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NASA NTRS1983

Ultraviolet observations of the transient X-ray sources A0535 + 26 and A0620-00

Observations of A0535+26 (HDE 245770) by the ANS in September 1975 and March 1976 when it was at the X-ray low state are discussed. Also observed were 58 early-type stars lying within 10 deg of HDE 245770; these stars are used to derive a localized extinction curve. On the basis of the depth of the 2200 A interstellar absorption feature observed in the ANS flux distribution of HDE 245770 and the shape of the localized extinction curve, an E(B-V) = 0.72 is derived for HDE 245770. Observations were made of this system during its X-ray flare-up (October 1980) and quiescent (November 1981) states by the IUE. It is noted that the fine error sensor on board the IUE detected an increase in the optical brightness of HDE 245770 during the X-ray outburst. This greatly corroborates the identification of HDE 245770 as the optical counterpart of A0535+26. No significant change in the absorption-line profiles during the X-ray high and low periods is found, indicating that there was no significant increase in the stellar wind density when the X-ray flare-up occurred. The UV continuum level increased by less than 6 percent when it was near peak X-ray luminosity. The UV spectrum of HDE 245770 suggests that it is a B0 V or a B0 III star with its dereddened continuum slope slightly in favor of being a giant.

Wu, C.-C.↗

NASA NTRS1987

Finite element models of non-Newtonian crater relaxation

The effects of a non-Newtonian rheology on the profiles of relaxing craters (such as those seen on the surfaces of the icy Galilean and Saturnian satellites) were studied. Two-dimensional finite element simulations of non-Newtonian viscous flow were performed, and the results were compared with those associated with Newtonian rheology. Viscous relaxation of craters in a non-Newtonian medium was significantly different from that in a Newtonian medium. Crater rims are observed to relax at a more rapid rate in a non-Newtonian region as a result of the movement of the low viscosity region to underneath the crater rim after the initial relaxation of the bowl. Significant differences are also found when central depth is plotted as a function of time. For a Newtonian medium, crater relaxation is exponential in form. In contrast, non-Newtonian crater relaxation is initially rapid, in response to the large initial stresses and small viscosities; however, as stresses decrease, this relaxation becomes extremely gradual.

Thomas, Paul J.↗

NASA NTRS2001

Quantifying Residual Stresses by Means of Thermoelastic Stress Analysis

This study focused on the application of the Thermoelastic Stress Analysis (TSA) technique as a tool for assessing the residual stress state of structures. TSA is based on the fact that materials experience small temperature changes when compressed or expanded. When a structure is cyclically loaded, a surface temperature profile results which correlates to the surface stresses. The cyclic surface temperature is measured with an infrared camera. Traditionally, the amplitude of a TSA signal was theoretically defined to be linearly dependent on the cyclic stress amplitude. Recent studies have established that the temperature response is also dependent on the cyclic mean stress (i.e., the static stress state of the structure). In a previous study by the authors, it was shown that mean stresses significantly influenced the TSA results for titanium- and nickel-based alloys. This study continued the effort of accurate direct measurements of the mean stress effect by implementing various experimental modifications. In addition, a more in-depth analysis was conducted which involved analyzing the second harmonic of the temperature response. By obtaining the amplitudes of the first and second harmonics, the stress amplitude and the mean stress at a given point on a structure subjected to a cyclic load can be simultaneously obtained. The experimental results showed good agreement with the theoretical predictions for both the first and second harmonics of the temperature response. As a result, confidence was achieved concerning the ability to simultaneously obtain values for the static stress state as well as the cyclic stress amplitude of structures subjected to cyclic loads using the TSA technique. With continued research, it is now feasible to establish a protocol that would enable the monitoring of residual stresses in structures utilizing TSA.

