Burning Observation Project (BBOP) field campaign and show that initial smoke organic aerosol mass concentrations can help predict changes in smoke aerosol aging markers, number concentration, and number mean diameter between 40–262 nm. Because initial field measurements of plumes are generally >10 min downwind, smaller plumes will have already undergone substantial dilution relative to larger plumes and have lower concentrations of smoke species at these observations closest to the fire. The extent to which dilution has occurred prior to the first observation is not a directly measurable quantity. We show that initial observed plume concentrations can serve as a rough indicator of the extent of dilution prior to the first measurement, which impacts photochemistry, aerosol evaporation, and coagulation. Cores of plumes have higher concentrations than edges. By segregating the observed plumes into cores and edges, we find evidence that particle aging, evaporation, and coagulation occurred before the first measurement. We further find that on the plume edges, the organic aerosol is more oxygenated, while a marker for primary biomass burning aerosol emissions has decreased in relative abundance compared to the plume cores. Finally, we attempt to decouple the roles of the initial concentrations and physical age since emission by performing multivariate linear regression of various aerosol properties (composition, size) on these two factors.

54 ENVIRONMENTAL SCIENCES↗

Atmospheric processing and aerosol aging responsible for observed increase in absorptivity of long-range-transported smoke over the southeast Atlantic

Biomass burning aerosol (BBA) from agricultural fires in southern Africa contributes about one-third of the global carbonaceous aerosol load. These particles have strong radiative effects in the southeast Atlantic (SEA), which depend in part on the radiative contrast between the aerosol layer in the free troposphere (FT) and the underlying cloud layer. However, there is large disagreement in model estimates of aerosol-driven climate forcing due to uncertainties in the vertical distribution, optical properties, and life cycle of these particles. This study applies a novel method combining remote sensing observations with regional model outputs to investigate the aging of the BBA and its impact on the optical properties during transatlantic transport from emission sources in Africa to the SEA. Results show distinct variations in extinction Ångström exponent (EAE) and single-scattering albedo (SSA) as aerosols age. Near the source, fresh aerosols are characterized by low mean SSA (0.84) and high EAE (1.85), indicating smaller, highly absorbing particles. By isolating marine contributions from the total column during BBA transport across the SEA, our analysis reveals an initial decrease in BBA absorptivity, with mean FT SSA of 0.87 after 6–7 d, followed by increased absorptivity with mean FT SSA of 0.84 after 10 d, suggesting enhanced absorption due to chemical aging. These findings indicate that BBA becomes more absorbing during extended transport across the SEA, with implications for reducing model uncertainties. Our remote-sensing-based results agree well with previous in situ studies and offer new insights into aerosol–radiation interactions and the energy balance over the SEA.

54 ENVIRONMENTAL SCIENCES↗

Cosmogenic 21 Ne exposure ages on late Pleistocene moraines in Lassen Volcanic National Park, California, USA

We report new cosmogenic 21 Ne in quartz exposure ages from 18 samples on three distinct moraines deposited in the Lost Creek drainage, approximately 3–7 km down-valley from Lassen Peak in Lassen Volcanic National Park. Although measuring 21 Ne in quartz is generally straightforward, accurate 21Ne exposure dating of deposits of late Pleistocene is rarely possible due to the significant quantities of non-cosmogenic 21 Ne present in most lithologies. Young quartz-bearing volcanic rocks have been observed to be an exception. We take advantage of moraine boulders sourced from the ~28 ka dacite of Lassen Peak to generate a chronology of alpine deglaciation in Lassen Volcanic National Park. Ages from three distinct moraines are in stratigraphic order at 22.1 ± 3.8, 20.2 ± 2.4, and 15.3 ± 3.8 ka and generally agree with other terminal and some recessional moraine ages across the Cascade Range and Sierra Nevada of the western United States. To date, these are among the youngest surfaces ever dated using cosmogenic 21 Ne and provide a cost-effective proof-of-concept approach to dating moraines where applicable.

58 GEOSCIENCES↗

Accelerated Aging and Evaluation of Hose-In-Hose Transfer Lines in the Hanford Waste Transfer System - 20312

Nonmetallic materials are used in the United States Department of Energy's Hanford Site Tank Farm waste transfer system. These materials include the inner primary hoses in the hose-in-hose transfer lines (HIHTLs), Garlock{sup R} gaskets, ethylene propylene diene monomer (EPDM) O-rings, and other nonmetallic materials. These nonmetallic materials are exposed to β and γ radiation, caustic solutions as well as high temperature and pressure stressors. How the nonmetallic components react to each of these stressors individually has been well established. However, simultaneous exposure of these stressors has not been evaluated and is of great concern to Hanford Site engineers. Florida International University's Applied Research Center engineers worked closely with key Hanford's Washington River Protection Solutions personnel to develop an experimental test plan that determines how these nonmetallic components react to various simultaneous stressor exposures. In this paper, research on the experimental testing of the hose-in-hose transfer lines used in the Hanford tank farm waste transfer system under simultaneous stressor exposures is presented. The stressor exposure experiments consisted of various combinations of simultaneous stressor exposure of caustic solution, high temperature and high pressure stressors. Research efforts focused on evaluating the aging behavior of EPDM by exposing samples of HIHTLs as well as EPDM dog bone shaped specimens to a 25% NaOH solution at (38 deg. C), operating (54 deg. C) and design temperatures (77 deg. C) for 6 months and 12 months. In addition, HIHTL and the EPDM dog-bone specimens were exposed to only hot water at 77 deg. C for a duration of one year. The mechanical and material properties of the samples were characterized and compared with those of the unexposed samples (baseline). Evaluations included burst pressure tests of the EPDM hose-in-hose transfer lines and material tensile strength test of EPDM dog-bone coupons. Both the tensile strength of the EPDM material dog bones and the burst pressure of the HIHTLs significantly decreased with the increasing temperature and increasing exposure time. When compared with the baseline samples, the burst pressure decreased by 28.75% for the sample aged at 77 deg. C after 12 months, in comparison to sample aged at 38 deg. C and 54 deg. C which had about 1.34% and 5.70% loss in burst pressures, respectively, after 12-month exposure. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Effects of Contaminant-Aging on Decontamination Efficacy for Rapid Remediation of Concrete Surfaces - 20412

