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At least 127 records · Page 7

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SiO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2,7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil simular in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. The elemental composition and structure of the precursor molecules were characterized. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors.

Sibille, L.↗

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil similar JSC-1 in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. Characterization of the precursor molecules and efforts to further concentrate and hydrolyze the products to obtain gel materials will be presented for evaluation as ceramic precursors.

Sibille, L.↗

An Unusual Precursor Burst with Oscillations from SAX J1808.4-3658

We report the finding of an unusual, weak precursor to a thermonuclear X-ray burst from the accreting millisecond pulsar SAX 51808.4-3658. The burst in question was observed on Oct. 19, 2002 with the Rossi X-Ray Timing Explorer (RXTE) proportional counter array (PCA). The precursor began approx. equal to 1 s prior to the onset of a strong radius expansion burst, lasted for about 0.4 s, and exhibited strong oscillations at the 401 Hz spin frequency. Oscillations are not detected in the approx. equal to 0.5 s interval between the precursor and the main burst. The estimated peak photon flux and energy fluence of the precursor are about 1/25, and 1/500 that of the main burst, respectively. From joint spectral and temporal modeling, we find that an expanding burning region with a relatively low temperature on the spinning neutron star surface can explain the oscillations, as well as the faintness of the precursor with respect to the main part of the burst. We discuss some of the implications of our findings for the ignition and spreading of thermonuclear flames on neutron stars.

Bhattacharyya, Sudip↗

CME-Producing Precursors to the 2006 December 13 X-Flare

We revisit one of the largest explosions observed during the Hinode era, the X4.3 class event of 2006 Dec 13. We gain insight into the main eruption through study of two sub-C-class precursor eruptions, occurring within 12 hours of and originating from the same (or nearby) neutral line as the X-flare. The precursors share some features in common with the main eruption, and their lower energy and consequent slower development renders interpretation of these features easier to decipher than in the rapidly explosive main eruption. In addition, because the weak precursors occurred in a magnetically strong region, magnetic connections indicated by soft X-ray loops are readily visible in these cases, while such connections can be much less apparent in weaker-region eruptions. Hinode/SOT magnetograms indicate that photospheric magnetic dynamic activity in the "magnetic core" is the likely ultimate source of the eruptions. All the eruptions, however, produce Coronal Mass Ejections (CMEs) that have wider spatial extent than the localized source region; this is a long-observed but puzzling phenomena, which can address directly here using the high-quality Hinode data. For the precursor eruptions, Hinode/XRT images show that the initial eruptions occur inside larger-scale magnetic structures that encompass the core. The exploding core field blows out this larger-scale structure, resulting in the CME having angular extent far exceeding that of the source-region core alone; this is the arch-arch-blowout scenario for CMEs of Moore & Sterling (2007). Similar processes occur in the main eruption, except that the much larger energy release in that eruption compared to the precursors results in much faster and larger-scale phenomena.

Sterling, Alphonse C.↗

Precursors of Short Gamma-Ray Bursts

We carried out a systematic search of precursors on the sample of short GRBs observed by Swift. We found that approx. 8-10% of short GRBs display such early episode of emission. One burst (GRB 090510) shows two precursor events, the former approx.13 s and the latter approx. 0.5 s before the GRB. We did not find any substantial difference between the precursor and the main GRB emission, and between short GRBs with and without precursors. We discuss possible mechanisms to reproduce the observed precursor emission within the scenario of compact object mergers. The implications of our results on quantum gravity constraints are also discussed.

Troja, E.↗

Using ADOPT Algorithm and Operational Data to Discover Precursors to Aviation Adverse Events

The US National Airspace System (NAS) is making its transition to the NextGen system and assuring safety is one of the top priorities in NextGen. At present, safety is managed reactively (correct after occurrence of an unsafe event). While this strategy works for current operations, it may soon become ineffective for future airspace designs and high density operations. There is a need for proactive management of safety risks by identifying hidden and "unknown" risks and evaluating the impacts on future operations. To this end, NASA Ames has developed data mining algorithms that finds anomalies and precursors (high-risk states) to safety issues in the NAS. In this paper, we describe a recently developed algorithm called ADOPT that analyzes large volumes of data and automatically identifies precursors from real world data. Precursors help in detecting safety risks early so that the operator can mitigate the risk in time. In addition, precursors also help identify causal factors and help predict the safety incident. The ADOPT algorithm scales well to large data sets and to multidimensional time series, reduce analyst time significantly, quantify multiple safety risks giving a holistic view of safety among other benefits. This paper details the algorithm and includes several case studies to demonstrate its application to discover the "known" and "unknown" safety precursors in aviation operation.

aviation safet↗

Can Machine Learning Reveal Precursors of Reversals of the Geomagnetic Axial Dipole Field?

