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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.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Final Report on Aerosol Pretreatment Technology Performance and Benchmarking

Solvent-based post-combustion CO 2 capture (PCC) technology remains one of the leading methods to combat global CO 2 emissions produced from large-scale coal-fired power production. Advanced solventbased PCC technology has made significant improvements in design and performance that reduce capital and operating costs to enable its commercial use. Key to low cost, manageable logistics, and environmentally safe operation of solvent-based PCC technology are minimal solvent losses from the process through the treated gas stream exiting PCC plant absorbers. High flue gas aerosol particle concentrations (>10 5 particles/cm 3 ) for particles in the range of 70-200 nm have been shown to cause significant amine solvent losses for solvent-based PCC processes through several mechanisms including absorption of solvent and water into growing aerosol particles. Flue gas aerosol pretreatment technology is the only realistic and economically attractive method to reduce very high aerosol particle concentrations (>10 7 particles/cm 3 ) to enable solvent-based PCC for existing power plants lacking sufficient particle removal systems, such as baghouses. The overall goal of this project was to design, construct, independently test, and evaluate three flue gas aerosol pretreatment technologies identified to significantly reduce high aerosol particle concentrations (>10 7 particles/cm 3 ) in the 70-200 nm particle size range: (1) a novel, high-velocity water injection spray concept developed by RWE and tested by Linde, (2) an innovative electrostatic precipitator (ESP) device with optimized operating conditions developed by Washington University in St. Louis (WUSTL), and (3) a non-regenerative sorbent-based filter technology developed by InnoSepra for SO x and NO x removal from coal-fired power plant flue gas. Each technology has been validated with tests on 500-1000 scfm of actual coal-fired flue gas and evaluated in terms of particle removal efficiency (%), cost competitiveness, and environmental impact. Aerosol measurements were performed upstream and downstream of each aerosol reduction unit during independent testing of each technology using advanced instrumentation and analytical methods provided by WUSTL. To perform aerosol measurements, isokinetic probes were inserted into flanged pipes attached to the flue gas piping, and a small suction pump was used to sample gas containing aerosol particles. Aerosol particle number concentrations (# particles/cm 3 ) and size distributions were then measured using a scanning mobility particle sizer (SMPS, TSI Inc.) for very fine particles (<1,000 nm) and a particle counter manufactured by GRIMM for particles larger than 1,000 nm. This report summarizes the aerosol removal performance results from pilot scale testing of each technology. Performance results have been benchmarked against pre-defined targets and other flue gas aerosol pretreatment technologies with documented performance. Linde Gas North America LLC has been the prime contractor to DOE responsible for overall project management and provided the design for the high-velocity water spray-based aerosol removal technology based on a design concept developed by the German utility company RWE.

20 FOSSIL-FUELED POWER PLANTS↗
NASA NTRSDate not supplied

Improving the Fidelity of Capability & Resource Weighting in A Probalistic Risk Assessment Model for Spaceflight

INTRODUCTION NASA’s Informing Mission Planning via Analysis of Complex Tradespaces (IMPACT) tool uses Probabilistic Risk Assessment (PRA) to provide an evidence-based, data-driven estimate of how medical system capabilities affect mission outcomes. IMPACT maps condition incidence to available resources thereby facilitating the calculation of outcome metrics that allow the estimation of mission medical risk. Conditions can be nominally categorized as either treated or untreated depending on the availability of necessary diagnostic and therapeutic capabilities. This categorization enables IMPACT to estimate the effect of various medical system configurations on mission outcomes such as crew mortality, disability, crew member down-time, return to duty/recovery, and need for evacuation. IMPACT currently employs an equal weighting, “partial credit” approach to define treatment in which each of the capabilities associated with a given condition contributes an equal amount to management of the condition. This feature enables IMPACT to report values in between “fully untreated” and “fully treated” based on the proportion of capabilities available within the model. However, as is normal in medical/clinical practice, not all individual capabilities contribute equally to medical care. For example, the ability to provide intramuscular epinephrine during an anaphylactic episode contributes more likelihood of overall management success than does the administration of oral diphenhydramine. We hypothesize that weighting the relative contribution of each capability to each specific condition will improve outcome prediction and therefore will better provide mission planners with more nuanced and accurate options when designing space medical systems. METHODS Using a five-point Fibonacci scaling sequence (1, 2, 3, 5, 8) subject matter experts from NASA’s Exploration Medical Capabilities (ExMC) element assigned relative contribution weighting values to each identified capability within IMPACT. Since the relative importance of each capability varies depending on the specific condition, the resulting “partial” weighting was completed for more than 1,600 individual weighting assignments for 666 capabilities across 121 conditions. Each assignment required three-physician concurrence based on the overall importance of the capability to the diagnosis and management of the condition being considered and the difficulty with which it could be improvised by the crew. Once complete, 100,000 IMPACT simulations were run for a 6-month Lunar mission with a 30-day surface stay to evaluate the effect of this modification of the model. RESULTS Partial weighting significantly decreased predicted task time loss (TTL), evacuation, and loss of crew life without causing significant changes to the recommended medical system design. CONCLUSIONS The paucity of real-world referent data to support long-duration space missions of this type limits the ability to judge one predictive analytics method as superior to another. However, since the proposed method significantly reduces and optimizes outcome risks—without changing the medical system design—incorporating a partial weighting methodology is likely to provide a more accurate and operationally-relevant representation of medical risk without compromising IMPACTs ability to inform overarching medical system requirements.

