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Fabrication and Characterization of Brazed Joints for SiC-Metallic Systems Utilizing Refractory Metals

Metal to ceramic joining plays a key role for the integration of ceramics into many nuclear, ground and aero based technologies. In order to facilitate these technologies, the active metal brazing of silicon carbide (CVD beta-SiC, 1.1 mm thick, and hot-pressed alpha-SiC, 3 mm thick) to the refractory metals molybdenum and tungsten using active braze alloys was studied. The joint microstructure, composition, and microhardness were evaluated by optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Knoop hardness testing. The braze alloys, Cusil-ABA, Ticusil and Copper-ABA, all formed sound joints with excellent wetting and chemical bonding with the SiC substrate. Despite the close thermal expansion match between the metal substrates and SiC, hairline cracks formed in alpha-SiC while beta-SiC showed no signs of residual stress cracking. The use of ductile interlayers to reduce the effect from residual stresses was investigated and joints formed with copper as an interlayer produced crack free systems utilizing both CVD and hot-pressed SiC.

Coddington, Bryan

SiC Composite Turbine Vanes

Turbine inlet guide vanes have been fabricated from composites of silicon carbide fibers in silicon carbide matrices. A unique design for a cloth made from SiC fibers makes it possible to realize the geometric features necessary to form these vanes in the same airfoil shapes as those of prior metal vanes. The fiber component of each of these vanes was made from SiC-fiber cloth coated with boron nitride. The matrix was formed by chemical-vapor infiltration with SiC, then slurry-casting of SiC, followed by melt infiltration with silicon. These SiC/SiC vanes were found to be capable of withstanding temperatures 400 F (222 C) greater than those that can be withstood by nickel-base-superalloy turbine airfoils now in common use in gas turbine engines. The higher temperature capability of SiC/SiC parts is expected to make it possible to use them with significantly less cooling than is used for metallic parts, thereby enabling engines to operate more efficiently while emitting smaller amounts of NOx and CO. The SiC/SiC composite vanes were fabricated in two different configurations. Each vane of one of the configurations has two internal cavities formed by a web between the suction and the pressure sides of the vane. Each vane of the other configuration has no web (see Figure 1). It is difficult to fabricate components having small radii, like those of the trailing edges of these vanes, by use of stiff stoichiometric SiC fibers currently preferred for SiC/SiC composites. To satisfy the severe geometric and structural requirements for these vanes, the aforementioned unique cloth design, denoted by the term Y-cloth, was conceived (see Figure 2). In the regions away from the trailing edge, the Y-cloth features a fiber architecture that had been well characterized and successfully demonstrated in combustor liners. To form a sharp trailing edge (having a radius of 0.3 mm), the cloth was split into two planes during the weaving process. The fiber tows forming the trailing-edge section were interlocked, thereby enhancing through-thickness strength of the resulting composite material. For vanes of the webless configuration, each made from a layup of six plies of Ycloth, the length of each Y-cloth layer was cut so that the two strips corresponding to the aforementioned two planes would wrap around the perimeter of a graphite vane preform tool with a 10-mm overlap. The overlap was used to join the two strips in a fringe splice. To make the external sixth ply, a standard woven cloth was cut to the required final length and a fringe splice joined the two ends of the cloth at the trailing edge. The cloth was then prepregged. The entire assembly was then placed into an aluminum compaction tool designed to form the outer net shape of the vane. After the prepreg material was allowed to dry, the preform was removed from the aluminum tooling and placed into an external graphite tool before being shipped to a vendor for matrix infiltration. To make the SiC fiber preform for a vane having an internal web, a slightly different initial approach was followed. Each of two sections forming the internal cavities (and ultimately the web) was created by first slipping two concentric layers of a two-dimensional, 2-by-2, 45 - braided tube around a net-shape graphite mandrel. The tubes on both mandrels were prepregged and allowed to dry. The resulting two subassemblies were put together, then four additional plies were wrapped around them in the same fashion as that described above for the six plies of the vaneless configuration. The consolidation of the SiC fiber preforms into SiC/SiC composite parts was performed by commercial vendors using their standard processes. The capability of two of the webless SiC/SiC turbine vanes was demonstrated in tests in a turbine environment. The tests included 50 hours of steady-state operation and 102 two-minute thermal cycles. A surface temperature of 1,320 C was reached during the tests.

