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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Precursor and Neutral Loss Scans in an RF Scanning Linear Quadrupole Ion Trap

Methodology for performing precursor and neutral loss scans in an RF scanning linear quadrupole ion trap is described and compared to the unconventional ac frequency scan technique. In the RF scanning variant, precursor ions are mass selectively excited by a fixed frequency resonance excitation signal at low Mathieu q while the RF amplitude is ramped linearly to pass ions through the point of excitation such that the excited ion’s m/z varies linearly with time. Ironically, a nonlinear ac frequency scan is still required for ejection of the product ions since their frequencies vary nonlinearly with the linearly varying RF amplitude. In the case of the precursor scan, the ejection frequency must be scanned so that it is fixed on a product ion m/z throughout the RF scan, whereas in the neutral loss scan, it must be scanned to maintain a constant mass offset from the excited precursor ions. Both simultaneous and sequential permutation scans are possible; only the former are demonstrated here. The scans described are performed on a variety of samples using different ionization sources: protonated amphetamine ions generated by nanoelectrospray ionization (nESI), explosives ionized by low-temperature plasma (LTP), and chemical warfare agent simulants sampled from a surface and analyzed with swab touch spray (TS). We lastly conclude that the ac frequency scan variant of these MS/MS scans is preferred due to electronic simplicity. In an accompanying manuscript, we thus describe the implementation of orthogonal double resonance precursor and neutral loss scans on the Mini 12 using constant RF voltage. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

A water-soluble precursor for efficient silica polymerization by silicateins

Highlights: • New water-soluble silica acid precursor was suggested. • New precursor was highly effective with silicatein A1. • Optimal conditions for the silicatein activity were determined. Silicateins, the spicule-forming proteins from marine demosponges capable to polymerize silica, are popular objects of biomineralization studies due to their ability to form particles varied in shape and composition under physiological conditions. Despite the occurrence of the many approaches to nanomaterial synthesis using silicateins, biochemical properties of this protein family are poorly characterized. The main reason for this is that tetraethyl orthosilicate (TEOS), the commonly used silica acid precursor, is almost insoluble in water and thus is poorly available for the protein. To solve this problem, we synthesized new water-soluble silica precursor, tetra(glycerol)orthosilicate (TGS), and characterized biochemical properties of the silicatein A1 from marine sponge Latrunculia oparinae. Compared to TEOS, TGS ensured much greater activity of silicatein and was less toxic for the mammalian cell culture. We evaluated optimum conditions for the enzyme - pH range, temperature and TGS concentration. We concluded that TGS is a useful silica acid precursor that can be used for silica particles synthesis and in vivo applications.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Predicting cost-effective carbon fiber precursors: Unraveling the functionalities of oxygen and nitrogen-containing groups during carbonization from ReaxFF simulations

Blends of polyacrylonitrile (PAN) and poly(p-phenylene-2,6-benzobisoxazole) (PBO) as precursors may offer an opportunity to reduce the cost of carbon fiber (CF) production. The all-carbon ring formations and volatile gas production during the heating and carbonization for 9 PAN/PBO blend precursors with varying mixing ratios are studied via the ReaxFF reactive molecular dynamics simulations. Evolutions of oxygen-containing (O-containing) and nitrogen-containing (N-containing) groups are detailed, in order to reveal the reaction mechanisms of the O and N-based CF precursors. Particularly, the O-containing groups are identified to be more efficient for initiating the carbonization, whereas N-containing groups are far longer retained in the graphitic materials and play a key role in capturing and converting carbon radical species into the graphitic networks. Additionally, the PAN/PBO blend precursor with a mole ratio of 1:1 is compared with the pre-oxidized PAN, PAN, and PBO. As a result, it is found that the PAN/PBO blends could be a promising alternative for the cost-effective PAN-based CF precursors, since they can decrease the cost of the CF production by means of: (a) eliminating the pre-oxidation process, (b) having considerable all-carbon ring formations within a short period, and (c) having a relatively fast conversion rate, reaching 95% 6-membered carbon ring formation.

