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An analytical approach is outlined to calculate the evaporative segregation behavior in metallic alloys. The theoretical predictions are based on a 'normal' evaporation model and have been examined for Fe-Ni and Ni-Cr alloys. A fairly good agreement has been found between the predicted values and the experimental results found in the literature.
The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr and Fe-Cr-Ni alloys were developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary system were displayed on plots of log P sub S sub 2 versus the conjugate extensive variable which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase diagram data of geophysical literature. These constructed stability field diagrams were in excellent agreement with the sulfide phases and compositions determined during a sulfidation experiment.
Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys.
A cyclic furnace study was conducted between 990 - 280 C and 1095 - 280 C to evaluate the effects of yttrium, chromium, and aluminum concentrations in nickel base alloy bond coatings and also the effect of the bond coating thickness on the performance of yttria-stabilized zirconia thermal barrier coatings. The presence and the concentration of yttrium is very critical. Without yttrium, rapid oxidation of Ni-Al, Ni-Cr, and Ni-Cr-Al bond coatings causes zirconia thermal barrier coatings to fail very rapidly. Concentrations of chrominum and aluminum in Ni-Cr-Al-Y bond coating have a very significant effect on the thermal barrier coating life. This effect, however, is not as great as that due to yttrium. Furthermore, the thickness and the thickness uniformity also have a very significant effect on the life of the thermal barrier system.
Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.
Studies have been conducted to examine the effect of low concentrations of NaCl(g) on the high temperature oxidation behavior of complex superalloys and potential coating formulations modified by silicon and reactive element (i.e., yttrium and hafnium) additions. Depending on alloy composition, a variety of effects were thermogravimetrically produced. Aluminum free alloys such as MAR-M509 and Hastelloy X with molybdenum and tungsten in solid solution showed accelerated (or breakaway) kinetics similar to that observed for Ni-Cr alloys. For IN-792, an alloy high in chromium and low in aluminum, molybdenum and tungsten present in solid solution does not adversely affect oxidation kinetics in the presence of NaCl(g). On the other hand, nickel-base alloys high in aluminum and molybdenum are catastrophically attacked by NaCl-bearing atmospheres. Silicon additions were, in general, observed to slightly improve the oxidation resistance of Ni, Ni-40Cr and CoCrAlY compositions in NaCl(g)-bearing atmospheres. To the degree that processes responsible for Al2O3 whisker formation deleteriously affect protective scale adherence, the addition of yttrium or hafnium can inhibit such whisker growth.
An analysis of impact melt samples from a drill hole at the Brent crater in Ontario for siderophile trace elements indicative of meteoritic contamination, has resulted in 823-857 m-deep basalt melt zone samples enriched in Ir, Os, Pd, Ni, Co, Cr and Se over basement. The abundance pattern suggests a chondritic projectile and, from a Ni-Cr correlation of 10 melt samples, an L or LL chondrite is inferred. Data from the Manicouagan, Mitastin, and Zhamanshin craters are also assessed, and large differences in siderophile element concentrations are found among the tektites which otherwise have similar chemical compositions. There are now four known craters formed by chondrites, with Brent being the smallest among them.
Processing-technology development of a multiphase, self-lubricating, plasma-spray powder resulted in greater uniformity and reproducibility of plasma-sprayed coats. The effect of particle-size variation, binder concentration, and reproducible processing parameters are reported. Greater adhesive strengths of coats to substrates were achieved by particle-size variation, use of an intermediate bond coat such as Ni-Cr, or heat treatment. Quantitative analyses of polished, coated specimens are also given.
The present historical account of the X-15 hypersonic research aircraft development program, which began in 1952 with the determination by NACA's Committee on Aeronautics to attempt speeds of Mach 10-12 and altitudes of 12-50 miles. While the technical proposal adopted by the program in 1954 reduced speed requirements to Mach 6.6, representing the state-of-the-art capability in high temperature structures, the X-15 would ultimately reach a speed of Mach 6.7. The structural material employed was Inconel X, an Ni-Cr alloy slightly heavier than steel. The X-15 program studied problems in exoatmospheric flight control, structural heating, control in weightlessness, and atmospheric reentry. The last flights were conducted in 1968.
