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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS2023

Effect of the Electrostatic Field due to the Surface Monolayer Metal Atoms on the Dissociation of Homonuclear Diatomic Gases in Gas-Metal Surface Reactions

The present paper examines the role of an electrostatic field generated by the outermost monolayer of metal ions prior to gas adsorption in aiding the dissociation of homonuclear diatomic gas molecules. The interaction of five homonuclear diatomic gases, Cl 2 , F 2 , H 2 , N 2 and O 2 , with several pure metals are examined using Coulomb’s law to calculate the attractive and repulsive forces between the electrons or ions in the gas molecule and the free surface metallic electrons or ions assuming a Bohr model. These calculations demonstrate that the total energy of the electrostatic fields from the metals can exceed the molecular binding energies of Cl 2 , F 2 , and O 2 at some distance from the metallic surface thereby suggesting that these gases interact primarily with the metallic surface in their atomic states after molecular bond dissociation prior to reaction. In contrast, H 2 and N 2 gases do not dissociate prior to reaching the metal surface due to the fact that the effective charge of the gas ions is less than the total electron charge at the outermost electronic shell. The present results correlate linearly with the electrochemical series standard reduction potential as well as with the Pauling electronegativity for several metals.

Gas-metal reactions↗
NASA NTRS2008

Using ALD To Bond CNTs to Substrates and Matrices

Atomic-layer deposition (ALD) has been shown to be effective as a means of coating carbon nanotubes (CNTs) with layers of Al2O3 that form strong bonds between the CNTs and the substrates on which the CNTs are grown. ALD is a previously developed vaporphase thin-film-growth technique. ALD differs from conventional chemical vapor deposition, in which material is deposited continually by thermal decomposition of a precursor gas. In ALD, material is deposited one layer of atoms at a time because the deposition process is self-limiting and driven by chemical reactions between the precursor gas and the surface of the substrate or the previously deposited layer.

Wong, Eric W.↗
NASA NTRS1994

Theoretical Study of the Low-Lying States of MgN+2

The structure and binding energies of the low-lying states of MgN2+ have been computed at the multireference configuration interaction level of theory. The effect of Mg inner-shell correlation have been included using the core-polarization potential method. The charge-quadrupole interaction results in a linear 2Sigma+ ground state as expected. The excited states can arise from either the interaction of the 2-P state of Mg+ with N2 or from charge transfer states with Mg(sup 2+)N2- bonding character. The lowest lying excited state, 2-B2, is mixture of these two mechanisms, which results in a C2v, geometry with Mg atoms sitting at the N2 bond midpoint. The small barrier in the bending potential exists between this state and the 2-II State which is the lowest lying linear excited state.

Maitre, Philippe↗
NASA NTRS2000

Anisotropic Nanomechanics of Boron Nitride Nanotubes: Nanostructured "Skin" Effect

The stiffness and plasticity of boron nitride nanotubes are investigated using generalized tight-binding molecular dynamics and ab-initio total energy methods. Due to boron-nitride BN bond buckling effects, compressed zigzag BN nanotubes are found to undergo novel anisotropic strain release followed by anisotropic plastic buckling. The strain is preferentially released towards N atoms in the rotated BN bonds. The tubes buckle anisotropically towards only one end when uniaxially compressed from both. A "skin-effect" model of smart nanocomposite materials is proposed which will localize the structural damage towards the 'skin' or surface side of the material.

Srivastava, Deepak↗
NASA NTRS1998

Substrate Effects for Atomic Chain Electronics

A substrate for future atomic chain electronics, where adatoms are placed at designated positions and form atomically precise device components, is studied theoretically. The substrate has to serve as a two-dimensional template for adatom mounting with a reasonable confinement barrier and also provide electronic isolation, preventing unwanted coupling between independent adatom structures. For excellent structural stability, we demand chemical bonding between the adatoms and substrate atoms, but then good electronic isolation may not be guaranteed. Conditions are clarified for good isolation. Because of the chemical bonding, fundamental adatom properties are strongly influenced: a chain with group IV adatoms having two chemical bonds, or a chain with group III adatoms having one chemical bond is semiconducting. Charge transfer from or to the substrate atoms brings about unintentional doping, and the electronic properties have to be considered for the entire combination of the adatom and substrate systems even if the adatom modes are well localized at the surface.

