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At least 163 records · Page 9

Nature and origin of interstellar diamond from the Allende CV3 meteorite

Data and experimental evidence which support the contention that the C delta diamonds may result from grain-grain collisions in supernova shocks in the interstellar medium are presented. Fragments of the Allende CV3 chondrite were acid-treated. A whitish powder was obtained. For the Analytical Electron Microscopy (AEM) a small drop of ethanol suspension was transferred onto holey carbon support films on 3 mm EM grids. The AEM was performed on transmission-thin fragments of the material which overlay holes in the film, to eliminate interference from the substrate. Electron Spectroscopy for Chemical Analysis (ESCA) was performed on a large aliquot of C. Diamond was identified by selected area electron diffraction. Scanning Transmission Electron Microscope / Energy Dispersive X-ray (STEM-EDS) microanalyses of the C delta diamond, using a light-element detector, show that oxygen and possibly nitrogen are the only impurities consistently present. ESCA spectra from bulk C delta material confirm the presence of N at a level of 0.35 percent or less. Under UV irradiation a yellow-red fluorescence is observed, consistent with that of natural diamonds containing substitutional N. Electron Energy Loss Spectra (EELS) were recorded at 2 eV resolution from the C delta diamond, high pressure synthetic diamond, a diamond film produced in a low pressure plasma by chemical vapor deposition (CVD) on a heated silicon substrate (Roy, 1987), graphite, and amorphous arc sputtered carbon. Comparison of the carbon K edge shape and fine structure shows the Allende C delta phase to be largely diamond, but with a significant pre-edge absorption feature indicative of transitions of C 1s electrons into pi asterisk orbitals which are absent in the purely sp(3)-bonded diamond but present in graphite and amorphous carbon.

Blake, David↗

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

The tribological properties of chemical-vapor-deposited (CVD) diamond films vary with the environment, possessing a Jekyll-and-Hyde character. CVD diamond has low coefficient of friction and high wear resistance in air but high coefficient of friction and low wear resistance in vacuum. Improving the tribological functionality of materials (such as achieving low friction and good wear resistance) was an aim of this investigation. Three studies on the surface design, surface engineering, and tribology of CVD diamond have shown that its friction and wear are significantly reduced in ultrahigh vacuum. The main criteria for judging whether diamond films are an effective wear-resistant, self-lubricating material were coefficient of friction and wear rate, which must be less than 0.1 and on the order of 10(exp 6) cu mm/N(dot)m, respectively. In the first study the presence of a thin film (less than 1 micron thick) of amorphous, nondiamond carbon (hydrogenated carbon, also called diamondlike carbon or DLC) on CVD diamond greatly decreased the coefficient of friction and the wear rate. Therefore, a thin DLC film on CVD diamond can be an effective wear-resistant, lubricating coating in ultrahigh vacuum. In the second study the presence of an amorphous, nondiamond carbon surface layer formed on CVD diamond by ion implantation significantly reduced the coefficient of friction and the wear rate in ultrahigh vacuum. Therefore, such surface layers are acceptable for effective self-lubricating, wear-resistant applications of CVD diamond. In the third study CVD diamond in contact with cubic boron nitride exhibited low coefficient of friction in ultra high vacuum. Therefore, this materials combination can provide an effective self-lubricating, wear-resistant couple in ultrahigh vacuum.

