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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Formation of uranium disulfide from a uranium thioamidate single-source precursor

A single-source-precursor approach was developed to synthesize uranium-based materials outside of the typically-studied oxides. This approach allows for shorter reaction times, milder reaction conditions, and control over the chemicals present in synthesis. To this end, the first homoleptic uranium thioamidate complex was synthesized as a precursor for US 2 materials. Pyrolysis of the thioamidate results in decomposition via an alkene elimination pathway and formation of γ-US 2 , which has historically been hard to access without the need for a secondary sulfur source. Despite the oxophilicity of uranium, the method successfully forms US 2 without the inclusion of oxygen in the bulk final product. These findings are supported by simultaneous thermal analysis, elemental analysis, powder X-ray diffraction, and uranium L 3 -edge X-ray absorption fine-structure spectroscopy. This work represents the first example of a single-source precursor approach to target and synthesize actinide materials other than the oxides.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRSDate not supplied

On the Importance of Producing and Characterizing Laboratory Analogs of Cosmic Grains, Planetary Atmospheric Aerosols, and Surface Materials

Carbonaceous dust and aerosols have been observed in interstellar/circumstellar and planetary environments. Dedicated laboratory experiments have been developed to produce analogs of these solid materials under different experimental conditions (molecular precursors, temperature, pressure, energy source…). These experimental studies are key to investigating the physical and chemical processes that drive the formation of solid particles from gas and solid phase molecular precursors in astrophysical and planetary environments. They also allow the characterization of the physical, optical, and chemical properties of these laboratory-generated analogs, hence providing critical information that can be used as input parameters in models for the analysis and interpretation of observational data. Here, as an example of these laboratory efforts, we will present various studies that combined (1) experiments performed with the NASA Ames COSmIC facility to produce analogs of Titan’s atmospheric aerosols and cosmic grains from gas phase molecular precursors, and (2) the characterization of these analogs with the NASA Ames Optical Constants Facility (OCF) to provide the real and imaginary parts of their refractive indices, n + ik, to the community, from the visible to the far-infrared (0.59–200 µm, 16,950–50 per cm). We will also discuss the importance of the wavelength and spectral range coverage of these optical constants, n and k, for their use in radiative transfer, atmospheric and reflectance models, and present a new effort to develop an Optical Constant database (OCdb) to provide this critical data to the scientific community.

Cosmic Grains↗
DOE OSTI2021

Radiolysis of thermally dehydrated gibbsite

Aluminum hydroxide (gibbsite, Al (OH) 3 ) powders and their thermally dehydrated forms were rehydrated and irradiated with gamma rays to examine the effects of the collapse of the crystalline gibbsite structure as it is converted to alumina on the transport of precursors of molecular hydrogen to the surface. The amount of hydrogen gas, H 2 , production from irradiated gibbsite and its transition phases with adsorbed water increased substantially with increasing temperature for dehydration of the samples, up to a point. Furthermore, the production of H 2 for samples without water was considerably lower than the hydrated samples signifying the importance of surface water and the transport of precursors to the surface. EPR spectroscopy showed that the major radiolytic products are trapped electrons and related O – centers. Thermal gravimetric analysis (TGA) measurements of gibbsite dehydration established the temperatures of phase transitions from gibbsite to alumina. Changes to the surface and structure of gibbsite and its transition phases following irradiation were analyzed using nitrogen adsorption, powder X-ray diffraction (pXRD), Raman spectroscopy, electron paramagnetic resonance (EPR), and scanning electron microscopy (SEM). pXRD and Raman spectra showed amorphorization at about 300 °C, coupled to a substantial increase in specific surface area due to increasing porosity.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Support Effect and Surface Reconstruction in In 2 O 3 / m- ZrO 2 Catalyzed CO 2 Hydrogenation

