Environmental Stability and Durability of Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites
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Graphite fibers intercalated with bromine, iodine monochloride, ferric chloride, and cupric chloride were subjected to stability tests under four environments which are encountered by engineering materials in the aerospace industry: ambient laboratory conditions, as would be experienced during handling operations and terrestrial applications; high vacuum, as would be experienced in space applications; high humidity, as would be experienced in marine applications; and high temperature, as would be experienced in some processing steps and applications. Monitoring the resistance of the fibers at ambient laboratory conditions revealed that only the ferric chloride intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were stable for long periods under high vacuum. Ferric chloride, cupric chloride, and iodine monochloride intercalated fibers were sensitive to high humidity conditions. All intercalated fibers began to degrade above 250 C. The order of their thermal stability, from lowest to highest, was cupric chloride, iodine monochloride, bromine, and ferric chloride. Of the four types of intercalated fibers tested, the bromine intercalated fibers appear to have the most potential for application, based on environmental stability.
Graphite fibers intercalated with bromine, iodine monochloride, ferric chloride, and cupric chloride were subjected to stability tests under four environments which are encountered by engineering materials in the aerospace industry: ambient laboratory conditions, as would be experienced during handling operations and terrestrial applications; high vacuum, as would be experienced in space applications; high humidity, as would be experienced in marine applications; and high temperature, as would be experienced in some processing steps and applications. Monitoring the resistance of the fibers at ambient laboratory conditions revealed that only the ferric chloride intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were stable for long periods under high vacuum. Ferric chloride, cupric chloride, and iodine monochloride intercalated fibers were sensitive to high humidity conditions. All intercalated fibers began to degrade above 250 C. The order of their thermal stability, from lowest to highest, was cupric chloride, iodine monochloride, bromine, and ferric chloride. Of the four types of intercalated fibers tested, the bromine intercalated fibers appear to have the most potential for application, based on environmental stability.
Ceramic environmental barrier coatings (EBC) and SiCSiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiCSiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, environmental durable environmental barrier coating systems. In this paper, the durability and performance of advanced Electron Beam-Physical Vapor Deposition (EB-PVD) NASA HfO2-Si and YbGdSi(O) EBC bond coat top coat systems for SiCSiC CMC have been summarized. The high temperature thermomechanical creep, fatigue and oxidation resistance have been investigated in the laboratory simulated high-heat-flux environmental test conditions. The advanced NASA EBC systems showed promise to achieve 1500C temperature capability, helping enable next generation turbine engines with significantly improved engine component temperature capability and durability.
The residual bromine graphite intercalation compounds of high modulus pitch-based fibers (Amoco P-55, P-75, P-100, and P-120) were formed and their resistances were monitored under a variety of environmental conditions. A threshold graphitization was observed below which the bromination reaction does not occur to an appreciable extent. The graphitization of the P-55 fibers falls below that threshold, precluding an extensive reaction. The P-75, P-100, and P-120 fibers all form bromination compounds which are stable at ambient conditions, under vacuum, and under high humidity (100 percent humidity at 60 C). The thermal stability of the resistivity increased with decreasing graphitization, with the stable temperature for P-120 being 100 C; for P-100, 200 C; and for P-75, 250 C. When cost is a consideration, bromination of pitch-based fibers is an economical way to achieve low resistivities.
During the past few years the Boeing Company was screening graphite composites for use in hot areas of engine nacelle structure. Structural and thermal analyses have shown that there is the potential for a 25 to 30 percent weight savings by using a graphite polyimide (Gr/PI) composite material in this type of structure. Work conducted on the NASA CASTS program (Composites for Advanced Space Transportation Systems) amply demonstrated the capability of Graphite/PMR-15 for short term service (125 hours) at temperatures up to 589 K (600 F). In addition, the CASTS program demonstrated that large structures could be fabricated using Gr/PMR-15. In commercial applications, however, the requirement exists for long term service capability (tens of thousands of hours) at temperatures ranging upwards from 449 K (350 F). The results of Graphite/PMR-15 materials characterization efforts conducted at Boeing are presented with emphasis on materials properties after isothermal aging at temperatures of 449 K (350 F) and above.
It was found that relatively small addition of Zn can improve the stress corrosion cracking (SCC) resistance of Al-Li alloys. However, the mechanism by which this is accomplished is unclear. The role that Zn plays in altering the behavior of Alloy 8090 is investigated. Early results suggest that Zn additions increase the volume fraction of delta(Al3Li) precipitation and differential scanning calorimetry (DSC) on these alloys confirms this. The four alloys studied each had initial compositions lying in the 8090 window and had varying amounts of Zn added to them. Alloy 8090, like other Al-Li alloys, displays a delta' precipitate free zone (PFZ) upon artificial aging along the grain and subgrain boundaries. However Zn additions greatly decreased or eliminated a delta' PFZ after 100 hours at 160 C. This implies that the subgrain boundary precipitation kinetics are being altered and suppressed. Furthermore, there appears to be a window of Zn concentration above which a delta ' PFZ can reappear with the nucleation and growth of a currently unidentified precipitate on the boundaries. Polarization experiments were performed and the results presented. The experiments were performed in deaerated 3.5 w/o NaCl in both as received (T3) condition and at peak aging of 100 hours at 160 C. The aging profile was determined via Vickers Hardness tests.
