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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Fiberboard Properties and Degradation Rates for Storage of 9975 Shipping Packages in KAC (2021 Status Report)

Thermal, mechanical, and physical properties have been measured on fiberboard samples following accelerated aging for up to 16 years. The aging environments include elevated temperature up to 250 ºF (the maximum allowed service temperature for fiberboard in 9975 packages) and elevated humidity. Accelerated aging results have been analyzed and used to build aging models. Correlations relating several properties (thermal conductivity, energy absorption, weight, dimensions, and density) to their rate of change in potential storage environments have been developed. Combined with an estimate of the actual conditions the fiberboard experiences in K-Area Complex (KAC), these models allow development of service life predictions. KAC completed calculations that supported extending the service life of 9975 packages with 3013 and non3013 containers in storage from 15 years to 20 years. These calculations addressed the potential for degraded fiberboard properties following 20 years in storage using degradation models developed previously. The updated degradation models developed in this report have been compared to the assumptions in these calculations, and the current results for fiberboard dimensions, density, radial thermal conductivity, and energy absorption remain consistent with those calculations. The axial thermal conductivity degradation rate slightly exceeds calculations estimate of 0.5% per year between 130 and 160 °F. Additional data will continue to be collected to permit future refinements to the models and assumptions. Some of the predicted degradation rates presented in this report are extreme. However, these relate to environments that do not exist within KAC or would be postulated only as upset conditions that would not likely persist for an extended period. For a typical package stored in KAC with approximately 10-12 watts internal heat load or less, and ambient temperatures below 90 ºF, the fiberboard assemblies experience storage conditions less severe than any of the aging environments. Fiberboard in conforming packages with lower internal heat loads should experience little or no degradation and is expected to provide a service life beyond the currently approved 20 year storage period. Packages with higher internal heat loads may not continue to perform their required safety functions beyond 20 years. Ultimately, service life will be determined by the cumulative effect of degradation from all the conditions these packages might encounter. The results and model predictions presented in this report are applicable to 9975 packages with cane or softwood fiberboard overpack assemblies. These degradation models do not address the effects of nonconforming conditions such as the presence of excess moisture and mold or beetle infestations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Fiberboard Properties and Degradation Rates for Storage of 9975 Shipping Package in KAC (2022 Status Report)

Thermal, mechanical, and physical properties have been measured on fiberboard samples following accelerated aging for up to 17 years. The aging environments include elevated temperature up to 250 °F (the maximum allowed service temperature for fiberboard in 9975 packages) and elevated humidity. Accelerated aging results have been analyzed and used to build aging models. Correlations relating several properties (thermal conductivity, energy absorption, weight, dimensions, and density) to their rate of change in potential storage environments have been developed. Combined with an estimate of the actual conditions the fiberboard experiences in K-Area Complex (KAC), these models allow development of service life predictions. KAC completed calculations that supported extending the service life of 9975 packages with 3013 containers in storage from 20 years to 40 years. These calculations addressed the potential for degraded fiberboard properties following 40 years in storage using degradation models developed previously. Due to differences in containers, 9975 packages with non-3013 containers are only approved for 20 years of storage. The updated degradation models developed in this report have been compared to the assumptions in those calculations, and the current results for fiberboard dimensions, density, radial thermal conductivity, and energy absorption remain consistent with those calculations. The axial thermal conductivity degradation rate slightly exceeds calculations estimate of 0.5% per year between 130 and 160 °F. Additional data will continue to be collected to permit future refinements to the models and assumptions. Some of the predicted degradation rates presented in this report are extreme. However, these relate to environments that do not exist within KAC or would be postulated only as upset conditions that would not likely persist for an extended period. For a typical package stored in KAC with approximately 10-12 watts internal heat load or less, and ambient temperatures below 90 °F, the fiberboard assemblies experience storage conditions less severe than any of the aging environments. Fiberboard in conforming packages with lower internal heat loads should experience little or no degradation and is expected to provide a service life beyond the currently approved 40 year storage period. Packages with higher internal heat loads may not continue to perform their required safety functions beyond 40 years. Ultimately, service life will be determined by the cumulative effect of degradation from all the conditions these packages might encounter. The results and model predictions presented in this report are applicable to 9975 packages with cane or softwood fiberboard overpack assemblies. These degradation models do not address the effects of non-conforming conditions such as the presence of excess moisture and mold or beetle infestations.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Development of process parameters and post-build conditions for qualification of LPBF 316 SS

