Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “sample complexity analysis”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14

Maximizing machine learning interatomic potential transferability for the discovery of the novel stellated octadecagon Bi18-Pt24 cage structure

Achieving true transferability remains the central challenge for Machine Learning Interatomic Potentials (ML-IAPs) in modeling complex bimetallic nanoclusters across their vast potential energy surfaces. We systematically investigate data selection strategies to optimize the Chebyshev Interaction Model for Efficient Simulation (ChIMES) potential for the Bi-Pt nanoclusters by comparing three innovative sampling methods: Principal Component Analysis (PCA)/k-means (structural diversity), t-distributedStochasticNeighborEmbedding (t-SNE)/k-means (force-space diversity), and hierarchical clustering. Quantitatively, the PCA/k-means strategy proved most effective for global accuracy, yielding the lowest force errors and achieving energy root mean square errors (RMSE) values competitive with Density Functional Theory (DFT), demonstrating excellent accuracy (19.16meV/atom). Structural validation on 34 unique DFT-optimized isomers further confirmed the potential’s high fidelity, with the best model PCA/k-means reproducing structures with an average root mean square deviation (RMSD) of 0.10 Å. However, the t-SNE methods, by maximizing diversity in the force space, demonstrated superior extrapolative power, leading to the more precise prediction of a novel stellated octadecagon Bi18⁢Pt24 cage structure, demonstrating the potential for exploring previously unseen morphologies. Our results establish a clear methodology for strategic data sampling that successfully maximizes ML-IAP transferability, providing an accurate and computationally efficient tool that accelerates the theoretical discovery of complex bimetallic architectures.

Vangheluwe, Raphaël [Université Paris-Saclay, CNRS↗

Machine learning approaches to streamline and enhance the analysis of multiscale imaging data for bioaerosol and soil particles

Bioaerosol and soil particles are ubiquitous in the environment. They are multicomponent and complex in nature displaying mixed inorganic and organic components. The way components are mixed in a bioaerosol sample is referred to as its mixing state. Soil particles are also a mixture of inorganic (mineral) and organic (soil organic matter) components. Bioaerosol particles contribute to a major fraction of coarse mode atmospheric particles, especially in the tropical areas, contributing up to 80 % of the particle mass concentration. The mixing state of particles is crucial to evaluate because it impacts several important environmental processes such as warm and cold cloud formation and radiation budget. Mixing states in aerosols are accompanied by chemical reactions across solid-liquid-gas interfaces. In this study, we utilized elemental compositions and microcopy images of thousands of atmospheric particles acquired by computer-controlled scanning electron microscope equipped with an energy-dispersive x-ray spectrometer to compute the mixing state of atmospheric particles. A 2D convolutional neural network (CNN), also known as convnet, was used to model the relationship between low resolution imaging data and higher resolution spectroscopy data, with the former as training input and the latter as target output. Two types of CNNs were implemented and tested; a basic CNN and an Inception-v3 network. For binary classification, the basic CNN achieved an accuracy of 84.29 % across all atom types, and the Inception-v3-like network achieved an accuracy 85.51 %. This study demonstrates the applicability of deep learning to handle large amounts of imaging/chemical spectroscopy data efficiently and evaluate particle mixing state from a range of environmental samples.

54 ENVIRONMENTAL SCIENCES↗

High throughput automated characterization of enamel microstructure using synchrotron tomography and optical flow imaging

The remarkable damage-tolerance of enamel has been attributed to its hierarchical microstructure and the organized bands of decussated rods. A thorough characterization of the microscale rod evolution within the enamel is needed to elucidate this complex structure. While prior efforts in this area have made use of single particle tracking to track a single rod evolution to various degrees of success, such a process can be both computationally and labor intensive, limited to the evolution path of a single rod, and is therefore prone to error from potentially tracking outliers. Particle image velocimetry (PIV) is a well-established algorithm to derive field information from image sequences for processes that are time-dependent, such as fluid flows and structural deformation. In this work, we demonstrate the use of PIV in extracting the full-field microstructural distribution of rods within the enamel. Further, enamel samples from a wild African lion were analyzed using high-energy synchrotron X-ray micro-tomography. Results from the PIV analysis provide sufficient full-field information to reconstruct the growth of individual rods that can potentially enable rapid analysis of complex microstructures from high resolution synchrotron datasets. Such information can serve as a template for designing damage-tolerant bioinspired structures for advanced manufacturing.

