Ceramic On-Demand Extrusion (CODE) of Functionally Graded ZrB2-Mo
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Martin, Austin↗
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Preliminary investigation of zirconium boride ceramals for gas-turbine blade applications
Zirconium boride ZrB2 ceramals were investigated for possible gas-turbine-blade application. Included in the study were thermal shock evaluations of disks, preliminary turbine-blade operation, and observations of oxidation resistance. Thermal shock disks of the following three compositions were studied: (a) 97.5 percent ZrB2 plus 2.5 percent B by weight; (b) 92.5 percent ZrB2 plus 7.5 percent B by weight; and (c) 100 percent ZrB2. Thermal shock disks were quenched from temperatures of 1800 degrees, 2000 degrees, 2200 degrees, and 2400 degrees F. The life of turbine blades containing 93 percent ZrB2 plus 7 percent B by weight was determined in gas-turbine tests. The blades were run at approximately 1600 degrees F and 15,000 to 26,000 rpm. The thermal shock resistance of the 97.5 percent ZrB2 plus 2.5 percent boron ceramals compares favorably with that of TiC plus Co and TiC plus Ni ceramals. Oxidation of the disks during the thermal shock evaluation was slight for the comparatively short time (8.3 hr) up through 2000 degrees F. Oxidation of a specimen was severe, however, after 100 hours at 2000 degrees F. The turbine blade performance evaluation of the 93 percent ZrB2 plus 7 percent B composition was preliminary in scope ; no conclusions can be drawn.
Hoffman, Charles A↗
Investigation of the fracture mechanics of boride composites
Significant results were obtained in fabrication studies of the role of metallic additives of Zr, Ti, Ni, Fe and Cr on the densification of ZrB2. All elemental additions lower the processing temperatures required to effect full densification of ZrB2. Each addition effects enhanced densification by a clearly distinguishable and different mechanism and the resulting fabricated materials are different. A significant improvement in strength and fracture toughness was obtained for the ZrB2/Ti composition. Mechanical characterization studies for the ZrB2/SiC/C composites and the new ZrB2/Metal materials produced data relevant to the effect of impacting load on measured impact energies, a specimen configuration for which controlled fracture could occur in a suitably hard testing apparatus, and fracture strength data. Controlled fracture--indicative of measurable fracture toughness--was obtained for the ZrB2-SiC-C composite, and a ZrB2/Ti composite fabricated from ZrB2 with an addition of 30 weight per cent Ti. The increased strength and toughness of the ZrB2/Ti composite is consistent with the presence of a significantly large amount of a fine grained acicular phase formed by reaction of Ti with ZrB2 during processing.
Clougherty, E. V.↗
Final-stage densification kinetics of direct current–sinteredZrB2
Final-stage sintering was analyzed for nominally phase pure zirconium diboride synthesized by borothermal reduction of high-purity ZrO2. Analysis was conducted on ZrB2 ceramics with relative densities greater than 90% using the Nabarro–Herring stress–directed vacancy diffusion model. Temperatures of 1900°C or above and an applied uniaxial pressure of 50 MPa were required to fully densify ZrB2 ceramics by direct current sintering. Ram travel data were collected and used to determine the relative density of the specimens during sintering. Specimens sintered between 1900 and 2100°C achieved relative densities greater than 97%, whereas specimens sintered below 1900°C failed to reach the final stage of sintering. The average grain size ranged from 1.0 to 14.7 μm. The activation energy was calculated from the slope of an Arrhenius plot that used the Kalish equation. The activation energy was 162 ± 34 kJ/mol, which is consistent with the activation energy for dislocation movement in ZrB2. The diffusion coefficients for dislocation motion that controls densification were 5.1 × 10−6 cm2/s at 1900°C and 5.1 × 10−5 cm2/s at 2100°C, as calculated from activation energy and average grain sizes. This study provides evidence that the dominant mechanism for final-stage sintering of ZrB2 ceramics is dislocation motion.