To harness the potential of laser powder bed fusion (LPBF) 316H stainless steel (SS) for use in advanced nuclear reactors, extensive research efforts are needed to develop optimal laser processing parameters and appropriate heat treatments, taking into account various manufacturing platforms and locations. Furthermore, it is crucial to assess the material properties in environments relevant to reactor operating conditions. In collaboration with Oak Ridge National Laboratory (ORNL) and Los Alamos National Laboratory (LANL), Argonne National Laboratory (ANL) is dedicated to gaining insights into how the manufacturing process and post-build treatments impact the performance of LPBF 316H SS. This report provides an overview of ANL's research findings for FY23, focusing on LPBF 316H SS produced using a Renishaw AM400 laser system. Specifically, our research has concentrated on three key areas: 1) Optimum laser processing parameters: Leveraging the high-throughput printing technology, we systematically varied the laser power, exposure time and point distance within the same build. By measuring the as-printed porosity, we identified an optimum printing parameter window that produced materials with near-complete density; 2) Post-built treatment development: Materials printed with the optimum laser parameters underwent treatments including stress relief, solution annealing, and hot isostatic pressing. Subsequently, we fabricated tension, creep, and fatigue specimens from materials subjected to these different conditions. Over the next year, a series of scoping tests will be conducted to facilitate the selection of the most suitable post-build treatment condition; 3) Thermal aging effects on microstructure and properties: thermal aging at 550°C, 650°C and 750°C was conducted on LPBF 316H SS specimens up to 2500 h. Microstructural characterization was performed with electron microscopy, and the evolution of the dislocation cell structures and secondary phases was studied. Microhardness tests and tension tests were conducted to quantify changes in mechanical properties. The results revealed that the aged LPBF 316H SS exhibited a high density of Cr-rich and Mo-rich fine precipitates within grains due to the presence of a high density of dislocations and the globally distributed dislocation cell structures, which served as heterogeneous nucleation sites for secondary phases. Along grain boundaries, a Mo-Cr-rich phase, observed in 750°C-aged conditions, displayed significant thermal coarsening. Throughout the aging process, various mechanisms, including stress relaxation, dislocation cell structure recovery, solution hardening, and precipitation hardening, competed to influence materials strength. These results contribute towards establishing the technical basis for qualifying LPBF 316H SS for advanced nuclear reactor applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

2024 Status Report - Fiberboard Properties and Degradation Rates for Storage of 9975 Shipping Package in KAC

Fiberboard assemblies in the 9975 package were identified as susceptible to aging and degradation under long-term storage conditions. Thermal, mechanical, and physical properties have been measured on fiberboard samples aging for up to 19 years at accelerated conditions. The aging environments include elevated temperature up to 250 ºF (the maximum allowed service temperature for fiberboard in 9975 packages) and elevated humidity. Accelerated aging results have been analyzed and used to build aging models. Correlations relating several properties (thermal conductivity, energy absorption, weight, dimensions, and density) to their rate of change in potential storage environments have been developed. Combined with an estimate of the actual conditions the fiberboard experiences in K-Area Complex (KAC), these models allow development of service life predictions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probabilistic Multi-Hazard Performance Assessment of Concrete Structures in Nuclear Installations

