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DOE OSTI2021

Development of Corrosion- and Erosion-Resistant Coatings for Advanced Ultra-Supercritical Materials

This final report summarized the research efforts and major findings of the Phase I Project “Development of Corrosion- and Erosion-Resistant Coatings for Advanced Ultra-Supercritical Materials”, for the period of October 1, 2019 – Sept. 30, 2021. This project is a collaborative endeavor between Tennessee Tech University, Purdue University, Oak Ridge National Laboratory, Siemens Corporation, and Eastern Plating, LLC, aiming at improving the durability and lifetime of high-pressure (HP) steam turbine blades in advanced ultra-supercritical (A-USC) coal-fired power plants through the development of corrosion/erosion-resistant coatings manufactured via a low-cost electrolytic codeposition process. While Tribaloy alloy T-400C was identified by the U.S. A-USC Materials Consortium as a promising coating composition, further composition optimization is needed to enhance its corrosion and erosion resistance for protecting the A-USC Ni-base turbine components. An integrated computational and experimental approach was employed to optimize coating composition/microstructure and processing parameters. In order to identify candidate coating compositions that could offer balanced properties, thermodynamic calculations were performed to explore the γ+Laves composition space in the Co-Ni-Cr-Mo-Si system with different alloying additions at 600-800 °C. Guided by the calculation results, experimental assessment of selected alloys led to the development of a new generation of Tribaloy compositions with the optimal levels of Cr, Mo and Si, reactive element (e.g., 0.4-0.6 wt.% Y) and other alloying additions. The low-cost and non-line-of-sight electro-codeposition process was employed to deposit a Ni(Co)-CrMoSiY composite coating on commercial Haynes 282 (H282) Ni-base alloy. A diffusion treatment was subsequently applied to convert the composite to the Tribaloy-type coating. Both the codeposition parameters and heat treatment conditions were varied to achieve the desired coating composition, microstructure and phase constituents. In addition, since additive manufacturing (AM) may be an alternative cost-saving option for potential A-USC turbine repair, laser direct deposition was explored to fabricate the H282 alloy with minimal defects. The electro-codeposited Tribaloy coating was also applied to the AM H282 substrate to demonstrate the viability of the coating process in improving the surface finish of AM alloys. Both high-temperature oxidation performance and solid particle erosion (SPE) resistance of model alloys and electro-codeposited coatings were evaluated. About 25 model alloys with various Cr/Mo ratios and reactive element levels, as well as partial substitution of Mo with Nb were evaluated with regard to their oxidation resistance in both air and pure steam at 760-800°C. Compositions based on Ni(Co)-20Cr-18Mo-2.6Si-0.6Y (wt.%) showed significantly improved oxidation resistance over the baseline T400-C. Based on the alloy development results, three generations of new Tribaloy coatings (Gen-1, Gen-2, and Gen-3) with various Mo/Cr contents and Y levels were prepared via electro-codeposition and their microstructure/performance were evaluated. Outstanding air and steam oxidation resistance was achieved for the Gen-2 and Gen-3 coatings. Furthermore, while the SPE resistance of the coatings depended on many factors such as temperature, environment, erodent, velocity and impact angle, the coated samples exhibited similar or better SPE resistance compared to the H282 substrate when magnetite was used as erodent (which is a realistic erodent in A-USC steam turbines). The new Tribaloy coatings also had good long-term compatibility with the H282 alloy substrate. The two large-sized rotating barrels were designed, constructed, and employed to coat dummy HP blades. Uniform coating thickness and microstructure were achieved at various blade locations. Also, a preliminary techno-economic analysis of the proposed coating process was conducted to quantify the cost-effectiveness and to assess the commercial viability of the corrosion- and erosion-resistant coatings. It is estimated that a cost reduction of ~30% could be achieved with the electro-codeposition coating process over the state-of-the-art high velocity oxygen fuel (HVOF) thermal spray. Compared to the leading Tribaloy coating technologies such as HVOF and plasma transfer alloying, electro-codeposition based process has advantages such as low-cost process equipment, uniform deposition even for complex shapes, low levels of contaminants/porosities, reduction of powder waste, and potentially better surface finish and longer turbine service life. The Phase 1 study has demonstrated that it is feasible to develop an electro-codeposited Tribaloy coating with balanced corrosion and erosion properties, even though additional research efforts such as further coating process scale-up and longer-term performance evaluation under realistic A-USC conditions are clearly needed.

