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At least 199 records · Page 11

Carbon isotopic signatures of super-deep diamonds mediated by iron redox chemistry

Among redox sensitive elements, carbon is specifically important because it may have been a driver rather than a passive recorder of Earth’s redox evolution. The extent to which the isotopic composition of carbon records the redox processes that shaped the Earth is still debated. In particular, the highly reduced deep mantle may be metal-saturated, yet, it is still unclear how the presence of metallic phases influences the carbon isotopic compositions of super-deep diamonds. Here we report ab initio results for the vibrational properties of carbon in carbonates, diamond, and Fe 3 C under pressure and temperature conditions relevant to super-deep diamond formation. Previous work on this question neglected the effect of pressure on the equilibrium carbon isotopic fractionation between diamond and Fe 3 C but our calculations show that this assumption overestimates the fractionation by a factor of ~1.3. Our calculated probability density functions for the carbon isotopic compositions of super-deep diamonds derived from metallic melt can readily explain the very light carbon isotopic compositions observed in some super-deep diamonds. Our results therefore support the view that metallic phases are present during the formation of super-deep diamonds in the mantle below ~250 km.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A genetic metasomatic link between eclogitic and peridotitic diamond inclusions

Diamond inclusions sample the otherwise inaccessible archive of Earth’s deep interior. The geochemical and petrological diversity of diamond inclusions reflects either pre-metasomatic upper mantle heterogeneity or metasomatism coeval with diamond formation. We focus on the origin of lithospheric garnet and clinopyroxene inclusions by simulating metasomatic reactions between eclogitic fluids and mantle peridotites at 5 GPa, 1000 °C, and across a range of redox conditions (logƒO 2 = -1 to -6 ΔFMQ). Our results demonstrate that fluid-rock interaction can result in the formation of eclogitic, websteritic, and peridotitic silicates from a single fluid during a single diamond-forming metasomatic event. Ergo, the petrogenesis of diamond and their inclusions can be syngenetic, and the petrological diversity of diamond inclusions can reflect metasomatism coeval with diamond formation. Furthermore, during the metasomatism, refractory peridotite can be converted to fertile websterite which could become a pyroxenitic mantle source for oceanic basalts.

58 GEOSCIENCES↗

Helium isotopic variability within single diamonds from the Orapa kimberlite pipe

The possible relationships between diamond mineralogy and helium isotopes were investigated by measuring the distribution and isotopic composition of He in a suite of well-characterized one-carat diamonds from the Orapa kimberlite, Botswana. The results of crushing in vacuo experiments indicated that most of He was contained in the matrix, rather than in the inclusions of the diamonds. Step-heating of individual diamonds at 2000 C released He of He-3/He-4 ratios that differed by up to a factor of 100 among the two heating steps, revealing large isotopic variations within individual diamonds. It is suggested that this internal isotopic variability is the result of stepwise graphitization: the first heating step initiates graphitization which nucleates around defects in a diamond, and the second step graphitizes the relatively defect-free regions of the diamond. This explanation predicts that the highest He-3/He-4 ratios should be found in most perfect crystals.

Kurz, Mark D.↗

Diamonds in detonation soot

Diamonds 4 to 7 nm in diameter have been identified and partially isolated from soot formed in detonations of carbon-forming composite explosives. The morphology of the soot has been examined by transmission electron microscopy (TEM), and the identity of the diamond has been established by the electron diffraction pattern of the TEM samples and by the X-ray diffraction (XRD) pattern of the isolated solid. Graphite is also present in the form of ribbons of turbostatic structure with a thickness of 2 to 4 nm. A fraction, about 25 percent of the soot by weight, was recovered from the crude soot after oxidation of the graphite with fuming perchloric acid. This fraction showed a distinct XRD pattern of diamond and the diffuse band of amorphous carbon. The IR spectrum of these diamonds closely matches that of diamonds recovered from meteorites (Lewis et al., 1987), perhaps indicating similar surface properties after the oxidation. If these diamonds are produced in the detonation itself or during the initial expansion, they exhibit a phenomenal crystal growth rate (5 nm/0.00001 s equal 1.8 m/hr) in a medium with a very low hydrogen/carbon ratio. Because the diamonds will be carried along with the expanding gases, they will be accelerated to velocities approaching 8 km/s.

Greiner, N. Roy↗

Electron energy loss spectrometry of interstellar diamonds

The results are reported of electron energy loss spectra (EELS) measurements on diamond residues from carbonaceous meteorites designed to elucidate the structure and composition of interstellar diamonds. Dynamic effective medium theory is used to model the dielectric properties of the diamonds and in particular to synthesize the observed spectra as mixtures of diamond and various pi-bonded carbons. The results are shown to be quantitatively consistent with the idea that diamonds and their surfaces are the only contributors to the electron energy loss spectra of the diamond residues and that these peculiar spectra are the result of the exceptionally small grain size and large specific surface area of the interstellar diamonds.

