Kinetics and mechanism of high-temperature oxidation of dilute cobalt-chromium alloys

Kinetics of oxidation of Co-Cr alloys containing 0.4%–15% Cr was studied as a function of temperature (1273–1573 K) and oxygen pressure (4 × 10²–10⁵Pa). The oxidation process was found to be approximately parabolic and faster than that for pure cobalt. The scales are double-layered and consist of a compact outer CoO layer and a porous inner layer containing CoO slightly doped by chromium and spinel CoCr₂O₄. The oxidation mechanism was investigated by means of platinum markers and the¹⁸O isotope. The scale on the alloys containing less than 1% Cr grows exclusively by outward diffusion of cobalt, while that on the alloys containing more chromium—with a significant contribution of inward oxygen transport from atmosphere. This transport is not a lattice diffusion, but proceeds presumably through microfissures resulting from the secondary process of perforating dissociation of the outer scale layer.     

Oxidation of γ-Ni−Al−Si alloys at 1073 K

The formation and development of oxides in Ni–4Al and Ni–4Al–xSi (at.%, x=1, 3, 5) alloys at 5–9×10^–6 and 1 atm oxygen pressure at 1073 K have been studied. The oxidation rate increased with an increase of silicon content in the alloy at the early stage of oxidation, but decreased after longer time exposure due to formation of an intermediate layer composed of NiO and spinel (NiAl₂O₄ and Ni₂SiO₄) between the top NiO layer and the internal-oxidation zone. This intermediate layer became a barrier for releasing stress, generated by the volume expansion associated with oxidation of solute atoms, resulting in high dislocation density and severe distortion in the internal-oxidation zone for the Ni–Al–Si alloys. In Ni–4Al alloy where no complete intermediate-layer formation occurred, stress was easily released by an enhanced vacancy gradient, and therefore an enhanced vacancy-injection rate into the alloy, resulting in a higher oxidation rate than the situation where a sample was oxidized at an oxygen pressure associated with the dissociation of NiO.     

The oxidation of Co−Nb alloys under low oxygen pressures at 600–800°C

The oxidation of two Co–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H₂–CO₂ mixtures providing an oxygen pressure of 10^–24 atm at 600°C and 10^–20 atm at 700 and 800°C, below the dissociation pressure of cobalt oxide. At 600 and 700°C both alloys showed only a region of internal oxidation composed, of a mixture of alpha cobalt and of niobium oxides (NbO₂ and Nb₂O₅) and at 700°C also the double oxide CoNb₂O₆, which formed from the Nb-rich Co₃Nb phase. No Nb-depleted layer formed in the alloy at the interface with the region of internal oxidation at these temperatures. Upon oxidation at 800°C a transition between internal and external oxidation of niobium was observed, especially for Co–30Nb. This corrosion mode is associated with the development of a single-phase, Nb-depleted region at the surface of the alloy. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in cobalt and to the relation between the microstructures of the alloys and of the scales.     

Selective oxidation of FeCr alloys in the 295–450 K temperature range

A series of iron-chromium alloys were oxidized for 10² to 6×10⁴ s in air and in the 295–500 K temperature range. Room-temperature oxidation of iron, chromium, antimony, and copper were also conducted at extended times. Oxidation characteristics such as oxide thickness and composition of the oxide and of the underlying alloy were evaluated from measurements by electron spectroscopy for chemical analysis (ESCA). An initial selective oxidation of chromium with a concomitant chromium depletion in the alloy was found. This initial oxidation step is followed by growth of an outer, iron rich oxide which causes the former chromium depletion to vanish. Apparent activation energies extracted from parabolic oxidation kinetics (295–500 K) of the investigated metals were found to be in the 10–20 kcal/mole range.     