The determination of the tribilogically optimum composition of chromium-carbide-based solid lubricant coatings using a foil gas bearing test apparatus is described. The coatings contain a wear resistant chromium carbide `base stock' with the lubricant additives silver and BaF2-CaF2 eutectic. The coating composition is optimized for air-lubricated foil gas bearings at temperatures ranging from 25 to 650 C. The various compositions were prepared by powder blending, then plasma sprayed onto Inconel 718 test journals and diamond ground to the desired coating thickness and surface finish. The journals were operated against preoxidized Ni-Cr alloy foils, and the test bearings were subjected to repeated start-stop cycles under a bearing unit of 14 kPa. Sliding contact between the coated journal and the smooth foil occurs during bearing start-up before lift-off or hydrodynamic lubrication by the air film and during bearing coast-down. The bearings were tested for 9000 start-stop cycles or until specimen reached a predetermined failure level.
LCR304 is a solid lubricant coating composed of Ni-10Cr, Cr2O3, BaF2-CaF2 and Ag and developed for dimensional stability in high temperature air. This coating is a modification of PS304, which differs in that the Ni-Cr constituent contains 20wt% Cr. The tribological characteristics of LCR304 were evaluated by pin-on-disk and foil air bearing rig testing from 25 to 650 C and compared to previous test results with PS304. For both tests, the friction coefficient decreased as temperature increased from 25 to 650 C. Wear generally decreased with increasing temperature for all pin-on-disk tests. LCR304 coated components produced the least wear of Inconel X-750 counterface materials at 427 and 650 C. These results indicate that the LCR304 coating has potential as a replacement for PS304 in, for example, low cycle (minimum wear) applications where dimensional stability is imperative.
Increasing temperatures in aero gas turbines is resulting in oxidation and hot corrosion attack of turbine disks. Since disks are sensitive to low cycle fatigue (LCF), any environmental attack, and especially hot corrosion pitting, can potentially seriously degrade the life of the disk. Application of metallic coatings are one means of protecting disk alloys from this environmental attack. However, simply the presence of a metallic coating, even without environmental exposure, can degrade the LCF life of a disk alloy. Therefore, coatings must be designed which are not only resistant to oxidation and corrosion attack, but must not significantly degrade the LCF life of the alloy. Three different Ni-Cr coating compositions (29, 35.5, 45wt. Cr) were applied at two thicknesses by Plasma Enhanced Magnetron Sputtering (PEMS) to two similar Ni-based disk alloys. One coating also received a thin ZrO2 overcoat. The coated samples were also given a short oxidation exposure in a low PO2 environment to encourage chromia scale formation. Without further environmental exposure, the LCF life of the coated samples, evaluated at 760C, was less than that of uncoated samples. Hence, application of the coating alone degraded the LCF life of the disk alloy. Since shot peening is commonly employed to improve LCF life, the effect of shot peening the coated and uncoated surface was also evaluated. For all cases, shot peening improved the LCF life of the coated samples. Coated and uncoated samples were shot peened and given environmental exposures consisting of 500 hrs of oxidation followed by 50 hrs of hot corrosion, both at 760C). The high-Cr coating showed the best LCF life after the environmental exposures. Results of the LCF testing and post-test characterization of the various coatings will be presented and future research directions discussed.
