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At least 199 records · Page 11

Energetics of high temperature degradation of fentanyl into primary and secondary products

Fentanyl is a synthetic opioid used for managing chronic pain. Due to its higher potency (50–100×) than morphine, fentanyl is also an abused drug. A sensor that could detect illicit fentanyl by identifying its thermally degraded fragments would be helpful to law enforcement. While experimental studies have probed the thermal degradation of fentanyl, little theoretical work has been done to understand the mechanism. Here, we studied the thermal degradation pathways of fentanyl using extensive ab initio molecular dynamics simulations combined with enhanced sampling via multiple-walker metadynamics. We calculated the free energy profile for each bond suggested earlier as a potential degradation point to map the thermodynamic driving forces. In conclusion, we also estimated the forward attempt rate of each bond degradation reaction to gain information about degradation kinetics.

Poudel, Bharat↗

Damp Heat Induced Degradation of Silicon Heterojunction Solar Cells With Cu-Plated Contacts

Damp heat exposure is one of the most stringent environments for testing the durability of solar cells in packaged modules. Damp heat stresses and induces a variety of degradation modes in solar cells and modules: for example, moisture-induced corrosion of electrodes and interconnections, deterioration of polymeric materials, and/or thermally activated diffusion processes. To screen for these and other potential degradation modes, we subject one-cell modules containing silicon heterojunction (SHJ) solar cells with Cu-plated contacts to extended damp heat tests at 85 °C/85% relative humidity. SHJ cells were laminated with two common encapsulants: ethylene vinyl acetate (EVA) and polyolefin elastomer (POE), and two constructions: glass-backsheet and glass-glass. We observe degradation in all components of solar cell maximum power (PMP): current, voltage, and fill factor, and find evidence of increased carrier recombination and nonideal diode behavior with increasing stress. For glass-backsheet constructions, EVA samples generally degrade more than POE by a factor of approximately 1.5x PMP, and the different encapsulants produce different degradation patterns. Similar trends are observed in glass-glass modules, but to a lesser degree. In a different experiment, we observe a decrease in effective minority carrier lifetime of nonmetallized SHJ precursors measured after damp heat. This implies that some degradation unrelated to the contacts is to be expected and confirms the observation of increasing recombination.

14 SOLAR ENERGY↗

The drivers and impacts of Amazon forest degradation

Approximately 2.5 × 10 6 square kilometers of the Amazon forest are currently degraded by fire, edge effects, timber extraction, and/or extreme drought, representing 38% of all remaining forests in the region. Carbon emissions from this degradation total up to 0.2 petagrams of carbon per year (Pg C year –1 ), which is equivalent to, if not greater than, the emissions from Amazon deforestation (0.06 to 0.21 Pg C year –1 ). Amazon forest degradation can reduce dry-season evapotranspiration by up to 34% and cause as much biodiversity loss as deforestation in human-modified landscapes, generating uneven socioeconomic burdens, mainly to forest dwellers. Projections indicate that degradation will remain a dominant source of carbon emissions independent of deforestation rates. In conclusion, policies to tackle degradation should be integrated with efforts to curb deforestation and complemented with innovative measures addressing the disturbances that degrade the Amazon forest.

54 ENVIRONMENTAL SCIENCES↗

Capacity of Arctic fjord sediments to degrade carbohydrates from permafrost active layer

The degradation of organic matter (OM) by microorganisms in thawing permafrost produces greenhouse gases. Terrestrial OM is transported into fjords through hydrological runoff, but it is unclear whether the microbial mechanisms of OM degradation on land persist after soils enter marine environments, which differ greatly in conditions and microbial communities. This question is particularly relevant for low-OM soils, which dominate Arctic landscapes and are more exposed to oxidants. Here, we compared OM-degrading capacity in permafrost-affected active layer soils and adjacent fjord sediments from Kongsfjorden, Svalbard, focusing on carbohydrate-active enzymes (CAZymes), which target some of the most abundant types of organic matter in soils. Using multi-omics approaches—metagenomics, metagenome-assembled genomes (MAGs), metabolomics, metatranscriptomics, and metaproteomics—we examined CAZyme presence, distribution, and activity. Despite environmental differences, both soils and sediments harbored diverse glycoside hydrolases and polysaccharide lyases, most of which showed evidence of activity. Verrucomicrobia expressed the highest number of CAZyme transcripts, indicating that they dominated active carbohydrate degradation in fjord sediments, while Acidobacteria and Actinobacteria were more active in soils. Notably, CAZymes in fjord sediments targeted primarily soil-derived OM, and the proportions of enzymes degrading terrestrial OM, marine OM, and microbial necromass—remnants of dead microbial cells were similar across both environments. These results suggest that microbial communities in both soils and fjord sediments are equipped to degrade carbohydrates, and that burial of terrestrial-derived OM in fjord sediments may not protect it from microbial breakdown under Arctic warming.

