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An Overview of 2014 SBIR Phase I and Phase II Materials Structures for Extreme Environments

NASA's Small Business Innovation Research (SBIR) program focuses on technological innovation by investing in development of innovative concepts and technologies to help NASA mission directorates address critical research needs for Agency programs. This report highlights nine of the innovative SBIR 2014 Phase I and Phase II projects that emphasize one of NASA Glenn Research Center's six core competencies-Materials and Structures for Extreme Environments. The technologies cover a wide spectrum of applications such as high temperature environmental barrier coating systems, deployable space structures, solid oxide fuel cells, and self-lubricating hard coatings for extreme temperatures. Each featured technology describes an innovation, technical objective, and highlights NASA commercial and industrial applications. This report provides an opportunity for NASA engineers, researchers, and program managers to learn how NASA SBIR technologies could help their programs and projects, and lead to collaborations and partnerships between the small SBIR companies and NASA that would benefit both.

barrier coating system; deployable space structure↗

Internal coating of air cooled gas turbine blades

Six coating systems were evaluated for internal coating of decent stage (DS) eutectic high pressure turbine blades. Sequential deposition of electroless Ni by the hydrazine process, slurry Cr, and slurry Al, followed by heat treatment provided the coating composition and thickness for internal coating of DS eutectic turbine blades. Both NiCr and NiCrAl coating compositions were evaluated for strain capability and ductile to brittle transition temperature.

Ahuja, P. L.↗

Performance of two-layer thermal barrier systems on directionally solidified Ni-Al-Mo and comparative effects of alloy thermal expansion on system life

A promising two-layer thermal barrier coating system (TBS), Ni-16.4Cr-5.1A1-0.15Y/ZrO2-6.1Y2O3 (all in weight percent), was identified for directionally solidified Ni-Al-Mo (gamma/gamma' alpha). In cyclic furnace tests at 1095 C this system on gamma/gamma' alpha was better than Ni-16. 4Cr-5.1Al-0.15Y/ZrO2-7.8Y2O3 by about 50 percent. In natural gas - oxygen torch rig tests at 1250 C the ZrO2-6.1Y2O3 coating was better than the ZrO2-7.8Y2O3 coating by 95 percent, on MAR-M509 substrates and by 60 percent on gamma/gamma' alpha substrates. Decreasing the coefficient of thermal expansion of the substrate material from 17-18x10 to the -6 power/C (MAR-M200 + Hf and MAR-M509) to 11x10 to the -6 power/C (gamma/gamma' alpha) also resulted in improved TBS life. For example, in natural gas - oxygen torch rig tests at 1250 C, the life of Ni-16.4Cr-5.1Al-0.15Y/ZrO26.1Y2O3 was about 30 percent better on gamma/gamma' alpha than on MAR-M509 substrates. Thus compositional changes in the bond and thermal barrier coatings were shown to have a greater effect on TBS life than does the coefficient of thermal expansion.

Stecura, S.↗

Thermal and Environmental Barrier Coatings for Advanced Propulsion Engine Systems

Ceramic thermal and environmental barrier coatings (TEBCs) are used in gas turbine engines to protect engine hot-section components in the harsh combustion environments, and extend component lifetimes. For future high performance engines, the development of advanced ceramic barrier coating systems will allow these coatings to be used to simultaneously increase engine operating temperature and reduce cooling requirements, thereby leading to significant improvements in engine power density and efficiency. In order to meet future engine performance and reliability requirements, the coating systems must be designed with increased high temperature stability, lower thermal conductivity, and improved thermal stress and erosion resistance. In this paper, ceramic coating design and testing considerations will be described for high temperature and high-heat-flux engine applications in hot corrosion and oxidation, erosion, and combustion water vapor environments. Further coating performance and life improvements will be expected by utilizing advanced coating architecture design, composition optimization, and improved processing techniques, in conjunction with modeling and design tools.

Zhu, Dong-Ming↗

Development of an improved coating for polybenzimidazole foam

An improved coating system was developed for Polybenzimidazole (PBI) foam to provide coating stability, ruggedness, moisture resistance, and to satisfy optical property requirements (alpha sub (s/epsilon) or = 0.4 and epsilon 0.8) for the space shuttle. The effort was performed in five tasks: Task 1 to establish material and process specifications for the PBI foam, and material specifications for the coatings; Task 2 to identify and evaluate promising coatings; Task 3 to establish mechanical and thermophysical properties of the tile components; Task 4 to determine by systems analysis the potential weight trade-offs associated with a coated PBI TPS; and Task 5 to establish a preliminary quality assurance program. The coated PBI tile was, through screening tests, determined to satisfy the design objectives with a reduced system weight over the baseline shuttle silica LRSI TPS. The developed tile provides a thermally stable, extremely rugged, low thermal conductivity insulator with a well characterized optical coating.

