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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Adsorption of O2, SO2, and SO3 on nickel oxide. Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.

Mehandru, S. P.↗
NASA NTRS1991

Laser studies of the photodissociation dynamics of cometary radicals

In the past year, it was shown that in the 193 nm photolysis of C2H, the C2 radical is produced in a variety of electronic, vibrational, and rotational states. The relative population of the vibrational and rotational states of C2(A 1 Pi u), C2(B 1 Sigma g +), and C2(A 3 Pi u) were determined in a static gas cell and in a pulsed molecular beam. It seems as though the original angular momentum of the C2H molecule appears as part of the angular momentum of the C2 radical. A attempt is being made to discover the mathematical relationship that governs this mapping. New information about the bond dissociation energy of the C2 radical was produces. C2(b 3 Sigma g -) and C2( 1 Delta g) were detected in the photolysis of C2H via time resolved infrared emission spectroscopy. In the former case, vibrational excitation up to v'' = 4 is observed. All of the results suggest that the C2 models in comets need to consider the presence of vibrationally excited C2 radicals in comets. The laser induced fluorescence spectra of the C3 was observed as a product of the 193 nm photolysis of allene and propyne. The populations of the rotational levels are identical in both cases. This result has led us to conclude that an isomerization reaction occurs in the photolysis of propyne which leads to the same C3H2 intermediate that is formed in the photolysis of C3H4. Since the former molecule is one of the most abundant in the interstellar medium it is also likely that its precursor is also present in comets. This would explain why C3 is observed in comets.

Jackson, William M.↗
NASA NTRS1993

Syntheses, structures and properties of polycarbosilanes formed directly by polymerization of Alkenylsilanes

Vinylsilane polymerizes to form predominantly a carbosilane polymer using dimethyltitanocene catalyst. This is in contrast to alkylsilanes, which afford polysilanes under the same conditions. The mechanism of polymerization of alkenylsilanes has been shown to be fundamentally different from that for the polymerization of alkylsilanes. The silyl substitute apparently activates a double bond to participate in a number of polymerization processes in this system, particularly hydrosilation. Isotopic labeling indicates the involvement of silametallocyclic intermediates, accompanied by extensive nuclear rearrangement. Polymers and copolymers derived from alkenylsilanes have relatively high char yields even for conditions which afford low molecular weight distributions. Formation of crystalline beta-SiC is optimum for a copolymer of an alkylsilane and an alkenylsilane having a silane/carbosilane backbone ratio of 85/15 and a C/Si ratio of 1.3/1.

Masnovi, John↗
NASA NTRS2003

New Endcaps for Improved Oxidation Resistance in PMR Polyimides

A polyimide is a polymer composed of alternating units of diamine and dianhydride, linked to each other via an imide bond. PMR polyimides, commonly used in the aerospace industry, are generally capped at each end by an endcap (such as the nadic endcap used in PMR 15) which serves a double function: (1) it limits the number of repeating units and, hence, the average molecular weight of the various polymer chains (oligomers), thereby improving processibility; (2) Upon further treatment (curing), the endcap crosslinks the various oligomer strands into a tough heat-resistant piece. It is this very endcap, so important to processing, that accounts for much of the weight loss in the polymer on aging in air at elevated temperatures. Understanding this degradation provides clues for designing new endcaps to slow down degradation, and prolong the lifetime of the material.

Frimer, Aryeh A.↗
NASA NTRS2003

Reevaluation of Tetrahydrophthalic Anydrides as Endcaps for Improved Oxidation Resistance in Addition to Polyimides

A polyimide is a polymer composed of alternating units of diamine and dianhydride, linked to each other via an imide bond. PMR polyimides, commonly used in the aerospace industry, are generally capped at each end by an endcap (such as the nadic endcap used in PMR 15) which serves a double function: (1) it limits the number of repeating units and, hence, the average molecular weight of the various polymer chains (oligomers), thereby improving processibility; (2) Upon further treatment (curing), the endcap crosslinks the various oligomer strands into a tough heat-resistant piece. It is this very endcap, so important to processing, that accounts for much of the weight loss in the polymer on aging in air at elevated temperatures. Understanding this degradation provides clues for designing new endcaps to slow down degradation, and prolong the lifetime of the material.

