The kinetics and mechanism of catastrophic oxidation of metals

A set of independent methods has been used to study the catastrophic oxidation of copper in the system Cu–Me_xO_y (where Me is Bi, W, Mo, or V). Two stages of the catastrophic oxidation have been revealed: a rapid stage (K10^–4 kg² m^–4 sec^–1) and a super rapid stage when the metal is oxidized within1–5 sec. The weight ratios of metal to oxidizer and the partial oxygen pressure for the superrapid copper oxidation have been established. The mechanism of the catastrophic oxidation of metals is considered.     

Parabolic oxidation of metals to metal deficit oxides

A stepwise mechanism is outlined for diffusion-controlled oxidation of a metal Me to a metal deficit oxide Me_3–zO, where z is the normal valence of Me in Me_3–zO and may equal either 1 or 2. Specifically, oxidation is postulated to occur by (1) chemisorption of a singly ionized oxygen atom O^– on the oxide surface with the concomitant formation of an electron holeprobably localized on a lattice site as a more electropositive cation Me^z+1, (2) subsequent further ionization of chemisorbed O^– and its incorporation into the oxide with the formation of singly charged cation vacancies V and, in the case z=1, an additional compensating hole Me^z+1, (3) migration of Me^z ions and electrons via the V and Me^z+1 defects from the underlying metal to the surface, and (4) annihilation of the defects V and Me^z+1 at the oxide-metal interface by the passage of metal atoms from the metal into the oxide. Such a mechanism leads to an eighth root pressure dependency for monovalent cation systems like O₂-Cu₂O-Cu and a fourth root pressure dependency for bivalent systems like O₂-NiO-Ni and O₂-CoO-Co. The behavior of copper and nickel are shown to be as predicted; whereas, in the case of cobalt, defect interaction results in deviations from the predicted behavior.     

In situ SEM study of the high-temperature oxidation of an Fe-Mn-Al-Si alloy

The oxidation behavior of a low-carbon Fe-30Mn-10Al-Si alloy was studied at 1100 and 1150C in a hot-stage environmental scanning electron microscope. The oxidation experiments were performed in pure oxygen at a partial pressure of 10 ^–4 atm. Under these conditions, nodule nuclei of manganese and iron oxide appeared after a few minutes of oxidation, indicating the local destruction of the protective Al₂O₃ scale. The nodules grew and coalesced and finally overgrew the entire specimen surface. The composition of the nodules changed during the growth process; the amount of iron decreased, and the manganese content increased to about 95 wt%. All the nodules were located in symmetrically shaped pits which intrude into the metal.     

Volatilization and Transport Mechanisms During Cr Oxidation at 300 °C Studied In Situ by ToF-SIMS

The oxidation of chromium at 300 °C was investigated in situ by ToF-SIMS for three different oxygen pressures (\(P_{{{\text{O}}_{2} }} = 2.0 \times 10^{ - 7}\), 6.0 × 10^?7 and 2.0 × 10^?6 mbar). Sequential exposure to the ¹⁸O isotopic tracer was performed to reveal the governing transport mechanism in the oxide film. The evolution of the oxide thickness was monitored. Volatilization of Cr₂O₃ was evidenced. A model was used to describe the kinetics resulting from the measurements. Both the parabolic and volatilization constants showed a dependence on oxygen partial pressure like \(P_{{{\text{O}}_{2} }}^{ - 1/n}\), with n = 1.9 ± 0.1, indicating a defect structure mainly consisting of oxygen vacancies. The re-oxidation in ¹⁸O₂ shows a growth of the oxide layer at the metal/oxide interface, demonstrating an oxidation process governed by anionic transport via oxygen vacancies. The diffusion coefficient of oxygen in the oxide was determined by fitting the ToF-SIMS depth profiles. It is 2.0 × 10^?18 cm² s^?1.     

Influence of silicon on the oxidation of titanium between 550 and 700°C

The oxidation behavior of Ti-Si alloys (0.25, 0.5, and 1 Wt. % Si) was investigated between 550 and 700°C; in oxygen by continuous thermogravimetry for a maximum duration of about 500 hr and, in air by daily weighing for durations from a few hundred to several thousand hours. The kinetics results revealed that the presence of silicon leads to a decrease in oxidation rate which is more evident when the temperature is raised and the silicon content is increased. Morphological and structural examinations revealed that silicon modifies the internal architecture of oxide layers when compared with unalloyed titanium; in particular, reduced porosity in the layers is observed. Analysis showed that silicon is uniformly distributed in the oxide layer. However, while part of the silicon is in solid solution in the rutile, some is also precipitated as small crystals ( <1 m at 850°C) of SiO₂, of cristobalite structure. The adherence of oxide layers to the metal substrate was measured after cooling of samples; the addition of silicon has been observed to modify, in a manner dependent on its content, the adherence of oxide layers.     

