Elucidating the role of anionic chemistry towards high-rate intermediate-temperature Na-metal halide batteries
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A new approach is developed for estimating entrainment and detrainment rates in cumulus clouds based on aircraft observations. Equations relating entrainment and detrainment rates to gross entrainment and detrainment are derived. This approach is applied to the Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecosystems field campaign, supported by the U.S. Department of Energy's Atmospheric Radiation Measurement program. The results show that both entrainment and detrainment rates decrease with increasing height. Sensitivity tests with different detrained air assumptions yield similar results. The entrainment and detrainment rates can reproduce the cloud thermodynamic variables. Partial correlation analysis indicates that entrainment rate is positively correlated with environmental relative humidity (RH), and detrainment rate is negatively correlated with environmental RH and positively correlated with entrainment rate. This new approach can be applied to other cloud observations to obtain a data set of entrainment and detrainment rates in cumulus clouds.
Battery electrodes materials undergo significant mechanical instabilities which affects their longevity and exert rate-limitations during the cycling process. In this study, we investigate the rate-dependent mechanical response of sodium iron phosphate (NaFePO4, NFP) cathodes during Na intercalation via galvanostatic cycling at different rates by employing digital image correlation, electrochemical methods, and mathematical model. The mechanical behaviour of the electrode shows strong dependance on the applied scan rate. At slower rates, electrode shows asymmetrical strain generation between anodic and cathodic cycles, which is attributed to the formation of cathode-electrolyte interface layers. The electrode undergoes smaller strain generation when cycled at slower rates when the same amount of Na ions is removed or inserted into the electrode. A mathematical model was developed to predict strain evolution in the composite electrode as well as the concentration profile of the Na ions in the electrode particles. Rate-dependent and time dependent factors on the strain generation in the electrode are attributed to the capacity-dependent intercalation strains, rate-dependent mismatch strains, and time-dependent irreversible strains. The combination of in situ strain measurements with the analytical model provided new insight into the electrochemically induced mechanical deformations in Na-ion cathode electrodes.
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Amorphous elastomers exhibit significant rate-stiffening and unique viscous flow characteristics across a wide range of strain rates, often undergoing glass transition above a strain rate threshold. We have developed a thermodynamically-consistent and micromechanically-inspired constitutive model for soft elastomeric materials to capture the rate-dependent stress-strain behavior and hysteresis when subjected to low to high strain rates. Here, our proposed constitutive model encapsulates the viscous flow of materials through molecular motion at low strain rates and local rearrangement and alignment of the molecules trying to overcome the intermolecular resistance at high strain rates, essentially covering the glass transition. We applied our constitutive model to uniaxial compression experiments performed at low and high strain rates for polyborosiloxane (PBS) to identify the material parameters, and subsequently, performed numerical simulations of single and multi-cycle compression, stress relaxation, and small amplitude oscillatory tension-compression. Our analyses indicate that the model predicts higher total energy dissipation with increasing strain rate; however, dissipation associated with molecular relaxation decreases (forming a cusp) because, beyond a crossover strain rate, intermolecular rearrangement and alignment become dominant, which is consistent with the onset of the glass transition. For cyclic loading-unloading, we observed that dissipation over a cycle remains constant at low strain rates but decreases non-monotonically at high strain rates before becoming constant, with the peak stress over the cycle becoming higher, which can be interpreted as more loading being carried elastically by the polymer network as the intermolecular rearrangement process occurs. Additionally, our model was able to predict the qualitative nature of the storage modulus and loss modulus in the limit of small strain over a wide range of frequency sweeps.