36 MATERIALS SCIENCE↗

Conceptual Advances from Werner Complexes to Metal–Organic Frameworks

Alfred Werner's work on the geometric aspects of how ligands bind to metal ions at the end of the 19th century has given rise, in the molecular realm, to organometallic, bioinorganic, and cluster chemistries. By stitching together organic and inorganic units into crystalline porous metal-organic frameworks (MOFs), the connectivity, spatial arrangement, and geometry of those molecular complexes can now be fixed in space and become directly addressable. The fact that MOFs are porous provides additional space within which molecules can further be transformed and their chemistry controlled. Finally, an aspect not available in molecular chemistry but a direct consequence of Werner's analysis of coordination complexes is the ability to have multivariable functionality in MOFs to bring about a continuum of chemical environments, within the repeating order of the framework, from which a substrate can sample and be transformed in ways not possible in molecular complex chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimizing Sub-Sampled STEM Imaging for Beam Sensitive Materials and Dynamic Processes

The goal of this research is to quantify how sub-sampling and inpainting (broadly classified as methods in Artificial Intelligence) can be used to obtain the highest resolution images under any experimental conditions, and to use this to reproducibly control dynamic in-situ processes in gases and liquids on the nanoscale. As atomic diffusion under non-extreme conditions is typically in the sub-ms time domain, the ability to use this sub-sampling approach to reduce the effect of the electron beam and to speed-up the imaging process represents the optimum combination of spatial and temporal resolution achievable in a conventional microscope. This LDRD funding demonstrated the feasibility of imaging dynamics in complex energy systems using this methodology by establishing the optimum experimental sampling conditions (optimizing the number of pixels, speed, contrast and resolution) for each experiment. For in-situ liquid cell experiments this analysis shows that simply by distributing the same dose and dose rate maximally in space and time, the kinetics for radiolysis products can be modified significantly. The final stage of this work, i.e. the experimental demonstration of its use for nucleation and growth, was severely curtailed by issues with COVID19. However, all the experiments are designed and currently underway, with the goal to complete the final demonstration and publication as soon as safety concerns for laboratory access are met.

36 MATERIALS SCIENCE↗

Protein Conformational States—A First Principles Bayesian Method

Automated identification of protein conformational states from simulation of an ensemble of structures is a hard problem because it requires teaching a computer to recognize shapes. We adapt the naïve Bayes classifier from the machine learning community for use on atom-to-atom pairwise contacts. The result is an unsupervised learning algorithm that samples a ‘distribution’ over potential classification schemes. We apply the classifier to a series of test structures and one real protein, showing that it identifies the conformational transition with >95% accuracy in most cases. A nontrivial feature of our adaptation is a new connection to information entropy that allows us to vary the level of structural detail without spoiling the categorization. This is confirmed by comparing results as the number of atoms and time-samples are varied over 1.5 orders of magnitude. Further, the method’s derivation from Bayesian analysis on the set of inter-atomic contacts makes it easy to understand and extend to more complex cases.

97 MATHEMATICS AND COMPUTING↗

A Bayesian approach to calibrating hydrogen flame kinetics using many experiments and parameters