Calomino, Anthony M.

Additive Manufacturing of SiC Based Ceramics and Ceramic Matrix Composites

Silicon carbide (SiC) ceramics and SiC fiber reinforcedSiC ceramic matrix composites (SiCSiC CMCs) offer high payoff as replacements for metals in turbine engine applications due to their lighter weight, higher temperature capability, and lower cooling requirements. Additive manufacturing approaches can offer game changing technologies for the quick and low cost fabrication of parts with much greater design freedom and geometric complexity. Four approaches for developing these materials are presented. The first two utilize low cost 3D printers. The first uses pre-ceramic pastes developed as feed materials which are converted to SiC after firing. The second uses wood containing filament to print a carbonaceous preform which is infiltrated with a pre-ceramic polymer and converted to SiC. The other two approaches pursue the AM of CMCs. The first is binder jet SiC powder processing in collaboration with rp+m (Rapid Prototyping+Manufacturing). Processing optimization was pursued through SiC powder blending, infiltration with and without SiC nano powder loading, and integration of nanofibers into the powder bed. The second approach was laminated object manufacturing (LOM) in which fiber prepregs and laminates are cut to shape by a laser and stacked to form the desired part. Scanning electron microscopy was conducted on materials from all approaches with select approaches also characterized with XRD, TGA, and bend testing.

3-D printing

Comprehensive new insights on the potential use of SiC as plasma-facing materials in future fusion reactors

Abstract The performance of silicon carbide as an alternative plasma facing material (PFM) was studied at various irradiation conditions relevant to ion energies and fluxes of a fusion reactor. This analysis involves detailed modeling of subsurface plasma/material interactions, sputtered particle transport above the surface and redeposition, and related changes in material composition and microstructure induced by steady-state and Edge Localized Mode ion fluxes. Transition of a crystalline SiC surface to semi-crystalline and amorphous phases was analyzed based on advanced modeling of DIII-D tokamak experiments where SiC was irradiated in single- and multiple- L-mode and H-mode discharges. This analysis shows that displacement damage, particle deposition/redeposition, and D accumulation on the SiC divertor surface can lead to significant microstructural changes that result in enhanced sputtering erosion in comparison with the original crystalline material. However, the resulting total net erosion rate for a full-coverage, advanced tokamak, SiC coated divertor may well be acceptably low. Moreover, the C sputtering yield from the evolved SiC surface can be seven times lower than from a pure graphite surface; this would imply significantly reduced tritium co-deposition rates in a D-T tokamak reactor, compared with a pure carbon surface. It was also determined that chemical sputtering of both C and Si should not result in any noticeable effect on the net erosion, for attached plasma regimes. Our results thus show encouraging results overall for use of SiC as a PFM in tokamaks.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Performance Evaluation of an Additively Manufactured ultra-High Operating Temperature SiC Solar-Thermal Air Receiver (HOTSSTAR) Test Module

Increasing operating temperatures of solar receivers is paramount to the efficiency of concentrated solar thermal and solar power systems. GE Aerospace Research in collaboration with Heliogen Inc and Sandia National Laboratories (SNL) is engaged in the development of ultra-High Operating Temperature SiC-matrix Solar Thermal Air Receiver (HOTSSTAR) enabled by additive manufacturing. HOTSSTAR goal is to demonstrate SiC receiver with air exit temperatures up to 1100oC. We discuss fabrication and on-sun test results of a prototype 50kWth test module. The receiver architecture is based on a radial airflow design and consists of a series of radial SiC receiver sectors organized around central absorber. These components were fabricated using binder-jet printed SiC followed by melt-infiltration reaction bonding process. To enhance the thermo-mechanical reliability of SiC test articles in thermal gradient/ shock environment of the application, the components were laminated with GE’s MI SiC CMC. A dedicated test facility was constructed at SNL Solar Tower to evaluate the operational performance of HOTSSTAR module under solar fluxes >200 W/cm2. We report on our final 50kW test module fabrication, integration at the test facility at Sandia, and discuss on-sun test results. We compare the performance of HOTSSTAR module relative to our model predictions.

