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NASA NTRS1993

Extraction of oxygen from the Mars atmosphere using glow-discharge and permeation techniques

Oxygen can be extracted from carbon dioxide via thermal dissociation at elevated temperatures. However, temperatures in excess of 1000 K are needed to effect significant levels of dissociation. The experiments reported here have examined the feasibility of using a glow-discharge in low-pressure carbon dioxide to produce increased atomic oxygen yields at lower temperatures (on the order of 800 K). The experiments have shown that when silver membranes are used simultaneously as anodes for the glow discharge and as permeable membranes for oxygen separation, oxygen yields which are comparable to the permeation rates for pure oxygen, can be produced. Since the silver membrane can be employed as the electrode interface between Mars atmosphere and a stabilized-zirconia electrochemical pump, glow-discharge enhancement can be considered as a complementary technology which can be used with the zirconia-based oxygen extraction systems described previously by others. Not only can glow-discharge be used to increase oxygen yields at lowered temperatures, but it can also be considered as a possible way to avoid filtration and compression of Mars atmosphere, since the glow-discharge can be sustained in Mars ambient pressures.

Wu, Dongchuan↗

NASA NTRS1991

Thick thermal barrier coatings for diesel components

An engineered thick thermal barrier coating consisting of multiple layers of zirconia and CoCrAlY with a zirconia top layer and having a system thermal conductance less than 410 w/m(exp 2)K exceeded the 100 hour engine durability goals set forth in this program. The thermal barrier coatings were intact at the test conclusion. Back to back single cylinder research engine tests were conducted with watercooled, metal hardware and oil-cooled, thermal barrier coating insulated hardware to determine apparent heat release and fuel economy. Apparent heat release data revealed that the insulated engine had a shorter ignition delay and a longer combustion duration than the metal engine. The insulated engine fuel economy was approximately two percent worse on average for this series of tests. There was no attempt to optimize engine efficiency of the insulated engine by modifying the engine timing, coating, or other techniques.

Yonushonis, T. M.↗

NASA NTRS1993

Testing and evaluation of oxide-coated iridium/rhenium chambers

Iridium-coated rhenium provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase iridium/rhenium rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated iridium/rhenium, 22 N rocket chambers were tested on gaseous hydrogen/gaseous oxygen propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia or zirconia. Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of zirconia infiltrated with sol gel hafnia. The other chamber had a coating composed of an iridium/oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. The iridium/oxide composite coated chamber included testing for over 29 minutes at mixture ratio 16. The thicker-walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner-walled coatings did not experience the macrocracking and chipping of the chambers seen with the thick, monolithic coatings. However, burnthroughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stochiometric. The burn-throughs were probably the result of oxygen-diffusion through the oxide coating that allowed the underlying iridium and rhenium layers to be oxidized. The results of this test program indicated that the thin-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

Reed, Brian D.↗

NASA NTRS1994

Quality optimization of thermally sprayed coatings produced by the JP-5000 (HVOF) gun using mathematical modeling

Currently, thermal barrier coatings (TBC) of gas-turbine blades and similar applications have centered around the use of zirconia as a protective coating for high thermal applications. The advantages of zirconia include low thermal conductivity and good thermal shock resistance. Thermally sprayed tungsten carbide hardface coatings are used for a wide range of applications spanning both the aerospace and other industrial markets. Major aircraft engine manufacturers and repair facilities use hardface coatings for original engine manufacture (OEM), as well as in the overhaul of critical engine components. The principle function of these coatings is to resist severe wear environments for such wear mechanisms as abrasion, adhesion, fretting, and erosion. The (JP-5000) thermal spray gun is the most advanced in the High Velocity Oxygen Fuel (HVOF) systems. Recently, it has received considerable attention because of its relative low cost and its production of quality coatings that challenge the very successful but yet very expensive Vacuum Plasma Spraying (VPS) system. The quality of thermal spray coatings is enhanced as porosity, oxidation, residual stress, and surface roughness are reduced or minimized. Higher densification, interfacial bonding strength, hardness and wear resistance of coating are desirable features for quality improvement.