Frimer, Aryeh A.↗
NASA NTRS2022

Controlling Triboelectrification Effects on Spacecraft Ethernet Cabling

Triboelectric charging of a spacecraft and launch vehicles on ascent may occur due to the process of contact and separation between the vehicle skin and aerosols, dust, ice, water droplets, smoke, and other particulates encountered in the flight path. Depending on characteristics at the atomic and molecular levels of the vehicle skin’s surface and the substances and particulates encountered, electrical charge will transfer between the vehicle and the encountered substances, resulting in an accumulation of electrical charge on the vehicle skin. If the vehicle skin is conductive and electrically bonded such that in its entirety it presents an equipotential surface, then the accumulated electrical charge will spread in a nearly uniform manner leaving all regions with a nearly equal potential with respect to each other and the surrounding environment. Regions that are not electrically bonded as described, or surfaces that have resistivity values, can reach different potentials than the surrounding surfaces. When this happens, the differing potentials may grow to very large magnitudes, leading to electrostatic discharge events between the regions. As the vehicle rises in altitude, the breakdown potential between these regions of differing potential decreases commensurate with decreases in atmospheric density and pressure. If the potential differences between surfaces of the vehicle become equal to or exceed the breakdown potential, one or more discharge events may occur, each of them generating voltage and current transients that can easily damage or interfere with the designed operation of on-board electrical, avionic, and communications and navigation systems. This lesson learned discusses an in-flight anomaly caused by triboelectric discharge events and exacerbated by the lack of adequate cable shielding that affected flight computer communication links. Also discussed are mitigations to prevent this occurrence.

Ethernet↗
NASA NTRS1982

Polyimides: Tribological properties and their use as lubricants

Friction, wear, and wear mechanisms of several different polyimide films, solid bodies, composites, and bonded solid lubricant films are compared and discussed. In addition, the effect of such parameters as temperatures, type of atmosphere, contact stress, and specimen configuration are investigated. A friction and wear transition occurs in some polyimides at elevated temperatures and this transition is related to molecular relaxations that occur in polyimides. Friction and wear data from an accelerated test (pin-on-disk) are compared to similar data from an end use test device (plain spherical bearing), and to other polymers investigated in a similar geometry.

Fusaro, R. L.↗
NASA NTRS1984

Polyimides - Tribological properties and their use as lubricants

Friction, wear, and wear mechanisms of several different polyimide films, solid bodies, composites, and bonded solid lubricant films are compared and discussed. In addition, the effect of such parameters as temperatures, type of atmosphere, contact stress, and specimen configuration are investigated. A friction and wear transition occurs in some polyimides at elevated temperatures and this transition is related to molecular relaxations that occur in polyimides. Friction and wear data from an accelerated test (pin-on-disk) are compared to similar data from an end use test device (plain spherical bearing), and to other polymers investigated in a similar geometry.

Fusaro, R. L.↗
NASA NTRS2002

A large iris-like expansion of a mechanosensitive channel protein induced by membrane tension

MscL, a bacterial mechanosensitive channel of large conductance, is the first structurally characterized mechanosensor protein. Molecular models of its gating mechanisms are tested here. Disulfide crosslinking shows that M1 transmembrane alpha-helices in MscL of resting Escherichia coli are arranged similarly to those in the crystal structure of MscL from Mycobacterium tuberculosis. An expanded conformation was trapped in osmotically shocked cells by the specific bridging between Cys 20 and Cys 36 of adjacent M1 helices. These bridges stabilized the open channel. Disulfide bonds engineered between the M1 and M2 helices of adjacent subunits (Cys 32-Cys 81) do not prevent channel gating. These findings support gating models in which interactions between M1 and M2 of adjacent subunits remain unaltered while their tilts simultaneously increase. The MscL barrel, therefore, undergoes a large concerted iris-like expansion and flattening when perturbed by membrane tension.

NASA Discipline Cell Biology↗
NASA NTRS1976

PMR polyimide/graphite fiber composite fan blades

Ultrahigh speed fan blades, designed in accordance with the requirements of an ultrahigh tip speed blade axial flow compressor, were fabricated from a high strength graphite fiber tow and a PMR polyimide resin. The PMR matrix was prepared by combining three monomeric reactants in methyl alcohol, and the solution was applied directly to the reinforcing fiber for subsequent in situ polymerization. Some of the molded blades were completely finished by secondary bonding of root pressure pads and an electroformed nickel leading edge sheath prior to final machining. The results of the spin testing of nine PMR fan blades are given. Prior to blade fabrication, heat resin tensile properties of the PMR resin were examined at four formulated molecular weight levels. Additionally, three formulated molecular weight levels were investigated in composite form with both a high modulus and a high strength fiber, both as-molded and postcured, in room temperature and 232 C transverse tensile, flexure and short beam shear. Mixed fiber orientation panels simulating potential blade constructions were also evaluated. Flexure tests, short beam shear tests, and tensile tests were conducted on these angle-plied laminates.

