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At least 19 records

Sputter coating of Nb₃Sn into SRF cavity using stoichiometric target

Nb₃Sn has emerged as a leading alternative material due to its higher superconducting critical temperature (Tc) and superheating field (Hsh), promising a viable solution to the intrinsic performance limit currently faced by Nb superconducting radiofrequency (SRF) cavities. We sputter-coated Nb₃Sn inside Nb SRF cavity using a stoichiometric Nb₃Sn tube target in a DC cylindrical magnetron sputter coater. The target was fabricated by growing an estimated >20 μm thick Nb₃Sn layer on a Nb tube via Sn vapor diffusion using Jefferson Lab’s coating system. Approximately 150 nm thick Nb-Sn films were sputter-deposited onto flat Nb samples at positions representing the beam tubes and equator of a 2.6 GHz Nb cavity. Post-deposition annealing at 950 °C for 3 h resulted in the formation of Nb₃Sn. Microstructural analysis of the annealed films was carried out to investigate the morphology and structure of the Nb₃Sn films. Later, a 2.6 GHz Nb SRF cavity was coated with a ~1.2 μm thick sputtered Nb-Sn film using a stoichiometric Nb₃Sn target, followed by annealing. Cryogenic RF testing of the annealed cavity demonstrated a Tc of 17.8 K, indicating the formation of Nb₃Sn. After a light Sn recoating treatment, the cavity achieved a quality factor (Q0) of 6.7E+08 at lower field at 2.0 K.

Accelerator Physics↗

Methods of forming near-net shape structures from non-stoichiometric oxides

A method of forming a near-net shape structure comprises forming a structure comprising non-stoichiometric metal oxide comprising at least one metal and less than a stoichiometric amount of oxygen, and electrochemically reducing the non-stoichiometric metal oxide in an electrochemical cell to form a structure having a near-net shape and comprising the at least one metal having less than about 1,500 ppm oxygen. Related methods of forming a non-stoichiometric metal oxide by sintering, annealing, or additive manufacturing, and forming a near-net shape structure from the non-stoichiometric metal oxide, as well as related electrochemical cells are also disclosed.

Tripathy, Prabhat K.↗

Plasma-Assisted Pre-Chamber Ignition System for Highly Dilute Stoichiometric Heavy-Duty Natural Gas Engines (Final Technical Report)

This project explored advanced ignition technologies to significantly enhance efficiency and reduce operating costs for heavy-duty natural gas engines operating at stoichiometric conditions, while meeting ultra-low NOx emission standards. The main goal was to develop and validate a plasma-assisted pre-chamber ignition system that could deliver at least a 2% increase in brake thermal efficiency (BTE) and a 4% decrease in total cost of ownership (TCO) compared to a typical multi-cylinder engine with three-way catalyst aftertreatment, ensuring compatibility with the expected 2027 EPA/CARB regulations. In the first half of the project, the research team concentrated on developing and testing plasma-assisted pre-chamber ignition using nanosecond pulsed discharges. Extensive experiments were conducted in an optically accessible rapid-compression and expansion machine, a constant-volume chamber, and an optical single-cylinder engine. Experiments were coupled with CFD simulations. The work produced unique insights into pre-chamber flame formation, jet ignition, dilution effects, and flame quenching at pressures, temperatures, and dilution levels relevant to engines. Although plasma-assisted ignition showed promise in controlled lab settings, the research also identified fundamental and practical challenges when applying this technology to real engine conditions. Midway through the project, a crucial pivot was made, guided by three key findings. First, the power electronics required for nanosecond plasma discharges were found to be too costly for commercial use, undermining the project’s cost-of-ownership goals. Second, nanosecond plasma ignition was highly sensitive to turbulent flow in the pre-chamber, resulting in lower ignition reliability than traditional spark under engine-like conditions. Third, achieving a truly diffuse low-temperature plasma at high pressures near top dead center was not possible, reducing the anticipated chemical enhancement benefits. These results collectively suggested that continuing with plasma-assisted ignition was unlikely to meet both efficiency and cost objectives. In response, the project shifted focus to a more realistic approach: enhancing traditional spark-based pre-chamber ignition with significantly less spark energy. Using insights gained earlier in the project, the team redesigned the pre-chamber to maintain high dilution tolerance and quick combustion, even with lower ignition energy. Testing confirmed that with optimized pre-chamber design and combustion timing, a lower-energy spark could reliably ignite highly diluted stoichiometric mixtures, reduce burn time, and boost thermal efficiency. Final engine testing and techno-economic analysis verified that this revised approach successfully achieved the project goals. The optimized pre-chamber ignition system provided over a 2% increase in calculated brake thermal efficiency compared to the baseline engine. Notably, the lower ignition energy and simplified hardware reduced component stress, extended maintenance intervals, and lowered the total cost of ownership. When used with stoichiometric operation and traditional three-way aftertreatment, the system remained compatible with near-zero NOx emissions targets without increasing cost or complexity in the emissions control system. In summary, although the project deviated from its initial plasma-assisted ignition idea, the work produced a more practical and commercially viable solution. The results show that precisely optimized, low-energy pre-chamber spark ignition can significantly improve efficiency and reduce overall ownership costs for heavy-duty natural gas engines. This directly aligns with DOE goals for cleaner, more efficient, and cost-effective transportation technologies.

