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At least 19 records

X-Ray Absorption Spectroscopy in High Temperature Oxidation of Metals and Alloys

An experimental technique is described that allows for the joint study of the kinetics and of the oxide structure during the high temperature oxidation of metal surfaces. Oxygen is supplied at the metal through an electrochemical oxygen pump and the oxygen pressure, at the metal surface, is measured during oxidation by a YSZ (yttria stabilized zirconia) oxygen sensor. XAS (x-ray absorption spectroscopy) is performed in fluorescence mode at the cation K edge and after each oxidation step. An appropriate analysis of the XAS spectra could provide information on both the oxidation kinetics and oxide structure. Experimental data on the high temperature oxidation of nickel, cobalt, and Fe(64%)Ni(36%) alloy, at low oxygen pressure, are reported and analyzed according to the proposed data reduction. These results indicate the presented technique to be particularly suitable for studying the hot corrosion of oxide film too thick for common surface spectroscopy (AUGER, ESCA) and too thin for conventional thermogravimetric technique.

Daniele Gozzi↗

Phase-field modeling of alloy oxidation at high temperatures

Oxide growth is a complex process involving transport of reactive species, heterogeneous reactions, and microstructure evolution. Predicting oxidation kinetics and especially the oxide morphological change has been a long-standing challenge. Here we develop a phase-field model for predicting the oxide growth kinetics of a multicomponent alloy during high temperature oxidation, focusing on internal oxidation (non-protective) and its transition to external oxidation (protective). In this work, the predicted kinetics and oxide morphology are analyzed and compared to the classical Wagner’s theory and an existing analytical model by Zhao and Gleeson. Some assumptions used in the analytical models and the limitation are discussed. In addition, it is demonstrated that the morphology and distribution of the initial oxide nuclei play an important role in the later stage oxide connectivity and thus the transition to external oxidation.

36 MATERIALS SCIENCE↗

High Temperature Oxidation of Boron Nitride: Monolithic Boron Nitride - Part 1

High temperature oxidation of monolithic boron nitride (BN) is examined. Hot pressed BN and both low and high density CVD BN were studied. It is shown that oxidation rates are quite sensitive to microstructural factors such as orientation, porosity, and degree of crystallinity. In addition small amounts of water vapor lead to volatilization of the B2O3 oxide as H(x)B(y)O(z). For these reasons, very different oxidation kinetics were observed for each type of BN.

Jacobson, Nathan↗

High-temperature oxidation and ignition of metals

A study of the high-temperature oxidation of several aircraft construction materials was undertaken to assess the possibility of ignition under high-temperature flight conditions.Tests have been made both in open and closed jets, and, in addition, the burning of metals has been observed under static conditions in a pressurized vessel containing either air, oxygen, or nitrogen. When heated in an atmosphere of oxygen or when heated and plunged into a supersonic airstream, titanium, iron, carbon steel, and common alloys such as 4130 were found to have spontaneous-ignition temperatures in the solid phase (below melting) and they melted rapidly while burning. Inconel, copper, 18-8 stainless steel, Monel, and aluminum could not be made to ignite spontaneously at temperatures up to melting with the equipment available. Magnesium ignited spontaneously in either type of test at temperatures just above the melting temperature.A theory for the spontaneous ignition of metals, based on the first law of thermodynamics, is presented. Good correlation was obtained between calculated spontaneous-ignition temperatures and values measured in supersonic jet tests. There appears at the present time to be no need for concern regarding the spontaneous ignition of Inconel, the stainless steels, copper, aluminum, or magnesium for ordinary supersonic airplane or missile applications where the material temperature is kept within ordinary structural limits or at least below melting. For hypersonic applications where the material is to be melted away to absorb the heat of convection, the results of the present tests do not apply sufficiently to allow a conclusion.

Hill, Paul R↗

Chromium segregation-induced oxide evolution in Ni-10Cr alloys during high-temperature oxidation

The oxidation behavior of a Ni-10(wt%)Cr alloy under high-temperature O 2 conditions is investigated using transmission electron microscopy and first-principles calculations. Results reveal that chromium segregation plays a central role in driving the evolution of complex oxide phase structures during oxidation. At low Cr concentrations, Cr preferentially segregates to NiO grain boundaries or internal pores, substituting for Ni atoms and forming Ni(Cr)O solid solutions. As Cr content increases, enhanced diffusion promotes Cr penetration into the NiO lattice, leading to the formation of multiphase oxide structures. First-principles modeling corroborates these findings: at low Cr concentrations, Cr atoms favor surface and grain-boundary segregation, while higher concentrations lead to Cr aggregation within the NiO bulk. Furthermore, the integrated experimental-theoretical approach provides atomistic insights into Cr-mediated mass transport mechanisms during alloy oxidation and offers valuable guidance for controlling oxide growth kinetics and phase stability in Ni-Cr alloys, with implications for improving oxidation resistance in high-temperature structural applications.

36 MATERIALS SCIENCE↗

Thin coatings for protecting titanium aluminides in high-temperature oxidizing environments

Titanium aluminides have high specific strengths at high temperatures but are susceptible to environmental attack. Their use in many aerospace applications would require that they be protected with coatings that, for structural efficiency, must be thin. It is conceivable that acceptable coatings might be found in several oxide systems, and consequently, oxide coatings of many compositions were prepared from sol-gels for study. Response-surface methodology was used to refine coating compositions and factorial experiments were used to develop coating strategies. Oxygen permeability diagrams of two-layer coatings for several oxide systems, an analysis of multiple-layer coatings on rough and polished surfaces, and modeling of the oxidation weight gain are presented.

