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Laboratory studies suggest that microdiamonds will be quite elusive in interstellar space, being detectable only if more than 10 per cent of the carbon is present as diamond. The diamonds apparently formed by condensation in cool stellar atmospheres, and were then impregnated with isotopically anomalous noble gases, such as Xe, from a supernova.
Plasma chemical vapor deposition (CVD) at 13.56 MHz has been used to produce diamond particles in two different inductively coupled systems with a mixture of methane and hydrogen. The effect of a diamondlike carbon (DLC) overcoating on silicon, niobium, and stainless-steel substrates has been investigated and in the case of silicon has been found to enhance particle formation as compared to uncoated polished silicon. In addition the use of carbon monoxide in hydrogen has been found to produce well-defined individual faceted particles as well as polycrystalline films on quartz and DLC coated silicon substrates. Plasma CVD is a competitive approach to production of diamond films. It has the advantage over microwave systems of being easily scaled to large volume and high power.
The results of Ar-40/Ar-39 laser-probe analyses of individual eclogitic clinopyroxene inclusions from Premier diamonds are reported which yield a mean age of 1198 + or - 14 Myr. This age agrees well with Sm-Nd and Ar-40/Ar-39 analyses on similar Premier inclusions and is indistinguishable from the inferred time of emplacement of the host kimberlite, which implies that diamond formation was essentially synchronous with kimberlite generation. The extrapolated nonradiogenic Ar-40/Ar-36 ratio of 334 + or - 102 is similar to the present-day atmospheric composition. This value is inconsistent with Sr and Nd isotopic signatures from Premier eclogite inclusions, which suggest a depleted mantle source. Preentrapment equilibration of the inclusions with an Ar-36-rich fluid is the most probable explanation for the low nonradiogenic composition.
Noble gas measurements were carried out on two identical splits of a finely powdered harshly acid-washed sample derived from fragments of a single alluvial diamond from Sierra Leone, with essentially identical results obtained for both splits. Isotopic ratios for Ar, Kr, and Xe were found to be atmospheric. Their elemental abundances were high relative to published data, owing to the effect of shock implantation in the crushing step, as was verified in a supplementary experiment. No Ne was detected above the blank level. The He-3 was exceptionally abundant, while He-4 was exceptionally depleted, possibly due to the acid wash. The He-3/He-4 ratio was anomalously high at an R/Ra value of 246 + or - 16. The results support the hypothesis that the He-3 excess in diamonds is cosmogenic.
The formation of carbon dust in the outflow from stars and the subsequent evolution of this so called stardust in the interstellar medium is reviewed. The chemical and physical processes that play a role in carbon stardust formation are very similar to those occurring in sooting flames. Based upon extensive laboratory studies of the latter, the structure and physical and chemical properties of carbon soot are reviewed and possible chemical pathways towards carbon stardust are discussed. Grain-grain collisions behind strong interstellar shocks provide the high pressures required to transform graphite and amorphous carbon grains into diamond. This process is examined and the properties of shock-synthesized diamonds are reviewed. Finally, the interrelationship between carbon stardust and carbonaceous meteorites is briefly discussed.
A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.
Two projects which are carried out under the Summer Faculty Fellowship Program-1991 are discussed. A conceptual design of a solar cell manufacturing plant on a lunar base is discussed. This is a large program that requires a continuous and expanded effort, the present status of which is reflected here. An experiment on the synthesis of diamond film is discussed. Encouraging, but not yet conclusive evidence has been obtained on a new method to synthesize diamond film. The procedures and observations are presented. A third project is an analysis of the solar cell performance over five years on the moon based on Apollo missions. A paper has been completed and will be submitted to the journal Solar Cells for publication.