20 FOSSIL-FUELED POWER PLANTS↗

NASA NTRS1980

Plasma Spray System

Computer aided, fully-automatic TRW system sprays very hot plasma onto a turbine blade. Composed of gas into which metallic and ceramic powders have been injected, the plasma forms a two-layer coating which insulates the blade. Critical part of operation is controlling the thickness of the deposit which is measured in thousandths of an inch. This is accomplished by an optical detector which illuminates spots at various locations on the blade and determines thickness by measuring the light reflections. Optical sensor monitors spraying process until precise thickness is attained, then computer halts the spraying.

Source record↗

NASA NTRS1978

Predicted inlet gas temperatures for tungsten fiber reinforced superalloy turbine blades

A procedure is presented for predicting the magnitude of the turbine inlet gas temperatures potentially achievable using first generation tungsten fiber reinforced superalloys (TFRS) turbine blades. Both uncoated blades and blades with thermal barrier coatings are considered. The thermal conductivities of two representative TFRS were measured over a range of temperatures. The results show that cooled TFRS blades may allow significantly higher gas temperatures than are possible with superalloy blades. For one design, the difference is about 150-200 K.

Winsa, E. A.↗

NASA NTRS1986

A study on thermal barrier coatings including thermal expansion mismatch and bond coat oxidation

The present investigation deals with a plasma-sprayed thermal barrier coating (TBC) intended for high temperature applications to advanced gas turbine blades. Typically, this type of coating system consists of a zirconia-yttria ceramic layer with a nickel-chromium-aluminum bond coat on a superalloy substrate. The problem on hand is a complex one due to the fact that bond coat oxidation and thermal mismatch occur in the TBC. Cracking in the TBC has also been experimentally illustrated. A clearer understanding of the mechanical behavior of the TBC is investigated. The stress states in a model thermal barrier coating as it cools down in air is studied. The powerful finite element method was utilized to model a coating cylindrical specimen. Four successively refined finite element models were developed. Some results obtained using the first two models have been reported previously. The major accomplishment is the successful development of an elastic TBC finite element model known as TBCG with interface geometry between the ceramic layer and the bond coat. An equally important milestone is the near-completion of the new elastic-plastic TBC finite element model called TBCGEP which yielded initial results. Representative results are presented.

Chang, George C.↗

NASA NTRS2011

Programmable Aperture with MEMS Microshutter Arrays

A microshutter array (MSA) has been developed for use as an aperture array for multi-object selections in James Webb Space Telescope (JWST) technology. Light shields, molybdenum nitride (MoN) coating on shutters, and aluminum/aluminum oxide coatings on interior walls are put on each shutter for light leak prevention, and to enhance optical contrast. Individual shutters are patterned with a torsion flexure that permits shutters to open 90 deg. with a minimized mechanical stress concentration. The shutters are actuated magnetically, latched, and addressed electrostatically. Also, micromechanical features are tailored onto individual shutters to prevent stiction. An individual shutter consists of a torsion hinge, a shutter blade, a front electrode that is coated on the shutter blade, a backside electrode that is coated on the interior walls, and a magnetic cobalt-iron coating. The magnetic coating is patterned into stripes on microshutters so that shutters can respond to an external magnetic field for the magnetic actuation. A set of column electrodes is placed on top of shutters, and a set of row electrodes on sidewalls is underneath the shutters so that they can be electrostatically latched open. A linear permanent magnet is aligned with the shutter rows and is positioned above a flipped upside-down array, and sweeps across the array in a direction parallel to shutter columns. As the magnet sweeps across the array, sequential rows of shutters are rotated from their natural horizontal orientation to a vertical open position, where they approach vertical electrodes on the sidewalls. When the electrodes are biased with a sufficient electrostatic force to overcome the mechanical restoring force of torsion bars, shutters remain latched to vertical electrodes in their open state. When the bias is removed, or is insufficient, the shutters return to their horizontal, closed positions. To release a shutter, both the electrode on the shutter and the one on the back wall where the shutter sits are grounded. The shutters with one or both ungrounded electrodes are held open. Sub-micron bumps underneath light shields and silicon ribs on back walls are the two features to prevent stiction. These features ensure that the microshutter array functions properly in mechanical motions. The MSA technology can be used primarily in multi-object imaging and spectroscopy, photomask generation, light switches, and in the stepper equipment used to make integrated circuits and MEMS (microelectromechanical systems) devices.