Chukwufumnanya, Abuah [University of Tennessee, Kn↗

First degraded beams in the CEBAF injector

The electron beam degrader in the Continuous Electron Beam Accelerator Facility (CEBAF) injector at Jefferson Lab serves to generate electron beams with transverse emittance over 10x the nominal values, with the ultimate goal of using degraded electron beams to measure machine acceptance. Electron beams are degraded through multiple scattering in thin carbon foils, and maximum transverse emittance is defined through two collimating apertures. The degrader device was installed in late 2024, with commissioning and first beams on degrader targets during the 2025 physics run. We report on first operation of the degrader device. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Nuclear Physics under contract DE-AC05-06OR23177.

Sy, A. [Thomas Jefferson National Accelerator Faci↗

Materials and Approaches for Mitigation of SOFC Cathode Degradation in SOFC Power Systems

Perovskites such as doped lanthanum manganite and cobaltite have been used successfully as a cathode material in SOFC power systems operating between 700-1000°C. The electrodes, however, remain prone to degradation in presence of Cr containing gas atmosphere under systems operating conditions. Cathode in SOFCs is considered as one of the largest contributors of electrochemical performance degradations, leading to significant increase in ohmic and non-ohmic losses as well as interfacial compound formation. These degradations are mostly irreversible due to permanent changes to chemical and morphological alterations in the electrodes, resulting in the blockage of triple phase boundary (TPB) sites and decrease in oxygen reduction reactions (ORR). Fundamental mechanistic understanding has been developed to elucidate the reaction pathways of electrode poisoning in electronically conducting electrodes (LSM) as well as mixed ionic and electronically conducting electrodes (LSCF). The overall goal of this program has been identification and development of cost effective solutions to mitigate electrode degradations under “real world” systems operating conditions. The overall technological innovations and impact from this work are: The research provides an understanding of the degradation mechanism and cost-effective approaches for implementation in SOFC systems; Develop mitigation processes utilizing low cost getters using conventional synthesis and fabrication route; Develop tailored high surface area powders and coatings for high Cr capture capacity under systems operating conditions; >Developed computational models to understand mechanistic behavior; Experimentally measure rate of Cr evaporation from chromia and alumina forming alloys under SOFC operating conditions; Developed conditions to minimize Cr evaporation from balance-of-plant alloys; This innovation will support the development of getter platform to capture both intrinsic and extrinsic impurities present in air; and, Applications under wide operating temperature range (500-900°C) as well for wide high-temperature electrochemical systems (SOFC, SOEC, and OTM). The work has been successfully developed, validated experimentally and implemented. Successful technology transfer of this knowledge with industrial partners has been accomplished and the getters have been independently tested and validated under their systems operating conditions. The innovation will also find application in related high temperature electrochemical systems such as OTM and SOEC for the prevention of Cr assisted performance degradation. The proposed approach for Cr capture can also be applied to oxy-combustion and other advanced combustion techniques for the reduction of Cr vapor in the exhaust gas stream. This fundamental knowledge gained also has led to the path forward for developing advanced getters for capturing more than one contaminant in air.

01 COAL, LIGNITE, AND PEAT↗

Exploring Si Heterojunction Solar Cell Degradation: Bulk and Interface Processes Analyzed by Simulations and Experiments in Order to Develop Mitigation Strategies

The Si technology with the highest conversion efficiency is a-Si/c-Si heterojunction (HJ) PV. Its market penetration, however, is slowed by reports that fielded HJ modules degraded at twice the rate of regular c-Si modules. Our very recent work confirmed this degradation and attributed it to enhanced recombination at the a-Si/c-Si interface, caused by the slow, order-of-magnitude increase of the defect density. We propose to comprehensively explore degradation mechanisms in Si HJ cells by combining simulations and experiments. Theoretically, we will: (1) simulate structure of a-Si and a-Si/c-Si interfaces, identify defects; (2) determine statistics of energy barriers that control defect formation; (3) compute growth of defect density from the barrier distribution, and the resulting degradation of Voc. Experimentally, we will: (1) create a series of HJ-cell-representative stacks with varying layer thicknesses and deposition conditions by using PECVD tools; (2) use temperature and injection-dependent lifetime spectroscopy to determine effective lifetimes; (3) deconvolve the data to separate bulk and interface effects, and the effects of charge density and interface defects to analyze long time degradation. The goal is to identify material and device degradation mechanisms, to develop mitigation strategies for improved stability, such as the introduction of capping layers and hydrogen diffusion control.

