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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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Carbon in the Allende meteorite - Evidence for poorly graphitized carbon rather than carbyne

A carbon-rich acid residue from the Allende carbonaceous chondrite was examined by high-resolution transmission electron microscopy (HRTEM) and also by analytical electron microscopy. A TEM mount of this residue that has previously been reported to contain carbyne forms of carbon was shown to contain sheet silicate contaminants. These sheet silicate grains give electron diffraction patterns similar to those reported for carbynes, thus raising questions about the previous report of carbynes in this residue. Furthermore, two crystals from a glacier microspherule, which had previously been identified as carbyne VIII, were shown by microanalysis to be talc. In view of these observations it is suggested that identifications of carbyne by electron diffraction should be supported by microanalyses of the individual grains. HRTEM investigations of the Allende carbon indicate that it is a poorly crystalline graphite, structurally similar to 'glassy' carbon

Smith, P. P. K.↗
NASA NTRS1980

Carbynes in meteorites - Detection, low-temperature origin, and implications for interstellar molecules

The presence, origin and implications of carbynes in meteorites are investigated. A sample of the Allende meteorite was pyrolyzed at temperatures from 25 to 750 C and examined by solid probe time-of-flight mass spectrometry and high-resolution mass spectrometry. Fragments released upon heating at 250 to 330 C are found to be composed of macromolecules containing triply bonded carbon units and cyanoacetylenes, as well as some methyl- and phenylacetylenes. Although carbynes are well known to form from the condensation of carbon vapors above 2600 K or by shock greater than 600 kbar, which would be unlikely in Allende, it is found that carbynes rather than graphite are formed metastably by the disproportionation of CO at low temperatures when chromite is present as a catalyst. Results imply that metastable formation mechanisms may be the principal source of interstellar polycyanoacetylenes and meteoritic and terrestrial carbynes.

Hayatsu, R.↗
NASA NTRS1982

Carbyne forms of carbon - Do they exist

Carbynes, or polymorphs of elemental carbon first reported synthesized by Kasatochkin et al (1967), have generally been recognized by their characteristic hexagonal electron diffraction pattern. It is pointed out, however, that sheet silicate minerals give rise to hexagonal diffraction patterns with a similar range of interplanar spacings. A reexamination of reported occurrences of carbynes, including chaoite, by means of TEM shows that nontronite and quartz contaminants could account for most of the cases previously attributed to chaoite. It is recommended that in future searches for carbyne, energy-dispersive X-ray analyses should be conducted to verify the chemistry of individual, carbyne-candidate grains.

Smith, P. P. K.↗
NASA NTRS1993

Are crystalline C-(H-O-N) carbons the elusive meteoritic carbynes?

I present an internally consistent reinterpretation of carbyne diffraction data making a few plausible assumptions. The results support that carbynes could be crystalline, randomly interstratified (or mixed-layered) carbons with variable C/(C+H+O+N) ratios rather than thermodynamically stable carbon allotropes. The metastable carbynes are likely the result of incomplete, kinetically-inhibited, low-temperature pyrolysis of precursor material. A renewed interest in meteoritic carbynes should seek to combine light-element chemistry and crystallography of these elusive carbons.

Rietmeijer, Frans J. M.↗
DOE OSTI2019

Epitaxial Carbyne: Analytical Results

The Green’s function method in the tight-binding approximation is used to obtain analytical expressions for the electronic spectra and densities of states for two carbyne structural modifications (cumulene and polyyne). Metal and semiconductor substrates are considered and charge-transfer estimates are deduced. Criteria for the occurrence of a charge-density wave in free-standing and epitaxial carbynes are proposed taking into account the intra- and interatomic Coulomb repulsion. Analytical expressions for the phonon spectrum of free-standing carbyne are presented. The data obtained are compared with the results of numerical calculations performed by other researchers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1980

Carbynes - Carriers of primordial noble gases in meteorites

Five carbynes (triply bonded allotropes of carbon) have been found by electron diffraction in the Allende and Murchison carbonaceous chondrites: carbon VI, VIII, X, XI, and (tentatively) XII. From the isotopic composition of the associated noble-gas components, it appears that the carbynes in Allende (C3V chondrite) are local condensates from the solar nebula, whereas at least two carbynes in Murchison (C2 chondrite) are of exotic, presolar origin. They may be dust grains that condensed in stellar envelopes and trapped isotropically anomalous matter from stellar nucleosynthesis.