Miyoshi, Kazuhisa↗

The Petrography of Meteoritic Nano-Diamonds

At least some meteoritic nanodiamonds are likely of presolar origin because of their association with anomalous Xe-HL and Te isotopic components indicative of a supernova (SN) origin. But the abundance of Xe is such that only approx. 1 in 10(exp 6) nano-diamonds contains a Xe atom, and the bulk C-13/C-12 composition of nano-diamond acid residues is chondritic (solar). Therefore, it is possible that a significant fraction of meteoritic nano-diamonds formed within the solar nebula. Nano-diamonds have recently been detected for the first time within the accretion discs of young stars by the Infrared Space Observatory (ISO). No comparable evidence of nanodiamonds in the interstellar medium has yet been found. We have identified nano-diamonds in acid etched thin-sections of meteorites, polar micrometeorites, and interplanetary dust particles (IDPs) with the goal of determining their distribution as a function of heliocentric distance. (It is assumed the meteorites and the polar micrometeorites are from asteroids at 2-4 AU and at least some of the IDPs are from comets at >50AU). We found that nano-diamonds are heterogeneously distributed throughout carbon-rich meteoritic materials (we identified them in some IDPs and not in others), and that their abundance may actually decrease with heliocentric distance, consistent with the hypothesis that some of them formed within the inner solar system and not in a presolar (SN) environment. In order to gain further insight about the origins of meteoritic nano-diamonds we are currently investigating their distribution in unetched thin-sections. We have examined a chondritic cluster IDP (U220GCA), fragments of the Tagish Lake (CM1) meteorite, and a SN graphite spherule (KE3d8) isolated from the Murchison (CM) meteorite. We selected U220GCA because its nano-diamond abundance (in acid etched thin-sections) appears to be as much as approx. 10X higher than in Murchison matrix, Tagish Lake because it has a higher reported nano-diamond abundance than other carbonaceous chondrites (approx. 3650-4330 ppm), and KE3d8 because it is a carbon spherule with an isotopic composition suggesting that it is a bone fide presolar SN grain.

Dai, Z. R.↗

Triphasic Tooling with Small Oriented Diamond Tip for Turning and Smoothing Lightweight Mirrors

We are developing a new method for the growth of small diamond crystals at very high temperatures and pressures directly from a carbon melt. A prototype "Supercell" has been developed for this purpose. This system is capable of high rate crystal growth in relatively large working volumes. The resulting high quality diamond crystals will be incorporated into a triphasic diamond/titanium carbide/titanium composite tool, with an oriented diamond crystal at its tip. High pressure is needed to prevent degradation of diamond at high temperature, and to ensure the formation of a crack & composite structure. After grinding and polishing, the composite material will be joined to a steel holder, thus forming a diamond-tipped tool for turning and smoothing of a mirror surface. A properly oriented single-crystal diamond cuts and smoothes much better than a conventional polycrystalline diamond crystal. This is because the hardness depends on crystallographic orientation-the difference corresponds to 60-100 GPa on the Knoop scale. Our goal is to achieve surface roughness of about 1 nm, which will be accomplished by precision cutting and smoothing. The hardness of the functionally-graded diamond/titanium carbide/titanium composite tool varies from 100 GPa at its tip to 15 GPa at its base. Previous work has shown that the mass of machined material using an oriented-diamond tool is much larger than that for a standard diamond-metal composite tool.

Voronov, O. A.↗

Synthesizing Diamond from Liquid Feedstock

A relatively economical method of chemical vapor deposition (CVD) has been developed for synthesizing diamond crystals and films. Unlike prior CVD methods for synthesizing diamond, this method does not require precisely proportioned flows of compressed gas feedstocks or the use of electrical discharges to decompose the feedstocks to obtain free radicals needed for deposition chemical reactions. Instead, the feedstocks used in this method are mixtures of common organic liquids that can be prepared in advance, and decomposition of feedstock vapors is effected simply by heating. The feedstock used in this method is a solution comprising between 90 and 99 weight percent of methanol and the balance of one or more other oxyhydrocarbons that could include ethanol, isopropanol, and/or acetone. This mixture of compounds is chosen so that dissociation of molecules results in the desired proportions of carbon-containing radicals (principally, CH3) and of OH, H, and O radicals. Undesirably, the CVD temperature and pressure conditions thermodynamically favor the growth of graphite over the growth of diamond. The H radicals are desirable because they help to stabilize the growing surface of diamond by shifting the thermodynamic balance toward favoring the growth of diamond. The OH and O radicals are desirable because they preferentially etch graphite and other non-diamond carbon, thereby helping to ensure the net deposition of pure diamond. The non-methanol compounds are included in the solution because (1) methanol contains equal numbers of C and O atoms; (2) an excess of C over O is needed to obtain net deposition of diamond; and (3) the non-methanol molecules contain multiple carbon atoms for each oxygen atom and thus supply the needed excess carbon A typical apparatus used in this method includes a reservoir containing the feedstock liquid and a partially evacuated stainless-steel reaction chamber. The reservoir is connected to the chamber via tubing and a needle valve or other suitable flow controller. When the liquid enters the low-pressure environment inside the chamber, it evaporates to form a vapor mixture of the same chemical composition. In addition to the inlet for the feedstock liquid, the chamber is fitted with an outlet connected to a vacuum pump (not shown) through a throttle valve (also not shown) that is automatically controlled to keep the pressure at or near the required value throughout the deposition process. Inside the chamber, a spiral filament made of tungsten, tantalum, graphite, or other high-melting-temperature material is electrically heated to a temperature >2,000 C high enough to cause dissociation of vapor molecules into the aforementioned radicals. A deposition substrate typically, a diamond-polished silicon wafer about 2.5 cm square is positioned about 2 cm away from the filament. The exact location of the substrate is chosen so that the substrate becomes heated by the filament to a deposition temperature in the approximate range of 800 to 1,000 C.

