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At least 289 records · Page 16

Active Oxidation of a UHTC-Based CMC

The active oxidation of ceramic matrix composites (CMC) is a severe problem that must be avoided for multi-use hypersonic vehicles. Much work has been performed studying the active oxidation of silicon-based CMCs such as C/SiC and SiC-coated carbon/carbon (C/C). Ultra high temperature ceramics (UTHC) have been proposed as a possible material solution for high-temperature applications on hypersonic vehicles. However, little work has been performed studying the active oxidation of UHTCs. The intent of this paper is to present test data indicating an active oxidation process for a UHTC-based CMC similar to the active oxidation observed with Si-based CMCs. A UHTC-based CMC was tested in the HyMETS arc-jet facility (or plasma wind tunnel, PWT) at NASA Langley Research Center, Hampton, VA. The coupon was tested at a nominal surface temperature of 3000 F (1650 C), with a stagnation pressure of 0.026 atm. A sudden and large increase in surface temperature was noticed with negligible increase in the heat flux, indicative of the onset of active oxidation. It is shown that the surface conditions, both temperature and pressure, fall within the region for a passive to active transition (PAT) of the oxidation.

Glass, David E.↗

Performance, Stability and Compatibility of Oxygen/RP-1 Multi-Element Oxidizer-Rich Staged-Combustion Injectors

In 2015 and 2016, the National Aeronautics and Space Administration Marshall Space Flight Center designed, fabricated, assembled and hot-fire tested an oxygen/RP-1 propellant multi-element oxidizer-rich staged-combustion test article. The main objective was to provide thrust chamber combustion stability data as part of the Combustion Stability Tool Development program, although demonstration of performance and compatibility of oxidizer-rich main injectors was also important. Funding was provided by the Air Force Space and Missile Systems Center. Five configurations of main injectors were designed and fabricated, using conventional gas-centered swirl coaxial injector element designs generally similar to those used in oxygen/kerosene oxidizer-rich staged combustion engines such as the Russian RD-180 or NK-33 engines. Variations of element features included element size, recess depth, fuel gap width, and the presence of the sleeve separating the swirling fuel flow from the axial oxidizer flow. Ablative combustion chambers were fabricated based on hardware previously used at the NASA MSFC for testing at similar size and pressure. Existing oxygen/RP-1 oxidizer-rich subscale preburner injectors and hot gas ducts from a previous NASA-funded program were modified for use to supply the oxidizer-rich combustion products to the oxidizer circuit of the main injector of the thrust chamber. Testing of the resulting integrated test article - which included the preburner, inter-connecting hot gas duct, main injector, and ablative combustion chamber - was conducted at Test Stand 116 at the East Test Area of the NASA MSFC. The test article was well instrumented with static and dynamic pressure, temperature, and vibration sensors. This paper presents and discusses all the hot-fire test results of the integrated test article thrust chamber. Eighteen successful hot-fire tests of the integrated rig were conducted. Testing was accomplished with all five of the injector element concepts. Main combustion chamber pressures ranged from 710 to 2350 psia, and main combustion chamber mixture ratios ranged from 2.47 to 2.87. A chamber barrier fuel film coolant of about 2% to 4% of the total fuel flow was used for most tests. Characteristic exhaust velocity efficiency excluding the influence of the fuel film cooling ranged from 91% to 98% of theoretical. All tests of the thrust chamber exhibited stable combustion, even down to 40% of nominal operating pressures. Compatibility of the injector face and combustion chamber walls was acceptable. This paper is a follow-on to publication of preliminary test data presented at the 2016 JANNAF Liquid Propulsion Subcommittee meeting.

Hulka, J. R.↗

Parallelized Carbon Oxidation and Surface Recession Model in Direct-Simulation Monte Carlo Code, SPARTA

Ablative thermal protection system (TPS) materials for spacecraft are composites that often consist of a carbon-based reinforcement and a polymeric matrix. During Earth re-entry, they endure high-temperature oxidation and surface recession. Oxidation is an important mechanism for ablation, sometimes leading to the weakening, spallation, or failure of the oxidized fibers at the surface and in the char layer. However, more details are required including accurate material properties of the fiber microstructure, whether the fibers recede homogenously or localized at pits, and the role of pyrolysis outgassing in order to evaluate the role oxidation plays in the degradation and failure mechanisms of these materials. In this work, we demonstrate a parallelizable oxidation-driven ablation model developed for detailed, large-scale simulations in the DSMC code SPARTA. We also develop robust algorithms which handle the conservation of the surface state after an ablation step. Finally, we verify our model for both simple and more complex chemistry as well as microstructures with reaction statistics, oxidation depth calculations, and detailed visualization of oxidation-induced material recession at the microscale.