Mathematical relations prescribing unidirectional forward and reverse rates originally derived based on single-path reaction sequences do not apply to interconnected reaction networks. The presence of branches in reaction networks, leading to alternative stable products, decreases unidirectional rates in reference to those calculated by single-path functional forms, as shown by simulated isotopic exchange rates, but impacts the unidirectional forward and reverse rates equally such that the functional form of effective reversibility remains unchanged. Regardless of stoichiometric numbers and network connectivity, the application of the pseudo-steady-state hypothesis on reactive intermediates in conjunction with consideration of unidirectional rates toward the product of interest and all alternative stable products results in mathematical expressions that accurately reflect simulated isotopic exchange rates. Further analyses based on kinetic resistance, a property akin to electrical resistance, illustrate the manifestation of nodal resistances in addition to the single-path kinetic resistance for interconnected reaction networks. The generalized formalism for assessing rates and reversibilities in interconnected networks derived herein enables us to demonstrate that unidirectional rates cannot be assessed solely from effective reversibilities and net rates of generation of stable species in such networks. Furthermore, isotopic exchange rates, under the condition that each elementary step in the overall reaction sequence forms a unique reactive intermediate that is consumed solely by the subsequent step, can be utilized to determine unidirectional rates and can serve to validate postulated reaction pathways in highly interconnected reaction networks (e.g., CO x hydrogenation).
The rate of conversion of nuclear waste melter feed to glass is affected by the selection of melter feed materials and by melter design and operation. The melting rate correlation (MRC) is an equation that relates the glass production rate with two types of variables: (1) feed and melt properties: conversion heat, cold-cap bottom temperature, and glass melt viscosity; and (2) melter design and operation parameters: melter geometry, melter operating temperature, and gas bubbling rate. The MRC shows good agreement for an extended melting-rate data set of high-level waste (HLW) melter feeds and a data set generated for low-activity waste (LAW) melter feeds. Laboratory observation of heated melter feed samples is often used to assess the cold-cap bottom temperature of HLW melter feeds (moderately foaming feeds), but this technique appears inadequate for LAW melter feeds (vigorously foaming feeds). For LAW feeds, an adequate assessment of the cold-cap bottom temperature was achieved using evolved gas analysis, which allows identification of the collapse of primary foam for oxidized feeds. This assessment shows that the cold-cap bottom temperature for vigorously foaming LAW feeds is higher than that for moderately foaming HLW feeds. When the results of MRC are compared, LAW feeds are generally less sensitive to the bubbling rate and melt viscosity, and more sensitive to the cold-cap bottom temperature than HLW feeds. The MRC qualifies as a promising tool to support the selection of melter feed materials and melter operating conditions, which is determined from expensive independent scaled melter experiments, and sophisticated mathematical models.
Abstract We present a suite of strain rate models for the western United States based on geologic and geodetic data. The geologic data consist of Quaternary fault-slip rates and the geodetic data consists of a new compilation of Global Positioning System (GPS) velocities derived from continuous, semicontinuous, and campaign measurements. We remove postseismic deformation from the GPS time series in order for our geodetic strain rate model to best capture the interseismic strain accumulation rate. We present models based on either geologic or geodetic data, but also create a hybrid model. Although there are some differences between the models, the large-scale features are the same, with the noticeable exception for the Pacific Northwest where interseismic strain is naturally more distributed than the long-term strain release. We also present a map of earthquake rate densities based on mainshocks, and the result has similar spatial features similar to the strain rate models (at least in the southwestern United States). We perform a general correlation analysis between strain rate and seismicity rate (south of Cascadia) and find a change in linearity between seismicity and strain rates from slow to faster deforming areas with seismicity rates relatively lower for the latter. The extent of that change depends a bit on assumptions made on the declustering and completeness of the catalog, but the finding of a change in slope is robust across the different strain rate models. Linearity for all areas is only expected when Gutenberg–Richter parameters and parameters involved in the conversion from strain to moment rate are uniform across the study area. We discuss these qualifications, but find no single satisfactory explanation for our observation. Moreover, when considering a rather short time and space, theoretical considerations of sampling from a power-law distribution actually predict there to be a power law instead of a linear relationship, generally consistent with our observation.