Steller JG↗
DOE OSTI2021

Fluorescence Microscopic Investigations of Molecular Dynamics in Self–Assembled Nanostructures

Many analytical methods employ self-assembled nanostructured materials as chemical recognition media. Molecular permeation through these materials exhibits unique selectivity owing to nanoconfinement-induced enhancement of permeant–nanostructure interactions. This Personal Account introduces our efforts to investigate the detailed dynamics of single or a small number of molecules in nanostructured materials. Here, we developed new experimental and analysis approaches built upon laser-based fluorescence microscopy to measure the detailed translational and orientational dynamics of molecules diffusing in horizontally-oriented, cylindrical nanostructures, including surfactant micelles, silica mesopores, block copolymer microdomains, and bolaamphiphile-based organic nanotubes. Our studies clarified nanoscale details on the structural/chemical heterogeneity of the nanostructures, and their impacts on molecular mass transport dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A hidden analytic structure of the Rabi model

The Rabi model describes the simplest interaction between a cavity mode with a frequency ω{sub c} and a two-level system with a resonance frequency ω{sub 0}. It is shown here that the spectrum of the Rabi model coincides with the support of the discrete Stieltjes integral measure in the orthogonality relations of recently introduced orthogonal polynomials. The exactly solvable limit of the Rabi model corresponding to Δ=ω{sub 0}/(2ω{sub c})=0, which describes a displaced harmonic oscillator, is characterized by the discrete Charlier polynomials in normalized energy ϵ, which are orthogonal on an equidistant lattice. A non-zero value of Δ leads to non-classical discrete orthogonal polynomials ϕ{sub k}(ϵ) and induces a deformation of the underlying equidistant lattice. The results provide a basis for a novel analytic method of solving the Rabi model. The number of ca. 1350 calculable energy levels per parity subspace obtained in double precision (cca 16 digits) by an elementary stepping algorithm is up to two orders of magnitude higher than is possible to obtain by Braak’s solution. Any first n eigenvalues of the Rabi model arranged in increasing order can be determined as zeros of ϕ{sub N}(ϵ) of at least the degree N=n+n{sub t}. The value of n{sub t}>0, which is slowly increasing with n, depends on the required precision. For instance, n{sub t}≃26 for n=1000 and dimensionless interaction constant κ=0.2, if double precision is required. Given that the sequence of the lth zeros x{sub nl}’s of ϕ{sub n}(ϵ)’s defines a monotonically decreasing discrete flow with increasing n, the Rabi model is indistinguishable from an algebraically solvable model in any finite precision. Although we can rigorously prove our results only for dimensionless interaction constant κ<1, numerics and exactly solvable example suggest that the main conclusions remain to be valid also for κ≥1. -- Highlights: •A significantly simplified analytic solution of the Rabi model. •The spectrum is the lattice of discrete orthogonal polynomials. •Up to 1350 levels in double precision can be obtained for a given parity. •Omission of any level can be easily detected.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