The growth and structure of oxide films on Fe. II. Oxidation of polycrystalline Fe at 240–320°C

The influence of surface pretreatment and metal orientation on the oxidation of coarse-grained polycrystalline Fe has been studied at 240 to 320°C in 5×10^–3 Torr O₂ using electron diffraction, electron microscopy, and Mössbauer spectroscopy to complement kinetic data. Consistent with previous studies on Fe single crystals, differences in oxidation kinetics for surfaces covered with an electropolish film from those with a similar thickness prior oxide formed by dry oxidation at room temperature are interpreted in terms of differing densities of leakage paths in the oxide layers. The more complex kinetics for electropolished polycrystalline Fe are a result of the leakage path density, the degree of oxide separation, and the extent of -Fe₂O₃ formation varying with substrate orientation. Where adherent Fe₃O₄ layers are formed on polycrystalline and single-crystal Fe surfaces, the parabolic rate constants give an activation energy which is consistent with a previous value of 32 kcal · mole^–1, suggesting that at these low temperatures the transport mechanism for magnetite growth is cation diffusion via easy diffusion paths in the oxide.     

Influence of the Oxygen Partial Pressure on the Oxidation of Inconel 617 Alloy at High Temperature

Ni-based superalloy Inconel 617 (IN617) is one of the main candidate structural materials for high temperature components (heat exchanger) of the gas-cooled fast reactor (GFR), a possible candidate for generation IV nuclear reactor. The material in operating conditions will be exposed to impure He at a temperature of around 850 °C. The impurities are expected to be oxidizing (such as O₂, H₂O) but since no feedback experience is available for this type of reactor, the level of impurities is completely unknown. Hence, an attempt has been made to understand the influence of oxygen partial pressure on oxide composition and on the oxidation mechanisms of IN617 at 850 °C. To achieve this, oxidation tests were performed at 3 different range of partial pressure: 10^?5, 0.2 and 200 mbar. Tests were performed from 1 h to 28 days and the obtained oxide layers were characterized using MEB, EDX, XPS, XRD and GD-OES. The oxide layers were mainly composed of chromia containing TiO₂ and thickening with time. Aluminium oxide formed internally. Other oxides were detected in the scale, such as NiO, CoO, MoO₃ and MnO₂, except for the lowest oxygen partial pressure experiments, where a selective oxidation took place. The scale-growth mechanism was cationic for low and medium oxygen partial pressure conditions. A growth following a transient oxidation mechanism was observed for high oxygen partial pressure.     

The initiation of selective oxidation of a ferritic stainless steel at low temperatures and oxygen pressures

Oxidation of a ferritic stainless steel of type Fe-18Cr-2Mo has been performed in the temperature range 285–495°C and oxygen partial pressure range 10^?9-10^?8 torr. The chemical composition of thin oxide layers formed has been analysed by means of Auger Electron Spectroscopy and interpreted in terms of available chromium, iron and oxygen at the solid/gas interface. The selective oxidation of chromium is considered by different probabilities for the oxidation of available chromium and iron respectively. At oxide thicknesses below 100 Å the supplies of chromium and iron are ruled by diffusion in the steel matrix. The results have been used to predict the chemical compositions of two subsequently growing oxide layers provided the thickness of the first oxide layer is below 50 Å.     

Oxide nucleation on thin films of copper duringin Situ oxidation in an electron microscope

single-crystalline thin films of copper were oxidized at an isothermal temperature of 425°C and at an oxygen partial pressure of 5×10^–3 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. The predominantly observed crystallographic orientations of Cu₂O on {100} and {110} copper films were epitaxial, parallel {100} and {110} orientations, respectively. In addition, a Cu₂O {111} orientation with Cu₂O 770//Cu 110 was found frequently on {100}-oriented copper films. The distinct particle shapes observed most frequently were square and hexagonal, representing {100} and {111} orientations, respectively. An induction period of about 30 min was found, which did not depend on the film thickness but did depend strongly on the oxygen partial pressure and the oxygen exposure prior to the oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu₂O nucleation sites. The growth of Cu₂O nuclei was found to be 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 formation of a supersaturated zone near the surface, and (c) nucleation, followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.This work was performed at the Ames Research Center and funded by NASA Grants NCA2-OP390-403 and NSG-2025.     