Here, we investigate the chemical and structural dynamics at the interface of In 2 O 3 /m-ZrO 2 and their consequences on the CO 2 hydrogenation reaction (CO 2 HR) under reaction conditions. While acting to enrich CO 2 , monoclinic zirconia (m-ZrO 2 ) was also found to serve as a chemical and structural modifier of In 2 O 3 that directly governs the outcome of the CO 2 HR. These modifying effects include the following: (1) Under reaction conditions (above 623 K), partially reduced In 2 O 3 , i.e., InO x (0 < x < 1.5), was found to migrate in and out of the subsurface of m-ZrO 2 in a semireversible manner, where m-ZrO 2 accommodates and stabilizes InO x by serving as a reservoir. The decreased concentration of surface InO x under elevated temperatures coincides with significantly decreased selectivity toward methanol and a sharp increase of the reverse water–gas shift reaction. The reconstruction-induced variation of InO x concentration appears to be one of the most important factors contributing to the altered catalytic performance of CO 2 HR at different reaction conditions. (2) The strong interactions and reactions between m-ZrO 2 and In 2 O 3 result in the activation of a pool of In–O bonds at the In 2 O 3 /m-ZrO 2 interface to form oxygen vacancies. On the other hand, the high dispersity of In 2 O 3 nanostructures onto m-ZrO 2 prevents their over-reduction under catalytically relevant conditions (up to 673 K), when bare In 2 O 3 is unavoidably reduced into the metallic phase (In 0 ). The relationship between the extent of reduction of In 2 O 3 and catalytic performance (CO 2 conversion, CH 3 OH selectivity, or yield of CH 3 OH) suggests the presence of an optimum coverage of surface InO x and oxygen vacancies under reaction conditions. The conventional model that links catalytic performance solely to the coverage of oxygen vacancies appears invalid in the present case. In situ analysis also allows the observation of surface reaction intermediates and their interconversions, including the reduction of CO 3 * into formate, a precursor for the formation of methanol and CO. The combinative ex situ and in situ study sheds light on the reaction mechanism of the CO 2 HR on In 2 O 3 /m-ZrO 2 -based catalysts. Our findings on the large-scale surface reconstructions, support effect, and the reaction mechanism of In 2 O 3 /m-ZrO 2 for CO 2 HR may apply to other related metal oxide catalyzed CO 2 reduction reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Characteristics and Global Impact of Aerosols from Southern Africa and Eastern Asia

Supported mainly by the NASA GACP and ACMAP, we have made significant progress in the global modeling of tropospheric aerosols and their precursors in the past few years, especially in the development of the GOCART model, simulation of anthropogenic and natural aerosols, data analysis of field observations and satellite retrievals, assessment of global and regional budgets, estimate of aerosol direct radiative forcing, and aerosol forecasting and data analysis for the ACE-Asia field experiment. Our results and findings are summarized in Chin et al. Model calculated multiple-year optical thickness for individual and total aerosols are at internet. These results have been frequently used by other groups, for example, to impose initial conditions for regional models, provide dust source functions for other global models, supply aerosol fields for chemistry and climate models, help data group interpret their measurements, select monitoring sites for ground observation network, and assist satellite retrievals.

Chin, Mian↗
NASA NTRS2004

Ultrasonic Apparatus for Pulverizing Brittle Material

The figure depicts an apparatus that pulverizes brittle material by means of a combination of ultrasonic and sonic vibration, hammering, and abrasion. The basic design of the apparatus could be specialized to be a portable version for use by a geologist in collecting powdered rock samples for analysis in the field or in a laboratory. Alternatively, a larger benchtop version could be designed for milling and mixing of precursor powders for such purposes as synthesis of ceramic and other polycrystalline materials or preparing powder samples for x-ray diffraction or x-ray fluorescence measurements to determine crystalline structures and compositions. Among the most attractive characteristics of this apparatus are its light weight and the ability to function without need for a large preload or a large power supply: It has been estimated that a portable version could have a mass <0.5 kg, would consume less than 1 W h of energy in milling a 1-cm3 volume of rock, and could operate at a preload <10 N. The basic design and principle of operation of this apparatus are similar to those of other apparatuses described in a series of prior NASA Tech Briefs articles, the two most relevant being Ultrasonic/ Sonic Drill/Corers With Integrated Sensors (NPO-20856), Vol. 25, No. 1 (January 2001), page 38 and Ultrasonic/ Sonic Mechanisms for Deep Drilling and Coring (NPO-30291), Vol. 27, No. 9 (September 2003), page 65. As before, vibrations are excited by means of a piezoelectric actuator, an ultrasonic horn, and a mass that is free to move axially over a limited range. As before, the ultrasonic harmonic motion of the horn drives the free-mass in a combination of ultrasonic harmonic and lower-frequency hammering motion. In this case, the free-mass is confined within a hollow cylinder that serves as a crushing chamber, and the free-mass serves as a crushing or milling tool. The hammering of the free-mass against a material sample at the lower end of the chamber grinds the sample into powder in a relatively short time. The restriction of the free-mass to axial motion only makes the grinding very efficient. The free-mass can be fabricated to have teeth on its lower face to enhance the grinding effect. Optionally, there can be a hole at the bottom of the chamber covered with a sieve to tailor the size distribution of the powder leaving the crushing chamber.