Gyekenyesi, Andrew L.↗

NASA NTRS2003

Sunlight Transmission through Desert Dust and Marine Aerosols: Diffuse Light Corrections to Sun Photometry and Pyrheliometry

Desert dust and marine aerosols are receiving increased scientific attention because of their prevalence on intercontinental scales and their potentially large effects on Earth radiation and climate, as well as on other aerosols, clouds, and precipitation. The relatively large size of desert dust and marine aerosols produces scattering phase functions that are strongly forward- peaked. Hence, Sun photometry and pyrheliometry of these aerosols are more subject to diffuse-light errors than is the case for smaller aerosols. Here we quantify these diffuse-light effects for common Sun photometer and pyrheliometer fields of view (FOV), using a data base on dust and marine aerosols derived from (1) AERONET measurements of sky radiance and solar beam transmission and (2) in situ measurements of aerosol layer size distribution and chemical composition. Accounting for particle non-sphericity is important when deriving dust size distribution from both AERONET and in situ aerodynamic measurements. We express our results in terms of correction factors that can be applied to Sun photometer and pyrheliometer measurements of aerosol optical depth (AOD). We find that the corrections are negligible (less than approximately 1% of AOD) for Sun photometers with narrow FOV (half-angle eta less than degree), but that they can be as large as 10% of AOD at 354 nm wavelength for Sun photometers with eta = 1.85 degrees. For pyrheliometers (which can have eta up to approximately 2.8 degrees), corrections can be as large as 16% at 354 nm. We find that AOD correction factors are well correlated with AOD wavelength dependence (hence Angstrom exponent). We provide best-fit equations for determining correction factors from Angstrom exponents of uncorrected AOD spectra, and we demonstrate their application to vertical profiles of multiwavelength AOD.

Russell, P. B.↗

NASA NTRS1993

Mechanism of incipient oxidation of bulk chemical vapor deposited Si3N4

X-ray photoelectron spectroscopy was employed, in conjunction with ion bombardment, to analyze the chemical composition profile across thin (less than 50 nm) oxide films on chemically vapor deposited Si3N4. The thermal oxides were grown in dry oxygen at 1100 C on samples with or without native oxide film (formed in room air). The results show that the thermal oxidation product was silicon oxynitride of graded N:O ratio, and that the presence of a native oxide film promotes the formation of a SiO2 crust over the oxynitride. It is proposed that the fundamental mechanism of Si3N4 oxidation is progressive O-for-N substitution in the silicon oxynitride unit tetrahedron, which is best designated SiN(2-x)O(2+x), where x is also an index of depth. The corresponding equation for nonstoichiometric oxidation of Si3N4 describes a bulk (rather than an interface) reaction process, with significant implications for O2 and N2 fluxes and diffusivities.

Ogbuji, L. U. T.↗

DOE OSTI2021

Lithium-Ion Battery Life Model with Electrode Cracking and Early-Life Break-in Processes

This paper develops a physically justified reduced-order capacity fade model from accelerated calendar- and cycle-aging data for 32 lithium-ion (Li-ion) graphite/nickel-manganese-cobalt (NMC) cells. The large data set reveals temperature-, charge C-rate-, depth-of-discharge-, and state of charge (SOC)-dependent degradation patterns that would be unobserved in a smaller test matrix. Model structure is informed by incremental capacity analysis that shows loss of lithium inventory and cathode-material loss as the dominant capacity fade mechanisms. The model includes terms attributable to solid-electrolyte interface (SEI) growth, electrode cracking, cycling-driven acceleration of SEI growth, and "break-in" mechanisms that slightly decrease or increase available Li inventory early in life. The study explores what mathematical couplings of these mechanisms best describe calendar aging, cycle aging, and mixed calendar/cycle aging. Various approaches are discussed for extracting relevant stress factors from complex cycling profiles to predict lifetime during real-world battery loads using models trained on constant-current laboratory test results. The complexity of the present human-driven model identification process motivates future work in machine learning to more widely search and statistically discern the optimal model that correctly extrapolates capacity fade based on physical knowledge.

