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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
NASA NTRS1973

Thermodynamics and kinetics of pack aluminide coating formation on IN-100

An investigation of the effects of pack variables on the formation of aluminide coatings on nickel-base superalloy IN-100 was conducted. Also, the thermodynamics and kinetics of coating formation were analyzed. Observed coating weights were in good agreement with predictions made from the analysis. Pack temperature rather than pack aluminum activity controls the principal coating phase formed. In 1 weight percent aluminum packs, aluminum weight gains were related to the halide pack activator. Solid-state nickel diffusion controlled coating formation from sodium fluoride and chloride and ammonium fluoride activated packs. In other ammonium and sodium halide activated 1 weight percent aluminum packs, gaseous diffusion controlled coating formation.

Levine, S. R.↗
NASA NTRS1973

Thermodynamics and kinetics of pack aluminide coating formation on IN-100

An investigation of the effects of pack variables on the formation of aluminide coatings on nickel-base superalloy IN-100 was conducted. Also, the thermodynamics and kinetics of coating formation were analyzed. Observed coating weights were in good agreement with predictions made from the analysis. Pack temperature rather than pack aluminum activity controls the principal coating phase formed. Solid-state nickel diffusion controlled coating formation from sodium fluoride and chloride and ammonium fluoride activated packs. In other ammonium and sodium halide activated 1 weight percent aluminum packs, gaseous diffusion controlled coating formation.

Levine, S. R.↗
NASA NTRS1974

Kinetics of oxygen atom formation during the oxidation of methane behind shock waves

An experimental and analytical study of the formation of oxygen atoms during the oxidation of methane and methane-hydrogen mixtures behind incident shock waves was carried out over the temperature range 1790-2584 K at reaction pressures between 1.2 and 1.7 atm. Oxygen atom levels were determined indirectly by measurement of emission from reaction of O with CO. On the basis of these data and ignition-delay data reported in the literature, a kinetic scheme for methane oxidation was assembled. The proposed kinetic mechanism, in general, predicts higher peak oxygen atom levels than the current oxidation mechanisms proposed by Bowman and Seery and by Skinner and his co-workers.

Jachimowski, C. J.↗
DOE OSTI2024

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti–O●−) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance—a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode’s cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3 ps and a time constant of 0.48 ± 0.09 ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Chemistry↗
DOE OSTI2024

Kinetic study of shock formation and particle acceleration in laser-driven quasi-parallel magnetized collisionless shocks

Quasi-parallel magnetized collisionless shocks are believed to be one of the most efficient accelerators in the universe. Compared to quasi-perpendicular shocks, quasi-parallel shocks are more difficult to form in the laboratory and to simulate because of their large spatial scales and long formation times. Our two-dimensional particle-in-cell simulations show that the early stages of quasi-parallel shock formation are achievable in experiments planned for the National Ignition Facility and that particles accelerated by diffusive shock acceleration (DSA) are expected to be observable in the experiment. Repetitive ion acceleration by crossings of the shock front, a key feature of DSA, is seen in the simulations. Other characteristic features of quasi-parallel shocks such as upstream wave excitation by energetic ions are also observed, and energy partition between the ions and the electrons in the downstream of the shock is briefly discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Dynamics of inverse metal oxides on metal catalysts using spectro-kinetics: reversible Brønsted acid site formation and irreversible reduction

Brønsted acid sites (BASs) in inverse catalysts are vital for the selective hydrogenolysis of polyols, specifically cleaving secondary C–O bonds. These BASs form dynamically in situ in an H 2 environment. While H 2 enables rapid BAS generation on short timescales, it reduces the catalyst at prolonged exposures. The active center for BAS generation, the kinetics of BAS formation, its reverse decomposition, and the irreversible oxide reduction have lacked direct experimental evidence. Here, aided by advanced spectro-kinetic studies, we identify trimeric W 3 O x sites on Pt as the active centers for BAS generation, whereas isolated WO x species on SiO 2 act merely as spectator species, demonstrated using an inverse WO x /Pt catalyst as a representative system. A detailed kinetic profile capturing the dynamics of W 3 O x sites on Pt is also established. The rate constant for BAS formation is two orders of magnitude higher than for its decomposition, which is one order of magnitude faster than the irreversible site reduction. Co-fed H 2 O suppresses the site reduction by ∼50%. Furthermore, the H 2 partial pressure plays an important role. While lower gas-phase H 2 partial pressure does not influence the reversible BAS formation, it can significantly (∼3×) suppress catalyst reduction. Finally, these findings offer critical insights into optimizing reaction conditions through periodic H 2 pulsing, enhancing catalyst stability and performance in hydrogenolysis reactions.

