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Materials Data on Cr3C2 by Materials Project

Cr3C2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are three inequivalent Cr+2.67+ sites. In the first Cr+2.67+ site, Cr+2.67+ is bonded in a 2-coordinate geometry to five C4- atoms. There are a spread of Cr–C bond distances ranging from 2.02–2.58 Å. In the second Cr+2.67+ site, Cr+2.67+ is bonded to five C4- atoms to form a mixture of distorted edge, face, and corner-sharing CrC5 trigonal bipyramids. There are a spread of Cr–C bond distances ranging from 2.00–2.11 Å. In the third Cr+2.67+ site, Cr+2.67+ is bonded to five C4- atoms to form a mixture of edge, face, and corner-sharing CrC5 square pyramids. There are a spread of Cr–C bond distances ranging from 2.02–2.09 Å. There are two inequivalent C4- sites. In the first C4- site, C4- is bonded in a 6-coordinate geometry to eight Cr+2.67+ atoms. In the second C4- site, C4- is bonded in a 7-coordinate geometry to seven Cr+2.67+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Cr3C2 by Materials Project

Cr3C2 crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. there are two inequivalent Cr+2.67+ sites. In the first Cr+2.67+ site, Cr+2.67+ is bonded to four C4- atoms to form corner-sharing CrC4 tetrahedra. There is two shorter (1.95 Å) and two longer (1.96 Å) Cr–C bond length. In the second Cr+2.67+ site, Cr+2.67+ is bonded in a 5-coordinate geometry to five C4- atoms. There are a spread of Cr–C bond distances ranging from 1.99–2.41 Å. There are two inequivalent C4- sites. In the first C4- site, C4- is bonded in a 6-coordinate geometry to eight Cr+2.67+ atoms. In the second C4- site, C4- is bonded to six Cr+2.67+ atoms to form a mixture of edge and corner-sharing CCr6 octahedra. The corner-sharing octahedral tilt angles are 56°.

36 MATERIALS SCIENCE↗

Erosion Coatings for High-Temperature Polymer Composites: A Collaborative Project With Allison Advanced Development Company

The advantages of replacing metals in aircraft turbine engines with high-temperature polymer matrix composites (PMC's) include weight savings accompanied by strength improvements, reduced part count, and lower manufacturing costs. Successfully integrating high-temperature PMC's into turbine engines requires several long-term characteristics. Resistance to surface erosion is one rarely reported property of PMC's in engine applications because PMC's are generally softer than metals and their erosion resistance suffers. Airflow rates in stationary turbine engine components typically exceed 2.3 kg/sec at elevated temperatures and pressures. In engine applications, as shown in the following photos, the survivability of PMC components is clearly a concern, especially when engine and component life-cycle requirements become longer. Although very few publications regarding the performance of erosion coatings on PMC's are available particularly in high-temperature applications the use of erosion-resistant coatings to significantly reduce wear on metallic substrates is well documented. In this study initiated by the NASA Glenn Research Center at Lewis Field, a low-cost (less than $140/kg) graphite-fiber-reinforced T650 35/PMR 15 sheet-molding compound was investigated with various coatings. This sheet-molding compound has been compression molded into many structurally complicated components, such as shrouds for gas turbine inlet housings and gearboxes. Erosion coatings developed for PMC s in this study consisted of a two-layered system: a bondcoat sprayed onto a cleaned PMC surface, followed by an erosion-resistant, hard topcoat sprayed onto the bondcoat as shown in following photomicrograph. Six erosion coating systems were evaluated for their ability to withstand harsh thermal cycles, erosion resistance (ASTM G76 83 "Standard Practice for Conducting Erosion Tests by Solid Particle Impingement Using Gas Jets") using Al2O3, and adhesion to the graphite fiber polyimide composite (ASTM D 4541 95 "Pull Off Strength of Coatings"). Glenn and Allison Advanced Development Company collaborated to optimize erosion coatings for gas turbine fan and compressor applications. All the coating systems survived aggressive thermal cycling without spalling. During erosion tests (see the final photo), the most promising coating systems tested had Cr3C2-NiCr and WC-Co as the hard topcoats. In all cases, these coating systems performed significantly better than that with a TiN hard topcoat. When material depth (thickness) loss is considered, the Cr3C2-NiCr and WC-Co coating systems provided, on average, an erosion resistance 8.5 times greater than that for the uncoated PMR 15/T650 35 composite. Similarly, Cr3C2-NiCr and WC-Co coating systems adhered to the PMC substrate during tensile tests significantly better than systems containing a TiN topcoat. Differences in topcoats of Cr3C2-NiCr and WC-Co were determined by considering issues such as cost and environmental impact. The preferred erosion-resistant coating system for PMR 15/T650 35 has WC-Co as the hard topcoat. This system provides the following benefits in comparison to the coating system with Cr3C2-NiCr topcoat: lower powder material cost (15 to 20 percent), environmentally friendly materials (Cr3C2-NiCr is hazardous), and higher deposition yield (10 to 15 percent), which results in less waste.