Concrete structures in nuclear installations are subject to time-dependent degradation mechanisms that can deteriorate their physical and mechanical properties, potentially exacerbating the risk of structural failure under external forces such as a seismic event. Previous research has extensively investigated the seismic response of nuclear concrete structures and the associated risk, as well as their effect on structural components safety margins. However, substantial work is still necessary to incorporate concrete aging effects into such evaluations. In fact, most models in the literature assume pristine concrete conditions and do not account for the impact of aging on the structural components’ fragility curves. This work identifies relevant time-dependent degradation mechanisms and provides simplified models to predict the the evolution of key material properties based on data from the literature. Namely, this work focuses on the aging effects of corrosion, alkali–silica reaction (ASR), and irradiation on reinforced concrete within US Department of Energy (DOE) nuclear facilities and nuclear power plants (NPP) structures. Furthermore, degradation models based on literature data are presented that define the relationship between probabilistic material properties and the concrete’s age. In this work, sampled material properties served as input for a simplified finite element model (FEM) of a critical nuclear structural system, with the output of the FEM being the seismic response for a given ground motion. The results of the FEM were then used within a probabilistic performance assessment with a statistically significant number of samples. The research presented herein addresses the detrimental effects of hazards caused by natural phenomena on deteriorated concrete elements of nuclear installations. This work directly benefits the safety analysis performed on US DOE/ National Nuclear Security Administration (NNSA) nuclear facilities located in areas prone to seismic activity. The results presented herein could aid in the improvement of DOE-STD-1020, the DOE Standard that addresses seismic risk analysis and capacity evaluation in DOE facilities. DOE-STD-1020 refers to the requirements in American Society of Civil Engineers (ASCE) 4-98, now superseded by ASCE 4-16, that shall be met in performing dynamic response analyses and generating in-structure response spectra, provided that such requirements are consistent with the requirements of ASCE/Structural Engineering Institute (SEI) 43-05. Moreover, the results presented herein could also aid in the updating of section C3.1.1. of ASCE 4-16 to account for the effects of aging on the stiffness of reinforced elements and American Concrete Institute (ACI) 349.3R-18, “Report on Evaluation and Repair of Existing Nuclear Safety-Related Concrete Structures.” Ultimately, this work can assist the risk assessment of potential lifetime extension of the existing US commercial nuclear fleet (light water reactors) and the safety analysis of the emerging advanced nuclear reactors. The proposed proof-of-concept methodology employs open-source DOE computational tools and is transferable to commercial software commonly used by engineering firms.

42 ENGINEERING↗
DOE OSTI2026

Battery Life Prediction Using Reduced-Order Physics Models and Machine Learning (CRADA Final Report)

Phase 1 (Original CRADA, plus no-cost extension modifications #1-3, 6/1/2017 to 3/13/2021): The Australian Department of Defence (AUDoD) is performing accelerated aging tests of Li-ion batteries to benchmark their reliability and degradation characteristics. Using its previously developed battery lifetime predictive model framework, the National Laboratory of the Rockies (NLR) will develop analytical models based the AUDoD data to predict lifetime of the multiple Li-ion battery chemistries under real-world use scenarios of interest to AUDoD. The NLR model is based on physical degradation mechanisms encountered by Li-ion batteries and has been previously validated. Phase 2 (CRADA modification #4, plus no-cost extension modification #5, 2/22/2021 to 3/30/2025): Train and support Australian Department of Defence personnel to use NLR software for model-based estimation of Li-ion battery lifetime using accelerated battery aging data collected by the Australian Department of Defence. Under separate DOE funding from 2019 to 2021, NLR enhanced its battery life-prediction software using machine learning algorithms to automate portions of the model-fitting process, requiring significantly less labor and expert judgment and also adding uncertainty quantification, increasing statistical rigor. Under Phase 2, NLR will customize NLR Software and provide it to AuDoD. NLR will enhance its NLR Model to capture aging modes of AuDoD's multi-cell modules, including cell-balancing effects. NLR will develop example single-cell and multi-cell models based on one AuDoD battery aging dataset. NLR will train AuDoD personnel on NLR Software. By the conclusion of the project, NLR will have provided AuDoD the training materials, a user manual and software needed to perform their own analysis of additional and/or future battery aging datasets.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

Spontaneous bodily coordination varies across affective and intellectual child-adult interactions

Research on child-adult interactions has identified that the morphology of bodily coordination seems to be sensitive to age and type of interaction. Mirror-like imitation emerges earlier in life and is more common during emotionally laden interactions, while anatomical imitation is acquired later and associated with cognitive tasks. However, it remains unclear whether these morphologies also vary with age and type of interaction during spontaneous coordination. Here we report a motion capture study comparing the spontaneous coordination patterns of thirty-five 3-year-old (20 girls; M age = 3.15 years) and forty 6-year-old children (20 girls; M age = 6.13 years) interacting with unacquainted adults during two storytelling sessions. The stories narrated the search of a character for her mother (Predominantly Affective Condition) or an object (Predominantly Intellectual Condition) inside a supermarket. Results show that children of both ages consistently coordinated their spontaneous movements towards adult storytellers, both in symmetric and asymmetric ways. However, symmetric coordination was more prominent in 3-year-old children and during predominantly emotional interactions, whereas asymmetric coordination prevailed in 6-year-old children and during predominantly intellectual interactions. These results add evidence from spontaneous interactions in favor of the hypothesis that symmetric coordination is associated with affective interactions and asymmetric coordination with intellectual ones.

