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EXD HME MicroCT Data Acquisition, Processing and Data Request Overview

This document is a short summary of the steps required for MicroCT evaluation of a specimen. This includes data acquisition through image analysis, for the EXD HME program. Expected outputs for each stage are provided. Data shall be shipped to LLNL as described herein.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Detection of Inorganic Salt-Based Homemade Explosives (HME) by Atmospheric Flow Tube–Mass Spectrometry

Using a commercial mass spectrometer interfaced with an atmospheric flow tube (AFT) allowed detection of a variety of inorganic compounds used as oxidizers in homemade explosives at picogram levels. The AFT provides reaction times between 3-5 seconds with flows of 6 L/min, enabling detection levels, after thermal desorption, similar to those previously demonstrated for RDX vapors in the low parts-per-quadrillion range. The thermal desorption of chlorate and perchlorate salts resulted in the production of the corresponding anions which have higher electron affinities than the nitrate reactant ions. A dielectric barrier discharge, used as the ionization source, produced the nitrate reactant ions. In some instances, the molecular salt formed adducts with the nitrate, chlorate, and/or perchlorate anions, giving insight into the original identity of the salt cation. Urea nitrate, guanidine nitrate, and potassium nitrate were also detected as adducts with the nitrate reactant ion. Direct room-temperature vapor detection of urea nitrate and hydrogen peroxide, which have relatively high vapor pressures compared to the other salts in this study, is also demonstrated. Room-temperature vapor detection of chlorate and perchlorate salts is possible by the addition of a dilute acid which converts the salt into a more volatile acidic form. A discussion of the instrumentation, methods used, and the ionization chemistry is provided.

chlorate, perchlorate, nitrate, detection, hydroge↗

HME MicroCT Data Acquisition, Processing and Data Request Overview

This document is a short summary of the steps required for MicroCT evaluation of a specimen. This includes data acquisition through image analysis, for the Explosives Threat Assessment (ETA) program. Expected outputs for each stage are outlined. Information and data shall be shipped to LLNL as described herein.

42 ENGINEERING↗

Toddler home math environment: Triangulating multi-method assessments in a U.S. Sample

Introduction Current research has documented the home math environment (HME) of preschoolers and kindergarteners. Very few studies, however, have explored the number and spatial activities in which parents engage with children during their toddler years. Methods This study examined the HME of 157 toddlers using several methodologies, including surveys, time diaries, and observations of math talk. Further, it examined correlations within and across data sources to identify areas of convergence and triangulation, and correlated HME measures with measures of toddlers’ number and spatial skills. Results Findings showed that, in general, uses of different types of math activities, including both number and spatial, were intercorrelated within method. Across methods, there was high intercorrelation between the frequency of math activities reported on parent surveys and the diversity of types of math activities endorsed in time diary interviews. Parent math talk gleaned from semi-structured interviews functioned as a separate aspect of the HME; different types of math talk shared few intercorrelations with engagement in math activities as reported in either surveys or time diaries. Finally, several HME measures positively correlated with toddlers’ math skills. Discussion Given extant research demonstrating that both math activities and math talk predict children’s math skills, our results stress the need for multimethod studies that differentiate among these HME opportunities.

Miller, Portia↗

Magnetic photocurrents in multifold Weyl fermions

Here, we examine the magneto-optical response of chiral multifold fermions. Specifically, we show that they are ideal candidates for observing the helical magnetic effect (HME) previously predicted for simple Weyl fermions. Unlike Weyl fermions, the HME is present in multifold fermions even in the simplest case where the low-energy dispersion is linear and spherically symmetric. In this ideal case, we derive an analytical expression for the HME and find it is proportional to the circular photogalvanic effect; for realistic parameters and accounting for the geometry of the setup, the HME photocurrent could be roughly the same order of magnitude as the circular photogalvanic effect observed in multifold fermions. Additional nonlinear and symmetry-breaking terms will ruin the quantization but not hurt the observation of the HME.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Preparation of cupric sulfate-based self-emulsifiable nanocomposites and their application to the photothermal therapy of colon adenocarcinoma