Tzeng, Yonhua↗

Current generation from radiation with diamond diode-based devices for detection or power generation

Diamond diode-based devices are configured to convert radiation energy into electrical current, useable for sensing (i.e., detection) or delivery to a load (i.e., energy harvesting). A diode-based detector includes an intrinsic diamond layer arranged between p-type diamond and n-type diamond layers, with the detector further including at least one of (i) a boron containing layer arranged proximate to the n-type and/or the intrinsic diamond layers, or (ii) an intrinsic diamond layer thickness in a range of 10 nm to 300 microns. A diode-based detector may be operated in a non-forward biased state, with a circuit used to transmit a current pulse in a forward bias direction to reset a detection state of the detector. An energy harvesting device may include at least one p-i-n stack (including an intrinsic diamond layer between p-type diamond and n-type diamond layers), with a radioisotope source arranged proximate to the at least one p-i-n stack.

Holmes, Jason M.↗

Fabrication of diamond based sensors for use in extreme environments

Electrical and magnetic sensors can be lithographically fabricated on top of diamond substrates and encapsulated in a protective layer of chemical vapor deposited single crystalline diamond. This process when carried out on single crystal diamond anvils employed in high pressure research is termed as designer diamond anvil fabrication. These designer diamond anvils allow researchers to study electrical and magnetic properties of materials under extreme conditions without any possibility of damaging the sensing elements. We describe a novel method for the fabrication of designer diamond anvils with the use of maskless lithography and chemical vapor deposition in this paper. This method can be utilized to produce diamond based sensors which can function in extreme environments of high pressures, high and low temperatures, corrosive and high radiation conditions. Here, we demonstrate applicability of these diamonds under extreme environments by performing electrical resistance measurements during superconducting transition in rare earth doped iron-based compounds under high pressures to 12 GPa and low temperatures to 10 K.

36 MATERIALS SCIENCE↗

A Study of the Radiation Tolerance of CVD Diamond to 70 MeV Protons, Fast Neutrons and 200 MeV Pions