Sherrit, Stewart↗
NASA NTRS2012

Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au, Ru and Pd in minerals (olivine and diopside) and in silicate melts, but also to characterize the sizes, density and chemistry of HSE nuggets when present in the samples.

Malavergne, V.↗
NASA NTRS2018

The Zwicky Transient Facility: System Overview, Performance, and First Results

The Zwicky Transient Facility (ZTF) is a new optical time-domain survey that uses the Palomar 48 inch Schmidt telescope. A custom-built wide-field camera provides a 47 deg ^(2) field of view and 8 s readout time, yielding more than an order of magnitude improvement in survey speed relative to its predecessor survey, the Palomar Transient Factory. We describe the design and implementation of the camera and observing system. The ZTF data system at the Infrared Processing and Analysis Center provides near-real-time reduction to identify moving and varying objects. We outline the analysis pipelines, data products, and associated archive. Finally, we present on-sky performance analysis and first scientific results from commissioning and the early survey. ZTF’s public alert stream will serve as a useful precursor for that of the Large Synoptic Survey Telescope.

Eric C. Bellm↗
DOE OSTI2023

Mechanisms of metabolic adaptation in the duckweed Lemna gibba: an integrated metabolic, transcriptomic and flux analysis

Abstract Background Duckweeds are small, rapidly growing aquatic flowering plants. Due to their ability for biomass production at high rates they represent promising candidates for biofuel feedstocks. Duckweeds are also excellent model organisms because they can be maintained in well-defined liquid media, usually reproduce asexually, and because genomic resources are becoming increasingly available. To demonstrate the utility of duckweed for integrated metabolic studies, we examined the metabolic adaptation of growing Lemna gibba cultures to different nutritional conditions. Results To establish a framework for quantitative metabolic research in duckweeds we derived a central carbon metabolism network model of Lemna gibba based on its draft genome. Lemna gibba fronds were grown with nitrate or glutamine as nitrogen source. The two conditions were compared by quantification of growth kinetics, metabolite levels, transcript abundance, as well as by 13 C-metabolic flux analysis. While growing with glutamine, the fronds grew 1.4 times faster and accumulated more protein and less cell wall components compared to plants grown on nitrate. Characterization of photomixotrophic growth by 13 C-metabolic flux analysis showed that, under both metabolic growth conditions, the Calvin-Benson-Bassham cycle and the oxidative pentose-phosphate pathway are highly active, creating a futile cycle with net ATP consumption. Depending on the nitrogen source, substantial reorganization of fluxes around the tricarboxylic acid cycle took place, leading to differential formation of the biosynthetic precursors of the Asp and Gln families of proteinogenic amino acids. Despite the substantial reorganization of fluxes around the tricarboxylic acid cycle, flux changes could largely not be associated with changes in transcripts. Conclusions Through integrated analysis of growth rate, biomass composition, metabolite levels, and metabolic flux, we show that Lemna gibba is an excellent system for quantitative metabolic studies in plants. Our study showed that Lemna gibba adjusts to different nitrogen sources by reorganizing central metabolism. The observed disconnect between gene expression regulation and metabolism underscores the importance of metabolic flux analysis as a tool in such studies.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Effect of the Ionic Liquid Structure on the Melt Processability of Polyacrylonitrile Fibers

The production of high-strength carbon fibers is an energy-intensive process, where a significant cost involves the wet or dry-spinning of polyacrylonitrile (PAN) fiber precursors. Melt-spinning PAN fibers would allow for significant reduction in the production cost and production hazards. Ionic liquids (ILs) are an attractive fiber-processing medium because of their negligible vapor pressure and low toxicity. In addition, they are carbon-forming precursors; upon carbonization, residual ILs can enhance the carbon yield, although primarily useful for plasticized melt-spinning of PAN precursor fibers. Here, we investigated the influence of the molecular structure of ILs and the control of plasticizing interactions with PAN during melt-spinning. The structural, thermal, and mechanical properties of the melt-spun PAN fibers were obtained by a combination of various characterization methods, such as differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and mechanical testing. These results demonstrated that the IL structure and counteranions influence the PAN fiber formation. More specifically, ILs containing bromide counteranions produced PAN precursor fibers with increased mechanical properties compared to ILs containing chloride anions. Our research can provide a foundation to understand the influence of ILs on melt-spinning of PAN fibers and provides us the guidelines for a higher cost-/energy-efficient production of PAN-based carbon fibers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Automating data analysis for hydrogen/deuterium exchange mass spectrometry using data-independent acquisition methodology

