Engineering Papers⌕ Search

Engineering topics

Bradley, John P.

Publications and source records attributed to Bradley, John P..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A dehydrated space-weathered skin cloaking the hydrated interior of Ryugu

Abstract Without a protective atmosphere, space-exposed surfaces of airless Solar System bodies gradually experience an alteration in composition, structure and optical properties through a collective process called space weathering. The return of samples from near-Earth asteroid (162173) Ryugu by Hayabusa2 provides the first opportunity for laboratory study of space-weathering signatures on the most abundant type of inner solar system body: a C-type asteroid, composed of materials largely unchanged since the formation of the Solar System. Weathered Ryugu grains show areas of surface amorphization and partial melting of phyllosilicates, in which reduction from Fe 3+ to Fe 2+ and dehydration developed. Space weathering probably contributed to dehydration by dehydroxylation of Ryugu surface phyllosilicates that had already lost interlayer water molecules and to weakening of the 2.7 µm hydroxyl (–OH) band in reflectance spectra. For C-type asteroids in general, this indicates that a weak 2.7 µm band can signify space-weathering-induced surface dehydration, rather than bulk volatile loss.

Astronomy & Astrophysics↗
DOE OSTI2022

On the provenance of GEMS, a quarter century post discovery

The provenance of GEMS (glass with embedded metal and sulfides) in cometary type interplanetary dust particles is investigated using analytical scanning transmission electron microscopy and secondary ion mass spectrometry. We review the current state of knowledge and closely examine the densities, elemental compositions and distributions, iron oxidation states, and isotopic compositions of a subset of GEMS in chondritic porous interplanetary dust. We find that GEMS are underdense with estimated densities that are 35–65% of compositionally equivalent crystalline aggregates. GEMS low densities result in a lower contribution to the bulk compositions of IDPs than has been assumed based on their volume fraction. We also find that element/Si ratios, assumed to be primary (indigenous), are instead perturbed by contamination and secondary alteration, including pulse heating during atmospheric entry. Fe in pyrrhotite inclusions was oxidized and Mg, S, Ca, and Fe were depleted relative to lithophile Al and Si, resulting in reduction in element/Si ratios. Because they trap outgassing elements, Fe-rich oxide rims that formed on the surface of GEMS are serendipitous “witness plates” to the changes in composition that accompany atmospheric entry. As a result of alteration, GEMS elemental compositions cannot reliably inform about their provenance. Except for highly anomalous oxygen isotope ratios measured in some large GEMS grains that indicate a contribution from circumstellar dust, oxygen isotope compositions are generally poor indicators of provenance. Prior work indicates that most GEMS fall close to the terrestrial oxygen isotope composition, which, however, does not exclude a presolar interstellar origin. Nitrogen isotopic compositions are more diagnostic. Elevated 15 N/ 14 N ratios indicate that GEMS accreted in conjunction with formation of organic matter by ion–molecule reactions in a cold (<50 K) presolar environment like the extreme outer nebula or interstellar medium. Considering all observations, we conclude that GEMS are most likely processed interstellar silicates.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗
DOE OSTI2021

Solar wind contributions to Earth’s oceans

The isotopic composition of water in Earth’s oceans is challenging to recreate using a plausible mixture of known extraterrestrial sources such as asteroids—an additional isotopically light reservoir is required. The Sun’s solar wind could provide an answer to balance Earth’s water budget. Here, we used atom probe tomography to directly observe an average ~1 mol% enrichment in water and hydroxyls in the solar-wind-irradiated rim of an olivine grain from the S-type asteroid Itokawa. We also experimentally confirm that H + irradiation of silicate mineral surfaces produces water molecules. These results suggest that the Itokawa regolith could contain ~20 l m -3 of solar-wind-derived water and that such water reservoirs are probably ubiquitous on airless worlds throughout our Galaxy. The production of this isotopically light water reservoir by solar wind implantation into fine-grained silicates may have been a particularly important process in the early Solar System, potentially providing a means to recreate Earth’s current water isotope ratios.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Room temperature facile synthesis of olivine-Co 2 SiO 4 nanoparticles utilizing a mechanochemical method

Co 2 SiO 4 is a ceramic pigment and promising battery material of significant technological interest, as well as a model end-member of one of the most important mineral families in the Earth's crust and upper mantle. All previously developed methods for synthesis of Co 2 SiO 4 require high-temperature processing, which promotes grain growth, while the nanocrystalline form is required for some important technological applications. Here, we report a successful method for synthesizing nanocrystalline Co 2 SiO 4 via a simple and inexpensive high-energy ball milling mechanochemical process. Products of the synthesis were characterized by a combination of XRD and TEM, and their crystal structures and elemental compositions are reported.

