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Conversion of silicon carbide to crystalline diamond-structured carbon at ambient pressure.

Synthetic diamond is formed commercially using high-pressure, chemical-vapour-deposition and shock-wave processes, but these approaches have serious limitations owing to low production volumes and high costs. Recently suggested alternative methods of diamond growth include plasma activation, high pressures, exotic precursors or explosive mixtures, but they suffer from very low yield and are intrinsically limited to small volumes or thin films. Here we report the synthesis of nano- and micro-crystalline diamond-structured carbon, with cubic and hexagonal structure, by extracting silicon from silicon carbide in chlorine-containing gases at ambient pressure and temperatures not exceeding 1,000 degrees C. The presence of hydrogen in the gas mixture leads to a stable conversion of silicon carbide to diamond-structured carbon with an average crystallite size ranging from 5 to 10 nanometres. The linear reaction kinetics allows transformation to any depth, so that the whole silicon carbide sample can be converted to carbon. Nanocrystalline coatings of diamond-structured carbon produced by this route show promising mechanical properties, with hardness values in excess of 50 GPa and Young's moduli up to 800 GPa. Our approach should be applicable to large-scale production of crystalline diamond-structured carbon.

Journal Article↗

Effectiveness of the Ultraflex Diamond stent for the palliation of malignant biliary obstruction.

BACKGROUND AND STUDY AIMS: Endoscopically placed metallic biliary stents provide durable drainage for malignant biliary obstruction. The best-studied metal stent is the Wallstent, which has a greater duration of patency than polyethylene stents. Recently, the Ultraflex Diamond stent has been introduced, with reports from Europe which suggest efficacy similar to that of the Wallstent. We report our experience with this new metal stent and compare it with a historical cohort of Wallstent-treated patients. PATIENTS AND METHODS: Between July 1997 and July 1998 all metal stents placed for malignant biliary obstruction were Diamond stents (10 mm diameter, 6 or 8 cm length). Prospective follow-up details with regard to patient death or stent occlusion were obtained. In total, 32 patients underwent stenting, but 11 patients were excluded because of the following: death from pre-existing cholangitis (2); placement of bilateral hilar stents (2); placement of stent through occluded metal stents (3); failure to palliate jaundice due to complex hilar stricture (2) or concomitant liver failure (1); or inability to obtain follow-up (1), leaving 21 patients for analysis. Occlusion rates and stent patency were also determined retrospectively for 19 patients with malignant biliary obstruction who had Wallstents (10 mm diameter, 6.8 cm length) placed during the preceding year and for whom accurate and complete follow-up details were available. RESULTS: In the Diamond stent group there were 14 men and seven women, mean age 73. In the Wallstent group there were 11 men and eight women, mean age 66. The types of cancer, level of stricture and percentage with prior polyethylene stenting were similar in both groups. Stent occlusion occurred in 9/21 (43%), Diamond stents at a mean of 74 +/- 43 days compared with 8/19 (42%) Wallstents at a mean of 178 +/- 138 days (P < 0.04). Mean time of stent patency was 110 +/- 89 days for Diamond stents and 253 +/- 218 days for Wallstents (P < 0.01). Analysis of occlusion-free survival using a Kaplan-Meier plot showed a trend favoring the Wallstent (P = 0.12; Wilcoxon test). CONCLUSIONS: The occlusion rate and patency of Diamond stents for malignant biliary obstruction appear to be inferior to those of Wallstents and similar to reported values for polyethylene stents. Prospective randomized comparisons of Wallstents and newer self-expanding metal stents are warranted.

Aged↗

A theoretical study of the structure of the liquid Ga-diamond (111) interface.

