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Gaussian Process Modeling For Experimental Procedure Uncertainty

Many laboratory experiments generate data that are characterized by a form of uncertainty that differs from noise: experimental procedure uncertainty. The origin of this type of uncertainty is the difficulty in controlling a subset of experimental conditions in such a way that the experiment is perfectly reproducible within noise. In this report, we describe a Gaussian Process modeling-based method that accounts for experimental procedure uncertainty. The method accounts for variations in conditions from experiment to experiment that are independent between experiments, but correlated within each experiment, and incorporates the resulting uncertainty into predictions at future experimental settings. The method is discussed in the context of a specific chemistry application in which Raman scattering spectra are measured from three-component mixtures.

42 ENGINEERING↗

Fractionation of Lignin for Selective Shape Memory Effects at Elevated Temperatures

We report a facile approach to control the shape memory effects and thermomechanical characteristics of a lignin-based multiphase polymer. Solvent fractionation of a syringylpropane-rich technical organosolv lignin resulted in selective lignin structures having excellent thermal stability coupled with high stiffness and melt-flow resistance. The fractionated lignins were reacted with rubber in melt-phase to form partially networked elastomer enabling selective programmability of the material shape either at 70 °C, a temperature that is high enough for rubbery matrix materials, or at an extremely high temperature, 150 °C. Utilizing appropriate functionalities in fractionated lignins, tunable shape fixity with high strain and stress recovery, particularly high-stress tolerance were maintained. Detailed studies of lignin structures and chemistries were correlated to molecular rigidity, morphology, and stress relaxation, as well as shape memory effects of the materials. The fractionation of lignin enabled enrichment of specific lignin properties for efficient shape memory effects that broaden the materials’ application window. Electron microscopy, melt-rheology, dynamic mechanical analysis and ultra-small angle neutron scattering were conducted to establish morphology of acrylonitrile butadiene rubber (NBR)-lignin elastomers from solvent fractionated lignins.

36 MATERIALS SCIENCE↗

Martian surface simulations

Computer generated surfaces have been created to aid in imaging, landing and rover studies for Mars and the moon. They are also being applied to the study of cratering histories. The surfaces are generated in steps which attempt to mimic geologic episodes. Surface roughness is realized fractally, while craters and other specific features have shapes and distributions dictated by observation. Surface materials are assigned appropriate albedos, making the images more realistic. With the inclusion of correlations between crater and rock distributions, the simulations are beginning to acquire a predictive capability.

Gaskell, Robert W.↗

Fingerprinting the K/T impact site and determining the time of impact by U-Pb dating of single shocked zircons from distal ejecta

U-Pb isotopic dating of single 1 - 3 micrograms zircons from K/T distal ejecta from a site in the Raton Basin, Colorado provides a powerful new tool with which to determine both the time of the impact event and the age of the basement at the impact site. Data for the least shocked zircons are slightly displaced from the 544 +/- 5 Ma primary age for a component of the target site, while those for highly shocked and granular grains are strongly displaced towards the time of impact at 65.5 +/- 3.0 Ma. Such shocked and granular zircons have never been reported from any source, including explosive volcanic rocks. Zircon is refractory and has one of the highest thermal blocking temperatures; hence, it can record both shock features and primary and secondary ages without modification by post-crystallization processes. Unlike shocked quartz, which can come from almost anywhere on the Earth's crust, shocked zircons can be shown to come from a specific site because basement ages vary on the scale of meters to kilometers. With U-Pb zircon dating, it is now possible to correlate ejecta layers derived from the same target site, test the single versus multiple impact hypothesis, and identify the target source of impact ejecta. The ages obtained in this study indicate that the Manson impact site, Iowa, which has basement rocks that are mid-Proterozoic in age, cannot be the source of K/T distal ejecta. The K/T distal ejecta probably originated from a single impact site because most grains have the same primary age.

Krogh, T. E.↗

The Use of a Satellite Climatological Data Set to Infer Large Scale Three Dimensional Flow Characteristics

Ever since the first satellite image loops from the 6.3 micron water vapor channel on the METEOSAT-1 in 1978, there have been numerous efforts (many to a great degree of success) to relate the water vapor radiance patterns to familiar atmospheric dynamic quantities. The realization of these efforts is becoming evident with the merging of satellite derived winds into predictive models (Velden et al., 1997; Swadley and Goerss, 1989). Another parameter that has been quantified from satellite water vapor channel measurements is upper tropospheric relative humidity (UTH) (e.g., Soden and Bretherton, 1996; Schmetz and Turpeinen, 1988). These humidity measurements, in turn, can be used to quantify upper tropospheric water vapor and its transport to more accurately diagnose climate changes (Lerner et al., 1998; Schmetz et al. 1995a) and quantify radiative processes in the upper troposphere. Also apparent in water vapor imagery animations are regions of subsiding and ascending air flow. Indeed, a component of the translated motions we observe are due to vertical velocities. The few attempts at exploiting this information have been met with a fair degree of success. Picon and Desbois (1990) statistically related Meteosat monthly mean water vapor radiances to six standard pressure levels of the European Centre for Medium Range Weather Forecast (ECMWF) model vertical velocities and found correlation coefficients of about 0.50 or less. This paper presents some preliminary results of viewing climatological satellite water vapor data in a different fashion. Specifically, we attempt to infer the three dimensional flow characteristics of the mid- to upper troposphere as portrayed by GOES VAS during the warm ENSO event (1987) and a subsequent cold period in 1998.