2D HSQC Chemical Shifts of Impurities from Biomass Pretreatment

Two dimensional (2D) heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) is a powerful analytical method which can be used to elucidate the structure of biomass. During processing, biomass is typically subjected to some form of chemical treatment which can be performed with a variety of compounds. The presence of these compounds, even in trace amounts, has the potential to contaminate the sample and lead to misinterpretation of the HSQC spectra. Here we report the chemical shifts of 29 compounds commonly used in biomass processing which have the potential to contaminate the biomass samples and lead to the misinterpretation of peaks associated with biomass (Populus trichocarpa ) pretreated via autohydrolysis. The identification of these chemical shifts could serve as a valuable tool in preventing errors in characterizing biomass via HSQC.

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

Formation of monomeric Sn(ii) and Sn(iv) perfluoropinacolate complexes and their characterization by 119 Sn Mössbauer and 119 Sn NMR spectroscopies

The synthesis and characterization of a series of Sn(II) and Sn(IV) complexes supported by the highly electron-withdrawing dianionic perfluoropinacolate (pinF) ligand are reported herein. Three analogs of [Sn IV (pin F ) 3 ] 2- with NEt 3 H + (1), K + (2), and {K(18C6)} + (3) counter cations and two analogs of [SnII(pinF)2]2- with K+ (4) and {K(15C5) 2 } + (5) counter cations were prepared and characterized by standard analytical methods, single-crystal X-ray diffraction, and 119 Sn Mössbauer and NMR spectroscopies. The six-coordinate SnIV(pinF) complexes display 119 Sn NMR resonances and 119 Sn Mössbauer spectra similar to SnO 2 (cassiterite). In contrast, the four-coordinate SnII(pinF) complexes, featuring a stereochemically-active lone pair, possess low 119 Sn NMR chemical shifts and relatively high quadrupolar splitting. Furthermore, the Sn(II) complexes are unreactive towards both Lewis bases (pyridine, NEt 3 ) and acids (BX 3 , Et 3 NH + ). Calculations confirm that the Sn(II) lone pair is localized within the 5s orbital and reveal that the Sn 5p x LUMO is energetically inaccessible, which effectively abates reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

In situ analysis of free radicals from the photodecomposition of hydrogen peroxide using a frequency-mixing magnetic detector

We present an analytical method for the real-time detection of free radicals from the photodecomposition (ultraviolet radiation, {lambda} = 254 nm) of hydrogen peroxide (H{sub 2}O{sub 2}) using frequency-mixing magnetic detection. We monitored the free radicals in situ without catalysts or probe molecules. Both water and H{sub 2}O{sub 2} produced frequency-mixing signals under UV radiation, but the water signal was much weaker. The root mean square amplitude of the frequency-mixing signal was found to depend on the initial H{sub 2}O{sub 2} concentration. Considering the physical properties of the reactants, the frequency-mixing signal is attributed to the generation of paramagnetic free radicals by the photodecomposition of H{sub 2}O{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Two-Dimensional Electronic–Vibrational Spectroscopy of Coupled Molecular Complexes: A Near-Analytical Approach

This work presents theoretical calculations of the two-dimensional electronic–vibrational (2DEV) spectrum of a vibronically coupled molecular dimer using a near-analytical method. In strongly coupled dimers, where the IR mode is resonant with the electronic energy gap between the excitons, multiple infrared transitions become allowed that are forbidden in weakly coupled systems that have a nonresonant IR mode. This formalism enables the coherences and population contributions to be explored separately and allows efficient calculation of relaxation rates between the vibronic states. At short times, we find strong contributions of vibronic coherences to the 2DEV spectra. They decay fairly rapidly, giving rise to strong population signals. Although the interpretation of 2DEV spectra is considerably more complex than that for weakly coupled systems, the richness of the spectra and the necessity to consider both visible and infrared transition moments suggest that such analysis will be very valuable in characterizing the role of vibronic effects in ultrafast molecular dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Enter Gaussian Mixture Modeling Extensions for Improved False Discovery Rate Estimation in GC-MS Metabolomics