Yamada, Toshishige↗
NASA NTRS2004

Application of Simulated Annealing and Related Algorithms to TWTA Design

Simulated Annealing (SA) is a stochastic optimization algorithm used to search for global minima in complex design surfaces where exhaustive searches are not computationally feasible. The algorithm is derived by simulating the annealing process, whereby a solid is heated to a liquid state and then cooled slowly to reach thermodynamic equilibrium at each temperature. The idea is that atoms in the solid continually bond and re-bond at various quantum energy levels, and with sufficient cooling time they will rearrange at the minimum energy state to form a perfect crystal. The distribution of energy levels is given by the Boltzmann distribution: as temperature drops, the probability of the presence of high-energy bonds decreases. In searching for an optimal design, local minima and discontinuities are often present in a design surface. SA presents a distinct advantage over other optimization algorithms in its ability to escape from these local minima. Just as high-energy atomic configurations are visited in the actual annealing process in order to eventually reach the minimum energy state, in SA highly non-optimal configurations are visited in order to find otherwise inaccessible global minima. The SA algorithm produces a Markov chain of points in the design space at each temperature, with a monotonically decreasing temperature. A random point is started upon, and the objective function is evaluated at that point. A stochastic perturbation is then made to the parameters of the point to arrive at a proposed new point in the design space, at which the objection function is evaluated as well. If the change in objective function values (Delta)E is negative, the proposed new point is accepted. If (Delta)E is positive, the proposed new point is accepted according to the Metropolis criterion: rho((Delta)f) = exp((-Delta)E/T), where T is the temperature for the current Markov chain. The process then repeats for the remainder of the Markov chain, after which the temperature is decremented and the process repeats. Eventually (and hopefully), a near-globally optimal solution is attained as T approaches zero. Several exciting variants of SA have recently emerged, including Discrete-State Simulated Annealing (DSSA) and Simulated Tempering (ST). The DSSA algorithm takes the thermodynamic analogy one step further by categorizing objective function evaluations into discrete states. In doing so, many of the case-specific problems associated with fine-tuning the SA algorithm can be avoided; for example, theoretical approximations for the initial and final temperature can be derived independently of the case. In this manner, DSSA provides a scheme that is more robust with respect to widely differing design surfaces. ST differs from SA in that the temperature T becomes an additional random variable in the optimization. The system is also kept in equilibrium as the temperature changes, as opposed to the system being driven out of equilibrium as temperature changes in SA. ST is designed to overcome obstacles in design surfaces where numerous local minima are separated by high barriers. These algorithms are incorporated into the optimal design of the traveling-wave tube amplifier (TWTA). The area under scrutiny is the collector, in which it would be ideal to use negative potential to decelerate the spent electron beam to zero kinetic energy just as it reaches the collector surface. In reality this is not plausible due to a number of physical limitations, including repulsion and differing levels of kinetic energy among individual electrons. Instead, the collector is designed with multiple stages depressed below ground potential. The design of this multiple-stage collector is the optimization problem of interest. One remaining problem in SA and DSSA is the difficulty in determining when equilibrium has been reached so that the current Markov chain can be terminated. It has been suggested in recent literature that simulating the thermodynamic properties opecific heat, entropy, and internal energy from the Boltzmann distribution can provide good indicators of having reached equilibrium at a certain temperature. These properties are tested for their efficacy and implemented in SA and DSSA code with respect to TWTA collector optimization.

Radke, Eric M.↗
NASA NTRS1984

Theoretical study of electron correlation effects in transition metal dimers

Introduction of partially localized orbitals is shown to reduce the number of terms needed to describe the bonding in transition metal clusters. Using this formalism, it is possible to compute the various intra- and inter-atomic electron correlation contributions to the bond energy. Calculations demonstrate the relative importance of several kinds of electron correlation terms involving the 3p, 3d, and 4s electrons. Improved interaction potentials are obtained for the dimers V(2) and Cr(2) when additional correlation is added to the CAS SCF results of Walch, Bauschlicher, Roos, and Nelin (1983).

Das, G. P.↗
NASA NTRS1987

Mixed Cu-simple metal dimers and trimers - CuLi, CuLi2, CuNa, CuK, CuBe, CuBe2, Cu2Be, CuAl, and CuAl2

Theoretical studies of selected diatomic and triatomic molecules containing copper and the simple metals Li, Na, K, Be, and Al are presented, with emphasis on elucidating the nature of the bonding in mixed transition metal-simple metal systems. Large Gaussian basis sets are used in the diatomic calculations, and are used to calibrate the triatomic calculations, in which somewhat smaller Gaussian basis sets are employed. Electron correlation is incorporated using both the single-reference singles plus doubles configuration interaction and coupled pair functional methods. It is found that alkali atoms form very polar sigma bonds with copper, and that the ionicity increases with the inclusion of higher excitations because they improve the electron affinity of copper, which in turn allows a larger negative charge on copper. Aluminum is found to form stronger bonds than beryllium, since it does not have to undergo sp hybridization. Some of the trimers bond by forming three-center three-electron bonds. These multicenter bonds are quite strong even when compared to the two-electron bonds in the dimers or to other bonding mechanisms in the trimers.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1987