First-principles Markov Chain Monte Carlo sampling is used to investigate uncertainty quantification and uncertainty propagation in parameters describing hydrogen kinetics. Specifically, we sample the posterior distribution for thirty-one parameters focusing on the H 2 O 2 and HO 2 reactions resulting from conditioning on ninety-one experiments. Established literature values are used for the remaining parameters in the mechanism as well as other thermodynamic and transport data needed to specify fluid properties. The samples are computed using an affine invariant sampler starting with broad, noninformative priors. Autocorrelation analysis shows that O(1M) samples are sufficient to obtain a reasonable sampling of the posterior. The resulting distribution identifies strong positive and negative correlations and several non-Gaussian characteristics. Using samples drawn from the posterior, we investigate the impact of parameter uncertainty on the prediction of two more complex flames: a 2D premixed flame kernel and the ignition of a hydrogen jet issuing into a heated chamber. The former represents a combustion regime similar to the target experiments used to calibrate the mechanism and the latter represents a different combustion regime. For the premixed flame, the net amount of product after a given time interval has a standard deviation of less than 2% whereas the standard deviation of the ignition time for the jet is more than 10%. The samples used for these studies are posted online. These results indicate the degree to which parameters consistent with the target experiments constrain predicted behavior in different combustion regimes. Finally, this process provides a framework for both identifying reactions for further study from candidate mechanisms as well as combining uncertainty quantification and propagation to, ultimately, tie uncertainty in laboratory flame experiments to uncertainty in end-use numerical predictions of more complicated scenarios.

97 MATHEMATICS AND COMPUTING↗

Method for Hot Real-Time Sampling of Pyrolysis Vapors

Biomass Pyrolysis has been an increasing topic of research, in particular as a replacement for crude oil. This process utilizes moderate temperatures to thermally deconstruct the biomass which is then condensed into a mixture of liquid oxygenates to be used as fuel precursors. Pyrolysis oils contain more than 400 compounds, up to 60 percent of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during the condensation and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition before condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors, many challenges must be overcome. Sampling must occur within a narrow range of temperatures to reduce product composition changes from overheating or partial condensation or plugging of lines from condensed products. Residence times must be kept at a minimum to reduce further reaction chemistries. Pyrolysis vapors also form aerosols that are carried far downstream and can pass through filters resulting in build-up in downstream locations. The co-produced bio-char and ash from the pyrolysis process can lead to plugging of the sample lines, and must be filtered out at temperature, even with the use of cyclonic separators. A practical approach for considerations and sampling system design, as well as lessons learned are integrated into the hot analytical sampling system of the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU) to provide industrially relevant demonstrations of thermochemical transformations of biomass feedstocks at the pilot scale.

09 BIOMASS FUELS↗

Metal (hydr)oxide surface precipitates and their effects on potassium sorption

Surface precipitation has been shown to occur on rapid time scales in clay and metal oxide mineral systems. The formation of surface precipitates is hypothesized to present new potential sorption sites for potassium (K), where K can become incorporated into newly formed interlayer spaces (e.g., between tetrahedral–octahedral–tetrahedral stacked sheets). The objective of this study is to determine the effects of newly formed mineral surface precipitates on K sorption. Potassium adsorption experiments were conducted by utilizing Al 2 O 3 and SiO 2 sorbents in the presence of various cations (magnesium, zinc, and nickel) that helped to catalyze the formation of surface precipitates. Dissolved concentrations of elements were monitored via inductively coupled plasma optical emission spectrometry (ICP-OES). Solids were characterized via X-ray diffraction (XRD), and K surface complexation was analyzed via X-ray absorption near edge structure (XANES) spectroscopy. X-ray diffraction analysis indicated bayerite, layered double hydroxides (LDH), and silicated LDH were formed as reaction products, thus creating new surface sites for potential K adsorption. The presence of Si increased K adsorption perhaps due to its role in the formation of LDH surface precipitates. When the differences between observed and theoretical surface area normalized K sorption densities were averaged, a 31% increase in K adsorption was observed in the presence of Si. XANES analysis indicated that the binding mechanism of K to Si is different than that of K to Al, perhaps due to the presence of inner-sphere complexation of K to Al-oxide. Samples reacted for one month versus one week yielded more intense XANES post-edge peaks which indicated that the K sorption complex changes over time. Altogether, our findings provide novel insights into the mechanisms of K fixation in soil and has high implication in providing improved K fertilizer recommendation to growers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Bayesian approach to time-domain photonic Doppler velocimetry analysis