Highlights: • CuSO{sub 4} nanocomposites (NCs) were fabricated by hot-melt extrusion method. • Dispersion of CuSO{sub 4} in NCs was identified by several solid-state studies. • CuSO{sub 4} NCs exhibited improved photothermal therapeutic efficacies in Caco-2 cells. Nanocomposites (NCs) of cupric sulfate monohydrate (CuSO{sub 4}) were fabricated by hot-melt extrusion (HME) system equipped with twin screws. Micron-sized bulk powder of CuSO{sub 4} was dispersed in the mixture of surfactants (Span 80 and Tween 80) and hydrophilic polymer (polyethylene glycol (PEG) 6000) by HME process. Reduction of surface tension by surfactants and homogeneous dispersion in hydrophilic polymer along with HME technique were introduced to prepare CuSO{sub 4} NCs. Dispersion of CuSO{sub 4} NCs exhibited approximately 204 nm hydrodynamic size, unimodal size distribution, and positive zeta potential values. Encapsulation of CuSO{sub 4} in CuSO{sub 4} NCs and the physicochemical interactions between CuSO{sub 4} and pharmaceutical excipients were investigated by solid-state studies. Of note, CuSO{sub 4} NCs group exhibited higher antiproliferation efficacies, compared with bulk CuSO{sub 4}, in Caco-2 (human adenocarcinoma) cells at 75 and 100 μg/mL CuSO{sub 4} concentrations (p < 0.05). Also, near-infrared laser irradiation to CuSO{sub 4} NCs group elevated the antiproliferation efficacies, compared with non-irradiation group, in Caco-2 cells. After intravenous injection in mice, CuSO{sub 4} NCs did not show severe in vivo toxicities. Developed CuSO{sub 4} NCs can be one of promising candidates of photothermal therapeutic agents for colon cancers.

60 APPLIED LIFE SCIENCES↗

Trimethyltriazacyclohexane coordination chemistry of simple rare-earth metal salts

Reactions of 1,3,5-trimethyl-triazacyclohexane (Me 3 tach) with common rare-earth metal iodide, chloride, and triflate salts were examined to determine the capacity of this inexpensive chelate to provide alternative precursors for THF-free reactions. The reaction of LaI 3 (THF) 4 and CeI 3 (THF) 4 with 1,3,5-trimethyl-triazacyclohexane in THF generated toluene soluble (Me 3 tach) 2 LnI 3 , 1-Ln , in which the Ln center has a tri-capped trigonal prismatic geometry with two eclipsed Me 3 tach rings. Reaction with NdI 3 (THF) 3.5 forms the analogous 1-Nd , but a different structure with one outer sphere iodide, [(Me 3 tach) 2 NdI 2 ][I], 2-Nd , is also accessible and has a structure reminiscent of bent metallocenes. The reaction of LaCl 3 and Me 3 tach forms the less soluble (Me 3 tach) 2 LaCl 3 , which has a structure analogous to 1-Ln with eclipsed Me 3 tach rings. The mono-ring yttrium complex, (Me 3 tach)YCl 3 (THF) 2 , could be isolated from the reaction of YCl 3 with Me 3 tach. Reactions of La(OTf) 3 with Me 3 tach were sensitive to the presence of residual proton sources as exemplified by the isolation of {[(Me 3 tach)La(μ-OH)(μ-OTf)] 2 (μ-OTf) 2 } 2 , 5-La , and [HMe 3 tach][(Me 3 tach) 2 La-(OTf) 4 ], 6-La . SmI 2 reacts with Me 3 tach to produce the Sm( II ) complex, (Me 3 tach) 2 SmI 2 (THF), 7-Sm , but 2-Sm can also form in this reaction. Complexes of the larger 1,4,7-trimethyltriazacyclononane (Me 3 tacn) ligand, namely (Me 3 tacn)LaI 3 (THF), (Me 3 tacn)YCl 3 , and (Me 3 tacn)SmI 2 (THF) were synthesized for comparison. Several examples of the protonated ligands with simple counteranions, [HMe 3 tach][X] (X = Cl, Br, I) and [HMe 3 tacn][OTf], were identified in the course of these studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchical mixture of experts and diagnostic modeling approach to reduce hydrologic model structural uncertainty