42 ENGINEERING↗
DOE OSTI2026

Sintering effects on NpO 2 grain size and morphology: The role of precursor Np phase

Neptunium dioxide (NpO 2 ) is a key phase in nuclear material processing as a target material for the production of plutonium-238 ( 238 Pu) and has been historically synthesized via the calcination of a Np oxalate precursor. Alternative synthesis methods for NpO 2 are now more prevalent, necessitating their study and comparison with the more common oxalate route. The purpose of this work was to investigate the microstructural properties of NpO 2 synthesized from a nitrate-based Np precursor phase via the assessment of NpO 2 particle size and morphology as a function of calcination temperature and time. Scanning electron microscopy (SEM) was used to probe the primary grain size and morphology of NpO 2 after calcination at temperatures ranging from 700 to 1100 °C and hold times ranging from 1 to 10 h. Post-image analysis using ImageJ software enabled the quantification of mean particle diameter. This analysis indicated that particle diameter increases with both increasing calcination temperature and hold time. Primary particles were shown to be clumped in irregular patterns into the overall rough, blocky aggregates, but this macroscopic morphology was not affected by calcination time or temperature. Although trends in primary grain size of NpO 2 were consistent with available literature from other Np precursor phases, the macroscopic morphology of the NpO 2 aggregates was quite different than reported for other precursors. Through comparison with historical literature on Np oxalate, this work emphasizes the importance of Np precursor on the physical properties of NpO 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Cp* versus Bis-carbonyl Iridium Precursors as CH Oxidation Precatalysts

We previously reported a dimeric Ir IV -oxo species as the active water oxidation catalyst formed from a Cp*Ir(pyalc)Cl {pyalc = 2-(2'-pyridyl)-2-propanoate} precursor, where the Cp* is lost to oxidative degradation during catalyst activation; this system can also oxidize unactivated CH bonds. We now show that the same Cp*Ir(pyalc)Cl precursor leads to two distinct active catalysts for CH oxidation. In the presence of external CH substrate, the Cp* remains ligated to the Ir center during catalysis; the active species—likely a high-valent Cp*Ir(pyalc) species—will oxidize the substrate instead of its own Cp*. If there is no external CH substrate in the reaction mixture, the Cp* will be oxidized and lost, and the active species is then an iridium-$μ$-oxo dimer. Additionally, the recently reported Ir(CO) 2 (pyalc) water oxidation precatalyst is now found to be an efficient, stereoretentive CH oxidation precursor. We compare the reactivity of Ir(CO) 2 (pyalc) and Cp*Ir(pyalc)Cl precursors and show that both can lose their placeholder ligands, CO or Cp*, to form substantially similar dimeric IrIV-oxo catalyst resting states. The more efficient activation of the bis-carbonyl precursor makes it less inhibited by obligatory byproducts formed from Cp* degradation, and therefore the dicarbonyl is our preferred precatalyst for oxidation catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Autonomous and dynamic precursor selection for solid-state materials synthesis

Abstract Solid-state synthesis plays an important role in the development of new materials and technologies. While in situ characterization and ab-initio computations have advanced our understanding of materials synthesis, experiments targeting new compounds often still require many different precursors and conditions to be tested. Here we introduce an algorithm (ARROWS 3 ) designed to automate the selection of optimal precursors for solid-state materials synthesis. This algorithm actively learns from experimental outcomes to determine which precursors lead to unfavorable reactions that form highly stable intermediates, preventing the target material’s formation. Based on this information, ARROWS 3 proposes new experiments using precursors it predicts to avoid such intermediates, thereby retaining a larger thermodynamic driving force to form the target. We validate this approach on three experimental datasets, containing results from over 200 synthesis procedures. In comparison to black-box optimization, ARROWS 3 identifies effective precursor sets for each target while requiring substantially fewer experimental iterations. These findings highlight the importance of domain knowledge in optimization algorithms for materials synthesis, which are critical for the development of fully autonomous research platforms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Vaccination induces broadly neutralizing antibody precursors to HIV gp41

A key barrier to the development of vaccines that induce broadly neutralizing antibodies (bnAbs) against human immunodeficiency virus (HIV) and other viruses of high antigenic diversity is the design of priming immunogens that induce rare bnAb-precursor B cells. The high neutralization breadth of the HIV bnAb 10E8 makes elicitation of 10E8-class bnAbs desirable; however, the recessed epitope within gp41 makes envelope trimers poor priming immunogens and requires that 10E8-class bnAbs possess a long heavy chain complementarity determining region 3 (HCDR3) with a specific binding motif. We developed germline-targeting epitope scaffolds with affinity for 10E8-class precursors and engineered nanoparticles for multivalent display. Scaffolds exhibited epitope structural mimicry and bound bnAb-precursor human naive B cells in ex vivo screens, protein nanoparticles induced bnAb-precursor responses in stringent mouse models and rhesus macaques, and mRNA-encoded nanoparticles triggered similar responses in mice. Thus, germline-targeting epitope scaffold nanoparticles can elicit rare bnAb-precursor B cells with predefined binding specificities and HCDR3 features.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Insights into the mechanism of SARS-CoV-2 main protease autocatalytic maturation from model precursors