Whittaker, A. G.↗
DOE OSTI2019

Photosensitive free-standing ultra-thin carbyne–gold films

In the article we introduce the experiment of the photostimulation effect in the tunneling conductivity of free-standing thin carbyne-gold films. We observe a sharp increase of the conductivity of hybrid film due to the electromagnetic exciting at the frequencies which are close to the plasmon resonance of gold nanoparticles. The use of carbyne threads as a stabilizing matrix makes it possible to obtain free-standing thin films that demonstrate a good structural stability. The tunnel current–voltage measurements demonstrate a strong dependence of the current value on the intensity of green laser radiation used to photostimulate thin C–Au in area of the measuring experiment.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Estimations of the Fermi Velocity and Effective Mass in Epitaxial Graphene and Carbyne

It is shown that the Fermi velocity of electrons is a natural characteristic of gapless graphene and cumulene modification of carbyne weakly coupled with the substrate. At the same time, in the presence of gap (graphene with a gap and polyyne modification of carbyne), the corresponding characteristic is the effective electron mass. The corresponding analytical estimations have been performed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

O -Functionalization of a cobalt carbonyl generates a terminal cobalt carbyne

Despite efforts toward extending multiple bonding motifs to late metal systems, examples of late transition metal carbynes remain scarce. Herein, we describe the synthesis of a series of L 3 Co(CO) complexes supported by a trisphosphine ligand framework, with the most reduced of these complexes being amenable to O-functionalization. Furthermore, this transformation provides access to the second reported example of a terminal Co-carbyne complex, in this case stabilized in a pseudotetrahedral geometry (i.e., L 3 Co≡C-OSiR 3 ). Its geometry makes its electronic structure suitable for comparison to structurally-related examples of terminal Co-imido and oxo species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Electron microscopy of carbonaceous matter in Allende acid residues

On the basis of characteristic diffuse ring diffraction patterns, much of the carbonaceous matter in a large suite of Allende acid residues has been identified as a variety of turbostratic carbon. Crystallites of this phase contain randomly stacked sp(2) hybridized carbon layers and diffraction patterns resemble those from carbon black and glassy carbon. Carbynes are probably absent, and are certainly restricted to less than 0.5% of these acid residues. The work of Ott et al. (1981) provides a basis for the possibility that turbostratic carbon is a carrier of noble gases, but an additional component - amorphous carbon - may be necessary to explain the high release temperatures of noble gases as well as the glassy character of many of the carbonaceous particles. Carbynes are considered to be questionable as important carriers of noble gases in the Allende acid residues.

Lumpkin, G. R.↗
DOE OSTI2019

Carbon Nanostructures on a Semiconductor Substrate

The analytical expressions for the density of states and the occupation numbers are obtained for simple models of carbon nanostructures (graphene–boron nitride lateral heterostructure, decorated zigzag edges of semi-infinity graphene and graphene nanoribbons, and decorated carbyne). The main attention is placed to the strong-coupling regime of the nanostructures with a semiconducting substrate. The numerical estimations are given for the SiC substrate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

The transformation of diamond to graphite: Experiments reveal the presence of an intermediate linear carbon phase

Natural diamonds that have been partially replaced by graphite have been observed to occur in natural rocks. While the graphite-to-diamond phase transition has been extensively studied the opposite of this (diamond to graphite) remains poorly understood. We performed high-pressure and temperature hydrous and anhydrous experiments up to 1.0 GPa and 1300 °C using Amplex premium virgin synthetic diamonds (20–40 μm size) as the starting material mixed with Mg(OH) 2 as a source of H 2 O for the hydrous experiments. The experiments revealed that the diamond-to-graphite transformation at P = 1.0 GPa and T = 1300 °C was triggered by the presence of H 2 O and was accomplished through a three-stage process. Stage 1: diamond reacts with a supercritical H 2 O producing an intermediate 200–500 nm size “globular carbon” phase. This phase is a linear carbon chain; i.e. a polyyne or carbyne. Stage 2: the linear carbon chains are unstable and highly reactive, and they decompose by zigzagging and cross-linking to form sp 2 -hybridized structures. Stage 3: normal, disordered, and onion-like graphite is produced by the decomposition of the sp-hybridized carbon chains which are re-organized into sp 2 bonds. Our experiments show that there is no direct transformation from sp 3 C-bonds into sp 2 C-bonds. Our hydrous high-pressure and high-temperature experiments show that the diamond-to-graphite transformation requires an intermediate metastable phase of a linear hydrocarbon. This process also provides a simple mechanism for the substitution of other elements into the graphite structure (e.g. H, S, O).