Cornejo, Carlos↗
DOE OSTI2023

Study on the Thermal Stabilizing Process of Layered Double Hydroxides in PVC Resin

Poly(vinyl chloride) (PVC) is widely used in various fields and requires the use of thermal stabilizers to enhance its thermal stability during processing because of its poor thermal stability. Layered double hydroxides (LDHs) are widely considered to be one kind of highly efficient and environmentally friendly PVC thermal stabilizer. To investigate the thermal stabilizing process of layered double hydroxides (LDHs) in PVC resin, PVC and MgAl-LDHs powders with different interlayer anions (CO 3 2- , Cl - , and NO 3 - ) were physically mixed and aged at 180 °C. The structure of LDHs at different aging times was studied using XRD, SEM, and FT-IR. The results show that the thermal stabilizing process of LDHs on PVC mainly has three stages. In the first stage, the layers of LDHs undergo a reaction with HCl, which is released during the thermal decomposition of PVC. Subsequently, the ion exchange process occurs between Cl - and interlayer CO 3 2- , resulting in the formation of MgAl-Cl-LDHs. Finally, the layers of MgAl-Cl-LDHs react with HCl slowly. During the thermal stabilizing process of MgAl-Cl-LDHs, the peak intensity of XRD reduces slightly, and no new XRD peak emerges. It indicates that only the first step happens for MgAl-Cl-LDHs. The TG-DTA analysis of LDHs indicates that the interaction of LDHs with different interlayer anions has the following order: NO 3 - < CO 3 2- < Cl - , according to the early coloring in the thermal aging test of PVC composites. The results of the thermal aging tests suggest that LDHs with a weak interaction between interlayer anions and layers can enhance the early stability of PVC significantly. Furthermore, the thermal aging test demonstrates that LDHs with high HCl absorption capacities exhibit superior long-term stabilizing effects on PVC resin. This finding provides a valuable hint for designing an LDHs/PVC resin with a novel structure and excellent thermal stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Exploring the Evolution of Stellar Rotation Using Galactic Kinematics

The rotational evolution of cool dwarfs is poorly constrained after ∼1–2 Gyr due to a lack of precise ages and rotation periods for old main-sequence stars. In this work, we use velocity dispersion as an age proxy to reveal the temperature-dependent rotational evolution of low-mass Kepler dwarfs and demonstrate that kinematic ages could be a useful tool for calibrating gyrochronology in the future. We find that a linear gyrochronology model, calibrated to fit the period–T{sub eff} relationship of the Praesepe cluster, does not apply to stars older than around 1 Gyr. Although late K dwarfs spin more slowly than early-K dwarfs when they are young, at old ages, we find that late K dwarfs rotate at the same rate or faster than early-K dwarfs of the same age. This result agrees qualitatively with semiempirical models that vary the rate of surface-to-core angular momentum transport as a function of time and mass. It also aligns with recent observations of stars in the NGC 6811 cluster, which indicate that the surface rotation rates of K dwarfs go through an epoch of inhibited evolution. We find that the oldest Kepler stars with measured rotation periods are late K and early M dwarfs, indicating that these stars maintain spotted surfaces and stay magnetically active longer than more massive stars. Finally, based on their kinematics, we confirm that many rapidly rotating GKM dwarfs are likely to be synchronized binaries.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

A KELT–TESS Eclipsing Binary in a Young Triple System Associated with the Local “Stellar String” Theia 301

HD 54236 is a nearby, wide common-proper-motion visual pair that has been previously identified as likely being very young by virtue of strong X-ray emission and lithium absorption. Here, we report the discovery that the brighter member of the wide pair, HD 54236A, is itself an eclipsing binary (EB), comprising two near-equal solar-mass stars on a 2.4 days orbit. It represents a potentially valuable opportunity to expand the number of benchmark-grade EBs at young stellar ages. Using new observations of Ca ii H and K emission and lithium absorption in the wide K-dwarf companion, HD 54236B, we obtain a robust age estimate of 225 ± 50 Myr for the system. This age estimate and Gaia proper motions show HD 54236 is associated with Theia 301, a newly discovered local “stellar string,” which itself may be related to the AB Dor moving group through shared stellar members. Applying this age estimate to AB Dor itself alleviates reported tension between observation and theory that arises for the luminosity of AB Dor C when younger age estimates are used.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Photometric and Kinematic Study of the Open Clusters SAI 44 and SAI 45