36 MATERIALS SCIENCE↗
Ultra-High-Temperature Ceramics Evaluated for Aeropropulsion Use
Ultra-high-temperature ceramics (UHTC) are a group of materials consisting of zirconium diboride (ZrB2) or hafnium diboride (HfB2) plus silicon carbide (SiC), and in some instances, carbon (C). They offer a combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTCs perform well in the environment for such applications (i.e., air at low pressures). The purpose of this study at the NASA Glenn Research Center was to examine three of these materials under conditions more representative of a propulsion environment: that is, higher oxygen partial pressure and total pressure. Relatively long, multiple-exposure cycles were emphasized. We completed an in-house study of ZrB2 plus 20 vol% SiC (abbreviated as ZS), ZrB2 plus 14 vol% SiC and 30 vol% C (ZSC), and SCS-9a SiC fiber-reinforced ZrB2 plus 20 vol% SiC (ZSS). HfB2-based compositions were not included in the study because of their high cost. The capability of UHTC for propulsion applications must be compared with that of mature, available, and commercially used ceramics such as silicon nitride (e.g., AS-800) to put things in proper perspective. In terms of mechanical properties, UHTCs fall short in terms of strength and fracture toughness. At about 1300 C, the creep resistance of ZS appears to be superior to the creep resistance reported for AS-800. However, the stress rupture life for Si3N4 under stress and temperature conditions similar to those used in this study is measured in hundreds of hours. Because of oxidation, ZS could not achieve such lives. In terms of oxidation resistance, acceptable amounts of material recession in 1 hour to thousands of hours, depending on the specific propulsion application, are on the order of 100 to 300 mm. This converts to an acceptable range of parabolic recession rate constants kp" of approximately less than or equal to 10(exp -1) to 10(exp -2) square millimeters per hour for a 1-hr application. For a 100-hr application, an acceptable range of kp" would be less than or equal to those values divided by 100. For the more oxidation resistant ZS material, measured parabolic recession rate constants were 4.7 x 10(exp -3) millimeters per hour at 1327 C, 7.8 x 10(exp -2) square millimeters per hour at 1627 C, and 1.3 millimeters per hour at 1927 C. Thus, recession rate constants for ZS are acceptable at 1327 C for a 1-hr application, but here silicon nitride is a superior material. At 1627 C, ZS oxidation is marginal for a 1-hr application, but dimensional growth would be an issue. In a 100-hr application, ZS cannot be considered at any temperature. Our cursory examination of thermal shock, both from a theoretical and experimental viewpoint, indicated that the ZS and ZSC UHTCs are inferior to AS-800 silicon nitride. On the basis of this limited study, UHTCs are not ready to be considered as aeropropulsion materials for any applications longer than a few minutes. Current materials suffer from aggressive oxidation and moisture attack (Quynhgiao Nguyen, NASA Glenn, and Raymond C. Robinson, QSS Group, Inc., Cleveland, OH, 2002, private communication), and they are susceptible to thermal shock. For long-term propulsion applications, major improvements in environmental durability are needed. Work is in progress to improve the oxidation resistance of UHTC materials.
Levine, Stanley R.↗
Joining of Zirconium Diboride-Based Ceramic Composites to Metallic Systems for High-Temperature Applications
Three types of hot-pressed zirconium diboride (ZrB2)-based ultra-high-temperature ceramic composites (UHTCC), ZrB2-SiC (ZS), ZrB2-SiC-C (ZSC), and ZrB2-SCS9-SiC (ZSS), were joined to Cu-clad-Mo using two Ag-Cu brazes (Cusil-ABA and Ticusil, T(sub L) approx.1073-1173 K) and two Pd-base brazes (Palco and Palni, T(sub L) approx.1493-1513 K). Scanning Electron Microscopy (SEM) coupled with energy-dispersive spectroscopy (EDS) revealed greater chemical interaction in joints made using Pd-base brazes than in joints made using Ag-Cu based active brazes. The degree of densification achieved in hot pressed composites influenced the Knoop hardness of the UHTCC and the hardness distribution across the braze interlayer. The braze region in Pd-base system displayed higher hardness in joints made using fully-dense ZS composites than in joints made using partially-dense ZSS composites and the carbon-containing ZSC composites. Calculations indicate a small negative elastic strain energy and an increase in the UHTCC's fracture stress up to a critical clad layer thickness . Above this critical thickness, strain energy in the UHTCC is positive, and it increases with increasing clad layer thickness. Empirical projections show a reduction in the effective thermal resistance of the joints and highlight the potential benefits of joining the UHTCC to Cu-clad-Mo.