Moseley, Samuel↗

NASA NTRS1988

Durability of thermal barrier coatings in a high heat flux environment

Thermal shock is a significant factor in the limited service life of Space Shuttle Main Engine (SSME) high pressure, fuel turbopump (HPFTP) turbine blades. Addition of advanced thermal barrier coatings (TBCs) to the blades could serve to dampen the thermal shock, thereby increasing the life of the blades. However, testing and use of TBCs to date is performed primarily under moderate heat flux conditions which are typical of aircraft turbines. Only limited testing was conducted that addresses high heat flux and severe thermal shock conditions. Therefore, it is not clear if TBCs can survive severe thermal shocks or provide adequate thermal shock protection to the HPFTP turbine blades. The purpose is to experimentally evaluate the potential durability and protective capability of a variety of advanced TBCs in a cyclic thermal shock environment. A secondary goal is to identify significant parameters affecting TBC life during high heat flux testing. Parameters investigated include top coat thickness, bond coat thickness, substrate type, and substrate geometry.

Brindley, William J.↗

NASA NTRS1985

Top-Coating Silicon Onto Ceramic

Polycrystalline silicon for solar cells produced at low cost. Molten silicon poured from quartz trough onto moving carbon-coated ceramic substrate. Doctor blade spreads liquid silicon evenly over substrate. Molten material solidifies to form sheet of polycrystalline silicon having photovoltaic conversion efficiency greater than 10 percent. Method produces 100-um-thick silicon coatings at speed 0.15 centimeter per second.

Heaps, J. D.↗

NASA NTRS2007

Multistage Passive Cooler for Spaceborne Instruments

A document describes a three-stage passive radiative cooler for a cryogenic spectrometer to be launched into a low orbit around the Moon. This cooler is relatively lightweight and compact, and its basic design is scalable and otherwise adaptable to other applications in which there are requirements for cooling instrumentation in orbit about planets. The cooler includes multiple lightweight flat radiator blades alternating with cylindrical parabolic infrared reflectors. The radiator blades are oriented at an angle chosen to prevent infrared loading from the Moon limb at the intended orbital altitude and attitude. The reflectors are shaped and oriented to position their foci outside the radiator surfaces. There are six radiator-blade/reflector pairs - two pairs for each stage of cooling. The radiator blades and reflectors are coated on their front and back surfaces with materials having various infrared emissivities, infrared reflectivities, and solar reflectivities so as to maximize infrared radiation to cold outer space and minimize inadvertent solar heating. The radiator blades and reflectors are held in place by a lightweight support structure, the components of which are designed to satisfy a complex combination of thermal and mechanical requirements.

Rodriquez, Jose I.↗

NASA NTRS1978

A computer program for full-coverage film-cooled blading analysis including the effects of a thermal barrier coating

The program input, coolant flow and heat transfer model, and the program output are discussed. As an example, sections of the suction and pressure sides of a high temperature, high pressure turbine vane are analyzed to show the effects of a thermal barrier coating. Compared to the uncoated design, the coating halves the required coolant flow, while simultaneously reducing metal outer temperatures by over 111 K.

Source record↗

DOE OSTI2024

Micro–macro finite element modeling method for rub response in abradable coating materials

Gas turbine engines experience “rub” when the rotating blades come in contact with a static abradable coating. This results in extreme strain rates and dynamics inside a high-temperature/high-pressure environment. Current rub models are phenomenological and do not reflect the underlying microstructures, thus limiting their prediction accuracy. In this work, a microstructure-informed, reduced order modeling framework is introduced for simulating abradable coating “rub" behavior. This framework comprises a microscale model constructed based on digitized abradable microstructure and explicitly simulates the mechanical behavior of each constituent phases and their interactions. After calibration and validation with experiment data, the calibrated microscale model is used to generate data across a vast range of applied strain rates and temperature with various load paths. Then, the virtually generated data are used to fit the macroscopic-reduced order model, which enables fast component scale rub simulation without compromising the integrity of the complex material behavior. In conclusion, the proposed effort will address the technical challenge of predicting abradable material behavior during rub through the application of multiscale modeling from microstructure to engines behavior, effectively reducing the development costs and time of new abradable material for better “rub” properties.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Rare-earth doped thermal barrier coating bond coat for thermally grown oxide luminescence sensing

A thermal barrier coated component, such as a turbine blade formed from a superalloy substrate, includes a thermal barrier coating applied onto the substrate. A metallic bond coat layer is on the substrate and includes rare-earth luminescent dopants. A ceramic top coat layer is on the bond coat layer. A temperature sensing thermally grown oxide (TGO) layer is formed at the interface of the bond coat layer and ceramic top coat layer. The temperature sensing TGO layer includes grown rare-earth luminescent ions migrated from the metallic bond coat layer in an amount sufficient to enable luminescence sensing of the TGO layer for real-time phosphor thermometry temperature measurements at the TGO layer.