We present the results of a computer simulation study of the structure of the interface between liquid Ga and the (111) face of diamond, with which we reinterpret the findings from an x-ray reflectivity study of that interface [W. J. Huisman, J. F. Peters, M. J. Zwanenburg, S. A. de Vries, T. E. Derry, D. Abernathy, and J. F. van der Veen, Nature (London) 390, 379 (1997); Surf. Sci. 402-404, 866 (1998)]. That experimental study has been interpreted to show that the contact of Ga with the (111) face of diamond induces the formation of Ga(2) molecules for several layers into the bulk liquid, with the axes of the Ga(2) molecules in successive layers oriented perpendicular to the diamond surface. No driving force for the proposed formation of Ga(2) molecules is identified. The simulations reported in this paper are based on a model that permits chemical binding of Ga, as a dimer, to the C=C double bonds in the reconstructed (111) face of diamond, thereby identifying the driving force for dimerization. We show that an isolated pi complex with the Ga(2) axis perpendicular to the C=C double bond is stable. We then modify the pseudopotential-based self-consistent Monte Carlo simulation scheme for describing inhomogeneous liquid metals, using the calculated potential-energy surface of Ga(2)(C=C) in the region close to the diamond surface. In this model only the Ga adjacent to the diamond is composed of dimers. The interfacial density distribution obtained from the simulations predicts an x-ray reflectivity that is in good agreement with that observed.

Journal Article↗

Very high growth rate chemical vapor deposition of single-crystal diamond.

Diamond possesses extraordinary material properties, a result that has given rise to a broad range of scientific and technological applications. This study reports the successful production of high-quality single-crystal diamond with microwave plasma chemical vapor deposition (MPCVD) techniques. The diamond single crystals have smooth, transparent surfaces and other characteristics identical to that of high-pressure, high-temperature synthetic diamond. In addition, the crystals can be produced at growth rates from 50 to 150 mum/h, which is up to 2 orders of magnitude higher than standard processes for making polycrystalline MPCVD diamond. This high-quality single-crystal MPCVD diamond may find numerous applications in electronic devices as high-strength windows and in a new generation of high-pressure instruments requiring large single-crystal anvils.

Journal Article↗

Fossilized high pressure from the Earth's deep interior: the coesite-in-diamond barometer.

Mineral inclusions in diamonds provide an important source of information about the composition of the continental lithosphere at depths exceeding 120-150 km, i.e., within the diamond stability field. Fossilized high pressures in coesite inclusions from a Venezuela diamond have been identified and measured by using laser Raman and synchrotron x-ray microanalytical techniques. Micro-Raman measurements on an intact inclusion of remnant vibrational band shifts give a high confining pressure of 3.62 (+/-0.18) GPa. Synchrotron single-crystal diffraction measurements of the volume compression are in accord with the Raman results and also revealed direct structural information on the state of the inclusion. In contrast to olivine and garnet inclusions, the thermoelasticity of coesite favors accurate identification of pressure preservation. Owing to the unique combination of physical properties of coesite and diamond, this "coesite-in-diamond" geobarometer is virtually independent of temperature, allowing an estimation of the initial pressure of Venezuela diamond formation of 5.5 (+/-0.5) GPa.

Journal Article↗

Osteogenic sarcoma in a child with transfusion-dependent Diamond-Blackfan anemia.

PURPOSE: Diamond-Blackfan anemia or congenital pure red blood cell aplasia is one of the best defined congenital hematopoietic disorders. Although it has been suggested that affected patients are predisposed to developing acute leukemia, there have been no reports of sarcoma in patients with Diamond-Blackfan anemia. We describe a child who had Diamond-Blackfan anemia and who developed an osteogenic sarcoma. PATIENT AND METHODS: A case is presented of a 5-year-old girl who had transfusion-dependent Diamond-Blackfan anemia and hemochromatosis and who developed an osteogenic sarcoma of the tibia. RESULTS: The patient had an initial response with an ifosfamide-containing chemotherapy regimen but died of multiple pulmonary metastases. CONCLUSION: Our patient is the 10th reported case of malignancy in Diamond-Blackfan anemia but the first instance of sarcoma. Given the increased rate of leukemia in Diamond-Blackfan anemia patients, we speculate there may also exist an association between osteogenic sarcoma occurring at a particularly young age and this uncommon hematologic disorder.

Adolescent↗

Visualization of diamond nucleation and growth from energetic species.

The mystery of diamond nucleation by energetic species is resolved via a special deposition scheme. The evolution of the precursor material for diamond nucleation and the development of the nanodiamond crystallites are visualized by high resolution electron microscopy and other spectroscopies. The diamond precipitation and growth are explained in terms of our recently proposed mechanism [Science 297, 1531 (2002)]]: (i) precipitation of sp(3) clusters a small fraction of which are perfect diamond; (ii) growth of diamond crystallites by preferential displacement of amorphous carbon atoms leaving diamond atoms intact. This general scheme is applicable to other materials such as cubic boron nitride.