An Ultralow Oxygen Partial Pressure-Controlling System and Its Application to Oxidation Studies

An ultralow oxygen partial pressure-controlling system, based on solid-stateelectrochemical principles, has been developed. This system consists of anoxygen sensor and an oxygen pump and is controlled by a PC computer. Theoxygen sensor is used to measure the oxygen partial pressure in an enclosedsystem, while the oxygen pump is used to transport oxygen from the ambientair into the enclosed system or from the enclosed system to the ambientair. The operating conditions of this system have been studied. The resultsshowed that it can be used to establish a stable oxygen partial pressure inthe range of 10–185×105 Pa (1×10–235 atm)in the enclosed system. This system has been used to investigate theselective oxidation of the Cr and the oxide formation on the surface of aNi–Cr alloy under three different low oxygen partial pressures. Theoxide morphology was studied using atomic force microscopy (AFM). The resultsagreed well with those in the literature and also confirm the reliability of this system.     

Oxidation characteristics of Ti-4.37 wt.% Ta alloy in the temperature range 1258–1473 K

Oxidation kinetics of Ti-4.37 wt.% Ta (1.19 at.%) alloy in either air or oxygen have been investigated in the temperature range 1258–1473 K and at three pressure levels: 0.013, 0.133, and 1.0 bar. X-ray data reveal only TiO₂ (rutile) as the main oxide and, in addition, TiO₂, S-TiN, and -TiN at the metal surface for oxidation in air at 1273 K. The -TiN phase was not detected at higher temperatures. Electron microprobe analyses are used to determine the concentration profiles of Ti, Ta, O, and N across the oxide scale and in the metal. Microhardness traverses follow the oxygen distribution in the alloy. The oxygen diffusion coefficient,D = 60.8 exp(–235.1/RT), as determined from weight-gain measurements, is in reasonable agreement with that calculated from microhardness data. The oxidation mechanisms for oxidation of the alloy in air or oxygen are proposed.The existence of interstitial Ti cations in the oxide is suggested.Presently on academic leave at Max-Planck-Institut für Metallforschung, Institut für Werk-stoffwissenschaften, Stuttgart, German Federal Republic.     

Electronic transport in thermally grown Cr2O3

Electrical conductivity of thermally grown Cr₂O₃ has been measured as a function of temperature and over a range of oxygen partial pressures from that of air to that of the Cr/Cr₂O₃ equilibrium. The conductivity showed p-type behavior over the range of the present investigation. At temperatures above 1000°C, the conductivity values were independent of oxygen partial pressure and indicated intrinsic semiconductor behavior. The mobility of holes, determined by measuring conductivity at fixed compositions (i.e., fixed in Cr_2-O₃), increased with temperature. This behavior can be attributed to hopping-type conduction. For 10^–5, the activation energy for hole hopping was 0.248 eV, and the calculated hole mobilities were 5.4x10^–2 and 2.4x10^–1 V/cm² · s at 500 and 1000°C, respectively. The oxidation kinetics of Cr were determined by measuring the electrical conductivity and electromotive force across the oxide layer at 875°C. The result agreed well with the oxidation data obtained in thermogravimetric tests.     

Characterization of oxide structures formed on nickel-chromium alloy during low pressure oxidation at 500–600°C

Low pressure oxidation studies of Ni-18%Cr alloy were carried out at temperatures of 500–600°C for very brief periods. Detailed XPS, AES, SEM, and TEM studies identified four stages in the initial oxidation. These are: (1) formation of a mixed nickel-chromium oxide overlayer; (2) growth of submicron-sized oxide nodules; (3) development of dark hole-like patches on the surface; and (4) growth of second generation oxide nodules. Both types of nodules consist primarily of a nickel structure depleted in oxygen. Their formation appears to result from a very rapid outward movement of nickel from localized defects in the metal. The dark patches result from the presence of a chromium oxide-rich underlayer, which appears to form by a lateral migration of chromium from adjacent oxide/metal interface regions and from grain boundaries.     

Kinetics and mechanisms of the oxidation of cobalt at 600–800°C

Two-phase layered scales comprising CoO and Co ₃O₄ formed on cobalt during oxidation at 600°, 700°, and 800°C and at oxygen partial pressures in the range 0.001–1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, non-parabolic stage of oxidation. The monoxide consisted of relatively large grains (10 ) and the spinel comprised small grains (3 ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinel layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co₃O₄.     

