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Development of Additive Manufacturing Technologies for 3D Printing of Spacecraft Heat Shields

Introduction: Ablative heat shields are an enabling technology for entry into planetary atmospheres. From the PICA heatshields used for several Mars rovers to the carbon phenolic material used for Galileo’s Jupiter entry probe, the heat shield manages the heat load transferred to the payload, protecting the sensitive scientific instruments carried on entry probes. The Additive Manufacturing of Thermal Protection Systems (AMTPS) project, an Early Career Initiative (ECI) funded by NASA’s Space Technology Mission Directorate and led by NASA Johnson Space Center, seeks to develop materials and processes for 3D printing ablative heat shields for spacecraft. Current methods for producing ablative heat shields are extremely labor intensive and re-quire extensive hands-on processes and quality control characterization. Additive manufacturing (AM) offers the possibility of reduced production times, improved reliability, and enhanced performance via graded compositions. Costs will also be reduced by reducing the time and labor required for heat shield production. Direct integration of the heat shield onto the structure during processing simplifies integration and reduces risk. Material Development: A critical challenge for the project is development of a material system that can (1) be printed in a near-net shape process and (2) perform well as an ablator. Achieving printability requires the material to flow under applied pressure, but maintain its shape once extruded from the printer nozzle. Ablative performance is measured by a multitude of markers, including char yield, char strength, thermal conductivity, and recession rate. Furthermore, there are several mechanical and thermal property considerations for vehicle integration including coefficient of thermal expansion (CTE) and residual stress. AM technology will be leveraged to grade the material formulation and properties through the thickness of the heat shield, an architecture not possible with current manufacturing processes. To this end, “robust” material formulations have been pre-pared with higher density for use on the surface where most ablation will occur. “Insulative” material formulations, with lower density and lower thermal conductivity, are prepared for use in the depth of the heat shield. This graded architecture will re-duce the overall mass of the heat shield and reduce costs and/or increase scientific payload capacities. To achieve a material system with the required properties, multiple resins have been investigated in collaboration with NASA Ames Research Center. To tune printability and performance, resin additives were studied to improve flexibility of the cured material while maintaining acceptable ablative performance. Material coupons were printed and studied via a suite of mechanical and thermal characterization methods. Arc jet testing was conducted at NASA Ames Research Center to evaluate ablative performance and thermal protection under conditions expected in atmospheric entry. Manufacturing Scale-Up: A partnership with Oak Ridge National Laboratory (ORNL) aims to enable full-scale fabrication of a 3D printed heat shield. Leveraging expertise in manufacturing and 3D printing at ORNL, a mid-scale manufacturing demonstration unit will be built and tested, using a dual-layer ablative system printed directly onto the titanium structure. Work on robotic system integration is ongoing and efforts to scale up material mixing with a material compound will ensure accurate and homogenous composition. Flight Test: A hypersonic sub-orbital flight test will provide a rigorous test of material performance ranging from ablation, thermal management, and mechanical integrity. Design of the capsule has taken place in collaboration with the University of Kentucky. Data collected from the flight will inform future design efforts in material formulation, printing methodology, and heat shield-capsule integration.

additive manufacturing↗
NASA NTRS2016

Comparison of Key Absorption and Optical Properties Between Pure and Transported Anthropogenic Dust over East and Central Asia

Asian dust particulate is one of the primary aerosol constituents in the Earth-atmosphere system that exerts profound influences on environmental quality, human health, the marine biogeochemical cycle, and Earth's climate. To date, the absorptive capacity of dust aerosol generated from the Asian desert region is still an open question. In this article, we compile columnar key absorption and optical properties of mineral dust over East and Central Asian areas by utilizing the multiyear quality-assured datasets observed at 13 sites of the Aerosol Robotic Network (AERONET). We identify two types of Asian dust according to threshold criteria from previously published literature. (1) The particles with high aerosol optical depth at 440 nm (AOD(440) > or = 0.4) and a low Angstrom wavelength exponent at 440-870 nm (alpha < 0.2) are defined as Pure Dust (PDU), which decreases disturbance of other non-dust aerosols and keeps high accuracy of pure Asian dust. (2) The particles with AOD(440) > or = 0.4 and 0.2 < alpha < 0.6 are designated as Transported Anthropogenic Dust (TDU), which is mainly dominated by dust aerosol and might mix with other anthropogenic aerosol types. Our results reveal that the primary components of high AOD days are predominantly dust over East and Central Asian regions, even if their variations rely on different sources, distance from the source, emission mechanisms, and meteorological characteristics. The overall mean and standard deviation of single-scattering albedo, asymmetry factor, real part and imaginary part of complex refractive index at 550 nm for Asian PDU are 0.935 +/- 0.014, 0.742 +/- 0.008, 1.526 +/- 0.029, and 0.00226 +/- 0.00056, respectively, while corresponding values are 0.921 +/- 0.021, 0.723 +/- 0.009, 1.521 +/- 0.025, and 0.00364 +/- 0.0014 for Asian TDU. Aerosol shortwave direct radiative effects at the top of the atmosphere (TOA), at the surface (SFC), and in the atmospheric layer (ATM) for Asian PDU (alpha < 0.2) and TDU (0.2 < alpha < 0.6) computed in this study, are a factor of 2 smaller than the results of Optical Properties of Aerosols and Clouds (OPAC) mineral-accumulated (mineral-acc.) and mineral-transported (mineral-tran.) modes. Therefore, we are convinced that our results hold promise for updating and improving accuracies of Asian dust characteristics in present-day remote sensing applications and regional or global climate models.