25 ENERGY STORAGE↗

NASA NTRS2010

Analyzing the Effect of Intraseasonal Meteorological Variability and Land Cover on Aerosol-Cloud Interactions During the Amazonian Biomass Burning Season

High resolution aerosol, cloud, water vapor, and atmospheric profile data from the Moderate Resolution Imaging Spectroradiometer (MODIS) are utilized to examine the impact of aerosols on clouds during the Amazonian biomass burning season in Rondnia, Brazil. It is found that increasing background column water vapor (CWV) throughout this transition season between the Amazon dry and wet seasons exerts a strong effect on cloud properties. As a result, aerosol-cloud correlations should be stratified by column water vapor to achieve a more accurate assessment of the effect of aerosols on clouds. Previous studies ignored the systematic changes to meteorological factors during the transition season, leading to possible misinterpretation of their results. Cloud fraction is shown generally to increase with aerosol optical depth (AOD) for both low and high values of column water vapor, whereas the relationship between cloud optical depth (COD) and AOD exhibits a different relationship. COD increases with AOD until AOD approx. 0.25 due to the first indirect (microphysical) effect. At higher values of AOD, COD is found to decrease with increasing AOD, which may be due to: (1) the inhibition of cloud development by absorbing aerosols (radiative effect) and/or (2) a retrieval artifact in which the measured reflectance in the visible is less than expected from a cloud top either from the darkening of clouds through the addition of carbonaceous biomass burning aerosols or subpixel dark surface contamination in the measured cloud reflectance. If (1) is a contributing mechanism, as we suspect, then a linear relationship between the indirect effect and increasing AOD, assumed in a majority of GCMs, is inaccurate since these models do not include treatment of aerosol absorption in and around clouds. The effect of aerosols on both column water vapor and clouds over varying land surface types is also analyzed. The study finds that the difference in column water vapor between forest and pasture is not correlated with aerosol loading, supporting the assumption that temporal variation of column water vapor is primarily a function of the larger-scale meteorology. However, a difference in the response of cloud fraction to increasing AOD is observed between forest and pasture. This suggests that dissimilarities between other meteorological factors, such as atmospheric stability, are likely to have an impact on aerosol-cloud correlations between different land-cover types.

TenHoeve, J. E.↗

NASA NTRS2020

Terrestrial Planets Comparative Climatology (TPCC) mission concept

The authors and co-signers of the Terrestrial Planets Comparative Climatology (TPCC) mission concept white paper advocate that planetary science in the next decade would greatly benefit from comparatively studying the fundamental behavior of the atmospheres of Venus and Mars, contemporaneously and with the same instrumentation, to capture atmospheric response to the same solar forcing, and with a minimum of instrument-related variability. NASA’s vision is to understand the effects of the Sun on the solar system and the potential for life elsewhere (Obj,1.1 of [1]). This vision directly motivates the study of terrestrial climate histories and evolution, with the ultimate goal of understanding what factors allow the emergence and sustainability of life/biosphere. It is widely accepted that Venus, Mars, and Earth were formed at the same time and in the same neighborhood of the solar nebula [2,3], and had water—a necessary ingredient for life. In spite of strong overlap in the atmospheric composition of these planets, their current climatic states are vastly different. While Earth retains water, both Mars and Venus’ surfaces are now dry. The manner in which these terrestrial bodies evolved, and whether Mars or Venus currently hosts or previously hosted life, are fundamental mysteries in planetary science. As such, the TPCC mission concept has been developed.The TPCC guiding science goals are:(1) to understand Venus’ evolutionary history compared to Mars and Earth, and (2) to elucidate the driving forces and mechanisms of global circulation at Mars and Venus. These goals address the science question: Why have Mars’ and Venus’ climates evolved so differently from each other and from Earth’s? Furthermore, a greater depth of understanding our own solar system, enables us to understand the variability and likelihood of habitable conditions within extra-solar planetary systems.We suggest a mission architecture and payload that would determine the noble gas content and isotopic ratios, including the D/H ratio, at Venus with sufficient accuracy to identify the timeline of Venus’ climatic evolution for comparison with Mars. In addition, our concept would systematically “follow the energy” at Mars and Venus, in order to establish how solar forcing on the two atmospheric systems leads to the current balance of dynamical, chemical, and radiative processes responsible for each planet’s climatic state.This would include acquisition of the first global atmospheric wind profiles on either planet;global, continuous profiles of aerosols, gases, and water vapor at vertical resolutions higher than any previous mission;and regular UV and IR night glow observations tracking global circulation on both planets.To increase the fidelity of the planned planetary comparisons, the TPCC mission concept baseline (estimated to be New Frontiers Class)would send a single spacecraft to visit one planet and then the next, allowing measurements of each planet with the same instrumentation within similar parts of the solar cycle. The concept uses commercial solar-electric propulsion (SEP; e.g., [4])similar to the Psyche mission [5], plus a probesent deep into Venus’ atmosphere(e.g., LLISSE concept; [6]).Alternatively, “twin” spacecraft (with added probe to the Venus craft),developed at the same time,and launched close in time,would increase the overlap in operation periods and should also be studied. Either architecture is a timely alternative to independently developed and launched spacecraft payloads, which ultimately are more costly and difficult to inter-calibrate.