Identifying small molecules (e.g., metabolites) is key towards driving scientific advancement in metabolomics, and gas chromatography–mass spectrometry (GC-MS) is an analytic method that may be applied to facilitate this process. The typical GC-MS identification workflow involves quantifying the similarity of an observed sample spectrum and other features (e.g. retention index) to that of several references, noting the compound of the best-matching reference spectrum as the identified metabolite. While a deluge of similarity metrics exists, none characterize the error rate of generated identifications, thereby presenting an unknown risk of false identification or discovery. To quantify this unknown risk, we propose a model-based framework for estimating the false discovery rate (FDR) among a set of identifications. Extending the traditional mixture modeling framework, our method incorporates both similarity score and experimental information in estimating the FDR. We apply these models to identification lists derived from across 548 samples of varying complexity and sample type (e.g., fungal species, standard mixtures, etc.), comparing their performance to that of the traditional Gaussian mixture model (GMM). Through simulation, we additionally assess the impact of reference library size on the accuracy of FDR estimates. In comparing the best performing model extensions to the GMM, our results indicate relative decreases in median absolute estimation error (MAE) ranging from 12% to 70%, based on comparisons of the median MAEs across all hit-lists. Results indicate that these relative performance improvements generally hold despite library size, however FDR estimation error typically worsens as the set of reference compounds diminishes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Sonic Boom Prediction and Minimization of the Douglas Reference OPT5 Configuration

Conventional CFD methods and grids do not yield adequate resolution of the complex shock flow pattern generated by a real aircraft geometry. As a result, a unique grid topology and supersonic flow solver was developed at Northrop Grumman based on the characteristic behavior of supersonic wave patterns emanating from the aircraft. Using this approach, it was possible to compute flow fields with adequate resolution several body lengths below the aircraft. In this region, three-dimensional effects are diminished and conventional two-dimensional modified linear theory (MLT) can be applied to estimate ground pressure signatures or sonic booms. To accommodate real aircraft geometries and alleviate the burdensome grid generation task, an implicit marching multi-block, multi-grid finite-volume Euler code was developed as the basis for the sonic boom prediction methodology. The Thomas two-dimensional extrapolation method is built into the Euler code so that ground signatures can be obtained quickly and efficiently with minimum computational effort suitable to the aircraft design environment. The loudness levels of these signatures can then be determined using a NASA generated noise code. Since the Euler code is a three-dimensional flow field solver, the complete circumferential region below the aircraft is computed. The extrapolation of all this field data from a cylinder of constant radius leads to the definition of the entire boom corridor occurring directly below and off to the side of the aircraft's flight path yielding an estimate for the entire noise "annoyance" corridor in miles as well as its magnitude. An automated multidisciplinary sonic boom design optimization software system was developed during the latter part of HSR Phase 1. Using this system, it was found that sonic boom signatures could be reduced through optimization of a variety of geometric aircraft parameters. This system uses a gradient based nonlinear optimizer as the driver in conjunction with a computationally efficient Euler CFD solver (NIIM3DSB) for computing the three-dimensional near-field characteristics of the aircraft. The intent of the design system is to identify and optimize geometric design variables that have a beneficial impact on the ground sonic boom. The system uses a simple wave drag data format to specify the aircraft geometry. The geometry is internally enhanced and analytic methods are used to generate marching grids suitable for the multi-block Euler solver. The Thomas extrapolation method is integrated into this system, and hence, the aircraft's centerline ground sonic boom signature is also automatically computed for a specified cruise altitude and yields the parameters necessary to evaluate the design function. The entire design system has been automated since the gradient based optimization software requires many flow analyses in order to obtain the required sensitivity derivatives for each design variable in order to converge on an optimal solution. Hence, once the problem is defined which includes defining the objective function and geometric and aerodynamic constraints, the system will automatically regenerate the perturbed geometry, the necessary grids, the Euler solution, and finally the ground sonic boom signature at the request of the optimizer.