Cavano, P. J.↗
NASA NTRS1978

H-H, C-H, and C-C NMR spin-spin coupling constants calculated by the FP-INDO method for aromatic hydrocarbons

The FP-INDO (finite perturbation-intermediate neglect of differential overlap) method is used to calculate the H-H, C-H, and C-C coupling constants in hertz for molecules of six different benzenoid hydrocarbons: benzene, naphthalene, biphenyl, anthracene, phenanthrene, and pyrene. The calculations are based on both the actual and the average molecular geometries. It is found that only the actual molecular geometries can always yield the correct relative order of values for the H-H coupling constants. For the calculated C-C coupling constants, as for the calculated C-H coupling constants, the signs are positive (negative) for an odd (even) number of bonds connecting the two nuclei. Agreements between the calculated and experimental values of the coupling constants for all six molecules are comparable to those reported previously for other molecules.

Long, S. A. T.↗
NASA NTRS1995

Scattering of water from the glycerol liquid-vacuum interface

Molecular dynamics calculations of the scattering of D2O from the glycerol surface at different collision energies are reported. The results for the trapping probabilities and energy transfer are in good agreement with experiments. The calculations demonstrate that the strong attractive forces between these two strongly hydrogen bonding molecules have only a minor effect on the initial collision dynamics. The trapping probability is influenced to a significant extent by the repulsive hard sphere-like initial encounter with the corrugated surface and, only at a later stage, by the efficiency of energy flow in the multiple interactions between the water and the surface molecules.

NASA Center ARC↗
NASA NTRS2010

Multiscale Modeling of Thermal Conductivity of Polymer/Carbon Nanocomposites

Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between nanoparticles and amorphous and crystalline polymer matrices. Bulk thermal conductivities of the nanocomposites were then estimated using an established effective medium approach. To study functionalization, oligomeric ethylene-vinyl alcohol copolymers were chemically bonded to a single wall carbon nanotube. The results, in a poly(ethylene-vinyl acetate) matrix, are similar to those obtained previously for grafted linear hydrocarbon chains. To study the effect of noncovalent functionalization, two types of polyethylene matrices. -- aligned (extended-chain crystalline) vs. amorphous (random coils) were modeled. Both matrices produced the same interfacial thermal resistance values. Finally, functionalization of edges and faces of plate-like graphite nanoparticles was found to be only modestly effective in reducing the interfacial thermal resistance and improving the composite thermal conductivity

Clancy, Thomas C.↗
NASA NTRS1997

Formation of Carbon Nanotube Based Gears: Quantum Chemistry and Molecular Mechanics Study of the Electrophilic Addition of o-Benzyne to Fullerenes, Graphene, and Nanotubes

Considerable progress has been made in recent years in chemical functionalization of fullerene molecules. In some cases, the predominant reaction products are different from those obtained (using the same reactants) from polycyclic aromatic hydrocarbons (PAHs). One such example is the cycloaddition of o-benzyne to C60. It is well established that benzyne adds across one of the rings in naphthalene, anthracene and other PAHs forming the [2+4] cycloaddition product (benzobicyclo[2.2.2.]-octatriene with naphthalene and triptycene with anthracene). However, Hoke et al demonstrated that the only reaction path for o-benzyne with C60 leads to the [2+2] cycloaddition product in which benzyne adds across one of the interpentagonal bonds (forming a cyclobutene ring in the process). Either reaction product results in a loss of aromaticity and distortion of the PAH or fullerene substrate, and in a loss of strain in the benzyne. It is not clear, however, why different products are preferred in these cases. In the current paper, we consider the stability of benzyne-nanotube adducts and the ability of Brenner's potential energy model to describe the structure and stability of these adducts. The Brenner potential has been widely used for describing diamondoid and graphitic carbon. Recently it has also been used for molecular mechanics and molecular dynamics simulations of fullerenes and nanotubes. However, it has not been tested for the case of functionalized fullerenes (especially with highly strained geometries). We use the Brenner potential for our companion nanogear simulations and believe that it should be calibrated to insure that those simulations are physically reasonable. In the present work, Density Functional theory (DFT) calculations are used to determine the preferred geometric structures and energetics for this calibration. The DFT method is a kind of ab initio quantum chemistry method for determining the electronic structure of molecules. For a given basis set expansion, it is comparable in accuracy to the MP2 method (better than Hartree Fock, but less accurate than more extensive electron correlation methods such as MP4 or CCSD). However, for systems with large numbers of basis functions it more efficient than any other methods that include electron correlation effects. In this presentation we show the results of DFT calculations for the reaction of benzyne with naphthalene, C60, and nanotube models. We compare energies for [2+2] and [2+4] cycloaddition products. The preferred products for the naphthalene and C60 reactions have been determined by experiment and, thus, these cases serve as a validation of our quantum chemical approach. We also compare the DFT and Brenner potential results. Finally we can predict the likelihood of reaction between benzyne and nanotubes.