In most water resources applications, a single model structure might be inadequate to capture the dynamic multi-scale interactions among different hydrological processes. Calibrating single models for dynamic catchments, where multiple dominant processes exist, can result in displacement of errors from structure to parameters, which in turn leads to over-correction and biased predictions. An alternative to a single model structure is to develop local expert structures that are effective in representing the dominant components of the hydrologic process and adaptively integrate them based on an indicator variable. In this study, the Hierarchical Mixture of Experts (HME) framework is applied to integrate expert model structures representing the different components of the hydrologic process. Various signature diagnostic analyses are used to assess the presence of multiple dominant processes and the adequacy of a single model, as well as to identify the structures of the expert models. The approaches are applied for two distinct catchments, the Guadalupe River (Texas) and the French Broad River (North Carolina) from the Model Parameter Estimation Experiment (MOPEX), using different structures of the HBV model. Furthermore, the results show that the HME approach has a better performance over the single model for the Guadalupe catchment, where multiple dominant processes are witnessed through diagnostic measures. Whereas, the diagnostics and aggregated performance measures prove that French Broad has a homogeneous catchment response, making the single model adequate to capture the response.

54 ENVIRONMENTAL SCIENCES↗

Ion Mobility Spectrometry - High Resolution LTQ-Orbitrap Mass Spectrometry for Analysis of Homemade Explosives

The detailed chemical characterization of homemade explosives (HMEs) and other chemicals that can mimic or mask the presence of explosives is important for understanding and improving the performance of commercial instrumentation used for explosive detection. To that end, an atmospheric-pressure drift tube ion mobility spectrometry (IMS) instrument has been successfully coupled to a commercial tandem mass spectrometry (MS) system. The tandem MS system is comprised of a linear ion trap and a high resolution Orbitrap analyzer. This IMS-MS combination allows extensive characterization of threat chemical compounds, including HMEs, and complex real-world background chemicals that can interfere with detection. Here, the composition of ion species originating from a specific HME, erythritol tetranitrate, has been elucidated using accurate mass measurements, isotopic ratios, and tandem MS. Gated IMS-MS and high-resolution MS have been used to identify minor impurities that can be indicative of the HME source and/or synthesis route. Comparison between data obtained on the IMS/MS system and on commercial stand-alone IMS instruments used as explosive trace detectors (ETDs) has also been performed. Such analysis allows better signature assignments of threat compounds, modified detection algorithms, and improved overall ETD performance. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Explosive Formulation Code Naming SOP

The purpose of this SOP is to provide a procedure for giving individual HME formulations code names. A code name for an individual HME formulation consists of an explosive family code, given by the classified code dictionary, followed by a dash, -, and a number.