Stress corrosion cracking (SCC) remains a problem in both Al-Li and conventional Al heat treatable alloys. It has recently been found that relatively small additions (less than or approximately 1 wt-percent) of Zn can dramatically improve the SCC performance of alloy 8090 (Al-Li-Cu-Mg-Zr). Constant load time to failure experiments using cylindrical tensile samples loaded between 30 and 85 percent of TYS indicate improvements of orders of magnitude over the baseline 8090 for the Zn-containing alloys under certain aging conditions. However, the toughnesses of the alloys were noticeably degraded due to the formation of second phase particles which primarily reside on grain and subgrain boundaries. EDS revealed that these intermetallic particles were Cu and Zn rich. The particles were present in the T3 condition and were not found to be the result of quench rate, though their size and distribution were. At 5 hours at 160 C, the alloys displayed the greatest susceptibility to SCC but by 20 hours at 160 C the alloys demonstrated markedly improved TTF lifetimes. Aging past this time did not provide separable TTF results, however, the alloy toughnesses continued to worsen. Initial examination of the alloys microstructures at 5 and 20 hours indicated some changes most notably the S' and delta' distributions. A possible model by which this may occur will be explored. Polarization experiments indicated a change in the trend of E(sub BR) and passive current density at peak aging as compared to the baseline 8090. Initial pitting experiments indicated that the primary pitting mechanism in chloride environments is one occurring at constituent (Al-Fe-Cu) particles and that the Cu and Zn rich boundary precipitates posses a breakaway potential similar to that of the matrix acting neither anodic or cathodic in the first set of aerated 3.5 w/o NaCl experiments. Future work will focus on the identification of the second phase particles, evaluation of K(sub 1SCC) and plateau da/dt via both DCB and slow strain rate techniques. A lower Zn content variant will be examined in the near future in hopes of optimizing toughness, density and SCC performance.
The environmental stability and thermal gradient cyclic durability performance of SA Tyrannohex composites were investigated for turbine engine component applications. The work has been focused on investigating the combustion rig recession, cyclic thermal stress resistance and thermomechanical low cycle fatigue of uncoated and environmental barrier coated Tyrannohex SiC SA composites in simulated turbine engine combustion water vapor, thermal gradients, and mechanical loading conditions. Flexural strength degradations have been evaluated, and the upper limits of operating temperature conditions for the SA composite material systems are discussed based on the experimental results.
We developed an interferometric testbed to stabilize environmental motions over timescales of several hours and a lengthscale of 1m. Typically, thermal and seismic motions on the ground are larger than 1 micron over these scales, affecting the precision of more sensitive measurements. To suppress such motions, we built an active stabilization system composed of interferometric sensors, a hexapod actuator, and a frequency stabilized laser. With this stabilized testbed, environmental motions were suppressed down to nm level. This system will allow us to perform sensitive measurements, such as ground testing of LISA (Laser Interferometer Space Antenna), in the presence of environmental noise.
The development of 2700 degF capable environmental barrier coating (EBC) systems, particularly, the Rare Earth "Hafnium" Silicon bond coat systems, have significantly improved the temperature capability and environmental stability of SiC/SiC Ceramic Matrix Composite Systems. We have specifically developed the advanced 2700 degF EBC systems, integrating the EBC to the high temperature SA Tyrannohex SiC fiber composites, for comprehensive performance and durability evaluations for potential turbine engine airfoil component applications. The fundamental mechanical properties, environmental stability and thermal gradient cyclic durability performance of the EBC - SA Tyrannohex composites were investigated. The paper will particularly emphasize the high pressure combustion rig recession, cyclic thermal stress resistance and thermomechanical low cycle fatigue testing of uncoated and environmental barrier coated Tyrannohex SiC SA composites in these simulated turbine engine combustion water vapor, thermal gradients, and mechanical loading conditions. We have also investigated high heat flux and flexural fatigue degradation mechanisms, determined the upper limits of operating temperature conditions for the coated SA composite material systems in thermomechanical fatigue conditions. Recent progress has also been made by using the self-healing rare earth-silicon based EBCs, thus enhancing the SA composite hexagonal fiber columns bonding for improved thermomechanical and environmental durability in turbine engine operation environments. More advanced EBC- composite systems based on the new EBC-Fiber Interphases will also be discussed.
The design of ARCO Solar, Inc.'s Genesis G100 photovoltaic module was driven by several criteria, including environmental stability (both electrical and mechanical), consumer aesthetics, low materials costs, and manufacturing ease. The module circuitry is designed as a 12 volt battery charger, using monolithic patterning techniques on a glass superstrate. This patterning and interconnect method proves amenable to high volume, low cost production throughput, and the use of glass serves the dual role of handling ease and availability. The mechanical design of the module centers on environmental stability. Packaging of the glass superstrate circuit must provide good resistance to thermal and humidity exposure along with hi-pot insulation and hailstone impact resistance. The options considered are given. Ethylene vinyl acetate (EVA) is chosen as the pottant material for its excellent weatherability.