We measured the radiation tolerance of commercially available diamonds grown by the Chemical Vapor Deposition process by measuring the charge created by a 120 GeV hadron beam in a 50 μm pitch strip detector fabricated on each diamond sample before and after irradiation. We irradiated one group of samples with 70 MeV protons, a second group of samples with fast reactor neutrons (defined as energy greater than 0.1 MeV), and a third group of samples with 200 MeV pions, in steps, to (8.8±0.9) × 1015 protons/cm2, (1.43±0.14) × 1016 neutrons/cm2, and (6.5±1.4) × 1014 pions/cm2, respectively. By observing the charge induced due to the separation of electron–hole pairs created by the passage of the hadron beam through each sample, on an event-by-event basis, as a function of irradiation fluence, we conclude all datasets can be described by a first-order damage equation and independently calculate the damage constant for 70 MeV protons, fast reactor neutrons, and 200 MeV pions. We find the damage constant for diamond irradiated with 70 MeV protons to be 1.62±0.07(stat)±0.16(syst)× 10−18 cm2/(p μm), the damage constant for diamond irradiated with fast reactor neutrons to be 2.65±0.13(stat)±0.18(syst)× 10−18 cm2/(n μm), and the damage constant for diamond irradiated with 200 MeV pions to be 2.0±0.2(stat)±0.5(syst)× 10−18 cm2/(π μm). The damage constants from this measurement were analyzed together with our previously published 24 GeV proton irradiation and 800 MeV proton irradiation damage constant data to derive the first comprehensive set of relative damage constants for Chemical Vapor Deposition diamond. We find 70 MeV protons are 2.60 ± 0.29 times more damaging than 24 GeV protons, fast reactor neutrons are 4.3 ± 0.4 times more damaging than 24 GeV protons, and 200 MeV pions are 3.2 ± 0.8 more damaging than 24 GeV protons. We also observe the measured data can be described by a universal damage curve for all proton, neutron, and pion irradiations we performed of Chemical Vapor Deposition diamond. Finally, we confirm the spatial uniformity of the collected charge increases with fluence for polycrystalline Chemical Vapor Deposition diamond, and this effect can also be described by a universal curve.

36 MATERIALS SCIENCE↗

Boron isotopes in blue diamond record seawater-derived fluids in the lower mantle

Boron is a quintessential crustal element but its conspicuous presence in diamond – a mantle mineral – raises questions about potential subduction pathways for boron and other volatiles. It has been a long-standing goal to characterize the isotopic composition of boron in blue, boron-bearing (Type IIb) diamonds to reveal its origin. Mineral inclusions indicate that Type IIb diamonds crystallize at transition zone to lower mantle depths, meaning that if the boron is subducted it would trace a pathway of volatile elements into the deep mantle. Here, using off-line laser ablation sampling, we present the first boron isotope compositions, along with trace element contents and carbon isotope compositions, of a suite of blue diamonds mainly sourced from the Cullinan diamond mine in South Africa. The ten analyzed blue diamonds have a wide range in δ 11 B, between -9.2 ± 2‰ and -0.5 ± 2‰, compared to the more restricted range for mid-ocean ridge basalts (-7.1 ± 0.9‰). Carbon isotope values for the blue diamonds range between -20.6 and -1.8‰, with a mode at -17‰, significantly more negative than the main mantle mode at -5‰. Combined, the boron and carbon isotope compositions require fluid input from subducted oceanic lithosphere down into deep mantle source regions of blue diamonds. This finding highlights a deep subduction pathway for volatiles to stoke the source regions of deeply-derived magmas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct-bonded diamond membranes for heterogeneous quantum and electronic technologies

Diamond has superlative material properties for a broad range of quantum and electronic technologies. However, heteroepitaxial growth of single crystal diamond remains limited, impeding integration and evolution of diamond-based technologies. Here, we directly bond single-crystal diamond membranes to a wide variety of materials including silicon, fused silica, sapphire, thermal oxide, and lithium niobate. Our bonding process combines customized membrane synthesis, transfer, and dry surface functionalization, allowing for minimal contamination while providing pathways for near unity yield and scalability. We generate bonded crystalline membranes with thickness as low as 10 nm, sub-nm interfacial regions, and nanometer-scale thickness variability over 200 by 200 μm 2 areas. We measure spin coherence times T 2 for nitrogen vacancy centers in 150 nm-thick bonded membranes of up to 623 ± 21 μs, suitable for advanced quantum applications. We demonstrate multiple methods for integrating high quality factor nanophotonic cavities with the diamond heterostructures, highlighting the platform versatility in quantum photonic applications. Furthermore, we show that our ultra-thin diamond membranes are compatible with total internal reflection fluorescence (TIRF) microscopy, which enables interfacing coherent diamond quantum sensors with living cells while rejecting unwanted background luminescence. The processes demonstrated herein provide a full toolkit to synthesize heterogeneous diamond-based hybrid systems for quantum and electronic technologies.