Tawfik, Hazem↗

NASA NTRS1995

Combination Thermal Barrier And Wear Coatings For Engines

Thermal-barrier layers covered with self-lubricating surface layers. Zirconia thermal-barrier coat applied to surface of combustion chamber in engine by plasma-arc spraying. Then PS-200 plasma-arc sprayed onto zirconia. Self-lubricating coat prevents sliding contact between thermal barrier and piston ring, effectively preventing both wear and production of additional heat via friction. Other combinations of thermal-barrier and self-lubricating, wear-resistant coating materials used as long as two materials adhere to each other, applied by use of similar or compatible processes, have similar coefficients of thermal expansion, sufficiently strong at high temperatures, and affordable.

Weingart, Mike↗

NASA NTRS1998

Investigation of Thermal High Cycle and Low Cycle Fatigue Mechanisms of Thick Thermal Barrier Coatings

Ceramic thermal barrier coatings have attracted increased attention for diesel engine applications. The advantages of using the ceramic coatings include a potential increase in efficiency and power density and a decrease in maintenance cost. Zirconia-based ceramics are the most important coating materials for such applications because of their low thermal conductivity, relatively high thermal expansivity and excellent mechanical properties. However, durability of thick thermal barrier coatings (TBCS) under severe temperature cycling encountered in engine conditions, remains a major question. The thermal transients associated with the start/stop and no-load/full-load engine cycle, and with the in-cylinder combustion process, generate thermal low cycle fatigue (LCF) and thermal high cycle fatigue (HCF) in the coating system. Therefore, the failure mechanisms of thick TBCs are expected to be quite different from those of thin TBCs under these temperature transients. The coating failure is related not only to thermal expansion mismatch and oxidation of the bond coats and substrates, but also to the steep thermal stress gradients induced in the coating systems. Although it has been reported that stresses generated by thermal transients can initiate surface and interface cracks in a coating system, the mechanisms of the crack propagation and of coating failure under the complex LCF and HCF conditions are still not understood. In this paper, the thermal fatigue behavior of an yttria partially stabilized zirconia coating system under simulated LCF and HCF engine conditions is investigated. The effects of LCF and HCF on surface crack initiation and propagation are also discussed.

Zhu, Dong-Ming↗

NASA NTRS1959

Measurements of Total Hemispherical Emissivity of Several Stably Oxidized Metals and Some Refractory Oxide Coatings

A description of the apparatus and methods used for obtaining total hemispherical emissivity is presented, and data for several stably oxidized metals are included. The metals which were tested included type 347 stainless steel, tungsten, and Haynes alloys B, C, X, and 25. No values of emissivity were obtained for tungsten or Haynes alloy B because of the nature of the oxides produced. The refractory oxide coatings tested were flame-sprayed alumina and zirconia. The results of the investigation indicate that strongly adherent, oxidized surfaces of a high stable emissivity can be produced on type 347 stainless steel for which the total hemispherical emissivity varied from 0.87 to 0.91 for temperatures from 600 F to 2,000 F. For this same temperature range, the Haynes alloys tested showed values of total hemispherical emissivity from 0.90 to 0.96 for alloy C, from 0.85 to 0.88 for alloy X, and from 0.85 to 0.89 for alloy 25. Haynes alloy B and tungsten formed nonadherent oxides at elevated temperatures and, therefore, stable emissivities were not obtained. The results obtained for the flame-sprayed ceramics (alumina and zirconia) showed considerably higher values of total emissivity than those measured for coatings applied by other methods. Emissivity values ranging from 0.69 to 0.44 for aluminum oxide and from 0.62 to 0.44 for zirconium oxide were measured for temperatures from 800 F to 2,000 F.

Wade, William R.↗

NASA NTRS1999

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet, and magnesium oxide.

Zhu, Dongming↗

NASA NTRS1999

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

Zhu, Dongming↗

NASA NTRS1999

Transient Thermal Analysis of a Refractive Secondary Solar Concentrator

A secondary concentrator is an optical device that accepts solar energy from a primary concentrator and further intensifies and directs the solar flux. The refractive secondary is one such device; fabricated from an optically clear solid material that can efficiently transmit the solar energy by way of refraction and total internal reflection. When combined with a large state-of-the-art rigid or inflatable primary concentrator, the refractive secondary enables solar concentration ratios of 10,000 to 1. In support of potential space solar thermal power and propulsion applications, the NASA Glenn Research Center is developing a single-crystal refractive secondary concentrator for use at temperatures exceeding 2000K. Candidate optically clear single-crystal materials like sapphire and zirconia are being evaluated for this application. To support this evaluation, a three-dimensional transient thermal model of a refractive secondary concentrator in a typical solar thermal propulsion application was developed. This paper describes the model and presents thermal predictions for both sapphire and zirconia prototypes. These predictions are then used to establish parameters for analyzing and testing the materials for their ability to survive thermal shock and stress.