The oxidation of Ni-Nb alloys at low-oxygen pressures at 600–800°C

The oxidation of two Ni–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H₂–CO₂ mixtures providing an oxygen pressure of 10^–24 atm at 600° C and 10^–20 atm O₂ at 700 and 800° C, these pressures being less than the dissociation pressure of nickel oxide. The scales formed on both alloys at 600 and 700° C show only a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb₂O₅ or/and NbO₂), which formed from both the metal phases present, i.e., Ni₈Nb and Ni₃Nb. Only small, or even no, Nb depletion was observed in the alloys close to the interface with the zone of internal oxidation at these temperatures. On the contrary, samples of both alloys corroded at 800° C produced a continuous external scale of niobium oxides without internal oxidation. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in nickel.     

Internal oxidation of Ag-in alloys: Stress relief and the influence of imposed strain

The kinetics of internal oxidation of silver-indium alloys containing 3.5, 5.9, and 9.8 at.% In in air at temperatures 773 to 973 K were established by TGA with no load applied to the specimens. Silver nodules free of oxide particles were observed to form at the surface during internal oxidation. The volume of these silver nodules was comparable to the total volume increase caused by internal oxidation. The alloys were also creep tested during oxidation in air at creep rates varying from 10^–7 to 5×10^–5 s^–1 at 773, 873, and 973 K. The parabolic rate constants k_p for the internal oxidation of the solute were determined from the measured widths of the internal oxidation zones. A small increase in k_p was observed with increased strain rate. The large volume change associated with internal oxide formation resulted in a stress gradient between the stress-free surface and the internal oxidation front which is under a high compressive stress. Stress relief occurred by transport of silver to the surface. A Nabarro-Herring creep type mechanism based on lattice diffusion of Ag cannot account for the high rate of silver transport to the surface. Pipe-diffusion controlled creep is proposed as the mechanism of stress accommodation by silver diffusion.     

Interdiffusion in β-Ti–Zr binary alloys

The aim of this study is the determination of the interdiffusion characteristics in the β-solid solution of Ti–Zr alloys (from 830 to 1730 °C). The interdiffusion coefficients in this binary system are calculated by the den Broeder method. The interdiffusion coefficients are weakly dependent on the composition: their values lie between approximately 10⁻⁹ and 10⁻⁷ cm²/s. The Hall method is used to determine the diffusion coefficients at the Ti-rich and Zr-rich sides. These coefficients are compared with the impurity diffusion coefficients in the pure metals from the literature, and with coefficients calculated by the Vignes and Birchenhall relation. Whereas the impurity diffusion coefficients in Ti and Zr show the anomalous diffusion already observed in many body-centered-cubic metals and alloys, this behaviour is not observed for the interdiffusion in the Ti–Zr alloys. These results are compared with the results obtained in the binary systems Ti–Hf and Zr–Hf.     

Effect of creep on the oxidation characteristics of Fe-Si alloys at 973–1073 K

Studies of the simultaneous creep and oxidation of Fe-1Si and Fe-4Si alloys at a constant tensile stress of 16 N· mm^–2 at 973–1073 K have shown that scales formed at oxygen partial pressures of 20–1013 mbar were thicker by a factor of 2 than those formed on uncrept specimens. Scales on uncrept alloys comprised alternate layers of wustite and fayalite, whereas scales on crept alloys exhibited an additional external layer of magnetite. Only intergranular oxidation (fayalite) was observed in uncrept alloys, but crept alloys showed both intra- and intergranular oxidation (silica). Uniquely nodular scales were formed only on the Fe-4Si alloy on crept and uncrept specimens. Oxidized, uncrept Fe-1Si showed a fine-grained ferrite substrate which was absent in the crept alloy. It is believed that oxide growth stresses stimulated a recrystallization process.     

