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Results for “kinetic stabilization”

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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

Mars - Photodesorption from mineral surfaces and its effects on atmospheric stability

Kinetic constraints are employed to identify the reactive chemisorbed complexes, to describe the mechanism of UV-accelerated desorption from Fe (+2) on mineral surfaces, and to estimate the photodesorption rate on Mars. In particular, it is proposed that gases such as O2, CO2, CO, H2O and N2 undergo an adsorption-desorption process at octahedrally coordinated Fe (+2) surface sites to produce seven-coordinate transition-state complexes. The ligand field stabilization energy acquired by these complexes lies between 16 and 18 kcal per mole. Published photocatalysis data are used to assess the role of photodesorption in Martian atmospheric chemistry and stability.

Huguenin, R. L.↗
NASA NTRS1990

Morphological stability and kinetics in crystal growth from vapors

The following topics are discussed: (1) microscopy image storage and processing system; (2) growth kinetics and morphology study with carbon tetrabromide; (3) photothermal deflection vapor growth setup; (4) bridgman growth of iodine single crystals; (5) vapor concentration distribution measurement during growth; and (6) Monte Carlo modeling of anisotropic growth kinetics and morphology. A collection of presentations and publications of these results are presented.

Rosenberger, Franz↗
NASA NTRS2005

Growth from Solutions: Kink dynamics, Stoichiometry, Face Kinetics and stability in turbulent flow

1. Kink dynamics. The first segment of a polygomized dislocation spiral step measured by AFM demonstrates up to 60% scattering in the critical length l*- the length when the segment starts to propagate. On orthorhombic lysozyme, this length is shorter than that the observed interkink distance. Step energy from the critical segment length based on the Gibbs-Thomson law (GTL), l* = 20(omega)alpha/(Delta)mu is several times larger than the energy from 2D nucleation rate. Here o is tine building block specific voiume, a is the step riser specific free energy, Delta(mu) is the crystallization driving force. These new data support our earlier assumption that the classical Frenkel, Burton -Cabrera-Frank concept of the abundant kink supply by fluctuations is not applicable for strongly polygonized steps. Step rate measurements on brushite confirms that statement. This is the1D nucleation of kinks that control step propagation. The GTL is valid only if l* <Dk/vk, the diffusion path of a kink that has diffusivity Dk and average growth velocity vk. This is equivalent to supersaturations sigma less than approx. alpha/2l*, where alpha is the building block size. For lysozyme, sigma much less than (1%). Conventionally used interstep distance generated by screw dislocation, 19(omega)alpha/Delta(mu) should be replaced by the very different real one, approx.4l*. 2. Stoichiometry. Kink, and thus step and face rates of a non-Kossel complex molecular monocomponent or any binary, AB, lattice was found theoretically to be proportional to 1/(zeta(sup 1/2) + zeta(sup - 1/2)), where zeta = [B]/[A] is the stoichiometry ratio in solution. The velocities reach maxima at zeta = 1. AFM studies of step rates on CaOxalate monohydrate (kidney stones) from aqueous solution was found to obey the law mentioned above. Generalization for more complex lattice will be discussed. 3. Turbulence. In agreement with theory, high precision in-situ laser interferometry of the (101) KDP crystal face shows step bunching if solution flows parallel to the step flow. The bunch height increases with the distance the bunch travels, i.e. with the face size. However, when the flow rate, u, increases, at u greater than approx. 1 m / s , the average step bunch height decreases as 1/u. The pheonomenon is attributed to the turbulent rather than laminar viscous boundary layer where diffusivity Dt = 0.5u(sub tau),y, i.e. increases linearly with the distance y from the solid face. Friction velocity, u(sub tau) approx. u(sup 7/8). Dramatically larger rate of the mass/heat transport within the turbulent, as compared to the laminar, viscous layer will be discussed.