A fine grain diamond film has been developed by microwave plasma assisted chemical vapor deposition. Various analytical techniques, including Rutherford backscattering, proton recoil analysis, Raman spectroscopy, and X-ray diffraction, were utilized to characterize the diamond films. The grain size of the film was determined from bright and dark field electron micrographs, and found to be 200-1000 A. The films exhibited good optical transmission between 2.5 and 10 microns, with a calculated absorption coefficient of 490/cm. The friction coefficients of this film were found to be 0.035 and 0.030 at dry nitrogen and humid air environments, respectively, and the films had low wear rates.
The feasibility of using polycrystalline CVD diamond films as temperature sensors in harsh aerospace environment associated with hypersonic flights was tested using patterned diamond resistors, fabricated on flat or curved oxidized Si surfaces, as temperature sensors at temperatures between 20 and 1000 C. In this temperature range, the measured resistance was found to vary over 3 orders of magnitude and the temperature coefficient of resistance to change from 0.017/K to 0.003/K. After an annealing treatment, the resistance change was reproducible within 1 percent on the entire temperature range for short measuring times.
Superconducting YBa2Cu3O(7-x) films on nanocrystalline diamond thin films have been fabricated. A composite buffer layer system consisting of diamond/Si3N4/YSZ/YBCO was explored for this purpose. The as-deposited YBCO films were superconducting with Tc of about 84 K and a relatively narrow transition width of about 8 K. SEM cross sections of the films showed very sharp interfaces between diamond/Si3N4 and between Si3N4/YSZ. The deposited YBCO film had a surface roughness of about 1000 A, which is suitable for high-temperature superconductive (HTSC) bolometer fabrication. It was also found that preannealing of the nanocrystalline diamond thin films at high temperature was very important for obtaining high-quality YBCO films.
Low-pressure microwave plasma nucleation and deposition of diamond films were investigated in the pressure range 10-mtorr to 10 torr, at substrate temperatures 400-750 C and with CH4 and O2 concentrations in H2 plasma of 2-15 percent and 2-10 percent, respectively. The experiments were performed in a microwave plasma system consisting of a microwave plasma chamber, a downstream deposition chamber, and an RF induction heated sample stage. Scanning electron microscopy of diamond films deposited at 600 C with 5 percent CH4 and 5 percent O2 in H2 plasmas showed high-quality well faceted crystallites of 1/2 micron size. Cathodoluminescence measurements of these films showed very few nitrogen impurities and no detectable silicon impurities.
An analytical solution has been obtained for the equations of motion of water droplets impinging on a wedge in a two-dimensional supersonic flow field with a shock wave attached to the wedge. The closed-form solution yields analytical expressions for the equation of the droplet trajectory, the local rate of impingement and the impingement velocity at any point on the wedge surface, and the total rate of impingement. The analytical expressions are utilized to determine the impingement on the forward surfaces of diamond airfoils in supersonic flow fields with attached shock waves. The results presented include the following conditions: droplet diameters from 2 to 100 microns, pressure altitudes from sea level to 30,000 feet, free-stream static temperatures from 420 degrees to 460 degrees R. Also, free-stream Mach numbers from 1.1 to 2.0, semi-apex angles for the wedge from 1.14 degrees to 7.97 degrees, thickness-to-chord ratios for the diamond airfoil from 0.02 to 0.14, chord lengths from 1 to 20 feet, and angles of attack from zero to the inverse tangent of the airfoil thickness-to-chord ratio.
Thin films of polycrystalline, pure, cubic boron nitride (c-BN) formed on various substrates, according to proposal, by chemical vapor deposition onto interlayers of polycrystalline diamond. Substrate materials include metals, semiconductors, and insulators. Typical substrates include metal-cutting tools: polycrystalline c-BN coats advantageous for cutting ferrous materials and for use in highly oxidizing environments-applications in which diamond coats tend to dissolve in iron or be oxidized, respectively.