Asthana, R.↗
Microstructural characterization of as-fabricated monolithic plates with boron carbide, aluminum boride, and zirconium boride burnable absorbers
The use of burnable absorbers can be beneficial for nuclear reactors by extending the fuel’s operational cycle, providing additional criticality control, and flattening the power profile. In this work, three burnable absorber materials (boron carbide, aluminum boride, and zirconium boride) embedded in aluminum have been fabricated into foils and clad in AA-6061 for potential use in high performance research reactors. The as-fabricated boron-containing phases were determined using transmission electron microscopy to be AlB2, B4C, and ZrB2. TEM also revealed weak bonding at the B4C-matrix interface. SEM showed a relatively uniform spatial distribution of boron-containing phases for all the candidate materials. Higher porosity was observed in the foil containing ZrB2 in its as-rolled condition. The porosity in the ZrB2 foil was reduced by hot isostatic pressing. The size and shape distributions of the boron-containing phases were analyzed on the criteria of cross-sectional area, perimeter, roundness, circularity, and aspect ratio. A method of converting the 2D burnable absorber dispersoids seen in cross-sectional microscopy images into 3D volumes was derived using both spherical and ellipsoidal geometry models. The difference in calculated burnable absorber dispersoid average volume between the two models ranges from 20% to 100%, which could impact burnable absorber burnout rates due to differences in neutron self-shielding.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Investigation of the fracture mechanics of boride composites
Fracture energies of WC-6Co, Boride 5 (ZrB2+SiC), Boride 8(ZrB2+SiC+C) and Boride 8-M2(ZrB2+SiC+C) were measured by slow bend and impact tests of notched charpy bars. Cobalt bonded tungsten carbide exhibited impact energies of 0.76 ft-lb or 73.9 in-lb/square inch. Boride 5 and the Boride 8 exhibit impact energies one third and one quarter of that observed for WC-6Co comparing favorably with measurements for SiC and Si3N4. Slow bend-notched bar-fracture energies for WC-6Co were near 2.6 in-lb/square inch or 1/20 the impact energies. Slow bend energies for Boride 8-M2, Boride 8 and Boride 5 were 58%, 42% and 25% of the value observed for WC-6Co. Fractograph showed differences for WC-6Co where slow bend testing resulted in smooth transgranular cleavage while samples broken by impact exhibited intergranular failures. By contrast the boride fractures showed no distinction based on testing method. Fabrication studies were conducted to effect alteration of the boride composites by alloying and introduction of graphite cloth.
Kaufman, L.↗
Development of dispersion-strengthened XD (trademark) Cu alloys for high heat-flux applications
In a previous effort sponsored by NASA LeRC, the XD(trademark) process was used to produce ZrB2 particulate reinforcements in Cu and the resulting extruded material was microstructurally characterized and evaluated in tension over a range of temperatures. A problem that was encountered in that study was microstructural inhomogeneity resulting from the frequent presence of 'ZrB2 agglomerates' that were several microns in size. The presence of these agglomerates was attributed to improper mixing of powders in the green compact used in the XD process for elemental boron powder segregation. In this program, several milling parameters were examined in an effort to optimize this processing step; two levels of ZrB2 reinforcements were considered (7 vol. percent and 15 vol. percent). Microstructures of the reacted powder mass were examined to verify the absence of these agglomerates. Larger bathes of powder were then mixed, reacted, machined to size, canned, and extruded. The microstructure and tensile properties of these extrusions were examined, and the measured properties were correlated with the observed microstructure. Large unreacted or partially reacted Zr particles were present. These particles affected the mechanical properties deleteriously, and their presence is attributed to insufficient heat of reaction during XD synthesis. Alternate processing routes are recommended.
