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At least 55 records · Page 3

Method of fabricating porous silicon carbide (SiC)

Porous silicon carbide is fabricated according to techniques which result in a significant portion of nanocrystallites within the material in a sub 10 nanometer regime. There is described techniques for passivating porous silicon carbide which result in the fabrication of optoelectronic devices which exhibit brighter blue luminescence and exhibit improved qualities. Based on certain of the techniques described porous silicon carbide is used as a sacrificial layer for the patterning of silicon carbide. Porous silicon carbide is then removed from the bulk substrate by oxidation and other methods. The techniques described employ a two-step process which is used to pattern bulk silicon carbide where selected areas of the wafer are then made porous and then the porous layer is subsequently removed. The process to form porous silicon carbide exhibits dopant selectivity and a two-step etching procedure is implemented for silicon carbide multilayers.

Shor, Joseph S.

Improved toughness of silicon carbide

Several techniques were employed to apply or otherwise form porous layers of various materials on the surface of hot-pressed silicon carbide ceramic. From mechanical properties measurements and studies, it was concluded that although porous layers could be applied to the silicon carbide ceramic, sufficient damage was done to the silicon carbide surface by the processing required so as to drastically reduce its mechanical strength. It was further concluded that there was little promise of success in forming an effective energy absorbing layer on the surface of already densified silicon carbide ceramic that would have the mechanical strength of the untreated or unsurfaced material. Using a process for the pressureless sintering of silicon carbide powders it was discovered that porous layers of silicon carbide could be formed on a dense, strong silicon carbide substrate in a single consolidation process.

Palm, J. A.

Friction and fracture of single-crystal silicon carbide in contact with itself and titanium

An investigation was conducted to examine the friction properties and mechanical behavior of single-crystal silicon carbide (0001) surface sliding against itself and against polycrystalline titanium. The results indicate hexagon-shaped pits of silicon carbide and the formation of platelet hexagon-shaped wear debris of silicon carbide due to cleavages of both prismatic and basal planes as a result of silicon carbide sliding against itself. The fracturing of silicon carbide also occurs near the adhesive bond to titanium. The wear debris produced by brittle fracture plows the titanium and transfers to it. Further, the silicon carbide wear debris, which adhered and transferred to titanium, plows the silicon carbide surface and transfers back to it

Miyoshi, K.

XPS, AES and friction studies of single-crystal silicon carbide

The surface chemistry and friction behavior of a single crystal silicon carbide surface parallel to the 0001 plane in sliding contact with iron at various temperatures to 1500 C in a vacuum of 3 x 10 nPa are investigated using X-ray photoelectron and Auger electron spectroscopy. Results show that graphite and carbide-type carbon are seen primarily on the silicon carbide surface in addition to silicon at temperatures to 800 C by both types of spectroscopy. The coefficients of friction for iron sliding against a silicon carbide surface parallel to the 0001 plane surface are found to be high at temperatures up to 800 C, with the silicon and carbide-type carbon at maximum intensity in the X-ray photoelectron spectroscopy at 800 C. The concentration of the graphite increases rapidly on the surface as the temperature is increased above 800 C, while the concentrations of the carbide-type carbon and silicon decrease rapidly and this presence of graphite is accompanied by a significant decrease in friction. Preheating the surfaces to 1500 C also gives dramatically lower coefficients of friction when reheating in the sliding temperature range of from room temperature to 1200 C, with this reduction in friction due to the graphite layer on the silicon carbide surface.

Miyoshi, K.

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamic maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of Region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicon carbide is the single stable solid phase in Region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4, and SiH. Analysis of the kinetics of reaction for Region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to Regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamics maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicone carbide is the single stable solid phase in region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4 and SiH. Analyses of the kinetics of reaction for region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.