Geng, Steven M.↗

NASA NTRS2001

A Survey of Alternative Oxygen Production Technologies

Utilization of the Martian atmosphere for the production of fuel and oxygen has been extensively studied. The baseline fuel production process is a Sabatier reactor, which produces methane and water from carbon dioxide and hydrogen. The oxygen produced from the electrolysis of the water is only half of that needed for methane-based rocket propellant, and additional oxygen is needed for breathing air, fuel cells and other energy sources. Zirconia electrolysis cells for the direct reduction of CO2 arc being developed as an alternative means of producing oxygen, but present many challenges for a large-scale oxygen production system. The very high operating temperatures and fragile nature of the cells coupled with fairly high operating voltages leave room for improvement. This paper will survey alternative oxygen production technologies, present data on operating characteristics, materials of construction, and some preliminary laboratory results on attempts to implement each. Our goal is to significantly improve upon the characteristics of proposed zirconia cells for oxygen production. To achieve that goal we are looking at electrolytic systems that operate at significantly lower temperatures, preferably below 31C to allow the incorporation of liquid CO2 in the electrolyte. Our preliminary results indicate that such a system will have much higher current densities and have simpler cathode construction than a porous gas feed electrode system. Such a system could be achieved based on nonaqueous electrolytes or ionic liquids. We are focusing our research on the anode reaction that will produce oxygen from a product generated at the cathode using CO2 as the feed. Operation at low temperatures also will open up the full range of polymer and metal materials, allowing a more robust system design to withstand the rigors of flight, landing, and long term unattended operation on the surface of Mars.

Lueck, Dale E.↗

NASA NTRS2001

Thermal Conductivity of Ceramic Thermal Barrier and Environmental Barrier Coating Materials

Thermal barrier and environmental barrier coatings (TBC's and EBC's) have been developed to protect metallic and Si-based ceramic components in gas turbine engines from high temperature attack. Zirconia-yttria based oxides and (Ba,Sr)Al2Si2O8(BSAS)/mullite based silicates have been used as the coating materials. In this study, thermal conductivity values of zirconia-yttria- and BSAS/mullite-based coating materials were determined at high temperatures using a steady-state laser heat flux technique. During the laser conductivity test, the specimen surface was heated by delivering uniformly distributed heat flux from a high power laser. One-dimensional steady-state heating was achieved by using thin disk specimen configuration (25.4 mm diam and 2 to 4 mm thickness) and the appropriate backside air-cooling. The temperature gradient across the specimen thickness was carefully measured by two surface and backside pyrometers. The thermal conductivity values were thus determined as a function of temperature based on the 1-D heat transfer equation. The radiation heat loss and laser absorption corrections of the materials were considered in the conductivity measurements. The effects of specimen porosity and sintering on measured conductivity values were also evaluated.