14 SOLAR ENERGY↗

Key Degradation Products in Nitroplasticizer Thermal Aging

Upon thermal aging, nitroplasticizer (NP) can thermally degrade and release numerous degradation products depending on aging conditions. In this report, we summarize our recent findings, a library of key degradation products in the NP thermal aging is provided. The library contains 25 identified species with their corresponding MS/MS spectrum and intensity profiles, which are derived from our 44-month thermal aging experiment of NP conducted in air, nitrogen, and water at room temperature (RT), 38, 45, 55, and 64°C. To provide a comprehensive yet simplified overview of NP degradation, we summarized the proposed mechanisms of HONO elimination and decomposition, acid generation, PBNA nitrosation and nitration, acid-catalyzed hydrolyses of NP and polynitrated PBNAs, as well as the formation of NP degradants. As the last part of a series of publications and reports on the investigation of NP degradation mechanisms, this work further unfolds complex chemistry that occurs in the entire aging process of NP.

36 MATERIALS SCIENCE↗

Activity assays of NnlA homologs suggest the natural product N -nitroglycine is degraded by diverse bacteria

Linear nitramines (R–N(R′)NO 2 ; R′ = H or alkyl) are toxic compounds, some with environmental relevance, while others are rare natural product nitramines. One of these natural product nitramines is N -nitroglycine (NNG), which is produced by some Streptomyces strains and exhibits antibiotic activity towards Gram-negative bacteria. An NNG degrading heme enzyme, called NnlA, has recently been discovered in the genome of Variovorax sp. strain JS1663 ( Vs NnlA). Evidence is presented that NnlA and therefore, NNG degradation activity is widespread. To achieve this objective, we characterized and tested the NNG degradation activity of five Vs NnlA homologs originating from bacteria spanning several classes and isolated from geographically distinct locations. E. coli transformants containing all five homologs converted NNG to nitrite. Four of these five homologs were isolated and characterized. Each isolated homolog exhibited similar oligomerization and heme occupancy as Vs NnlA. Reduction of this heme was shown to be required for NnlA activity in each homolog, and each homolog degraded NNG to glyoxylate, NO 2 − and NH 4 + in accordance with observations of Vs NnlA. It was also shown that NnlA cannot degrade the NNG analog 2-nitroaminoethanol. The combined data strongly suggest that NnlA enzymes specifically degrade NNG and are found in diverse bacteria and environments. These results imply that NNG is also produced in diverse environments and NnlA may act as a detoxification enzyme to protect bacteria from exposure to NNG.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation Dynamics of Perovskite Solar Cells Under Fixed Reverse Current Injection

Previous studies of reverse-bias stability in perovskite solar cells have focused primarily on voltage controlled reverse-bias tests. Here we instead present an investigation of perovskite solar cell degradation under well-defined, constant reverse-current stress. We show that the choice of hole-transport layer dictates the dominant degradation pathway: cells using thick poly(triphenylamine) (PTAA) layers with better indium-doped tin oxide (ITO) coverage can tolerate high reverse bias but quickly undergo catastrophic breakdown under fixed reverse current near their one-sun maximum power-point. In contrast, cells modified with the phosphonic-acid interface layer MeO-2PACz, with poorer ITO coverage compared to PTAA, exhibit soft, gradual, and largely recoverable degradation, regardless of the shading conditions. For MeO-2PACz devices, degradation increases with both current magnitude and duration. Importantly, when normalized by injected charge (current times duration), lower currents applied over longer times cause more severe degradation than higher currents over shorter periods. Combining electrical measurements with spatially resolved photoluminescence imaging, we argue against shunt formation and instead support an ion- and charge-mediated interfacial electrochemical degradation mode.

Applied Physics (physics.app-ph)↗

Crater degradation on Mercury and the moon - Clues to surface evolution

A preliminary investigation was conducted regarding the variations in the morphological characteristics of Mercurian craters that appear to be associated with a degradation of fresh craters. Craters are classified according to relative states of degradation in order to provide evidence on degradation styles and rates on Mercury, and to correlate degradation with major geologic events in the history of the planet. Processes and relative rates of degradation on Mercury and the moon are also compared. Degradation trends of crater morphology are found to be parallel on Mercury and the moon. The severe destruction of interior structures in lunar craters may have resulted from more widespread distribution of ejecta due to the moon's lower gravity. The possibility is considered that the smooth plains on the surface of Mercury were formed early in the history of that planet.