Lerner, Jeffrey A.↗

Continued Analysis of EUVE Solar System Observations

This is the final report for this project. We proposed to continue our work on extracting important results from the EUVE (Extreme UltraViolet Explorer) archive of lunar and jovian system observations. In particular, we planned to: (1) produce several monochromatic images of the Moon at the wavelengths of the brightest solar EUV emission lines; (2) search for evidence of soft X-ray emissions from the Moon and/or X-ray fluorescence at specific EUV wavelengths; (3) search for localized EUV and soft X-ray emissions associated with each of the Galilean satellites; (4) search for correlations between localized Io Plasma Torus (IPT) brightness and volcanic activity on Io; (5) search for soft X-ray emissions from Jupiter; and (6) determine the long term variability of He 58.4 nm emissions from Jupiter, and relate these to solar variability. However, the ADP review panel suggested that the work concentrate on the Jupiter/IPT observations, and provided half the requested funding. Thus we have performed no work on the first two tasks, and instead concentrated on the last three. In addition we used funds from this project to support reduction and analysis of EUVE observations of Venus. While this was not part of the original statement of work, it is entirely in keeping with extracting important results from EUVE solar system observations.

Gladstone, G. Randall↗

Influence of the Gas Pressure on Single-wall Carbon Nanotubes Formation

Experiments and modeling have been performed to predict the effect of gas pressure on species distribution and nanotube growth rate under specific conditions of synthesis of singlewall carbon nanotubes (SWCNTs) by arc discharge. Numerical results were compared with experiments in order to find a consistent correlation between the nanotube growth and the pressure. We used argon and helium as buffer gases with a total pressure varied between 0.1 and 1 bar. We experimentally observed that both the anode erosion rate and the Brunauer-Emmett-Teller (BET) surface area of the as produced nanotube soot material are very sensitive to the total gas pressure in the reactor

Hinkov, I.↗

Acoustic Emission Analysis of Damage Progression in Thermal Barrier Coatings Under Thermal Cyclic Conditions

Damage evolution of electron beam-physical vapor deposited (EBVD-PVD) ZrO2-7 wt.% Y2O3 thermal barrier coatings (TBCs) under thermal cyclic conditions was monitored using an acoustic emission (AE) technique. The coatings were heated using a laser heat flux technique that yields a high reproducibility in thermal loading. Along with AE, real-time thermal conductivity measurements were also taken using infrared thermography. Tests were performed on samples with induced stress concentrations, as well as calcium-magnesium-alumino-silicate (CMAS) exposure, for comparison of damage mechanisms and AE response to the baseline (as-produced) coating. Analysis of acoustic waveforms was used to investigate damage development by comparing when events occurred, AE event frequency, energy content and location. The test results have shown that AE accumulation correlates well with thermal conductivity changes and that AE waveform analysis could be a valuable tool for monitoring coating degradation and provide insight on specific damage mechanisms.

calcium-magnesium-alumino-silicate (CMAS)↗

The Far Ultraviolet M-dwarf Evolution Survey. I. The Rotational Evolution of High-energy Emissions

M-dwarf stars are prime targets for exoplanet searches because of their close proximity and favorable properties for both planet detection and characterization. However, the potential habitability and atmospheric characterization of these exoplanetary systems depends critically on the history of high-energy stellar radiation from X-rays to NUV, which drive atmospheric mass loss and photochemistry in the planetary atmospheres. With the Far Ultraviolet M-dwarf Evolution Survey, we have assessed the evolution of the FUV radiation, specifically eight prominent emission lines, including Lyα, of M-dwarf stars with stellar rotation period and age. We demonstrate tight power-law correlations between the spectroscopic FUV features, and measure the intrinsic scatter of the quiescent FUV emissions. The luminosity evolution with rotation of these spectroscopic features is well-described by a broken power law, saturated for fast rotators, and decays with increasing Rossby number, with a typical power-law slope of −2, although likely shallower for Lyα. Our regression fits enable FUV emission-line luminosity estimates relative to bolometric from known rotation periods to within ∼0.3 dex, across eight distinct UV emission lines, with possible trends in the fit parameters as a function of source layer in the stellar atmosphere. Our detailed analysis of the UV luminosity evolution with age further shows that habitable-zone planets orbiting lower-mass stars experience much greater high-energy radiative exposure relative the same planets orbiting more massive hosts. Around early- to mid-M dwarfs, these exoplanets, at field ages, accumulate up to 10–20× more EUV energy, relative to modern Earth. Moreover, the bulk of this UV exposure likely takes place within the first Gyr of the stellar lifetime.