It is well known that the axial dipole part of Earth’s magnetic field reverses polarity, so that the magnetic North Pole becomes the South Pole and vice versa. The timing of reversals is well documented for the past 160 Myr, but the conditions that lead to a reversal are still not well understood. It is not known if there are reliable ‘precursors’ of reversals (events that indicate that a reversal is upcoming) or what they might be. We investigate if machine learning (ML) techniques can reliably identify precursors of reversals based on time-series of the axial magnetic dipole field. The basic idea is to train a classifier using segments of time-series of the axial magnetic dipole. This training step requires modification of standard ML techniques to account for the fact that we are interested in rare events—a reversal is unusual, while a non-reversing field is the norm. Without our tweak, the ML classifiers lead to useless predictions. Perhaps even more importantly, the usable observational record is limited to 0–2 Ma and contains only five reversals, necessitating that we determine if the data are even sufficient to reliably train and validate an ML algorithm. To answer these questions we use several ML classifiers (linear/non-linear support vector machines and long short-term memory networks), invoke a hierarchy of numerical models (from simplified models to 3-D geodynamo simulations), and two palaeomagnetic reconstructions (PADM2M and Sint-2000). The performance of the ML classifiers varies across the models and the observational record and we provide evidence that this is not an artefact of the numerics, but rather reflects how ‘predictable’ a model or observational record is. Studying models of Earth’s magnetic field via ML classifiers thus can help with identifying shortcomings or advantages of the various models. For Earth’s magnetic field, we conclude that the ability of ML to identify precursors of reversals is limited, largely due to the small amount and low frequency resolution of data, which makes training and subsequent validation nearly impossible. Put simply: the ML techniques we tried are not currently capable of reliably identifying an axial dipole moment (ADM) precursor for geomagnetic reversals. This does not necessarily imply that such a precursor does not exist, and improvements in temporal resolution and length of ADM records may well offer better prospects in the future.

Kyle Gwirtz↗

Non-PGM cathode catalysts for fuel cell application derived from heat treated heteroatomic amines precursors

A method of preparing M-N--C catalysts utilizing a sacrificial support approach and inexpensive and readily available polymer precursors as the source of nitrogen and carbon is disclosed. Exemplary polymer precursors include non-porphyrin precursors with no initial catalytic activity. Examples of suitable non-catalytic non-porphyrin precursors include, but are not necessarily limited to low molecular weight precursors that form complexes with iron such as 4-aminoantipirine, phenylenediamine, hydroxysuccinimide, ethanolamine, and the like.

30 DIRECT ENERGY CONVERSION↗

Development of a Lower Cost, High Volume, Commercially Available, Precursor for Lower Cost Carbon Fiber for Automotive and Wind Blade Applications

Essentially all carbon fibers used in structural applications are presently manufactured from solution spun polyacrylonitrile (PAN) precursor. Solution spinning is accomplished at relatively low temperatures using very large amounts of environmentally unfriendly solvents that impart major impact to line speed and costs involved with handling and reclaiming the solvents and associated “waste streams” required in spinning and extracting those solvents. Dralon and others have demonstrated the dry spinning of PAN in the production of some acrylic fibers for textile applications, but to this point it has not been demonstrated in the production of carbon fibers. In dry spinning, the PAN polymer is also dissolved into similar solvents, although typically less solvent is utilized to maintain a somewhat higher solids content of 20-50%. The use of lower overall solvent quantities and elimination of the need for solvent/water separation simplifies and reduces the cost of solvent recovery operations. Other portions of the precursor production and carbon fiber manufacturing processes are quite similar. The work described in this report demonstrated that dry spun acrylic fiber can be an attractive candidate for carbon fiber precursor of potential interest to applications looking to capture the specific stiffness (stiffness per unit mass) and specific strength (strength per unit mass) of carbon fiber when produced at a discount relative to commercial carbon fibers in the market today. Dralon has determined that the dry spinning process utilized for producing fibers used as precursors in this project requires 27% less energy versus producing comparable fibers via the industry standard wet spinning process. Identification of carbon fiber manufacturers, as well as applications development and targeted marketing, will be required to achieve significant in-roads into mission areas of interest to DOE, such as automotive applications and wind turbine blades. In support of that activity, initial data produced in this project indicate the innovative approach as described in this report can meet at least the baseline property requirements identified for these applications.

36 MATERIALS SCIENCE↗

ACBC to Balcite: Bioinspired Synthesis of a Highly Substituted High-Temperature Phase from an Amorphous Precursor

Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca 0.5 Ba 0.5 CO 3 ) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca 1- x Ba x CO 3 ·1.2H 2 O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sites that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.