Hydrogen Adsorption, Reactivity, and Catalysis on Colloidal Iron Carbide Nanoparticles

Supported iron carbide particles have long served as catalysts for CO hydrogenation (the Fischer Tropsch synthesis, FTS) and continue to be attractive. Despite this, little is known about their chemistry. Reported here is a colloidal Fe x C nanoparticle (NP) model system that allows direct observation of surface hydrogen and CO, as well as quantification of the surface H. Dodecylamine-capped Fe x C NPs (DDA-Fe x C NPs) were synthesized through solution-phase carburization of Fe NPs and form stable colloids in low-polarity organic solvents. Treatment of these colloids with H 2 or D 2 produced highly hydrogenated materials, and FTIR spectra of DDA-Fe x C-D n showed that most of the D binds to carbides, with at least four distinct v(C-D) modes. The surface C-H(D) bonds were all reactive, transferring hydrogen to alkenes and other reagents in solution. Titration and ICP measurements showed a 0.17:1 ratio of added H:total Fe, or roughly. 40 H per 1.8 nm DDA-Fe x C NP. Conversely, CO was preferentially bound to surface Fe sites, with FTIR spectra showing a single broad v(CO) that shifted with CO coverage or co-adsorption of H 2 . The DDA-Fe x C NPs were active catalysts for both olefin hydrogenation and the FTS, under mild conditions and without catalyst pre-treatment. The CO hydrogenation reactions yielded a broad distribution of long-chain linear paraffins and olefins. Though quantitative comparisons with typical FTS results are not possible because of our use of sealed batch reactors and other factors, the observations of high catalytic reactivity demonstrate the relevance of this model system to iron-carbide catalysis. DFT calculations on model slab surfaces with varying iron carbide stoichiometries revealed that the thermodynamically preferred surface adsorption sites are C for H ads and Fe for CO ads . A variety of binding sites and binding energies were found for each adsorbate. We are unaware of previous studies indicating that a diverse array of C-H bonds is the primary source of reactive H on iron carbides. Experimentally, the diversity of *C-H sites was evident in reactions with H-atom donors and abstractors of different strengths, from both the reaction stoichiometries and IR spectra. The different surface–H binding energies correlate with the v(C-D) stretching frequencies. Furthermore, these insights into complex iron carbide surfaces and catalysis could assist catalyst design, and they showcase the importance of stoichiometric studies of reaction intermediates.

08 HYDROGEN

Investigation of Corrosion Behavior of Carbide Phase Strengthened Nickel‐Based Alloy in Molten Fluoride Salt

The corrosion behavior of a high creep strength carbide-phase strengthened Ni-based alloy in molten FLiNaK (LiF-NaF-KF: 46.5-11.5-42 mol%) salt in the temperature range of 700°C–750°C has been investigated as a part of the development of structural alloys for fluoride salt-based molten salt reactors (MSRs). The alloy composition was designed based on Hastelloy-N, but with the goal of improving creep strength. Cr depletion depth, a measure of corrosion, was observed to be single micrometers after several hundred hours of corrosion testing. Sequential corrosion testing involving testing of pre-tested samples in fresh salt coupled with SEM-EDS, scanning transmission electron microscopy (STEM) examinations and thermodynamic and kinetic modeling, suggest that the corrosion rate at the alloy-salt interface is governed by diffusion of elements from the alloy bulk to the surface. The carbide phases in the corrosion-tested sample microstructure were identified to be largely M 6 C-type Mo-rich carbides and MC-type mixed carbides. Atom probe tomography (APT) showed some partitioning of Cr and Ti to the carbide phase and showed the carbide phases to be stable at the salt-facing surface.

