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NASA NTRS1997

Diamond Composite Films for Protective Coatings on Metals and Method of Formation

Composite films consisting of diamond crystallites and hard amorphous films such as diamond-like carbon, titanium nitride, and titanium oxide are provided as protective coatings for metal substrates against extremely harsh environments. A composite layer having diamond crystallites and a hard amorphous film is affixed to a metal substrate via an interlayer including a bottom metal silicide film and a top silicon carbide film. The interlayer is formed either by depositing metal silicide and silicon carbide directly onto the metal substrate, or by first depositing an amorphous silicon film, then allowing top and bottom portions of the amorphous silicon to react during deposition of the diamond crystallites, to yield the desired interlayer structure.

Ong, Tiong P.↗

NASA NTRS1994

The origin of variations in the 2175 A extinction bump

In this paper, small graphite grains are assumed to produce the 2175 A interstellar extinction bump. The principal observational characteristic of the bump in the invariance of its central wavelength (2174 +/- 9 A) among various lines of sight through diverse environments. On the other hand, its Full Width at Half Maximum (FWHM) varies from about 0.80/micrometer to 1.2/micrometer among the same lines of sight. In this paper, the variations in bump width among different sight lines is attributed to coatings on the graphite grains. The necessary properties of the coating material are investigated. Simple neutral polycycli aromatic hydrocarbons (PAHs) have measured laboratory absorptions remarkably similar to those required to explain the broadening of the bump. Only 1.5% of cosmic carbon in PAHs is required to produce very broad bumps. Alternatively, about 2%-4% of the combined abundances of the refractory elements Fe and Mg, more highly depleted onto grains in dense regions than in the diffuse interstellar medium, could explain the mantles if their absorption rises rapidly with energy, as it does for MgO. Coatings of amorphous carbon, hydrogenated or not, diamond-like bonded carbon, or water ice do not have published optical constants that vary rapidly enough in wavenumber to produce the variations.

Mathis, John S.↗

NASA NTRS1996

The infrared spectrum of the Galactic center and the composition of interstellar dust

We have obtained 5-8 micrometers spectra of the Galactic center from the Kuiper Airborne Observatory at resolving powers of approximately 50, approximately 150, and approximately 300. These spectra show absorption features at 5.5, 5.8, 6.1, and 6.8 micrometers. Together with previously observed features in the 3 micrometers region, these features are compared with laboratory spectra of candidate materials. The 3.0 and 6.1 micrometers features are due to the OH stretching and bending variations of H2O and are well fitted by water of hydration in silicates (e.g., talc). The 3.0 micrometer band is equally well fitted by ice mixtures containing 30% H2O, but such mixtures do not provide a good fit to the observed 6.1 micrometer band. The 3.4 and 6.8 micrometers features are identified with the CH stretching and deformation modes in CH2 and CH3 groups in saturated aliphatic hydrocarbons. The 6.1 micrometer band shows a short wavelength shoulder centered on 5.8 micrometer, attributed to carbonyl (C double bond O) groups in this interstellar hydrocarbon dust component. Finally, the narrow 5.5 micrometer feature is also attributed to carbonyl groups, but in the form of metal carbonyls [e.g., Fe(CO)4]. We have derived column densities and abundances along the line of sight toward the Galactic center for the various identified dust components. This analysis shows that hydrocarbon grains contain only 0.08 of the elemental abundance of C and contribute only a relatively minor fraction (0.1) of the total dust volume. Most of the interstellar dust volume is made up of silicates (approximately 0.6). Small graphite grains, responsible for the 2200 angstroms bump, account for 0.07 of the total dust volume. The remaining one-quarter of the interstellar dust volume consists of a material(s) without strong IR absorption features. Likely candidates include large graphite grains, diamonds, or amorphous carbon grains, which all have weak or no IR active modes. Finally, various models for the origin of the hydrocarbon dust component of the interstellar dust are discussed. All of them face some problems in explaining the observations, in particular, the absence of the spectroscopic signature of hydrocrbon grains in sources associated with molecular clouds.

