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Sintering Behaviors of ZrC, NbC, and TaC Mono-and Binary Carbides

Nuclear Thermal Propulsion (NTP) has undergone development as an alternate in-space propulsion system to traditional chemical propulsion methods since the 1950s. In an NTP system, the energy released from fission in the core is utilized as the heat source to directly heat a propellant for propulsion, rather than chemical combustion in a traditional rocket. NTP has many desirable capabilities including flexible mission launch dates and reduced transit times due to it’s capability for high specific impulse. One of the main challenges with NTP systems is the structural integrity of the fuel. The fuel form required in the reactor core must withstand temperatures above 2700 Kelvin. Ceramic-metallic matrix fuel, ceramic-ceramic matrix fuel, and solid solution carbide fuels are the three strongest candidates for the extreme environments. Solid solution carbides have the potential to exhibit promising behavior as a fuel form in an NTP system. Of the multiple refractory metal carbides of interest, here we focus on zirconium carbide (ZrC), niobium carbide (NbC), and tantalum carbide (TaC). ZrC, NbC, and TaC powders were consolidated in monocarbide (ZrC, NbC, and TaC) and bi-carbide (ZrC-NbC, ZrC-TaC, NbC-TaC) forms using spark plasma sintering (SPS). In addition to the pure endpoint carbides, the examined compositions of the various bi-carbides ranged from 25-75 mol%. The sintering temperatures, pressures, and hold times were varied to determine the ideal sintering conditions. Grain size analysis, Archimedes’ density, scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersion spectroscopy (EDS) were used to determine and characterize the grain size, ideal density, porosity, phase stability, and chemical composition of each sample. The data from each sample was then used to generate a Master Sintering Curve (MSC) unique to each monocarbide or bi-carbide.

nuclear thermal propulsion↗

Homogeneity Study of ZrC, NbC, and TaC Binary Carbide Fuels for the Application of Nuclear Thermal Propulsion

In alignment with NASA and DARPA goals, efforts towards Nuclear Thermal Propulsion (NTP) have increased in recent years. As progress is made, a main challenge still exists; the fuel in an NTP system must survive the extreme environment experienced during operating conditions. Three fuel forms have been studied including a ceramic-metallic matrix, a ceramic-ceramic matrix, and solid solution carbides. Solid solution carbides were studied previously as a fuel for NTP and was shown to be a promising technology; however, the programs were canceled before demonstration in an NTP engine test. Of the refractory metal carbides of interest, zirconium carbide (ZrC), niobium carbide (NbC) and tantalum carbide (TaC) were studied. ZrC, NbC, and TaC powders were consolidated in monocarbide (ZrC, NbC, TaC) and bi-carbide (ZrC-NbC, ZrC-TaC, NbC-TaC) forms using spark plasma sintering (SPS), with 50-50 mol% compositions of the bi-carbides of interest. The time and temperature conditions to achieve a completely homogeneous solid solution for the mixed carbides is of interest for NTP fuel applications, since this homogeneity is considered to be essential for this fuel form. Homogeneity is typically not achieved during sintering, as surface diffusion (predominant for sintering to near ideal density) tends to occur at lower temperatures than bulk volumetric diffusion (required for solute interdiffusion to achieve a homogeneous solid solution). High temperature isochronal annealing was performed to identify the conditions to achieve a chemically homogeneous sample. The solute interpenetration vs annealing temperature was quantified using energy dispersion spectroscopy (EDS) in a scanning electron microscope (SEM). X-ray diffraction (XRD) was used to accurately measure the phase stability and lattice parameter as a function of annealing conditions. The diffusion data from each sample was then used to determine self-diffusion coefficients for interdiffusion of the Nb, Zr, and Ta solutes and compared to existing literature values. The minimum annealing conditions to achieve complete chemical homogeneity for each carbide was determined.

nuclear thermal propulsion↗

Alternative Processing of High Temperature Hafnium and Zirconium Based Materials

The behavior of refractory hafnium and zirconium based materials are being investigated at NASA Ames as part of ongoing research aimed at developing superior heat resistant materials for aerospace applications. Hafnium and zirconium diboride based materials have shown high temperature capabilities in simulated reentry environments indicating that these materials may successfully operate as reusable oxidation resistant components for leading edge applications. Due to the refractory nature of these materials, processing of fine-grained uniform microstructures poses a number of challenges. To better understand the process-property-microstructure relationship, processing of these materials has been carried out with conventional hot pressing in addition to the novel approach of Spark Plasma Sintering (SPS). The two processing methods are compared and contrasted in an evaluation of the sintering behavior of high temperature diboride based materials and preliminary physical and mechanical properties are presented.

Gasch, Matthew↗

Sintering Behavior of Diboride Based Materials

A brief history of diboride research, an overview of processing, and sintering studies are covered in this viewgraph presentation. UHTCs are a family of ceramic materials, including diborides of Hf and Zr, with extremely high melting temperatures. Spark Plasma Sintering (SPS) is a novel processing technique useful in consolidating difficult materials. The presentation also contains microphotographs of the microstructure of HfB2 and ZrB2 processed in different ways.