Sutter, James K.↗

Static evaluation of surface coatings for compliant gas bearings in an oxidizing atmosphere to 650 C

Hard wear-resistant coatings and soft low shear strength coatings were developed for an air-lubricated compliant journal bearing for a future automotive gas turbine engine. The coatings were expected to function in either 540 or 650 C ambient. Soft lubricant coatings were generally limited in temperature. Therefore emphasis was on the hard wear-resistant coatings. The coating materials covered were TiC, B4C, Cr3C2, WC, SiC, CrB2, TiB2, Cr2O3, Al2O3, Si3N4, Tribaloy 800, CaF2, CaF2-BaF2 eutectic, Ni-Co, silver, CdO-graphite and proprietary compounds. The coatings on test coupons were subjected to static oven screening tests. The test consisted of exposure of material samples in an oven for 300 h at the maximum temperature (540 or 650 C) and ten temperature cycles from room temperature to the maximum service temperature. On the basis of the specimen examinations the following coatings were recommended for future wear tests: TiC (sputtered), Cr2O3 (sputtered), Si3N4 (sputtered), CdO and graphite (fused), Kaman DES (a proprietary coating), CrB2 (plasma sprayed), Cr3C2 (detonation gun) and NASA PS-106 (plasma sprayed).

Bhushan, B.↗

Tribological and microstructural comparison of HIPped PM212 and PM212/Au self-lubricating composites

The feasibility of replacing the silver with the volumetric equivalent of gold in the chromium carbide-based self-lubricating composite PM212 (70 wt. percent NiCo-Cr3C2, 15 percent BaF2/CaF2 eutectic) was studied. The new composite, PM212/Au has the following composition: 62 wt. percent NiCo-Cr3C2, 25 percent Au, 13 percent BaF2/CaF2 eutectic. The silver was replaced with gold to minimize the potential reactivity of the composite with possible environmental contaminants such as sulfur. The composites were fabricated by hot isostatic pressing (HIPping) and machined into pin specimens. The pins were slid against nickel-based superalloy disks. Sliding velocities ranged from 0.27 to 10.0 m/s and temperatures from 25 to 900 C. Friction coefficients ranged from 0.25 to 0.40 and wear factors for the pin and disk were typically low 10(exp -5) cu mm/N-m. HIPped PM212 measured fully dense, whereas PM212/Au had 15 percent residual porosity. Examination of the microstructures with optical and scanning electron microscopy revealed the presence of pores in PM212/Au that were not present in PM212. Though the exact reason for the residual porosity in PM212/Au was not determined, it may be due to particle morphology differences between the gold and silver and their effect on powder metallurgy processing.