color center↗

Focused-ion-beam overlay-patterning of three-dimensional diamond structures for advanced single-photon properties

Sources of single photons are of fundamental importance in many applications as to provide quantum states for quantum communication and quantum information processing. Color centers in diamond are prominent candidates to generate and manipulate quantum states of light, even at room temperature. However, the efficiency of photon collection of the color centers in bulk diamond is greatly reduced by refraction at the diamond/air interface. To address this issue, diamond structuring has been investigated by various methods. Among them, focused-ion-beam (FIB) direct patterning has been recognized as the most favorable technique. But it has been noted that diamond tends to present significant challenges in FIB milling, e.g., the susceptibility of forming charging related artifacts and topographical features. In this work, periodically-positioned-rings and overlay patterning with stagger-superimposed-rings were proposed to alleviate some problems encountered in FIB milling of diamond, for improved surface morphology and shape control. Cross-scale network and uniform nanostructure arrays have been achieved in single crystalline diamond substrates. High quality diamond solid immersion lens and nanopillars were sculptured with a nitrogen-vacancy center buried at the desired position. Compared with the film counterpart, an enhancement of about ten folds in single photon collection efficiency was achieved with greatly improved signal to noise ratio. All these results indicate that FIB milling through over-lay patterning could be an effective approach to fabricate diamond structures, potentially for quantum information studies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermal conductivity changes upon neutron transmutation of {sup 10}B doped diamond

{sup 10}B doped p-type diamond samples were subjected to neutron transmutation reaction using thermal neutron flux of 0.9 × 10{sup 13} cm{sup −2} s{sup −1} and fast neutron flux of 0.09 × 10{sup 13} cm{sup −2} s{sup −1}. Another sample of epilayer grown on type IIa (110) single crystal diamond substrate was subjected to equal thermal and fast neutron flux of 10{sup 14} cm{sup −2} s{sup −1}. The defects in the diamond samples were previously characterized by different methods. In the present work, thermal conductivity of these diamond samples was determined at room temperature by transient thermoreflectance method. The thermal conductivity change in the samples as a function of neutron fluence is explained by the phonon scattering from the point defects and disordered regions. The thermal conductivity of the diamond samples decreased more rapidly initially and less rapidly for larger neutron fluence. In addition, the thermal conductivity in type IIb diamond decreased less rapidly with thermal neutron fluence compared to the decrease in type IIa diamond subjected to fast neutron fluence. It is concluded that the rate of production of defects during transmutation reaction is slower when thermal neutrons are used. The thermal conductivity of epilayer of diamond subjected to high thermal and fast neutron fluence is associated with the covalent carbon network in the composite structure consisting of disordered carbon and sp{sup 2} bonded nanocrystalline regions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Novel phase of carbon, ferromagnetism, and conversion into diamond

We report the discovery of a new phase of carbon (referred to as Q-carbon) and address fundamental issues related to direct conversion of carbon into diamond at ambient temperatures and pressures in air without any need for catalyst and presence of hydrogen. The Q-carbon is formed as result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs. T) of carbon and show that by rapid quenching kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. It is shown that nanosecond laser heating of diamond-like amorphous carbon on sapphire, glass, and polymer substrates can be confined to melt carbon in a super undercooled state. By quenching the carbon from the super undercooled state, we have created a new state of carbon (Q-carbon) from which nanodiamond, microdiamond, microneedles, and single-crystal thin films are formed depending upon the nucleation and growth times allowed for diamond formation. The Q-carbon quenched from liquid is a new state of solid carbon with a higher mass density than amorphous carbon and a mixture of mostly fourfold sp{sup 3} (75%–85%) with the rest being threefold sp{sup 2} bonded carbon (with distinct entropy). It is expected to have new and improved mechanical hardness, electrical conductivity, chemical, and physical properties, including room-temperature ferromagnetism (RTFM) and enhanced field emission. Here we present interesting results on RTFM, enhanced electrical conductivity and surface potential of Q-carbon to emphasize its unique properties. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g{sup −1}. From the Q-carbon, diamond phase is nucleated and a variety of micro- and nanostructures and large-area single-crystal diamond sheets are grown by allowing growth times as needed. Subsequent laser pulses can be used to grow nanodiamond into microdiamond and nucleate other nanostructures of diamond on the top of existing microdiamond and create novel nanostructured materials. The microstructural details provide insights into the mechanism of formation of nanodiamond, microdiamond, nanoneedles, microneedles, and single-crystal thin films. This process allows carbon-to-diamond conversion and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp{sup 3} bonding for diamond formation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Photoconductive Switch with High Sub-Bandgap Responsivity in Nitrogen-Doped Diamond