J Sebastian Pineda↗

First-results from the Perseverance SHERLOC Investigation: Aqueous Alteration Processes and Implications for Organic Geochemistry in Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.

E L Scheller↗

Assessment of Near-Angle Scatter on Exo-Earth Coronagraphy

Near-Angle Scatter (NAS) of the host star’s light into the coronagraph dark hole may limit the ability of a potential Habitable Worlds Observatory (HWO) to detect and characterize an Earth-like planet around a Sun-like star. This paper summarizes a 5-year investigation of the impact of NAS on high-contrast coronagraphy. Science requirements were flowed down to a draft flux ratio noise ratio (FRN) error budget with allocations for NAS. The modeled sources of NAS include correlated (low and mid-spatial) surface structure, uncorrelated surface microroughness and coating structure, particulate contamination, micrometeoroid impacts and polarization leakage. The paper develops specifications for these sources of scattered light that meet their FRN error budget allocations, distinguishing between scatter that can and cannot be modulated. The development process utilizes an analytical expression that predicts scatter throughput into the dark hole based on BRDF/BSDF. Using this relationship, Photon Engineering performed a FRED® straylight analysis of the HWO EAC-1 (Exploratory Analytical Case #1) coronagraph to parametrically study predicted scattered light contrast in the dark hole. The model revealed that primary mirror microroughness or contamination is not a significant source of scattered light; the most critical surfaces are the smallest and those located closest to the coronagraph focal plane mask. The assessment found that uncorrelated microstructure, contamination, and micrometeoroid impacts require more investigation and potential significant sources of unmodulated scattered light, and highlights that slow thermal wavefront drift is an order of magnitude more impactful than fast mechanical jitter.

coronagraphy↗

Visualization of the flat electronic band in twisted bilayer graphene near the magic angle twist

Bilayer graphene was theorized to host a moire miniband with flat dispersion if the layers are stacked at specific twist angles known as the magic angles. Recently, such twisted bilayer graphene (tBLG) with the first magic angle twist was reported to exhibit correlated insulating state and superconductivity, where the presence of the flat miniband in the system is thought to be essential for the emergence of these ordered phases in the transport measurements. Tunneling spectroscopy and electronic compressibility measurements in tBLG have revealed a van Hove singularity that is consistent with the presence of the flat miniband. However, a direct observation of the flat dispersion in the momentum-space of such moire miniband in tBLG is still elusive. Here, we report the visualization of the flat moire miniband by using angle-resolved photoemission spectroscopy with nanoscale resolution (nanoARPES). The high spatial resolution in nanoARPES enabled the measurement of the local electronic structure of the tBLG. We clearly demonstrate the existence of the flat moire band near the charge neutrality for tBLG close to the magic angle at room temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Transition correlation in subsonic flow over a flat plate

A 2D subsonic flow over a flat plate with a freestream Mach number M(infinity) up to 0.8 is considered. The flow can experience continuous uniform suction through the wall and the wall can be heated or cooled continuously with a fixed wall temperature. For a specific combination of M(infinity), suction velocity, and level of heat transfer, the mean flow problem is solved and linear stability calculations are performed to compute the location on the flat plate where the factor representing the integration of growth rates reaches nine. These calculations are repeated for several combinations of flow parameters and the theoretically predicted transition location is presented in the form of a correlation that can account for the effect of wall suction, heat transfer, and Mach number.

Masad, J. A.↗

Strong Correlation Between the Magnetocaloric Properties of Nanotubes of La{sub 0.325}Pr{sub 0.3}Ca{sub 0.375}MnO{sub 3} and their Diameters

Under 0.01 T applied magnetic field variation, the calculation of magnetocaloric properties for 200 and 800 nm nanotubes of La{sub 0.325}Pr{sub 0.3}Ca{sub 0.375}MnO{sub 3} (LPCMO) perovskite such as magnetic entropy change, full-width at half-maximum (δT FWHM), relative cooling power, and magnetic specific heat change have been done. Magnetocaloric properties of 800-nm nanotubes of LPCMO is more than MCE of 200 nm ones. LPCMO nanotubes have hopeful application for magnetic refrigeration (MR) in an extended high-temperature range due to high values of δT{sub FWHM}. Therefore, nanotubes of LPCMO are very significant for MR applications, especially nitrogen liquefier.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Double-peak specific heat and spin freezing in the spin-2 triangular lattice antiferromagnet FeAl 2 Se 4