Chernov, A. A.↗
NASA NTRS1994

The kinetic response of a stochastic plasma to low frequency perturbations

Following suggestion that substorm breakup might be caused by an interchange or ballooning instability, several magnetohydrodynamic (MHD) and gyro-kinetic stability analysis have been performed for plasma sheet magnetic field geometries. However, the stochastic ion dynamics in the highly stressed, thin high-beta near earth plasma sheet violate the locality requirements of MHD and the invarience of the magnetic moment, mu, required by gyro-kinetic theories. In this paper we develop a new linear Vlasov kinetic theory (for low frequency modes omega less than omega(sub b), omega(sub b) being the bounce frequency) which includes the dynamics of stochastic ions.

Hurricane, Omar A.↗
NASA NTRS2002

Theoretical Study of Decomposition Pathways for HArF and HKrF

To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

Chaban, Galina M.↗
NASA NTRS1985

Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research

High pressure differential scanning calorimetry (DSC) was studied as an alternate method for performing high temperature fuel thermal stability research. The DSC was used to measure the heat of reaction versus temperature of a fuel sample heated at a programmed rate in an oxygen pressurized cell. Pure hydrocarbons and model fuels were studied using typical DSC operating conditions of 600 psig of oxygen and a temperature range from ambient to 500 C. The DSC oxidation onset temperature was determined and was used to rate the fuels on thermal stability. Kinetic rate constants were determined for the global initial oxidation reaction. Fuel deposit formation is measured, and the high temperature volatility of some tetralin deposits is studied by thermogravimetric analysis. Gas chromatography and mass spectrometry are used to study the chemical composition of some DSC stressed fuels.

Neveu, M. C.↗
NASA NTRS2001

Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

Microporous materials include a large group of solids of varying chemical composition as well as porosity. These materials are characterized by channels and cavities of molecular dimensions. The framework structure is made up of interconnecting T-O-T' bonds, where T and T' can be Si, Al, P, Ga, Fe, Co, Zn, B and a host of other elements. Materials with Si-O-Al bonding in the framework are called zeolites and are extensively used in many applications. Ion-exchange properties of these materials are exploited in the consumer and environmental industries. Chemical and petroleum industries use zeolites as catalysts in hydrocarbon transform ations. Synthesis of new microporous frameworks has led to the development of new technologies, and thus considerable effort worldwide is expended in their discovery. Microporous materials are typically made under hydrothermal conditions. Influence of nature of starting reactants, structure directing agents, pH, temperature, and aging all have profound influence on the synthesis process. This is primarily because the most interesting open frameworks are not necessarily the stable structures in the reaction medium. Thus, the discovery of new frameworks is often tied to finding the right composition and synthesis conditions that allow for kinetic stabilization of the structure. This complexity of the synthesis process and limited understanding of it has made it difficult to develop directed is of microporous materials and most advances in this field have been made by trial and error. The basic issues in crystal growth of these materials include: (1) Nature of the nucleation process; (2) Molecular structure and assembly of nuclei; (3) Growth of nuclei into crystals; (4) Morphology control; and (5) Transformation of frameworks into other structures. The NASA-funded research described in this paper focuses on all the above issues and has been described in several publications. We present the highlights of our program, especially with the focus on possible experiments in microgravity.

Dutta, Prabir K.↗
NASA NTRS2020

Structural evolution, electrochemical kinetic properties, and stability of A-site doped perovskite Sr(1-x)Yb(x)CoO(3-δ)