We carry out a detailed photometric and kinematic study of the poorly studied sparse open clusters SAI 44 and SAI 45 using ground-based BVR {sub c} I {sub c} data supplemented by archival data from Gaia eDR3 and Pan-STARRS. The stellar memberships are determined using a statistical method based on Gaia eDR3 kinematic data, and we found 204 members in SAI 44 while only 74 members are identified in SAI 45. The average distances to SAI 44 and SAI 45 are calculated to be 3670 ± 184 and 1668 ± 47 pc. The logarithmic age of the clusters are determined to be 8.82 ± 0.10 and 9.07 ± 0.10 yr for SAI 44 and SAI 45, respectively. The color–magnitude diagram of SAI 45 hosts an extended main-sequence turnoff (eMSTO). The apparent age spread is found to be similar to the apparent age spread predicted on the basis of the age spread and cluster age relation predicted by rotation models. This indicates that eMSTO is a stellar evolution rather than star formation phenomenon in SAI 45. We conclude that eMSTO in SAI 45 is mainly caused by the different rotation rates of stars as the SYCLIST synthetic population with different rotation rates was able to reproduce the observed eMSTO, and stars in the red part of the eMSTO were preferentially concentrated in the inner region, which again hints at different rotations being the reason for the extension in the upper MS. This finding supports the theory attributing the origin of eMSTO to the different rotations of eMSTO stars. The mass function slopes are obtained as -2.24 ± 0.66 and -2.58 ± 3.20 in the mass rages 2.426–0.990 M{sub ⊙} and 2.167–1.202 M{sub ⊙} for SAI 44 and SAI 45, respectively. SAI 44 exhibits the signature of mass segregation while we found weak evidence of mass segregation in SAI 45 possibly due to tidal stripping. The dynamical relaxation times of these clusters indicate that both clusters are in a dynamically relaxed state. Using the AD-diagram method, the apex coordinates are found to be ([[Formula]], -[[Formula]]) for SAI 44 and (-[[Formula]], -[[Formula]]) for SAI 45. The average space velocity components of the clusters SAI 44 and SAI 45 are calculated in units of km s{sup -1} as (-15.14 ± 3.90, -19.43 ± 4.41, -20.85 ± 4.57) and (28.13 ± 5.30, -9.78 ± 3.13, -19.59 ± 4.43), respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Assessment of the Effectiveness of Three Aftermarket Gasoline Fuel Stabilizers in Preventing Gum Formation and Loss of Oxidation Stability

We note that fuel stabilizers have long been marketed to consumers to prevent oxidation and gum formation. In the past, gasoline storage for long periods of time was commonly limited to off-road equipment that was used infrequently. Cars and trucks that were driven regularly consumed the fuel in their tanks rapidly enough to avoid excessive fuel aging. However, plug-in hybrid electric vehicles (PHEVs) may be operated frequently without engine operation, raising the possibility that fuel may be stored in the tank for longer periods of time. Studies of the oxidation of gasoline have provided scientific understanding of the process, but there is little if any scientifically backed information aimed at aiding consumers in assessing the need to use an aftermarket fuel stabilizer if they anticipate lengthy periods of fuel storage in their fuel tank. This study was conceived to address this information gap by evaluating three aftermarket stabilizer products alongside baseline gasoline using sealed samples over a period of 12 months of aging. The aging was carried out under ambient temperature conditions with an additional series of samples kept in refrigerated storage. Analyses of vapor pressure, copper strip corrosion, oxidation stability, existent gums, and potential gums were carried out using standard ASTM tests to evaluate the samples as aging progressed. The results show that baseline gasoline remained compliant with relevant specifications to at least 12 months of aging without the use of aftermarket stabilizer additives. Use of two of the aftermarket additives increased the oxidation stability of the baseline gasoline, but this added stability was not necessary to comply with gasoline specifications.