Sourav, Sagar [Indian Inst. of Technology (IIT), M↗
NASA NTRS1983

Highly efficient peptide formation from N-acetylaminoacyl-AMP anhydride and free amino acid

The kinetics of formation of the N-blocked dipeptide, N-acetylglycylglycine, from N-acetylglycyl adenylate anhydride and glycine in aqueous solution at 25 C, and at various PH's are reported. The reaction is of interest in that over a physiologically relevant pH range (6-8), peptide synthesis proceeds more rapidly than hydrolysis, even at those pH's at which this compound becomes increasingly susceptible to base-catalyzed hydrolysis. Under similar conditions, the corresponding unblocked aminoacyl adenylate anhydrides are considerably more unstable, and undergo appreciable hydrlysis in the presence of free amino acid. Because N-blocked aminoacyl adenylate anhydrides serve as model compounds of peptidyl adenylate anhydrides, these results suggest that primitive amino acid polymerization systems may have operated by cyclic reactivation of the peptidyl carboxyl group, rather than that of the incoming amino acid.

Mullins, D. W., Jr.↗
NASA NTRS1975

The formation of lunar breccias - Sintering and crystallization kinetics

The process of clastic breccia formation by viscous sintering in a stress-free environment is analyzed by treating crystallization and sintering as concurrent, competing processes. The kinetic analysis of crystallization is based on the construction of continuous cooling curves corresponding to the degree of crystallinity observed in the matrix of the breccia. These curves are obtained from corresponding time-temperature-transformation curves, which in turn are constructed from measured values of the crystal growth rate together with calculated values of the nucleation frequency. The kinetic analysis of sintering is based on a modification of the Frenkel (1945) treatment of viscous sintering appropriate for conditions of continuous cooling. The analysis is applied to Lunar Composition 70019 to illustrate the approach. It is shown that it is possible from the kinetic analysis to estimate both the rate at which a given breccia cooled and the minimum temperature at which the matrix particles came in contact. The results obtained for Lunar Composition 70019 seem physically reasonable and suggest that this sample cooled on the surface of the moon in its present form rather than buried in an ejecta blanket from which it was later excavated.

Uhlmann, D. R.↗
NASA NTRS1993

Effects of Buoyancy on Laminar, Transitional, and Turbulent Gas Jet Diffusion Flames

Gas jet diffusion flames have been a subject of research for many years. However, a better understanding of the physical and chemical phenomena occurring in these flames is still needed, and, while the effects of gravity on the burning process have been observed, the basic mechanisms responsible for these changes have yet to be determined. The fundamental mechanisms that control the combustion process are in general coupled and quite complicated. These include mixing, radiation, kinetics, soot formation and disposition, inertia, diffusion, and viscous effects. In order to understand the mechanisms controlling a fire, laboratory-scale laminar and turbulent gas-jet diffusion flames have been extensively studied, which have provided important information in relation to the physico-chemical processes occurring in flames. However, turbulent flames are not fully understood and their understanding requires more fundamental studies of laminar diffusion flames in which the interplay of transport phenomena and chemical kinetics is more tractable. But even this basic, relatively simple flame is not completely characterized in relation to soot formation, radiation, diffusion, and kinetics. Therefore, gaining an understanding of laminar flames is essential to the understanding of turbulent flames, and particularly fires, in which the same basic phenomena occur. In order to improve and verify the theoretical models essential to the interpretation of data, the complexity and degree of coupling of the controlling mechanisms must be reduced. If gravity is isolated, the complication of buoyancy-induced convection would be removed from the problem. In addition, buoyant convection in normal gravity masks the effects of other controlling parameters on the flame. Therefore, the combination of normal-gravity and microgravity data would provide the information, both theoretical and experimental, to improve our understanding of diffusion flames in general, and the effects of gravity on the burning process in particular.