Gordon, Ryan [Univ. of Wisconsin, Madison, WI (Uni

Carbide coated fibers in graphite-aluminum composites

The study of protective-coupling layers of refractory metal carbides on the graphite fibers prior to their incorporation into composites is presented. Such layers should be directly wettable by liquid aluminum and should act as diffusion barriers to prevent the formation of aluminum carbide. Chemical vapor deposition was used to uniformly deposit thin, smooth, continuous coats of ZrC on the carbon fibers of tows derived from both rayon and polyacrylonitrile. A wet chemical coating of the fibers, followed by high-temperature treatment, was used, and showed promise as an alternative coating method. Experiments were performed to demonstrate the ability of aluminum alloys to wet carbide surfaces. Titanium carbide, zirconium carbide and carbide-coated graphite surfaces were successfully wetted. Results indicate that initial attempts to wet surfaces of ZrC-coated carbon fibers appear successful.

Imprescia, R. J.

Friction and deformation behavior of single-crystal silicon carbide

Friction and deformation studies were conducted with single-crystal silicon carbide in sliding contact with diamond. When the radius of curvature of the spherical diamond rider was large (0.3), deformation of silicon carbide was primarily elastic. Under these conditions the friction coefficient was low and did not show a dependence on the silicon carbide orientation. Further, there was no detectable cracking of the silicon carbide surfaces. When smaller radii of curvature of the spherical diamond riders (0.15 and 0.02 mm) or a conical diamond rider was used, plastic grooving occured and the silicon carbide exhibited anisotropic friction and deformation behavior. Under these conditions the friction coefficient depended on load. Anisotropic friction and deformation of the basal plane of silicon carbide was controlled by the slip system. 10101120and cleavage of1010.

Miyoshi, K.

Tribological properties of silicon carbide in metal removal process

Material properties are considered as they relate to adhesion, friction, and wear of single crystal silicon carbide in contact with metals and alloys that are likely to be involved in a metal removal process such as grinding. Metal removal from adhesion between sliding surfaces in contact and metal removal as a result of the silicon carbide sliding against a metal, indenting into it, and plowing a series of grooves or furrows are discussed. Fracture and deformation characteristics of the silicon carbide surface are also covered. The adhesion, friction, and metal transfer to silicon carbide is related to the relative chemical activity of the metals. The more active the metal, the higher the adhesion and friction, and the greater the metal transfer to silicon carbide. Atomic size and content of alloying elements play a dominant role in controlling adhesion, friction, and abrasive wear properties of alloys. The friction and abrasive wear (metal removal) decrease linearly as the shear strength of the bulk metal increases. They decrease as the solute to solvent atomic radius ratio increases or decreases linearly from unity, and with an increase of solute content. The surface fracture of silicon carbide is due to cleavages of 0001, 10(-1)0, and/or 11(-2)0 planes.

Miyoshi, K.

Changes in surface chemistry of silicon carbide (0001) surface with temperature and their effect on friction

Friction studies were conducted with a silicon carbide (0001) surface contacting polycrystalline iron. The surface of silicon carbide was pretreated: (1) by bombarding it with argon ions for 30 minutes at a pressure of 1.3 pascals; (2) by heating it at 800 C for 3 hours in vacuum at a pressure of 10 to the minus eighth power pascal; or (3) by heating it at 1500 C for 3 hours in a vacuum of 10 to the minus eighth power pascal. Auger emission spectroscopy was used to determine the presence of silicon and carbon and the form of the carbon. The surfaces of silicon carbide bombarded with argon ions or preheated to 800 C revealed the main Si peak and a carbide type of C peak in the Auger spectra. The surfaces preheated to 1500 C revealed only a graphite type of C peak in the Auger spectra, and the Si peak had diminished to a barely perceptible amount. The surfaces of silicon carbide preheated to 800 C gave a 1.5 to 3 times higher coefficient of friction than did the surfaces of silicon carbide preheated to 1500 C. The coefficient of friction was lower in the 11(-2)0 direction than in the 10(-1)0 direction; that is, it was lower in the preferred crystallographic slip direction.

Miyoshi, K.