Photonic Doppler velocimetry (PDV) is an established technique for measuring the velocities of fast-moving surfaces in high-energy-density experiments. In the standard approach to PDV analysis, the short-time Fourier transform (STFT) is used to generate a spectrogram from which the velocity history of the target is inferred. The user chooses the form, duration, and separation of the window function. Here, in this study, we present a Bayesian approach to infer the velocity directly from the PDV oscilloscope trace, without using the spectrogram for analysis. This is clearly a difficult inference problem due to the highly periodic nature of the data, but we find that with carefully chosen prior distributions for the model parameters, we can accurately recover the injected velocity from synthetic data. We validate this method using PDV data collected at the STAR two-stage light gas gun at Sandia National Laboratories, recovering shock-front velocities in quartz that are consistent with those inferred using the STFT-based approach and are interpolated across regions of low signal-to-noise data. Although this method does not rely on the same user choices as the STFT, we caution that it can be prone to misspecification if the chosen model is not sufficient to capture the velocity behavior. Analysis using posterior predictive checks can be used to establish whether a better model is required, although more complex models come with additional computational cost, often taking more than several hours to converge when sampling the Bayesian posterior. We, therefore, recommend it be viewed as a complementary method to that of the STFT-based approach.

Allison, James R. [First Light Fusion Ltd., Yarnto↗

Development of Direct Injection/Ionization Mass Spectrometry Methods for Whole Molecule Characterization

The objective of this work is to adapt ambient ionization mass spectrometry (AMS) techniques for the rapid analysis of intact uranium complexes, stable strontium, cerium, and explosive compounds. The methods used were “soft ionization” techniques, which facilitate the detection of whole molecule complexes. The soft ionization mass spectrometry (MS) techniques that were investigated include paper spray ionization (PSI), matrix-assisted ionization (MAI), electrospray ionization (ESI) and direct analysis in real time (DART). For the first time, PSI-MS methods were successfully developed for whole molecule uranium-containing analytes (uranyl acetate, uranyl nitrate, and uranyl-tributylphosphate complexes). This was also the first demonstration of uranium complex detection and characterization and one of the few examples of inorganic analysis using MAI techniques. Proof of concept experiments also putatively identified matrix-derived ions and ion complexes that have not previously been described in the literature. Additionally, PSI-MS on cotton swipe samples doped with a multi-element standard containing μg levels of U, Bi, Pb, Cd, Fe, and Zn were directly analyzed without purification, representing a major improvement over existing methods. Both PSI and MAI methods demonstrated limits of detection (LODs) in the 10 - 100’s ng for various uranyl species within a range of 10’s ppm - 100’s ppb, dependent on analytical method and analyte species. AMS methods were also developed for other inorganics, including Ce and Sr, and organic explosive residues to address specific challenges in environmental monitoring and forensics. Further refinement and qualification of the AMS techniques developed within this effort would lead to significant cost reduction and timeliness by facilitating the triage and queueing of samples for subsequent more sensitive and time-consuming analyses.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Improved Platform for the Benchtop Study of Complex Radiological Environments that Affect Fallout Formation: DHS Feasbility Study (Final Report)

Fallout analysis is a crucial field of study as it provides insight into the structural interactions that occur between radiological components and their surroundings following a nuclear event. Due to the complexity of actual fallout samples, setups like the plasma flow reactor (PFR) at LLNL have been developed to synthesize fallout in a controlled environment. While the PFR allows for control of parameters such as initial temperature, cooling rate, and concentration of radiological species, controlling the concentration of water has remained a challenge as samples are introduced into the setup via aqueous solution. To that end, our goal with this project was to develop methodologies to (1) monitor and (2) control the presence of water in the PFR. We found that a commercially available FTIR and MCT detector was sufficient to monitor the presence of both condensed and vapor-phase water, while a desolvating nebulizer could be used to control the amount of water injected into the system. In total, the results of this feasibility study have expanded the ability of the flow reactor to investigate key sensitivities that influence fallout formation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Portable and Cost-Effective Device for Reliable Detection of Counterfeit and Non-compliant Refrigerants in Diverse Applications

