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At least 19 records

Effect of chromia doping of thermal stability of silica fibers

Commercial silica fibers of the type being evaluated for reusable surface insulation for reentry vehicles were found to be porous and composed of subfibers. The effect on shrinkage and devitrification of soaking such silica fibers in water, acetic acid, chromium acetate, and chromium nitrate solutions was studied. Felted specimens made of chromia-doped fibers shrunk only about one-half as much as those made of untreated fibers after exposure in air for 4 hours at 1300 C. The devitrification rate of fibers given prolonged soaks in chromium nitrate was as low as that of as-received fibers.

Zaplatynsky, I.↗

Catalytic recombination of nitrogen and oxygen on iron-cobalt-chromia spinel

The energy-transfer catalytic recombination coefficient for nitrogen and oxygen recombination on iron-cobalt-chromia spinel is inferred from stagnation-point heat flux measurements in dissociated arc-jet flow. This material was coated on several Space Shuttle Orbiter thermal protection tiles. The resulting coefficients are correlated with an Arrhenius model for convenience, and these expressions may be used to account for catalytic recombination in predictions of the heat flux on the spinel-coated tiles flown on several Space Shuttle Orbiter flights. The results are compared with those inferred by Rakich, Stewart, and Lanfranco from an Orbiter flight and arc-jet experiments. Good agreement is obtained for oxygen recombination, but agreement for nitrogen is poor.

Scott, C. D.↗

Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments

Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.

Kohl, F. J.↗

Study of the effects of gaseous environments on sulfidation attack of superalloys

Studies were conducted to examine the effect of the gaseous corrodents NaCl, HCl, and NaOH on the high temperature oxidation and Na2SO4-induced corrosion behavior of the alumina former NiAl, the chromia former Ni-25 wt.% Cr, elemental Cr, and the superalloy B-1900. Experiments were conducted at 900 and 1050 C in air in the presence and absence of the gaseous corrodents. Effects involving both reaction rates and microstructural changes in oxide morphology were observed due to the presence of these corrodents at levels anticipated to be present in operating industrial and marine gas turbines. The effect of gaseous NaCl, HCl, and possibly NaOH on NiAl in simple oxidation was to remove aluminum from below the protective alumina layer and to simultaneously weaken the adherence of the protective alumina oxide scale to the substrate. The aluminum removed from below the oxide scale was redeposited on its surface as alpha-Al2O3 whiskers. With respect to the chromia formers, gaseous NaCl and HCl promoted breakaway oxidation kinetics and changes in the microstructures of the oxide scales.

Smeggil, J. G.↗

Volatility of Common Protective Oxides in High-Temperature Water Vapor: Current Understanding and Unanswered Questions

Many structural materials rely on the formation of chromia, silica or alumina as a protective layer when exposed in high temperature oxidizing environments. The presence of these oxide layers provides a protective diffusion barrier which slows down further oxidation. In atmospheres containing water vapor, however, reactions to form volatile hydroxide species occur which remove the surface oxide, thus, lowering the protective capability of the oxide scale. This paper summarizes the current understanding of volatility of chromia, silica and alumina in water vapor containing combustion environments. In addition unanswered questions in each system are discussed. Th current paper represents an update on the considerable information learned in the past five years for these systems.

Opila, Elizabeth J.↗

Cyclic Oxidation of High-Temperature Alloy Wires in Air

High-temperature alloy wires are proposed for use in seal applications for future re-useable space vehicles. These alloys offer the potential for improved wear resistance of the seals. The wires must withstand the high temperature environments the seals are subjected to as well as maintain their oxidation resistance during the heating and cooling cycles of vehicle re-entry. To model this, the wires were subjected to cyclic oxidation in stagnant air. of this layer formation is dependent on temperature. Slow growing oxides such as chromia and alumina are desirable. Once the oxide is formed it can prevent the metal from further reacting with its environment. Cyclic oxidation models the changes in temperature these wires will undergo in application. Cycling the temperature introduces thermal stresses which can cause the oxide layer to break off. Re-growth of the oxide layer consumes more metal and therefore reduces the properties and durability of the material. were used for cyclic oxidation testing. The baseline material, Haynes 188, has a Co base and is a chromia former while the other two alloys, Kanthal A1 and PM2000, both have a Fe base and are alumina formers. Haynes 188 and Kanthal A1 wires are 250 pm in diameter and PM2000 wires are 150 pm in diameter. The coiled wire has a total surface area of 3 to 5 sq cm. The wires were oxidized for 11 cycles at 1204 C, each cycle containing a 1 hour heating time and a minimum 20 minute cooling time. Weights were taken between cycles. After 11 cycles, one wire of each composition was removed for analysis. The other wire continued testing for 70 cycles. Post-test analysis includes X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) for phase identification and morphology.