42 ENGINEERING↗
DOE OSTI2020

Rapid evolution of aerosol particles and their optical properties downwind of wildfires in the western US

Abstract. During the first phase of the Biomass Burn Operational Project (BBOP) field campaign, conducted in the Pacific Northwest, the DOE G-1 aircraft was used to follow the time evolution of wildfire smoke from near the point of emission to locations 2–3.5 h downwind. In nine flights we made repeated transects of wildfire plumes at varying downwind distances and could thereby follow the plume's time evolution. On average there was little change in dilution-normalized aerosol mass concentration as a function of downwind distance. This consistency hides a dynamic system in which primary aerosol particles are evaporating and secondary ones condensing. Organic aerosol is oxidized as a result. On all transects more than 90 % of aerosol is organic. In freshly emitted smoke aerosol, NH4+ is approximately equivalent to NO3. After 2 h of daytime aging, NH4+ increased and is approximately equivalent to the sum of Cl, SO42, and NO3. Particle size increased with downwind distance, causing particles to be more efficient scatters. Averaged over nine flights, mass scattering efficiency (MSE) increased in ∼ 2 h by 56 % and doubled in one flight. Mechanisms for redistributing mass from small to large particles are discussed. Coagulation is effective at moving aerosol from the Aitken to accumulation modes but yields only a minor increase in MSE. As absorption remained nearly constant with age, the time evolution of single scatter albedo was controlled by age-dependent scattering. Near-fire aerosol had a single scatter albedo (SSA) of 0.8–0.9. After 1 to 2 h of aging SSAs were typically 0.9 and greater. Assuming global-average surface and atmospheric conditions, the observed age dependence in SSA would change the direct radiative effect of a wildfire plume from near zero near the fire to a cooling effect downwind.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Biomass burning and marine aerosol processing over the southeast Atlantic Ocean: a TEM single-particle analysis

This study characterizes single-particle aerosol composition from filters collected during the ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) and CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017 (CLARIFY-2017) campaigns. In particular the study describes aged biomass burning aerosol (BBA), its interaction with the marine boundary layer and the influence of biomass burning (BB) air on marine aerosol. The study finds evidence of BBA influenced by marine boundary layer processing as well as sea salt influenced by BB air. Secondary chloride aerosols were observed in clean marine air as well as in BB-influenced air in the free troposphere. Higher-volatility organic aerosol appears to be associated with increased age of biomass burning plumes, and photolysis or oxidation may be a mechanism for the apparent increased volatility. Aqueous processing and interaction with the marine boundary layer air may be a mechanism for the presence of sodium on many aged potassium salts. By number, biomass burning potassium salts and modified sea salts are the most observed particles on filter samples. The most commonly observed BC coatings are inorganic salts. These results suggest that atmospheric processes such as photolysis, oxidation and cloud processing are key drivers in the elemental composition and morphology of aged BBA. Fresh BBA inorganic salt content, as it has an important role in the particles' ability to uptake water, may be a key driver in how aqueous processing and atmospheric aging proceed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Machine-Learning Assisted Identification of Battery Life Models

Predictive battery life models are commonly utilized to extrapolate degradation trends observed during accelerated aging tests for simulation of degradation in real-world applications. Thus, fitting accelerated aging data as accurately as possible and with low uncertainty is crucial for making believable projections of battery lifetime, but it is challenging to identify algebraic expressions that accurately fit multivariate degradation trends. A review of models published in literature reveal some common expressions for fitting calendar aging data, which is only dependent on temperature and state-of-charge, but no consistency across many models for fitting cycle aging data, indicating the need for a statistically rigorous data driven approach for developing empirical models. This talk will describe a machine-learning assisted method for identification of predictive battery life models utilizing bilevel optimization and symbolic regression. Bilevel optimization with cross-validation is used to statistically determine cell- and stress-dependent model parameters, while symbolic regression identifies both linear and multiplicative candidate expressions to predict stress-dependent degradation rates by selecting low-order subsets of features from a generated feature library. Because model expressions are identified empirically, it is crucial to ensure resulting models behave according to physical expectations, so the stability of models for interpolation or extrapolation is interrogated qualitatively through simulation and quantitatively through cross-validation and uncertainty quantification via bootstrap resampling. This model identification approach substantially improves upon models identified purely using expert judgement in terms of both accuracy and uncertainty. Model simulation and validation is then conducted by deriving a state-equation form of the predictive model, enabling simulation of battery aging under dynamic stresses. This enables validation of the predictive battery model on lab-based tests with varying conditions or on drive-cycle or application-cycle testing protocols. Parameter uncertainty can be carried forward into model simulation, giving lifetime estimates and confidence windows for cell- or system-level lifetime. The financial impact of battery model uncertainty can be estimated by incorporating uncertainty into a technoeconomic model.