42 ENGINEERING↗

Degradable Biocomposite Thermoplastic Polyurethanes

In this project, the team developed tough and degradable biocomposite thermoplastic polyurethanes (TPUs) by incorporating bacterial spores into TPUs as a biofunctional living filler. The team screened various bacteria and selected the Bacillus subtilis ATCC 6633 strain as the final candidate, primarily due to its genomic availability, sporulation ability and TPU assimilation activity. The heat-shock tolerance of ATCC 6633 spores was further improved through evolutionary engineering via Adaptive Laboratory Evolution (ALE), demonstrating a 17.7-fold enhanced germination efficiency post heat-shock treatment compared to the wild-type strain (WT). The team fabricated biocomposite TPUs by incorporating lyophilized powder of heat-shock tolerized (HST) spores during the hot melt extrusion (HME) of TPU at 135 °C. The baseline TPU used in this project is a commercially available soft-grade TPU (BCF45) manufactured by BASF. Colony forming unit (CFU) assays quantified that WT and HST spores in the TPU matrix retained approximately 20% and 100% survivability, respectively, after HME. Tensile testing demonstrated that the spores behaved as a polymer-reinforcing filler, positively affecting the overall tensile properties of the biocomposite TPU. For example, biocomposite TPU with WT and HST spores (BC TPU WT and BC TPU HST , respectively) exhibited up to 25% and 37% improved toughness, respectively, compared to TPU without spores. BC TPU HST showed remarkably improved disintegration in autoclaved compost (92% mass loss in 5 months), which simulated a microbially poor environment for TPU degradation. When compared to TPU without spores (44% mass loss in 5 months) the acceleration of degradation is marked. Respirometry confirmed that 72% of BC TPU HST was biomineralized into CO2 within 6 months, indicating that spores in the biocomposite TPU were germinated by utilizing nutrients in the autoclaved compost, facilitating TPU degradation at the end of the material's life. The team demonstrated the scale-up of biocomposite TPU fabrication using continuous extrusion and injection molding techniques. Processing conditions optimized in a lab-scale microcompounder were successfully transferred to a continuous extruder with a 30-fold increased throughput. Biocomposite TPUs prepared using these industry-relevant processes showed comparable toughness improvements to samples prepared in the lab-scale extruder. Excitingly, following compounding in the pilot-extruder the composite material could be injection molded, while retaining high spore viability and similar toughness improvements. The team also found that spores in biocomposite TPU served as antioxidants, preventing toughness decay during the recycled extrusion of BC TPU HST . Long-term storage tests over one year showed that the addition of spores had no negative effect on the longevity of the TPU. Furthermore, the team demonstrated the fabrication of spore-bearing biocomposite polymers with other polyesters such as PBAT, PLA, and PCL. We obtained promising preliminary data that showed overall toughness improvements for all polymers with spore addition. Finally, life cycle assessment (LCA) and techno-economic analysis (TEA) were carried out, which indicated minimal additional cost of fabrication. Overall, a tough and degradable biocomposite thermoplastic was successfully developed through this project, with all tasks completed successfully, achieving >100% of the objectives.

36 MATERIALS SCIENCE↗

Hierarchical Mixture of Experts for Advanced Air Mobility Flight Phase Classification

Advanced Air Mobility (AAM) and Urban Air Mobility (UAM) operations will have numerous vehicles and aircraft flying in the airspace, which poses safety and security concerns. Commercial airlines utilize Air Traffic Management (ATM) and Air Traffic Control (ATC) for real-time monitoring, surveillance, traffic coordination, and rerouting to maintain safe and efficient flight patterns. Transferring ATM and ATC architectures to AAM/UAM will be challenging to implement since AAM/UAM aircraft fly at lower altitudes, have more static and dynamic obstacles, operate in highly dense environments, and have several more aircraft to monitor for a given volume of the national airspace (NAS). Aircraft typically have the following flight phases: takeoff, climb, cruise, descent, and landing. Classifying these flight phases provides insight into ensuring safe operations, providing situational awareness of the NAS, and monitoring flights in emergencies. Automatic flight phase classification will enhance the efficiencies of ATM/ATC-like architectures for AAM/UAM, especially since numerous aircraft will be flying in highly dense urban environments. Typical flight phase classification methods are all-or-nothing, which will not capture or accurately classify the transitions between flight phases. Utilizing hierarchical mixture of experts (HME) provides a flight phase classification solution that includes transitions between the flight phases by assigning weights based on ground-based distributed sensor readings from cameras and radar. Adding the transitions between flight phases increases the fidelity of flight phase classification and provides deeper insight into flight phase classification by leveraging distributed sensing concepts. Simulation results and post-processed flight test results demonstrate the utility of HME for automatic and robust flight phase classification for real-time AAM operations.

distributed sensing↗

Software For Depiction Of Three-Dimensional Objects

HME (Hierarchical Modeling Environment) is three-dimensional computer-graphics software system designed to give user complete access to total hierarchical mathematical model. Enables user to build, manipulate, and display hierarchical three-dimensional objects dynamically. Also includes created polygons in hierarchy. Establishes and edits proper coordination of eye points, sources of light, and connectivity of model necessary for accurate depiction of model. Written in C language.