Reigel, Marissa M.↗

Hydrogen plasma tests of some insulating coating systems for the nuclear rocket thrust chamber

Several plasma-sprayed and slurry-coated insulating coating systems were evaluated for structural stability in a low-pressure hot hydrogen environment at a maximum heat flux of 19.6 million watts/sq meter. The heat was provided by an electric-arc plasma generator. The coating systems consisted of a number of thin layers of metal oxides and/or metals. The materials included molybdenum, nichrome, tungsten, alumina, zirconia, and chromia. The study indicates potential usefulness in this environment for some coatings, and points up the need for improved coating application techniques.

Current, A. N.↗

Development of high-emittance scales on thoriated nickel-chromium-aluminum-base alloys

The surface regions of a DSNiCrAl alloy have been doped, by a pack diffusion process, with small amounts of Mn, Fe, or Co, and the effect of these dopants on the total normal emissivity of the scales produced by subsequent high temperature oxidation has been measured. While all three elements lead to a modest increase in emissivity, (up to 23% greater than the undoped alloy) only the change caused by manganese is thermally stable. However, this increased emissivity is within 85 percent of that of TDNiCr oxidized to form a chromia scale. The maganese-doped alloy is some 50 percent weaker than undoped DSNiCrAl after the doping treatment, and approximately 30 percent weaker after oxidation.

Seltzer, M. S.↗

The effects of dispersed oxides on the oxidation characteristics of superalloys

The high-temperature oxidation behavior of thoriated nickel and chromium superalloys is discussed on the basis of scanning electron micrographs and other experimental data. The beneficial effects of dispersed oxide particles are identified as a lower chromium content needed for the formation of external scale, an increased adhesion of scale, and lower growth rates of chromia as compared with those in alloys without dispersed oxide particles.

Jaffee, R. I.↗

Oxidation in oxygen at 900 deg and 1000 deg C of four nickel-base cast superalloys: NASA-TRW VIA, B-1900, alloy 713C, and IN-738

The oxidation at 900 and 1,000 C of four nickel-base superalloys in 1 atmosphere of slowly flowing oxygen was investigated. Thermogravimetric rate data were obtained for periods to 100 hours. The morphology and composition of the oxide scales formed after 100 hours were studied by optical microscopy, X-ray diffraction, electron microprobe, scanning electron microscopy, and X-ray photoelectron spectroscopy (ESCA). Alloys B-1900 and VIA were found to be primarily alumina formers, though probably 25 percent of their surface was covered by CR2O3-containing oxides at 900 C. Alloys 713C and IN-738 were primarily chromia formers, though the surface of 713C at 1,000 C was covered with NiO, and the surface of IN-738 at both temperatures was covered with a thin layer of TiO2.

Fryburg, G. C.↗

Volatile products from the interaction of KCl/g/ with Cr2O3 and LaCrO3 in oxidizing environments

Based on cooled target collection methods and high pressure mass spectrometer sampling, oxidative vaporization rates and emanating volatile products were evaluated for interactions of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments. It was found that: (1) increased rates of oxidative vaporization upon exposure to the reactants are exhibited by chromia and fresh lanthanum chromite samples, and (2) these increased rates result from the heterogeneous formation of complex molecules such as KCl sub 1,2,3CrO3 and KOH sub 1,2CrO3. No increased rates were observed for lanthanum chromite subjected to prolonged oxidative vaporization.

Kohl, F. J.↗

Study of the effects of gaseous environments on the hot corrosion of superalloy materials

The effect of the gaseous corrodent NaCl on the high temperature oxidation and sodium sulfate induced hot corrosion behavior of alumina formers, chromia formers, and the superalloy B-1900 was examined. Isothermal experiments were conducted at 900 C and 1050 C in air in the presence and absence of NaCl vapors. Microstructural changes in oxide morphology and increased rates of oxidation were observed when NaCl(g) was present. It is hypothesized that the accelerated rates of oxidation are the result of removal of aluminum from the scale substrate interface and the weakening of the scale substrate bonds. The aluminum removed was redeposited on the surfaces in the form of alumina whiskers. For the superalloy B-1900, alumina whiskers are also formed, and the alloy oxidizes at catastrophic rates. In the case of Ni-25Cr alloy, NaCl vapors interact with the scale depleting it of chromium.