Understanding the relationship between decontamination efficacy and contaminant aging is imperative for developing effective remediation strategies following a large-scale contamination event. Non-destructive decontamination of concrete following a contamination incident becomes more difficult with increased time between contamination and decontamination because contaminants may chemically bind to concrete and/or penetrate into the concrete subsurface. In this work, we evaluated the decontamination efficacy of two decontamination methods on concrete samples contaminated with soluble Cesium-137 (Cs-137) and silica particles with 0.5 μm and 2 μm diameters. Concrete samples were aged between 1 and 59 days, with half of the coupons receiving 1 mL of artificial rainwater about once every three days. After aging, coupons were either decontaminated or analyzed to determine contaminant penetration depths. Coupons were decontaminated with 0.1 M Potassium Chloride (KCI) solution applied either by flowing solution across the contaminated coupon face or non-destructive power washing. Contaminant depth profiles were created by removing the top surface of the coupon at least 15 times, measuring the activity in each removed layer, normalizing the total activity removed to the measured decontamination efficacy following the last layer removal, and determining the penetration thickness using the coupon dimensions, bulk density, and mass of material removed for each layer. Pressurized washing effectively removed particles, but not soluble cesium, despite the majority of Cs-137 being located within the first millimeter of the subsurface. Soluble cesium removal by flowing 0.1 M KCI solution across the contaminated surface dropped to less than 12% within the first ten days. This drop in Cs-137 removal efficacy occurred within the first five days for coupons experiencing artificial rainfall events. Flowing 0.1 M KCI solution across the contaminated face was ineffective at removing particles, likely because particles had localized in surface depressions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Extreme fast charge aging: Effect of electrode loading and NMC composition on inhomogeneous degradation in graphite bulk and electrode/electrolyte interface

Empowering extreme fast charging (XFC) requires a comprehensive understanding of its application with advanced anode and cathode materials in lithium-ion batteries. No report exists for the full extent of limitations for the anode with crosstalk effect from paired cathode as well as Li plating due to electrode loading under XFC. In this study, a combination of cell testing and multiple length characterization is used to investigate XFC aging mechanism in cells with a low loading of 1.5 mAh cm -2 and high loading of 2.5 mAh cm -2 for graphite (Gr)/Ni-rich LiNi x Mn y Co 1-x-y O 2 (NMCs). Operando XRD mappings show 1.5 mAh cm -2 loadings result in higher strain in graphite for all three cathode types. Among the three NMC cathodes, the graphite from NMC532 and NMC811 cells show comparable strain. Scanning electron microscopy (SEM) images show distinct differences between 6-C-charged anodes in two loadings. Significantly increased electrode thickness can be seen due to more damage in the graphite bulk and accumulation of the electrolyte decomposition products in electrode pores. X-ray photoelectron spectroscopy (XPS) reveals both cathode chemistry and Li plating influence the non-uniform SEI composition on graphite surface. We report higher Ni content in NMC811 promotes the higher levels of salt decomposition on the SEI and formation of higher mass of electrolyte aging products.

25 ENERGY STORAGE↗

Radiation Aging of Cable Insulation Systems to Support Extension of Cable Electrical Assessment Techniques - CRADA 562 (Final Report)

Radiation aging (primarily gamma radiation) affects a small subset of the LV cable population based on a 40-year operation. Increasing plant operating life to 60 or 80 years will result in additional cables experiencing degradation, either from radiation or from combined thermal and radiation effects. Previous research work done by EPRI and other researchers focuses on electrical diagnostics of thermal effects. However, the electrical diagnostic response of the cable system to radiation aging is minimally understood. In order to study the electrical responses from XLPE and EPR cabling and correlate these responses with radiation dose and level of thermal exposure, gamma radiation testing was performed at Pacific Northwest National Laboratory (PNNL). This report covers the radiation testing performed at PNNL, which involved irradiation of 30-foot long cables and short witness samples. The cabling was irradiated, at room temperature, using cobalt-60 gamma-rays to intervals of 10 million rads (10 Mrads), for a maximum of 70 Mrads. The results can be used to determine cable conditions (extent of damage) more accurately and localize where the degradation exists along the length of the cable (axial location). These insights can provide operators with the options to focus repair, mitigation, or replacement efforts locally.

36 MATERIALS SCIENCE↗