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Characterization of 3C-SiC Films Grown on 4H- and 6H-SiC Substrate Mesas During Step-Free Surface Heteroepitaxy

This paper reports detailed structural characterization of 3C-SiC heteroepitaxial films grown on 4H- and 6H-SiC mesa surfaces. 3C-SiC heterofilms grown by the "step-free surface heteroepitaxy" process, free of double-positioning boundary (DPB) and stacking-fault (SF) defects, were compared to less-optimized 3C-SiC heterofilms using High Resolution X-ray Diffraction (HRXRD), High Resolution Cross-sectional Transmission Electron Microscopy (HRXTEM), molten potassium hydroxide (KOH) etching, and dry thermal oxidation. The results suggest that step free surface heteroepitaxy enables remarkably benign partial lattice mismatch strain relief during heterofilm growth.

Neudeck, Philip G.

Advanced Environmental Barrier Coating Development for SiC-SiC Ceramic Matrix Composite Components

This presentation reviews the NASA advanced environmental barrier coating (EBC) system development for SiC-SiC Ceramic Matrix Composite (CMC) combustors particularly under the NASA Environmentally Responsible Aviation, Fundamental Aeronautics and Transformative Aeronautics Concepts Programs. The emphases have been placed on the current design challenges of the 2700-3000F capable environmental barrier coatings for low NOX emission combustors for next generation turbine engines by using advanced plasma spray based processes, and the coating processing and integration with SiC-SiC CMCs and component systems. The developments also have included candidate coating composition system designs, degradation mechanisms, performance evaluation and down-selects; the processing optimizations using TriplexPro Air Plasma Spray Low Pressure Plasma Spray (LPPS), Plasma Spray Physical Vapor Deposition and demonstration of EBC-CMC systems. This presentation also highlights the EBC-CMC system temperature capability and durability improvements under the NASA development programs, as demonstrated in the simulated engine high heat flux, combustion environments, in conjunction with high heat flux, mechanical creep and fatigue loading testing conditions.

CMAS

Atomic probe microscopy of 3C SiC films grown on 6H SiC substrates

The surface of 3C SiC films grown on 6H SiC substrates has been studied by atomic probe microscopy in air. Atomic-scale images of the 3C SiC surface have been obtained by STM which confirm the 111 line type orientation of the cubic 3C layer grown on the 0001 plane type surface of the hexagonal 6H substrate. The nearest-neighbor atomic spacing for the 3C layer has been measured to be 3.29 +/- 0.2 A, which is within 7 percent of the bulk value. Shallow terraces in the 3C layer have been observed by STM to separate regions of very smooth growth in the vicinity of the 3C nucleation point from considerably rougher 3C surface regions. These terraces are oriented at right angles to the growth direction. Atomic force microscopy has been used to study etch pits present on the 6H substrate due to high temperature HCl cleaning prior to CVD growth of the 3C layer. The etch pits have hexagonal symmetry and vary in depth from 50 nm to 1 micron.

Steckl, A. J.

SiC (SCS-6) Fiber Reinforced-Reaction Formed SiC Matrix Composites: Microstructure and Interfacial Properties

Microstructural and interfacial characterization of unidirectional SiC (SCS-6) fiber reinforced-reaction formed SiC (RFSC) composites has been carried out. Silicon-1.7 at.% molybdenum alloy was used as the melt infiltrant, instead of pure silicon, to reduce the activity of silicon in the melt as well as to reduce the amount of free silicon in the matrix. Electron microprobe analysis was used to evaluate the microstructure and phase distribution in these composites. The matrix is SiC with a bi-modal grain-size distribution and small amounts of MoSi2, silicon, and carbon. Fiber push-outs tests on these composites showed that a desirably low interfacial shear strength was achieved. The average debond shear stress at room temperature varied with specimen thickness from 29 to 64 MPa, with higher values observed for thinner specimens. Initial frictional sliding stresses showed little thickness dependence with values generally close to 30 MPa. Push-out test results showed very little change when the test temperature was increased to 800 C from room temperature, indicating an absence of significant residual stresses in the composite.

Singh, M.