A critical step for SARS-CoV-2 assembly and maturation involves the autoactivation of the main protease (MPro WT ) from precursor polyproteins. Upon expression, a model precursor of MPro WT mediates its own release at its termini rapidly to yield a mature dimer. A construct with an E290A mutation within MPro exhibits time dependent autoprocessing of the accumulated precursor at the N-terminal nsp4/nsp5 site followed by the C-terminal nsp5/nsp6 cleavage. In contrast, a precursor containing E290A and R298A mutations (MPro M ) displays cleavage only at the nsp4/nsp5 site to yield an intermediate monomeric product, which is cleaved at the nsp5/nsp6 site only by MPro WT . MPro M and the catalytic domain (MPro 1-199 ) fused to the truncated nsp4 region also show time-dependent conversion in vitro to produce MPro M and MPro 1-199 , respectively. The reactions follow first-order kinetics indicating that the nsp4/nsp5 cleavage occurs via an intramolecular mechanism. These results support a mechanism involving an N-terminal intramolecular cleavage leading to an increase in the dimer population and followed by an intermolecular cleavage at the C-terminus. Thus, targeting the predominantly monomeric MPro precursor for inhibition may lead to the identification of potent drugs for treatment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy

The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that ~14.5 ± 4.9% of the molecules in the precursor state desorbed into the gas phase. Finally, it was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new “vibrationally hot precursor” state was identified in the polarization-dependent XA spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Single crystal purification reduces trace impurities in halide perovskite precursors, alters perovskite thin film performance, and improves phase stability

Impurities present in commercially available halide perovskite precursors are known to affect photovoltaic performance. Here, we employ bulk single crystal growth of FAPbI 3 using solvent orthogonality induced crystallization (SONIC) to remove a broad set of extrinsic impurities from commercially available halide perovskite precursors, as verified by detailed chemical analysis. Following SONIC purification, FAPbI 3 films made from PbI 2 of originally low purity (99%) and high purity (99.99%) show improved phase purity and stability under light and heat relative to films made from raw precursors or precursors purified via retrograde powder crystallization (RPC) in 2-methoxyethanol, a method commonly utilized in recent reports of the highest-efficiency perovskite solar cells. In conclusion, single-crystal purification of precursors improves film stability under operational stressors, and the large enhancements in material purity provide a cleaner slate for improved isolation of compositional and additive effects on perovskite phase stability.

14 SOLAR ENERGY↗
DOE OSTI2016

Incomplete elimination of precursor ligands during atomic layer deposition of zinc-oxide, tin-oxide, and zinc-tin-oxide

For atomic layer deposition (ALD) of doped, ternary, and quaternary materials achieved by combining multiple binary ALD processes, it is often difficult to correlate the material properties and growth characteristics with the process parameters due to a limited understanding of the underlying surface chemistry. In this work, in situ Fourier transform infrared (FTIR) spectroscopy was employed during ALD of zinc-oxide, tin-oxide, and zinc-tin-oxide (ZTO) with the precursors diethylzinc (DEZ), tetrakis(dimethylamino)tin (TDMASn), and H 2 O. The main aim was to investigate the molecular basis for the nucleation delay during ALD of ZTO, observed when ZnO ALD is carried out after SnO 2 ALD. Gas-phase FTIR spectroscopy showed that dimethylamine, the main reaction product of the SnO 2 ALD process, is released not only during SnO 2 ALD but also when depositing ZnO after SnO 2 , indicating incomplete removal of the ligands of the TDMASn precursor from the surface. Transmission FTIR spectroscopy performed during ALD on SiO 2 powder revealed that a significant fraction of the ligands persist during both SnO 2 and ZnO ALD. These observations provide experimental evidence for a recently proposed mechanism, based on theoretical calculations, suggesting that the elimination of precursor ligands is often not complete. In addition, it was found that the removal of precursor ligands by H 2 O exposure is even less effective when ZnO ALD is carried out after SnO 2 ALD, which likely causes the nucleation delay in ZnO ALD during the deposition of ZTO. Furthermore, the underlying mechanisms and the consequences of the incomplete elimination of precursor ligands are discussed.