Leslie K. Tamppari↗

DOE OSTI2022

Freshwater Input and Vertical Mixing in the Canada Basin’s Seasonal Halocline: 1975 versus 2006–12

Abstract The Arctic seasonal halocline impacts the exchange of heat, energy, and nutrients between the surface and the deeper ocean, and it is changing in response to Arctic sea ice melt over the past several decades. Here, we assess seasonal halocline formation in 1975 and 2006–12 by comparing daily, May–September, salinity profiles collected in the Canada Basin under sea ice. We evaluate differences between the two time periods using a one-dimensional (1D) bulk model to quantify differences in freshwater input and vertical mixing. The 1D metrics indicate that two separate factors contribute similarly to stronger stratification in 2006–12 relative to 1975: 1) larger surface freshwater input and 2) less vertical mixing of that freshwater. The larger freshwater input is mainly important in August–September, consistent with a longer melt season in recent years. The reduced vertical mixing is mainly important from June until mid-August, when similar levels of freshwater input in 1975 and 2006–12 are mixed over a different depth range, resulting in different stratification. These results imply that decadal changes to ice–ocean dynamics, in addition to freshwater input, significantly contribute to the stronger seasonal stratification in 2006–12 relative to 1975. These findings highlight the need for near-surface process studies to elucidate the impact of lateral processes and ice–ocean momentum exchange on vertical mixing. Moreover, the results may provide insight for improving the representation of decadal changes to Arctic upper-ocean stratification in climate models that do not capture decadal changes to vertical mixing.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1980

The Apollo 17 drill core - Chemistry of size fractions and the nature of the fused soil component

It is shown that the Apollo 17 drill core 70009-70001 is heterogeneous with depth, containing five stratigraphic units, and has a bulk soil chemistry governed by the coarse fractions because of their greater weight proportions. The four components (1) KREEP, (2) anorthositic gabbro, (3) mare basalt, and (4) orange glass are used to model the compositions of the coarse and fine fractions of the entire drill core. It is found that the chemistry of the fused soil component in the five stratigraphic units is more similar to the chemistry of the fine, less than 20-micron fractions than the coarse fraction, suggesting that agglutinates may prefferentially meld and replicate the chemistry of the finer size fractions. The sources of Zn are the orange/black glasses, and the Zn profile is anticorrelated with the maturity index of Morris et al (1979), indicating the liberation of Zn during soil maturation.

Laul, J. C.↗

NASA NTRS1981

Effects of artificially produced defects on film thickness distribution in sliding EHD point contacts

The effects of artificially produced dents and grooves on the elastohydrodynamic (EHD) film thickness profile in a sliding point contact were investigated by means of optical interferometry. The defects, formed on the surface of a highly polished ball, were held stationary at various locations within and in the vicinity of the contact region while the disk was rotating. It is shown that the defects, having a geometry similar to what can be expected in practice, can dramatically change the film thickness which exists when no defects are present in or near the contact. This change in film thickness is mainly a function of the position of the defects in the inlet region, the geometry of the defects, the orientation of the defects in the case of grooves, and the depth of the defect relative to the central film thickness.