03 NATURAL GAS↗

Tensile Creep Fracture of Polycrystalline Near-Stoichiometric NiAl

Tensile creep fracture behavior of polycrystalline near-stoichiometric NiAl has been studied between 700 and 1200 K under initial applied stresses varying between 10 and 200 MPa. The stress exponent for fracture varied between 5.0 and 10.7 while the activation energy for fracture was 250 +/- 22 kJ/mol. The fracture life was inversely proportional to the secondary creep rate in accordance with the Monkman-Grant relation although there was extensive scatter in the data. This observation suggests that the fracture life for near-stoichiometric NiAl was influenced by creep under these stress and temperature conditions. Several different fracture morphologies were observed. Transgranular ductile cleavage fracture occurs at 700 K and at the higher stresses at 800 K. The fracture mode transitions to transgranular creep fracture at 900 and 1000 K and at lower stresses at 800 K, while plastic rupture and grain boundary cavitation occur at 1100 and 1200 K. An experimental fracture mechanism map is constructed for near-stoichiometric NiAl.

Raj, Sai V.↗

Molecular Dynamics Investigation of the Structural and Mechanical Properties of Off-Stoichiometric Epoxy Resins

Molecular dynamic (MD) simulations were performed to compute the mechanical properties of off-stoichiometric epoxy resins as a function of hardener/epoxy mixture ratio (r). Properties were characterized in relation to their microscopic structures. Such resins have been used recently for adhesive-free bonding of large-scale composite structures using the co-curing-ply method. In this process, two partially precured composite panels with hardener-poor (HP) off-stoichiometric resins are coupled with ply(ies) of complementary hardener-rich (HR) formulations and then cured simultaneously. This bonding process has the potential to produce reliable and certifiable composite joints without the need for additional fasteners, which are often required for many conventional bonding methods because even small amounts of contamination can cause a weak bond. The reflow and mixing of the HP/HR resin in this bonding process result in a joint with no discernable interface that should not be susceptible to surface contamination. However, incomplete mixing of the two offset resins may result in chemical heterogeneity of the cured polymeric joint. Thus, different r values may be obtained across the joint. Classical MD simulations were performed to compute the Young’s modulus of polymers with different r values and correlate their properties to network structures. High stiffness was associated with molecular packing due to chemical crosslinking, leading to a single network structure. Moreover, the networks became denser as the ratio approached the stoichiometric value r = 1. Thus, the r = 1 systems were single clusters, with high stiffness, high molecular weight, and a high degree of crosslinking. Structural properties such as radius of gyration and mean square displacement were determined to investigate the variation in the stiffness with respect to r. This MD simulation study was validated with experimental measurements.