36 MATERIALS SCIENCE↗

Engineering Perovskite Precursor Inks for Scalable Production of High‐Efficiency Perovskite Photovoltaic Modules

Abstract Blade coating of perovskite solar cells (PSCs) and modules has progressed considerably toward the industrial production of perovskite photovoltaics. Developing stable perovskite precursors is critical for achieving uniform coating over large areas. Here, the engineering of a perovskite precursor solution consisting of 2‐methoxyethanol (2‐Me) and 1,3‐dimethyl‐imidazolidinone (DMI) with superior intermediate phase stability that enables scalable production of efficient perovskite solar modules is reported. With this perovskite precursor solution, uniform and pinhole‐less perovskite film is deposited over a large area of > 100 cm 2 and higher‐efficiency PSCs and modules are obtained. The best‐performing unit cell and module with n‐i‐p configuration reach power conversion efficiencies of 23.4% and 20.1%, respectively. Additionally, a series of non‐destructive metrology methods, such as spectroscopic ellipsometry, hyperspectral photoluminescence, electroluminescence, and laser beam‐induced current mapping, are employed to assess and guide the development the blade‐coated perovskite modules. This results show that rational engineering of precursor inks for blade coating is promising for the scalable production of efficient perovskite solar modules.

36 MATERIALS SCIENCE↗

Fabrication of compact and stable perovskite films with optimized precursor composition in the fast-growing procedure

The fast-growing procedure (FGP) provides a simple, high-yield and lead (Pb)-release free method to prepare perovskite films. In the FGP, the ultra-dilute perovskite precursor solution is drop-cast onto a hot (~240 degrees C) substrate, where a perovskite film grows immediately accompanied by the rapid evaporation of the host solvent. In this process, all the raw materials in the precursor solution are deposited into the final perovskite film. The potential pollution caused by Pb can be significantly reduced. Properties of the FGP-processed perovskite films can be modulated by the precursor composition. While CH3NH3Cl (MACl) affects the crystallization process and leads to full surface coverage, CH(NH2)2I (FAI) enhances the thermal stability of the film. Based on the optimized precursor composition of PbI2(1-x)FAI xMACl, x=0.75, FGP-processed planar heterojunction perovskite solar cells exhibit power conversion efficiencies (PCEs) exceeding 15% with suppressed hysteresis and excellent reproducibility.

14 SOLAR ENERGY↗

Synthesis of aviation biofuel precursors from biomass-derived ketones: Substrate adsorption configuration-catalytic activity

The production of aviation biofuel precursors from biomass-derived ketones by heterogeneous catalysis has been hindered by the low catalytic activity. Herein, a series of Cu-doped metal oxide catalysts were prepared for the conversion of biomass-derived ketones to aviation biofuel precursors. Solvent-free cyclopentanone conversion via aldol condensation reached 91.1 % over Cu/Al 2 O 3 with 100 % selectivity toward dimer and trimer oxygenated species, all of which are aviation biofuel precursors. This catalyst primarily contains Cu 2 O and Cu nanoparticles which are uniformly dispersed across the Al 2 O 3 surface. From in situ DRIFTS and DFT results, the incorporation of Cu species onto Al 2 O 3 not only increased the diversity of Lewis acidic sites, but also changed the adsorption of C = O groups, which lead to the increased aldol condensation activity of Cu/Al 2 O 3 . In conclusion, this study provides insight on the design of heterogeneous catalysts suitable for the solvent-free synthesis of aviation biofuel precursors from biomass-derived ketones.

Adsorption configuration↗

Phase stability in Ag-Cu-In-Ga metal precursors for (Ag,Cu)(In,Ga)Se 2 thin films

The addition of Ag to Cu-Ga-In precursors for reaction to form (AgCu)(InGa)Se 2 has shown benefits including improved adhesion, greater process tolerance and potential for improved device performance. In this study, metal precursors were sputtered with a Cu-Ga/In/Ag-Ga sequence with Ag/(Cu+Ag) = 0.25 and (Ag+Cu)/(Ga+In) = 0.90. These precursor layers are shown to be unstable, with a phase evolution during storage at room temperature revealed by x-ray diffraction (XRD). This behavior was studied in samples annealed in the temperature range of 60–150 °C or stored for up to 90 days. XRD analyses indicated the formation of (Ag 1-x Cu x )In 2 with Cu content of 28% and 36% for samples annealed at 100 °C and 150 °C, respectively. Energy dispersive x-ray spectroscopy and XRD analyses on selenized samples showed a uniform distribution of Ag and Cu through the films and a Ga accumulation near the back interface. Solar cells fabricated from the selenized films showed improved device performance in V OC and FF as a result of the precursor anneal.