Bernatowicz, Thomas J.↗

Mechanism for diamond nucleation and growth on single crystal copper surfaces implanted with carbon

The nucleation and growth of diamond crystals on single-crystal copper surfaces implanted with carbon ions is studied. Microwave plasma-enhanced chemical-vapor deposition is used for diamond growth. The single-crystal copper substrates were implanted either at room or elevated temperature with carbon ions prior to diamond nucleation. This procedure leads to the formation of a graphite film on the copper surface which greatly enhances diamond crystallite nucleation. A simple lattice model is constructed for diamond growth on graphite as 111 line (diamond) parallel to 0001 line (graphite) and 110 line (diamond) parallel to 1 1 -2 0 (graphite).

Ong, T. P.↗

Degassing mechanisms of noble gases from carbonado diamonds

Diamonds are unique samples for inferring ancient mantle conditions, because of their enormous stability, antiquity and also of mantle origin. However, as temperatures in the mantle where diamonds have existed are very high (greater than 1000 C) and residence time of some diamonds could be more than a few billion years, it is imperative to examine whether or not diamonds have retained their pristine characteristics, especially those of noble gases, under such extreme conditions. As discussed in a review article by Ozima, there are rather large variations in the diffusivity of helium in diamonds obtained in the early determinations. The data are also limited to temperatures higher than 1200 C. In the present study, we conducted more refined diffusion experiments for He using carbonado diamonds, which have large amounts of radiogenic (4)He approximately 10(exp -2) cu cm STP/g. On the basis of the experimentally estimated diffusion coefficients, we will discuss retentivity of He in diamonds in the mantle condition.

Zashu, S.↗

Ion-Implanted Diamond Films and Their Tribological Properties

This paper reports the physical characterization and tribological evaluation of ion-implanted diamond films. Diamond films were produced by microwave plasma, chemical vapor deposition technique. Diamond films with various grain sizes (0.3 and 3 microns) and roughness (9.1 and 92.1 nm r.m.s. respectively) were implanted with C(+) (m/e = 12) at an ion energy of 160 eV and a fluence of 6.72 x 10(exp 17) ions/sq cm. Unidirectional sliding friction experiments were conducted in ultrahigh vacuum (6.6 x 10(exp -7)Pa), dry nitrogen and humid air (40% RH) environments. The effects of C(+) ion bombardment on fine and coarse-grained diamond films are as follows: the surface morphology of the diamond films did not change; the surface roughness increased (16.3 and 135.3 nm r.m.s.); the diamond structures were damaged and formed a thin layer of amorphous non-diamond carbon; the friction coefficients dramatically decreased in the ultrahigh vacuum (0.1 and 0.4); the friction coefficients decreased slightly in the dry nitrogen and humid air environments.

Wu, Richard L. C.↗

Surface Design and Engineering Toward Wear-Resistant, Self-Lubricant Diamond Films and Coatings

This chapter describes three studies on the surface design, surface engineering, and tribology of chemical-vapor-deposited (CVD) diamond films and coatings toward wear-resistant, self-lubricating diamond films and coatings. Friction mechanisms and solid lubrication mechanisms of CVD diamond are stated. Effects of an amorphous hydrogenated carbon on CVD diamond, an amorphous, nondiamond carbon surface layer formed on CVD diamond by carbon and nitrogen ion implantation, and a materials combination of cubic boron nitride and CVD diamond on the adhesion, friction, and wear behaviors of CVD diamond in ultrahigh vacuum are described. How surface modification and the selected materials couple improved the tribological functionality of coatings, giving low coefficient of friction and good wear resistance, is explained.

Miyoshi, Kazuhisa↗

Diamond Coatings

Advances in materials technology have demonstrated that it is possible to get the advantages of diamond in a number of applications without the cost penalty, by coating and chemically bonding an inexpensive substrate with a thin film of diamond-like carbon (DLC). Diamond films offer tremendous technical and economic potential in such advances as chemically inert protective coatings; machine tools and parts capable of resisting wear 10 times longer; ball bearings and metal cutting tools; a broad variety of optical instruments and systems; and consumer products. Among the American companies engaged in DLC commercialization is Diamonex, Inc., a diamond coating spinoff of Air Products and Chemicals, Inc. Along with its own proprietary technology for both polycrystalline diamond and DLC coatings, Diamonex is using, under an exclusive license, NASA technology for depositing DLC on a substrate. Diamonex is developing, and offering commercially, under the trade name Diamond Aegis, a line of polycrystalline diamond-coated products that can be custom tailored for optical, electronic and engineering applications. Diamonex's initial focus is on optical products and the first commercial product is expected in late 1990. Other target applications include electronic heat sink substrates, x-ray lithography masks, metal cutting tools and bearings.