Oxidation of high-chromium Ni-Cr alloys

The oxidation of binary Ni-Cr alloys containing 44 and 50 wt. % Cr has been studied over a range of oxygen partial pressures at temperatures between 800 and 1100°C. The effects of cold work, surface preparation, and distribution of the Cr-rich second phase have been studied. The oxidation behavior is complex and cannot be described by a single model. The oxide grows by short-circuit diffusion as well as bulk transport through Cr ₂ O ₃ scales. The scale-growth mechanism includes extensive metal-oxide separation requiring Cr vapor transport to the scale, compressive stresses within the oxide which result in scale bulging and cracking, and the formation of a second oxide layer which results in voids being incorporated into the scale. Any factor which reduces the oxide grain size, such as cold work, finer distribution of the Cr-rich phase or reduced oxygen pressure, results in an increased oxidation rate of binary alloys because of an increased number of grain-boundary short-circuit diffusion paths.This work is based on a portion of a thesis by G. M. Ecer submitted to the University of Pittsburgh in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Metallurgical and Materials Engineering.Formerly graduate student. Department of Metallurgical and Materials Engineering. University of Pittsburgh.     

Behavior of oxygen diffusion in buffer layers for coated conductors

We have evaluated the effect of annealing in oxygen atmosphere on the structure, texture and phase transformation of LZO films deposited on YSZ (yttria-stabilized zirconia) (0 0 l) single crystal substrates and textured NiW substrates by metal-organic deposition (MOD) method. The results show that the structure stability of the LZO films is heavily dependent on the oxygen partial pressure in annealing process. Then we have in details studied the behavior of oxygen diffusion in three kinds of buffer layer architectures on NiW substrates by varying the temperature, oxygen partial pressure and dwelling time in the annealing process. The oxygen diffusion within buffer layers leads to the oxidation of substrate, and even the texture and structure of buffer layers are destroyed with the increase of the thickness of the oxides layer related to NiW substrate. It reveals that the relative volume of oxides related to NiW substrate increases exponentially with the annealing temperature, and increases linearly with the annealing time at logarithmic scale. The relative intensity of texture peaks of buffer layers decreases and even disappears with the increase of the oxygen partial pressure in annealing process because of the acceleration of the oxidation reaction of substrate. The influence of annealing temperature, oxygen partial pressure and dwelling time on the oxygen diffusion is related to the intrinsic oxygen diffusion coefficient of buffer layers materials. Compared with the increase of oxygen partial pressure, the elongation of dwelling time shows a less effect on the oxidation rate of NiW substrate and a weak destruction of the texture of buffer layers. Except choosing the oxide materials with small oxygen diffusion coefficient as buffer layers in coated conductors, the degree of oxidation about NiW substrate could be greatly controlled and it would result in the less destruction of texture and structure of buffer layers by adjusting the annealing temperature, oxygen partial pressure and dwelling time in the process of YBCO deposition.     

The internal oxidation of Nb-Hf alloys

The internal oxidation of some binary Nb-Hf and several commercial Nb alloys containing Hf was studied at 1568 and 1755°C in oxygen pressures ranging from 5×10 ^–5 to 1×10^–3 torr.The reaction kinetics were linear, suggesting that diffusion of oxygen in the substrate was not rate-controlling. The dependence of the reaction rate on oxygen pressure was linear also. Well-defined reaction fronts were observed at higher pressures and the lower temperature, whereas ill-defined fronts occurred at lower pressures and at the higher temperature. The solubility product was much higher than normally encountered in Wagnerian-type behavior and gave rise to varying solute content across the internal-reaction zone. The solute-concentration profiles (EPMA/WDS) of the matrix between particles exhibited a sigmoidal shape for well-defined reaction fronts, whereas the profiles showed a gradual decrease in solute with distance near the front for ill-defined fronts, dropping fairly abruptly at the metal/gas interface. The solute concentration never reached zero at the surface for any condition studied. In contrast to classical, Wagnerian behavior, solute continued to precipitate out after the reaction zone had passed, leading to a variation in the mole fraction of oxide in the zone. SEM/EDXA and XRD showed that precipitation occurred by the formation of precursors (Hf-rich regions surrounded by Hf-depleted regions), followed by precipitation of tetragonalHfO₂,which in some cases transformed to monoclinicHfO₂ and subsequently coarsened. The precipitate morphology varied with solute concentration, temperature, oxygen pressure, and location within the reaction zone. High temperature and high oxygen pressure favored a Widmanstätten structure, whereas low temperature and low oxygen pressure favored a spheroidal precipitate structure. Widmanstätten plates were observed to spheroidize at longer times, suggesting that the interfacial energy between particles and matrix was very high. The presence of a small amount of Y (0.11 w/o in C129) always resulted in spheroidal particles. It appears that Y markedly increased the particle/matrix interfacial energy. Microhardness profiles showed decreasing values with distance into the sample for some conditions and alloys but increasing values in other cases. Hardness increases in the substrate in advance of the interface showed that oxygen activity did not reach zero at the reaction front, once again contrary to classical behavior but consistent with high solubility products of the oxide. Results are analyzed in terms of oxygen-trapping by reactive solutes as noted in the literature for both lattice-parameter measurements and oxygen diffusivity studies.     