Bi, Jianrong↗
NASA NTRS1976

Missile impact craters (White Sands Missile Range, New Mexico) and applications to lunar research: Contributions to astrogeology

Craters in natural materials at White Sands Missile Range, N. Mex., were produced by the impact of high-velocity to hypervelocity missiles traveling along oblique trajectories with kinetic energies between 2.1 and 81 × 1014 ergs. The oblique impacts produce craters 2 to 10 m across with morphologies and ejecta that are bilaterally symmetrical with respect to the plane of the missile trajectory. Rims are high and the amount of ejecta large in down-trajectory and lateral directions, whereas rims are low to nonexistent and ejecta thin to absent up-trajectory. Symmetry development and modifications of the symmetry are a function of target material, local topography, and angle of impact. Seven mappable units can be recognized in and around the craters. Three of these are ejecta: thick ejecta near the crater, thin to discontinuous ejecta at greater distances, and scattered ejecta at the greatest distances to the limit of throwout. These ejecta units may be absent on the up-trajectory side; if present, they are rarely as thick or continuous as on other sides of the crater. Three units are target materials: undeformed target material exposed in local patches through thin to discontinuous ejecta and everywhere between the fragments of scattered ejecta, tilted and broken target material exposed in upper crater walls, and shattered and fractured target material exposed on the up-trajectory crater wall. The seventh unit is slope material composed of talus and fallback within the crater. Development, character, and exposure of these units varies chiefly with the target material. Ejecta from the craters is chiefly broken but relatively undeformed target material that may range in size from very fine grained debris to large blocks. Where the target is porous, significant amounts of the ejecta are composed of sheared and compressed fragments, some coated with dark layers of mixed projectile pieces, powder, and fused metal mixed with crushed target material. For layered targets, the original stratigraphic sequence is crudely preserved and in inverted order in thick ejecta. Secondary impact craters are produced by the impact of ejected fragments when the surrounding surface materials are sufficiently weak. A wide variety of secondary impact crater relations may result. Secondary craters nearest the primary crater have blocks in them that are larger than or the same size as the crater they produced. Farther from the primary crater, the fragments are generally smaller than the secondary crater and are ejected from it. Excavation of four craters revealed a mixed breccia beneath the crater floor composed of missile pieces, sheared and compressed target material, and crushed debris. Banded, disaggregated target material and nonmixed breccia surrounded the mixed breccia, and these breccias were surrounded by a zone of conjugate fractures. Beneath the ejecta on the lateral and down-trajectory crater flanks, the target materials were tilted upward and broken. Up-trajectory, open fractures and downward displacement occurred in two of the craters. No displacement was observed for the other two. Beneath the down-trajectory rims of craters with distinct layering, overturned synclines were observed. Missile breakup and behavior during cratering are a function of target and missile properties. Missile breakup depends on missile velocity and is most extensive at high velocities, where the missile is fragmented, powdered, and partly fused. Burial of missile or its fragmented, powdered, and fused remains is greatest for porous targets and least for dense cohesive targets. For very porous targets, camouflet structures containing the fragmented missile may form. Least squares fit to the data on craters in dry to moist targets indicate V(a) = 10^(-11.433)E(p)^(1.205) where V(a) is the volume of the apparent crater and E(p) is the kinetic energy of the missile. This equation is consistent with expectations of the equations relating apparent depth and radius to kinetic energy. Extrapolation of displaced masses and kinetic energies for laboratory impacts with sand and rock converge near 10^(15) to 10^(16) ergs, where the extrapolations are near the data on missile impact craters, corrected for impact angle. Displaced masses of craters produced by missile impacts and by chemical explosives with small scaled depths of burial are about the same when the kinetic energies of the missiles (corrected for angle of impact) are equal to the TNT equivalent energy of the explosive. The problem of equivalent scaled depth of burst for an impact crater is complicated and not entirely resolved, however. Both missile impact craters and chemical explosive craters in water-saturated targets are larger than their counterparts in dry to moist materials. Data collected during the study of missile impact craters have helped resolve a number of problems in lunar research: (1) the soillike nature of lunar surface materials was predicted, (2) sizes of craters produced by artificial impacts were correctly predicted, (3) certain features imaged by Surveyor were found to be analogous to features associated with missile impact craters, {4) missile impacts were used in support of the Apollo passive seismic experiment, (5) craters seen in Apollo orbital photographs were found to be similar to some missile impact craters, (6) missile impact craters supplied data on sample collection and crater phenomenology used in training astronauts, and (7) some returned lunar samples are similar to coated, sheared, and compressed fragments ejected from missile impact craters.