Journal Article↗

Diamond genesis, seismic structure, and evolution of the Kaapvaal-Zimbabwe craton.

The lithospheric mantle beneath the Kaapvaal-Zimbabwe craton of southern Africa shows variations in seismic P-wave velocity at depths within the diamond stability field that correlate with differences in the composition of diamonds and their syngenetic inclusions. Middle Archean mantle depletion events initiated craton keel formation and early harzburgitic diamond formation. Late Archean accretionary events involving an oceanic lithosphere component stabilized the craton and contributed a younger Archean generation of eclogitic diamonds. Subsequent Proterozoic tectonic and magmatic events altered the composition of the continental lithosphere and added new lherzolitic and eclogitic diamonds to the Archean diamond suite.

Journal Article↗

Evaluation of the biocompatibility of two new diamond-like stent coatings (Dylyn) in a porcine coronary stent model.

UNLABELLED: Hydrogenated diamond-like carbon films (DLC, a-C:H), deposited using plasma-assisted or ion beam-assisted techniques, offer great potential as self-lubricating coatings in many tribological applications. Additionally, studies on biocompatibility have shown that DLC is an inert, impervious hydrocarbon with properties suitable for use in the biomedical field. One particular class of modified DLC coatings are diamond-like nanocomposite coatings (DLN or Dylyn , Bekaert, Kortrijk, Belgium), which offer promising solutions for many industrial applications. In this study, the biocompatibility of two diamond-like stent coatings are evaluated in a porcine coronary stent model. METHODS: Either coated or non-coated stents were randomly implanted in two coronary arteries of 20 pigs so that each group contained 13 stented arteries. Pigs underwent a control angiogram at 6 weeks and were then sacrificed. Quantitative coronary analysis before, immediately after stent implantation, and at 6 weeks was performed using the semi-automated Polytron 1000 system (Siemens, Erlangen, Germany). Morphometry was performed using a computerized morphometric program. Angiographic analysis showed similar baseline selected arteries and post-stenting diameters. At 6-week follow-up, there was no significant difference in minimal stent diameter. Histopathology revealed a similar injury score in the 3 groups. Inflammation was significantly increased in the DLN-DLC coating group. Thrombus formation was significantly decreased in both coated stent groups. Neointimal hyperplasia was decreased in both coated stent groups; however, the difference with the non-coated stents was not statistically significant. Area stenosis was lower in the DLN-coated stent group than in the control group (41 +/- 17% vs. 54 +/- 15%; p = 0.06). CONCLUSION: The results indicate that the diamond-like nanocomposite stent coatings are compatible, resulting in decreased thrombogenicity and decreased neointimal hyperplasia. Covering this coating with another diamond-like carbon film (DLC) resulted in an increased inflammatory reaction and no additional advantage compared to the single-layer diamond-like nanocomposite coating.

Animals↗

Surface acoustic wave properties of freestanding diamond films.

"Ideal" diamond has the highest acoustic velocity of any material known, and is of great interest as a substrate material for high frequency surface acoustic wave (SAW) device structures. However, little is known of the acoustic wave propagation properties of polycrystalline diamond grown by chemical vapour deposition (CVD) techniques, the commercially accessible form of this material. We report on propagation of laser-generated SAW on three forms of freestanding CVD diamond samples, "white" polycrystalline, "black" polycrystalline, and "highly oriented" diamond. Despite differing sample nature, SAW waves propagating along the smooth (nucleation) side of the diamond showed similar velocities in the range 10600-11900 ms(-1). These results are discussed in terms of the potential of each form of CVD diamond for SAW device fabrication.

Letter↗

[Spectroscopic studies on transition metal ions in colored diamonds].

Transition metals like nickel, cobalt and iron have been often used as solvent catalysts in high pressure high temperature (HPHT) synthesis of diamond, and nickel and cobalt ions have been found in diamond lattice. Available studies indicated that nickel and cobalt ions could enter the lattice as interstitial or substitutional impurities and form complexes with nitrogen. Polarized microscopy, SEM-EDS, EPR, PL and FTIR have been used in this study to investigate six fancy color natural and synthetic diamonds in order to determine the spectroscopic characteristics and the existing forms of transition metal ions in colored diamond lattice. Cobalt-related optical centers were first found in natural chameleon diamonds, and some new nickel and cobalt-related optical and EPR centers have also been detected in these diamond samples.