A simple interpretation of the Fe2(-) photoelectron spectrum

The photoelectron spectrum of Fe2(-) can be simply interpreted in terms of electron detachment from the mildly bonding 4s sigma sup * sub u orbital of a (4s sigma sub s)(sup 2) (4s sigma sup * sub u)(sup 2) (3d)(sup 13) anion. This interpretation implies a (4s sigma sub g)(sup 2) (4s sigma sup * sub u)(sup1) (3d)(sup13) configuration for the ground state of Fe2, correlating with one ground state (4s2 3d6) and one excited state (4s1 3d7) Fe atom. A comparison of the bond length and vibrational frequency of Fe2 to values for transition metal dimers containing single 4s-4s bonds is suggestive of 3d-3d bonding in this molecule. The results of preliminary full-valence configuration interaction calculations provide stron support for the proposed Fe2 and Fe2(-) configurations.

Leopold, Doreen G.↗
NASA NTRS1986

Chemisorption of O and H on an Al-13 cluster

Chemisorption of oxygen and hydrogen atoms onto a 13 atom aluminum cluster is investigated theoretically. Oxygen atoms are found to remain on the outside of the cluster, and at low coverage, to expand the Al-Al bond length by 0.42 bohr. Hydrogen atoms penetrate into the cluster resulting in a sizeable, 0.57 bohr expansion at high coverage. The difference between chemisorption on aluminum and beryllium clusters is discussed.

Patridge, H.↗
NASA NTRS1992

Theoretical study of the BeLi, BeNa, MgLi, MgNa, and AlBe molecules and their negative ions

The alkaline earth-alkali diatomics are found to have weak bonds, because the diffuse alkali valence s orbitals cannot form a bond of sufficient strength to pay the promotion energy of the alkaline-earth atoms. This leads to van der Waals bonding in the neutrals as well as the negative ions. In fact, the negative ions have larger binding energies than the neutrals as a result of the much larger polarizability of the negative ion. The binding energy of AlBe is significantly larger than the Be-alkali molecules, due to a covalent contribution to the bonding. The binding energy in AlBe(-) is considerably larger than AlBe; the binding energy of the X 3Sigma(-) state of AlBe(-) is computed to be 1.36 eV, as compared with 0.57 eV for the X 2Pi state of AlBe.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1974

X-ray powder diffraction study of poly/carbon monofluoride/, CF/1.12/

Data from X-ray diffraction studies of the poly(carbon monofluoride) with empirical formula CF(1.09-1.15) are reported, and possible intercalation arrangements for the substance are discussed. The data do not conform to true hexagonal symmetry, indicating that the carbon atoms are not coplanar. Each bond angle of carbon is 118.8 deg, and the carbon-carbon distance is 1.47 A. The interlayer distance is 5.76 A. A total absence of (hkl) reflections in the X-ray pattern shows that the separate CF layers are not regularly arranged with respect to one another.

Mahajan, V. K.↗
NASA NTRS1990

FTIR Monitoring Of Curing Of Composites

Infrared-sensing optical fiber system developed to monitor principal infrared absorption bands resulting from vibrations of atoms and molecules as chemical bonds form when resin cured. System monitors resin chemistry more directly. Used to obtain Fourier transform infrared (FTIR) spectrum from graphite fiber/polyimide matrix resin prepreg. Embedded fiber optic FTIR sensor used to indicate state of cure of thermosetting composite material. Developed primarily to improve quality of advanced composites, many additional potential applications exist because principal of operation applicable to all organic materials and most inorganic gases. Includes monitoring integrities of composite materials in service, remote sensing of hazardous materials, and examination of processes in industrial reactors and furnaces.

Druy, Mark A.↗
NASA NTRS2005

Rare Gases Inserted into Biological Building Blocks: A Theoretical Study of Glycine - Rg Compounds (Rg-Xe, Kr, Ar)

Compounds formed by insertion of rare-gas atoms (Xe, Kr, and Ar) into glycine molecule are investigated using accurate ab initio computational methods. Identification of such insertion compounds may open new frontiers in the field of rare-gas chemistry, such as possible existence of biological molecules that include chemically bound rare gas atoms. The most stable glycine-Rg configuration is found to correspond to insertion of Rg atoms into the 0-H bond of glycine. These NH2CH2COORgH compounds are metastable , but separated by sizable potential barriers from the Rg + glycine dissociation products. Preliminary calculations show that NH2CH2COOXeH compound is energetically stable with respect to another (3-body) dissociation channel (NH2CH2COO + Rg + H), while the corresponding Ar species is not stable in this respect. The compound with the inserted Kr is a borderline case, with the 3-body dissociation products being close in energy to the NH2CH2COOKrH minimum.