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

In situ Al 2 O 3 incorporation enhances the efficiency of CuIn(S,Se) 2 solar cells prepared from molecular-ink solutions

Here, we report an efficiency enhancement of solution-processed CuIn(S,Se) 2 (CISSe) thin film solar cells via in situ incorporation of Al 2 O 3 . These films were produced using inks containing CuCl, InCl 3 , AlNO 3 (Al/Al + In: 0.1) and thiourea dissolved in methanol. After spin coating of these solutions in air, samples were subjected to a selenization process. Auger electron spectroscopy depth-profiling analysis showed that Al is evenly distributed throughout the bulk of the film. Transmission electron microscopy revealed that AlNO 3 precursor reacted with oxygen to form nanosized amorphous Al 2 O 3 grains located within the bulk and grain boundaries of CISSe, as well as at both the top and bottom interfaces. Power conversion efficiency (PCE) as high as 11.6% (JS C : 35.8 mA cm –2 , V OC : 518 mV, FF: 62.2%, no anti-reflection coating) was achieved with Al–CISSe solar cell devices integrated with CdS (chemical bath deposition, thickness: 80 nm) and ZnO/ITO bilayers (sputtered, thickness: 300 nm). The average PCE (10.1%, $\langle$J SC $\rangle$: 34.5 mA cm –2 , $\langle$V OC $\rangle$: 491 mV, $\langle$FF$\rangle$: 59.8%) was nearly 4% (absolute) higher than that measured on CISSe baseline cells fabricated from solutions without Al ($\langle$PCE$\rangle$ = 6.4%, $\langle$J SC $\rangle$: 32.8 mA cm –2 , $\langle$V OC $\rangle$: 410 mV, $\langle$FF$\rangle$: 47.3%). This in situ Al 2 O 3 incorporation is speculated to play a role in the enhancement of the VOC and FF of the devices through passivation of defects in CISSe reducing interface and bulk recombination, as evidenced by a reduced defect density and an increased activation energy of the dominant recombination mechanism from capacitance and temperature-dependent VOC measurements, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Wide-Bandgap Cu(In,Ga)S 2 Photocathodes Integrated on Transparent Conductive F:SnO 2 Substrates for Chalcopyrite-Based Water Splitting Tandem Devices

Recently, whole-chalcopyrite-based tandem devices for photoelectrochemical (PEC) water splitting have emerged as a promising route for obtaining ~20% solar-to-hydrogen efficiencies. Here we pursue this approach by demonstrating integration of the top cell wide-bandgap (E G ) chalcopyrite onto a transparent conductor, which is a critical step in the realization of tandem devices. We report specifically on our efforts to synthesize photoactive Cu(In,Ga)S 2 thin films on transparent conductive F:SnO 2 (FTO), while preserving the optoelectronic properties of the FTO substrate and preventing the formation of a resistive SnS x interfacial layer. We demonstrate that such attributes can be achieved via close-space sulfurization (CSS) of lower EG Cu(In,Ga)Se 2 precursors, co-evaporated on FTO at low-temperature. Depending on Cu(In,Ga)Se 2 precursors’ Ga and In content, the resulting Cu(In,Ga)S 2 solar absorbers have E G energies spanning 2.05 eV to 2.45 eV. The CSS process, which includes a low-temperature annealing in sulfur vapor followed by a high-temperature crystallization under inert atmosphere, allowed for up to 95% Se substitution with S in the chalcopyrite lattice, tuning both E G and band edge positions that impact PEC performance. Photoelectrochemical measurements performed under AM1.5G illumination in 0.5M H 2 SO 4 on the 2.05 eV CuInGaS 2 photocathode revealed a saturation photocurrent density (J SAT ) of -5.25 mA/cm 2 , a value corresponding to 38% of the absorber’s optical limit. We further concluded that such low J SAT originates from sub-par optical absorption of Cu(In,Ga)S 2 absorbers. Further enhancements of the CSS process are expected to improve material quality towards our end goal of achieving whole-chalcopyrite tandem PEC devices.