Bogdanski, Michael S.↗

Tribological and microstructural comparison of HIPped PM212 and PM212/Au self-lubricating composites

The feasibility of replacing the silver with the volumetric equivalent of gold in the chromium carbide-based self-lubricating composite PM212 (70 wt percent NiCo-Cr3C2, 15 percent BaF2/CaF2 eutectic) was studied. The new composite, PM212/Au has the following composition: 62 wt percent NiCo-Cr3C2, 25 percent Au, 13 percent BaF2/CaF2 eutectic. The silver was replaced with gold to minimize the potential reactivity of the composite with possible environmental contaminants such as sulfur. The composites were fabricated by hot isostatic pressing (HIPping) and machined into pin specimens. The pins were slid against nickel-based superalloy disks. Sliding velocities ranged from 0.27 to 10.0 m/s and temperatures from 25 to 900 C. Frictions coefficients ranged from 0.25 to 0.40 and wear factors for the pin and disk were typically low 10(exp -5) cu mm/N-m. HIPped PM212 measured fully dense, whereas PM212/Au had 15 percent residual porosity. Examination of the microstructures with optical and scanning electron microscopy revealed the presence of pores in PM212/Au that were not present in PM212. Though the exact reason for the residual porosity PM212/Au was not determined, it may be due to practice morphology differences between the gold and silver and their effect on powder metallurgy processing.

Bogdanski, Michael S.↗

Microstructural and wear properties of sputtered carbides and silicides

Sputtered Cr3C2, Cr3Si2, and MoSi2 wear-resistant films (0.05 to 3.5 microns thick) were deposited on metal and glass surfaces. Electron transmission, electron diffraction, and scanning electron microscopy were used to determine the microstructural appearance. Strong adherence was obtained with these sputtered films. Internal stresses and defect crystallographic growth structures of various configurations within the film have progressively more undesirable effects for film thicknesses greater than 1.5 microns. Sliding contact and rolling element bearing tests were performed with these sputtered films. Bearings sputtered with a duplex coating (0.1-micron-thick undercoating of Cr3Si2 and subsequently 0.6-micron coating of MoS2) produced marked improvement over straight MoS2 films.

Spalvins, T.↗

Microstructural and wear properties of sputtered carbides and silicides

Sputtered Cr3C2, Cr3Si2, and MoSi2 wear-resistant films (0.05 to 3.5 microns thick) were deposited on metal and glass surfaces. Electron transmission, electron diffraction, and scanning electron microscopy were used to determine the microstructural appearance. Strong adherence was obtained with these sputtered films. Internal stresses and defect crystallographic growth structures of various configurations within the film have progressively more undesirable effects for film thicknesses greater than 1.5 microns. Sliding contact and rolling-element bearing tests were also performed with these sputtered films.

Spalvins, T.↗

Thermal fatigue behavior of H-13 die steel for aluminum die casting with various ion sputtered coatings

Sputtered coatings of Mo, W, Pt, Ag, Au, Co, Cr, Ni, Ag + Cu, Mo + Pt, Si3N4, A1N, Cr3C2, Ta5Si3, and ZrO2 were applied to a 2-inch-square, 7-inch-long thermal fatigue test specimen which was then internally water cooled and alternately immersed in molten aluminum and cooled in air. After 15,000 cycles the thermal fatigue cracks at the specimen corners were measured. Results indicate that a significant improvement in thermal fatigue resistance was obtained with platinum, molybdenum, and tungsten coatings. Metallographic examination indicates that the improvement in thermal fatigue resistance resulted from protection of the surface of the die steel from oxidation. The high yield strength and ductility of molybdenum and tungsten contributed to the better thermal fatigue resistance.

Nieh, C. Y.↗

Composition optimization of chromium carbide based solid lubricant coatings for foil gas bearings at temperatures to 650 C

A test program to determine the optimum composition of chromium carbide based solid lubricant coatings for compliant gas bearings is described. The friction and wear properties of the coatings are evaluated using a foil gas bearing test apparatus. The various coatings were prepared by powder blending, then plasma sprayed onto Inconel 718 test journals and diamond ground to the desired coating thickness and surface finish. The journals were operated against preoxidized nickel-chromium alloy foils. The test bearings were subjected to repeated start/stop cycles under a 14 kPa (2 psi) bearing unit load. The bearings were tested for 9000 start/stop cycles or until the specimen wear reached a predetermined failure level. In general, the addition of silver and eutectic to the chromium carbide base stock significantly reduced foil wear and increased journal coating wear. The optimum coating composition, PS212 (70 wt% metal bonded Cr3C2, 15 wt% Ag, 15% BaF2/CaF2 eutectic), reduced foil wear by a factor of two and displayed coating wear well within acceptable limits. The load capacity of the bearing using the plasma-sprayed coating prior to and after a run-in period was ascertained and compared to polished Inconel 718 specimens.