14 SOLAR ENERGY

Emerging continuous SiC fibers for high-temperature applications

Silicon carbide (SiC) fibers are responsible for the ultimate strength and toughness of SiC-fiber reinforced composites in harsh environments. The development of a new generation of continuous SiC fibers continues to advance the mechanical properties of composite materials. Tyranno™ SA4 fiber was recently released as a successor of Tyranno™ SA3 fiber. Laser-driven chemical vapor deposition (LCVD) has been adopted as an alternative fiber processing route to synthesizing high-strength SiC fiber with tailorable small diameters and chemical compositions. Both Tyranno™ SA4 and laser-driven CVD fibers show very high tensile strength, about 4 GPa in the as-fabricated condition. The degradation of thermal stability and strength due to annealing in an inert environment were similar for Tyranno™ SA3 and SA4 fibers because of their similar carbon-rich, crystalline microstructure. Silicon-rich fibers produced by LCVD possessed heterogeneous crystallinity, which was attributed to laser power distribution and showed microstructural instability at 1500 °C and above. Finally, the new SiC fibers demonstrated an increase in as-fabricated strength but faced the same challenges in environmental resistance as the traditional SiC fibers do.

36 MATERIALS SCIENCE

Wide bandgap photoconductor (SiC:V)-based optically addressed light valve for high fluence operation

Optically addressable light valves based on wide bandgap 4H- and 6H-SiC as photoconductors were designed to withstand higher operational laser fluences than the state of-the-art bismuth silicon oxide (BSO; Bi 12 SiO 20 ) based devices. Vanadium-doped SiC was selected as the photoconductors due to their reasonable photoresponsivity while many fold improvement in laser induced damage threshold as compared to BSO. The laser induced damage threshold values of the materials were measured after exposing ~ 200 sites on the samples to increasing levels of fluence of a gaussian pulsed Nd: YAG laser system (1064 nm) with a 5 Hz repetition rate. The measured damage threshold values for BSO, 4H- and 6H-SiC were 0.4 J/cm 2 , 1.75 J/cm 2 and 1.8 J/cm 2 , respectively. Photoconductive switches based on 4H and 6H-SiC samples were characterized at wavelengths of 380 nm, 405 nm, and 447 nm. The peak photoresponsivity values of the 4H- and 6H-SiC materials were measured to be under 380 nm and 405 nm, respectively. The photoconductor was bonded to a BK7 optical window with 5 μm diameter microspheres as spacers. A twisted nematic type E7 liquid crystal (LC) was filled in the 5 μm gap in a vacuum chamber. The desired alignment of the liquid crystal was achieved by mutually orthogonal orientation of LC alignment layers on the two mating faces (SiC and BK7). The fabricated devices were modulated using address beams of wavelengths 380 nm, 405 nm, and 447 nm. In conclusion, required transmission levels of > 90% was achieved for the fabricated OALVs for a sinusoidal voltage waveform that meets the lifetime requirement of the device.

36 MATERIALS SCIENCE

Greatly improved 3C-SiC p-n junction diodes grown by chemical vapor deposition

This paper reports the fabrication and initial electrical characterization of greatly improved 3C-SiC (beta-SiC) p-n junction diodes. These diodes, which were grown on commercially available 6H-SiC substrates by chemical vapor deposition, demonstrate rectification to -200 V at room temperature, representing a fourfold improvement in reported 3C-SiC diode blocking voltage. The reverse leakage currents and saturation current densities measured on these diodes also show significant improvement compared to previously reported 3C-SiC p-n junction diodes. When placed under sufficient forward bias, the diodes emit significantly bright green-yellow light. These results should lead to substantial advancements in 3C-SiC transistor performance.

Neudeck, Philip G.

Do SiC grains in Orgueil differ from those in Murchison?

Studies of individual presolar SiC grains have shown that most are enriched in Si-29, Si-30, and C-13, and depleted in N-15, compared to solar-system abundances and that many have large excesses of Mg-26, most plausibly from in situ decay of Al-26. Stone et al., observed that Si from a family of platy SiC grains define a linear array on a 3-isotope plot that does not pass through normal solar-system Si. In contrast, Si-isotope data from over 100 3-4 micron SiC grains from Murchison from an elongate ellipse enclosing the Stone et al. linear array but also including 'normal' solar-system Si. To investigate whether this difference in Si isotopes indicates different populations of SiC in the two meteorites and to improve the characterization of Orgueil SiC, we used the PANURGE ion microprobe to measure Si, C, N, and Mg isotopes and Al and Na concentrations in a suite of 2-5 micron SiC grains from a new sample of Orgueil.