To evaluate nitrogen-doped diamond as a candidate for Photoconductive Semiconductor Switches (PCSS) triggered in the sub-bandgap visible range, we have fabricated and tested diamond PCSS from a set of diamond grades of varying nitrogen concentration. The nitrogen-doped diamond PCSS have higher responsivity than other diamond optoelectronic devices in the visible range. We present a novel demonstration of sub-bandgap triggered diamond PCSS, which when scaled to higher voltage, can compete with and even surpass performance of existing ultraviolet-triggered diamond PCSS. This work suggests that nitrogen-doped diamond is a promising candidate for high-power, fast optoelectronic devices.

36 MATERIALS SCIENCE↗

Low-temperature synthesis of diamond films by photoemission-assisted plasma-enhanced chemical vapor deposition

Photoemission-assisted plasma-enhanced chemical vapor deposition (PA-PECVD), a process in which photoelectrons emitted from a substrate irradiated with ultraviolet light are utilized as a trigger for DC discharge, was investigated in this study; specifically, the DC discharge characteristics of PA-PECVD were examined for an Si substrate deposited in advance through hot-filament chemical vapor deposition with a nitrogen-doped diamond layer of thickness ∼1 μm. Using a commercially available Xe excimer lamp (hν = 7.2 eV) to illuminate the diamond surface with and without hydrogen termination, the photocurrents were found to be 3.17 × 10{sup 12} and 2.11 × 10{sup 11} electrons/cm{sup 2}/s, respectively. The 15-fold increase in photocurrent was ascribed to negative electron affinity (NEA) caused by hydrogen termination on the diamond surfaces. The DC discharge characteristics revealed that a transition bias voltage from a Townsend-to-glow discharge was considerably decreased because of NEA (from 490 to 373 V for H{sub 2} gas and from 330 to 200 V for Ar gas), enabling a reduction in electric power consumption needed to synthesize diamond films through PA-PECVD. In fact, the authors have succeeded in growing high-quality diamond films of area 2.0 cm{sup 2} at 540 °C with a discharge power of only 1.8 W, plasma voltage of 156.4 V, and discharge current of 11.7 mA under the glow discharge of CH{sub 4}/H{sub 2}/Ar mixed gases. In addition to having only negligible amounts of graphite and amorphous carbon, the diamond films exhibit a relatively high diamond growth rate of 0.5 μm/h at temperatures as low as 540 °C, which is attributed to Ar{sup +} ions impinging on the diamond surface, and causing the removal of hydrogen atoms from the surface through sputtering. This process leads to enhanced CH{sub x} radical adsorption, because the sample was applied with a negative potential to accelerate photoelectrons in PA-PECVD.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structure Formation of Hexagonal Diamond: Ab Initio Calculations

The formation of structure of hexagonal diamond from graphite and cubic diamond is simulated with the density functional theory. Orthorhombic AB graphite transforms into hexagonal diamond under uniaxial compression at pressures above 61 GPa. The pressure should be higher than 57 GPa to form hexagonal diamond from AA graphite. Another possible way to obtain hexagonal diamond is uniaxial compression of cubic diamond under pressures from 300 to 380 GPa. The theoretical calculations were used to interpret the diffraction data obtained after X-ray diffraction and electron microscopic analysis of natural and synthetic diamond-like materials. We found that there are no crystals with ideal cubic and hexagonal structures in diamond-like carbon materials, and their structure is characterized by random packing of molecular layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Superior wear resistance of diamond and DLC coatings