NASA Discipline Exobiology↗

NASA NTRS1995

The 5-8 Micron Infrared Spectrum of the Galactic Center and the Composition of Interstellar Dust

Interstellar dust is an important component of the interstellar medium which dominates the opacity and, hence, regulates radiative transfer, molecule formation, and thermal balance of the ISM. Much of our knowledge on the composition of interstellar dust results from infrared spect,oscopy. The extinction along the line of sight towards the galactic center is believed to be dominated by dust in the diffuse ISM. Because of the high extinction and high IR flux, IR spectra of galactic center sources have been a prime sampling ground for the characteristics of interstellar dust. We have obtained 5-8 micrometer spectra of the galactic center using the KAO. These spectra show absorption features at 5.5, 5.8, 6.1, and 6.8 micrometers. Together with features in the 3 micrometer region previously observed by us using the IRTF, these features are compared to laboratory spectra of candidate materials. We conclude that the 3.0 and 6.1 micrometer feature are carried by H2O, likely in the form of water of hydration in interstellar silicates. The 3.4, 5.5, 5.8, and 6.8 micrometer features are due to CH2, CH3 and C=O stretching and deformation modes in a hydrocarbon grain component. Comparing derived dust abundances, we conclude that silicates dominate the interstellar dust volume. Hydrocarbon and (small) graphite grains contribute each about 0.1. The remainder of the interstellar dust volume does not show strong IR absorption features and is likely in the form of large graphite, amorphous, carbon, or diamond grains.

Tielens, A. G. G. M.↗

NASA NTRS2005

Genesis Field Recovery

The Genesis mission returned to Earth on September 8, 2004 after a nearly flawless three-year mission to collect solar matter. The intent was to deploy a drogue chute and parafoil high over the Utah desert and to catch the fragile payload capsule in mid-air by helicopter. The capsule would then be opened in a clean-room constructed for that purpose at UTTR, and a nitrogen purge was to be installed before transporting the science canister to JSC. Unfortunately, both chutes failed to deploy, causing the capsule to fall to the desert floor at a speed of nearly 200 MPH. Still, Genesis represents a milestone in the US space program, comprising the first sample return since the Apollo Missions as well as the first return of materials exposed to the space environment outside of low Earth orbit and beyond the Earth s magnetosphere for an extended period. We have no other comparable materials in all of our collections on Earth. The goal of the Genesis Mission was to collect a representative sample of the composition of the solar wind and thus, the solar nebula from which our solar system originated. This was done by allowing the naturally accelerated species to implant shallowly in the surfaces of ultra-pure, ultra-clean collector materials. These collectors included single crystal silicon (FZ and CZ), sapphire, silicon carbide; those materials coated with aluminum, silicon, diamond like carbon, and gold; and isotopically enriched polycrystalline diamond and amorphous carbon. The majority of these materials were distributed on five collector arrays. Three of the materials were housed in an electrostatic concentrator designed to increase the flux of low-mass ions. There was also a two-inch diameter bulk metallic glass collector and a gold foil, polished aluminum, and molybdenum coated platinum foil collector. An excellent review of the Genesis collector materials is offered in reference [1].

McNamara, K. M.↗

NASA NTRS1986

Diamondlike carbon - A bibliography of published papers and reports

A bibliography of references on investigations of diamond-like carbon (DLC) materials is presented. The list was developed over several years of active research and by computerized searches for the following keywords: diamondlike carbon, diamond-like carbon, hard carbon, i-carbon, A-C:H, and amorphous hydrogenated carbon. The bibliography has 241 citations, begins in 1956, includes an author index and was last updated in August 1985.

Woollam, J. A.↗

NASA NTRS1996

Self-Lubricating, Wear-Resistant Diamond Films Developed for Use in Vacuum Environment

Diamond's outstanding properties--extreme hardness, chemical and thermal inertness, and high strength and rigidity--make it an ideal material for many tribological applications, such as the bearings, valves, and engine parts in the harsh environment found in internal-combustion engines, jet engines, and space propulsion systems. It has been demonstrated that chemical-vapor-deposited diamond films have low coefficients of friction (on the order of 0.01) and low wear rates (less than 10(sup -7) mm (sup 3/N-m)) both in humid air and dry nitrogen but that they have both high coefficients of friction (greater than 0.4) and high wear rates (on the order of 1(sup -4) mm sup 3/N-m)) in vacuum. It is clear that surface modifications that provide acceptable levels of friction and wear properties will be necessary before diamond films can be used for tribological applications in a space-like, vacuum environment. Previously, it was found that coatings of amorphous, non-diamond carbon can provide low friction in vacuum. Therefore, to reduce the friction and wear of diamond film in vacuum, carbon ions were implanted in an attempt to form a surface layer of amorphous carbon phases on the diamond films.