Neuner, G. J.↗

Segmented Thermal Barrier Coating

An article coated with a thermal barrier coating system, and method for preparation of a coated article. The article has a macro-segmented thermal barrier coating due to the presence of a pattern of three-dimensional features. The features may be a series of raised ribs formed on the substrate surface and being spaced from 0.05 inches to 0.30 apart. The ribs have a width W ranging from 0.005 inches to 0.02 inches, and a height R ranging from 25% to 100% of the thickness of the barrier coating. Alternately, the features may be a similar pattern of grooves formed in the surface of the substrate. Other embodiments provide segmentation by grooves or ribs in the bond coat or alternately grooves formed in the thermal barrier layer.

James L Smialek↗

Fatigue Behavior of Coated Titanium Alloys

Advanced multi-component TiAlCrTaSiN-based multilayered coatings were developed and processed onto Ti-6Al-4V (Ti-6-4) and GammaMet PX (GMPX or TiAl) alloys by a magnetron-enhanced physical vapor deposition technique. The coatings have recently been in development with the goal of improving advanced titanium alloy, turbine engine component durability and oxidation-erosion resistance. In this work, the performance of the multi-component coating system (including the outer layer nitride based coating and inner TiAlCrSi oxidation barrier bond coat) was studied, and the coating's influence on the fatigue behavior of the titanium-based alloys were compared. Although the multi-component coating was initially optimized to improve the coating's high temperature oxidation and erosion resistance, the lower ductility nitride-based coating needs further work on microstructure or composition to improve its mechanical stress resistance and strain tolerance for use in cyclically loaded, turbine blade operating conditions. This is particularly true for GMPX and other γ-TiAl alloys because these intermetallic titanium alloys have limited ductility and are very sensitive to defects such as coating cracks. However, the inner layer TiAlCrSi-coating had better adhesion and ductility, and may be a suitable choice to improve the oxidation resistance of titanium alloys.

Oxidation Barrier Coatings↗

Durability of YSZ coated Ti2AlC in 1300°C high velocity burner rig tests

A thermal barrier coating system survived 500 h in cyclic burner rig tests at 1300°C, exceeding the life of all previous systems. An yttria stabilized zirconia (7YSZ) thermal barrier coating (TBC) was plasma sprayed on the oxidation resistant Ti2AlC MAX phase and tested in a jet fuel burner. No coating spallation or recession was observed, only a 2.4 mg/sq.cm mass gain due to typical cubic Al2O3 oxidation kinetics. The modest weight gain contrasted with large TBC spallation or oxide volatility losses that might occur under cyclic, high velocity (~100 m/s) burner conditions. The coating surface exhibited colonies of [111]flourite fiber-textured columns separated by craze crack patterns, but with no visible moisture attack. The thickness of the alumina scale under the YSZ face was >20 μm, more than twice that formed on TBC/superalloy systems at failure. TiO2 nodules, initially formed on the uncoated backside, were then removed as volatile hydroxides formed in high temperature, high velocity water vapor (~10%). Overall, the test indicated the exceptional stability of the YSZ/Ti2AlC system under turbine conditions, due in large part to good thermal expansion matching.

alumina, MAX phases, thermal barrier coatings (TBC↗

Development of polymeric coatings for control of electro-osmotic flow in ASTP MA-011 electrophoresis technology experiment

The development of a methyl cellulose based coating system for control of electro-osmotic flow at the walls of electrophoresis cells is described. Flight electrophoresis columns were coated with this system, resulting in a flight set of six columns. In flight photography of MA-011 electrophoretic separations verified control of electro-osmotic flow.

Patterson, W. J.↗

Two-layer thermal barrier coating for high temperature components

A simple two-layer plasma-sprayed thermal barrier coating system was developed which has the potential for protecting high temperature air-cooled gas turbine components. Of the initially examined coatings, the most promising system is an Ni-16Cr-6Al-0.6Y (in wt%) bond coating (about 0.005 to 0.010 cm thick) and a ZrO2-12Y2O3 (in wt%) thermal barrier coating (about 0.025 to 0.064 cm thick). This thermal barrier substantially lowered the metal temperature of the air-cooled airfoil. The coating withstood 3200 cycles (80 s at 1280 C surface temperature) and 275 cycles (1 hr at 1490 C surface temperature) without cracking or spalling. No separation of the thermal barrier from the bond coating or the bond coating from the substrate was observed.