Cusano, C.↗

DOE OSTI2021

Spatially Quasi-Periodic Water Waves of Infinite Depth

Abstract We formulate the two-dimensional gravity-capillary water wave equations in a spatially quasi-periodic setting and present a numerical study of solutions of the initial value problem. We propose a Fourier pseudo-spectral discretization of the equations of motion in which one-dimensional quasi-periodic functions are represented by two-dimensional periodic functions on a torus. We adopt a conformal mapping formulation and employ a quasi-periodic version of the Hilbert transform to determine the normal velocity of the free surface. Two methods of time-stepping the initial value problem are proposed, an explicit Runge–Kutta (ERK) method and an exponential time-differencing (ETD) scheme. The ETD approach makes use of the small-scale decomposition to eliminate stiffness due to surface tension. We perform a convergence study to compare the accuracy and efficiency of the methods on a traveling wave test problem. We also present an example of a periodic wave profile containing vertical tangent lines that is set in motion with a quasi-periodic velocity potential. As time evolves, each wave peak evolves differently, and only some of them overturn. Beyond water waves, we argue that spatial quasi-periodicity is a natural setting to study the dynamics of linear and nonlinear waves, offering a third option to the usual modeling assumption that solutions either evolve on a periodic domain or decay at infinity.

Wilkening, Jon (ORCID:0000000327827596)↗

NASA NTRSDate not supplied

Observation of Stratospheric Intrusions and Ozone Transport using CrIS SiFSAP Products

The Single Field of View (SFOV) ozone (O3) profiles derived from the Cross-track Infrared Sounder (CrIS) onboard Suomi National Polar-Orbiting Partnership (SNPP), with a high horizontal resolution of approximately 14 km at nadir and good sensitivity to O3 in the upper troposphere and lower stratosphere (UTLS), provide a prominent opportunity to examine stratosphere to troposphere (STT) transport. A process-oriented analysis was performed to examine the fine-scale features of a stratospheric intrusion (SI) event on June 11-13, 2017 in the southwestern US using the CrIS SFOV products together with wind and potential velocity (PV) from models. It was found that the location and strength of O3 enhancement correlate well with the PV contours, and the intrusion depth can be characterized using the vertical cross-sections of O3 and relative humidity (RH). In addition, the capability to use total column ozone (TCO) to identify SI events was confirmed through analysis of TCO from CrIS SFOV and other satellite and reanalysis products. The ozone/PV ratio was derived using SFOV O3 and model PV, and the values, ranging from 23.2 to 35.8 ppbv PVU-1 (1 PV unit (PVU) = 10-6 km2 kg-1 s-1), are in the lower end of previous estimations. These results demonstrate the advantages of the SFOV products in monitoring the fine-scale ozone transport and thermodynamic structure of SI events, as well as their potential value for weather and climate study.

Xiaozhen Xiong↗

DOE OSTI2020

An Improved Model For Determining Salinity Recharge Time for Deep Borehole Disposal - 20405

In a previous publication (K. P. Travis, D. Burley and F. G. F. Gibb, WM2017 Conference, Phoenix Arizona paper no. 17480) we introduced a numerical model to estimate the time it would take for a pressure perturbation to subside following its creation from the construction of a deep geological borehole in water-saturated rock. The model was based on the notion of a point source of momentum - a solution of the time-dependent pressure-diffusion equation. Using the model, we estimated that it would take on the order of 10 k years for physical equilibrium to become re-established following the sinking of a 5 km borehole in granite. The significance of such a model is that it places an upper bound on the lifetime required of a borehole sealing system - a necessary input to a borehole post-closure safety case assessment. No engineered sealing system has ever been devised which is capable of retaining its sealing properties for 10 half-lives of long-lived radioisotopes in spent fuel or high-level waste. One of the key advantages of disposing of nuclear waste via Deep Borehole Disposal (DBD) is the natural sealing provided by density stratified groundwater. Upon sinking of a borehole, and subsequent filling with fresh water, brine or drilling mud, this natural barrier may be temporarily damaged. Over time, fresh brine from the far-field will flow towards or away from the hole (driven by a pressure gradient) and will eventually re-establish the original salinity gradient. It follows that the engineered seals need last only as long as the time required for this salinity gradient to reset itself. One of the limitations of our previous model was the use of a static boundary condition on the borehole wall. The model used a boundary pressure which varied quadratically with depth (arising from differences between the pressure of a column of fresh water in the borehole and that of a column of brine in the host rock). However as brine replaces fresh water in the borehole (driven by a pressure gradient), the boundary function must change with time. We now introduce an improved model which takes this time dependent boundary condition into account. The model also takes into account the time taken for a mixture of brine and fresh water to re-establish chemical equilibrium through the process of diffusion. The paper contains the mathematical details of our new iterative model as well as results showing the time taken to reach steady state, and concentration profiles for the components of the brine-filled borehole as a function of time together with a discussion on the implications of the results for developing a post-closure safety assessment for DBD. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Generating Co-expression Networks for Three Cyanobacteria: Synechococcus sp. PCC 7942, Synechococcus sp. PCC 7002, Synechocystis sp. PCC 6803