Bahadori, M. Yousef↗
DOE OSTI2021

Kinetics of Magnetic Skyrmion Crystal Formation from the Conical Phase

The particle-like magnetic skyrmion or skyrmion lattice (SkX) formation has promoted strong application and fundamental science interests. Despite extensive research, the kinetic of the SkX development is much less understood because of the ultrafast spin rotation and high sensitivity to external perturbations. In this work, using in situ Lorentz transmission electron microscopy, we successfully measured the dynamics of SkX formation from the conical phase with precise control of both the temperature and the magnetic field. We discovered that the Avrami equation can accurately describe the transition process with an initial Avrami constant around 1, suggesting that the rate-limiting step for the quasiparticle lattice formation is one-dimensional heterogeneous nucleation of individual skyrmions. A modified Arrhenius rate law is established, with an energy barrier that has a square-root dependence on temperature and a quadratic dependence on the magnetic field. This study paves the way toward precise and predictable manipulation of topological spin structures.

36 MATERIALS SCIENCE↗
NASA NTRS1970

Research on rechargeable oxygen electrodes.

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Giner, J.↗
DOE OSTI2025

Intrinsic activation energies for ring contraction of allylic cations in zeolites

Cyclic carbocations are important intermediates in zeolite-catalyzed chemistries such as methanol-to-hydrocarbons conversion, naphthenes ring opening, or coke formation. While information about their thermodynamic stability exists, little is known about the kinetics of formation and transformation of cyclic carbocations in zeolites. To fill this knowledge gap, ring contraction of the 1,3,5,5-tetramethylcyclohexenyl cation (C 10 H 17 + ), a representative of 6-membered ring allylic cations, was investigated by in situ UV–vis and IR spectroscopy. Protonic forms of zeolites served as catalysts, at temperatures from 80 °C to 135 °C. Significant oligomerization and hydride transfer in BEA and FAU hampered kinetics analysis, whereas ring contraction dominated in the channels of MOR. The reactant cation, characterized by an electronic absorption at 314 nm and an allylic stretch at 1549 cm −1 , contracted to both a 1,3-alkyl-substituted cyclopentenyl cation (287 nm and 1506 cm −1 ) and a 1,2,3-alkyl-substituted cyclopentenyl cation (297 nm and 1489 cm −1 ). Collection of time-resolved IR spectra and fitting of the intensities with various kinetic models revealed a third transformation, which is expected from thermodynamics: the 1,3-alkyl-substituted cyclopentenyl cation isomerizes to the 1,2,3-alkyl-substituted cyclopentenyl cation. Series of IR spectra recorded at different temperatures delivered intrinsic activation enthalpies (entropies) in MOR of 67 ± 2 kJ mol −1 (−130 ± 6 J mol −1 K −1 ) and 90 ± 3 kJ mol −1 (−70 ± 8 J mol −1 K −1 ) for the contraction to 1,3- and 1,2,3-substituted species, and of 88 ± 5 kJ mol −1 (−84 ± 12 J mol −1 K −1 ) for the isomerization. The findings characterize one path – via contraction of larger rings – to different cyclopentenyl species in zeolites; and the associated, moderate activation energies suggest such transformations contribute to many complex hydrocarbon reaction networks.

Acid catalysis↗
DOE OSTI2020

One-electron redox kinetics of aqueous transition metal couples Zn 2+/+ , Co 2+/+ , and Ni 2+/+ using pulse radiolysis

The one-electron redox potentials for aqueous metal couples Co 2+/+ and Ni 2+/+ have been investigated by using pulse radiolysis using their reactions with a series of reference compounds to establish the most positive upper limits of E 0 . Experiments with Zn + were also carried out to confirm the characteristic shape of the expected reduction kinetics. Both formate ions and t-BuOH were employed to scavenge ˙OH radicals and ˙H atoms. Kinetics and fitted first and second order reaction rates have been reported for reactions with methyl viologen, fluorescein, Ru(NH 3 ) 6 3+ , Co(en) 3 2+ , Co(sepulcrate) 3+ , Ru(bpy) 3 2+ , Cr(bpy)33+, and Ni(Me 6 [14]4,11-dieneN4) 2+ . Previous work demonstrated that both Co 2+ and Ni 2+ can be reduced by CO 2 ˙- radicals, giving a negative E 0 limit of -1.9 V vs. SHE. A definite reaction of Ni + with fluorescein di-anions provides a new upper limit of the Ni 2+/+ couple as -0.906 V vs. SHE. The reaction of Co + with Ru(bpy) 3 2+ has been confirmed, giving E 0 = -1.3 V vs. SHE as a rigorous upper limit of the Co 2+/+ couple. In the case of Co 2+/+ , kinetics were complicated by a self-catalyzed metal clustering phenomenon. Initiation rate constants of this process have also been reported.