Oxidation of copper-manganese alloys under pure oxygen

Oxidation, in oxygen gas at atmospheric pressure, of copper-manganese alloys (Mn content less than 40 at.%) has been investigated between 600 and 850° C. The reaction kinetics, determined by thermogravimetry, follow a parabolic law for alloys having a low manganese content (less than 10 at.% Mn) but are more complex for higher concentrations, particularly in the first stages of the oxidation process. Whereas in the early stages of oxidation the kinetics are controlled by surface reactions which accompany the formation of the different oxide layers, they are later controlled by the diffusion of a mobile species when the parabolic law is followed. In this condition an apparent activation energy may be determined from the rate constants. These energies are of the order of 120–140 kJ mol^–1, comparable with that for oxidation of pure copper (134 kj mol^–1), indicating a similar oxidation mechanism.The oxide layers formed were identified by cross-checking results of X-ray diffraction, electron microprobe analysis, and from glow discharge spectrometry. External layers of CuO and Cu₂O formed on alloys of lower manganese concentration, evolving towards one or several mixed copper-manganese oxide layers with increasing manganese content. Under the external layers, which were weakly adherent to the sample, an internal-oxidation layer formed, which was adherent and consisted of precipitates of Mn₃O₄/MnO dispersed in the copper lattice. For alloys richer in manganese (36 at. % Mn) and at temperatures above 850°C (20 at.% Mn), the internal-oxidation layer evolved into two zones: MnO particles beneath a zone of Mn₃U₄ particles.     

The oxidation properties of U-16.6 at.% Nb-5.6 at.% Zr and U-21 at.% Nb

The fundamental oxidation characteristics of two U-base alloys, U-16.6 at.% Nb-5.6 at.% Zr and U-21at.% Nb, in the temperature range 500–1000° C in oxygen at 0.05 Torr are described. Both alloys undergo large dimensional changes during oxidation at temperatures above 650° C due to stresses generated in the oxide during oxidation. Oxidation rate curves for both alloys were determined at 100° C intervals between 500 and 1000° C; the activation energy for the process is shown to be small. The morphology of the oxide scale formed on the two alloys is complex and is described in detail. Stresses estimated at 10⁶ psi are shown to develop in oxidizing specimens, and a mechanism for the generation of these stresses is proposed.Research sponsored by the U.S. Atomic Energy Commission under contract with the Union Carbide Corporation.     

Effect of 1 wt.% yttrium addition on high-temperature sulfidation behavior of Fe-15Cr-4Al alloy

High-temperature sulfidation studies have been carried out on Fe-15Cr-4Al with and without 1% Y in the temperature range 700–1000°C in an H ₂-H₂ S environment over the sulfur pressure range of 10 ^–9–10^–3 atm. Two-layered and three-layered sulfide scales were observed in both alloys at low and high sulfur pressures, respectively. The pegging phenomenon, similar to that occurring in high-temperature oxidation, across the innermost layer and substrate was observed in the case of the yttrium-containing alloy. Yttrium was found to be associated with aluminum and chromium sulfides. The role of yttrium was more evident at low than at high sulfur pressures and was found to reduce the parabolic rate constants by a factor of about one-half to one-seventh, respectively.     

Phase relations in an Fe-Cr-S system at temperatures of 1073 and 1173 K in the sulfur pressure range from 100 to 10−5 Pa

Phase relations and stability fields in the Fe-Cr-S system were investigated at 1073 and 1173 K in the sulfur pressure range 10⁰–10^–5 Pa. The sulfides, produced by the sulfidation-annealing process of Fe-Cr alloys followed by rapid quenching, were characterized using X-ray diffraction powder analysis at room temperature. The Cr₃S₄ in the Cr-S system extends beyond the FeCr₂S₄ stoichiometry in the Fe-Cr-S ternary system at intermediate sulfur pressures. The spinel-monoclinic transition of the FeCr₂S₄ was observed at sulfur pressures of 10^–3–10^–3.5Pa at 1073 K and at 10⁰–10^–0.5 Pa at 1173 K. The free energy change for formation of the spinel, FeCr₂S₄, from a monoclinic (Cr, Fe)₃S_4–y, hexagonal (Fe, Cr)_1–xS, and sulfur vapor is given by the relation G = –1523 + 1.09 T (kJ/mol). The phase-transition mechanism of FeCr₂S₄ is discussed on the basis of an enhancement of the cation coordination numbers from 4-6-6 for the spinel to 6-6-6 for the monoclinic, when the sulfur partial pressure decreases.Emeritus Professor.     