We present a hydrogen/deuterium exchange workflow coupled to tandem mass spectrometry (HX-MS 2 ) that supports the acquisition of peptide fragment ions alongside their peptide precursors. The approach enables true auto-curation of HX data by mining a rich set of deuterated fragments, generated by collisional-induced dissociation (CID), to simultaneously confirm the peptide ID and authenticate MS 1 -based deuteration calculations. The high redundancy provided by the fragments supports a confidence assessment of deuterium calculations using a combinatorial strategy. The approach requires data-independent acquisition (DIA) methods that are available on most MS platforms, making the switch to HX-MS 2 straightforward. Importantly, we find that HX-DIA enables a proteomics-grade approach and wide-spread applications. Considerable time is saved through auto-curation and complex samples can now be characterized and at higher throughput. We illustrate these advantages in a drug binding analysis of the ultra-large protein kinase DNA-PKcs, isolated directly from mammalian cells.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Local chemical ordering of a neutron-irradiated CrFeMnNi compositionally complex alloy

While ion-irradiation studies are a critical first step in studying compositionally complex alloys (CCAs) for nuclear applications, they do not capture all the microstructural changes occurring under the low irradiation dose rates and different particles’ scattering patterns experienced in a nuclear reactor setting. To explore these phenomena in reactor-relevant conditions for the first time in CCA, the single-phase solid-solution Cr 10 Fe 30 Mn 30 Ni 30 was neutron irradiated up to 6.61 displacements per atom at 395 and 579 °C. Irradiation-enhanced local chemical ordering (LCO) well beyond the range of short range ordering was observed, and is predicted to be the precursor to the precipitation of a coherent Ni-Mn L1 0 phase and a Cr-rich α’ phase, though TEM analysis did not indicate the presence of either in any irradiation condition. The line density of faulted dislocation loops decreased from 6.47 to 1.69 ∙ 10 15 m -2 from 3.43 to 6.61 dpa at 579 °C despite no appreciable faulted loop content in the unirradiated material. LCO is expected to increase the complexity of the energy landscape within this alloy, restricting interstitial point defect mobility and creating local regions of greater stacking fault energy. These contribute to the negative correlation between irradiation dose and faulted dislocation loop density in this study, as well as the lack of void swelling observed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Impact of Pendent Ammonium Groups on Solubility and Cycling Charge Carrier Performance in Nonaqueous Redox Flow Batteries

The synthesis, characterization, electrochemical performance, and theoretical modeling of two base-metal charge carrier complexes incorporating a pendent quaternary ammonium group, [Ni(bppn-Me3)][BF4], 3′, and [Fe(PyTRENMe)][OTf]3, 4’, are described. Both complexes were produced in high yield and fully characterized using NMR, IR, and UV–vis spectroscopies as well as elemental analysis and single-crystal X-ray crystallography. The solubility of 3′ in acetonitrile showed a 283% improvement over its neutral precursor, whereas the solubility of complex 4’ was effectively unchanged. Cyclic voltammetry indicates an ∼0.1 V positive shift for all waves, with some changes in reversibility depending on the wave. Bulk electrochemical cycling demonstrates that both 3′ and 4’ can utilize the second more negative wave to a degree, whereas 4’ ceases to have a reversible positive wave. Flow cell testing of 3′ and 4’ with Fc as the posolyte reveals little improvement to the cycling performance of 3′ compared with its parent complex, whereas 4’ exhibits reductions in capacity decay when cycling either negative wave. Postcycling CVs indicate that crossover is the likely source of capacity loss in complexes 3, 3′, and 4’ because there is little change in the CV trace. Density functional theory calculations indicate that the ammonium group lowers the HOMO energy in 3′ and 4’, which may impart stability to cycling negative waves while making positive waves less accessible. The incorporation of a positively charged species can improve solubility, stored electron density, and capacity decay depending on the complex, features critical to high energy density redox flow battery performance.