Gasch, Matt↗

Nuclear Rocket Ceramic Metal Fuel Fabrication Using Tungsten Powder Coating and Spark Plasma Sintering

Nuclear thermal propulsion is an enabling technology for crewed Mars missions. An investigation was conducted to evaluate spark plasma sintering (SPS) as a method to produce tungsten-depleted uranium dioxide (W-dUO2) fuel material when employing fuel particles that were tungsten powder coated. Ceramic metal fuel wafers were produced from a blend of W-60vol% dUO2 powder that was sintered via SPS. The maximum sintering temperatures were varied from 1,600 to 1,850 C while applying a 50-MPa axial load. Wafers exhibited high density (>95% of theoretical) and a uniform microstructure (fuel particles uniformly dispersed throughout tungsten matrix).

Barnes, M. W.↗

Demonstration of Subscale Cermet Fuel Specimen Fabrication Approach Using Spark Plasma Sintering and Diffusion Bonding

Nuclear thermal propulsion (NTP) has the potential to expand the limits of human space exploration by enabling crewed missions to Mars and beyond. The viability of NTP hinges on the development of a robust nuclear fuel material that can perform in the harsh operating environment (> or = 2500K, reactive hydrogen) of a nuclear thermal rocket (NTR) engine. Efforts are ongoing to develop fuel material and to assemble fuel elements that will be stable during the service life of an NTR. Ceramic-metal (cermet) fuels are being actively pursued by NASA Marshall Space Flight Center (MSFC) due to their demonstrated high-temperature stability and hydrogen compatibility. Building on past cermet fuel development research, experiments were conducted to investigate a modern fabrication approach for cermet fuel elements. The experiments used consolidated tungsten (W)-60vol%zirconia (ZrO2) compacts that were formed via spark plasma sintering (SPS). The consolidated compacts were stacked and diffusion bonded to assess the integrity of the bond lines and internal cooling channel cladding. The assessment included hot hydrogen testing of the manufactured surrogate fuel and pure W for 45 minutes at 2500 K in the compact fuel element environmental test (CFEET) system. Performance of bonded W-ZrO2 rods was compared to bonded pure W rods to access bond line integrity and composite stability. Bonded surrogate fuels retained structural integrity throughout testing and incurred minimal mass loss.

Barnes, Marvin W.↗

Development of New Rocket Engine Liner Materials Based on Copper Alloys with Diamond Particle Additions

Novel copper-diamond materials containing particulate dispersions of diamond within a copper alloy matrix have been produced as next-generation rocket engine combustion chamber liner materials. These Copper-Diamond (Cu-D) composite materials have significantly higher thermal conductivity than conventional liner materials and have the potential to increase the engine performance significantly. Liner fabrication techniques include hot pressing and spark plasma sintering (SPS), which are capable of scale up to full-size production parts. The materials have been evaluated for thermal cycling resistance and ease of manufacturing. The results indicate great promise of these materials and associated economics to replace state-of-the-art combustion chamber liner materials such as GRCop-84 and NARloy-Z. Combustion chamber fabrication processes are also discussed, including SPS and additive manufacturing.

Bhat, Biliyar N.↗

Exploring the Effect of EBC Composition on CMAS Wetting Behavior

Rare-earth disilicate (REDS) materials are existing materials used in environmental barrier coating (EBC) for the protection of structural materials in the hot-section of turbine engines. REDS interactions with molten calcium-magnesium-aluminosilicate (CMAS) debris are of interest to understand molten CMAS attack and improve CMAS mitigation strategies. This work assesses the effect of REDS composition on CMAS wetting by investigating wetting angle, spreading, and reactivity. Freestanding atmospheric plasma spray (APS) REDS coatings (for RE = Y, La, Nd, Gd, Yb, Lu) were exposed to 10 mg of CMAS (Ca33-Mg9-Al13-Si45 in single cation mol%) in stagnant lab air at 1250C. APS YbDS was compared to a dense spark plasma sintered (SPS) phase-pure Yb2Si2O7 and a nominal 20 vol% phase-mixture of Yb 2 SiO 5 in Yb 2 Si 2 O 7 (20YbMS/YbDS). CMAS mass was held constant but specimen surface areas varied, yielding a range of loading between ~6 and 10 mg/cm2. CMAS was loaded as a cylindrical rod atop the specimen surface, polished to 4000 grit, and heated to temperature in a Linseis L74/HS/1700 heating microscope. The heating microscope measured the evolution of molten CMAS diameter, height, and contact angle. Molten CMAS diameter at 1150C and contact angle measurements after two hours of exposure at 1250C yielded a positive trend with rare-earth cation size. There was no statistically significant difference in CMAS wetting behavior between SPS YbDS and 20YbMS/YbDS. Post-exposure specimens were examined in plan view and cross-section with XRD, SEM, and EDS. CMAS spreading was cross-examined using plan view SEM, while reactivity utilized plan view XRD and cross-sectional SEM/EDS.

Clark Luckhardt↗