Cyanobacteria are photosynthetic organisms capable of high growth rate and represent a promising bioplatform for harnessing the sun’s energy to make biofuel. Additionally, the process of photosynthesis absorbs CO2 from the environment. Understanding the metabolic processes involved in photosynthesis could lead to solutions to the recent rise of CO2 concentration in Earth’s atmosphere and the associated climate change. More research on the transcriptional regulation of these cells is needed to learn how to harness the untapped potential of cyanobacteria for these applications. Transcriptional analysis via RNA-seq provides an understanding of how gene expression changes at the mRNA level under diverse growing conditions. I systematically collected and analyzed RNA-Seq data obtained under a variety of conditions and available on the NCBI database for three cyanobacteria model organisms: Synechococcus elongatus sp. PCC 7942, Synechococcus sp. PCC 7002, and Synechocystis sp. PCC 6803. For each organism, the data was mapped to a reference genome to characterize the RNA expression profile. Samples were checked for quality based on the number of reads and the correlation of the expression profile between labeled replicates. All samples were transformed into transcripts per million reads, followed by a log transformation to account for the wide range of sample sizes. Gene co-expression networks were generated and analyzed for each species using Cytoscape. These networks provide a base level of gene expression for each species. The network topology and high-betweeness nodes of these networks need to be analyzed further to provide insight on potential ways to harness cyanobacteria genetics. Additionally, these datasets can be used together to form a core genome network analysis- one that includes only the genes that are homologous between the three species. This project has prepared the way for a more in-depth study on photosynthetic microbes on a genetic level.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

A Distributed Temperature Profiling System for Vertically and Laterally Dense Acquisition of Soil and Snow Temperature: Supporting Data

This dataset was used to assess the potential of a Distributed Temperature Profiling System developed and presented in the article named "A Distributed Temperature Profiling System for Vertically and Laterally Dense Acquisition of Soil and Snow Temperature" and submitted to Cryosphere. There are three comma-delimited data files (.csv). Each of them contains snow or soil temperature with times (UTC) in the first column and temperature at various vertical distance from the ground surface (positive means in air/snow) or below the ground surface (negative means in soil). The measurements were acquired every 15 minutes. Data collected at the East River, Colorado site with two probes: 1) measuring air/snow temperature from 1.1 m above the ground surface to the ground surface (with 5 or 10 cm spacing between sensors) and 2) measuring soil temperature from the ground surface to 0.7 m depth (with 5 or 10 cm spacing between sensors). Data collected at the Teller road (mile 27) site near Nome, Alaska with one probe: measuring soil temperature from 5 cm above the ground surface to 1.05 m depth (with 5 or 10 cm spacing between sensors). Additional metadata included in *.csv and *.pdf files. NGEE Arctic Project Summary: The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering

Donor-acceptor (D-A) conjugated polymers are high-performance organic electronic materials that exhibit complex aggregation behavior. Understanding the solution state conformation and aggregation of conjugated polymers is crucial for controlling morphology during thin-film deposition and the subsequent electronic performance. However, a precise multiscale structure of solution state aggregates is lacking. Here, we present an in-depth small-angle X-ray scattering (SAXS) analysis of the solution state structure of an isoindigo-bithiophene-based D-A polymer (PII-2T) in chlorobenzene and decane as our primary system. Modeling the system as a combination of hierarchical fibrillar aggregates mixed with dispersed polymers, we extract information about conformation and multiscale aggregation and also clarify the physical origin of features often observed but unaddressed or misinterpreted in small-angle scattering patterns of conjugated polymers. The persistence length of the D-A polymer extracted from SAXS agrees well with a theoretical model based on the dihedral potentials. Additionally, we show that the broad high q structure factor peak seen in scattering profiles can be attributed to lamellar stacking occurring within the fibril aggregates and that the low q aggregate scattering is strongly influenced by the polymer molecular weight. Overall, the SAXS profiles of D-A polymers in general exhibit a sensitive dependence on the co-existence of fibrillar aggregate and dispersed polymer chain populations. We corroborate our findings from SAXS with electron microscopy of freeze-dried samples for direct imaging of fibrillar aggregates. Finally, we demonstrate the generality of our approach by fitting the scattering profiles of a variety of D-A polymers based on thieno-isoindigo (PTII-2T), diketopyrrolopyrrole (DPP2T-TT, DPP-BTZ, PDPP2FT-C- 16 ), naphthalenediimide (P(NDI2OD-T2)), and a conjugated block copolymer P3HT-b-DPPT-T. The results presented here establish a picture of the D-A polymer solution state structure and provide a general method of interpreting and analyzing their scattering profiles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

On the differences in the vertical distribution of modeled aerosol optical depth over the southeastern Atlantic

Abstract. The southeastern Atlantic is home to an expansive smoke aerosol plume overlying a large cloud deck for approximately a third of the year. The aerosol plume is mainly attributed to the extensive biomass burning activities that occur in southern Africa. Current Earth system models (ESMs) reveal significant differences in their estimates of regional aerosol radiative effects over this region. Such large differences partially stem from uncertainties in the vertical distribution of aerosols in the troposphere. These uncertainties translate into different aerosol optical depths (AODs) in the planetary boundary layer (PBL) and the free troposphere (FT). This study examines differences of AOD fraction in the FT and AOD differences among ESMs (WRF-CAM5, WRF-FINN, GEOS-Chem, EAM-E3SM, ALADIN, GEOS-FP, and MERRA-2) and aircraft-based measurements from the NASA ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) field campaign. Models frequently define the PBL as the well-mixed surface-based layer, but this definition misses the upper parts of decoupled PBLs, in which most low-level clouds occur. To account for the presence of decoupled boundary layers in the models, the height of maximum vertical gradient of specific humidity profiles from each model is used to define PBL heights. Results indicate that the monthly mean contribution of AOD in the FT to the total-column AOD ranges from 44 % to 74 % in September 2016 and from 54 % to 71 % in August 2017 within the region bounded by 25∘ S–0∘ N–S and 15∘ W–15∘ E (excluding land) among the ESMs. ALADIN and GEOS-Chem show similar aerosol plume patterns to a derived above-cloud aerosol product from the Moderate Resolution Imaging Spectroradiometer (MODIS) during September 2016, but none of the models show a similar above-cloud plume pattern to MODIS in August 2017. Using the second-generation High Spectral Resolution Lidar (HSRL-2) to derive an aircraft-based constraint on the AOD and the fractional AOD, we found that WRF-CAM5 produces 40 % less AOD than those from the HSRL-2 measurements, but it performs well at separating AOD fraction between the FT and the PBL. AOD fractions in the FT for GEOS-Chem and EAM-E3SM are, respectively, 10 % and 15 % lower than the AOD fractions from the HSRL-2. Their similar mean AODs reflect a cancellation of high and low AOD biases. Compared with aircraft-based observations, GEOS-FP, MERRA-2, and ALADIN produce 24 %–36 % less AOD and tend to misplace more aerosols in the PBL. The models generally underestimate AODs for measured AODs that are above 0.8, indicating their limitations at reproducing high AODs. The differences in the absolute AOD, FT AOD, and the vertical apportioning of AOD in different models highlight the need to continue improving the accuracy of modeled AOD distributions. These differences affect the sign and magnitude of the net aerosol radiative forcing, especially when aerosols are in contact with clouds.

54 ENVIRONMENTAL SCIENCES↗