Stecura, S.↗

Abradable dual-density ceramic turbine seal system

A plasma sprayed dual density ceramic abradable seal system for direct application to the HPT seal shroud of small gas turbine engines. The system concept is based on the thermal barrier coating and depends upon an additional layer of modified density ceramic material adjacent to the gas flow path to provide the desired abradability. This is achieved by codeposition of inert fillers with yttria stabilized zirconia (YSZ) to interrupt the continuity of the zirconia struture. The investigation of a variety of candidate fillers, with hardness values as low as 2 on Moh's scale, led to the conclusion that solid filler materials in combination with a YSZ matrix, regardless of their hardness values, have a propensity for compacting rather than shearing as originally expected. The observed compaction is accompanied by high energy dissipation in the rub interaction, usually resulting in the adhesive transfer of blade material to the stationary seal member. Two YSZ based coating systems which incorported hollow alumino silicate spheres as density reducing agents were surveyed over the entire range of compositions from 100 percent filler to 100 percent YSZ. Abradability and erosion characteristics were determined, hardness and permeability characterized, and engine experience acquired with several system configurations.

Clingman, D. L.↗

Thermal Conductivity of EB-PVD Thermal Barrier Coatings Evaluated by a Steady-State Laser Heat Flux Technique

The thermal conductivity of electron beam-physical vapor deposited (EB-PVD) Zr02-8wt%Y2O3 thermal barrier coatings was determined by a steady-state heat flux laser technique. Thermal conductivity change kinetics of the EB-PVD ceramic coatings were also obtained in real time, at high temperatures, under the laser high heat flux, long term test conditions. The thermal conductivity increase due to micro-pore sintering and the decrease due to coating micro-delaminations in the EB-PVD coatings were evaluated for grooved and non-grooved EB-PVD coating systems under isothermal and thermal cycling conditions. The coating failure modes under the high heat flux test conditions were also investigated. The test technique provides a viable means for obtaining coating thermal conductivity data for use in design, development, and life prediction for engine applications.

Zhu, Dongming↗

Thermal barrier coating life prediction model development

This report describes work performed to determine the predominat modes of degradation of a plasma sprayed thermal barrier coating system and to develop and verify life prediction models accounting for these degradation modes. The primary TBC system consisted of a low pressure plasma sprayed NiCrAlY bond coat, an air plasma sprayed ZrO2-Y2O3 top coat, and a Rene' 80 substrate. The work was divided into 3 technical tasks. The primary failure mode to be addressed was loss of the zirconia layer through spalling. Experiments showed that oxidation of the bond coat is a significant contributor to coating failure. It was evident from the test results that the species of oxide scale initially formed on the bond coat plays a role in coating degradation and failure. It was also shown that elevated temperature creep of the bond coat plays a role in coating failure. An empirical model was developed for predicting the test life of specimens with selected coating, specimen, and test condition variations. In the second task, a coating life prediction model was developed based on the data from Task 1 experiments, results from thermomechanical experiments performed as part of Task 2, and finite element analyses of the TBC system during thermal cycles. The third and final task attempted to verify the validity of the model developed in Task 2. This was done by using the model to predict the test lives of several coating variations and specimen geometries, then comparing these predicted lives to experimentally determined test lives. It was found that the model correctly predicts trends, but that additional refinement is needed to accurately predict coating life.

Hillery, R. V.↗

History of the Development of Liquid-Applied Coatings for Protection of Reinforced Concrete

Corrosion of reinforcing steel in concrete is an insidious problem for structures at Kennedy Space Center (KSC). KSC is located on the coast of Florida in a highly corrosive atmosphere. Launch pads, highway bridge infrastructure, and buildings are strongly affected. To mitigate these problems, NASA initiated a development program for a Galvanic Liquid-Applied Coating System (GLACS). A breakthrough in this area would have great commercial value in transportation, marine and construction industry infrastructures. The patented NASA GLACS system has undergone considerable testing to meet the needs of commercialization. A moisture-cure coating gives excellent adhesion with ease of application compared to existing galvanic products on the market. The latest development, GalvaCori; can be sprayed or hand applied to almost any structure shape. A self-adhesive conductive tape system has been devised to simplify current collection within the coating areas. In testing programs, millivolt potential and milliamp output per square foot of anode have been closely studied at actual test sites. These two parameters are probably the most challenging items of a resin-based, room-temperature-applied, galvanic coating. Extensive re-formulation has resulted in a system that provides the needed polarization for catholic protection of reinforcing steel in concrete in a variety of structure environments. The rate of corrosion of rebar in concrete is greatly affected by the environment of the structure. In addition to this, for any given concrete structure; moisture level, carbonization, and chloride contamination influences the rate of rebar corrosion. Similarly, the cathodic protection level of galvanic systems is also dependent on the moisture level of the concrete. GalvaCorr is formulated to maintain galvanic activity as the moisture level of the structure declines. GalvaCorr is available as a three-part kit. The mixing step requires about ten minutes. The viscosity can be easily adjusted to meet the application needs. The pot or working life is four to six hours, depending on the temperature. GalvaCorr can be thought of as a spray-on coating, battery ready to provide up to -1.4 volts (relative to CSE) of cathodic protection (CP) potential.