Low Temperature Ohmic Contact Formation of Ni2Si on N-type 4H-SiC and 6H-SiC

Nickel Silicide (Ni2Si) is investigated as possible ohmic contact to heavily nitrogen-doped N-type 4H-SiC and 6H-SiC. Nickel Silicide was deposited via electron gun with various thicknesses on both Si and C faces of the SiC substrates. The Ni2Si contacts were formed at room temperature as well as at elevated temperatures (400 to 1000 K). Contact resistivities and I-V characteristics were measured at temperatures between 100 and 700 C. To investigate the electric properties, I-V characteristics were studied and the Transmission Line Method (TLM) was used to determine the specific contact resistance for the samples at each annealing temperature. Both Rutherford Backscattering Spectroscopy (RBS) and Auger Electron Spectroscopy (AES) were used for depth profiling of the Ni2Si, Si, and C. X-ray Photoemission Spectroscopy (XPS) was used to study the chemical structure of the Ni2Si/SiC interface.

Elsamadicy, A. M.

The impact resistance of SiC and other mechanical properties of SiC and Si3N4

Studies focused on the impact and mechanical behavior of SiC and Si3N4 at high temperatures are summarized. Instrumented Charpy impact testing is analyzed by a compliance method and related to strength; slow crack growth is related to processing, and creep is discussed. The transient nature of flaw populations during oxidation under load is emphasized for both SiC and Si3N4.

Bradt, R. C.

Stressed-Oxidation Lifetime of Different SiC Fiber, CVI Matrix SiC Minicomposites in Air

The stressed-oxidation lifetime properties of several minicomposites composed of single fiber tows with a CVI SiC matrix were compared. The minicomposites were made up of Nicalon(Tm) and Hi-Nicalon(Tm) SiC fibers with carbon or BN interphases. Constant load stress-rupture tests were performed between 600 and 13000 C in air for all of the minicomposite systems. Cyclic load testing was performed on the Hi-Nicalon minicomposite systems. The factors controlling the different lifetime behaviors: fiber rupture properties, interphase oxidation, fiber degradation, and fiber-matrix bonding, are discussed in light of different minicomposite constituents. All of the systems were subject to intermediate temperature embrittlement. The Hi-Nicalon fiber, BN interphase system, performed the best for constant load conditions. For cyclic load conditions, both the BN- interphase and C-interphase minicomposites displayed poor, but different failure behavior.

Morscher, Gregory N.

Fractographic Analysis of HfB2-SiC and ZrB2-SiC Composites

Hafnium diboride-silicon carbide and zirconium diboride-silicon carbide composites are potential materials for high temperature leading edge applications on reusable launch vehicles. In order to establish material constants necessary for evaluation of in-situ fracture, bars fractured in four point flexure were examined using fractographic principles. The fracture toughness was determined from measurements of the critical crack sizes and the strength values, and the crack branching constants were established to use in forensic fractography of materials for future flight applications. The fracture toughnesses range from about 13 MPam (sup 1/2) at room temperature to about 6 MPam (sup 1/2) at 1400 C for ZrB2-SiC composites and from about 11 MPam (sup 1/2) at room temperature to about 4 MPam (sup 1/2) at 1400 C for HfB2-SiC composites.

Mecholsky, J.J., Jr.

Enlargement of Step-Free SiC Surfaces by Homoepitaxial Web-Growth of Thin SiC Cantilevers

Lateral homoepitaxial growth of thin cantilevers emanating from mesa patterns that were reactive ion etched into on-axis commercial SiC substrates prior to growth is reported. The thin cantilevers form after pure stepflow growth removes almost all atomic steps from the top surface of a mesa, after which additional adatoms collected by the large step-free surface migrate to the mesa sidewall where they rapidly incorporate into the crystal near the top of the mesa sidewall. The lateral propagation of the step-free cantilevered surface is significantly affected by pregrowth mesa shape and orientation, with the highest lateral expansion rates observed at the inside concave comers of V-shaped pregrowth mesas with arms lengthwise oriented along the {1100} direction. Complete spanning of the interiors of V's and other mesa shapes with concave comers by webbed cantilevers was accomplished. Optical microscopy, synchrotron white beam x-ray topography and atomic force microscopy analysis of webbed regions formed over a micropipe and closed-core screw dislocations show that c-axis propagation of these defects is terminated by the webbing. Despite the nonoptimized process employed in this initial study, webbed surfaces as large as 1.4 x 10(exp -3) square centimeters, more than four times the pregrowth mesa area, were grown. However, the largest webbed surfaces were not completely free of bilayer steps, due to unintentional growth of 3C-SiC that occurred in the nonoptimized process. Further process optimization should enable larger step-free webs to be realized.