Siclari, Michael J.↗
DOE OSTI2024

Determining sulfur speciation in oxidatively crosslinked degradable polymers using sulfur K-edge X-ray absorption spectroscopy

A new family of water-degradable elastic polymers prepared by oxidative crosslinking of the parent polythionolactones shows promise in a broad range of applications, but the compositions of these materials elude conventional analytical methods. Here, in this work, we use sulfur K-edge X-ray absorption spectroscopy to quantify the amounts of thioether, disulfide, sulfone, sulfate ester, and thionoester in each polymer and to rule out the presence of several other functional groups, including sulfonate, thiosulfonate, sulfate, and sulfoxide. We rationalize this speciation as a function of linker flexibility in the context of sulfinyl cycloaddition reactions and propose a mechanism of aggregation for the oxidized polymers. Our results correlate with swelling ratios but not with porosity nor crosslink density measurements, demonstrating the importance of pairing mechanical and chemical techniques when characterizing heterogeneous organic polymers. Finally, we take advantage of the proximity of the gold M 4,5 -edges to the sulfur K-edge to analyze the binding and reactivity of Au(III) with the crosslinked polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Optimization of structural and energy characteristics of adsorbents for methane storage

Using numerical and analytical methods, a model for microporous carbon adsorbents with slit-shaped pores of different widths was developed. Such pores are formed during activation procedure by the removal of the hexagonal carbon layers burnt out in a graphite-like crystallites. Dubinin’s theory of volume filling of micropores was used to calculate methane adsorption equilibria on these model adsorbents. Isobaric dependences of methane adsorption on pore width, specific micropore volumes, and the specific surface were plotted in the range of pressures from 1 to 10 MPa. It was found that the isobaric adsorption curves had a maximum the position of which depends on both the structural-energy characteristics of the adsorbent and thermodynamic conditions chosen to operate the adsorption system. As pressure increased, the maximum of adsorption shifts to the porous systems with wider pores and larger micropore volume.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

LX-17 Thermal Decomposition-Characterization of Solid Residues from Cook-Off in a Small-Scale Vessel Under Confinement

Concerns surround whether insensitive (or any) energetic materials are more dangerous to handle when exposed to abnormal thermal environments. This study characterizes the residual material remaining after LX-17 (92.5 % 1,3,5-triamino 2,4,6-trinitro benzene (TATB) and 7.5 % Kel-F) is exposed to various thermal environments in a sealed small-scale vessel cook-off test reactor (heated at 0.1 to 100 °C/min until the reactor opened at 3000 psi (20.7 MPa)). Previous work has shown no additional sensitivity of these residues as evaluated by small-scale safety analysis, but characterization on the molecular scale indicates the TATB is transformed to more reactive compounds as well as the residue could be precursors to toxic gases. The solids and chars were characterized by various analytical methods. Heat-flow measurements indicated exothermic release is due to a mixture of residual TATB and related decomposition products (which may be more energetic). The N/C and O/N ratios indicated a material much more degraded than TATB. Primarily, the solids were a network of amorphous C inter-dispersed with N and O. Types of bonding include C–C, C–N, N–H, N–C, N=C, N≡C, C–O=, and –OH. Solvent extracts of the solids showed TATB decomposition intermediates benzo-furazans and benzo-furoxans, substituted TATB (mono-nitroso, hydroxyl, and chlorinated) along with several unidentified smaller molecules. These results indicate thermal treatment produces an amorphous carbon residue with heteroatoms incorporated through differing functionality, varying depending upon the thermal severity of exposure. These structures also could further decompose producing toxic light gases (such as cyanide).

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

Direct Measurements of Dimethyl Sulfide Oxidation Chemistry: Uncovering the Primary Pathways from Gas Phase to Sulfate Aerosols

We report experimental measurements of dimethyl sulfide oxidation, focusing on a major chemical intermediate, hydroperoxymethyl thioformate (HPMTF). The (photo)chemistry and transport properties of HPMTF, which are critical to accurate modeling of tropospheric sulfur, are not known, partly because current analytical methods are not optimized for elusive chemical intermediates. We investigated dimethyl sulfide oxidation using a custom time-resolved photoionization mass spectrometer, interfaced with pulsed laser photolysis, continuous photolysis, and liquid droplet reactors. We detected and characterized HPMTF (along with other reaction intermediates), quantified its yield, and measured its formation rate coefficient. We also developed a clean, intense, online HPMTF source, suitable for further experimental investigations. Lastly, we measured the mass accommodation coefficient of HPMTF on water droplets – a critical quantity for modeling its atmospheric partitioning between the gas and condensed phases. The experimental platform we developed here enables the exploration of other critical elusive reaction intermediates.