Chaban, Galina M.↗
NASA NTRS2009

The Lunar Regolith as a Remote Sensing Target for the Lunar Reconnaissance Orbiter (LRO)

Of the 6 instruments and one technology demonstration aboard the LRO, only CRaTER does not measure some kind of interaction of particles with the lunar regolith. LEND detects neutron fluence that contains information about the number density of protons in the upper regolith. To infer the presence of protons, the PI must assume a model that characterizes the surface as a collection of atoms. Thus, LEND does not sense the regolith as a structure. LROC, LOLA, and LAMP sense reflected photons whose wavelength is much shorter than the median particle size in the regolith. The photons interact with electrons, either in atomic shells or in chemical bonds. These interactions occur within a nanometer or so of the surface of a particle. Thus, the particles are macroscopic objects and models of the reflection process invoke ray-tracing optics. DIVINER senses photons that have been emitted by surface particles through thermal phonon processes. The wavelengths detected by the instrument are of the same order as the median particle size, and the photons contain information on particle dimensions as well as the molecular bonds in the constituent compounds. The Mini-RF synthetic aperture radar generates and detects photons of a few centimeters wavelength that interact with the regolith as a dielectric, the dielectric properties of the particulate component being described through effective medium theory. However, the interaction with rocks (macroscopic objects of interest to geologists) can be characterized using Fresnel or Mie models of electromagnetic properties.

Mendell, Wendell W.↗
NASA NTRS2011

Moisture-Induced TBC Spallation on Turbine Blade Samples

Delayed failure of TBCs is a widely observed laboratory phenomenon, although many of the early observations went unreported. "The weekend effect" or "DeskTop Spallation" (DTS) is characterized by initial survival of a TBC after accelerated laboratory thermal cycling, then failure by exposure to ambient humidity or water. Once initiated, failure can occur quite dramatically in less than a second. To this end, the water drop test and digital video recordings have become useful techniques in studies at NASA (Smialek, Zhu, Cuy), DECHMA (Rudolphi, Renusch, Schuetze), and CNRS Toulouse/SNECMA (Deneux, Cadoret, Hervier, Monceau). In the present study the results for a commercial turbine blade, with a standard EB-PVD 7YSZ TBC top coat and Pt-aluminide diffusion bond monitored by weight change and visual appearance. Failures were distributed widely over a 5-100 hr time range, depending on temperature. At some opportune times, failure was captured by video recording, documenting the appearance and speed of the moisture-induced spallation process. Failure interfaces exhibited alumina scale grains, decorated with Ta-rich oxide particles, and alumina inclusions as islands and streamers. The phenomenon is thus rooted in moisture-induced delayed spallation (MIDS) of the alumina scale formed on the bond coat. In that regard, many studies show the susceptibility of alumina scales to moisture, as long as high strain energy and a partially exposed interface exist. The latter conditions result from severe cyclic oxidation conditions, which produce a highly stressed and partially damaged scale. In one model, it has been proposed that moisture reacts with aluminum in the bond coat to release hydrogen atoms that 'embrittle' the interface. A negative synergistic effect with interfacial sulfur is also invoked.

Smialek, James L.↗
NASA NTRS2011

Moisture-Induced TBC Spallation on Turbine Blade Samples

Delayed failure of TBCs is a widely observed laboratory phenomenon, although many of the early observations went unreported. The weekend effect or DeskTop Spallation (DTS) is characterized by initial survival of a TBC after accelerated laboratory thermal cycling, then failure by exposure to ambient humidity or water. Once initiated, failure can occur quite dramatically in less than a second. To this end, the water drop test and digital video recordings have become useful techniques in studies at NASA (Smialek, Zhu, Cuy), DECHMA (Rudolphi, Renusch, Schuetze), and CNRS Toulouse/SNECMA (Deneux, Cadoret, Hervier, Monceau). In the present study the results for a commercial turbine blade, with a standard EB-PVD 7YSZ TBC top coat and Pt-aluminide diffusion bond coat are reported. Cut sections were intermittently oxidized at 1100, 1150, and 1200 C and monitored by weight change and visual appearance. Failures were distributed widely over a 5-100 hr time range, depending on temperature. At some opportune times, failure was captured by video recording, documenting the appearance and speed of the moisture-induced spallation process. Failure interfaces exhibited alumina scale grains, decorated with Ta-rich oxide particles, and alumina inclusions as islands and streamers. The phenomenon is thus rooted in moisture-induced delayed spallation (MIDS) of the alumina scale formed on the bond coat. In that regard, many studies show the susceptibility of alumina scales to moisture, as long as high strain energy and a partially exposed interface exist. The latter conditions result from severe cyclic oxidation conditions, which produce a highly stressed and partially damaged scale. In one model, it has been proposed that moisture reacts with aluminum in the bond coat to release hydrogen atoms that embrittle the interface. A negative synergistic effect with interfacial sulfur is also invoked.

Smialek, James↗