Neudeck, Philip G.

Design Guidelines for In-Plane Mechanical Properties of SiC Fiber-Reinforced Melt-Infiltrated SiC Composites

In-plane tensile stress-strain, tensile creep, and after-creep retained tensile properties of melt-infiltrated SiC-SiC composites reinforced with different fiber types were evaluated with an emphasis on obtaining simple or first-order microstructural design guidelines for these in-plane mechanical properties. Using the mini-matrix approach to model stress-strain behavior and the results of this study, three basic general design criteria for stress and strain limits are formulated, namely a design stress limit, a design total strain limit, and an after-creep design retained strength limit. It is shown that these criteria can be useful for designing components for high temperature applications.

Morscher, Gregory N.

Oxidation of SiC Fiber-Reinforced SiC Matrix Composites with a BN Interphase

SiC-fiber reinforced SiC matrix composites with a BN interphase were oxidized in reduced oxygen partial pressures of oxygen to simulate the environment for hypersonic vehicle leading edge applications. The constituent fibers as well as composite coupons were oxidized in oxygen partial pressures ranging from 1000 ppm O2 to 5% O2 balance argon. Exposure temperatures ranged from 816 C to 1353 C (1500 F to 2450 F). The oxidation kinetics of the coated fibers were monitored by thermogravimetric analysis (TGA). An initial rapid transient weight gain was observed followed by parabolic kinetics. Possible mechanisms for the transient oxidation are discussed. One edge of the composite coupon seal coat was ground off to simulate damage to the composite which allowed oxygen ingress to the interior of the composite. Oxidation kinetics of the coupons were characterized by scanning electron microscopy since the weight changes were minimal. It was found that sealing of the coupon edge by silica formation occurred. Differences in the amount and morphology of the sealing silica as a function of time, temperature and oxygen partial pressure are discussed. Implications for use of these materials for hypersonic vehicle leading edge materials are summarized.

Opila, Elizabeth

Improved BN Coatings on SiC Fibers in SiC Matrices

Modifications of BN-based coatings that are used as interfacial layers between the fibers and matrices of SiCfiber/SiC-matrix composite materials have been investigated to improve the thermomechanical properties of these materials. Such interfacial coating layers, which are also known as interphases (not to be confused with interphase in the biological sense), contribute to strength and fracture toughness of a fiber/matrix composite material by providing for limited amounts of fiber/matrix debonding and sliding to absorb some of the energy that would otherwise contribute to the propagation of cracks. Heretofore, the debonding and sliding have been of a type called inside debonding because they have taken place predominantly on the inside surfaces of the BN layers that is, at the interfaces between the SiC fibers and the interphases. The modifications cause the debonding and sliding to include more of a type, called outside debonding, that takes place at the outside surfaces of the BN layers that is, at the interfaces between the interphases and the matrix (see figure). One of the expected advantages of outside debonding is that unlike in inside debonding, the interphases would remain on the crack-bridging fibers. The interphases thus remaining should afford additional protection against oxidation at high temperature and should delay undesired fiber/fiber fusion and embrittlement of the composite material. A secondary benefit of outside debonding is that the interphase/matrix interfaces could be made more compliant than are the fiber/interphase interfaces, which necessarily incorporate the roughness of the SiC fibers. By properly engineering BN interphase layers to favor outside debonding, it should be possible, not only to delay embrittlement at intermediate temperatures, but also to reduce the effective interfacial shear strength and increase the failure strain and toughness of the composite material. Two techniques have been proposed and partially experimentally verified as candidate means to promote outside debonding in state-of-the-art SiC/SiC composites.

Morscher, Gregory N.