36 MATERIALS SCIENCE↗
DOE OSTI2021

Neural network representation of electronic structure from ab initio molecular dynamics

Despite their rich information content, electronic structure data amassed at high volumes in ab initio molecular dynamics simulations are generally under-utilized. Here we introduce a transferable high-fidelity neural network representation of such data in the form of tight-binding Hamiltonians for crystalline materials. This predictive representation of ab initio electronic structure, combined with machine-learning boosted molecular dynamics, enables efficient and accurate electronic evolution and sampling. When it is applied to a one-dimension charge-density wave material, carbyne, we are able to compute the spectral function and optical conductivity in the canonical ensemble. The spectral functions evaluated during soliton-antisoliton pair annihilation process reveal significant renormalization of low-energy edge modes due to retarded electron-lattice coupling beyond the Born–Oppenheimer limit. The availability of an efficient and reusable surrogate model for the electronic structure dynamical system will enable calculating many interesting physical properties, paving the way to previously inaccessible or challenging avenues in materials modeling.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Cumulene Wires Display Increasing Conductance with Increasing Length

One-dimensional sp-hybridized carbon wires, including cumulenes and polyynes, can be regarded as finite versions of carbynes. They are likely to be good candidates for molecular-scale conducting wires as they are predicted to have a high-conductance. In this study, we first characterize the single-molecule conductance of a series of cumulenes and polyynes with a backbone ranging in length from 4 to 8 carbon atoms, including [7]cumulene, the longest cumulenic carbon wire studied to date for molecular electronics. We observe different length dependence of conductance when comparing these two forms of carbon wires. Polyynes exhibit conductance decays with increasing molecular length, while cumulenes show a conductance increase with increasing molecular length. Their distinct conducting behaviors are attributed to their different bond length alternation, which is supported by theoretical calculations. Furthermore, this study confirms the long-standing theoretical predictions on sp-hybridized carbon wires and demonstrates that cumulenes can form highly conducting molecular wires.

36 MATERIALS SCIENCE↗
DOE OSTI2023

U–C Bond Insertion, Ring-Opening, and C–H Activation in a Uranium Bis(diisopropylamino)cyclopropenylidene (BAC) Adduct

Reaction of [U(NR 2 ) 3 ] (R = SiMe 3 ) with 1 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in Et 2 O results in the formation of [(NR 2 ) 3 U(BAC)] (1), which can be isolated in modest yields. Thermolysis of 1 in C 6 D 6 at 85 °C results in the formation of the ring-opened U(IV) product, [(NR 2 ) 2 U{N(R)(SiMe 2 CH=C(NiPr 2 )C(NiPr 2 )=CH)}] (2), which can be isolated in low yields. Mechanistic studies suggest that the formation of 2 proceeds via dissociation of BAC from 1 to regenerate [U(NR 2 ) 3 ], which converts into [U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] at the elevated temperatures. BAC then inserts into the U–C bond of [U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] to generate a cyclopropenyl intermediate, which undergoes ring opening and C–H activation to afford the final product, 2. We hypothesize that the ring-opening generates an unobserved carbene intermediate. Notably, thermolysis of a 1:1 mixture of independently prepared [U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] and BAC results in clean formation of 2, providing strong support for the proposed mechanism. The formulations of both 1 and 2 were confirmed by X-ray crystallography. Finally, theoretical calculations indicate that the hypothesized uranium carbene intermediate features strong U–C bonding, potentially with some carbyne character in the electronic structure.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Structural transition and chemical reactivity of atomic carbon chains

The sp-hybridized carbon chain (carbyne) is a representative 1D atomic material, whose bonding structure and chemical reactivity have remained a mystery for a century. Here, in this work, we report the unexpected alternating bond orders of 1.4 and 2.6 for the most stable carbon chain and the in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) detection of the temperature-dependent reversible change of the bond order alternation. Moreover, we revealed its reactivities with O 2 , H 2 , and CO 2 at temperatures up to 600 °C and created an end-group-protection strategy to stabilize it. These observations open a new door to the chemistry of atomic materials.

25 ENERGY STORAGE↗