V Arias↗

Pathways of organic carbon oxidation in three continental margin sediments

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

NASA Discipline Exobiology↗

Mass Flow Rate and Isolation Characteristics of Injectors for Use with Self-Pressurizing Oxidizers in Hybrid Rockets

Self-pressurizing rocket propellants are currently gaining popularity in the propulsion community, particularly in hybrid rocket applications. Due to their high vapor pressure, these propellants can be driven out of a storage tank without the need for complicated pressurization systems or turbopumps, greatly minimizing the overall system complexity and mass. Nitrous oxide (N2O) is the most commonly used self pressurizing oxidizer in hybrid rockets because it has a vapor pressure of approximately 730 pounds per square inch (5.03 megapascals) at room temperature and is highly storable. However, it can be difficult to model the feed system with these propellants due to the presence of two-phase flow, especially in the injector. An experimental test apparatus was developed in order to study the performance of nitrous oxide injectors over a wide range of operating conditions. Mass flow rate characterization has been performed to determine the effects of injector geometry and propellant sub-cooling (pressurization). It has been shown that rounded and chamfered inlets provide nearly identical mass flow rate improvement in comparison to square edged orifices. A particular emphasis has been placed on identifying the critical flow regime, where the flow rate is independent of backpressure (similar to choking). For a simple orifice style injector, it has been demonstrated that critical flow occurs when the downstream pressure falls sufficiently below the vapor pressure, ensuring bulk vapor formation within the injector element. It has been proposed to leverage the insensitivity of critical mass flow rate to downstream pressure as a means of preventing the occurrence of feed system coupled combustion instabilities in hybrid rockets utilizing nitrous oxide. Additionally, observations indicate that the existence of two-phase flow can attenuate pressure fluctuations traveling upstream through the injector, providing a degree of isolation between the feed line and downstream pressure disturbances. In consideration of safety, carbon dioxide (CO2) has been used as an analog to nitrous oxide in many of these studies. It has been observed experimentally that carbon dioxide serves as a good analog to nitrous oxide in both the single-phase and two-phase flow regimes.

Oxidizer↗

On the Oxidation of the Silicon Bond Coat in Environmental Barrier Coatings

Deal and Grove’s formulation is applied to model the oxidation of the silicon bond coat in environmental barrier coatings. The approach is similar to the author’s previous study, except now the oxidant is assumed to flow through the coating as oxygen ions via vacancies on the oxygen sublattice. The use of an “effective permeability” of the oxidant in the coating is required under the vacancy diffusion assumption. It is found that the linear-parabolic growth equation from Deal and Grove, , is still applicable for the oxidation of the silicon bond coat, but the equation for the parameter A must be modified to account for the coating. The expression for B is the same as that obtained by Deal and Grove and thus is unaffected by the presence of a coating. The modified expression for A is a linear function of the coating thickness and includes the ratio of the oxidant permeability in the oxide to its effective permeability in the coating.

silicon oxidation, ionic diffusion, permeation, li↗

Exploring Oxidation in the Remote Free Troposphere: Insights From Atmospheric Tomography (ATom)

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO2) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO2 agree to within combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6-km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO2 abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values.

atmosphere's primary oxidant, hydroxyl (OH), and h↗

Measuring the Wear and Abrasive Resistance of Air Plasma Sprayed Aluminum Oxide for Lunar Exploration