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

Al-alkyls as acceptor dopant precursors for atomic-scale devices

Atomically precise ultradoping of silicon is possible with atomic resists, area-selective surface chemistry, and a limited set of hydride and halide precursor molecules, in a process known as atomic precision advanced manufacturing (APAM). It is desirable to expand this set of precursors to include dopants with organic functional groups and in this work we consider aluminium alkyls, to expand the applicability of APAM. We explore the impurity content and selectivity that results from using trimethyl aluminium and triethyl aluminium precursors on Si(001) to ultradope with aluminium through a hydrogen mask. Comparison of the methylated and ethylated precursors helps us understand the impact of hydrocarbon ligand selection on incorporation surface chemistry. Combining scanning tunneling microscopy and density functional theory calculations, we assess the limitations of both classes of precursor and extract general principles relevant to each.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Precursor selection in hybrid molecular beam epitaxy of alkaline-earth stannates

One of the challenges of oxide molecular beam epitaxy (MBE) is the synthesis of oxides containing metals with high electronegativity (metals that are hard to oxidize). The use of reactive organometallic precursors can potentially address this issue. To investigate the formation of radicals in MBE, we explored three carefully chosen metal-organic precursors of tin for SnO 2 and BaSnO 3 growth: tetramethyltin (TMT), tetraethyltin (TET), and hexamethylditin (HMDT). All three precursors produced single-crystalline, atomically smooth, and epitaxial SnO 2 (101) films on r-Al 2 O 3 (101¯2) in the presence of oxygen plasma. The study of growth kinetics revealed reaction-limited and flux-limited regimes except for TET, which also exhibited a decrease in the deposition rate with increasing temperature above ~800 °C. Contrary to these similarities, the performance of these precursors was dramatically different for BaSnO 3 growth. TMT and TET were ineffective in supplying adequate tin, whereas HMDT yielded phase-pure, stoichiometric BaSnO 3 films. Significantly, HMDT resulted in phase-pure and stoichiometric BaSnO 3 films even without the use of an oxygen plasma (i.e., with molecular oxygen alone). Furthermore, these results are discussed using the ability of HMDT to form tin radicals and therefore assisting with Sn → Sn 4+ oxidation reaction. Structural and electronic transport properties of films grown using HMDT with and without oxygen plasma are compared. This study provides guideline for the choice of precursors that will enable the synthesis of metal oxides containing hard-to-oxidize metals using reactive radicals in MBE.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Sulfur-Donor Additives Preferentially Coordinate Pb 2+ in Perovskite Precursor Solutions

Lewis base solvents, such as dimethylsulfoxide (DMSO), that strongly coordinate with Pb 2+ are commonly added to hybrid organic-inorganic perovskite (HOIP) precursor solutions to improve thin-film morphology and subsequent photovoltaic (PV) performance. Although nearly all previous studies of precursor solution chemistry have focused on oxygen-donor solvents as Lewis base additives, we expect “softer,” sulfur-donor solvents to coordinate more strongly with Pb 2+ , a borderline-soft Lewis acid. To confirm this hypothesis, we performed extended X-ray absorption fine structure (EXAFS) spectroscopy at the Pb LIII absorption edge to probe the coordination environment of Pb 2+ in solutions comprising mixtures of S- and O-donor solvents. Of the S- and O-donor solvent pairs examined, the S-donor solvent consistently outcompetes its O-donor structural analog for coordination sites around Pb 2+ . In the specific comparison between N-methyl-2-pyrrolidone thione (NMPT) and N-methylpyrrolidone (NMP), density-functional theory calculations indicate that NMPT coordination with Pb 2+ is favored by 10 kcal/mol relative to NMP coordination with Pb 2+ . Similar to the addition of DMSO to precursor solutions, the incorporation of NMPT in fractional quantities provides morphological control of the perovskite film. Unlike DMSO, however, we found NMPT to be stable against undesired transmethylation or disproportionation reactions with methylammonium [1]. Consequentially, films processed with NMPT exhibit no sub-gap electronic states near the valence band edge, in contrast with films prepared using DMSO. We thus believe NMPT merits serious consideration as a solution additive for producing stable HOIP precursor solutions and high-quality HOIP thin films. [1] Hamill, J. C.; Sorli, J. C.; Pelczer, I.; Schwartz, J. and Loo, Y. -L. Acid-catalyzed reactions activate DMSO as a reagent in perovskite precursor inks. Chemistry of Materials 2019, 31, 2114-2120.