Fouliard, Quentin↗

DOE OSTI2023

Method for forming a temperature sensing layer within a thermal barrier coating

Fouliard, Quentin↗

DOE OSTI2022

Thermally Grown Oxide Stress in PS-PVD and EB-PVD Thermal Barrier Coatings Observed at Various Lifetimes Via Synchrotron X-ray Diffraction

The current standard application method for thermal barrier coatings (TBCs) on turbine blades for jet engines is electron-beam physical vapor deposition (EB-PVD) due to its high strain tolerance and low thermal conductivity. An emerging deposition method, plasma-spray physical vapor deposition (PS-PVD), presents an opportunity for a tailorable microstructure, and non-line-of-sight deposition that is faster and less expensive. To compare the lifetime behavior of both PS-PVD and EB-PVD coatings, samples subjected to 300 and 600 thermal cycles were measured during a 1 h thermal cycle to determine the strains, which were converted to stress, in the thermally grown oxide (TGO) layer of the TBCs using synchrotron X-ray diffraction (XRD). Room temperature XRD measurements indicated among samples that PS-PVD coatings experienced greater variation in in-plane room temperature strain in the TGO after cycling than the EB-PVD coatings. In-situ XRD measurements indicated similar high-temperature strain and no spallation after 600 thermal cycles for both coatings. Further, microscopy imaging after cycling showed greater rumpling in PS-PVD coatings that led to different failure modes between the two coatings’ TGO layers. The tailorability of PS-PVD coatings allows for adjustments in the processing parameters to improve their overall performance after aging and bridge the differences between the two deposition methods.

36 MATERIALS SCIENCE↗

NASA NTRS2009

Environmental Barrier Coatings for Turbine Engines: A Design and Performance Perspective

Ceramic thermal and environmental barrier coatings (TEBC) for SiC-based ceramics will play an increasingly important role in future gas turbine engines because of their ability to effectively protect the engine components and further raise engine temperatures. However, the coating long-term durability remains a major concern with the ever-increasing temperature, strength and stability requirements in engine high heat-flux combustion environments, especially for highly-loaded rotating turbine components. Advanced TEBC systems, including nano-composite based HfO2-aluminosilicate and rare earth silicate coatings are being developed and tested for higher temperature capable SiC/SiC ceramic matrix composite (CMC) turbine blade applications. This paper will emphasize coating composite and multilayer design approach and the resulting performance and durability in simulated engine high heat-flux, high stress and high pressure combustion environments. The advances in the environmental barrier coating development showed promise for future rotating CMC blade applications.

Zhu, Dongming↗

NASA NTRS2002

Techniques Optimized for Reducing Instabilities in Advanced Nickel-Base Superalloys for Turbine Blades

The High-Speed Research (HSR) Airfoil Alloy program developed fourth-generation single-crystal superalloys with up to an 85 F increase in creep rupture capability over current production airfoil alloys. Recent results have been generated at the NASA Glenn Research Center on these fourth-generation alloys, but in coated form, for subsonic turbine blade applications under NASA's Ultra-Efficient Engine Technology (UEET) Program. One goal for UEET is to optimize the airfoil alloy/thermal barrier coating system for 3100 F turbine inlet temperatures. The state-of-the art turbine blade airfoil system consists of a superalloy single crystal that provides the basic mechanical performance of the airfoil. A thermal barrier coating is used to reduce the temperature of the base superalloy, and a bondcoat is deposited between the base material and the thermal barrier coating. The bondcoat improves the oxidation and corrosion resistance of the base superalloy and improves the spallation resistance of the thermal barrier coating. A commercial platinum aluminide bondcoat was applied to the HSR-developed alloys, and a diffusion zone developed as a result of interaction between the bondcoat and the superalloy. Optimized strength is obtained for superalloys when the refractory element content is high and the limits of microstructural stability are approached or exceeded slightly. For fourthgeneration alloys, instability leads to the formation of topologically close packed (TCP) phases, which form internally in the superalloy, and a secondary reaction zone (SRZ), which forms under the diffusion zone. There was a concern that excessive quantities of either TCP or SRZ might decrease the mechanical properties of the superalloy, with SRZ thought to be particularly detrimental and its formation unpredictable. Thus, an SRZreduction effort was initiated in the NASA UEET Program so that methods developed during the HSR project could be optimized further to reduce or eliminate the SRZ. An SRZ is a three-phase constituent composed of TCP and stringers of gamma phase in a matrix of gamma prime. An incoherent grain boundary separates the SRZ from the gammagamma prime microstructure of the superalloy. The SRZ is believed to form as a result of local chemistry changes in the superalloy due to the application of the diffusion aluminide bondcoat. Locally high surface stresses also appear to promote the formation of the SRZ. Thus, techniques that change the local alloy chemistry or reduce surface stresses have been examined for their effectiveness in reducing SRZ. These SRZ-reduction steps are performed on the test specimen or the turbine blade before the bondcoat is applied. Stressrelief heat treatments developed at NASA Glenn have been demonstrated to reduce significantly the amount of SRZ that develops during subsequent high-temperature exposures. Stress-relief heat treatments reduce surface stresses by recrystallizing a thin surface layer of the superalloy. However, in alloys with very high propensities to form SRZ, stress relief heat treatments alone do not eliminate SRZ entirely. Thus, techniques that modify the local chemistry under the bondcoat have been emphasized and optimized successfully at Glenn. One such technique is carburization, which changes the local chemistry by forming submicron carbides near the surface of the superalloy. Detailed characterizations have demonstrated that the depth and uniform distribution of these carbides are enhanced when a stress relief treatment and an appropriate surface preparation are employed in advance of the carburization treatment. Even in alloys that have the propensity to develop a continuous SRZ layer beneath the diffusion zone, the SRZ has been completely eliminated or reduced to low, manageable levels when this combination of techniques is utilized. Now that the techniques to mitigate SRZ have been established at Glenn, TCP phase formation is being emphasized in ongoing work under the UEET Program. The limitsf stability of the fourth-generation alloys with respect to TCP phase formation are currently being defined along with high-temperature creep rupture properties. In addition, a regression model is being developed at Glenn for the prediction of the presence of TCP phase in the microstructure and SRZ under the diffusion zone. The model is based on a design-of-experiments methodology with emphasis on the potential synergistic effects of alloying elements.