Chang Woon Jang↗

Coherent-Precipitation-Stabilized Phase Formation in Over-Stoichiometric Rocksalt-Type Li Superionic Conductors

Rationalizing synthetic pathways is crucial for material design and property optimization, especially for polymorphic and metastable phases. Over-stoichiometric rocksalt (ORX) compounds, characterized by their face-sharing configurations, are a promising group of materials with unique properties; however, their development is significantly hindered by challenges in synthesizability. Here, taking the recently identified Li superionic conductor, over-stoichiometric rocksalt Li–In–Sn–O (o-LISO) material as a prototypical ORX compound, the mechanisms of phase formation are systematically investigated. It is revealed that the spinel-like phase with unconventional stoichiometry forms as coherent precipitate from the high-temperature-stabilized cation-disordered rocksalt phase upon fast cooling. This process prevents direct phase decomposition and kinetically locks the system in a metastable state with the desired face-sharing Li configurations. This insight enables us to enhance the ionic conductivity of o-LISO to be >1 mS cm -1 at room temperature through low-temperature post-annealing. This work offers insights into the synthesis of ORX materials and highlights important opportunities in this new class of materials.

36 MATERIALS SCIENCE↗

Structure and Reactivity of Binuclear Cu Active Sites in Cu-CHA Zeolites for Stoichiometric Partial Methane Oxidation to Methanol

Aluminosilicate zeolites exchanged with copper ions facilitate partial methane oxidation (PMO) to methanol in stoichiometric oxidation and reduction cycles, yet the identities of active Cu sites and details of the reaction mechanism remain debated. Here, we use the high-symmetry chabazite (CHA) zeolite framework as a model support to probe the relationship between bulk composition, Cu speciation, and response to various oxidizing and reducing treatments. Density functional theory and first-principles thermodynamics combined with statistical models reveal that Cu speciation and composition depend strongly on Al configuration and external gas conditions. Cu-CHA samples were synthesized to survey broad regions of Si/Al and Cu/Al composition space and framework Al proximity. Characterization by in situ X-ray absorption and UV–visible spectroscopy during exposure to different oxidation conditions reveal that the extent of Cu oxidation is sensitive to activation conditions and thus that both kinetic and thermodynamic factors influence Cu oxidizability in a given material. Similar characterizations during CO reduction reveal that CO titrates Cu 2+ in amounts suggesting the presence of both O- and O 2 -bridged species. In contrast, CH 4 and autoreduction (He) treatments reduce similar but smaller numbers of Cu sites than CO, implicating O 2 -bridged Cu dimers as a potential common intermediate in the former reduction pathways. Furthermore, a systematic increase in methanol yields (per Cu) in stoichiometric PMO cycles increase with the fraction of binuclear O x -bridged Cu sites suggests these species as active sites, as depicted in an updated PMO reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metaproteomics-informed stoichiometric modeling reveals the responses of wetland microbial communities to oxygen and sulfate exposure