Low Cost Fabrication of Silicon Carbide Based Ceramics and Fiber Reinforced Composites

A low cost processing technique called reaction forming for the fabrication of near-net and complex shaped components of silicon carbide based ceramics and composites is presented. This process consists of the production of a microporous carbon preform and subsequent infiltration with liquid silicon or silicon-refractory metal alloys. The microporous preforms are made by the pyrolysis of a polymerized resin mixture with very good control of pore volume and pore size thereby yielding materials with tailorable microstructure and composition. Mechanical properties (elastic modulus, flexural strength, and fracture toughness) of reaction-formed silicon carbide ceramics are presented. This processing approach is suitable for various kinds of reinforcements such as whiskers, particulates, fibers (tows, weaves, and filaments), and 3-D architectures. This approach has also been used to fabricate continuous silicon carbide fiber reinforced ceramic composites (CFCC's) with silicon carbide based matrices. Strong and tough composites with tailorable matrix microstructure and composition have been obtained. Microstructure and thermomechanical properties of a silicon carbide (SCS-6) fiber reinforced reaction-formed silicon carbide matrix composites are discussed.

Singh, M.

Development and Processing of Nickel Aluminide-Carbide Alloys

With the upper temperature limit of the Ni-based superalloys attained, a new class of materials is required. Intermetallics appear as likely candidates because of their attractive physical properties. With a relatively low density, high thermal conductivity, excellent oxidation resistance, high melting point, and simple crystal structure, nickel aluminide (NiAl) appears to be a potential candidate. However, NiAl is limited in structural applications due to its low room temperature fracture toughness and poor elevated temperature strength. One approach to improving these properties has been through the application of eutectic composites. Researchers have shown that containerless directional solidification of NiAl-based eutectic alloys can provide improvement in both the creep strength and fracture toughness. Although these systems have shown improvements in the mechanical properties, the presence of refractory metals increases the density significantly in some alloys. Lower density systems, such as the carbides, nitrides, and borides, may provide NiAl-based eutectic structure. With little or no information available on these systems, experimental investigation is required. The objective of this research was to locate and develop NiAl-carbide eutectic alloys. Exploratory arc-melts were performed in NiAl-refractory metal-C systems. Refractory metal systems investigated included Co, Cr, Fe, Hf, Mo, Nb, Ta, Ti, W, and Zr. Systems containing carbides with excellent stability (i.e.,HfC, NbC, TaC, TiC, and ZrC) produced large blocky cubic carbides in an NiAl matrix. The carbides appeared to have formed in the liquid state and were randomly distributed throughout the polycrystalline NiAl. The Co, Cr, Fe, Mo, and W systems contained NiAl dendrites with a two-phase interdendritic microconstituent present. Of these systems, the NiAl-Mo-C system had the most promising microstructure for in-situ composites. Three processing techniques were used to evaluate the NiAl-Mo-C system: arc-melting, slow cooling, and containerless directional solidification. Arc-melting provided a wide range of compositions in an economical and simple fashion. The slow cooled ingots provided larger ingots and slower cooling rates than arc-melting. Directional solidification was used to produce in-situ composites consisting of NiAl reinforced with molybdenum carbides.

Newport, Timothy Scott

Fully Deuterated Aliphatic Hydrocarbons Obtained From Iron Carbide Treated with DCl and D2O