In a prior companion study (Ref. 1), three different Ni-Cr coating compositions (29, 35.5, 45 wt% Cr) were applied at two thicknesses by Plasma Enhanced Magnetron Sputtering (PEMS) to two similar Ni-based disk alloys. One coating also received a thin ZrO2 overcoat. The low cycle fatigue (LCF) life of each coating was determined at 760 °C and was less than that of the uncoated specimens. In this followon effort, shot peening was examined as a means to improve the as-deposited coating morphology as well as impart a residual compressive stress in the near-surface region. After evaluating the effect of the shot peening on the LCF life, the effectiveness of the shot-peened coating in protecting the disk alloy from oxidation and hot corrosion attack was evaluated. This evaluation was accomplished by exposing coated and shot-peened specimens to 500 h of oxidation followed by 50 h of hot corrosion, both at 760 °C in air. These exposed specimens were then tested in fatigue and compared to similarly treated and exposed uncoated specimens. For all cases, shot peening improved the LCF life of the coated specimens. More specifically, the highest Cr coating showed the best LCF life of the coated specimens after shot peening, as well as after the environmental exposures. Characterization of the coatings after shot peening, oxidation, hot corrosion and LCF testing is presented and discussed.
The oxidation behavior of a Ni–5Cr (at.%) alloy was evaluated at 420 ° C using the Rhines pack method and simultaneous tensile and compressive stress states via a miniature four-point bending fixture. At this moderate temperature, grain boundaries dominate mass transport and the resulting oxidation response. Oxidation produced approximately 1μm-wide protective Cr 2 O 3 films capping some grain boundaries and penetrative, intergranular Cr-rich oxides at other grain boundaries. Externally applied tensile and compressive stress during oxidation increased the prevalence of Cr 2 O 3 cap formation compared to no applied stress, with tensile stress resulting in more Cr 2 O 3 caps than compressive stress. The observed oxide cap morphology was similar across all test conditions. Regions under compressive stress showed an order of magnitude greater Cr depletion depth along the grain boundary. Chromium nitrides (CrN), likely from N contamination of the Rhines pack cell, were observed both at the oxide–metal interface and intergranularly within the alloy. Collectively these results demonstrate that applied stress promotes localized protective oxide cap formation over grain boundaries, with compressive stress additionally promoting deeper Cr depletion. Furthermore the experimental approach helped separate out the effects of stress on local oxide formation and grain boundary passivation.
Nickel-based alloys are leading contenders for use as structural materials in molten salt reactors. While there have been extensive studies on the impact of fluoride/chloride-based molten salt corrosion on the microstructural evolution of various nickel-based alloys, the effects of simultaneous molten salt corrosion and radiation on the mechanical integrity of grain boundaries (GBs) remain underexplored. In this study, we use a Ni-20Cr model alloy to investigate this issue, subjecting it to simultaneous molten fluoride salt corrosion and proton irradiation. We performed cross-sectional and chemically-sensitive electron microscopy characterization of the microstructures of these materials, identifying the characteristic corrosion-induced microstructure and local chemical heterogeneity near GBs. After developing a sample preparation method for reliable characterization of GB strength, we assess the mechanical degradation of GBs using in situ push-to-pull micro tensile tests. Our findings reveal that voids induced by corrosion are the primary influence on the failure mode of GBs, regardless of whether proton irradiation is present. For materials that exhibit ductile fracture, those subjected to simultaneous corrosion and radiation exhibit lower yield strengths than those exposed to corrosion alone, which may be linked to the previously observed phenomenon of proton irradiation-decelerated intergranular corrosion in molten salt.
The high-temperature oxidation of Ni–Cr alloys leads to complex oxide scales comprising Ni(Cr)O solid solutions, NiCr 2 O 4 spinel, and Cr 2 O 3 corundum within the NiO matrix. Understanding the atomic-scale mechanisms of Cr segregation and precipitate formation is crucial for enhancing oxidation resistance. Here, we employ density functional theory calculations to investigate Cr behavior on NiO(100), (110), and (111) surfaces and in the bulk. Our results reveal that isolated Cr atoms preferentially segregate to the surfaces, stabilizing Ni(Cr)O solid solutions via strong Cr–O bonding, whereas Cr pairs and clusters favor subsurface migration and bulk aggregation, promoting nucleation of NiCr 2 O 4 and Cr 2 O 3 phases. These findings elucidate a size-dependent segregation mechanism linking Cr coordination environments to oxide phase evolution. This atomic-scale insight informs strategies to tailor oxide microstructures and enhance the high-temperature oxidation resistance of Ni–Cr alloys.