Abstract Climate changes significantly impact greenhouse gas emissions from wetland soil. Specifically, wetland soil may be exposed to oxygen (O 2 ) during droughts, or to sulfate (SO 4 2- ) as a result of sea level rise. How these stressors – separately and together – impact microbial food webs driving carbon cycling in the wetlands is still not understood. To investigate this, we integrated geochemical analysis, proteogenomics, and stoichiometric modeling to characterize the impact of elevated SO 4 2- and O 2 levels on microbial methane (CH 4 ) and carbon dioxide (CO 2 ) emissions. The results uncovered the adaptive responses of this community to changes in SO 4 2- and O 2 availability and identified altered microbial guilds and metabolic processes driving CH 4 and CO 2 emissions. Elevated SO 4 2- reduced CH 4 emissions, with hydrogenotrophic methanogenesis more suppressed than acetoclastic. Elevated O 2 shifted the greenhouse gas emissions from CH 4 to CO 2 . The metabolic effects of combined SO 4 2- and O 2 exposures on CH 4 and CO 2 emissions were similar to those of O 2 exposure alone. The reduction in CH 4 emission by increased SO 4 2- and O 2 was much greater than the concomitant increase in CO 2 emission. Thus, greater SO 4 2- and O 2 exposure in wetlands is expected to reduce the aggregate warming effect of CH 4 and CO 2 . Metaproteomics and stoichiometric modeling revealed a unique subnetwork involving carbon metabolism that converts lactate and SO 4 2- to produce acetate, H 2 S, and CO 2 when SO 4 2- is elevated under oxic conditions. This study provides greater quantitative resolution of key metabolic processes necessary for the prediction of CH 4 and CO 2 emissions from wetlands under future climate scenarios.

59 BASIC BIOLOGICAL SCIENCES↗

Stoichiometrically-informed symbolic regression for extracting chemical reaction mechanisms from data

A data-driven computational method is introduced to extract chemical reaction mechanisms from time series chemical concentration data. It is realized through the use of dynamic symbolic regression in which a sparse analytical form for a dynamical system is discoverable from the underlying data. We specifically develop the stoichiometrically-informed symbolic regression (SISR) method to address a standing challenge in complex chemical reaction networks: given a time-series dataset of concentrations of several components, what is the mechanism and the associated rate constants? SISR finds the optimal mechanism, kinetic equations and rate constants by combining differential optimization with a genetic optimization approach that searches a symbolic space of possible reaction mechanisms. Use of SISR in several paradigmatic examples spanning linear and nonlinear reaction schemes results in excellent agreement between true and predicted mechanisms, including when the method is applied to noisy data. The advantages of a stoichiometrically-informed approach such as SISR to address reaction discovery is illustrated through comparison with the use of generic state-of-the-art data-driven approaches.

36 MATERIALS SCIENCE↗

Swirl-can combustor performance to near-stoichiometric fuel-air ratio

Emissions and performance characteristics were determined for full-annulus swirl-can modular combustors operated to near stoichiometric fuel air ratios. The purposes of the tests were to obtain stoichiometric data at inlet air temperatures up to 894 K and to determine the effect of module number by investigating 120 and 72 module swirl-can combustors. The maximum average exit temperature obtained with the 120-module swirl-can combustor was 2465 K with a combustion efficiency of 95 percent at an inlet-air temperature of 894 K. The 72-module swirl-can combustor reached a maximum average exit temperature of 2306 K with a combustion efficiency of 92 percent at an inlet air temperature of 894 K. At a constant inlet air temperature, maximum oxides of nitrogen emission index values occurred at a fuel-air ratio of 0.037 for the 72-module design and 0.044 for the 120-module design. The combustor average exit temperature and combustion efficiency were calculated from emissions measurements. The measured emissions included carbon monoxide, unburned hydrocarbons, oxides of nitrogen, and smoke.

Diehl, L. A.↗

Swirl-can combustor performance to near-stoichiometric fuel-air-ratio

Emissions and performance characteristics were determined for two full-annulus swirl-can modular combustors operated to near-stoichiometric fuel air ratios. The purposes of the tests were to obtain stoichiometric data at inlet-air temperatures up to 894 K and to determine the effect of module number by investigating 120 and 72 module swirl-can combustors. The maximum average exit temperature obtained with the 120-module swirl-can combustor was 2465 K with a combustion efficiency of 95 percent at an inlet-air temperature of 894 K. The 72-module swirl-can combustor reached a maximum average exit temperature of 2306 K with a combustion efficiency of 92 percent at an inlet-air temperature of 894 K. At a constant inlet air temperature, maximum oxides of nitrogen emission index values occurred at a fuel-air ratio of 0.037 for the 72-module design and 0.044 for the 120-module design. The combustor average exit temperature and combustion efficiency were calculated from emissions measurements. The measured emissions included carbon monoxide, unburned hydrocarbons, oxides of nitrogen, and smoke.