Mixed ionic and electronic conducting (MIEC) perovskite SrCoO(3-δ) is a widely studied (electro)catalyst for the oxygen reduction reaction (ORR) and possesses different crystal structures at different temperatures. These temperature dependent phase transitions significantly impact the ordering of oxygen vacancies and electrochemical kinetic properties as well as the reliability of the related devices. Some of the crystal structures formed, e.g. hexagonal phases, turn out to be almost impermeable to oxygen gas. Therefore, it is important to stabilize the crystal structure of SrCoO(3-δ) that favors the ORR over a wide temperature range. Herein, the partial substitution of the A-site Sr with Yb is systematically studied, including synthesis, characterization and analysis of structural evolution, electrochemical kinetic properties, thermal stability, and stability in a CO2-containing atmosphere. The results indicate that Sr(0.90)Yb(0.10)CoO(3-δ) is able to stabilize the tetragonal crystal structure with less ordered oxygen vacancies, leading to polarization resistances of 0.051, 0.115 and 0.272 U sq.cm at 750, 700 and 650 °C, respectively, on symmetrical cells. Sr(0.90)Yb(0.10)CoO(3-δ) demonstrates a very stable surface oxygen vacancy distribution and electronic structure near oxygen vacancies but dissociation of adsorbed oxygen molecules into atomic oxygen is affected by surface Sr segregation, and polarization resistance degradation is mainly induced by surface Sr segregation. Furthermore, Sr(0.90)Yb(0.10)CoO(3-δ) exhibits excellent thermal stability as well as excellent recovery stability and improved polarization performance after a few pure air/CO2-containing air treatment cycles at 700 °C. However, a hysteresis behavior of polarization performance is observed at 650 °C during gas cycling treatment, which may cause long-term degradation of the Sr(0.90)Yb(0.10)CoO(3-δ) electrode. The different polarization behaviors during gas cycling treatment are induced by different sensitivities of the formed surface strontium carbonate and chemisorbed surface oxo-carbonaceous species to different operating temperatures.

electrochemical kinetic↗
NASA NTRS1998

Increased Stability in Crystal Growth Kinetics in Response to Bulk Transport Enhancement

High-resolution interferometry on facets of lysozyme crystals growing under steady external conditions revealed intrinsic kinetics instabilities that occur as fluctuations in the spacing of growth steps. The amplitude of these fluctuations is reduced by forced solution flow. This increased stability is interpreted in terms of the ratio of the characteristic rates of lattice incorporation and bulk transport. Apparently a steady state is approached as an asymptote of a continuous family of unsteady states.

Vekilov, Peter G.↗
NASA NTRS1997

Thermal Stability of Jet Fuels: Kinetics of Forming Deposit Precursors

The focus of this study was on the autoxidation kinetics of deposit precursor formation in jet fuels. The objectives were: (1) to demonstrate that laser-induced fluorescence is a viable kinetic tool for measuring rates of deposit precursor formation in jet fuels; (2) to determine global rate expressions for the formation of thermal deposit precursors in jet fuels; and (3) to better understand the chemical mechanism of thermal stability. The fuels were isothermally stressed in small glass ampules in the 120 to 180 C range. Concentrations of deposit precursor, hydroperoxide and oxygen consumption were measured over time in the thermally stressed fuels. Deposit precursors were measured using laser-induced fluorescence (LIF), hydroperoxides using a spectrophotometric technique, and oxygen consumption by the pressure loss in the ampule. The expressions, I.P. = 1.278 x 10(exp -11)exp(28,517.9/RT) and R(sub dp) = 2.382 x 10(exp 17)exp(-34,369.2/RT) for the induction period, I.P. and rate of deposit precursor formation R(sub dp), were determined for Jet A fuel. The results of the study support a new theory of deposit formation in jet fuels, which suggest that acid catalyzed ionic reactions compete with free radical reactions to form deposit precursors. The results indicate that deposit precursors form only when aromatics are present in the fuel. Traces of sulfur reduce the rate of autoxidation but increase the yield of deposit precursor. Free radical chemistry is responsible for hydroperoxide formation and the oxidation of sulfur compounds to sulfonic acids. Phenols are then formed by the acid catalyzed decomposition of benzylic hydroperoxides, and deposit precursors are produced by the reaction of phenols with aldehydes, which forms a polymer similar to Bakelite. Deposit precursors appear to have a phenolic resin-like structure because the LIF spectra of the deposit precursors were similar to that of phenolic resin dissolved in TAM.