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

Cathodic NH 4 + leaching of nitrogen impurities in CoMo thin-film electrodes in aqueous acidic solutions

Electrocatalytic reduction of dinitrogen (N 2 ) to ammonium (NH 4 + ) in acidic aqueous solutions was investigated at ambient temperature and pressure using a cobalt–molybdenum (CoMo) thin-film electrode prepared by magnetron reactive sputtering. Increased concentrations of ammonium ions (NH 4 + ) were consistently detected in the electrolyte using ion chromatography (IC) after constant-potential electrolysis at various potentials (≤-0.29 V vs. RHE). Using a newly developed analytical method based on ammonia derivatization, performing the experiments with 15 N 2 -labelled gas led however to the detection of increased 14 NH 4 + concentrations instead of 15 NH 4 + . X-ray photoelectron spectroscopic (XPS) analysis of the electrode surface revealed the presence of Mo[triple bond, length as m-dash]N and Mo–NH x species. Several contamination sources were identified that led to substantial increases in the concentration of ammonium ions, including 15 NH 3 impurities in 15 N 2 gas. The observed ammonium concentrations can be consistently ascribed to leaching of nitrogen ( 14 N) impurities incorporated in the CoMo film during the sputtering process. Therefore, researchers in the field are urged to adopt extended protocols to identify and eliminate sources of ammonia contamination and to very carefully monitor the ammonium concentrations in each experimental step.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Towards a heat- and mass-balanced kinetic model of TATB decomposition

We report TATB (1,3,5-triamino-2,4,6-trinitrobenzene) was thermally degraded by two small-scale analytical methods – simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) and a hot-stage microscope with Fourier Transform Infrared (FTIR) analysis capabilities. SDT used ramped heating, isothermal soaking, and thermal pretreatment at various conditions. The heat flow and mass loss were monitored during various treatment conditions to derive chemical decomposition kinetics and Arrhenius parameters. FTIR experiments used isothermal heating, and changes were monitored spectroscopically. Solid samples generated at specific conditions were collected from both methods and were analyzed by DMSO extraction followed by chemical speciation by optical and mass spectrometric methods. Characterization provided the following reaction insights: TATB decreases in a sigmoidal pattern in isothermally heated samples. Other soluble products gradually increase in concentration and then abruptly decline in concentration during the second exotherm, such as diamino-dinitro-benzofurazan and amino-nitro-benzodifurazan. FTIR showed gradual changes in the amino and nitro functionality, shifting positions and decreasing intensity for the first 40 min. Then the solid gradually appeared more like an amorphous C with N incorporated, similar to previous studies on thermally degraded TATB-type materials. Extracted residues (DMSO-soluble components removed) examined by FTIR showed an abrupt change in chemical composition between 40- and 45-min isothermal treatment, indicating early forming solids are different than later forming residues. A reliable mass- and energy-balanced global reaction network must include at least two autocatalytic reactions, either in parallel or series, and at least one must have an explicit initiation reaction having a low activation energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Revisiting the K-edge X-ray absorption fine structure of Si, Ge–Si alloys, and the isoelectronic series: CuBr, ZnSe, GaAs, and Ge

Extended X-ray absorption fine structure (EXAFS) has evolved into an unprecedented local-structure technique that is routinely used to study materials’ problems in the biological, chemical, and physical sciences. Like many other experimental techniques, EXAFS also requires that several key atomic parameters must be known a priori before structural information can be quantitatively determined. Utilizing current analytical methods, we revisit the isoelectronic series CuBr, ZnSe, GaAs, and Ge originally studied by Stern et al. during the early development of EXAFS. We demonstrate that the ab initio EXAFS code FEFF accurately predicts the atomic phase shifts and backscattering amplitudes that are primarily functions of the sum of atomic numbers Z along an EXAFS scattering path. We also investigate quantitative fitting and first- and second-shell phase transferability together with problems that arise if a backscattering atom is identified incorrectly in an EXAFS fitting model. Features in the near-edge region, on the other hand, are shown to require a comprehensive treatment of the band structure and density-of-states, including effects of the screened Coulomb interaction between the photoelectron and core hole. Here, we demonstrate that the Bethe–Salpeter equation (BSE) accurately captures the NEXAFS (or XANES) portion of the spectrum for the isoelectronic series in addition to Si and Ge–Si alloys, including within a few eV of the absorption edge, where band structure and excitonic effects are most important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