Influence of oxidation rate and alloy composition on alloy enrichments of anodized Al–W alloys

The effect of oxidation rate on enrichment of tungsten in metastable, solid-solution Al–W alloys during anodizing has been investigated by Rutherford backscattering spectroscopy and medium energy ion scattering. The oxidation rate has negligible influence upon enrichment for current densities in the range 0.01–100 mA cm⁻², with levels between 1.3 × 10¹⁵ and 1.5 × 10¹⁵ W atoms cm⁻² for an Al–0.7at.%W alloy. Further, enrichment factors, expressing the ratio of the enrichment of tungsten in the alloy, in units of 10¹⁵ atoms cm⁻², to the bulk composition of the alloy, in units of at.%, for alloys of compositions in the range 0.1–30 at.%W, decrease progressively in the approximate range 2.5–0.2.     

Synthesis of FCC Mg–Zr and Mg–Hf hydrides using GPa hydrogen pressure method and their hydrogen-desorption properties

Magnesium-based hydrides with Zr or Hf have been synthesized by means of an ultra-high pressure technique. Powder mixtures of MgH₂ and ZrH₂ or HfH₂ have been heated up to 873 K under 4–8 GPa in a multi-anvil cell. New ternary phases (Mg–Zr–H and Mg–Hf–H) with a face centered cubic (FCC) structure have been formed. In the Mg–Zr hydride, the FCC phase with disordered metal–atom occupancy was observed, while a Ca₇Ge-type super-lattice structure was observed in the Mg–Hf hydride. By the temperature programmed desorption (TPD) measurements, these new hydrides exhibit the hydrogen-desorption at around 543–583 K, which were 130–70 K lower than that of MgH₂ at a heating rate of 10 K/min under vacuum. Desorbed hydrogen contents were estimated to be 4.2 and 3.0 mass% for Mg–Zr and Mg–Hf hydrides, respectively.     

Selective oxidation of Fe-30Cr at low temperatures: 743–823 K

Fe-30 Cr specimens were oxidized for 6×10²–3.6×10⁴ s at 743–823 K in pure oxygen at a pressure of 1.33×10⁴ Pa. Depth profiling of oxidized surfaces was performed with the simultaneous use of Auger electron spectroscopy (AES) and inert gas-ion (Ar⁺ or Xe⁺) sputter-etching technique. Chromium was selectively oxidized, and a chromium-depletion zone was formed in the underlying alloy. The values (10^–16–10^–15 cm² s^–1) of the interdiffusion coefficient, D, of the underlying alloy evaluated from the depth-composition profiles were compared in magnitude with the values extrapolated from lattice diffusion data of the corresponding alloy obtained at high temperature. The apparent activation energy obtained from an Arrhenius plot of the evaluated diffusion coefficient, however, was one-third of the value for the corresponding alloy at high temperatures. Discussion was made on the possible mechanism of selective oxidation at low temperatures.     

Defect structure of NiO and rates and mechanisms of formation from atomic oxygen and nickel

The oxidation of nickel by atomic oxygen at pressures from 6×10^–3 to 0.33 Torr between 1050 and 1250 K has been investigated. In these ranges, the oxidation was found to follow the parabolic rate law, viz.k _p = 1.14×10^–5 exp(–13410/T)g² cm^–4sec^–1 for films of greater than 1 m thickness and was pressure-independent. The activation enthalpy for the oxidation reaction was 27±3 kcal mole^–1. Of a number of possible mechanisms and defect structures considered, it was shown that, based on reaction activation enthalpies, impurity effects, pressure independence, and magnitudes of the rates, the most likely was a saturated surface defect model for atomic oxidation. A possible model judged somewhat less likely was one having equilibrium concentrations of doubly ionized cationic defects rate-controlling in both atomic and molecular oxygen. From comparisons of the appropriate processes, the following enthalpy values were derived: H* (Ni diffusion in NiO) = 26.5 ± 8 kcal mole^–1 and H _f ⁰ (doubly ionized cation vacancies in NiO from atomic oxygen) = – 2.1 ± 6.0 kcal mole^–1. The recombination coefficient of atomic oxygen on oxidized nickel was determined to be 0.14 ± 0.06 in the temperature range 985 to 1100 K.     