Diehl, L. A.↗

Effect of Flame Stabilizer Design on Performance and Exhaust Pollutants of a Two-Row Swirl-Can Combustor Operated to Near-Stoichiometric Conditions

Emissions and performance characteristics were determined for two full annulus modular combustors operated to near stoichiometric fuel air ratios. The tests were conducted to obtain stoichiometric data at inlet air temperatures from 756 to 894 K and to determine the effects of a flat plate circular flame stabilizer with upstream fuel injection and a contraswirl flame stabilizer with downstream fuel injection. Levels of unburned hydrocarbons were below 0.50 gram per kilogram of fuel for both combustors and thus there was no detectable difference in the two methods of fuel injection. The contraswirl flame stabilizer did not produce the level of mixing obtained with a flat plate circular flame stabilizer. It did produce higher levels of oxides of nitrogen, which peaked at a fuel air ratio of 0.037. For the flat plate circular flame stabilizer, oxides of nitrogen emission levels were still increasing with fuel air ratio to the maximum tested value of 0.045.

Biaglow, James A.↗

Thermoelectric properties of non-stoichiometric lanthanum sulfides

The lanthanum sulfides are promising candidate materials for high-efficiency thermoelectric applications at temperatures up to 1300 C. The non-stoichiometric lanthanum sulfides (LaS(x), where x is in the range 1.33-1.50) appear to possess the most favorable thermoelectric properties. The Seebeck coefficient and resistivity vary significantly with composition, so that an optimum value of alpha sq/rho (where alpha is the Seebeck coefficient and rho is the resistivity) can be chosen. The thermal conductivity remains approximately constant with stoichiometry, so a material with an optimum value of alpha sq/rho should possess the optimum figure-of-merit. Data for the Seebeck coefficient and electrical resistivity of non-stoichiometric lanthanum sulfides will be pressed, together with structural properties of these materials.

Shapiro, E.↗

Vickers indentation hardness of stoichiometric and reduced single crystal TiO2 (rutile) from 25 to 800 C

The indentation microhardness of stoichiometric and reduced single crystal rutile (TiO2) from 25 to 800 C is presented in this paper. The results serve two main purposes. One is to assess the effect of rutile's stoichiometry on its hardness. The other is to test recently suggested theory on solid lubrication with sub Stoichiometric rutile in an effort to better understand shear controlled phenomenon. Microhardness was measured using a Vickers diamond indentor on both vacuum and hydrogen reduced single crystal rutile from 25 to 800 C. The results indicate that stoichiometry and temperature have a pronounced effect on rutile's hardness. The measured effects lend support to theory on solid lubrication by enhanced crystallographic slip and suggest that solid lubricant materials may be produced by careful atomic level tailoring (stoichiometry control).

Dellacorte, Christopher↗

Low Temperature Creep of Hot-Extruded Near-Stoichiometric NiTi Shape Memory Alloy: Isothermal Creep - Part I

This two-part paper is the first published report on the long term, low temperature creep of hot-extruded near-stoichiometric NiTi. Constant load tensile creep tests were conducted on hot-extruded near-stoichiometric NiTi at 300, 373 and 473 K under initial applied stresses varying between 200 and 350 MPa as long as 15 months. These temperatures corresponded to the martensitic, two-phase and austenitic phase regions, respectively. Normal primary creep lasting several months was observed under all conditions indicating dislocation activity. Although steady-state creep was not observed under these conditions, the estimated creep rates varied between 10(exp -10) and 10(exp -9)/s. The creep behavior of the two phases showed significant differences. The martensitic phase exhibited a large strain on loading followed by a primary creep region accumulating a small amount of strain over a period of several months. The loading strain was attributed to the detwinning of the martensitic phase whereas the subsequent strain accumulation was attributed to dislocation glide-controlled creep. An "incubation period" was observed before the occurrence of detwinning. In contrast, the austenitic phase exhibited a relatively smaller loading strain followed by a primary creep region, where the creep strain continued to increase over several months. It is concluded that the creep of the austenitic phase occurs by a dislocation glide-controlled creep mechanism as well as by the nucleation and growth of deformation twins.