Wood, C. A.↗

Thermal oxidative degradation reactions of linear perfluoroalky lethers

Thermal and thermal oxidative stability studies were performed on linear perfluoro alkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors are reported. The liner perfluoro alkylethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoro alkylether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating.

Jones, W. R., Jr.↗

Thermal oxidative degradation reactions of linear perfluoroalkyl ethers

Thermal and thermal oxidative stability studies were performed on linear perfluoroalkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors is reported. The linear perfluoroalkyl ethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoroalkyl ether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating. Previously announced in STAR as N82-26468

Jones, W. R., Jr.↗

Heat and Mass Transport from Thermally Degrading Thin Cellulosic Materials in a Microgravity Environment

Attention is given to a theoretical model describing the behavior of a thermally thin cellulosic sheet heated by external thermal radiation in a quiescent microgravity environment. This model describes thermal and oxidative degradation of the sheet and the heat and mass transfer of evolved degradation products from the heated cellulosic surface into the gas phase. Two calculations are carried out: heating without thermal degradation, and heating with thermal degradation of the sheet with endothermic pyrolysis, exothermic thermal oxidative degradation, and highly exothermic char oxidation. It is shown that pyrolysis is the main degradation reaction. Self-sustained smoldering is controlled and severely limited by the reduced oxygen supply.

Kushida, G.↗

Study of the Staebler-Wronski degradation effect in a-Si:H based p-i-n solar cell

Conversion of solar energy into electricity using environmentally safe and clean photovoltaic methods to supplement the ever increasing energy needs has been a cherished goal of many scientists and engineers around the world. Photovoltaic solar cells on the other hand, have been the power source for satellites ever since their introduction in the early sixties. For widespread terrestrial applications, however, the cost of photovoltaic systems must be reduced considerably. Much progress has been made in the recent past towards developing economically viable terrestrial systems, and the future looks highly promising. Thin film solar cells offer cost reductions mainly from their low processing cost, low material cost, and choice of low cost substrates. These are also very attractive for space applications because of their high power densities (power produced per kilogram of solar cell pay load) and high radiation resistance. Amorphous silicon based solar cells are amongst the top candidates for economically viable terrestrial and space based power generation. Despite very low federal funding during the eighties, amorphous silicon solar cell efficiencies have continually been improved - from a low 3 percent to over 13 percent now. Further improvements have been made by the use of multi-junction tandem solar cells. Efficiencies close to 15 percent have been achieved in several labs. In order to be competitive with fossil fuel generated electricity, it is believed that module efficiency of 15 percent or cell efficiency of 20 percent is required. Thus, further improvements in cell performance is imperative. One major problem that was discovered almost 15 years ago in amorphous silicon devices is the well known Staebler-Wronski Effect. Efficiency of amorphous silicon solar cells was found to degrade upon exposure to sunlight. Until now their is no consensus among the scientists on the mechanism for this degradation. Efficiency may degrade anywhere from 10 percent to almost 50 percent within the first few months of operation. In order to improve solar cell efficiencies, it is clear that the cause or causes of such degradation must be found and the processing conditions altered to minimize the loss in efficiency. This project was initiated in 1987 to investigate a possible link between metallic impurities, in particular, Ag, and this degradation. Such a link was established by one of the NASA scientists for the light induced degradation of n+/p crystalline silicon solar cells.

Naseem, H. A.↗

Degradation of selected terrestrial and Martian impact craters

The history of degradation of 50,000-yr-old 1.2-km-diam Meteor Crater in Arizona is defined using field mapping, and the degradation states of the progressively more degraded 68,000-yr-old 1.8-km-diam Lonar Crater in Indiana and 0.5-3.0 Myr old 1.75-km-diam Talemzane Crater in Algeria are assessed using air photos. The results on these terrestrial craters are then compared with the gradational morphology associated with craters in southern Ismenius Lacus on Mars, in order to develop first-order constraints on gradational activity. Common degradation signatures associated with craters on both planets are described. These signatures are used to assemble a first-order degradational sequence for the terrestrial craters that is then compared with the Martian degradational signatures to infer past processes and climate.

Grant, John A.↗

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Cunningham, Ronan A.↗

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Cunningham, Ronan A.↗