English Abstract↗

Ulnar neuropathy at the elbow in diamond assorters.

Unilateral ulnar neuropathy at the elbow was detected in 12 men employed as diamond assorters. Asymptomatic diamond assorters were studied as controls. In the symptomatics, the ulnar neuropathy was restricted to the hand which held the eye-glass used for inspecting the diamonds. Electrophysiological studies using several parameters revealed neurapraxia sometimes combined with axonal degeneration in the ulnar nerve at the elbow, compatible with compression at that site. The most sensitive parameters of abnormality in the symptomatic subjects were segmental slowing of motor nerve conduction velocity across the elbow (P less than 0.001) and the amplitude of the compound muscle action potential obtained on stimulating the nerve above the elbow (P less than 0.001). In the 18 asymptomatic diamond assorters, electrophysiological studies revealed an ulnar neuropathy in two (again in the hand used for holding the eye-glass). Ulnar mononeuropathy at the elbow thus seems to be an occupational hazard for diamond assorters and it is worthwhile to elicit occupational history from patients presenting with an ulnar mononeuropathy, especially in Bombay and Gujarat where diamond industry is concentrated.

Adult↗

[Physical properties of an intraocular lens coated with diamond-like carbon film].

I have invented an intraocular lens (IOL) coated with diamond-like carbon film and have investigated its physical properties. Diamond-like carbon film is an ultrathin film which is composed of many carbon atoms and very few hydrogen atoms, and has properties very similar to diamond. I have measured the following properties of the polymethylmethacrylate (PMMA) plates or IOLs coated with diamond-like carbon film: light transmission curve, resistance against Nd:YAG laser capsulotomy, peel-off test, and contact angle. The plates or lenses are more ultraviolet-absorbing than uncoated PMMA plates, and PMMA plates coated with 50 nm-thick diamond-like carbon film have a light transmission curve very similar to that of a 25-year-old human crystalline lens. The pits and cracks due to Nd:YAG laser emission were smaller in the coated IOLs were more hydrophobic and oleophilic than uncoated IOLs. Diamond-like carbon film coated IOLs are thought to be very promising.

Adult↗

Microchip capillary electrophoresis with a boron-doped diamond electrochemical detector for analysis of aromatic amines.

The attractive features of a boron-doped diamond (BDD) thin-film detector for microchip capillary electrophoretic (CE) separations of dye-related amino-substituted aromatic compounds are described. The diamond electrode was employed in the end-column amperometric detection of 4-aminophenol (4-AP), 1,2-phenylenediamine (1,2-PDA), 2-aminonaphthalene (2-AN), 2-chloroaniline (2-CA), and o-aminobenzoic acid (o-ABA), and its attractive behavior was compared to commonly used screen-printed carbon and glassy-carbon electrodes. These conventional electrode materials exhibit a significant degree of passivation and low sensitivity to the above-mentioned environmental pollutants. The diamond-based electrochemical detection system displayed a favorable analytical performance, including lower noise levels, higher peak resolution with enhanced sensitivity, and improved resistance against electrode passivation. Factors influencing the on-chip analysis were assessed and optimized. The diamond detector displayed detection limits of 2.0 and 1.3 microM for 4-AP and 2-AN, respectively, and a wide linear response for these compounds over the 2-50 microM range. The enhanced stability was demonstrated by relative standard deviation (RSD) values of 1.4% and 4.7% for 100 microM 1,2-PDA and 200 microM 2-CA, respectively, for repetitive detections (n = 7). Besides, the simultaneously observed current decrease was 2.4 and 9.1% for 1,2-PDA and 2-CA, respectively (compared to 21.8 and 41.0% at the screen-printed carbon electrode and 28.3 and 34.1% at the glassy carbon electrode, respectively). The favorable properties of the diamond electrode indicate great promise for environmental applications in CE and other microchip devices.

Amines↗

Ordered growth of neurons on diamond.