Lunar regolith, especially finer dust particles traveling at high velocities, can cause significant wear and abrasive damage to structural components that ensure a prolongated presence on the surface of the Moon. With the absence of an atmosphere and lower gravity than on Earth, regolith particles maintain high velocities at large distances from where they were generated, for example next to lunar landers. Wear-resistant ceramic and ceramic composite materials can improve the durability of spacecraft components during long missions on the Moon’s surface. Aluminum oxide coatings are lightweight, have multifunctional properties, and have high strength including high hardness and wear resistance. These properties can help improve the durability of structures used in space exploration. Air plasma sprayed (APS) aluminum oxide coatings have demonstrated the potential to protect critical structures. This study investigated the abrasive wear resistance of APS aluminum oxide coatings via Taber abrasion experiments. Taber abrasion offers the advantage of quantifying the abrasive wear behavior of particles with different shapes on a surface. In this work, an abrasive wheel made of silicon carbide was utilized to evaluate wear properties of specimens progressively over 5000 cycles. This experiment focused on testing two series of specimens to determine whether a bond coat composed of nickel, chromium, aluminum, and yttrium (NiCrAlY) improved the protective behavior of the APS aluminum oxide coating. The specimens varied in topcoat thickness and were made with and without an approximately 100 µm bond coat layer. The mass of the specimens was measured at 400 cycles, 800 cycles, 3800 cycles, and 5000 cycles. Increasing thickness was found to result in higher wear for samples with and without a bond coat. Increased mass loss in samples with a bond coat was observed indicating a need for further studies on the overall impact of the use of a bond coat on the protective behavior of the coatings. To continue designing wear resistant coatings for structural protection in space missions, the multifunctional properties of the APS aluminum oxide coating will be studied. Future experiments will determine whether the APS aluminum oxide coating can protect the structures from other aspects of the harsh space environment, such as extreme temperature variations and ionizing radiation.

aluminum oxide↗

Effects of Oxide Dispersion on Failure Modes in an Additively Manufactured Superalloy

Additive manufacturing opens new paths for introducing oxide particles into superalloys, to potentially provide oxide dispersion strengthening (ODS) at high temperatures. This provides opportunities to study how such dispersions can influence failure modes for a given superalloy, after nearly identical material processing paths. The objective of this study was to compare monotonic failure modes for additively manufactured superalloys with versus without an introduced oxide dispersion. The superalloy for each case was produced by laser powder bed fusion additive manufacturing. Specimens were subsequently given consistent thermal treatment paths and then tested in tensile and creep tests at varied temperatures. Failure modes were then compared. Additively manufactured NiCrAl without ODS had randomly oriented equiaxed grains while this alloy with 0.25 wt% Y 2 O 3 ODS additions had elongated [001] oriented grains in the build direction. Material made without ODS (“No-ODS”) was nearly completely single phase gamma, while ODS additions resulted in gamma, chromium carbide, and Y-Al-Cr oxide phases, with carbide and oxide phases contents estimated at no more than 13 and 1 vol%, respectively. Compared to No-ODS, material made with ODS had higher tensile strengths at room, 760 and 1093 °C. The elongation of ODS material was lower than No-ODS at room temperature, but higher at 760 °C. At 1093 °C ODS material had higher elongation than No-ODS when tested in the build direction, however elongation was lower for ODS material in the transverse direction at 1093 °C. Creep rupture strain, life, and area reduction at 760 and 1093 °C were all much higher for ODS material compared to No-ODS; 760 °C rupture life was nearly 100 times longer for ODS material. The presence of Y in the ODS material significantly improved oxidation resistance.

supperalloys↗

Oxidation of TD nickel at 1050 C and 1200 C as compared with three grades of nickel of different purity

The isothermal oxidation of three nickels of different purity, Ni-200, Ni-270, and JM-Ni, was compared with that of TD-Ni in air at 1050 and 1200 C. The samples were oxidized as ground, as polished, or as annealed and polished. Weight change, metal loss, scale thickness, oxide morphology, and scale texture were determined. In degree of oxidation, TD-Ni was nearly the same as the higher purity materials, Ni-270 and JM-Ni; and less pure Ni-200 oxidized more than the others. However, in microstructure and scale texture the TD-Ni more closely resembled Ni-200. Grinding only charged the texture of the oxides of Ni_200 and TD-Ni.

Lowell, C. E.↗

Studies of reaction geometry in oxidation and reduction of the alkaline silver electrode

Two methods of surface area estimations of sintered silver electrodes have given roughness factors of 58 and 81. One method is based on constant current oxidation, the other is based on potentiostatic oxidation. Examination of both wire and sintered silver electrodes via scanning electron microscopy at various stages of oxidation have shown that important structural features are mounds of oxide. In potentiostatic oxidations these appear to form on sites instantaneously nucleated while in constant current oxidations progressive nucleation is indicated.