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

Improving nanoparticle superlattice stability with deformable polymer gels

The self-assembly of colloidal nanoparticles into ordered superlattices typically uses dynamic interactions to govern particle crystallization, as these non-permanent bonds prevent the formation of kinetically trapped, disordered aggregates. However, while the use of reversible bonding is critical in the formation of highly ordered particle arrangements, dynamic interactions also inherently make the structures more prone to disassembly or disruption when subjected to different environmental stimuli. Thus, there is typically a trade-off between the ability to initially form an ordered colloidal material and the ability of that material to retain its order under different conditions. Here, we present a method for embedding colloidal nanoparticle superlattices into a polymer gel matrix. This encapsulation strategy physically prevents the nanoparticles from dissociating upon heating, drying, or the introduction of chemicals that would normally disrupt the lattice. However, the use of a gel as the embedding medium still permits further modification of the colloidal nanoparticle lattice by introducing stimuli that deform the gel network (as this deformation in turn alters the nanoparticle lattice structure in a predictable manner). Moreover, encapsulation of the lattice within a gel permits further stabilization into fully solid materials by removing the solvent from the gel or by replacing the solvent with a liquid monomer that can be photopolymerized. This embedding method therefore makes it possible to incorporate ordered colloidal arrays into a polymer matrix as either dynamic or static structures, expanding their potential for use in responsive materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2012

Contribution to "AIAA Aerospace Year in Review" article

The NASA Marshall Space Flight Center Microgravity Science Program is dedicated to promoting our understanding of materials processing by conducting relevant experiments in the microgravity environment and supporting related modeling efforts with the intent of improving ground-based practices. Currently funded investigations include research on dopant distribution and defect formation in semiconductors, microstructural development and transitions in dendritic casting alloys, coarsening phenomena, competition between thermal and kinetic phase formation, and the formation of glassy vs. crystalline material. NASA Microgravity Materials Science Principle Investigators are selected for funding either through a proposal in response to a NASA Research Announcement or by collaborating on a team that has successfully proposed to a foreign space agency research announcement. In the latter case, a US investigator can then apply to NASA for funding through an unsolicited proposal. The International Space Station (ISS) facilities used for the experimental investigations are provided primarily by partnering with foreign agencies and often US investigators are working as a part of a larger team studying a specific area of materials science. Facilities for conducting experiments aboard the ISS include the European Space Agency (ESA) Low Gradient Facility (LGF) and the Solidification and Quench (SQF) modular inserts to the Materials Research Rack/Materials Science Laboratory and are primarily used for controlled solidification studies. The French Space Agency (CNES) provided DECLIC facility allows direct observation of morphological development in transparent materials that solidify analogously to metals. The ESA provided Electro ]Magnetic Levitator (EML) is designed to levitate, melt and then cool samples in order to determine material properties, study nucleation behavior, and document phase transitions. Finally, the Microgravity Science Glovebox (MSG) serves as a onboard facility for supporting the hardware required to conduct a number of smaller, short-term investigations.

Grugel, Richard N.↗
NASA NTRS2011

Kinetic Simulations of Current-Sheet Formation and Reconnection at a Magnetic X Line

The integration of kinetic effects into macroscopic numerical models is currently of great interest to the plasma physics community, particularly in the context of magnetic reconnection. We are examining the formation and reconnection of current sheets in a simple, two-dimensional X-line configuration using high resolution particle-in-cell (PIC) simulations. The initial potential magnetic field is perturbed by thermal pressure introduced into the particle distribution far from the X line. The relaxation of this added stress leads to the development of a current sheet, which reconnects for imposed stress of sufficient strength. We compare the evolution and final state of our PIC simulations with magnetohydrodynamic simulations assuming both uniform and localized resistivities, and with force-free magnetic-field equilibria in which the amount of reconnect ion across the X line can be constrained to be zero (ideal evolution) or optimal (minimum final magnetic energy). We will discuss implications of our results for reconnection onset and cessation at kinetic scales in dynamically formed current sheets, such as those occurring in the terrestrial magnetotail and solar corona.

Black, C.↗