Kumar, K. Sharvan↗
Evaluation of Ultra-High Temperature Ceramics for Aeropropulsion Use
Among the ultra-high temperature ceramics (UHTC) are a group of materials consisting of zirconium diboride or hafnium diboride plus silicon carbide, and in some instances, carbon. These materials offer a good combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTC perform well in the environment for such applications, i.e., air at low pressure. The purpose of this study was to examine three of these materials under conditions more representative of a propulsion environment, i.e., higher oxygen partial pressure and total pressure. Results of strength and fracture toughness measurements, furnace oxidation and high velocity thermal shock exposures are presented for ZrB2 plus 20 volume % SiC, ZrB2 plus 14 volume % SiC plus 30 volume % C, and SCS-9a SiC fiber reinforced ZrB2 plus 20 volume % SiC. The poor oxidation resistance of UHTCs is the predominant factor limiting their applicability to propulsion applications.
Levine, Stanley R.↗
Oxidation of Ultra-High Temperature Ceramics in Water Vapor
Ultra high temperature ceramics (UHTCs) including HfB2 + SiC (20% by volume), ZrB2 + SiC (20% by volume) and ZrB2 + SiC (14% by volume) + C (30% by volume) have historically been evaluated as reusable thermal protection systems for hypersonic vehicles. This study investigates UHTCs for use as potential combustion and aeropropulsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline comparison. Weight change measurements, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results will be compared with tests ran in static air at temperatures of 1327, 1627, and 1927 C. Oxidation comparisons will also be made to the study by Tripp. A small number of high pressure burner rig (HPBR) results at 1100 and 1300 C will also be discussed. Specific weight changes at all three temperatures along with the SIC results are shown. SiC weight change is negligible at such short duration times. HB2 + SiC (HS) performed the best out of all the tested UHTCS for all exposure temperatures. ZrB2 + Sic (ZS) results indicate a slightly lower oxidation rate than that of ZrBl + SiC + C (ZCS) at 1200 and 1400 C, but a clear distinction can not be made based on the limited number of tested samples. Scanning electron micrographs of the cross-sections of all the UHTCs were evaluated. A representative area for HS is presented at 1400 C for 26 hours which was the composition with the least amount of oxidation. A continuous SiO2 scale is present in the outer most edge of the surface. An image of ZCS is presented at 1400 C for 10 hours, which shows the most degradation of all the compositions studied. Here, the oxide surface is a mixture of ZrSiO4, ZrO2 and SO2.
Nguyen, QuynhGiao N.↗
Producing Zirconium Diboride Components with Complex, Near-Net Shape Geometries by Aqueous Room-Temperature Injection Molding
Room-temperature injection molding is proposed as a novel, low-cost and more energy efficient manufacturing process capable of forming complex-shaped zirconium diboride (ZrB2) parts. This innovative processing method utilized aqueous suspensions with high powder loading and a minimal amount (5 vol.) of water-soluble polyvinylpyrrolidone (PVP), which was used as a viscosity modifier. Rheological characterization was performed to evaluate the room-temperature flow properties of ZrB2-PVP suspensions. ZrB2 specimens were fabricated with high green body strength and were machinable prior to binder removal despite their low polymer content. After binder burnout and pressureless sintering, the bulk density and microstructure of specimens were characterized using Archimedes technique and scanning electron microscopy. X-Ray Diffraction was used to determine the phase compositions present in sintered specimens. Ultimate strength of sintered specimens will be determined using ASTM C1323-10 compressive C-ring test.