H. J. Moore↗
NASA NTRS2011

Reconciling LCROSS and Orbital Neutron Water Abundance Estimates in Cabeus Crater

The Lunar Prospector Neutron Spectrometer (LPNS) first revealed Cabeus crater (84.9 deg S, 35.5degW) as having the highest inferred hydrogen on the Moon. Because of the broad LPNS footprint (approximately 40 km FWHM), the apparent peak water-equivalent hydrogen (WEH) concentration is only approximately 0.25 wt%, but could be much higher in smaller areas than the spectrometer footprint. Earlier image reconstruction work suggested that areas within permanent shadow have abundances approximately 1 wt% WEH. However, the LCROSS impact yielded total water estimates, ice plus vapor, of between 3 and 10 wt%. The large disagreement between LCROSS and apparent orbital values imply that either the ice is buried, by perhaps as much as 50 to 100 cm; or the ice distribution within Cabeus is spatially inhomogeneous, or both. Modeling reveals that the areal extent of a "shallow permafrost zone" is far greater than the area of permanent shadow. Ice can be virtually stable for billions of years within a few tens of centimeters of the surface in these areas. However, the LCROSS impact took place in an area of permanent shadow. If stably-trapped volatiles can be found in locales that receive occasional, oblique sunlight, landed missions may target these sites and eventual resource exploitation may be done more easily. Are orbital neutron data consistent with areally-extensive, volatile-rich cold traps? Orbital epithermal neutron data over the northern half of Cabeus (near the LCROSS impact site) are consistent with 0.2 wt% WEH or less in the "permafrost zone" near the crater. On the other hand, pixon reconstructions that confine the hydrogen enhancements to permanent shadow result in higher abundance estimates -- around 1 wt% if homogeneously mixed. But if the PSR abundance is increased to 10 wt%, consistent with the sum of all H-bearing compounds seen by LCROSS, a much larger-than-observed reduction in neutron count rate would be seen from orbit. It is likely that volatiles are inhomogeneously distributed, due to both impact processes and emplacement history. Two possibilities may bring consistency to the orbital and LCROSS measurements. Inhomogeneous lateral distribution: Consider the extreme case of a bimodal distribution within the crater -- dry and wet. In this case the epithermal leakage flux seen from orbit is a mixture of two different values, weighted according to fractional areas. Two possible outcomes, depending on whether the inferred leakage flux for the PSR or "permafrost" areas are considered. In the first case, approximately 40% of the PSR may be "wet", the remainder dry (and LCROSS was slightly lucky). However, if the whole area of permafrost is considered, then as little as 20% of the area will be as "wet" as the LCROSS results (and LCROSS was quite lucky). Inhomogeneous depth distribution: The leakage flux of thermal and epithermal neutrons depends on depth of burial of an icy layer beneath dry ferroan anorthosite soil (FAn). For the Cabeus PSR, the pixon reconstruction values for the epithermal flux allows a range of abundance and burial depth, while that of the thermal+epi detector constrains this range. (Uncertainties in iron abundance in the FAn can have significant impact on thermal neutron leakage flux estimates.) Between 20% and 40% of the Cabeus floor may be "wet", or alternatively a 5-10 wt% "wet" layer exists between 50 and 100 cm beneath a layer of dry regolith within the PSR. But volatile abundances of 5 wt% or more, distributed uniformly and homogeneously throughout the Cabeus PSR do not agree with orbital measurements

Elphic, Richard↗
NASA NTRS1991

Report on carbon and nitrogen abundance studies

The aim of the proposal was to determine the nitrogen to carbon abundance ratios from transition layer lines in stars with different T(sub eff) and luminosities. The equations which give the surface emission line fluxes and the measured ratio of the NV to CIV emission line fluxes are presented and explained. The abundance results are compared with those of photospheric abundance studies for stars in common with the photospheric investigations. The results show that the analyses are at least as accurate as the photospheric determinations. These studies can be extended to F and early G stars for which photospheric abundance determinations for giants are hard to do because molecular bands become too weak. The abundance determination in the context of stellar evolution is addressed. The N/C abundance ratio increases steeply at the point of evolution for which the convection zone reaches deepest. Looking at the evolution of the rotation velocities v sin i, a steep decrease in v sin i is related to the increasing depth of the convection zone. It is concluded that the decrease in v sin i for T(sub eff) less than or approximately = 5800 K is most probably due to the rearrangement of the angular momentum in the stars due to deep convective mixing. It appears that the convection zone is rotating with nearly depth independent angular momentum. Other research results and ongoing projects are discussed.

Boehm-Vitense, Erika↗
NASA NTRS2000

Phase Shift Interferometer and Growth Set Up to Step Pattern Formation During Growth From Solutions. Influence of the Oscillatory solution Flow on Stability