A vacuum arc from a spot at the face of a graphite cathode to a graphite anode produces a beam of carbon ions and atoms. A carbon coating from this beam is deposited on an ion beam sputtered target to produce diamond-like carbon flakes. A graphite tube encloses the cathode, and electrical isolation is provided by an insulating sleeve. The tube forces the vacuum arc spot to be confined to the surface on the outermost end of the cathode. Without the tube the arc spot will wander to the side of the cathode. This spot movement results in low rates of carbon deposition, and the properties of the deposited flakes are more graphite-like than diamond-like.
There is a growing body of theoretical and experimental evidence suggesting that the uniformity, rate, adhesion, quality, and other key properties of Chemical Vapor Deposition (CVD) diamond coatings are influenced by the gas mixing kinetics in the thermal plasma environment of the reaction chamber. The implementation of, for example, Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD) process in microgravity has, thus, been suggested. Such a diamond deposition system, which overcomes the limitations of present systems and which is distiguishable from them by the use of high pressure MPECVD and recirculation of the would be effluent hydrogen and carbon, is described. Given the key fact that there is nothing in the effluent of the MPECVD process that is truly a byproduct or 'waste', the system can, at least in principle, lend itself to being closed loop yet dynamic. The exhaust contains hydrogen and carbon species which can be recirculated to the plasma reactor, that is, since there are no unusable reaction byproducts, the effluent can be fed back to the reaction chamber with no detriment, thus allowing deployment in a microgravity environment.
The synchrotron x-ray microprobe is being used to obtain oxidation state information on planetary materials with high spatial resolution. Initial results on chromium in olivine from various sources including laboratory experiments, lunar basalt, and kimberlitic diamonds are reported. The lunar olivine was dominated by Cr(2+) whereas the diamond inclusions had Cr(2+/Cr(3+) ratios up to about 0.3. The simpliest interpretation is that the terrestrial olivine crystallized in a more oxidizing environment than the lunar olivine.
Application of the (40)Ar-(39)Ar method and noble gas studies to diamonds has increased our understanding of their age relationships to the host kimberlite or lamproite, and of the source and composition of volatile-rich fluids in the upper mantle. The properties of diamond (inert, high mechanical strength and low gas diffusivities) means they are especially useful samples for studying gases trapped deep within the earth (less than 150 km) as they are unlikely to have undergone loss or exchange of entrapped material since formation. Volatile-rich fluids (H2O-CO2) are important agents for metasomatic processes in the upper mantle, and the noble gases and halogens preferentially partition into this phase leading to a strong geochemical coherence between these groups of elements. The abundances of the halogens in the major reservoirs of the Earth shows a marked progression from chlorine, concentrated in the oceans, through to iodine which, through its affinity to organic material, is concentrated mainly in sediments. Abundances in the upper mantle are low. This is particularly true for iodine which is of special interest in view of its potential significance as an indicator of sediment recycling and by way of its link to (129)Xe amomalies in the mantle through the low extinct isotope (129)I. Extensions of the (40)Ar-(39)Ar technique enable measurements of halogens and other elements (K, Ca, Ba, U) by production of noble gas isotopes from these species during neutron irradiation. Samples analyzed in this way include 15 coated stones from an unknown source in Zaire, 3 boarts from the Jwaneng and 1 boart from the Orapa kimberlites, both in Botswana.
Field emission has been observed from chemical vapor deposited diamond grown on Mo and Si substrates. Emission was observed at fields as low as 20 kV/cm. The samples were tested in the as-grown form, and after coating with thin films of Au, CsI, and Ni. The emission current was typically maximum at the onset of the applied field, but was unstable, and decreased rapidly with time from the as-grown films. Thin Au layers, approximately 15 nm thick, vacuum deposited onto the diamond samples significantly improved the stability of the emission current at values approximately equal to those from uncoated samples at the onset of the applied field. Thin layers of CsI, approximately 5 nm thick, were also observed to improve the stability of the emission current but at values less than those from the uncoated samples at the onset of the applied field. While Au and CsI improved the stability of the emission, Ni was observed to have no effect.