Curran, Joseph J.↗

Two-layer thermal barrier coating for turbine airfoils - furnace and burner rig test results

A simple, two-layer plasma-sprayed thermal barrier coating system was developed which has the potential for protecting high temperature air-cooled gas turbine components. Of those coatings initially examined, the most promising system consisted of a Ni-16Cr-6Al-0.6Y (in wt%) thermal barrier coating (about 0.005 to 0.010 cm thick) and a ZrO2-12Y2O3 (in wt%) thermal barrier coating (about 0.025 to 0.064 cm thick). This thermal barrier substantially lowered the metal temperature of an air-cooled airfoil. The coating withstood 3,200 cycles (80 sec at 1,280 C surface temperature) and 275 cycles (1 hr at 1,490 C surface temperature) without cracking or spalling. No separation of the thermal barrier from the bond coating or the bond coating from the substrate was observed.

Stecura, S.↗

Summary of NASA research on thermal-barrier coatings

This paper summarizes the work conducted at the NASA Lewis Research Center to evolve and evaluate a two-layer, thermal-barrier coating system. A durable, two-layer, plasma-sprayed coating consisting of a ceramic layer over a metallic layer was developed that has the potential of insulating hot engine parts and thereby reducing metal temperatures and coolant flow requirements and/or permitting use of less costly and complex cooling configurations and materials. The investigations evaluated the reflective and insulative capability, microstructure, and durability of several coating materials on flat metal specimens, a combustor liner, and turbine vanes and blades. In addition, the effect on the aerodynamic performance of a coated turbine vane was measured. The tests were conducted in furnaces, cascades, hot-gas rigs, an engine combustor, and a research turbojet engine. Included also are summaries of current research related to the coating and potential applications for the coating.

Stepka, F. S.↗

Further industrial tests of ceramic thermal barrier coatings

The NASA Lewis Research Center made technical assistance arrangements (contracts) with several commercial organizations under which Lewis designed plasma-sprayed thermal-barrier coatings (TBC) for their products. Lewis was then furnished with the test conditions and evaluations of coating usefulness. The coating systems were developed and sprayed at Lewis. All of the systems incorporated a two-layer, ceramic-bond coating concept. Coating thickness and chemical composition were varied to fit three applications: the leading edges of first-stage turbine vanes for an advanced gas turbine engine; the flame impingement surfaces of a combustor transition section; and diesel engine valves and head surfaces. The TBC incorporated yytria-stabilized zirconia, which lowered metal temperatures, protected metal parts, and increased metal part life. In some cases metal burning, melting, and warping were eliminated. Additional benefits were realized from these endeavors: hands-on experience with thermal-barrier coatings was provided to industry; the success of these endeavors encourages these and other organizations to accelerate the implementation of TBC technology.

Liebert, C. H.↗

Thermal Modelling of Various Thermal Barrier Coatings in a High Flux Rocket Engine

A thermal model was developed to predict the thermal response of coated and uncoated tubes tested in a H2/O2 rocket engine. Temperatures were predicted for traditional APS ZrO2-Y2O3 thermal barrier coatings, as well as APS and LPPS ZrO2-Y2O3/NiCrAlY cermet coatings. Good agreement was observed between predicted and measured metal temperatures at locations near the tube surface or at the inner tube wall. The thermal model was also used to quantitatively examine the effect of various coating system parameters on the temperatures in the substrate and coating. Accordingly, the effect of the presence a metallic bond coat and the effect of radiation from the surface of the ceramic layer were examined. In addition, the effect of a variation in the values of the thermal conductivity of the ceramic layer was also investigated. It was shown that a variation in the thermal conductivity of the ceramic layer, on the order of that reported in the literature for plasma sprayed ZrO2-Y2O3 coatings, can result in temperature differences in the substrate greater than 100 C, a much greater effect than that due to the presence of a bond coat or radiation from the ceramic layer. The thermal model was also used to predict the thermal response of a coated rod in order to quantify the difference in the metal temperatures between the two substrate geometries in order to explain the previously-observed increased life of coatings on rods over that on tubes. It was shown that for the short duration testing in the rocket engine, the temperature in a tube could exceed that in a rod by more than 100 C. Lastly, a two-dimensional model was developed to evaluate the effect of tangential heat transfer around the tube and its impact on reducing the stagnation point temperature. It was also shown that tangential heat transfer does not significantly reduce the stagnation point temperature, thus allowing application of a simpler, one-dimensional model for comparing measured and predicted stagnation point temperatures.

Nesbitt, James A.↗