Source record↗

Very High Efficiency, Miniaturized, Long-Lived Alpha Particle Power Source Using Diamond Devices for Extreme Space Environments

A power source that converts a-particle energy into electricity by coulomb collision in doped diamond films is described. Alpha particle decay from curium-244 creates electron-hole pairs by free- ing electrons and holes inside the crystal lattice in N- and P-doped diamond films. Ohmic contacts provide electrical connection to an electronic device. Due to the built-in electric field at the rectifying junction across the hT- and P-doped diamond films, the free electrons are constrained to traveling in generally one direction. This one direction then supplies electrons in a manner similar to that of a battery. The radioactive curium layer may be disposed on diamond films for even distribution of a-particle radiation. The resulting power source may be mounted on a diamond substrate that serves to insulate structures below the diamond substrate from a-particle emission. Additional insulation or isolation may be provided in order to prevent damage from a-particle collision. N-doped silicon may be used instead of N-doped diamond.

Elizabeth A Kolawa↗

Diamond Heat-Spreader for Submillimeter-Wave Frequency Multipliers

The planar GaAs Shottky diode frequency multiplier is a critical technology for the local oscillator (LO) for submillimeter- wave heterodyne receivers due to low mass, tenability, long lifetime, and room-temperature operation. The use of a W-band (75-100 GHz) power amplifier followed by a frequency multiplier is the most common for submillimeter-wave sources. Its greatest challenge is to provide enough input power to the LO for instruments onboard future planetary missions. Recently, JPL produced 800 mW at 92.5 GHz by combining four MMICs in parallel in a balanced configuration. As more power at W-band is available to the multipliers, their power-handling capability be comes more important. High operating temperatures can lead to degradation of conversion efficiency or catastrophic failure. The goal of this innovation is to reduce the thermal resistance by attaching diamond film as a heat-spreader on the backside of multipliers to improve their power-handling capability. Polycrystalline diamond is deposited by hot-filament chemical vapor deposition (CVD). This diamond film acts as a heat-spreader to both the existing 250- and 300-GHz triplers, and has a high thermal conductivity (1,000-1,200 W/mK). It is approximately 2.5 times greater than copper (401 W/mK) and 20 times greater than GaAs (46 W/mK). It is an electrical insulator (resistivity approx. equals 10(exp 15) Ohms-cm), and has a low relative dielectric constant of 5.7. Diamond heat-spreaders reduce by at least 200 C at 250 mW of input power, compared to the tripler without diamond, according to thermal simulation. This superior thermal management provides a 100-percent increase in power-handling capability. For example, with this innovation, 40-mW output power has been achieved from a 250-GHz tripler at 350-mW input power, while the previous triplers, without diamond, suffered catastrophic failures. This breakthrough provides a stepping-stone for frequency multipliers-based LO up to 3 THz. The future work for this design is to apply the high output power from both the 250 and 300 GHz to multiple chains in order to generate milliwatts at 2.3 THz. Using the first generation of results for this innovation, 40 mW of output power were produced from a 240-GHz tripler at 350-mW input power, and 27- mW output power was produced from a 300-GHz tripler at 408-mW input power. This is two times higher than the current state-of-the-art output power capability. A finite-element thermal simulation also shows that 30-microns thick diamond dropped the temperature of the anodes by at least 200 C.

Lin, Robert H.↗

Diamond Synthesis Employing Nanoparticle Seeds

Iron nanoparticles were employed to induce the synthesis of diamond on molybdenum, silicon, and quartz substrates. Diamond films were grown using conventional conditions for diamond synthesis by hot filament chemical vapor deposition, except that dispersed iron oxide nanoparticles replaced the seeding. This approach to diamond induction can be combined with dip pen nanolithography for the selective deposition of diamond and diamond patterning while avoiding surface damage associated to diamond-seeding methods.

Uppireddi, Kishore↗

Diamond nanostructures with large surface area and method of producing the same

A method for forming diamond nanostructures with large specific area can include forming porous diamond nanostructures by means of selectively etching sp2-bonded carbon and partially removing sp3-bonded carbon in nanocrystalline diamond (NCD) and ultrananocrystalline diamond (UNCD® diamond). The diamond nanostructures achieved from the disclosed method can include a long shaft surrounded by a school of barbs. The nanostructure can provide a significantly larger surface area than diamond without such a nanostructure and its fabrication provides relative ease of manufacture compared to traditional techniques.