Creep, Fatigue and Fracture Behavior of Environmental Barrier Coating and SiC-SiC Ceramic Matrix Composite Systems: The Role of Environment Effects

Advanced environmental barrier coating (EBC) systems for low emission SiCSiC CMC combustors and turbine airfoils have been developed to meet next generation engine emission and performance goals. This presentation will highlight the developments of NASAs current EBC system technologies for SiC-SiC ceramic matrix composite combustors and turbine airfoils, their performance evaluation and modeling progress towards improving the engine SiCSiC component temperature capability and long-term durability. Our emphasis has also been placed on the fundamental aspects of the EBC-CMC creep and fatigue behaviors, and their interactions with turbine engine oxidizing and moisture environments. The EBC-CMC environmental degradation and failure modes, under various simulated engine testing environments, in particular involving high heat flux, high pressure, high velocity combustion conditions, will be discussed aiming at quantifying the protective coating functions, performance and durability, and in conjunction with damage mechanics and fracture mechanics approaches.

Environmental Barrier Coatings

Intermediate Temperature Stress Rupture of Woven SiC Fiber, BN Interphase, SiC Matrix Composites in Air

Tensile stress-rupture experiments were performed on woven Hi-Nicalon reinforced SiC matrix composites with BN interphases in air. Modal acoustic emission (AE) was used to monitor the damage accumulation in the composites during the tests and microstructural analysis was performed to determine the amount of matrix cracking that occurred for each sample. Fiber fractograph), was also performed for individual fiber failures at the specimen fracture surface to determine the strengths at which fibers failed. The rupture strengths were significantly worse than what would have been expected front the inherent degradation of the fibers themselves when subjected to similar rupture conditions. At higher applied stresses the rate of rupture "?as larger than at lower applied stresses. It was observed that the change in rupture rate corresponded to the onset of through-thickness cracking in the composites themselves. The primary cause of the sen,ere degradation was the ease with which fibers would bond to one another at their closest separation distances, less than 100 nanometers, when exposed to the environment. The near fiber-to-fiber contact in the woven tows enabled premature fiber failure over large areas of matrix cracks due to the stress-concentrations created b), fibers bonded to one another after one or a few fibers fail. i.e. the loss of global load sharing. An@, improvement in fiber-to-fiber separation of this composite system should result in improved stress- rupture properties. A model was den,eloped in order to predict the rupture life-time for these composites based on the probabilistic nature of indin,idual fiber failure at temperature. the matrix cracking state during the rupture test, and the rate of oxidation into a matrix crack. Also incorporated into the model were estimates of the stress-concentration that would occur between the outer rim of fibers in a load-bearing bundle and the unbridged region of a matrix crack after Xia et al. For the lower stresses, this source of stress-concentration was the likely cause for initial fiber failure that would trigger catastrophic failure of the composite.

Morscher, Gregory N.

Probabilistic Modeling of High-Temperature Material Properties of a 5-Harness 0/90 Sylramic Fiber/ CVI-SiC/ MI-SiC Woven Composite

An integrated probabilistic approach has been developed to assess composites for high temperature applications. This approach was used to determine thermal and mechanical properties and their probabilistic distributions of a 5-harness 0/90 Sylramic fiber/CVI-SiC/Mi-SiC woven Ceramic Matrix Composite (CMC) at high temperatures. The purpose of developing this approach was to generate quantitative probabilistic information on this CMC to help complete the evaluation for its potential application for HSCT combustor liner. This approach quantified the influences of uncertainties inherent in constituent properties called primitive variables on selected key response variables of the CMC at 2200 F. The quantitative information is presented in the form of Cumulative Density Functions (CDFs). Probability Density Functions (PDFS) and primitive variable sensitivities on response. Results indicate that the scatters in response variables were reduced by 30-50% when the uncertainties in the primitive variables, which showed the most influence, were reduced by 50%.

Nagpal, Vinod K.

Creep and Stress-strain Behavior After Creep from Sic Fiber Reinforced, Melt-infiltrated Sic Matrix Composites

Silicon carbide fiber (Hi-Nicalon Type S, Nippon Carbon) reinforced silicon carbide matrix composites containing melt-infiltrated Si were subjected to creep at 1315 C for a number of different stress conditions, This study is aimed at understanding the time-dependent creep behavior of CMCs for desired use-conditions, and also more importantly, how the stress-strain response changes as a result of the time-temperature-stress history of the crept material. For the specimens that did not rupture, fast fracture experiments were performed at 1315 C or at room temperature immediately following tensile creep. In many cases, the stress-strain response and the resulting matrix cracking stress of the composite change due to stress-redistribution between composite constituents during tensile creep. The paper will discuss these results and its implications on applications of these materials for turbine engine components.

Morscher, Gregory N.