Zhu, Dong-Ming↗

NASA NTRS2001

Environmental Barrier Coatings for Silicon-Based Ceramics

Silicon-based ceramics, such as SiC fiber-reinforced SiC (SiC/SiC ceramic matrix composites (CMC) and monolithic silicon nitride (Si3N4), are prime candidates for hot section structural components of next generation gas turbine engines. Silicon-based ceramics, however, suffer from rapid surface recession in combustion environments due to volatilization of the silica scale via reaction with water vapor, a major product of combustion. Therefore, application of silicon-based ceramic components in the hot section of advanced gas turbine engines requires development of a reliable method to protect the ceramic from environmental attack. An external environmental barrier coating (EBC) is considered a logical approach to achieve protection and CP long-term stability. The first generation EBC consisted of two layers, mullite (3Al2O3-2SiO2) bond coat and yttria-stabilized zirconia (YSZ, ZrO2-8 Wt.% Y2O3) top coat. Second generation EBCs, with substantially improved performance compared with the first generation EBC, were developed in the NASA High Speed Research-Enabling Propulsion Materials (HSR-EPM) Program. The first generation EBC consisted of two layers, mullite (3Al2O3-2SiO2) bond coat and yttria-stabilized zirconia (YSZ, ZrO2-8 wt.% Y2O3) top coat. Second generation EBCs, with substantially improved performance compared with the first generation EBC, were developed in the NASA High Speed Research-Enabling Propulsion Materials (HSR-EPM) Program (5). They consist of three layers, a silicon first bond coat, a mullite or a mullite + BSAS (BaO(1-x)-SrO(x)-Al2O3-2SiO2) second bond coat, and a BSAS top coat. The EPM EBCs were applied on SiC/SiC CMC combustor liners in three Solar Turbines (San Diego, CA) Centaur 50s gas turbine engines. The combined operation of the three engines has accumulated over 24,000 hours without failure (approximately 1,250 C maximum combustor liner temperature), with the engine in Texaco, Bakersfield, CA, accumulating about 14,000 hours. As the commercialization of Si-based ceramic components in gas turbines is on the horizon, a major emphasis is placed on EBCs for two reasons. First, they are absolute necessity for the protection of Si-based ceramics from water vapor. Second, they can enable a major enhancement in the performance of gas turbines by creating temperature gradients with the incorporation of a low thermal conductivity layer. Thorough understanding of current state-of-the-art EBCs will provide the foundation upon which development of future EBCs will be based. Phase stability and thermal conductivity of EPM EBCs are published elsewhere. This paper will discuss the chemical/environmental durability and silica volatility of EPM EBCs and their impact on the coating's upper temperature limit.

Lee, Kang N.↗

NASA NTRS2004

Furnace Cyclic Oxidation Behavior of Multi-Component Low Conductivity Thermal Barrier Coatings

Ceramic thermal barrier coatings will play an increasingly important role in advanced gas turbine engines because of their ability to further increase engine operating temperatures and reduce cooling, thus helping achieve future engine low emission, high efficiency and improved reliability goals. Advanced multi-component zirconia-based thermal barrier coatings are being developed using an oxide defect clustering design approach to achieve the required coating low thermal conductivity and high temperature stability. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of the candidate coating materials was conducted using conventional furnace cyclic oxidation tests. In this paper, furnace cyclic oxidation behavior of plasma-sprayed zirconia-based defect cluster thermal barrier coatings was investigated at 1163 C using 45 min hot cycles. The ceramic coating failure mechanisms were studied using scanning electron microscopy (SEM) combined with X-ray diffraction (XRD) phase analysis after the furnace tests. The coating cyclic lifetime is also discussed in relation to coating processing, phase structures, dopant concentration, and other thermo-physical properties.

Zhu, Dong-Ming↗

NASA NTRS2004

Residual Gas Effects on Detached Solidification in Microgravity

Our long term goal has been to make detached solidification reproducible, which requires a full understanding of the mechanisms underlying it. Our Moving Meniscus Model of steady-state detachment predicts that it depends strongly on the surface tension of the melt and the advancing contact angle with the ampoule wall. Thus, the objective of the current project was to determine the influence of residual gases on the surface tension and contact angle of molten semiconductors on typical ampoule materials. Our focus was on the influence of oxygen on indium antimonide on clean silica ("quartz"). The research was performed by three chemical engineering graduate students, the third of whom will complete his research in the summer of 2005. Originally, we had planned to use a sealed silica cell containing a zirconia electrochemical element to control the oxygen partial pressure. However, zirconia requires an operating temperature above the 530 C melting point of InSb and is difficult to form a gas-tight seal with silica. Thus, we decided instead to flow an oxygen-containing gas through the cell. A special apparatus was designed, built and perfected. A piece of InSb was placed on a horizontal silica plate in a quartz cell. High purity argon, helium or hydrogen-containing gas is passed continuously through the cell while the oxygen concentration in the effluent gas is measured. The shape of the resulting drop was used to determine contact angle and surface tension of Ga-doped and high purity InSb. Oxygen appeared to decrease the contact angle, and definitely did not increase it. The following section gives the background for the research. Section 2 summarizes the results obtained on Ga-doped InSb with relatively high oxygen concentrations. Section 3 describes recent improvements made to the apparatus and methods of analysis. Section 4 gives recent results for high-purity InSb at low oxygen concentrations. Final results will be obtained only this summer (2005). Each section has its own references.