Counterfeit refrigerants pose significant challenges to safety, system reliability, and operational effectiveness due to their harmful contaminants or incompatible chemical compositions. Utilizing these noncompliant products can lead to reduced efficiency, equipment failures, and expensive repairs. Additionally, heightened demand for alternative refrigerants during the industry's transition has created supply gaps, enabling counterfeit products to proliferate. Accurate detection and analysis tools are therefore essential to verify refrigerant authenticity and ensure system integrity in diverse applications. This paper presents the development of a portable device designed for reliable identification and detailed analysis of refrigerant composition. By integrating precision gas sampling, controlled pressure regulation, and automated sensor technology, the device not only detects deviations from standard refrigerant properties but also provides a comprehensive composition breakdown. Pre-calibrated sensors measure the refrigerant gas to identify specific concentrations and contaminants, with an intuitive LED-based indicator system ensuring quick interpretation of results. The user-friendly interface enables operators to select refrigerant types for targeted testing, further enhancing accuracy and usability for field technicians. Comprehensive testing was conducted on mildly flammable A2L refrigerants, showcasing the device’s robustness and adaptability in analyzing composition and detecting discrepancies. The device demonstrated consistent accuracy across a range of refrigerant samples, affirming its reliability in diverse operational environments. Its design minimizes contamination risks during sampling and provides detailed composition results within 90 seconds, ensuring efficient and precise analysis. With a projected price point under $150, the proposed solution delivers affordability alongside its lightweight portability and straightforward operation. Unlike complex and costly alternatives, such as gas chromatography systems, this device provides an accessible option for technicians, customs personnel, and industry operators in need of quick and effective refrigerant verification. Compatible with both current formulations and emerging refrigerant technologies, the device addresses critical counterfeit detection needs across a range of applications. By delivering accurate composition analysis and counterfeit identification, this innovation enhances system performance, safety, and operational reliability in crucial industries.

Cheekatamarla, Praveen [ORNL] (ORCID:0000000248827↗

PISCES two-detector covariance matrix fit for the NOvA Experiment

NOvA is a long-baseline neutrino oscillation experiment with two functionally identical detectors: a Near Detector (ND) at Fermilab, placed 1 km from the neutrino source, and a Far Detector (FD) located 810 km away from the ND in Minnesota. NOvA's primary physics goals are the precise measurements of neutrino oscillation parameters $\theta_{23}$ and $\Delta m^2_{32}$ , determine the neutrino mass ordering, and constrain the value of $\delta_{CP}$, via the study of muon neutrino to electron neutrino oscillation. In the standard NOvA three-flavor analysis, oscillation parameters are extracted using an extrapolation technique in which the ND data constrain the FD prediction through a ratio method. While this allows for systematic uncertainties sharing the same effects in both detectors to cancel, it remains an FD-only fit and does not fully leverage the constraining power of the high-statistics ND. This analysis proposes a simultaneous ND+FD fit using the PISCES method. PISCES (Parameter Inference with Systematic Covariance and Exact Statistics) is a framework designed to support complex configurations such as a joint ND+FD fit. This allows PISCES to take full advantage of the ND data to directly constrain systematic uncertainties across all samples. In PISCES, systematic uncertainties are encoded in a fractional covariance matrix, and statistical uncertainties are handled with a Poisson likelihood, making the approach well suited for low-statistics samples. For interpretability, we further use a Newton–Raphson + PCA method to recover per-systematic pulls from the covariance formulation. This poster presents the full PISCES joint ND+FD fit for the NOvA three-flavor analysis, describes its implementation and evaluates its performance through extensive robustness tests and fake data studies. It also provides a comparison between the PISCES joint ND+FD results and the standard NOvA extrapolation method.