Smeggil, J. G.↗

Hydrogen Annealing Of Single-Crystal Superalloys

Annealing at temperature equal to or greater than 2,200 degrees F in atmosphere of hydrogen found to increase ability of single-crystal superalloys to resist oxidation when subsequently exposed to oxidizing atmospheres at temperatures almost as high. Supperalloys in question are principal constituents of hot-stage airfoils (blades) in aircraft and ground-based turbine engines; also used in other high-temperature applications like chemical-processing plants, coal-gasification plants, petrochemical refineries, and boilers. Hydrogen anneal provides resistance to oxidation without decreasing fatigue strength and without need for coating or reactive sulfur-gettering constituents. In comparison with coating, hydrogen annealing costs less. Benefits extend to stainless steels, nickel/chromium, and nickel-base alloys, subject to same scale-adhesion and oxidation-resistance considerations, except that scale is chromia instead of alumina.

Smialek, James L.↗

Effect of Long-Term 1093 K Exposure to Air or Vacuum on the Structure of Several Wrought Superalloys

Long-term 1093 K heat treatments of three commercial superalloy sheet materials were undertaken in air -IAI and vacuum. With either exposure, significant precipitation of second phases occurred in the Co-base Haynes(R) Alloy 188 (HA 188) and the Ni-base Haynes(R) Alloy 230 (HA 230); however, much less precipitation was found in the exposed Ni-base alloy Inconel(R) 617 (IN 617). Although some grain growth occurred in HA 198, no changes in the grain size of either HA 230 or IN 617 were observed after 22,500 h at temperature. Oxidation during air heat treatments led to weight gain due to the formation of chromia + spinel scales and surface-connected grain boundary pits/oxides in all three superalloys. Both the weight gain and depth of intergranular attack were dependent on the square root of time, which is indicative of diffusion-controlled phenomena. Because many alloy samples had neighbors in close proximity, most vacuum heat treated specimens did not suffer significant loss of volatile elements. However, some exposed samples were subjected to unrestricted vacuum heat treatments, allowing estimates of volatilization to be made. Based on the data for HA 188, the weight loss during 1093 K vacuum exposure was diffusion controlled once the inhibiting effects of surface films on the as-received alloys were broken down.

J.D. Whittenberger↗

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Smialek, James L.↗

Design for Oxidation Resistance

Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

Smialek, James L.↗

Particle Morphology Effects on Flow Characteristics of PS304 Plasma Spray Coating Feedstock Powder Blend

The effects of BaF2-CaF 2 particle morphology on PS304 feedstock powder flow ability have been investigated. BaF2-CaF2 eutectic powders were fabricated by comminution (angular) and by gas atomization (spherical). The fluoride powders were added incrementally to the other powder constituents of the PS304 feedstock: nichrome, chromia, and silver powders. A linear relationship between flow time and concentration of BaF2-CaF2 powder was found. Flow of the powder blend with spherical BaF2-CaF2 was better than the angular BaF2-CaF2. Flow ability of the powder blend with angular fluorides decreased linearly with increasing fluoride concentration. Flow of the powder blend with spherical fluorides was independent of fluoride concentration. Results suggest that for this material blend, particle morphology plays a significant role in powder blend flow behavior, offering potential methods to improve powder flow ability and enhance the commercial potential. These findings may have applicability to other difficult-to-flow powders such as cohesive ceramics.

Stanford, Malcolm K.↗

Effects of Humidity On the Flow Characteristics of PS304 Plasma Spray Feedstock Powder Blend

The effects of environmental humidity on the flow characteristics of PS304 feedstock have been investigated. Angular and spherical BaF2-CaF2 powder was fabricated by comminution and by atomization, respectively. The fluorides were added incrementally to the nichrome, chromia, and silver powders to produce PS304 feedstock. The powders were dried in a vacuum oven and cooled to a Tom temperature under dry nitrogen. The flow of the powder was studied from 2 to 100 percent relative humidity (RH) The results suggest that the feedstock flow is slightly degraded with increasing humidity below 66 percent RH and is more affected above 66 percent RH. There was no flow above 88 percent RH. Narrower particle size distributions of the angular fluorides allowed flow up to 95 percent RH. These results offer guidance that enhances the commercial potential for this material system.

Stanford, Malcolm K.↗