The objective of this study was to evaluate the accuracy of short duration electrocardiographic (ECG) recordings extracted from ambulatory continuous ECG (Holter) to assess 24-hour mean heart rate in dogs with atrial fibrillation. In this retrospective study, Holter recordings obtained from 20 dogs with atrial fibrillation were selected for analysis. Ten out of 20 dogs were receiving drugs to control heart rate at the time of Holter evaluation. From the Holter recordings, heart rate averages were calculated for various sample durations (fiveminutes, 30 minutes, one-hour, two-hours, and three-hours) for each dog. Percentage of these shorter duration ECG obtained HR averages that fell within ±10%, ±15% and ± 20% of 24-hour mean heart rate was determined for each sample duration and for each dog. Seventy five percent of heart rate averages obtained from three-hour ECG recordings fell within ±10% of 24-hour mean HR. All the heart rate averages obtained from two-hour ECG recordings fell within ±20% of 24-hour mean heart rate. Based on the results of this study it can be concluded that the duration of the ECG recording affects the prediction accuracy for 24-hour Holter mean HR. Only two and three hours of Holter recordings provided all heart rate averages within ±20% of 24-hour mean heart rate. No significant differences were noted in the prediction accuracy of shorter duration ECG recordings based on rate control therapy status. Further prospective studies are needed to assess the accuracy of HR obtained at home using various ECG recording devices to predict 24-hour mean heart rate in dogs with atrial fibrillation.
The flow stress of a material can be strongly dependent on the rate of applied strain. Measuring the strain rate sensitivity can reveal key insights into the mechanisms that drive plastic deformation. Indentation techniques have been developed to measure the strain rate sensitivity at quasistatic strain rates, but accessing higher strain rate regimes has been saddled with experimental and technical challenges. With state-of-the-art indentation instrumentation now capable of recording load and displacement at data acquisition rates in excess of 1.25 MHz, we report how strain rate sensitivity testing methodologies, especially those aimed for higher indentation strain rates, may be validated using the well-studied time-dependent deformation behavior of tungsten. Here, the strain rate sensitivity for a (110) single crystal is shown to be consistent (m = 0.023 at 2 µm depth) across all tested strain rates and methods ranging from 10 -2 - 10 4 1/s.
The wood duck (Aix sponsa) is a common and important cavity-nesting duck in North America; however, we know very little about how changes in vital rates influence population growth rate (λ). We used estimates of fertility and survival of female wood ducks from our nest-box studies in South Carolina, Alabama, and Georgia, USA, to create a stage-based matrix population model. We conducted perturbation analyses and ranked elasticity values to examine the relative importance of 17 component vital rates to λ. Female survival is influenced by nest success, so we recognized this female heterogeneity in our analyses. Four vital rates showed the greatest importance to λ. Analytic elasticities were greatest for breeding season and nonbreeding season survival of females that nested successfully, followed by nest success and female recruitment to the breeding population. Differences in female quality were important to λ. Next, we used process variation of vital rates and conducted life-stage simulation analyses (LSA) followed by variance decomposition to determine the amount of variation in λ explained by each vital rate. Female recruitment to the breeding population explained 57.7% of the variation in λ followed by nest success (11.4%), and breeding and nonbreeding season survival of females that nested successfully (9.3% and 9.4%, respectively). Together these 4 vital rates explained 88% of the variation in λ. Mean asymptotic population growth rate (λ = 0.80 ± 0.08 [SD]) from LSA revealed a declining population. Recruitment of females hatched from nest boxes was insufficient to sustain the nest-box population. Furthermore, including yearling (SY) females that were produced outside of nest boxes (i.e., immigrants) increased recruitment rates 1.5 to 2 times more than when only SY females recruited from nest boxes were included. Future research that examines how emigration and immigration interact with survival and reproduction to influence local population dynamics of wood ducks will be important for identifying the value of nest-box programs to wood duck conservation and management.
Scientific computations are expected to be increasingly distributed across wide-area networks, and Message Passing Interface (MPI) has been shown to scale to support their communications over long distances. Application-level measurements of MPI operations reflect the connection Round-Trip Time (RTT) and loss rate, and machine learning methods have been previously developed to estimate them under deterministic periodic losses. In this paper, we consider more complex, random losses with unform, Poisson and Gaussian distributions. We study five disparate machine leaning methods, with linear and non-linear, and smooth and non-smooth properties, to estimate RTT and loss rate over 10Gbps connections with 0-366ms RTT. The diversity and complexity of these estimators combined with the randomness of losses and TCP’s non-linear response together rule out the selection of a single best among them; instead, we fuse them to retain their design diversity. Overall, the results show that accurate estimates can be generated at low loss rates but become inaccurate at loss rates 10% and higher, thereby illustrating both their strengths and limitations.