battery↗
DOE OSTI2022

Evaluation of Copper Catalytic Effects in Cable Insulation Polymers

This paper summarizes work performed to evaluate a phenomenon that occurs in electrical cable insulation polymers subjected to accelerated aging while in contact with copper metal. This effect, commonly known as the copper catalytic effect, is a result of chemical reactions that occur when copper ions diffuse into insulation polymers. This diffusion process is observed in various types of polymeric materials exposed to elevated temperatures and happens at the interface between the insulation and metallic components (e.g., conductor, shielding, etc.) in a cable. This polymer-metal interaction has only been observed in cables constructed with copper components (i.e., no interactions observed in cables with aluminum or other metal conductor/shielding) and results in a significant catalytic effect that increases the oxidation rate (e.g., aging) of the material. Under this research, the copper catalytic effects observed in cross-linked polyethylene, cross-linked polyolefin and ethylene propylene rubber insulated cables subjected to thermal accelerated aging were evaluated. These evaluations involved applying infrared spectroscopy, microscopy, and energy dispersive X-ray spectroscopy cross-sectional depth profiling to obtain an in-depth understanding of the aging characteristics of the materials under accelerated conditions. Based on the results of these assessments, the copper catalytic effect can have a significant impact on the mechanical, thermal, chemical, and electrical properties of cable insulation polymers. Here, the results acquired from this research provided the information needed to characterize the copper catalytic effects observed in these polymers, analyze how this phenomenon affected the polymer degradation process, and compare and understand the differences in the properties of the materials.

42 ENGINEERING↗
DOE OSTI2020

Thermal Stability of a Eutectic Mixture of Bis(2,2-dinitropropyl) Acetal and Formal: Part C. Kinetic Compensation Effect

Here, the aging behavior of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal [called NP here] has been studied in various atmospheres [dry (air or nitrogen) versus wet] at temperatures 70 °C and below. The properties of aged samples were analyzed using Fourier transform infrared (FTIR) spectroscopy, Karl Fischer (KF) titration, liquid chromatography/mass spectrometry (LC/MS), and thermogravimetric analysis (TGA) over a period of three years. The results indicate that at aging temperatures up to 55 °C, the initial rates of water production from nitrous acid (HONO) formation and decomposition into the water, NO, and NO 2 follows a 1st order rate law and the rate constants follow an Arrhenius law as a function of temperature. The activation energies and pre-factors for water and volatiles production yield a single linear kinetic compensation plot, suggesting a common degradation pathway between NP and the various combinations of its constituents. Within a narrow temperature range, around 55 °C, a trace amount of water in NP stabilizes its properties by preventing HONO elimination. When the aging temperature is substantially higher than 55 °C, the nature of the degradation mechanism changes. It is suspected that the degradation products of NO x , water, and HNO 3 serve as catalysts to auto-catalyze (kinetics beyond the 1st order) and further degrade NP. The effect of headspace volume on this auto-catalytic process will be discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Automated Scoring of Morphological Changes in Images of Pentaerythritol Tetranitrate

Recent advances in characterization techniques that generate large datasets of material microstructure images require robust, automated image-processing. We applied an unsupervised anomaly detection method called feature anomaly detection system (FADS) to automatically detect and quantify microstructure changes in images of the explosive pentaerythritol tetranitrate (PETN) aged at various temperatures. We demonstrated the FADS approach on two-dimensional images extracted from computed tomography scans, but the same technique can be readily applied to other imaging modalities. FADS calculates anomaly scores on the basis of differences in filter activations of nominal and test data in pretrained convolutional neural networks. The FADS scores successfully differentiated between pristine PETN and PETN aged at a temperature where material coarsening occurred. Morphological metric analysis of segmented images verified observed trends in FADS scores as a function of aging temperature and aging time, specifically by calculating volume fractions, specific boundary lengths, two-point correlation functions, and local thicknesses. Here, the FADS technique has two important advantages compared to traditional morphological analysis: First, it uses grayscale images as input, rather than images that are segmented to separate the appropriate phases; and second, FADS scores capture any type of changes among image sets, rather than requiring prior knowledge or selection of a relevant set of metrics.

Accelerated aging↗