Dellacorte, Christopher↗

Electrodeposition and codeposition under low gravity/nonconvecting conditions

An experimental electrodeposition system was developed for modeling the behavior of inert particles codepositing in an electroplating matrix under low-gravity conditions. The device consists of a Co-electrodeposition cell operating in a convectionless mode (cathode over anode) and containing polystyrene particles with density approximating that of the electroplating solution. Data were obtained in shielded cells at 1 g, and the experiment was duplicated at 0.01 g on a KC-135 flight. No difference was found between convection-free bench experiments and the 0.01 g KC-135 experiments with 0.0900 M CuSO4. Codeposition experiments using 11.8-micron matched-density polystyrene spheres in 1 M CoSO4 have revealed that a noticeable particle gradient is created as the solution density mismatches in the vicinity of the cathode; gentle stirring was required to maintain a homogeneous particle suspension. Cr3C2 dust, which readily disperses at 1 g, tended to coagulate into spherical globules at 0.01 g, when stirred.

Riley, Clyde↗

Development of graphite/copper composites utilizing engineered interfaces

In situ measurements of graphite/copper alloy contact angles were made using the sessile drop method. The interfacial energy values obtained from these measurements were then applied to a model for the fiber matrix interfacial debonding phenomenon found in graphite/copper composites. The formation obtained from the sessile drop tests led to the development of a copper alloy that suitably wets graphite. Characterization of graphite/copper alloy interfaces subjected to elevated temperatures was conducted using Scanning Electron Microscopy, Energy Dispersive Spectroscopy, Auger Electron Spectroscopy, and X Ray Diffraction analyses. These analyses indicated that during sessile drop tests conducted at 1130 C for 1 hour, copper alloys containing greater than 0.98 at pct chromium form continuous reaction layers of approx. 10 microns in thickness. The reaction layers are adherent to the graphite surface. The copper wets the reaction layer to form a contact angle of 60 deg or less. X ray diffraction results indicate that the reaction layer is Cr3C2.

Devincent, Sandra M.↗

The effect of prolonged exposure to 750 C air on the tribological performance of PM212

The effect of prolonged exposure to 750 C air on the tribological performance and dimensional stability of PM212, a high temperature, self-lubricating composite, is studied. PM212, by weight, contains 70 percent metal-bonded Cr3C2, 15 percent BaF2/CaF2 eutectic, and 15 percent silver. Rub blocks were fabricated from PM212 by cold isostatic pressing followed by sintering. Prior to tribo-testing, the rub blocks were exposed to 750 C air for periods ranging from 100 to 1000 hours. Then, the rub blocks were slid against nickel-based superalloy disks in a double-rub-block tribometer in air under a 66 N load at temperatures from 25 to 750 C with a sliding velocity of 0.36 m/s. Unexposed rub blocks were tested for baseline comparison. Friction coefficients ranged from 0.24 to 0.37 for the unexposed rub blocks and from 0.32 to 0.56 for the exposed ones. Wear for both the composite blocks and superalloy disks was typically in the moderate to low range of 10(exp -5) to 10(exp -6) mm(exp 3)/N-m. Friction and wear data were similar for the rub blocks exposed for 100, 500, and 1000 hours. Prolonged exposure to 750 C air increased friction and wear of the PM212 rub blocks at room temperature, but their triboperformance remained unaffected at higher temperatures, probably due to the formation of lubricious metal oxides. Dimensional stability of the composite was studied by exposing specimens of varying thicknesses for 500 hours in air at 750 C. Block thicknesses were found to increase with increased exposure time until steady state was reached after 100 hours of exposure, probably due to oxidation.

Bemis, Kirk↗