As the glass-water reaction proceeds, certain glass compositions undergo a delayed acceleration in the alteration rate – a phenomenon that is commonly referred to as Stage III behavior – which generally coincides with zeolite formation. However, studying Stage III in the laboratory is difficult because the time scale required to observe Stage III behavior can vary from months to several years, and the solution conditions that initiate this acceleration remain poorly understood. Consequently, the development of a corrosion test method capable of quantifying Stage III rates in a timely manner would be of great benefit to both the scientific community and policy makers concerned with nuclear waste disposal. In this work, we induced and measured the acceleration in the corrosion rate of the AFCI glass by seeding static corrosion tests with zeolite Na-P2 at fixed pH90°C values ranging from 9.5 to 11.5. The induced Stage III rates increased linearly with increasing pH and were measured to be between the forward and residual rates of AFCI. Tests designed to compare induced Stage III rates obtained for different seeding times showed that the induced Stage III rates were faster in the absence of an alteration layer. In summary, the use of the seeded test method allows for a conservative quantification of Stage III rates in a relatively short, one-month time period.
The vertical structure of radiative heating rates over the region of the tropi-cal Indian Ocean associated with the MJO during the DYNAMO/ARM MJO Investigation Experiment is presented. The mean and variability of heating rates during active, suppressed, and disturbed phases are determined from the Paci?c Northwest National Laboratory combined remote sensing retrieval (CombRet) from Gan Island, Maldives (0.69? S, 73.15? E). TOA and surface ?uxes from the CombRet product are compared with collocated three-hourly CERES SYN1deg Ed4A satellite retrievals. The ?uxes are correlated in time with correlation coef?cients around 0.9, yet CombRet time-mean OLR is 15 W m-2 larger. Previous work has suggested that CombRet under-samples high clouds, due to attenuation by low-level clouds and reduced instrument sensitivity with altitude. However, mean OLR differs between CombRet and CERES for all values of OLR, not just the lowest values corresponding to widespread high clouds. The discrepancy peaks for mid-range OLR, sugges-tive of precipitating, towering cumulus convective clouds, rather than strati-form cirrus clouds. Biases in the cloud-top height of thick clouds substantially contribute to the overestimate of OLR by CombRet. CombRet data is used to generate composite shortwave and longwave atmospheric heating rate pro-?les as a function of the local OLR. Though there is considerable variability in CombRet not directly related to OLR, the time-height structure of mean heating rate composites generated using OLR as the interpolant is broadly representative of tropical convective variability on intraseasonal time scales.
Constant strain rate nanoindentation is a popular technique for probing the local mechanical properties of materials but is usually restricted to strain rates ≤0.1 s -1 . Faster indentation potentially results in an overestimation of the hardness because of the plasticity error associated with the continuous stiffness measurement (CSM) method. This can have significant consequences in some applications, such as the measurement of strain rate sensitivity. The experimental strain rate range can be extended by increasing the harmonic frequency of the CSM oscillation. However, with commercial instruments, this is achievable only by identifying higher CSM frequencies at which the testing system is dynamically well behaved. Using these principles, a commercial system operated at the unusually high harmonic frequency of 1570 Hz was successfully used to characterize of the strain rate sensitivity of a Zn22Al superplastic alloy at strain rates up to 1 s -1 , i.e., an order of magnitude higher than with standard methods.
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We present results from data acquired by the SENSEI experiment at SNOLAB after a major upgrade in May 2023, which includes deploying 16 new sensors and replacing the copper trays that house the CCDs with a new light-tight design. We observe a single-electron event rate of (1.39±0.11)×10^{-5} e^{-}/pix/day, corresponding to (39.8±3.1) e^{-}/gram/day. This is an order-of-magnitude improvement compared to the previous lowest single-electron rate in a silicon detector and the lowest for any photon detector in the wavelength range between near-infrared and ultraviolet. We use these data to obtain a 90% confidence level upper bound of 1.53×10^{-5} e^{-}/pix/day and to set constraints on sub-GeV dark matter candidates that produce single-electron events. We hypothesize that the data taken at SNOLAB in the previous run, with an older tray design for the sensors, contained a larger rate of single-electron events due to light leaks. We test this hypothesis using data from the SENSEI detector located in the MINOS cavern at Fermilab.