Rajaoalisoa, Miriama [Cincinnati U.] (ORCID:000000↗

Coupling Ambient Pressure X-ray Photoelectron Spectroscopy with Density Functional Theory to Study Complex Surface Chemistry and Catalysis

Ambient pressure X-ray photoelectron spectroscopy (APXPS) experiments narrow the pressure and materials gaps between UHV surface science experiments and applications. Upon closing these gaps, ambiguity can enter the analysis of the spectra due to overlapping peaks from different elements or functional groups of both the sample and the gas phase. Additionally, reaction intermediates and mechanisms are often inaccessible from interpretation of APXPS data alone. In many cases, these issues can be overcome with the aid of density functional theory (DFT) calculations. Here, we outline our process of combining DFT calculations with APXPS experiments by describing our recent investigations of the adsorption of dimethyl methylphosphonate (DMMP) on MoO3 and CuO. We begin by showing the importance of the characterization of the isolated gas phase molecule before adsorption onto a surface. In particular, strong agreement between theory and experiment helps identify plausible decomposition pathways of the isolated molecule and provides a baseline for interpretation of spectra showing evidence of DMMP interaction with surfaces. The intact adsorption of DMMP on MoO3 offers an illustration of how moving beyond pristine single crystalline surfaces in calculations can enable better modeling of experimental trends that result from surface defects. Studies of DMMP adsorption on CuO exemplify the powerful synergy of APXPS combined with DFT for elucidation of complex reaction mechanisms on surfaces.

Chemistry↗

Revealing the complex chemistry of grain boundaries in K-doped BaFe 2 As 2 with atom probe tomography

Iron-based superconductors have attractive properties for high-field applications, but there is a lack of understanding of the effect of grain boundary chemistry on the in-field performance. The near atomic-scale resolution, ppm sensitivity and 3D analysis offered by atom probe tomography make it a powerful tool to investigate the nanoscale structure and chemistry of these defects in fine-grained K-doped BaFe 2 As 2 samples. A computational method to systematically extract and compare the Gibbsian interfacial excess of chemical species across grain boundaries has been explored in this work. The robustness of the method has been tested by evaluating the effects of selected variables on simulated APT datasets. The accuracy and precision of the calculated Gibbsian interfacial excess were found to be stable over a range of analysis conditions: varying grain boundary widths and detection efficiencies, spatial precisions below 1.5 nm, and bin widths between 1.2 and 1.6 nm. For the K-doped BaFe 2 As 2 samples studied, segregation of As, Ba, K and impurities of O, Na, and Sb were found at grain boundaries. The Gibbsian excess values were found to vary widely between different boundaries, showing the complexity of the grain boundary chemistry in this material. Possible links between the observed critical current density (Jc) of these samples and their nano- and micro-structure have also been investigated and discussed.

36 MATERIALS SCIENCE↗

Validity of Machine Learning in the Quantitative Analysis of Complex Scanning Near-Field Optical Microscopy Signals Using Simulated Data

Scattering-type scanning near-field optical microscope (s-SNOM) is a modern technique for subdiffractional optical imaging and spectroscopy. Over the past two decades, tremendous efforts have been devoted to modeling complex tip-sample interactions in s-SNOM, aimed at understanding the electrodynamics of materials at the nanoscale. However, due to complexities in analytical methods and the limited computation power for fully numerical simulations, compromises must be made to facilitate the modeling of tip-sample interaction, such as using quasistatic approximation or unrealistic tip geometries. Here, we apply a variety of widely utilized machine-learning methods, including k nearest neighbor and feedforward neural network etc. to study the phase-resolved spectroscopic near-field response. With only a small set of training data, which is simulated using the finite-dipole model, we demonstrate that the relation between the experimental near-field signal and sample optical constant can be one to one mapped without the need for tip modeling: for a given material with a moderate dielectric function, its complex near-field spectrum can be accurately determined within the mid-IR spectral range, and vice versa. Our preliminary study sets the stage for future exploration using real experimental data. Our method is beneficial for processing the increasing amount of data accumulated across many research groups and especially useful for user facilities such as synchrotron-based national laboratories where a large amount of data is generated on a daily basis.

36 MATERIALS SCIENCE↗