As the hardest known material, diamond and its coatings continue to generate significant attention for stringent applications involving extreme tribological conditions. Likewise, diamond-like carbon (DLC, especially the tetragonal amorphous carbon, ta-C) coatings have also maintained a high level interest for numerous industrial applications where efficiency, performance, and reliability are of great importance. Additionally, the strong covalent bonding or sp 3 -hybridizaiton in diamond and ta-C coatings assures high mechanical hardness, stiffness, chemical and thermal stability that make them well-suited for harsh tribological conditions involving high-speeds, loads, and temperatures. In particular, unique chemical and mechanical nature of diamond and ta-C surfaces plays an important role in their unusual friction and wear behaviors. As with all other tribomaterials, both diamond and ta-C coatings strongly interact with the chemical species in their surroundings during sliding and hence produce a chemically passive top surface layer which ultimately determines the extent of friction and wear. Thick micro-crystalline diamond films are most preferred for tooling applications, while thinner nano/ultranano-crysalline diamond films are well-suited for mechanical devices ranging from nano- (such as NEMS) to micro- (MEMS and AFM tips) as well as macro-scale devices including mechanical pump seals. The ta-C coatings have lately become indispensable for a variety of automotive applications and are used in very large volumes in tappets, piston pins, rings, and a variety of gears and bearings, especially in the Asian market. This paper is intended to provide a comprehensive overview of the recent developments in tribology of super-hard diamond and DLC (ta-C) films with a special emphasis on their friction and wear mechanisms that are key to their extraordinary tribological performance under harsh tribological conditions. Finally, based on the results of recent studies, the paper will also attempt to highlight what lies ahead for these films in tribology and other demanding industrial applications.

36 MATERIALS SCIENCE↗

Strength and deformation of shocked diamond single crystals: Orientation dependence

Understanding and quantifying the strength or elastic limit of diamond single crystals is of considerable scientific and technological importance, and has been a subject of long standing theoretical and experimental interest. To examine the effect of crystalline anisotropy on strength and deformation of shocked diamond single crystals, plate impact experiments were conducted to measure wave profiles at various elastic impact stresses up to ~120 GPa along [110] and [111] crystal orientations. Using laser interferometry, particle velocity histories and shock velocities in the diamond samples were measured and were compared with similar measurements published previously for shock compression along the [100] direction. Wave profiles for all three orientations showed large elastic wave amplitudes followed by time-dependent inelastic deformation. From the measured wave profiles, the elastic limits were determined under well characterized uniaxial strain loading conditions. The measured elastic wave amplitudes for the [110] and [111] orientations were lower for higher elastic impact stress (stress attained for an elastic diamond response), consistent with the result reported previously for [100] diamond. The maximum resolved shear stress (MRSS) on the {111}<110> slip systems was determined for each orientation, revealing significant orientation dependence. The MRSS values for the [100] and [110] orientations (~33 GPa) are 25-30% of theoretical estimates; the MRSS value for the [111] orientation is significantly lower (~23 GPa). Our results demonstrate that the MRSS depends strongly on the stress component normal to the {111} planes or the resolved normal stress (RNS), suggesting that the RNS plays a key role in inhibiting the onset of inelastic deformation. Lower elastic wave amplitudes at higher peak stress and the effect of the RNS are inconsistent with typical dislocation slip mechanisms of inelastic deformation, suggesting instead an inelastic response characteristic of shocked brittle solids. The present results show that the elastic limit (or material strength) of diamond single crystals cannot be described using traditional isotropic approaches, and typical plasticity models cannot be used to describe the inelastic deformation of diamond. Analysis of the measured wave profiles beyond the elastic limit, including characterization of the peak state, requires numerical simulations that incorporate a time-dependent, anisotropic, inelastic deformation response. Development of such a material description for diamond is an important need.

36 MATERIALS SCIENCE↗