An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C

The corrosion of M–Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10^–24 atm at 600°C and 10^–20 atm at 700–800°C). Except for the Co–Nb and Ni–Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O₂ pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.     

On the oxidation mechanism of alumina formers

The oxidation mechanism of the intermetallic compound -NiAl and Fe-23Cr-5Al-0.2Zr alloys modified by reactive-element additions was studied in the temperature range 1273–1473 K by means of the two-stage oxidation method using the oxygen isotope¹⁸O as a tracer. It was found that outward cation diffusion predominates in the scale on -NiAl. The contribution of the inward oxygen transport increased with increased reaction temperature and oxidation time. At 1473 K, implanted yttrium suppressed inward oxygen diffusion for oxidation times less than 1 hr. In the case of Fe-Cr-Al-Zr alloys the counter-current transport of reactants was observed on the non-implanted materials. Implanted yttrium was found to alter the transport mechanism. This effect appeared to be directly related to that of yttrium on the scale morphology and microstructure. Yttrium promoted the formation of cracks which provided an additional surface for the reaction.On leave from Academy of Mining and Metallurgy, Krakow.     

Microstructure and properties of Ti–Co–Si ternary intermetallic alloys

Ti–Co–Si ternary intermetallic alloys with Ti₅Si₃ as the main reinforcing phase and intermetallic TiCo as the toughening matrix were fabricated by the laser-melting deposition (LMD) process. Microstructure of the intermetallic alloys was characterized by OM, SEM, XRD and EDS. High-temperature oxidation resistance of the alloys was evaluated by isothermal oxidation at 1173 K and metallic dry-sliding wear property was evaluated at room temperature. The effect of reinforcing phase Ti₅Si₃ content on hardness, oxidation and wear resistance of the alloys was investigated. Results indicate that microstructure of the alloys transforms from hypoeutectic to hypereutectic, while hardness and oxidation resistance increases with the increasing Ti₅Si₃ content. The alloys have good oxidation resistance at 1173 K and the oxidation kinetic curves are approximately parabolic. Wear resistance of the alloys is insensitive to the microstructure and is up to 15–19 times higher than the hardened tool steel 1.0%C–1.5%Cr under dry-sliding wear test conditions. The excellent wear resistance of alloys is attributed to the effective reinforcement of Ti₅Si₃ and the excellent toughness of the intermetallic TiCo.     

Effects of preformed alumina scales on the behavior of FeCrAl alloys in simulated coal-gasifier atmospheres

Iron-based mechanical alloys containing 3.2–6.6 Al, 16.0–24.7 Cr, 0.5 Ti, and 0.5 Y₂O₃ (mass%) were preoxidized in air at 1373 K for 10–180 min. Alumina scales were formed. Scales were isolated and examined in a high-voltage transmission electron microscope. Specimen sections were examined in a scanning electron microscope. Specimens were exposed to atmospheres exhibiting oxygen activities from 1.5×10^–13 to 1.4×10^–14 and sulfur activities from 7.4×10^–7 to 3.6×10^–5 at 1123, 1223, and 1323 K. Alumina, chromia, and iron sulfide are thermodynamically stable under these conditions. Sulfidation did not occur at 1223 or 1323 K. Specimens exposed at 1123 K were sulfidized and formed a scale containing iron, chromium, and sulfur. The period before the onset of sulfidation was dependent on the preoxidation time. A model is developed to account for the temperature dependence of the sulfidation in terms of the alloy-interdiffusion rate of aluminum and the activity of the sulfidizing species at the scale-gas interface.