25 ENERGY STORAGE↗
DOE OSTI2019

Vertically-Aligned Carbon-Nanotubes Embedded in Ceramic Matrices for Hot Electrode Applications

The proposed is aimed to develop carbon nanotube-ceramic (CNT-C) composite structures, in which vertically aligned CNTs (VA-CNTs) are embedded in ceramic matrices for hot electrode applications in Magnetohydrodynamics (MHD) power systems, including four objectives: 1) Super growth of VA-CNT carpets; 2) Fabrication of CNT-boron nitride (CNT-BN) composite structures by chemical vapor infiltration; 3) Stability and resistance studies of the CNT-BN Composite structures; and 4) Thermionic emissions of the CNT-BN composite structures. The researchers will deploy water vapor-assisted chemical vapor deposition (CVD) method in the super growth of VA-CNT carpets on copper (Cu) with a maximum length up to 1 cm. Fabrication of the CNT-BN composite structures will be achieved by infiltrating gaseous boron precursors into the VA-CNTs followed by a universal heating, converting the precursors to solid BN crystals. Thermal stability and oxidation resistivity of the CNT-BN composite structures will be investigated using Thermogravimetric Analysis (TGA) and Differential thermal analysis (DTA) under an oxidation environment from room temperature to 3000 K. An oxy-acetylene flame will be employed to simulate the extreme environment in MHD channels for investigating the thermal and electrical conductivity, and corrosion and erosion resistance of the CNT-BN composite structures under the extreme conditions. Thermionic emission performance of the CNT-BN composite structures will be investigated to study the transport properties of the composite structures. If the CNT-BN composite does not perform as anticipated, selected ultra-high-temperature ceramics, such as titanium boride (TiB2), will be investigated as a backup candidate wrapping CNTs. Upon the successful completion of the propose research, CNT-C composite structures, such as CNT-BN and CNT-TiB2, will be developed for “hot” electrode applications. Fundamental understanding on the thermal and electrical transport properties of CNTs at high temperatures up to 3000 K will be established. Wrapping CNTs in ceramic matrices will isolate CNTs from the extreme environments in the MHD channels. The embedded CNTs will serve as conductive channels for heat and electricity transport. It is anticipated that the CNT-C composite structures would withstand the extreme environments in MHD channels and provide sufficient electrical and thermal conductivities for direct power extraction from seeded oxy-fuel combustion fluids. Successful development of the CNT-C composite structures will significant improve the reliability and promote the commercial applications of MHD generators, which are capable of large scale mass energy conversion at an unprecedented efficiency of 60% with reduced overall production of hazardous fossil fuel wastes.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2022

Quantifying urban, industrial, and background changes in NO2 during the COVID-19 lockdown period based on TROPOMI satellite observations

The COVID-19 lockdown had a large impact on anthropogenic emissions of air pollutants and particularly on nitrogen dioxide (NO 2 ). While the overall NO 2 decline over some large cities is well-established, understanding the details remains a challenge since multiple source categories contribute. In this study, a new method of isolation of three components (background NO 2 , NO 2 from urban sources, and NO 2 from industrial point sources) is applied to estimate the impact of the COVID-19 lockdown on each of them. The approach is based on fitting satellite data by a statistical model with empirical plume dispersion functions driven by a meteorological reanalysis. Population density and surface elevation data as well as coordinates of industrial sources were used in the analysis. The tropospheric NO 2 vertical column density (VCD) values measured by the Tropospheric Monitoring Instrument (TROPOMI) on board the Sentinel-5 Precursor over 261 urban areas for the period from 16 March to 15 June 2020 were compared with the average VCD values for the same period in 2018 and 2019. While the background NO 2 component remained almost unchanged, the urban NO 2 component declined by −18 % to −28 % over most regions. India, South America, and a part of Europe (particularly, Italy, France, and Spain) demonstrated a −40 % to −50 % urban emission decline. In contrast, the decline over urban areas in China, where the lockdown was over during the analysed period, was, on average, only -4.4± 8 %. Emissions from large industrial sources in the analysed urban areas varied greatly from region to region from -4.8 ± 6 % for China to -40 ± 10 % for India. Estimated changes in urban emissions are correlated with changes in Google mobility data (the correlation coefficient is 0.62) confirming that changes in traffic were one of the key elements in the decline in urban NO2 emissions. No correlation was found between changes in background NO2 and Google mobility data. On the global scale, the background and urban components were remarkably stable in 2018, 2019, and 2021, with averages of all analysed areas all being within ±2.5 % and suggesting that there were no substantial drifts or shifts in TROPOMI data. The 2020 data are clearly an outlier: in 2020, the mean background component for all analysed areas (without China) was -6.0 % ± 1.2 % and the mean urban component was -26.7 ± 2.6 % or 20σ below the baseline level from the other years.