Source record↗

DOE OSTI2025

Magnetized, radiofrequency-driven hollow cathode chemical-vapor deposition of ultrathick hydrogenated amorphous carbon

Amorphous carbon is an attractive material for next-generation inertial confinement fusion (ICF) ablators due to its amorphous structure, tunable density, compatibility with dopants, chemical inertness, and mechanical robustness. Ablators are typically deposited as ultrathick (10–200 μm) coatings on removable spherical templates. The deposition of such thick amorphous carbon films is challenging due to high intrinsic compressive stress, which causes film buckling and delamination. Here, we study the deposition of amorphous carbon films by magnetized, radiofrequency-driven hollow cathode chemical vapor deposition with a custom-designed source in Ne plasmas. Emphasis is on the hollow-cathode source design and effects of the plasma discharge power and the precursor flow rate on film properties. We demonstrate deposition rates of >1 μm/h for films with hydrogen content of ∼40 at. %, densities of 1.1–1.7 g/cm 3 , and trace quantities of oxygen impurities. In conclusion, we also demonstrate the feasibility of depositing thick hydrogenated amorphous carbon films (∼30 μm) for ICF applications.

Carbon based materials↗

DOE OSTI2025

Equation of state measurement of detonation carbon condensates using optical microscopy and interferometry

Thermochemical models of detonation that estimate performance (e.g., detonation velocity, energy delivery, etc.), are based on assumptions that carbon condensates (soot) formed during detonation is largely similar to bulk carbon. However, soot constituents can range from amorphous carbon to nanodiamond and include other material phases. Since thermodynamic properties of the soot such as compressibility are imperative for accurate thermochemical modeling of detonation reaction chemistry, experimental measurements of the equation of state (EOS) which determine the compressibility are vital. Due to the mixed-phase nature of detonation soot, typical methods to measure the EOS (e.g., x-ray diffraction) are untenable. In this study, the high-pressure EOS up to 20 GPa was determined for detonation soot collected from PBX 9502, Composition B (Comp B), Hexanitrostilbene (HNS), and LX-21 high explosives by employing a direct volume technique using optical microscopy and interferometry in a diamond anvil cell. Comp B soot was determined to be the least compressible [K 0 = 57.9(17) GPa] with HNS soot [K 0 = 53.7(15) GPa], LX-21 soot [K 0 = 45.8(51) GPa], and PBX 9502 soot [K 0 = 28.2(27) GPa] being more compressible, likely due to differences in nanodiamond content as compared to amorphous carbon and graphite content.

Amorphous materials↗

NASA NTRS1990

Electron cyclotron resonance deposition of diamond-like films

Electron cyclotron resonance (ECR) microwave plasma CVD has been developed at low pressures (0.0001 - 0.01 torr) and at ambient and high substrate temperatures (up to 750 C), to achieve large-area (greater than 4 in. diameter) depositions of diamondlike amorphous carbon (a - C:H) films. The application of a RF bias to the substrate stage, which induces a negative self-bias voltage, is found to play a critical role in determining carbon bonding configurations and in modifying the film morphology. There are two distinct types of ECR-deposited diamondlike films. One type of diamondlike film exhibits a Raman spectrum consisting of broad and overlapping, graphitic D (1360/cm, line width = 280/cm) and G (1590/cm, line width 140/cm) lines, and the other type has a broad Raman peak centered at appoximately 1500/cm. Examination of plasma species by optical emission spectroscopy shows no correlation between the CH-asterisk emission intensity and the deposition rate of diamondklike films.