We have assembled an experimental setup based on Michelson interferometry with the growing crystal surface as one of the reflective surfaces. The crystallization part of the device allows optical monitoring of a face of a crystal growing at temperature stable within 0.05 C in a flow of solution of controlled direction and speed. The reference arm of the interferometer contains a liquid crystal element that allows controlled shifts of the phase of the interferograms. We employ an image-processing algorithm, which combines five images with a pi/2 phase difference between each pair of images. The images are transferred to a computer by a camera capable of capturing 60 frames per second. The device allows data collection on surface morphology and kinetics during the face layers growth over a relatively large area (approximately 4 sq. mm) in situ and in real time during growth. The estimated depth resolution of the phase shifting interferometry is approximately 50 Angstroms. The data will be analyzed in order to reveal and monitor step bunching during the growth process. The crystal chosen as a model for study in this work is KH2PO4 (KDP). This optically non-linear material is widely used in frequency doubling applications. There have been a number of studies of the kinetics of KDP crystallization that can serve as a benchmark for our investigations. However, so far, systematic quantitative characteristics of step interaction and bunching are missing. We intend to present our first quantitative results on the onset, initial stages and development of instabilities in moving step trains on vicinal crystal surfaces at varying supersaturation, flow rate, and flow direction. Behavior of a vicinal face growing from solution flowing normal to the steps and periodically changing its direction in time was considered theoretically. It was found that this oscillating flow reduces both stabilization and destabilization effects resulted from the unidirectional solution flow directed up the step stream and down the step stream. This reduction of stabilization and destabilization comes from effective mixing which entangles the phase shifts between the spatially periodic interface perturbation and the concentration wave induced by this perturbation. Numerical results and simplified mixing criterion will be discussed.

Chernov, Alex A.↗
NASA NTRS2006

Processes Influencing Ozone Levels in Alaskan Forest Fires Plumes during Long-Range Transport over the North Atlantic

A case of long-range transport of a biomass burning plume from Alaska to Europe is analyzed using a Lagrangian approach. This plume was sampled several times in the free troposphere over North America, the North Atlantic and Europe by 3 different aircraft during the IGAC Lagrangian 2K4 experiment which was part of the ICARTT/ITOP measurement intensive in summer 2004. Measurements in the plume showed enhanced values of CO, VOCs and NOy, mainly in form of PAN. Observed O3 levels increased by 17 ppbv over 5 days. A photochemical trajectory model, CiTTyCAT, is used to examine processes responsible for the chemical evolution of the plume. The model was initialized with upwind data, and compared with downwind measurements. The influence of high aerosol loading on photolysis rates in the plume is investigated using in-situ aerosol measurements in the plume and lidar retrievals of optical depth as input into a photolysis code (Fast-J), run in the model. Significant impacts on photochemistry are found with a decrease of 18 percent in O3 production and 24 percent in O3 destruction over 5 days when including aerosols. The plume is found to be chemically active with large O3 increases attributed primarily to PAN decomposition during descent of the plume towards Europe. The predicted O3 changes are very dependent on temperature changes during transport, and also, on water vapor levels in the lower troposphere which can lead to O3 destruction. Simulation of mixing/dilution was necessary to reproduce observed pollutants level in the plume. Mixing was simulated using background concentrations from measurements in air masses in close proximity to the plume, and mixing timescales (averaging 6.25 days) were derived from CO changes. Observed and simulated O3/CO correlations in the plume are also compared in order to evaluate the photochemistry in the model. Observed slopes changed from negative to positive over 5 days. This change, which can be attributed largely to photochemistry, is well reproduced by multiple model runs even if slope values are slightly underestimated suggesting small underestimation of photochemical processes. The possible impact of this biomass burning plume on O3 levels in the Europe boundary layer is also examined by running the model for a further 5 days, and comparing with data collected at surface sites, such as Jungfraujoch, which showed small O3 increases and elevated CO levels. The model predicts significant changes in O3 over this 10 days due to photochemistry but the signal is largely lost due to the effects of dilution. However, measurement in several others BB plumes over Europe show that O3 impact of Alaskan fires can be punctually significant over Europe.

Real, E.↗
NASA NTRS1991

Mixed convective/dynamic roll vortices and their effects on initial wind and temperature profiles

The onset and development of both dynamically and convectively forced boundary layer rolls are studied with linear and nonlinear analyses of a truncated spectral model of shallow Boussinesq flow. Emphasis is given here on the energetics of the dominant roll modes, on the magnitudes of the roll-induced modifications of the initial basic state wind and temperature profiles, and on the sensitivity of the linear stability results to the use of modified profiles as basic states. It is demonstrated that the roll circulations can produce substantial changes to the cross-roll component of the initial wind profile and that significant changes in orientation angle estimates can result from use of a roll-modified profile in the stability analysis. These results demonstrate that roll contributions must be removed from observed background wind profiles before using them to investigate the mechanisms underlying actual secondary flows in the boundary layer. The model is developed quite generally to accept arbitrary basic state wind profiles as dynamic forcing. An Ekman profile is chosen here merely to provide a means for easy comparison with other theoretical boundary layer studies; the ultimate application of the model is to study observed boundary layer profiles. Results of the analytic stability analysis are validated by comparing them with results from a larger linear model. For an appropriate Ekman depth, a complete set of transition curves is given in forcing parameter space for roll modes driven both thermally and dynamically. Preferred orientation angles, horizontal wavelengths and propagation frequencies, as well as energetics and wind profile modifications, are all shown to agree rather well with results from studies on Ekman layers as well as with studies on near-neutral and convective atmospheric boundary layers.