Huss, Gary R.

SiC-Based Gas Sensors

Electronic grade Silicon Carbide (SiC) is a ceramic material which can operate as a semiconductor at temperatures above 600 C. Recently, SiC semiconductors have been used in Schottky diode gas sensor structures. These sensors have been shown to be functional at temperatures significantly above the normal operating range of Si-based devices. SiC sensor operation at these higher temperatures allows detection of gases such as hydrocarbons which are not detectable at lower temperatures. This paper discusses the development of SiC-based Schottky diode gas sensors for the detection of hydrogen, hydrocarbons, and nitrogen oxides (NO(x)). Sensor designs for these applications are discussed. High sensitivity is observed for the hydrogen and hydrocarbon sensors using Pd on SiC Schottky diodes while the NO(x) sensors are still under development. A prototype sensor package has been fabricated which allows high temperature operation in a room temperature ambient by minimizing heat loss to that ambient. It is concluded that SiC-based gas sensors have considerable potential in a variety of gas sensing applications.

Chen, Liang-Yu

Effects of Interface Coating and Nitride Enhancing Additive on Properties of Hi-Nicalon SiC Fiber Reinforced Reaction-Bonded Silicon Nitride Composites

Strong and tough Hi-Nicalon SiC fiber reinforced reaction-bonded silicon nitride matrix composites (SiC/ RBSN) have been fabricated by the fiber lay-up approach. Commercially available uncoated and PBN, PBN/Si-rich PBN, and BN/SiC coated SiC Hi-Nicalon fiber tows were used as reinforcement. The composites contained approximately 24 vol % of aligned 14 micron diameter SiC fibers in a porous RBSN matrix. Both one- and two-dimensional composites were characterized. The effects of interface coating composition, and the nitridation enhancing additive, NiO, on the room temperature physical, tensile, and interfacial shear strength properties of SiC/RBSN matrix composites were evaluated. Results indicate that for all three coated fibers, the thickness of the coatings decreased from the outer periphery to the interior of the tows, and that from 10 to 30 percent of the fibers were not covered with the interface coating. In the uncoated regions, chemical reaction between the NiO additive and the SiC fiber occurs causing degradation of tensile properties of the composites. Among the three interface coating combinations investigated, the BN/SiC coated Hi-Nicalon SiC fiber reinforced RBSN matrix composite showed the least amount of uncoated regions and reasonably uniform interface coating thickness. The matrix cracking stress in SiC/RBSN composites was predicted using a fracture mechanics based crack bridging model.

Bhatt, Ramakrishana T.

Development of Sic Gas Sensor Systems

Silicon carbide (SiC) based gas sensors have significant potential to address the gas sensing needs of aerospace applications such as emission monitoring, fuel leak detection, and fire detection. However, in order to reach that potential, a range of technical challenges must be overcome. These challenges go beyond the development of the basic sensor itself and include the need for viable enabling technologies to make a complete gas sensor system: electrical contacts, packaging, and transfer of information from the sensor to the outside world. This paper reviews the status at NASA Glenn Research Center of SiC Schottky diode gas sensor development as well as that of enabling technologies supporting SiC gas sensor system implementation. A vision of a complete high temperature microfabricated SiC gas sensor system is proposed. In the long-term, it is believed that improvements in the SiC semiconductor material itself could have a dramatic effect on the performance of SiC gas sensor systems.

Hunter, G. W.

Surface Characterization of 3C-SiC Mesa Heterofilms: Evidence for Growth by Edge/Corner Nucleation Mechanism

This paper presents the first detailed observations of unique surface morphologies of 3C-Sic films grown on 4W6H-SIC mesas by the step-free surface heteroepitaxy technique. The top surfaces of 3C-Sic films were extensively studied by optical microscopy and atomic force microscopy (AFM) as both film thickness (i.e,, growth time) and growth temperature (i.e., terrace nucleation rate) were varied following complete coverage of each 4W6H mesa by an initial 3C-Sic film. Almost all surface steps observed by AFM were 0.25 nm, the height of a single Si-C bilayer. However, strikingly different step patterns were observed, suggesting that radically different processes dominate the nucleation of new 3C-Sic bilayers on top of existing 3C-Sic film surfaces.