Near-Net Shape Forming↗
UHT-CAMANCHE: Ultra-High Temperature Ceramic Additively Manufactured Compact Heat Exchangers
The conceptual basis for this project is the convergence of advanced ultra-high temperature ceramic materials and additive manufacturing technologies to produce compact ceramic heat exchangers with complex internal flow path geometries. Task areas were broadly divided into materials and manufacturing development, heat exchanger design, component testing, and techno-economic analysis. Technical challenges included the design and commissioning of new test facilities, improving feature resolution and deposition rate of ceramic additive manufacturing techniques, establishing process-structure-property relationships in additively manufactured ultra-high temperature ceramics, and assessing high temperature materials compatibility in CO 2 environments. The primary candidate material evaluated in this work is a composite comprising zirconium diboride (ZrB2) with 30 vol. % silicon carbide (SiC) which was selected based on its desirable combination of high temperature mechanical properties, high thermal and electrical conductivities, and oxidation resistance. High solids loaded ZrB2-SiC pastes suitable for extrusion-based additive manufacturing were developed for the first time as part of this work. Materials compatibility studies indicate this material oxidizes in CO 2 to form a protective borosilicate scale which transforms to pure silica above 1000°C. Parts made by additive manufacturing displayed enlarged grain sizes produced by pressureless sintering as compared to hot-press sintering. Increases in microstructural coarseness have outsized effect on oxidation performance up to 1400°C due to incomplete oxidation of coarse large diameter SiC particles resulting in lower amounts of silica that apparently inhibit protective scale formation. Additive manufacturing as a forming technique did not appear to significantly affect thermal conductivity, hardness, or elastic modulus, though flexural strength was reduced by half or more as compared to traditionally hot-pressed materials. This effect was attributed to the presence of strength-limiting flaws (ca. 40 microns in size) originating from extrudate inhomogeneities that could potentially be eliminated with further process improvements. Attempts to attain economies of scale for production of multi-kilowatt scale heat exchangers by ceramic additive manufacturing proved difficult. Lack of automation and a modest extrusion rate while retaining fine feature resolution made the overall process labor intensive and limited experimental throughput. A number of full-scale components were taken through post-process heat treatments including drying, binder burnout, and sintering; however, none survived without significant flaws or cracks. Therefore, no operational data from a newly installed heat exchanger test loop were able to be obtained during the performance period. Continued research and development is recommended to improve economic feasibility of ceramic additive manufacturing by standardizing the use of advanced sensors, artificial intelligence, and automation tools to reduce associated labor costs and accelerate production rates. The materials and manufacturing techniques demonstrated in this work are likely to find applications in defense and energy applications.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Thermal design improvements for 30kWe arcjet engine
Two thermal design improvements for 30 kWe arcjet engines are described. A ZrB2 high temperature coating was used to increase the surface emissivity of the nozzle radiating surface, enabling lower temperature operation, which should lead to longer nozzle life. The ZrB2-coated engine operated 120 C cooler than the uncoated baseline engine indicating a 30 percent increase in the surface emissivity. An engine design which has fewer active seals than previous designs and operates at lower overall component temperatures is described. The nozzle on the engine operated at 1950 C at 30 kWe while the baseline engine nozzle reached 2000 C at 23 kWe. The back of the engine was more than a factor of two cooler when compared to the baseline engine.
Deininger, William D.↗
Thermal design improvements for 30kWe arcjet engines
This paper describes two thermal design improvements for 30 kWe arcjet engines. A ZrB2 high temperature coating was used to increase the surface emissivity of the nozzle radiating surface, enabling lower temperature operation, which should lead to longer nozzle life. The ZrB2-coated engine operated about 120 C cooler than the uncoated baseline engine indicating a 30 percent increase in the surface emissivity. Additionally, a new engine design which has fewer active seals than previous designs and operates at lower overall component temperatures is described in detail. The nozzle on the new engine operated at a temperature of 1950 C at 30 kWe while the baseline engine nozzle reached 2000 C at 23 kWe. In addition, the back of the new engine was more than a factor of two cooler when compared to the baseline engine.