Haack, Tracy↗
DOE OSTI2019

Identification and Characterization of Persistent Cold Pool Events from Temperature and Wind Profilers in the Columbia River Basin

Cold pool events occur when deep layers of stable, cold air remain trapped in a valley or basin for multiple days, without mixing out from daytime heating. With large impacts on air quality, freezing events, and es-pecially on wind energy production, they are often poorly forecast by modern mesoscale numerical weather prediction (NWP) models. Understanding the characteristics of cold pools is, therefore, important to provide more accurate forecasts. This study analyzes cold pool characteristics with data collected during the Second Wind Forecast Improvement Project (WFIP2), which took place in the Columbia River basin and Gorge of Oregon and Washington from fall 2015 until spring 2017. A subset of the instrumentation included three microwave radiometer pro?lers, six radar wind pro?lers with radio acoustic sounding systems, and seven sodars, which together provided seven sites with collocated vertical pro?les of temperature, humidity, wind speed, and wind direction. Using these collocated observations, we developed a set of criteria to determine if a cold pool was present based on stability, wind speed, direction, and temporal continuity, and then developed an automated algorithm based on these criteria to identify all cold pool events over the 18 months of the ?eld project. Characteristics of these events are described, including statistics of the wind speed distributions and pro?les, stability conditions, cold pool depths, and descent rates of the cold pool top. The goal of this study is a better understanding of these characteristics and their processes to ultimately lead to improved physical parameterizations in NWP models, and consequently improve forecasts of cold pool events in the study region as well at other locations that experiences similar events.

McCaffrey, Katherine L.↗
NASA NTRS2004

Aerosol Optical Properties Measured Onboard the Ronald H. Brown During ACE Asia as a Function of Aerosol Chemical Composition and Source Region

During the ACE Asia intensive field campaign conducted in the spring of 2001 aerosol properties were measured onboard the R/V Ronald H. Brown to study the effects of the Asian aerosol on atmospheric chemistry and climate in downwind regions. Aerosol properties measured in the marine boundary layer included chemical composition; number size distribution; and light scattering, hemispheric backscattering, and absorption coefficients. In addition, optical depth and vertical profiles of aerosol 180 deg backscatter were measured. Aerosol within the ACE Asia study region was found to be a complex mixture resulting from marine, pollution, volcanic, and dust sources. Presented here as a function of air mass source region are the mass fractions of the dominant aerosol chemical components, the fraction of the scattering measured at the surface due to each component, mass scattering efficiencies of the individual components, aerosol scattering and absorption coefficients, single scattering albedo, Angstrom exponents, optical depth, and vertical profiles of aerosol extinction. All results except aerosol optical depth and the vertical profiles of aerosol extinction are reported at a relative humidity of 55 +/- 5%. An over-determined data set was collected so that measured and calculated aerosol properties could be compared, internal consistency in the data set could be assessed, and sources of uncertainty could be identified. By taking into account non-sphericity of the dust aerosol, calculated and measured aerosol mass and scattering coefficients agreed within overall experimental uncertainties. Differences between measured and calculated aerosol absorption coefficients were not within reasonable uncertainty limits, however, and may indicate the inability of Mie theory and the assumption of internally mixed homogeneous spheres to predict absorption by the ACE Asia aerosol. Mass scattering efficiencies of non-sea salt sulfate aerosol, sea salt, submicron particulate organic matter, and dust found for the ACE Asia aerosol are comparable to values estimated for ACE 1, Aerosols99, and INDOEX. Unique to the ACE Asia aerosol was the large mass fractions of dust, the dominance of dust in controlling the aerosol optical properties, and the interaction of dust with soot aerosol.

Quinn, P. K.↗
DOE OSTI2025

Bottlebrush Block Copolymer Thin Films

The self-assembly of block copolymers (BCPs) in thin films is governed by interfacial interactions (enthalpy) between the blocks and interfaces (at both the substrate and the surface). Advantage can also be taken of entropy to control the polymer orientation. Here, we synthesized a series of bottlebrush block copolymers (BBCPs), with deuterated polystyrene (DPS) as the core block and poly­(solketal acrylate) (PSA) as the corona block, where the backbone length (N BB) and grafting densities (GDs) were varied. The hydrophobic PSA block was converted to a hydrophilic poly­(glyceryl acrylate) (PGA) block by solid-state hydrolysis, bringing the BBCP from a disordered state into an ordered state with a lamellar microdomain morphology. The orientation of the morphology as a function of distance from the interfaces was systematically investigated by atomic force microscopy (AFM), interference microscopy, grazing-incidence small-angle X-ray scattering (GISAXS), and grazing-incidence small angle neutron scattering (GISANS). For N BB = 1 (diblock BCP), a mixed lamellar orientation was found. For N BB = 5 (star-like BBCP), a vertical orientation of the lamellar microdomains was found dominantly at the interfaces that propagated into the bulk of the film due to the entropic penalty associated with constraints on the junction points. Increasing the N BB to 50 (rod-like BBCP) and 100 (worm-like BBCP) yielded a random orientation, as the side chains became overcrowded when aligned in the same direction. By reducing the grafting density (GD) of a N BB = 50 BBCP from 100% to 75% and 50% by the incorporation of spacers into the backbone, the steric hindrance of side chains is reduced markedly, facilitating a vertical orientation of the lamellar microdomains. However, the vertical orientation becomes more random within the bulk of the thin film for different BBCP architectures. By modifying the substrate with a layer of PS, the preferential interactions between the core block of the BBCP and the interfaces induce a reconfiguration of the BBCP, drawing the core block out to contact substrate directly driven by enthalpy. Under these conditions, N BB = 5 showed a predominantly parallel orientation of the lamellar microdomains with the corona block minimizing contact with the substrate. Higher N BB values of 50 and 100 showed a more random orientation of the lamellar microdomains at different depths on the PS-modified substrate. Overall, thin-film morphology was regulated by tuning the configuration of the BBCP, varying the entropic contribution to the microdomain orientation.