Shing, Y. H.↗

NASA NTRS2011

Coordinated Analyses of Diverse Components in Whole Stardust Cometary Tracks

Analyses of samples returned from Comet 81P/Wild-2 by the Stardust spacecraft have resulted in a number of surprising findings that show the origins of comets are more complex than previously suspected. However, these samples pose new experimental challenges because they are diverse and suffered fragmentation, thermal alteration, and fine scale mixing with aerogel. Questions remain about the nature of Wild-2 materials, such as the abundances of organic matter, crystalline materials, and presolar grains. To overcome these challenges, we have developed new sample preparation and analytical techniques tailored for entire aerogel tracks. We have successfully ultramicrotomed entire "carrot" and "bulbous" type tracks along their axis while preserving their original shapes. This innovation allowed us to examine the distribution of fragments along the track from the entrance hole all the way to the terminal particle (TP). We will present results of our coordinated analysis of the "carrot" type aerogel tracks #112 and #148, and the "bulbous" type aerogel tracks #113, #147 and #168 from the nanometer to the millimeter scale. Scanning TEM (STEM) was used for elemental and detailed mineralogy characterization, NanoSIMS was used for isotopic analyses, and ultrafast two-step laser mass spectrometry (ultra L2MS) was used to investigate the nature and distribution of organic phases. The isotopic measurements were performed following detailed TEM characterization for coordinated mineralogy. This approach also enabled spatially resolving the target sample from fine-scale mixtures of compressed aerogel and melt. Eight of the TPs of track #113 are dominated by coarse-grained enstatite (En90) that is largely orthoenstatite with minor, isolated clinoenstatite lamellae. One TP contains minor forsterite (Fo88) and small inclusions of diopside with % levels of Al, Cr and Fe. Two of the TPs contain angular regions of fine-grained nepheline surrounded by enstatite. Their O isotopic compositions are in the range of meteoritic materials, implying that they originated in the inner Solar System. Complex aromatic hydrocarbons are distributed along aerogel tracks and in TPs. These organics are likely cometary but were affected by shock heating. Three TPs of track #147 and two of track 168 have completely different mineralogy. TP2 of track #147 entirely consists of Fe-Ni alloy (5 at% Ni) and TP3 contains Fa28 with partial olivine-pyroxene intergrowth and minor albite. TP4 contains pentlandite, Fe-olivine, albite and high Ca pyroxene with Na and Cr (kosmochlor component). TP1 of #168 contains Fe-olivine, albite and pentlandite, and the concentric TP2 has a core of olivine grains with co-existing indigenous amorphous SiO2 surrounded by a carbon mantle, which in turn is surrounded by a layer of compressed aerogel. The TP of the carrot track #112 is a (16)O-rich forsteritic olivine grain that likely formed in the inner Solar System. The track also contains submicron-sized diamond grains of likely Solar System origin.

Nakamura-Messenger, Keiko↗

NASA NTRS1990

Survival of carbon grains in shocks

Supernova shocks play a significant part in the life of an interstellar grain. In a typical 10 to the 9th power year lifetime, a grain will be hit by an average of 10 shocks of 100 km s(sup -1) or greater velocity, and even more shocks of lower velocity. Evaluation of the results of this frequent shock processing is complicated by a number of uncertainties, but seems to give about 10 percent destruction of silicate grains and about half that for graphite grains. Because of the frequency of shocking, the mineralogy and sizes of the grain population is predominately determined by shock processing effects, and not by the initial grain nucleation and growth environment. One consequence of the significant role played by interstellar shocks is that a certain fraction (up to 5 percent) of the carbon should be transformed into the diamond phase. Diamond transformation is observed in the laboratory at threshold shock pressures easily obtainable in grain-grain collisions in supernova shocks. Yields for transforming graphite, amorphous carbon, glassy carbon, and other nearly pure carbon solids into diamond are quite high. Impurities up to at least the 10 percent level (for oxygen) are tolerated in the process. The typical size diamond expected from shock transformation agrees well with the observed sizes in the Lewis et al. findings in meteoritic material. Isotropic anomalies already contained in the grain are likely to be retained through the conversion process, while others may be implanted by the shock if the grain is close to the supernova. The meteoritic diamonds are likely to be the results of transformation of carbon grains in grain-grain collisions in supernova shock waves.

Seab, C. Gregory↗

NASA NTRS1990

Studies of mechano-chemical interactions in the tribological behavior of materials

Mechano-chemical interaction studies can contribute to the understanding of wear and friction of materials. Specific examples of experimental results relative to the subject are discussed. There are two parts: one describes the synergistic effect of corrosion and wear of iron sliding on sapphire in sulfuric acid, and the other describes the effect of surface films on the wear and friction of plasma-deposited diamondlike carbon (amorphous hydrogenated carbon) films in sliding contact with silicon nitride. The concentration of acid (pH) is an important factor in controlling the iron loss caused by wear-corrosion processes in sulfuric acid. The mechanical action can cause chemical reactions to proceed much faster than they would otherwise. The diamondlike carbon (DLC) films are shown to behave tribologically much like bulk diamond. In a dry nitrogen environment, a mechano-chemical reaction produces a substance which greatly decreases the coefficient of friction. In a moist air environment, mechano-chemical interactions drastically reduce the wear life of DLC films and water vapor greatly increases friction.

Miyoshi, Kazuhisa↗

NASA NTRS1990

Studies of mechanochemical interactions in the tribological behavior of materials

Mechanochemical interaction studies can contribute to the understanding of wear and friction of materials. Specific examples of experimental results relative to the subject are discussed. There are two parts: one describes the synergistic effect of corrosion and wear of iron sliding on sapphire in sulfuric acid, and the other describes the effect of surface films on the wear and friction of plasma-deposited diamondlike carbon (amorphous hydrogenated carbon) films in sliding contact with silicon nitride. The concentration of acid (pH) is an important factor in controlling the iron loss caused by wear-corrosion processes in sulfuric acid. The mechanical action can cause chemical reactions to proceed much faster than they would otherwise. The diamondlike carbon (DLC) films are shown to behave tribologically much like bulk diamond. In a dry nitrogen environment, a mechanochemical reaction produces a substance which greatly decreases the coefficient of friction. In a moist air environment, mechanochemical interactions drastically reduce the wear life of DLC films and water vapor greatly increases friction.