According to Oparin, Mendeleev thought that the origin of petroleum was the result of the hydrolysis of iron carbides by superheated steam under pressure from the deep interior of the Earth through geological formations where the metal carbides exist. As early as 1877, Mendeleev described the reaction leading to the synthesis of hydrocarbons according to the general equation 3Fe(sub m)C(sub n) + mH2O yields mFe3O4 + C(sub 3n)H(sub 8m). Other experimental studies on the production of hydrocarbons from cast iron have been reported. Because of the possibility that hydrocarbons may have been trapped within the carbon matrix of the cast iron, which usually has a high content of carbon, we have studied the reaction of pure iron carbide with deuterium chloride and deuterated water. This was done in order to distinguish any newly formed deuterated hydrocarbons from any possible impurities of trapped hydrocarbons. The experiments were carried out by simply allowing iron carbide to react with concentrated deuterium chloride in D2O. The volatile hydrocarbon fraction examined by gas chromatography-mass spectrometry (GC/MS), using a Finnigan 1020/OWA instrument. contained low molecular weight hydrocarbons in a range C3 to C7. Lower molecular weight hydrocarbons were not detected by GC/MS because the MS scanning mode was preset above mass 40 to exclude components of air. The identified hydrocarbons are similar to those obtained under prebiotic conditions using high frequency discharge. The hydrocarbons found in common were propane, butane, pentane, 3-methylpentane, hexane, and heptane. The percent yields decline with increasing carbon number (propane 11%, n-heptane 1%). Similar results have been obtained by the direct treatment of metal carbides by pulse laser vaporization mass spectrometry. These results show that the hydrolysis of iron carbides may have been a significant source of hydrocarbons on the primitive Earth. There appears to be a predominance of straight chain isomers, which may have been important in the prebiotic synthesis of membrane-forming compounds.

Marquez, C.

Irradiation-induced formation of G-phase precipitates and M 2 X carbides in self-ion irradiated HT-9

Ferritic-martensitic steels with high chromium content are a promising material group for advanced nuclear systems due to their high temperature strength and good irradiation tolerance. HT-9 is an optimized and often-studied alloy in this group, but additional studies are required on its radiation response under extreme conditions to be experienced in various types of nuclear reactors, especially with respect to phase stability under irradiation. Self-ion irradiation of HT-9 by 5 MeV Fe ions was used to simulate neutron-induced behavior reaching peak doses of 100 and 300 dpa at temperatures ranging from 450 to 550 °C. M 23 C 6 carbides that existed prior to irradiation were found to remain stable under all examined irradiation conditions. As irradiation progressed at 450 and 500 °C, however, formation of spherical-like G-phase precipitates and needle-like M 2 X carbides was observed. G-phase precipitates were found to be enriched in Ni, Si, and Mn, and show no interface segregation, whereas needle-like M 2 X carbides were rich in Cr and Mo and clearly displayed interface segregation of Ni and Si. M 2 X carbide formation is believed to be assisted by vacancies, while G-phase precipitation is thought to be assisted by interstitials. Finally, this difference in defect-mediated formation leads to a difference in distribution with depth. M 2 X carbides are distributed over shallower depths than that of G-phase precipitates, consistent with defect imbalance predictions that consider the influence of the injected interstitial effect.

atom probe tomography

Compatibility of buffered uranium carbides with tungsten.

Results of compatibility tests between tungsten and hyperstoichiometric uranium carbide alloys run at 1800 C for 1000 and 2500 hours. These tests compared tungsten-buffered uranium carbide with tungsten-buffered uranium-zirconium carbide. The zirconium carbide addition appeared to widen the homogeneity range of the uranium carbide, making additional carbon available for reaction. Reaction layers could be formed by either of two diffusion paths, one producing UWC2, while the second resulted in the formation of W2C. UWC2 acts as a diffusion barrier for carbon and slows the growth of the reaction layer with time, while carbon diffusion is relatively rapid in W2C, allowing equilibrium to be reached in less than 2500 hours at a temperature of 1800 C.

Phillips, W. M.

Carbides in lunar soils and rocks

Carbides and the surrounding metal of eight particles from Apollo 14, 16, and 17 soils were analyzed for C, Fe, Ni, and Co with the electron microprobe. In addition, carbide-containing metal particles in two Apollo 17 rocks were studied. Carbide-metal assemblages were found in anorthositic hornfels, melt rock, and agglutinate, but not in any primary igneous rocks. Carbon measurements show that cohenite is the carbide phase present in all the samples. Cohenite exsolves from the carbon-rich metal phase during cooling of the lunar metal particle in the host rocks or soil fragments. Measurements of two-phase interface compositions indicate equilibration for carbides and metal during cooling below 600 C and possibly below 500 C.

Goldstein, J. I.