Taylor, Frank↗

A Reusable Design for Precision Lunar Landing Systems

The top-level architecture to accomplish NASA's Vision for Space Exploration is to use Lunar missions and systems not just as an end in themselves, but also as testbeds for the more ambitious goals of Human Mars Exploration (HME). This approach means that Lunar missions and systems are most likely going to be targeted for (Lunar) polar missions, and also for long-duration (months) surface stays. This overacting theme creates basic top-level requirements for any next-generation lander system: 1) Long duration stays: a) Multiple landers in close proximity; b) Pinpoint landings for "surface rendezvous"; c) Autonomous landing of pre-positioned assets; and d) Autonomous Hazard Detection and Avoidance. 2) Polar and deep-crater landings (dark); 3) Common/extensible systems for Moon and Mars, crew and cargo. These requirements pose challenging technology and capability needs. Compare and contrast: 4) Apollo: a) 1 km landing accuracy; b) Lunar near-side (well imaged and direct-to-Earth com. possible); c) Lunar equatorial (landing trajectories offer best navigation support from Earth); d) Limited lighting conditions; e) Significant ground-in-the-loop operations; 5) Lunar Access: a) 10-100m landing precision; b) "Anywhere" access includes polar (potentially poor nav. support from Earth) and far side (poor gravity and imaging; no direct-to-Earth com); c) "Anytime" access includes any lighting condition (including dark); d) Full autonomous landing capability; e) Extensible design for tele-operation or operator-in-the-loop; and f) Minimal ground support to reduce operations costs. The Lunar Access program objectives, therefore, are to: a) Develop a baseline Lunar Precision Landing System (PLS) design to enable pinpoint "anywhere, anytime" landings; b) landing precision 10m-100m; c) Any LAT, LON; and d) Any lighting condition; This paper will characterize basic features of the next generation Lunar landing system, including trajectory types, sensor suite options and a reference system architecture.

Fuhrman, Linda↗

Hierarchical Mixture of Experts for Advanced Air Mobility Flight Phase Classification

Advanced Air Mobility (AAM) and Urban Air Mobility (UAM) operations will have numerous vehicles and aircraft flying in the airspace, which poses safety and security concerns. Commercial airlines utilize Air Traffic Management (ATM) and Air Traffic Control (ATC) for real-time monitoring, surveillance, traffic coordination, and rerouting to maintain safe and efficient flight patterns. Transferring ATM and ATC architectures to AAM/UAM will be difficult to implement since AAM/UAM aircraft fly at lower altitudes, have more static and dynamic obstacles, operate in highly dense environments, and have several more aircraft to monitor for a given volume of the national airspace (NAS). Automatic flight phase classification will enhance efficiencies of ATM/ATC-like architectures for AAM/UAM. Classifying the main flight phases (takeoff, climb, cruise, descent, and landing) provides insight to ensure safe operations, provide situational awareness of the NAS, and monitor flights in case there are any emergencies. Typical flight phase classification methods are all-or-nothing, which will not capture or accurately classify the transitions between flight phases. Utilizing hierarchical mixture of experts (HME) provides a flight phase classification solution that includes transitions between the flight phases by assigning weights based on ground-based distributed sensor readings from cameras and radar. Adding the transitions between flight phases increases the fidelity of flight phase classification and provides deeper insight for flight phase classification by leveraging distributed sensing concepts.

distributed sensing↗

Integrated Data Collection Analysis (IDCA) Program - Statistical Analysis of RDX Standard Data Sets

The Integrated Data Collection Analysis (IDCA) program is conducting a Proficiency Test for Small- Scale Safety and Thermal (SSST) testing of homemade explosives (HMEs). Described here are statistical analyses of the results for impact, friction, electrostatic discharge, and differential scanning calorimetry analysis of the RDX Type II Class 5 standard. The material was tested as a well-characterized standard several times during the proficiency study to assess differences among participants and the range of results that may arise for well-behaved explosive materials. The analyses show that there are detectable differences among the results from IDCA participants. While these differences are statistically significant, most of them can be disregarded for comparison purposes to assess potential variability when laboratories attempt to measure identical samples using methods assumed to be nominally the same. The results presented in this report include the average sensitivity results for the IDCA participants and the ranges of values obtained. The ranges represent variation about the mean values of the tests of between 26% and 42%. The magnitude of this variation is attributed to differences in operator, method, and environment as well as the use of different instruments that are also of varying age. The results appear to be a good representation of the broader safety testing community based on the range of methods, instruments, and environments included in the IDCA Proficiency Test.

round-robin test↗