Chen, Zhan↗
NASA NTRS2018

Satellite-Based View of the Aerosol Spatial and Temporal Variability in the Cordoba Region (Argentina) Using over Ten Years of High-Resolution Data

Space-based observations offer a unique opportunity to investigate the atmosphere and its changes over decadal time scales, particularly in regions lacking in situ and/or ground based observations. In this study, we investigate temporal and spatial variability of atmospheric particulate matter (aerosol) over the urban area of Córdoba (central Argentina) using over ten years (2003–2015) of high-resolution (1 km) satellite-based retrievals of aerosol optical depth (AOD). This fine resolution is achieved exploiting the capabilities of a recently developed inversion algorithm (Multiangle implementation of atmospheric correction, MAIAC) applied to the MODIS sensor datasets of the NASA-Terra and -Aqua platforms. Results of this investigation show a clear seasonality of AOD over the investigated area. This is found to be shaped by an intricate superposition of aerosol sources, acting over different spatial scales and affecting the region with different yearly cycles. During late winter and spring (August-October), local as well as near- and long-range transported biomass burning (BB) aerosols enhance the Córdoba aerosol load, and AOD levels reach their maximum values (>0.35 at 0.47 µm). The fine AOD spatial resolution allowed to disclose that, in this period, AOD maxima are found in the rural/agricultural area around the city, reaching up to the city boundaries pinpointing that fires of local and near-range origin play a major role in the AOD enhancement. A reverse spatial AOD gradient is found from December to March, the urban area showing AODs 40–80% higher than in the city surroundings. In fact, during summer, the columnar aerosol load over the Córdoba region is dominated by local (urban and industrial) sources, likely coupled to secondary processes driven by enhanced radiation and mixing effects within a deeper planetary boundary layer (PBL). With the support of modelled AOD data from the Modern-Era Retrospective Analysis for Research and Application (MERRA), we further investigated into the chemical nature of AOD. The results suggest that mineral dust is also an important aerosol component in Córdoba, with maximum impact from November to February. The use of a long-term dataset finally allowed a preliminary assessment of AOD trends over the Córdoba region. For those months in which local sources and secondary processes were found to dominate the AOD (December to March), we found a positive AOD trend in the Córdoba outskirts, mainly in the areas with maximum urbanization/population growth over the investigated decade. Conversely, a negative AOD trend (up to −0.1 per decade) is observed all over the rural area of Córdoba during the BB season, this being attributed to a decrease of fires both at the local and the continental scale.

aerosols↗
NASA NTRS1999

Mars Solar Balloon Landed Gas Chromatograph Mass Spectrometer

A Mars surface lander Gas Chromatograph Mass Spectrometer (GCMS) is described to measure the chemical composition of abundant and trace volatile species and isotope ratios for noble gases and other elements. These measurements are relevant to the study of atmospheric evolution and past climatic conditions. A Micromission plan is under study where a surface package including a miniaturized GCMS would be delivered to the surface by a solar heated hot air balloon based system. The balloon system would be deployed about 8 km above the surface of Mars, wherein it would rapidly fill with Martian atmosphere and be heated quickly by the sun. The combined buoyancy and parachuting effects of the solar balloon result in a surface package impact of about 5 m/sec. After delivery of the package to the surface, the balloon would ascend to about 4 km altitude, with imaging and magnetometry data being taken for the remainder of the daylight hours as the balloon is blown with the Martian winds. Total atmospheric entry mass of this mission is estimated to be approximately 50 kg, and it can fit as an Ariane 5 piggyback payload. The GCMS would obtain samples directly from the atmosphere at the surface and also from gases evolved from solid phase material collected from well below the surface with a Sample Acquisition and Transport Mechanism (SATM). The experiment envisioned in the Mars Micromission described would obtain samples from a much greater depth of up to one meter below the surface, and would search for organic molecules trapped in ancient stratified layers well below the oxidized surface. Insitu instruments on upcoming NASA missions working in concert with remote sensing measurement techniques have the potential to provide a more detailed investigation of mineralogy and the extent of simple volatiles such as CO2 and H2O in surface and subsurface solid phase materials. Within the context of subsequent mission opportunities such as those provided by the Ariane 5 piggyback payload based Micromissions, it is essential to implement an even broader chemical analysis and to enable a significant extension of previous isotope measurements. Such a development would enhance the presently very active study of questions of atmospheric evolution and loss and past climatic conditions. The method selected to implement this program can be based on well-established mass spectrometry techniques. Sampled gas is chemically and physically processed to separate the gas mixture into components using gas chromatograph and related enrichment techniques. This allows trace species to be identified and reveals isotopic distributions in many cases with improved precision. Samples of interest, such as organic molecules, may lie deep below the highly oxidized surface layer and the suggested program includes enhanced sampling techniques to measure volatiles preserved in solid phase material deep below the surface as well as gas from the well mixed atmosphere.