Trunek, Andrew J.

Step Free Surface Heteroepitaxy of 3C-SiC Layers on Patterned 4H/6H-SiC Mesas and Cantilevers

Most SiC devices are implemented in homoepitaxial films grown on 4H/6H-SiC wafers with surfaces 3 degrees to 8 degrees off-axis from the (0001) basal plane. This approach has not prevented many substrate crystal defects from propagating into SiC epilayers, and does not permit the realization of SiC heteropolytype devices. This presentation describes recent advances in SiC epitaxial growth that begun to overcome the above shortcomings for arrays of mesas patterned into on-axis 4H/6H-SiC wafers. First, we demonstrated that atomic-scale surface steps can be completely eliminated from 4H/6H-SiC mesas via on-axis homoepitaxial step-flow growth, forming (0001) basal plane surfaces (up to 0.4 mm x 0.4 mm) for larger than previously thought possible. Step-free surface areas were then extended by growth fo thin lateral cantilevers from the mesa tops. These lateral cantilevers enabled substrate defects to be reduced and relocated in homoepitaxial films in a manner not possible with off-axis SiC growth. Finally, growth of vastly improved 3C-SiC heterofilms was achieved on 4H/6H-SiC mesas using the recently develop step-free surface heteroepitaxy process. These epitaxial growth developments should enable improved homojunction and heterojunction silicon carbide prototype devices.

Neudeck, Philip G.

Web Growth Used to Confine Screw Dislocations to Predetermined Lateral Positions in 4H-SiC Epilayers

Silicon-carbide- (SiC-) based power devices could enable substantial aerospace electronics benefits over today's silicon-based electronics. However, present-day SiC wafers contain electrically harmful dislocations (including micropipes) that are unpredictably distributed in high densities across all commercial 4H- and 6H-SiC wafers. The NASA Glenn Research Center recently demonstrated a crystal growth process that moves SiC wafer dislocations to predetermined lateral positions in epitaxial layers so that they can be reproducibly avoided during subsequent SiC electronic device fabrication. The process starts by reactive ion etching mesa patterns with enclosed trench regions into commercial on-axis (0001) 4H- or 6H-SiC substrates. An example of a pregrowth mesa geometry with six enclosed triangular-shaped trench regions is shown. After the etch mask is stripped, homoepitaxial growth is carried out in pure stepflow conditions that enable thin cantilevers to grow laterally from the tops of mesas whose pregrowth top surfaces are not threaded by substrate screw dislocations. The image in the bottom figure shows the postgrowth structure that forms after the lateral cantilevers expand to coalesce and completely roof over each of the six triangular trench regions. Atomic force microscope (AFM) measurements of the roof revealed that three elementary screw dislocation growth spirals, each shown in the AFM insets of the bottom image on the previous page, formed in the film roof at three respective points of cantilever film coalescence. The image above shows the structure following an etch in molten potassium hydroxide (KOH) that produced surface etch pits at the dislocation defects. The larger KOH etch pits--S1, S2, and S3--shown in this image correspond to screw dislocations relocated to the final points of cantilever coalescence. The smaller KOH etch pits are consistent with epilayer threading edge dislocations from the pregrowth substrate mesa (P1, P3, and P4) and a final cantilever coalescence point (P2). No defects (i.e., no etch pits) are observed in other cantilevered portions of the film surface. On the basis of the principle of dislocation Burgers vector conservation, we hypothesize that all vertically propagating substrate dislocations in an enclosed trench region become combined into a single dislocation in the webbed film roof at the point of final roof coalescence. The point of final roof coalescence, and therefore the lateral location of a webbed roof dislocation, can be designed into the pregrowth mesa pattern. Screw dislocations with predetermined lateral positions can then be used to provide the new growth steps necessary for growing a 4H/6H-SiC epilayer with a lower dislocation density than the substrate. Devices fabricated on top of such films can be positioned to avoid the preplaced dislocations.