Butler, E. A.↗

The 1200 C cyclic oxidation behavior of two nickel-aluminum alloys (Ni3AL and NiAl) with additions of chromium, silicon, and titanium

The alloys Ni3Al and NiAl with and without 1 and 3 atomic percent chromium, silicon, and titanium replacing the aluminum were cyclically oxidized at 1200 C for times to 200 hours, and the results were compared with those obtained with the alloy B-1900 subjected to the same oxidation process. The evaluation was based on metal recession, specific weight change, metallography, electron microprobe analysis, and X-ray diffraction. The oxidation resistance of Ni3Al was improved by Si, unaffected by Ti, and degraded by Cr. The oxidation resistance of NiAl was slightly improved by Ti, unaffected by Si, and degraded by Cr. The oxidation resistance of Ni3Al with 1 atomic percent Si was nearly equal to that of NiAl. Alloy B-1900 exhibited oxidation resistance comparable to that of Ni3Al + Cr compositions.

Lowell, C. E.↗

Short-time oxidation of zirconium.

Study of zirconium oxidation kinetics for maximum exposure times of 3 min and in the temperature range 440 to 850 C. 'Discontinuous' oxidation runs were employed whereby a specimen was inserted into the gas stream for a predetermined time, removed and weighed, and reinserted into the oxidation atmosphere. It is considered that the increase in the observed activation energy for the early stage parabolic oxidation is a manifestation of a change from an n-type oxide to a predominantly p-type oxide, in agreement with the authors' earlier conclusion (1971) based on pressure effects.

Srivastava, L. P.↗

Mechanisms of oxidation in the Co-Cr system.

Oxidation has been studied both as a function of temperature in the range from 900 to 1300 C and of the partial pressure of oxygen in the range from 0.05 to 760 torr. In addition, microstructures of oxide scales have been studied and characterized in more detail utilizing metallographic and X-ray techniques combined with electron microprobe analysis. The parabolic rate constants in 1100 C and at 100 and 10 torr oxygen are presented in a graph as a function of chromium content. Three main different mechanisms of oxidation in the Co-Cr system have been identified. In two of these, the rate determining process controlling the oxidation is the solid state diffusion of cobalt through the oxide CoO. The rate controlling process governing the oxidation for the third mechanism is chromium diffusion in dichromium trioxide.

Kofstad, P. K.↗

Interference of oxygen, carbon dioxide, and water vapor on the analysis for oxides of nitrogen by chemiluminescence

The interference of small concentrations (less than 4 percent by volume) of oxygen, carbon dioxide, and water vapor on the analysis for oxides of nitrogen by chemiluminescence was measured. The sample gas consisted primarily of nitrogen, with less than 100 parts per million concentration of nitric oxide, and with small concentrations of oxygen, carbon dioxide, and water vapor added. Results obtained under these conditions indicate that although oxygen does not measurably affect the analysis for nitric oxide, the presence of carbon dioxide and water vapor causes the indicated nitric oxide concentration to be too low. An interference factor - defined as the percentage change in indicated nitric oxide concentration (relative to the true nitric oxide concentration) divided by the percent interfering gas present - was determined for carbon dioxide to be -0.60 + or - 0.04 and for water vapor to be -2.1 + or - 0.3.

Maahs, H. G.↗

Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

Stecura, S.↗

Prediction of oxidation performance of reinforced carbon-carbon material for Space Shuttle leading edges

A method was developed for predicting oxidation performance, in an earth atmospheric entry environment, of reinforced carbon-carbon material, coated for oxidation resistance. A model was developed which describes oxidation control mechanisms, and the equations defining these mechanisms were derived. These relations were used to correlate oxidation test data, and to infer pertinent rate constants. Predictions were made of material oxidation performance in a representative entry environment, and the predictions were compared with ground test data. Results indicate that the method can be successfully used for predicting material oxidation performance.

Medford, J. E.↗

Oxidation of metals and alloys in controlled atmospheres using in situ transmission electron microscopy and Auger spectrography

Single-crystalline thin films of copper were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of .005 Torr in situ in a high-resolution electron microscope. The specimens were prepared by epitaxial vapor deposition onto polished 100 and 110 faces of rocksalt and mounted in a hot stage inside an ultra-high-vacuum specimen chamber of the microscope. Large amounts of sulfur, carbon, and oxygen were detected by Auger electron spectroscopy on the surface of the as-received films and were removed in situ by ion-sputter etching immediately prior to the oxidation. The nucleation and growth characteristics of Cu2O on Cu were studied. Results show that neither stacking faults nor dislocations are associated with the Cu2O nucleation sites. The growth of Cu2O nuclei is linear with time. The experimental findings, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving (a) the formation of a surface-charge layer, (b) oxygen saturation in the metal and (c) nucleation, followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Rao, D. B.↗