Mahaffy, P.↗
NASA NTRS2018

An IR Sounding-Based Analysis of the Saharan Air Layer in North Africa

Intense daytime surface heating over barren-to-sparsely vegetated surfaces results in dry convective mixing. In the absence of external forcing such as mountain waves, the dry convection can produce a deep, well-mixed, nearly isentropic boundary layer that becomes a well-mixed residual layer in the evening. These well-mixed layers (WML) retain their unique mid-tropospheric thermal and humidity structure for several days. To detect the SAL and characterize its properties, AIRS Level 2 Ver. 6 temperature and humidity products (2003-Present) are evaluated against rawinsondes and compared to model analysis at each of the 55 rawinsonde stations in northern Africa. To distinguish WML from Saharan air layers (WMLs of Saharan origin), the detection involved a two-step process: 1) algorithm-based detection of WMLs in dry environments (less than 7 g per kilogram mixing ratio) 2) identification of Sahara air layers (SAL) by applying Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) back trajectories to determine the history of each WML. WML occurrence rates from AIRS closely resemble that from rawinsondes, yet rates from model analysis were up to 30% higher than observations in the Sahara due to model errors. Despite the overly frequent occurrence of WMLs from model analysis, HYSPLIT trajectory analysis showed that SAL occurrence rates (given a WML exists) from rawinsondes, AIRS, and model analysis were nearly identical. Although the number of WMLs varied among the data sources, the proportion of WMLs which were classified as SAL was nearly the same. The analysis of SAL bulk properties showed that AIRS and model analysis exhibited a slight warm and moist bias relative to rawinsondes in non-Saharan locations, but model analysis was notably warmer than rawinsondes and AIRS within the Sahara. The latter result is likely associated with the dearth of available data assimilated by model analysis in the Sahara. The variability of SAL thicknesses was reasonably captured by both AIRS and model analysis, but the former favor layers than are thinner than observations. Finally, further analysis of HYSPLIT trajectories revealed that fewer than 10% and 33% of all SAL back trajectories passed through regions with notable precipitation (>100 mm accumulated along the trajectory path) or Aerosol Optical Depth (AOD greater than 0.4, 75th percentile of AOD) on average, respectively. Trajectory analysis indicated that only 57% of Saharan and 24% of non-Saharan WMLs are definitively of Saharan origin (Saharan requirement: Two consecutive days in Sahara and 24 or more of those hours within 72 hours of detection). Non-SAL WMLs either originate from local-to-regionally generated residual layers or from mid-latitude air streams that do not linger over the Sahara for a sufficient time period. Initial analysis shows these non-SAL WMLs tend to be both notably cooler and slightly moister than their SAL counter parts. Continuing analysis will address what role Saharan and non-Saharan air masses characteristics may play on local and regional environmental conditions.

Nicholls, Stephen D.↗
DOE OSTI2020

Role of Alkali-Metal Cations in Electronic Structure and Halide Segregation of Hybrid Perovskites

The ability to control or prevent phase segregation in perovskites is crucial to realizing stable and tunable mixed-halide optoelectronic devices. Here, we systematically examine the impact of alkali-metal-cation (Cs + and K + ) concentration on the band structure, chemical composition, phase segregation, and polycrystalline microstructure on formamidinium-dominated mixed-halide mixed-cation perovskite films. It was found that the incorporation of Cs + and K + cations decreases the work function and the core levels of all components shift toward higher binding energy consistent with n-doping the perovskite film, which facilitates electron transfer to the electron transport layer TiO 2 . A concentration-dependent film structure was observed by X-ray photoemission spectroscopy and grazing incidence wide-angle X-ray scattering where the halides and cations are distributed evenly across perovskite films at low metallic cation concentration (5%). A high metal-cation ratio (20%) leads to halide segregation within the perovskite film and the surface becomes bromide-poor, whereas the bromide and metal cations diffuse more deeply within the film. These differences in electronic properties, element distribution, and film morphology were reflected in the device performance where the power conversion efficiency of low-metallic-cation concentration (5% of Cs + and K + ) perovskite solar cells is ≈5% higher than the high-concentration ones (20%). This study provides valuable chemical and physical insight into the underlying trade-offs in the careful tuning of electrical properties and film structure to optimize multication and mixed-halide hybrid perovskites.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Storm-driven Mixing and Potential Impact on the Arctic Ocean