08 HYDROGEN↗
DOE OSTI2018

Multiple generations of grain aggregation in different environments preceded solar system body formation

The solar system formed from interstellar dust and gas in a molecular cloud. Astronomical observations show that typical interstellar dust consists of amorphous (a-) silicate and organic carbon. Bona fide physical samples for laboratory studies would yield unprecedented insight about solar system formation, but they were largely destroyed. The most likely repositories of surviving presolar dust are the least altered extraterrestrial materials, interplanetary dust particles (IDPs) with probable cometary origins. Cometary IDPs contain abundant submicron a-silicate grains called GEMS (glass with embedded metal and sulfides), believed to be carbon-free. Some have detectable isotopically anomalous a-silicate components from other stars, proving they are preserved dust inherited from the interstellar medium. However, it is debated whether the majority of GEMS predate the solar system or formed in the solar nebula by condensation of high-temperature (>1,300 K) gas. Here, we map IDP compositions with single nanometer-scale resolution and find that GEMS contain organic carbon. Mapping reveals two generations of grain aggregation, the key process in growth from dust grains to planetesimals, mediated by carbon. GEMS grains, some with a-silicate subgrains mantled by organic carbon, comprise the earliest generation of aggregates. These aggregates (and other grains) are encapsulated in lower-density organic carbon matrix, indicating a second generation of aggregation. Since this organic carbon thermally decomposes above ~450 K, GEMS cannot have accreted in the hot solar nebula, and formed, instead, in the cold presolar molecular cloud and/or outer protoplanetary disk. We suggest that GEMS are consistent with surviving interstellar dust, condensed in situ, and cycled through multiple molecular clouds.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2016

Comet Dust: The Diversity of "Primitive" Particles and Implications

Comet dust is primitive and shows significant diversity. Our knowledge of the properties of primitive particles has expanded significantly through microscale investigations of cosmic dust samples ( IDP's(Interplanetary Dust Particles) and AMM's (Antarctic Micrometeorites)) and of comet dust samples (Stardust and Rosetta's COSIMA), as well as through remote sensing (spectroscopy and imaging) via Spitzer and via spacecraft encounters with 103P/Hartley 2 and 67P/Churyumov-Gerasimenko. Microscale investigations show that comet dust and cosmic dust are particles of unequilibrated materials, including aggregates of materials unequilibrated at submicron scales. We call unequilibrated materials "primitive" and we deduce they were incorporated into ice-rich (H2O-, CO2-, and CO-ice) parent bodies that remained cold, i.e., into comets, because of the lack of aqueous or thermal alteration since particle aggregation; yet some Stardust olivines suggest mild thermal metamorphism. Primitive particles exhibit a diverse range of: structure and typology; size and size distribution of constituents; concentration and form of carbonaceous and organic matter; D-, N-, and O- isotopic enhancements over solar; Mg-, Fe-contents of the silicate minerals; the compositions and concentrations of sulfides, and of less abundant mineral species such as chondrules, CAIs and carbonates. The uniformity within a group of samples points to: aerodynamic sorting of particles and/or particle constituents; the inclusion of a limited range of oxygen fugacities; the inclusion or exclusion of chondrules; a selection of organics. The properties of primitive particles imply there were disk processes that resulted in different comets having particular selections of primitive materials. The diversity of primitive particles has implications for the diversity of materials in the protoplanetary disk present at the time and in the region where the comets formed.

Wooden, Diane H.↗
DOE OSTI2015

The survivability of phyllosilicates and carbonates impacting Stardust Al foils: Facilitating the search for cometary water