(Ag,Cu)(In,Ga)Se2↗

Heterobinuclear Molecular Precursors Direct the Formation of Supported Subnanometer Cu–M Clusters with Tunable Catalytic Behavior

Subnanometer bimetallic clusters hold great promise for catalytic applications due to their unique electronic properties and high surface-to-volume ratios. However, precise control over their composition and size remains a major challenge, particularly for immiscible metal pairs. Here, we report a surface-anchored molecular approach for synthesizing ∼0.7–0.8 nm Cu–M (M = Ru, Mo, W, Fe) bimetallic clusters on mesoporous silica supports, using heterobinuclear N-heterocyclic carbene (NHC)-based complexes as precursors. The NHC ligand functionalized with an alkoxysilane anchor enables robust grafting to the silica interface. Controlled calcination and reduction lead to subnanometer clusters with tunable composition, dictated by the metal–metal bond stability in the precursor. In situ transmission electron microscopy reveals cluster growth proceeds via sintering of adjacent surface-bound units, while elevated temperatures above 300 °C triggering diffusion and phase separation. Catalytic testing in ethylene hydrogenation demonstrates composition-dependent activity and kinetics, with CuRu and CuW clusters exhibiting lower apparent activation energy barriers compared with monometallic Cu nanoparticles. This study establishes a generalizable strategy for the interfacial synthesis of alloyed clusters from molecular precursors and provides mechanistic insight into how precursor design governs nanostructure formation and catalytic behavior.

N-heterocyclic carbene↗

Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from Ir$_x$Cl$_y$ precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts–IrCl 3 , IrCl 4 , H 2 IrCl 6 , or Na 2 IrCl 6 –colloidal nanoparticles as small as Ir ~55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic ($fcc$) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl 3 or IrCl 4 , metallic iridium nanoparticles form rapidly from Ir$_x$Cl$_y$$^{n–}$ complexes, whereas using H 2 IrCl 6 or Na 2 IrCl 6 , the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H 2 IrCl 6 , the formation of different Ir$_n$ ($n$ = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. In conclusion, the results show that the synthesis of iridium nanoparticles from Ir$_x$Cl$_y$ is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precursor Reaction Method With High Ga Cu(In,Ga)(S,Se)$_{2}$ to Achieve Increased Open-Circuit Voltage

The precursor reaction process for the fabrication of Cu(In,Ga)Se 2 solar cells potentially allows for low-cost fabrication and scalable processing for manufacturing. Additionally, this process has yielded record efficiencies in lab-scale experiments. Thus far, research on the precursor reaction method has been restricted to relatively low Ga compositions with Ga/(In+Ga) ≈ 25%. By increasing the ratio of Ga, it is possible to increase the bandgap, and thus, increase the open-circuit voltage. This work develops and characterizes the precursor reaction process for use with Ga/(In+Ga) ≈ 50%, with the goal of improving the open-circuit voltage and efficiency. It is shown that with an increased Ga ratio, increased V ∞ is achieved, but the rate of conversion from the precursor to absorber phases is decreased. Additionally, increased Ga improves the film adhesion at increased selenization temperatures as well as improving the film morphology.

14 SOLAR ENERGY↗

Plasma enhanced atomic layer deposition of ZnO with diethyl zinc and oxygen plasma: Effect of precursor decomposition

Although atomic layer deposition (ALD) of ZnO using diethyl zinc (DEZ) precursor has been extensively reported, variation in growth-per-cycle (GPC) values and the range of substrate temperature (T{sub sub}) for ALD growth between related studies remain unexplained. For identical processes, GPC for the characteristic self-limiting ALD growth is expected to be comparable. Hence, a significant variation in GPC among published ZnO ALD studies strongly suggests a concealed non-ALD growth component. To investigate this, the authors report plasma-enhanced ALD growth of ZnO using DEZ precursor and O{sub 2} inductively coupled plasma. The effect of T{sub sub} on ZnO GPC was studied with deposition cycles (1) 0.02 s–15 s–6 s–15 s, (2) 0.10 s–15 s–15 s–15 s, and (3) 0.20 s–15 s–30 s–15 s, where the cycle parameters t{sub 1}–t{sub 2}–t{sub 3}–t{sub 4} denote duration of DEZ pulse, post-DEZ purge, plasma exposure, and postplasma purge, respectively. The non-ALD growth characteristics observed at T{sub sub} ≥ 60 °C are discussed and attributed to DEZ precursor decomposition. The authors demonstrate ZnO growth at T{sub sub} = 50 °C to be self-limiting with respect to both t{sub 1} and t{sub 3} giving GPC of 0.101 ± 0.001 nm/cycle. The effect of precursor decomposition related (non-ALD) growth at T{sub sub} ≥ 60 °C is illustrated from comparison of optical dielectric function, electrical resistivity, and surface roughness of ZnO films deposited at T{sub sub} = 50, 125, and 200 °C.

42 ENGINEERING↗