Observations of the ocean, atmosphere, and ice made by Ice-Ocean Environmental Buoys (IOEBs) indicate that mixing events reaching the depth of the halocline have occurred in various regions in the Arctic Ocean. Our analysis suggests that these mixing events were mechanically forced by intense storms moving across the buoy sites. In this study, we analyzed these mixing events in the context of storm developments that occurred in the Beaufort Sea and in the general area just north of Fram Strait, two areas with quite different hydrographic structures. The Beaufort Sea is strongly influenced by inflow of Pacific water through Bering Strait, while the area north of Fram Strait is directly affected by the inflow of warm and salty North Atlantic water. Our analyses of the basin-wide evolution of the surface pressure and geostrophic wind fields indicate that the characteristics of the storms could be very different. The buoy-observed mixing occurred only in the spring and winter seasons when the stratification was relatively weak. This indicates the importance of stratification, although the mixing itself was mechanically driven. We also analyze the distribution of storms, both the long-term climatology as well as the patterns for each year in the last two decades. The frequency of storms is also shown to be correlated- (but not strongly) to Arctic Oscillation indices. This study indicates that the formation of new ice that leads to brine rejection is unlikely the mechanism that results in the type of mixing that could overturn the halocline. On the other hand, synoptic-scale storms can force mixing deep enough to the halocline and thermocline layer. Despite a very stable stratification associated with the Arctic halocline, the warm subsurface thermocline water is not always insulated from the mixed layer.

Yang, Jiayan↗
DOE OSTI2022

Critical Shear Stress for Erosion Under Laminar Jet Flow

Particle erosion is an important process in both natural and manmade environments. For example, in natural environments particle or sediment erosion rates determine the course of rivers, depth of streams, and fate of deltas. The interplay between erosion rates and flow patterns can have dramatic impact on shorelines. Where hydrodynamic jet flows or rip currents change direction, sediments may accumulate or disperse altering the shape of coastlines and the ecosystems and economies that rely on them. In man-made systems, jet flows may be used to mobilize particles from surfaces or within industrial scale mixing tanks. For example, in the nuclear industry, impinging jet mixers may be used to mobilize and suspend sludges at the bottom of waste tanks. In each of these examples, the Shields diagram is useful to determine the conditions under which erosion occurs. This diagram plots the scaled critical shear stress for erosion as a function of the particle size as embedded in particle Reynolds numbers, Archimedes numbers, or their equivalents. Although the data, that carries a large spread, is largely in agreement with mathematical models, for the smallest particles, model predictions diverge from each other and from experimental data. Indeed, there is substantial uncertainty about the Shields diagrams at relatively small particle sizes and flow rates. Here we evaluate critical shear stresses for erosion under laminar jet flow. To date critical shear stresses for erosion, as embodied in Shields diagrams, have largely been developed for turbulent flow both experimental and mathematically. However, curves on the Shields diagrams diverge among various models at lower particle Reynolds numbers. Indeed, how critical shear stresses for erosion develop under fully laminar jet flow conditions (not simply laminar boundary layers under turbulent flow) remains unclear. Here we address this gap, which is particularly important for mobilization of the smallest particles. We find the Shields parameter to be inversely proportional to the particle Reynolds numbers under laminar jet flow conditions similar to turbulent conditions.

critical shear stresses, erosion rates, effective ↗
DOE OSTI2020

Exploration of Sn 70 Li 30 alloy as possible material for flowing liquid metal plasma facing components

As an advanced alternative to solid materials, Liquid Metals (LM) may offer more resilient and feasible Plasma Facing Components (PFCs). Particularly, regarding the unavoidable material erosion/degradation produced by particle/heat fluxes in future fusion devices where much longer duty cycles are expected. Furthermore, configurations that propose a flowing LM surface can add the advantage of a continuously fresh and clean layer facing the plasma. Although lithium is the most widely tested option, tin-lithium (SnLi) alloys have been proposed to attempt to combine the positive characteristics of both pure elements and ameliorate the specific issues of lithium. In this work, the potential use of Sn70Li30 alloy in such flowing concepts has been explored by addressing several preliminary and mandatory aspects for its utilization. Key issues such as wettability and compatibility of the alloy with relevant substrates have been studied in a multidisciplinary approach. The data obtained from deposited liquid tin-lithium droplets indicates approximate wetting temperatures of 360 °C, 390 °C and 405 °C for the fresh alloy on 316 stainless steel, molybdenum, and tungsten, respectively. However, the alloy contamination appeared to strongly affect the wetting characteristics of materials, increasing their wetting temperature by ~130 °C in the worst observed cases. Interestingly, in some instances, the instability of the liquid alloy surface was observed in the form of sudden gaseous ejection. The deposited droplets were posteriorly characterized in terms of absolute composition and depth profile by Inductively Coupled PlasmaOptical Emission Spectroscopy (ICP-OES) and Secondary Ion Mass Spectrometry (SIMS-ToF). Additionally, the nature and composition of the boundaries between the substrates and alloy microparticles was investigated by Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), and 3D Laser microscopy. The overall results of this post-mortem characterization revealed that first signs of corrosion induced by both alloy elements (lithium-chromium association and iron-tin intermetallic mixing) were present on 316 stainless steel after short exposures (≤3 h) at temperatures lower than 550 °C. Conversely, molybdenum and tungsten showed good compatibility with the alloy in equivalent conditions. The global implications of these results are finally addressed, focusing on the future perspectives and the more viable scenarios for the eventual utilization of these alloys in flowing liquid metal configurations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