Abstract Comet 81P/Wild 2 samples returned by NASA's Stardust mission provide an unequalled opportunity to study the contents of, and hence conditions and processes operating on, comets. They can potentially validate contentious interpretations of cometary infrared spectra and in situ mass spectrometry data: specifically the identification of phyllosilicates and carbonates. However, Wild 2 dust was collected via impact into capture media at ~6 km s −1 , leading to uncertainty as to whether these minerals were captured intact, and, if subjected to alteration, whether they remain recognizable. We simulated Stardust Al foil capture conditions using a two‐stage light‐gas gun, and directly compared transmission electron microscope analyses of pre‐ and postimpact samples to investigate survivability of lizardite and cronstedtite (phyllosilicates) and calcite (carbonate). We find the phyllosilicates do not survive impact as intact crystalline materials but as moderately to highly vesiculated amorphous residues lining resultant impact craters, whose bulk cation to Si ratios remain close to that of the impacting grain. Closer inspection reveals variation in these elements on a submicron scale, where impact‐induced melting accompanied by reducing conditions (due to the production of oxygen scavenging molten Al from the target foils) has resulted in the production of native silicon and Fe‐ and Fe‐Si‐rich phases. In contrast, large areas of crystalline calcite are preserved within the calcite residue, with smaller regions of vesiculated, Al‐bearing calcic glass. Unambiguous identification of calcite impactors on Stardust Al foil is therefore possible, while phyllosilicate impactors may be inferred from vesiculated residues with appropriate bulk cation to Si ratios. Finally, we demonstrate that the characteristic textures and elemental distributions identifying phyllosilicates and carbonates by transmission electron microscopy can also be observed by state‐of‐the‐art scanning electron microscopy providing rapid, nondestructive initial mineral identifications in Stardust residues.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2008

Transmission Electron Microscopy of Cometary Residues from Micron-Sized Craters in the Stardust Al-Foils

We report Transmission Electron Microscopy (TEM) investigations of micro-craters that originated from hypervelocity impacts of comet 81P/Wild 2 dust particles on the aluminium foil of the Stardust collector. The craters were selected by Scanning Electron Microscopy (SEM) and then prepared by Focused Ion Beam (FIB) milling techniques in order to provide electron transparent cross-sections for TEM studies. The crater residues contain both amorphous and crystalline materials in varying proportions and compositions. The amorphous component is interpreted as resulting from shock melting during the impact and the crystalline phases as relict minerals. The latter show evidence for shock metamorphism. Based on the residue morphology and the compositional variation, the impacting particles are inferred to have been dominated by mixtures of submicron olivine, pyroxene and Fe-sulfide grains, in agreement with prior results of relatively coarse-grained mineral assemblages in the aerogel collector.

Leroux, Hugues↗
NASA NTRS2005

Synthesis of GEMS from Shock-accelerated Crystalline Dust in Superbubbles: Model and Predictions

GEMS (Glass Embedded with Metals and Sulfides) are highly enigmatic yet common components of anhydrous IDPs. We have recently proposed a model of GEMS formation from shock-accelerated crystalline dust in superbubbles[1] which explains the three most perplexing properties of GEMS: pseudomorphism[2], their chemistry[3], and their size range. In this Abstract, we briefly review the main points of the model, and suggest tests that will either prove or rule out this hypothesis.

Westphal, Andrew J.↗
NASA NTRS1994

Electron energy-loss spectroscopy of carbon in interplanetary dust particles

The nature of the carbon-bearing phases in IDP's provides information regarding the chemical and physical processes involved in the formation and evolution of the early solar system. Several carbon-bearing materials have been observed in IDP's, but details of their nature, abundance, and distribution are still poorly known. A knowledge of the abundance and nature of carbon in IDP's is useful in constraining the sources of IDP's and for comparisons with other chondritic materials. Estimates of carbon abundance in anhydrous and hydrated IDP's indicate that most of these particles have significantly higher carbon than the carbonaceous chondrites. Mineralogical analyses show that carbonates are only a minor component of most hydrated IDP's, and so the high carbon abundances in this group of IDP's indicates that other carbon-bearing phases are present in significant concentrations. Using the technique of electron energy-loss spectroscopy (EELS), we have identified two forms of carbon in a hydrated IDP, oxidized carbon (carbonates), and amorphous elemental carbon.

Keller, Lindsay P.↗
NASA NTRS1992

Thin-sectioning and analysis of fine-grained meteoritic materials

The overall theme of the work was the identification of the sources and formation/aggregation mechanisms of the various classes of interplanetary dust particles (IDP's) and to clarify the relationship between IDP's and conventional meteorites. IDP's are believed to be derived from a much broader range of parent bodies than conventional meteorites. Some of these parent bodies (e.g., comets) have escaped that post accretional processing that has affected the parent bodies of meteorites. Therefore, IDP's are likely to preserve a record of early solar system and possibly presolar grain forming reactions. Using analytical electron microscopy (AEM) and more recently micro-infrared (IR) microspectroscopy to examine ultramicrotomed thin sections, we have addressed the questions of IDP formation mechanisms, sources, and their relationship to conventional meteorites. The following sections describe specific findings resulting from these studies.

Brooks, Donald A.↗