Diamond has a number of unique properties that make it an attractive electronic and bio-electronic material. Here we show the ordered growth of mammalian neurons, the principal electrogenic cells of the nervous system, on diamond. Proteins were specifically patterned on diamond surfaces by micro-contact printing. Mouse cortical neurons were then cultured on these substrates. Neuron adhesion and outgrowth was specific for those areas of the diamond that had been stamped with laminin, resulting in ordered growth of high resolution. Neurons survived in culture for the duration of the experiment, and laminin patterns were stable for at least 1 week in culture. The relative biocompatibility of diamond and the suitability of neuron interfacing with the hydrogen surface conductivity layer make this an interesting model for the formation of defined neuronal networks and for implants.

Adsorption↗

Anodic oxidation with doped diamond electrodes: a new advanced oxidation process.

Boron-doped diamond anodes allow to directly produce OH* radicals from water electrolysis with very high current efficiencies. This has been explained by the very high overvoltage for oxygen production and many other anodic electrode processes on diamond anodes. Additionally, the boron-doped diamond electrodes exhibit a high mechanical and chemical stability. Anodic oxidation with diamond anodes is a new advanced oxidation process (AOP) with many advantages compared to other known chemical and photochemical AOPs. The present work reports on the use of diamond anodes for the chemical oxygen demand (COD) removal from several industrial wastewaters and from two synthetic wastewaters with malic acid and ethylenediaminetetraacetic (EDTA) acid. Current efficiencies for the COD removal between 85 and 100% have been found. The formation and subsequent removal of by-products of the COD oxidation has been investigated for the first time. Economical considerations of this new AOP are included.

Boron↗

Evaluation of diamond-coated ultrasonic instruments for root-end preparation.

Ultrasonic instrumentation has been associated with cracking of the dentin in the area of the root-end preparation. The purpose of this study was to evaluate root-end preparations for cracking and to describe cavosurface morphology after the use of diamond-coated instruments. Forty teeth were inspected for intradentin cracks, incomplete canal cracks, and complete canal cracks before and after preparation with a stainless steel CT-5 ultrasonic instrument and again after root-end preparation with an S12D/90 degrees diamond-coated instrument. Six teeth had polyvinylsiloxane impressions taken of the root ends after preparation with the CT-5 and again after preparation with the diamond-coated instrument. Replicas were made, split, sputter-coated, and inspected using the scanning electron microscope. This study indicates that use of the diamond-coated instrument for root-end preparation does not result in significant root-end cracking and that it can remove cracks created by a prior instrument's use. The use of the diamond-coated instrument resulted in a heavily abraded, debris-covered cavosurface that may affect the apical seal.

Analysis of Variance↗

Electro-oxidation and amperometric detection of chlorinated phenols at boron-doped diamond electrodes: a comparison of microcrystalline and nanocrystalline thin films.

We report on the electro-oxidation and amperometric detection of phenol and chlorinated phenols, the latter coupled with flow injection analysis (FIA) and high performance liquid chromatography (HPLC), using boron-doped microcrystalline and nanocrystalline diamond thin-film electrodes. The low background current, good response without extensive pretreatment, and low susceptibility to fouling are properties that make diamond an attractive new electrode for monitoring this class of pollutants. Cyclic voltammetric studies were performed to evaluate the redox response of phenol, 2-chlorophenol, 3-chlorophenol,4-chlorophenol, and pentachlorophenol (PCP) in phosphate buffer, pH 3.5, as a function of the potential scan rate and cycle number. The diamond electrode performance for the amperometric detection of these contaminants in FIA-EC and HPLC-EC was evaluated in terms of the linear dynamic range, limit of quantitation, sensitivity, response precision, and response stability. Both diamond types yielded low mass limits of quantitation of 100-1000 pg for all the phenolic compounds in FIA-EC, except PCP which was 3 ng, and 100-600 pg for all the compounds in HPLC-EC. In all cases, the S/N was 3 or greater. Both electrode types also exhibited good sensitivity, excellent response reproducibility (av 2.7% for FIA-EC and av 4.2% for HPLC-EC), and superb response stability for all the analytes. The electrodes could be used from days to weeks in the measurement with only a periodic soak in distilled 2-propanol required to maintain optimum performance. Both types of diamond outperformed glassy carbon, which exhibited short-lived responsiveness as a consequence of fouling by reaction products and potential-dependent changes in the electrode's physiochemical properties. The use of the HPLC-EC assay for the determination of 2-chlorophenol in a contaminated soil sample is also demonstrated.

Boron↗