Naegeli, David W.↗
NASA NTRS2007

Effects of Rhenium Addition on the Temporal Evolution of the Nanostructure and Chemistry of a Model Ni-Cr-Al Superalloy: Analysis of the Coarsening Behavior - 2

The temporal evolution of the nanostructure and chemistry of a model Ni-8.5 at.% Cr-10 at.% Al alloy with the addition of 2 at.% Re was studied using transmission electron microscopy and atom-probe tomography in order to measure the number density and mean radius of the y' (LIZ) precipitates and the chemistry of the y'-precipitates and the y (fcc)-matrix. In this article, the coarsening behavior of the y'-precipitates is discussed in detail and compared with the Umantsev-Olson model for multi-component alloys. In addition, the experimental results are evaluated with PrecipiCalc(TradeMark) simulations. The results show that the diffusivities of the solute elements play a major role in the coarsening behavior of the y'-precipitates and that the addition of Re retards the coarsening kinetics and stabilizes the spheroidal morphology of the precipitates by reducing the interfacial energy.

Yoon, Kevin E.↗
NASA NTRS2005

Capture of Hydrogen Using ZrNi

Water, as ice, is thought to reside in craters at the lunar poles along with CH4 and H2 . A proposed robotic mission for 2012 will utilize metal/metal hydrides for H2 recovery. Specifications are 99% capture of H2 initially at 5 bar and 100C (or greater), and degassing completely at 300C. Of 47-systems examined using the van't Hoff equation, 4 systems, Mg/MgH2, Mg2Ni/Mg2NiH4, ZrNi/ZrNiH2.8, and Pd/PdH0.77, were considered likely candidates for further examination. It is essential, when selecting a system, to also examine questions regarding activation, kinetics, cyclic stability, and gas impurity effects. After considering those issues, ZrN1 was selected as the most promising candidate, as it is easily activated and rapidly forms ZrNiH 2.8 . In addition, it resists oxide poisoning by CO2, and H2O, while some oxidation by O2 is recommended for improved activation . The presence of hydrogen in the as received Zr-Ni alloy from Alfa Aesar posed additional technical problems. X-ray diffraction of the Zr-Ni powder (-325 mesh), with a Zr:Ni wt% ratio of 70:30, was found to consist of ZrH2, ZrNiH2.8, and ZrNi. ZrH2 in the alloy presented the risk that after degassing that both Zr and ZrNi would be present, and thus lead to erroneous results regarding the reactivity of ZrNi with H2 . Fortunately, ZrH2 is a highly stable hydride that does not degas H2 to any significant extent at temperatures below 300C. Based on equilibrium calculations for the decomposition of ZrH2, only 1 millionth of the hydride decomposed at 300C under a N2 atmosphere flowing at 25 ccm for 64 hours, the longest time for pretreatment employed in the investigation. It was possible, from the X-ray results and knowledge of the Zr:Ni ratio, to compute the composition of a pretreated specimen as being 76 wt% ZrNi and the balance ZrH2.

Patton, Lisa↗
NASA NTRS2012

Advanced Lithium-ion Batteries with High Specific Energy and Improved Safety for Nasa's Missions

High Energy Materials ( Cathodes, anodes and high voltage and safe electrolyte are required to meet the needs of the future space missions. A. Cathodes: The layered layered composites of of Li2MnO3 and LiMO2 are promising Power capability of the materials, however requires further improvement. Suitable morphology is critical for good performance and high tap (packing) density. Surface coatings help in the interfacial kinetics and stability. B. Electrolytes: Small additions of Flame Retardant Additives improves flammability without affecting performance (Rate and cycle life). 1.0 M in EC+EMC+TPP was shown to have good performance against the high voltage cathode; Performance demonstrated in large capacity prototype MCMB- LiNiCoO2 Cells. Formulations with higher proportions are looking promising. Still requires further validation through abuse tests (e.g., on 18650 cells).

NASA Missions↗
NASA NTRS2013

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