COVID-19↗
NASA NTRS1972

The organic analysis and carbon chemistry of lunar samples: Their significance for exobiology; Proceedings of the Conference, University of Maryland, College Park, Md., October 26-28, 1971.

Various methods used in the organic analysis of lunar samples are reviewed. The scope, advantages, and limitations of these methods are discussed, with particular emphasis on possible sources of contamination and experimental artifacts inherent in their use. A broad survey of the organogenic elements and compounds found in lunar samples covers the search for biogenic structures and viable organisms; the abundance and isotopic composition of various elements and compounds; the search for porphyrins, amino acids, or amino acid precursors; and the presence of heterocylics, aromatic hydrocarbons, and other organic compounds. The sources of the organogenic elements and compounds detected in lunar samples are discussed. The significance of the lunar organic analysis for exobiology is discussed in terms of its relevance to and implications for the studies of chemical evolution and terrestrial organic geochemistry. Individual items are announced in this issue.

Source record↗
DOE OSTI2025

Interplay between Cation “Coloring” and Stereochemically Active Lone Pairs in AgBiS 2 Thin Films

Solution-processed AgBiS 2 thin films were fabricated using novel thiol− amine precursor inks to investigate the stereochemical activity of Bi 3+ 6s 2 lone pairs and their impact on the structure. A dual-space analysis combining Bragg diffraction and hard X-ray photoelectron spectroscopy (HAXPES) revealed a rock salt-like average structure with local distortions linked to cation coloring. Density functional theory (DFT) and crystal orbital Hamilton population (COHP) analyses confirmed that local Bi-rich and Ag-rich nanodomains amplify stereochemical activity, whereas more mixed and cation-order nanodomains are less stereochemically active. This local, nanoscopic mixing of segregated and ordered domains would indeed explain an average Fm3̅m structure that is rock salt-like and that does not manifest the full anharmonicity and noncentrosymmetry evidenced in canonical structures with stereochemical expression. These findings provide insights into the local structural and electronic complexities governing the optoelectronic properties of AgBiS 2 thin films.

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

Quantifying Properties for a Mechanistic, Predictive Understanding of Aqueous Impact on Aging of Medium and Low Voltage AC and DC Cabling in Nuclear Power Plants