This presentation summarizes NASA's advanced thermal barrier and environmental barrier coating systems, and the coating performance improvements that has recently been achieved and documented in laboratory simulated rig test conditions. One of the emphases has been placed on the toughness and impact resistance enhancements of the low conductivity, defect cluster thermal barrier coating systems. The advances in the next generation environmental barrier coatings for SiCSiC ceramic matrix composites have also been highlighted, particularly in the design of a new series of oxide-silicate composition systems to be integrated with next generation SiC-SiC turbine engine components for 2700F coating applications. Major technical barriers in developing the thermal and environmental barrier coating systems are also described. The performance and model validations in the rig simulated turbine combustion, heat flux, steam and calcium-magnesium-aluminosilicate (CMAS) environments have helped the current progress in improved temperature capability, environmental stability, and long-term fatigue-environment system durability of the advanced thermal and environmental barrier coating systems.
The environmental stability of carbon fibre reinforced glass-matrix composites is assessed. Loss of composite strength due to oxidative exposure at elevated temperatures under no load, static load and cyclic fatigue as well as due to thermal cycling are all examined. It is determined that strength loss is gradual and predictable based on the oxidation of carbon fibres. The glass matrix was not found to prevent this degradation but simply to limit it to a gradual process progressing from the composite surfaces inward.
Guidelines for environmental habitability planning to facilitate individual and group stability
As a part of the Low Cost Solar Array Project an encapsulation task has been established to identify, develop, and evaluate new low-cost, long-life encapsulation systems capable of meeting the project cost and performance goals. Low-cost material system candidates have been identified and are being characterized in laboratory and field tests with detailed evaluation of their environmental stability when subjected to temperature cycling, humidity, ultraviolet radiation, dirt, and various other environmental hazards.
Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) systems will play a crucial role in future turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is a key to enable the applications of the envisioned CMC components to help achieve next generation engine performance and durability goals. This paper will primarily address the performance requirements and design considerations of environmental barrier coatings for turbine engine applications. The emphasis is placed on current candidate environmental barrier coating systems for SiCSiC CMCs, their performance benefits and design limitations in long-term operation and combustion environments. Major technical barriers in developing advanced environmental barrier coating systems, the coating integrations with next generation CMC turbine components having improved environmental stability, cyclic durability and system performance will be described. The development trends for turbine environmental barrier coating systems by utilizing improved compositions, state-of-the-art processing methods, and simulated environment testing and durability modeling will be discussed.
Over the past several years, our team at the NASA Goddard Space Flight Center (GSFC), in collaboration with the Jet Propulsion Laboratory (JPL) and the Naval Research Laboratory (NRL), have developed several new protected Al coating technologies with improved Far-Ultraviolet (FUV) reflectance performance and more robust environmental stability. These include Al protected with lithium-based fluoride (LiF) coatings such as hot deposited LiF (eLiF), XeF 2 -passivated LiF coatings (XeLiF), Li 3 AlF 6 overcoats, AlF 3 (plasma passivated), and XeF 2 passivated MgF 2 coatings (XeMgF 2 ). However, despite these developments, relatively little experimental information exists regarding the long-term stability of these coatings after simultaneous exposure to the Low Earth Orbit (LEO) environment. To evaluate their environmental durability and advance their Technology Readiness Level (TRL), representative samples of these coating technologies, Al+XeLiF, Al+eLiF, Al+Li 3 AlF 6 , Al+AlF 3 , Al+XeMgF 2 , and bare Al as reference samples, were flown onboard the International Space Station (ISS) as part of the Materials International Space Station Experiment 20 (MISSE-20). The MISSE platform is operated by Aegis Aerospace for relatively long-duration (e.g. 6 months) external exposure experiments in a space environment. The coatings were deposited on ULE and Zerodur substrates, and witness samples deposited on the same coatings runs, but on glass slides were left on Earth as control. A subset of the flight samples were fitted with MgF 2 windows to reduce direct exposure to atomic oxygen (AO) and charged particles, and still let through UV and other types of radiation on these samples. After approximately 6 months of exposure in the forward-facing (RAM) direction, the samples were returned to Earth and characterized by performing FUV/NUV/VIS/NIR reflectance measurements to quantify degradation, spectroscopic ellipsometry to evaluate coating thickness and optical constants, atomic force microscopy (AFM) to quantify surface roughness evolution during the flight in the ISS. The MgF 2 protective windows were also analyzed through FUV transmission measurements. Comparison with the witness samples left on the ground and with the flown bare Al samples (with just the naturally occurring Al 2 O 3 layer) provided a quantitative assessment of coating thickness variations, optical performance degradation, and morphological changes induced by prolonged exposure to the LEO environment.