36 MATERIALS SCIENCE↗

Scanning X-Ray Diffraction Microscopy for Diamond Quantum Sensing

An understanding of nano- and microscale crystal strain in chemical-vapor-deposition diamond is crucial to the advancement of diamond quantum technologies. In particular, the presence of such strain and its characterization presents a challenge to diamond-based quantum sensing and information applications-as well as for future dark-matter detectors, where the directional information about incoming particles is encoded in crystal strain. Here, we exploit nanofocused scanning x-ray diffraction microscopy to quantitatively measure crystal deformation from defects in diamond with high spatial and strain resolution. The combination of information from multiple Bragg angles allows stereoscopic three-dimensional modeling of strain-feature geometry; the diffraction results are validated via comparison to optical measurements of the strain tensor based on spin-state-dependent spectroscopy of ensembles of nitrogen-vacancy centers in the diamond. Finally, our results demonstrate both strain and spatial resolution sufficient for directional detection of dark matter via x-ray measurement of crystal strain and provide a promising tool for diamond growth analysis and improvement of defect-based sensing.

42 ENGINEERING↗

Sub-melt nanosecond pulsed-laser induced densification and strain-field relaxation in single-crystal diamond

Dislocations and polishing-induced defect networks in synthetic diamond introduce local strain fields and broaden Raman features, limiting performance in optical, thermal, and electronic applications. Laser annealing is emerging as a promising approach to repair surface and near-surface defects in diamond without entering the melt regime, yet surface densification, defect-state modification, and associated structural changes have not been well quantified. In this work, we show that sub-melt nanosecond pulsed-laser annealing (PLA) induces near-surface densification and defect-mediated strain relaxation in single-crystal Chemical Vapor Deposition (CVD) diamond. Single- and two-pulse PLA were applied, and structural evolution was quantified using co-registered ISO 25,178 white-light interferometry, depth-resolved Raman spectroscopy, and cross-sectional STEM with geometric phase analysis (GPA). Across a 5 × 6 grid (n = 30), responsive regions exhibit large reductions in local slope (Sdq 45–65%), developed area (Sdr 60–90%), height spread (Sp, Sz 30–65%), void volume (Vv 57–60%), and roughness amplitude (Sa, Sq 48–57%), consistent with densification of ∼4–6.5 nm. Raman profiling shows narrowing of the diamond line and improved spectral uniformity to depths of ∼2–3 μm. Given that the Raman probing depth significantly exceeds the densified layer thickness, this response is interpreted as consistent with long-range strain-field redistribution originating from the near-surface region. STEM-GPA strain maps further support this interpretation, showing smoother strain fields, suppressed hotspots, and redistribution of localized strain concentrations following PLA. These results are consistent with defect-mediated strain relaxation and densification-driven modification of the near-surface energy state. The approach provides a scalable pathway for improving near-surface structural quality in diamond relevant to electronic, photonic, and quantum applications.

Areal surface metrology (ISO 25,178)↗

Development of 3D diamond detectors for detector applications at ultra high luminosity facilities

During this project our group has succeeded in producing and measuring a number of 3D diamond devices. We have worked with manufacturers and shown that poly-crystalline CVD (pCVD) diamond can be grown reliably with a 5% uniformity in industry. We have produced 3D diamond devices and scaled up the production technology from roughly 100 cells on a device to 4000 cells on a device. We have increased the column yield from 92% to 99%. We have reduced the cell size from our safe initial choice 150μm x 150μm cells to the HL-LHC size of 50μm x 50μm cells. We have reduced the column diameter from 6-10 μm to 2.6 μm. In beam tests we have quantified the amount of charge each 3D device yields for minimizing ionizing particles and compared this to that produced by a planar diamond device. Very recently, we produced the first 3D diamond pixel devices read out with both ATLAS and CMS pixel electronics, tested them in particle beams at CERN and PSI. Finally we have successfully tested the first irradiated 3Ddiamond device after a fluence of 3.5 x 10 15 800 MeV p/cm 2 .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Diamond rotors

The resolution of magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra remains bounded by the spinning frequency, which is limited by the material strength of MAS rotors. Since diamond is capable of withstanding 1.5–2.5x greater MAS frequencies, compared to state-of-the art zirconia, we fabricated rotors from single crystal diamond. When combined with bearings optimized for spinning with helium gas, diamond rotors could achieve the highest MAS frequencies to date. Furthermore, the excellent microwave transmission properties and thermal conductivity of diamond could improve sensitivity enhancements in dynamic nuclear polarization (DNP) experiments. The fabrication protocol we report involves novel laser micromachining and produced rotors that presently spin at ω r = 111.000 ± 0.004 kHz, with stable spinning up to 124 kHz, using N 2 gas as the driving fluid. Here, we present the first proton-detected 13 C/ 15 N MAS spectra recorded using diamond rotors, a critical step towards studying currently inaccessible ex-vivo protein samples with MAS NMR. Previously, the high aspect ratio of MAS rotors (~10:1) precluded fabrication of MAS rotors from diamond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