To address the gap in knowledge in understanding degradation in relevant service conditions, this project aimed to develop a mechanistic, predictive model of medium and low voltage cable failure based on the primary environmental degradation parameters of aqueous immersion time, temperature, and the oxidation extent. To do so, we took a two-fold approach toward evaluating degradation as related to the aqueous condition. First, we evaluated the chemical, mechanical, and electrical properties of polymers that comprise the cabling insulation under varied aqueous conditions at different temperatures. Secondly, we evaluated the performance of insulation materials under similar accelerated aging conditions in addition to the dielectric breakdown of the cabling under submersion conditions. Thermal oxidation and immersion of LDPE thin films were done using a Parr vessel and the extent of oxidation was monitored using the carbonyl index from ATR-FTIR spectrum, a ratio quantifying the carbonyl functionality produced on the LDPE film surface. Increasing the temperature, oxidation time, and oxygen pressure increased the water-vapor permeability and the carbonyl content. Thermogravimetric analysis of the films confirmed that there is indeed an initial weight loss of the smaller molecular weight molecules and volatiles. At higher temperatures, there is a secondary mass loss. Up to 70°C, the mass loss curves were similar until 80°C, when the aged films decreased at a much greater rate with respect to increasing temperature. This was seen in the 10, 50, 90% weight loss temperatures. The mechanical properties of sheet PP and HDPE as well as injection molded LDPE, HDPE, HDPP dog bones were plotted with respect to the time spent in the Parr vessel during thermal oxidation. For the sheet PP and HDPE, the UTS and the modulus of elasticity decreased while the elongation increased. The injection-molded LDPE, HDPE, and HDPP dog bones experienced a similar trend where the changes in the properties were within experimental uncertainty. This analysis of LDPE in dry and immersive oxygen-rich environments is an important baseline for future experiments looking at other degradation mechanisms. A predictive aging model for low-density polyethylene insulative cable housings was developed. This model revealed a combination of physical and chemical processes which lead to an increase in permeability and a decrease in strength of the insulator. In creating this predictive model, a gap of knowledge in the literature was revealed in two areas: understanding how the crystallinity of a polymer changes with time and visualizing the predicted pores formed through the insulator which leads to failure. Developing and using an adapted ATR-FTIR method, crystallinity was monitored and compared to bulk crystallinity found via DSC. Inhomogeneity in crystallinity changes were observed but the FTIR method but was found to be less reliable. Pore visualization was found utilizing electrical impedance spectroscopy saturated aged polyethylene films with synthesized citrate-capped gold nanoparticles, and chloroauric acid precursor. results indicate a decreasing impedance of the polyethylene films caused by the transport of ions through the film. SEM imaging was then performed for elemental analysis of the films and counter electrodes for the presence of ions. Chloride and gold ions were detected; however, no nanoparticles were found. This gives an estimated pore size of at least 0.3 nm through the aged film. Cyclic submergence of polyethylene and polypropylene in aqueous solutions of copper sulfate and Harrison’s solution were examined. It was discovered that aging in these mixed conditions and at 90°C did cause a small, yet significant increase to tensile strength for both unaged polyethylene and polypropylene. The PE and PP in cycled and submerged conditions did not have tensile strengths significantly different from dry-aged after 16 weeks. For both solutions, it was determined that capacitance increases with both water tree depth and cable temperature and is relatively independent of changing water tree AR. As for resistance, there is no apparent change between depth percentages of 10 and 80 for both solutions. This is because the water tree has not yet entered the conductor and thus there is no shorting current flowing through the tree yet. Between 80 and 100% water tree depth, it is observed that for both solutions there is a rapid decrease in resistance because the tree is now impacting the conductor shield and allowing shorting current to flow through it. The relationship between resistance and temperature was found to be inversed. As temperature increases, resistance decreases for both water tree solutions with distilled water having the most apparent difference across the range of temperatures simulated. With regards to water tree AR, resistance was found to be relatively independent at depth percentages of 10, 50, and 70, but there was some relationship at 100% depth for both solutions. At this depth, as water tree AR increased, resistance was found to also increase. Through the examination of voltage and electric field distribution plots, it was confirmed for EPR cables that increasing water tree depth leads to increasing distortion. The increase in shorting current at 100% depth for aqueous copper sulfate compared to distilled water was also visualized. Lastly, the relationship between shorting current and temperature for narrow water trees was visualized and validated using the distribution plots. This study has led to a better understanding of the effect of cable temperature, water tree solution, and geometry of the tree region on cable degradation. Furthermore, this study has documented simulation results of water tree degradation in EPR MV cables, which had been previously lacking in information. Future work in this area will add frequency into the mix and examine what effect it has on the rate of cable degradation as a result of water treeing. To compliment the work being carried by UMD on different polymer chemistries, harvested medium voltage (MV) cables were selected for accelerated aging study at ORNL. These medium voltage cables are representative of the vintages and materials that are currently in use at existing nuclear power plants (NPPs). These cables were immersed in water at 90°C and energized for a period of two years at elevated voltage. Partial discharge was measured during this period of time to track potential degradation. Unfortunately, due to the absence of failure, the extent of integration between the UMD techniques and the harvested MV insulation was limited. However, based on the findings and from the UMD research in the previous sections on polyethylene and polypropylene, follow-on characterization for harvested MV cable insulation should focus on sample preparation to take advantage of the UMD techniques to better understand mechanistic degradation in MV cable insulations. This would include: 1.) Utilization of solutions and impedance measurement insulation to track permeability in harvested and accelerated aging insulation samples, 2.) Adaptation of gold nanoparticle synthesis for electrical impedance spectroscopy with supporting SEM characterization to study pore formation in harvested and accelerated aged insulation samples, & 3.) ATR-FTIR crystallinity with multiple temperature dependent harvested MV cable insulation under different air and submerged accelerated aging. In addition, low voltage dielectric spectroscopy and high voltage dissipation factor, tan δ, could be implemented as a condition monitoring tool for harvested MV cable insulation in submerged environments.

24 POWER TRANSMISSION AND DISTRIBUTION↗