Hamill, Joseph↗
DOE OSTI2026

Understanding spectral dependance of laser-induced damage precursors in dielectric materials (Abbreviated report_23-ERD-006)

High peak and average power laser systems are typically limited by the handling fluence of the optical components. In particular, the multilayer dielectric coatings are known to be much lower operational fluence than the more ideal bulk materials. In this project we proposed and succeeded in probing different established classes of damage prone precursors at different wavelengths to understand their fundamental laser damage response as a function of wavelength. This study helped to shed light on the fundamental physics of the non-linear precursors that govern laser damage phenomena for ns-regime pulsed laser damage. In this study, we utilized the onsite coating capabilities (VPL, IBS coating lab) to purposefully generate laser damage-prone precursors in hafnia-based coatings (both single and multi-layer coatings). Specifically, we engineered coatings with craze lines initiated by nodules, generated coatings with our xenon-based coating process to suppress nanobubble formation and generated hafnia coatings under controlled oxygen flow conditions to study hafnia sub-oxides and oxygen flow dependance. In these studies we found that craze lines are rife with precursors that are sensitive to ultra-violet light but not to infrared light; we found that the removal of nanobubbles helps with all wavelengths tested, but is most impactful for ultra-violet light; we also found that ultra-violet laser damage performance of hafnia is closely matched to oxygen flow rate, while the infrared performance may be slightly better at lower flow rates. During this LDRD we also successfully stood up a new laser damage testing capability, namely a wavelength agile damage test station to study the spectral response of known laser-induced damage precursors. This is a unique and important capability for Lawrence Livermore National Lab, allowing us to understand the spectral response of materials under high intensity irradiation and damage. This is a vital tool to understand non-linear optical response at wavelengths that we have previously been unable to test at.

36 MATERIALS SCIENCE↗
NASA NTRS1995

Gamma-Ray Burst Precursor Activity as Observed with BATSE

Gamma-ray burst time histories often consist of multiple episodes of emission with the count rate dropping to the background level between adjacent episodes. We define precursor activity as any case in which the first episode (referred to as the precursor episode) has a lower peak intensity than that of the remaining emission (referred to as the main episode) and is separated from the remaining burst emission by a background interval that is at least as long as the remaining emission. We find that approx. 3% of the bursts observed with the Burst and Transient Source Experiment (BATSE) on Compton Gamma Ray Observatory (CGRO) satisfy this definition. We present the results of a study of the properties of these events. The spatial distribution of these sources is consistent with that of the larger set of all BATSE gamma-ray bursts: inhomogeneous and isotropic. A correlation between the duration of the precursor emission and the duration of the main episode emission is observed at about the 3 sigma confidence level. We find no meaningful significant correlations between or among any of the other characteristics of the precursor or main episode emission. It appears that the characteristics of the main episode emission are independent of the existence of the precursor emission.

Koshut, Thomas M.↗
NASA NTRS2003

Dry Process for Manufacturing Hybridized Boron Fiber/Carbon Fiber Thermoplastic Composite Materials from a Solution Coated Precursor

An apparatus for producing a hybrid boron reinforced polymer matrix composite from precursor tape and a linear array of boron fibers. The boron fibers are applied onto the precursor tapes and the precursor tape processed within a processing component having an impregnation bar assembly. After passing through variable-dimension forming nip-rollers, the precursor tape with the boron fibers becomes a hybrid boron reinforced polymer matrix composite. A driving mechanism is used to pulled the precursor tape through the method and a take-up spool is used to collect the formed hybrid boron reinforced polymer matrix composite.

Harry L Belvin↗
NASA NTRS2003

Sol-Gel Precursors for Ceramics from Minerals Simulating Soils from the Moon and Mars

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 some preliminary 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 A12O3 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 simulant soils. Clear sol-gel precursors have been obtained by dissolution of silica from Lunar simulant soil in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Thermogravimetric Analysis and X-ray Photoelectron Spectroscopy were used to characterize the elemental composition and structure of the precursor molecules. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors. In the second set of experiments, we used the same starting materials to synthesize silicate esters in acidified alcohol mixtures. Preliminary results indicate the presence of silicon alkoxides in the product of distillation.

Sibille, Laurent↗