Jaffe, Richard↗
NASA NTRS1996

Template-Directed Ligation of Peptides to Oligonucleotides

Synthetic oligonucleotides and peptides have enjoyed a wide range of applications in both biology and chemistry. As a consequence, oligonucleotide-peptide conjugates have received considerable attention, most notably in the development of antisense constructs with improved pharmacological properties. In addition, oligonucleotide-peptide conjugates have been used as molecular tags, in the assembly of supramolecular arrays and in the construction of encoded combinatorial libraries. To make these chimeric molecules more accessible for a broad range of investigations, we sought to develop a facile method for joining fully deprotected oligonucleotides and peptides through a stable amide bond linkage. Furthermore, we wished to make this ligation reaction addressable, enabling one to direct the ligation of specific oligonucleotide and peptide components.To confer specificity and accelerate the rate of the reaction, the ligation process was designed to be dependent on the presence of a complementary oligonucleotide template.

Bruick, Richard K.↗
NASA NTRS1999

Anisotropic Plasticity of BN Nanotubes

Plastic collapse of compressed BN nanotubes are investigated and compared with carbon nanotubes of similar nature. Using a generalized tight-binding molecular dynamics (GTBMD) method for system containing B, N and C atoms we compute stiffness and plastic collapse of BN and C nanotubes under axial compression. For small compressional strain, BN nanotubes are found to be about 92% as stiff as similar C nanotubes. Due to BN bond buckling effect, however, the elastic limit of BN nanotubes is found to be more than C nanotubes. A route to plasticity is explored in which we find that at elastic limit the accumulated strain is released by a local plastic deformation of the nanotube. The mechanism of strain release and the resulting plastic deformation, however. are anisotropic in nature. The strain is released preferentially towards N as leading edge of a buckled BN bond and the tube, compressed at both ends, plastically collapses preferentially towards one end. Details of the anisotropic plasticity and prospective applications will be discussed in this presentation.

Madhu, Menon↗
NASA NTRS1993

Viewpoint 9--molecular structure of aqueous interfaces

In this review we summarize recent progress in our understanding of the structure of aqueous interfaces emerging from molecular level computer simulations. It is emphasized that the presence of the interface induces specific structural effects which, in turn, influence a wide variety of phenomena occurring near the phase boundaries. At the liquid-vapor interface, the most probable orientations of a water molecule is such that its dipole moment lies parallel to the interface, one O-H bond points toward the vapor and the other O-H bond is directed toward the liquid. The orientational distributions are broad and slightly asymmetric, resulting in an excess dipole moment pointing toward the liquid. These structural preferences persist at interfaces between water and nonpolar liquids, indicating that the interactions between the two liquids in contact are weak. It was found that liquid-liquid interfaces are locally sharp but broadened by capillary waves. One consequence of anisotropic orientations of interfacial water molecules is asymmetric interactions, with respect to the sign of the charge, of ions with the water surface. It was found that even very close to the surface ions retain their hydration shells. New features of aqueous interfaces have been revealed in studies of water-membrane and water-monolayer systems. In particular, water molecules are strongly oriented by the polar head groups of the amphiphilic phase, and they penetrate the hydrophilic head-group region, but not the hydrophobic core. At infinite dilution near interfaces, amphiphilic molecules exhibit behavior different from that in the gas phase or in bulk water. This result sheds new light on the nature of hydrophobic effect in the interfacial regions. The presence of interfaces was also shown to affect both equilibrium and dynamic components of rates of chemical reactions. Applications of continuum models to interfacial problems have been, so far, unsuccessful. This, again, underscores the importance of molecular-level information about interfaces.

Review, Tutorial↗