Powell, J. Anthony

New High-Performance SiC Fiber Developed for Ceramic Composites

Sylramic-iBN fiber is a new type of small-diameter (10-mm) SiC fiber that was developed at the NASA Glenn Research Center and was recently given an R&D 100 Award for 2001. It is produced by subjecting commercially available Sylramic (Dow Corning, Midland, MI) SiC fibers, fabrics, or preforms to a specially designed high-temperature treatment in a controlled nitrogen environment for a specific time. It can be used in a variety of applications, but it currently has the greatest advantage as a reinforcement for SiC/SiC ceramic composites that are targeted for long-term structural applications at temperatures higher than the capability of metallic superalloys. The commercial Sylramic SiC fiber, which is the precursor for the Sylramic-iBN fiber, is produced by Dow Corning, Midland, Michigan. It is derived from polymers at low temperatures and then pyrolyzed and sintered at high temperatures using boron-containing sintering aids (ref. 1). The sintering process results in very strong fibers (>3 GPa) that are dense, oxygen-free, and nearly stoichiometric. They also display an optimum grain size that is beneficial for high tensile strength, good creep resistance, and good thermal conductivity (ref. 2). The NASA-developed treatment allows the excess boron in the bulk to diffuse to the fiber surface where it reacts with nitrogen to form an in situ boron nitride (BN) coating on the fiber surface (thus the product name of Sylramic-iBN fiber). The removal of boron from the fiber bulk allows the retention of high tensile strength while significantly improving creep resistance and electrical conductivity, and probably thermal conductivity since the grains are slightly larger and the grain boundaries cleaner (ref. 2). Also, as shown in the graph, these improvements allow the fiber to display the best rupture strength at high temperatures in air for any available SiC fiber. In addition, for CMC applications under oxidizing conditions, the formation of an in situ BN surface layer creates a more environmentally durable fiber surface not only because a more oxidation-resistant BN is formed, but also because this layer provides a physical barrier between contacting fibers with oxidation-prone SiC surface layers (refs. 3 and 4). This year, Glenn demonstrated that the in situ BN treatment can be applied simply to Sylramic fibers located within continuous multifiber tows, within woven fabric pieces, or even assembled into complex product shapes (preforms). SiC/SiC ceramic composite panels have been fabricated from Sylramic-iBN fabric and then tested at Glenn within the Ultra-Efficient Engine Technology Program. The test conditions were selected to simulate those experienced by hot-section components in advanced gas turbine engines. The results from testing at Glenn demonstrate all the benefits expected for the Sylramic-iBN fibers. That is, the composites displayed the best thermostructural performance in comparison to composites reinforced by Sylramic fibers and by all other currently available high-performance SiC fiber types (refs. 3 and 5). For these reasons, the Ultra-Efficient Engine Technology Program has selected the Sylramic-iBN fiber for ongoing efforts aimed at SiC/SiC engine component development.

DiCarlo, James A.

Cryogenic Performance of Trex SiC Mirror

Low cost, high performance lightweight Silicon Carbide (Sic) mirrors provide an alternative to Beryllium mirrors. A Trex Enterprises 0.25m diameter lightweight Sic mirror using its patented Chemical Vapor Composites (CVC) technology was evaluated for its optical performance. CVC Sic is chemically pure, thermally stable, and mechanically stiff. CVC technology yields higher growth rate than that of CVD Sic. NASA has funded lightweight optical materials technology development efforts involving Sic mirrors for future space based telescope programs. As part of these efforts, a Trex Sic was measured interferometrically from room temperature to 30 degrees Kelvin. This paper will discuss the test goals, the test instrumentation, test results, and lessons learned.

Foss, Colby

SiC As An Energetic Particle Detector

Several new technologies have been introduced recently in the region of semiconductor material for solid state detectors (SSD). Of particular interest is silicon carbide (SIC) since its band gap is larger than that of pure silicon, reducing its dark current and making SIC capable of operating at high temperatures and more tolerant of radiation damage. But the trade off is that a higher band gap also means fewer electron hole pairs generated, and thus a smaller signal, for detecting incident radiation. To determine what the lower limit of SiC detectors to energetic particles is, we irradiated a SiC diode with particles ranging in energy from 50 keV to 1.6 MeV and masses from 1 to 16 amu. We found that the SiC detectors sensitivity was comparable to that of pure silicon, with the SiC detector being able to measure particles down to 50 keV/amu and possibly lower.

Yan, F.