Miyoshi, Kazuhisa↗

DOE OSTI2022

Discovering exceptionally hard and wear-resistant metallic glasses by combining machine-learning with high throughput experimentation

Lack of crystalline order in amorphous alloys, commonly called metallic glasses (MGs), tends to make them harder and more wear-resistant than their crystalline counterparts. However, finding inexpensive MGs is daunting; finding one with enhanced wear resistance is a further challenge. Relying on machine learning (ML) predictions of MGs alone requires a highly precise model; however, incorporating high-throughput (HiTp) experiments into the search rapidly leads to higher performing materials even from moderately accurate models. Here, we exploit this synergy between ML predictions and HiTp experimentation to discover new hard and wear-resistant MGs in the Fe–Nb–B ternary material system. Several of the new alloys exhibit hardness greater than 25 GPa, which is over three times harder than hardened stainless steel and only surpassed by diamond and diamond-like carbon. This ability to use less than perfect ML predictions to successfully guide HiTp experiments, demonstrated here, is especially important for searching the vast Multi-Principal-Element-Alloy combinatorial space, which is still poorly understood theoretically and sparsely explored experimentally.

36 MATERIALS SCIENCE↗

NASA NTRS1991

Friction and wear of plasma-deposited amorphous hydrogenated films on silicon nitride

An investigation was conducted to examine the friction and wear behavior of amorphous hydrogenated carbon (a-C:H) films in sliding contact with silicon nitride pins in both dry nitrogen and humid air environments. Amorphous hydrogenated carbon films approximately 0.06 micron thick were deposited on silicon nitride flat substrates by using the 30 kHz ac glow discharge of a planar plasma reactor. The results indicate that an increase in plasma deposition power gives an increase in film density and hardness. The high-density a-C:H films deposited behaved tribologically much like bulk diamond. In the dry nitrogen environment, a tribochemical reaction produced a substance, probably a hydrocarbon-rich layer, that decreased the coefficient of friction. In the humid air environment, tribochemical interactions drastically reduced the wear life of a-C:H films and water vapor greatly increased the friction. Even in humid air, effective lubrication is possible with vacuum-annealed a-C:H films. The vacuum-annealed high-density a-C:H film formed an outermost superficial graphitic layer, which behaved like graphite, on the bulk a-C:H film. Like graphite, the annealed a-C:H film with the superficial graphitic layer showed low friction when adsorbed water vapor was present.

Miyoshi, Kazuhisa↗

NASA NTRS2003

Electronic Power System Application of Diamond-Like Carbon Films

A prototype manufacturing technology for producing high volume efficiency and high energy density diamond-like carbon (DLC) capacitors has been developed. Unique dual ion-beam deposition and web-handling systems have been designed and constructed to deposit high quality DLC films simultaneously on both sides of capacitor grade aluminum foil and aluminum-coated polymer films. An optimized process, using inductively coupled RF ion sources, has been used to synthesize electrically robust DLC films. DLC films are amorphous and highly flexible, making them suitable for the production of wound capacitors. DLC capacitors are reliable and stable over a wide range of AC frequencies from 20 Hz to 1 MHz, and over a temperature range from .500 C to 3000 C. The compact DLC capacitors offer at least a 50% decrease in weight and volume and a greater than 50% increase in temperature handling capability over equal value capacitors built with existing technologies. The DLC capacitors will be suitable for high temperature, high voltage, pulsed power and filter applications.

Wu, Richard L. C.↗

NASA NTRS1989

Experimental evidence for amorphous carbon grains in comets

Amorphous carbon grains similar to those produced in the laboratory, but with a higher hydrogen content, appear to be good candidates to simulate both the IR continuum emission and the 3.4 micron band measured for P/Halley. The comparison of the cometary features with those detected in the laboratory for carbon grains characterized by various sp(exp 2)/sp(exp 3) ratios seems to indicate that a prevalent diamond-like (sp(exp 3)) structure should be present in cometary particles. These kinds of solid particles seem also suitable to explain the daily and monthly variations of the 3.4 micron band intensity, relative to the continuum, and, at the same time,- to fulfill the abundance constraints. The same grains appear to be able to reproduce the absorption bands detected in the IR galactic source IRS 7. This result may be considered as a first experimental evidence of a relation existing between interstellar dust and cometary materials.

Colangeli, Luigi↗