Wiedemann, K. E.↗

Diffusional aspects of the high-temperature oxidation of protective coatings

The role of diffusional transport associated with the high-temperature oxidation of coatings is examined, with special attention given to the low-pressure plasma spraying MCrAl-type overlay coatings and similar Ni-base alloys which form protective AlO3 scales. The use of diffusional analysis to predict the minimum solute concentration necessary to form and grow a solute oxide scale is illustrated. Modeling procedures designed to simulate the diffusional transport in coatings and substrates are presented to show their use in understanding coating degradation, predicting the protective life of a coating, and evaluating various coating parameters to guide coating development.

Nesbitt, J. A.↗

Niobium-aluminum base alloys having improved, high temperature oxidation resistance

A niobium-aluminum base alloy having improved oxidation resistance at high temperatures and consisting essentially of 48%-52% niobium, 36%-42% aluminum, 4%-10% chromium, 0%-2%, more preferably 1%-2%, silicon and/or tungsten with tungsten being preferred, and 0.1%-2.0% of a rare earth selected from the group consisting of yttrium, ytterbium and erbium. Parabolic oxidation rates, k.sub.p, at 1200.degree. C. range from about 0.006 to 0.032 (mg/cm.sup.2).sup.2 /hr. The new alloys also exhibit excellent cyclic oxidation resistance.

Hebsur, Mohan G.↗

Use of Modeling and Experiments to Assess the Effect of Minor Alloying Additions on Alumina Scale Formation during High-Temperature Oxidation

During the last decades, new generations of Ni-based superalloys have emerged with judiciously controlled chemistries. These alloys heavily rely on the addition of refractory elements to enhance their mechanical properties at elevated temperatures; however, a clear interpretation of the influence of these minor-element additions on the alloy's high-temperature oxidation behavior is still not well understood, particularly from the standpoint of predicting the transition from internal to external alumina formation. In this context, the present investigation describes a systematic study that addresses the intrinsic effects that minor element additions of Nb, Ta, and Re have on the oxidation behavior of alumina-scale forming γ-Ni alloys. By combining a novel simulation approach with high-temperature oxidation experiments, the present study evidences the generally positive effect associated with 2 at. % addition of Ta and Re as well as the detrimental consequences of Nb additions on the 1100 °C oxidation of (in at. %) Ni-6Al-(0,4,6,8)Cr alloys.

Rodriguez, Rafael↗

The microscopic mechanisms of high temperature oxidation of Haynes 282

Nickel-based superalloy finds widespread applications in aerospace and extreme environments. They are known for their high temperature oxidation resistance under extended periods. However, the oxide formation and evolution which sets the stages for the later parabolic oxidation kinetics is not fully understood. This paper aims to provide new insights into the transient stage oxidation mechanism and kinetics of a typical Ni-based superalloy (Haynes 282). While tracking the chemical and microstructural evolution under micrometer scale at 800°C, we show that the oxide scale and its grain boundary species change significantly during the initial stages of oxidation and can have a profound impact on the oxidation kinetics. Cr 2 O 3 forms initially at the grain boundary along with minor amount of Al 2 O 3 . Then, the grain boundary region is enriched with copious amounts TiO 2 while Cr migrates away from the grain boundary. A noticeable change in the isothermal oxidation kinetics observed likely results from a mechanistic change from uniform surface oxidation to preferential outward diffusion of Ti 4+ ions through the grain boundary. Through first-principles calculations combined with energy dispersive spectroscopy, we confirmed the preferential outward diffusion of Ti 4+ ions as the diffusion barrier is lower for Ti than Cr along the grain boundaries. In conclusion, these findings highlight the critical role of early-stage grain boundary oxidation dynamics in dictating the long-term oxidation resistance of Ni-based superalloys and provide a foundation for future strategies to enhance their performance in extreme environments.

DFT↗

Ceramic problems/challenges in high temperature oxide superconductors - Hysteretic force measurements as a new analysis tool

A technique is presented for analyzing high-temperature oxide superconductors using hysteretic magnetic force/distance measurements. Emphasis is placed on developing low weight, highly robust superconducting materials for space applications. Bi-Ca-Sr-Cu superconductors are prepared and characterized by standard techniques. It is found that standard techniques such as XRD, SEM, and TEM are insufficient to completely characterize superconductors. The magnetic properties of the superconductors are studied with the new technique, based on measuring the force between a magnet and the superconductor as a function of their separation.

Morgan, P. E. D.↗

High Temperature Oxidation Behavior of Ni-based High Entropy Superalloys

A new class of polycrystalline gamma-prime strengthened superalloys with alloy compositions of (wt%) Ni-20Co-13Cr-6Fe-4Al-3W-2Mo-(4-x)Nb-(x)Ti (x = 0,1,2) were subjected to cyclic oxidation exposures in dry air at 800 °C for 3600 h. The alloys were borderline chromia/alumina formers, showing good oxidation resistance relative to commercially available materials of similar composition. While all alloys formed alumina scales initially, only the alloy with the lowest Ti/Nb ratio retained an alumina scale for the duration of the exposure. Formation of a continuous layer of rutile TiO 2 at the alumina/alloy interface is proposed to cause eventual alumina failure for the alloys containing Ti.

36 MATERIALS SCIENCE↗