Raj, S. V.↗

Complex Intergrowths of Non-Stoichiometric Defect-Structured Hibonite and Al-Rich Spinel in an Allende Ca-Al-Rich Inclusion

Hibonite is a primary ultra-refractory mineral occurring in many Ca-Al-rich inclusions (CAIs) and is predicted to condense as the second major phase from a cooling gas of solar composition. Our previous microstructural studies of hibonite in carbonaceous chondrites revealed its unique microstructures consisting of numerous defects that contain Mg-enriched, wider spinel blocks in stoichiometric hibonite. Han, J. et al. [2 items] demonstrated experimentally that defect-structured hibonites can grow easily in the presence of minor Mg and are kinetically more stable than equilibrium assemblages predicted by thermodynamic calculations. However, a thermo-dynamic vs. structural stability of defect-structured hibonite relative to other early-condensed Al-rich phases such as corundum, grossite, and spinel remains poorly constrained. Here, we present the results of atomic resolution TEM (Transmission Electron Microscopy) imaging of hibonite in a compact Type A CAI in the Allende CV3 chondrite in order to better understand the crystal structure and chemistry of defect-structured hibonite and its associated Al-rich phases, especially non-stoichiometric, Al-rich spinel, in the context of the formation of first refractory solids in the early solar nebula.

Han, J.↗

Hydrogen motion in near stoichiometric yttrium dihydride at elevated temperatures

The high-temperature motion of hydrogen in near stoichiometric yttrium dihydride (YH x , x = 1.62 and 1.87 at.%) was investigated using incoherent quasi-elastic neutron scattering and Density Functional Theory (DFT) calculations as a function of hydrogen stoichiometry. Translational motion (diffusivity) of hydrogen in yttrium dihydride was only observed in a temperature range of 1073–1173 K under vacuum environment. Here, the hydrogen motion was found to be limited to the tetrahedral sublattice, and diffusivity of hydrogen was observed to increase with decreasing hydrogen stoichiometry. The same behavior was also supported with DFT calculations. The DFT results also indicated that certain migration paths with smaller energy barriers favored H jump resulting in higher diffusivities.

08 HYDROGEN↗

Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors

Amidate-based ligands (N-(tert-butyl)isobutyramide, ITA) bind κ 2 to form homoleptic, 8-coordinate complexes with tetravalent 237 Np (Np(ITA) 4 , 1-Np) and 242 Pu (Pu(ITA) 4 , 1-Pu). These compounds complete an isostructural series from Th, U–Pu and allow for the direct comparison between many of the early actinides with stable tetravalent oxidation states by nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction (SCXRD). The molecular precursors are subjected to controlled thermolysis under mild conditions with the exclusion of exogenous air and moisture, facilitating the removal of the volatile organic ligands and ligand byproducts. The preformed metal–oxygen bond in the precursor, as well as the metal oxidation state, are maintained through the decomposition, forming fully stoichiometric, oxidation-state pure NpO 2 and PuO 2 . Powder X-ray diffraction (PXRD), scanning transmission electron microscopy (STEM), and energy dispersive X-ray spectroscopy (EDS) elemental mapping supported the evaluation of these high-purity materials. This chemistry is applicable to a wide range of metals, including actinides, with accessible tetravalent oxidation states, and provides a consistent route to analytical standards of importance to the field of nuclear nonproliferation, forensics, and fundamental studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