Mechanism of isothermal oxidation of the intel-metallic TiAl and of TiAl alloys

The oxidation behavior of Ti36Al, Ti35Al-0.1C, Ti35Al-1.4V-0.1C, and Ti35 Al-5Nb-0.1C (mass-%) in air and oxygen has been studied between 700 and 1000°C with the major emphasis at 900°C. Generally an oxide scale consisting of two layers, an outward- and an inward-growing layer, formed. The outward-growing part of the scale consisted mainly of TiO₂ (rutile), while the inward-growing part is composed of a mixture of TiO₂ and -Al₂O₃. A barrier layer of Al₂O₃ on TiAl between the inner and the outer part of the scale was visible for up to 300 hr. Under certain conditions, the Al₂O₃ barrier dissolved and re-precipitated in the outer TiO₂ layer. This shift leads to an effect similar to breakaway oxidation. Only the alloy containing Nb formed a longlasting, protective Al₂O₃ layer, which was established at the metal/scale interface after an incubation period of 80–100 hr. During this time, Nb was enriched in the subsurface zone up to approximately 20 w/o. The growth of the oxide scale on TiAl-V obeyed a parabolic law, because no Al₂O₃ barrier layer formed; large Al₂O₃ particles were part of the outward-growing layer. A brittle 2-Ti₃Al-layer rich in O formed beneath the oxide scale as a result of preferential Al oxidation particularly when oxidized in oxygen. Oxidation in air can lead also to formation of nitrides beneath the oxide scale. The nitridation can vary between the formation of isolated nitride particles and of a metal/Ti₂AlN/ TiN/oxide, scale-layer system. Under certain conditions, nitride-layer formation seemed to favor protective Al₂O₂₃ formation at the metal/scale interface, however, in general nitridation was detrimental with the consequence that oxidation was generally more rapid in air than in oxygen.     

Oxidation of copper at high temperatures

The kinetics and mechanism of copper oxidation have been measured over the temperature range 900–1050°C and the pressure range 5×10^?3 to 8×10^?1 atm. It has been shown that, at the pressures lower than the dissociation pressure of CuO, the oxide scale formed on flat fragments of the copper specimens is compact and composed of a single layer, adhering closely to the metallic base. Growth of the scale proceeds under these conditions by outward diffusion of metal. The rate of the process under the conditions for which single-phase scales are formed increases with increasing oxygen pressure according to the equation: $${\text{k''}}_{\text{p}}^{} = const {\text{p}}_{{\text{O}}_{\text{2}} }^{{\text{1/3}}{\text{.9}}} $$ . the activation energy for oxidation is 24 ± 2 kcal/mole. On the basis of theFueki-Wagner method and the method proposed in the present work, the self-diffusioncoefficients of copper in cuprous oxide were calculated as a functionof oxygen pressure and temperature. It has been shown that distribution of thedefect concentration in the growing layer of the scale is linear.     

The oxidation behavior of a Zr-0.5Y alloy

A Zr-0.5 Y alloy was found to oxidize about 6 times faster than pure zirconium over the temperature range of 400 to 565°C. The activation energies were nearly identical (32 kcal/mole). The activation energies correspond to grain boundary diffusion of oxygen through the scale. The higher oxidation rate of the alloy was attributed to a higher anion vacancy concentration and the assumption that diffusion sites in the lattice and boundaries were in local equilibrium. Measurements on yttria-doped zirconia showed that ionic conductivity was increased markedly by yttrium and extended over a wide range of oxygen pressure. The defect structure of the doped oxide was changed to one of oxygen vacancies, even at the high end of the oxygen pressure range, 10^–8 to 0.2 atm, over which pure ziconia contains oxygen interstitials. The doped oxide was found to be extrinsic over the entire range of oxygen pressure and, although ionic conductivity predominated, electronic conductivity was still appreciable. The electronic conductivity, however, was still sufficiently high so that electron transport was not rate-controlling in the predominantly ionic-conducting scale.