We report the properties of a triangular lattice iron-chalcogenide antiferromagnet FeAl 2 Se 4 .The spin susceptibility reveals a significant antiferromagnetic interaction with a Curie-Weiss temperature Θ CW ≃ –200 K and a spin-2 local moment. Despite a large spin and a large |Θ CW |, the low-temperature behaviors are incompatible with conventional classical magnets. No long-range order is detected down to 0.4 K. Similar to the well-known spin-1 magnet NiGa 2 S 4 , the specific heat of FeAl 2 Se 4 exhibits a double-peak structure and a T 2 power law at low temperatures, which are attributed to the underlying quadrupolar spin correlations and the Halperin-Saslow modes, respectively. The spin freezing occurs at ~14 K, below which the relaxation dynamics is probed by the ac susceptibility. Our results are consistent with the early theory for the spin-1 system with Heisenberg and biquadratic spin interactions. We argue that the early proposal of the quadrupolar correlation and gauge glass dynamics may be well extended to FeAl 2 Se 4 . Furthermore, our results provide useful insights about the magnetic properties of frustrated quantum magnets with high spins.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Emergence of Moiré Dirac Fermions at the Interface of Topological and 2D Magnetic Insulators

Dirac Fermions on the surface of the topological insulator are spin-momentum locked and topologically protected, making them interesting for spintronics and quantum computing applications. When in proximity to magnetism and superconductivity, these electronic states could result in quantum anomalous Hall effect and Majorana Fermions, respectively. An even more dramatic enrichment of the topological insulators’ physics is expected for moiré superlattices, where, analogously to the twisted graphene layers, electronic correlations could be strongly enhanced, a task previously notoriously difficult to achieve in topological matter. Until now, the experimental confirmation of such moiré properties has remained elusive. Here, we grow the two-dimensional van der Waals magnetic insulators FeX 2 (where X = Cl or Br) on top of the topological insulator Bi 2 Se 3 and establish a moiré superlattice formation at the interface. By means of scanning tunneling microscopy and angle-resolved photoemission spectroscopy, we investigate the electronic properties of the formed moiré superlattice and demonstrate its tunability via the film choice. We reveal replicated Dirac cones and focus on their intersections, which, in the case of FeBr 2 /Bi 2 Se 3 , occur below the Fermi level. We identify the signatures of small gaps at the intersections around the M̅ i points that we attribute to the moiré interaction. These findings point to the specific type of magnetic moiré potential that breaks the time-reversal symmetry at these points but not at the $\barΓ$ point. Our observations provide an intriguing scenario of correlated topological phases induced by moiré superlattice that may result in topological superconductivity, high Chern number phases, and exotic noncollinear magnetic textures.

2D magnets↗

In situ microscopy and spectroscopy characterization of microsized Sn anode for sodium-ion batteries

Microsized Sn is a promising anode material for sodium-ion batteries in terms of cost, specific capacity, and volumetric energy density, which however suffers from huge volume changes and rapid cell degradation upon cycling. Despite recent advances via nanostructured electrode design and interface engineering, the correlation between mechanical stability, solid-electrolyte interphase (SEI) and reaction kinetics/reversibility remains controversial and elusive. Here, in this work, by combining in situ scanning electron microcopy and X-ray absorption spectroscopy as well as X-ray photoelectron spectroscopy, we have investigated the underlying electro-chemo-mechanical behavior and their coupling effects during charge/discharge of microsized Sn anode. Our results revealed that microsized Sn is pulverized into nanoparticles with simultaneous formation of numerous voids and pores upon the 1st charge/discharge, while the electrolytes composition plays a critical role on the consequent parasitic reactions and eventually the sodiation/de-sodiation reversibility. In contrast to carbonate-based electrolytes, ether-based electrolytes enabled formation of inorganic species dominated SEI with improved mechanical strength, thus leading to higher specific capacity and improved cycling stability. The present findings are crucial for future development of microsized anode materials for rechargeable batteries with high volumetric energy density.

25 ENERGY STORAGE↗

Experimental and theoretical study of the thermoelectric properties of copper selenide

The temperature dependences of the specific heat, thermal conductivity, coefficient of thermal expansion (CTE), and transport coefficients (electrical conductivity and thermoelectric power) of copper selenide are experimentally and theoretically investigated in the temperature range of 300–873 K. The calculation results correlate with the experimental data up to a temperature of ~773 K. The maximum thermoelectric figure of merit of nanostructured copper selenide is ZT ~ 1.8. The correlation dependence between ZT and the thermal conductivity within the entire temperature range under consideration is shown.

36 MATERIALS SCIENCE↗

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