Wilcox, William R.↗

NASA NTRS2006

Self-Calibrating Pressure Transducer

A self-calibrating pressure transducer is disclosed. The device uses an embedded zirconia membrane which pumps a determined quantity of oxygen into the device. The associated pressure can be determined, and thus, the transducer pressure readings can be calibrated. The zirconia membrane obtains oxygen .from the surrounding environment when possible. Otherwise, an oxygen reservoir or other source is utilized. In another embodiment, a reversible fuel cell assembly is used to pump oxygen and hydrogen into the system. Since a known amount of gas is pumped across the cell, the pressure produced can be determined, and thus, the device can be calibrated. An isolation valve system is used to allow the device to be calibrated in situ. Calibration is optionally automated so that calibration can be continuously monitored. The device is preferably a fully integrated MEMS device. Since the device can be calibrated without removing it from the process, reductions in costs and down time are realized.

Lueck, Dale E.↗

NASA NTRS2007

Ceramic Paste for Patching High-Temperature Insulation

A ceramic paste that can be applied relatively easily, either by itself or in combination with one or more layer(s) of high-temperature ceramic fabrics, such as silicon carbide or zirconia, has been invented as a means of patching cracks or holes in the reinforced carbon-carbon forward surfaces of a space shuttle in orbit before returning to Earth. The paste or the paste/fabric combination could also be used to repair rocket-motor combustion chambers, and could be used on Earth to patch similar high-temperature structures. The specified chemical composition of the paste admits of a number of variations, and the exact proportions of its constituents are proprietary. In general, the paste consists of (1) silicon carbide, possibly with addition of (2) hafnium carbide, zirconium carbide, zirconium boride, silicon tetraboride, silicon hexaboride, or other metal carbides or oxides blended with (3) a silazane-based polymer. Because the paste is viscous and sticky at normal terrestrial and outer-space ambient temperatures, high-temperature ceramic fabrics such as silicon carbide or zirconia fabric impregnated with the paste (or the paste alone) sticks to the damaged surface to which it is applied. Once the patch has been applied, it is smoothed to minimize edge steps as required [forward-facing edge steps must be < or equal to 0.030 in. (< or equal to 0.76 mm) in the original intended space-shuttle application]. The patch is then heated to a curing temperature thereby converting it from a flexible material to a hard, tough material. The curing temperature is 375 to 450 F (approx.190 to 230 C). In torch tests and arc-jet tests, the cured paste was found to be capable of withstanding a temperature of 3,500 F (approx. 1,900 C) for 15 minutes. As such, the material appears to satisfy the requirement, in the original space-shuttle application, to withstand re-entry temperatures of approx.3,000 F (approx. 1,600 C).

Adam, Steven J.↗

NASA NTRS2010

Heat Flux and Wall Temperature Estimates for the NASA Langley HIFiRE Direct Connect Rig

An objective of the Hypersonic International Flight Research Experimentation (HIFiRE) Program Flight 2 is to provide validation data for high enthalpy scramjet prediction tools through a single flight test and accompanying ground tests of the HIFiRE Direct Connect Rig (HDCR) tested in the NASA LaRC Arc Heated Scramjet Test Facility (AHSTF). The HDCR is a full-scale, copper heat sink structure designed to simulate the isolator entrance conditions and isolator, pilot, and combustor section of the HIFiRE flight test experiment flowpath and is fully instrumented to assess combustion performance over a range of operating conditions simulating flight from Mach 5.5 to 8.5 and for various fueling schemes. As part of the instrumentation package, temperature and heat flux sensors were provided along the flowpath surface and also imbedded in the structure. The purpose of this paper is to demonstrate that the surface heat flux and wall temperature of the Zirconia coated copper wall can be obtained with a water-cooled heat flux gage and a sub-surface temperature measurement. An algorithm was developed which used these two measurements to reconstruct the surface conditions along the flowpath. Determinations of the surface conditions of the Zirconia coating were conducted for a variety of conditions.

Cuda, Vincent, Jr.↗