Deininger, W. D.↗
Ultrahigh Temperature Ceramics for Thermal Protection of Next Generation Space Vehicles
Materials with improved properties are needed for thermal protection of next generation space vehicles. Sharp leading edges on these vehicles will have to withstand exposure to high temperatures (> 2200 C or 4000 F) and severe thermal cycling in both neutral and oxidizing environments. These extreme conditions will require materials that possess superior oxidation resistance, low creep, and excellent thermal shock properties. This presentation will first discuss the system requirements for thermal protection of advanced space vehicles and then show how they are driving development of new materials systems. The presentation will focus on ultrahigh temperature ceramics (UHTCs) that are promising candidates for such applications. ZrB2 and HfB2 and composites of those ceramics with SiC are two particular families of UHTCs that are currently under development for sharp leading edges. These ceramics are appealing because their melting temperatures are 3245 C (5873 F) for ZrB2 and 3380 C (6116 F) for HfB2 and because they may form protective, oxidation resistant coatings in use. The mechanical properties of the UHTCs are strongly dependent on phase purity and the processing route used to make them, both of which factors are being actively investigated. For example, oxide impurities could form glassy grain boundary phases that soften at high temperatures and make the ceramic susceptible to creep deformation. Results from scanning and transmission electron microscopic studies of the UHTCs have shown how their processing can be improved to give better properties. This presentation will discuss the UHTC characterization results in some detail, focusing particularly on the structure and composition of the ceramic grain boundaries. The presentation will conclude with some remarks on how the properties of these promising UHTCs can be further improved and how they might be made more economically.
Loehman, R. E.↗
Oxidation of Ultra-High Temperature Ceramics in Water Vapor
Ultra High Temperature Ceramics (UHTCs) including HfB2 + 20% SiC (HS), and ZrB2 + 20% SiC (ZC), and ZrB2 + 30% C + 14% SiC (ZCS) have been investigated for use as potential aeropropolsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperature of 1200, 1300, and 1400 C. CVD SiC was also evaluate as a baseline for comparison. Weight change, X-ray diffraction analysis, surface and cross-sectional SEM and EDS were performed. These results are compared with tests conducted in a stagnant air furnace at temperatures of 1327 C for 100 minutes, and with high pressure burner rig (HPBR) results at 1100 and 1300 C at 6 atm for 50 h. Total recession measurements are also reported for the two tests environments.
Nguyen, QuynGiao N.↗
Oxidation of Ultra High Temperature Ceramics in Water Vapor
Ultra High Temperature Ceramics (UHTCs) including HfB2 + 20v/0 SiC (HS), ZrB2 + 20v/0 SiC (ZS), and ZrB2 + 30v/0 C + 14v/0 SiC (ZCS) have been investigated for use as potential aeropropulsion engine materials. These materials were oxidized in water vapor (90 percent) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 h at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline for comparison. Weight change, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results are compared with tests ran in a stagnant air furnace at temperatures of 1327 C for 100 min, and with high pressure burner rig (HPBR) results at 1100 and 1300 C at 6 atm for 50 h. Low velocity water vapor does not make a significant contribution to the oxidation rates of UHTCs when compared to stagnant air. The parabolic rate constants at 1300 C, range from 0.29 to 16.0 mg(sup 2)cm(sup 4)/h for HS and ZCS, respectively, with ZS results between these two values. Comparison of results for UHTCs tested in the furnace in 90 percent water vapor with HPBR results was difficult due to significant sample loss caused by spallation in the increased velocity of the HPBR. Total recession measurements are also reported for the two test environments.
Nguyen, QuynhGiao N.↗