MacKay, Rebecca A.↗

DOE OSTI2022

Modeling deformation and failure in AlSi-polyester abradable sealcoating material using microstructure-based finite element simulation

A plasma-sprayed aluminum-silicon (AlSi)/polyester coating is applied in modern gas turbine engines as an abradable sealcoating to maintain tight clearances between the rotating blades and the static casing. While running the engine, the rotating blades “rub” with the abradable coating, which results in extreme strain rate (up to 10 6 ) dynamics and a high-temperature environment. Due to the difficulty of collecting direct measurements, predictive computational models are important for analyzing the deformation and failure of the abradable material, to help meet the design target of avoiding damage to the blade tip and maintaining high fuel efficiency. In this research, a microstructure-based finite element (FE) computational model was developed to capture the complex mechanical behavior of the AlSi/polyester microstructure. The model is based on a virtual representative-volume-element (RVE) of a metal-polymer microstructure, reconstructed from x-ray computed tomography. It models the plastic deformation of, and damage to, each AlSi and polyester constituents, as well as the failure at their interface. The model was calibrated and validated with uniaxial tension and compression experiments, conducted at two temperatures (298 K and 533 K) at an applied strain rate of 10 3 - 10 4 s -1 . The material exhibited strongly asymmetric tension-compression behavior and a sensitivity to temperature, which was well captured by the model. The model was further applied to investigate changes in mechanical behavior due to variations in constituents’ volume fractions, which provides guidance to the microstructural design of AlSi/polyester abradable materials. The model is expected to facilitate the development of improved abradable materials by bypassing the conventional trial-and-error approach and extensive testing requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1984

Overlay metallic-cermet alloy coating systems

A substrate, such as a turbine blade, vane, or the like, which is subjected to high temperature use is coated with a base coating of an oxide dispersed, metallic alloy (cermet). A top coating of an oxidation, hot corrosion, erosion resistant alloy of nickel, cobalt, or iron is then deposited on the base coating. A heat treatment is used to improve the bonding. The base coating serves as an inhibitor to interdiffusion between the protective top coating and the substrate. Otherwise, the protective top coating would rapidly interact detrimentally with the substrate and degrade by spalling of the protective oxides formed on the outer surface at elevated temperatures.

Gedwill, M. A.↗

NASA NTRS1981

Improving turbine engine compressor performance retention through airfoil coatings

In order to evaluate the potential effectiveness of coatings in limiting erosive damage to compressor airfoils, an effort was initiated to evaluate candidate coatings for substrate alloys typically used in commercial engine high compressor blades. Laboratory and rig erosion testing of plasma deposited and diffusion coatings described in this paper have shown the potential of a two to four fold improvement in erosion life. The selective application of these coatings to approximately the outer third of the airfoil avoids coating the fatigue critical region of the blade, thus providing erosion resistance potentially without compromising the fatigue strength of the blade. Both the plasma and the diffusion coatings also offer the advantage of low initial cost and a multi-source production base.

Friedrich, L. A.↗